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[0001] The following identified paragraphs will replace the
prior disclosure of the same paragraphs in the application.
This application is a continuation-in-part application of
United States Patent Application having Serial Nos.
11/303,670, 11/303,422, 11/303,892, 11/303,671, and 11/303,707
all filed December IS, 2005; and United States Patent
Application No. 11/3 03,832 filed December 16, 2005, which is a
continuataion-in-part application of United States Patent
Application No. 11/141,636, filed May 31, 2005, which is a
continuation-in-part application of United States Patent
Application No. 10/725,023 filed December 2, 2003 claiming the
benefit of priority of US Provisional Patent Application No.
60/435,537 filed December 20, 2002, which is a continuationin-
part application of United States Patent Application No.
10/287,716 filed November 5, 2002 claiming the benefit of
priority of US Provisional Patent Application No. 60/332,829
filed November 16, 2001.
[0002] The present invention relates to sulfur-containing
polyureaurethanes and methods for their'preparation,
[0003] A nijmber of organic polymeric materials, such as
plastics, have been developed as alternatives and replacements
for glass in applications such as optical lenses, fiber
optics, windows and automotive, nautical and aviation
transparencies. These polymeric materials can provide
advantages relative to glass, including, shatter resistance,
lighter weight for a given application, ease of molding and
ease of dying. However, the refractive indices of many
polymeric materials are generally lower than that of glass.
In ophthalmic applications, the use of a polymeric material
liaving a lower refractive index will require a thicker lens
relative to a material having a higher refractive index. A
thicker lens is not desirable.
[0004] Thus, there is a need in the art to develop a
polymeric material having an adequate refractive index and
good impact resistance/strength.
WO2007/09779G ¥erffi9mmUM9.
[0005] The present invention is directed to a sulfurcontaining
polyureaurethane when at least partially cvired
having a refractive index of at least 1.55, or at least 1.56,
or at least 1.57, or at least 1.58, or at least 1.59, or at
least 1.60, or at least 1.62, or at least 1.65; an Abbe number
of at least 32 and a density of at least 1.0, or at least 1.1,
or less than 1.2 grams/cm', or less than 1.3 grams/cm^.
[0006] As used herein and the claims, curing of a
polymerizable composition refers to subjecting said
composition to curing conditions such as but not limited to
thermal curing, leading to the reaction of the reactive endgroxips
of said composition, and resulting in polymerization
and formation of a solid polymerizate. When a polymerizable
composition is subjected to curing conditions, following
polymerization amd after reaction of most of the reactive end
groups occurs, the rate of reaction of the remaining vmreacted
reactive end groups becomes progressively slower. In a nonlimiting
embodiment, the polymerizcible composition can be
subjected to curing conditions until it is at least partially
cured. The teirm "at least partially cured" means subjecting
the polymerizable composition to curing conditions, wherein
reaction of at least a portion of the reactive end-groups of
said composition occurs, to form a solid polymerizate, such
that said polymerizate can be deraolded, and cut into test
pieces, or such that it may be subjected to machining
operations, including optical lens processing.
[0007] In a non-limiting embodiment, the polymerizable
composition can be subjected to curing conditions, such that a
stibstantially complete cure is attained and wherein further
curing results in no significant further improvement in
polymer properties, such as hardness.
[0008] For the purposes of this specification, unless
otherwise indicated, all numbers expressing quantities of
ingredients, reaction conditions, and so forth used in the
specification and claims are to be understood as being
modified in all instances by the term "about." Accordingly,
unless indicated to the contrary, the numerical parameters set
•^O 2667/097798 rCTAJS2006/01(;()ifl,
forth in the following- specification and attached claims are
approximations that may vary depending upon the desired
properties sought to be obtained by the present invention. At
the very least, and not as an attempt to limit the application
of the doctrine of ecpiivalents to the scope of the claims,
each numerical parameter should at least be construed in light
of the number of reported significant digits and by applying
ordinary rounding techniques.
[00091 Notwithstanding that the numerical ranges emd
parameters setting forth the broad scope of the invention are
approximations, the numerical values set forth in the specific
examples are reported as precisely as possible. Any numerical
value, however, inherently contain certain errors necessarily
resulting from the standard deviation found in.their
respective testing measurements.
[0010] In a non-limiting embodiment, the sulfur-containing
polyureaurethane of the present invention can be prepared by
combining polyisocyanate and/or polyisothiocyanate; active
hydrogen-containing material, and amine-containing curing
agent.
[0011] As used herein and the claims, the terms
"isocyainate" and "isothiocyanate" include \inblocked compounds
capable of forming a covalent bond with a reactive group such
as a thiol, hydroxyl, or amine functiorial group. In alternate
non-limiting embodiments, the polyisocyanate of the present
invention can contain at least two fionctional groups chosen
from isocyanate (NCO), the polyisothiocyanate can contain at
least two functional groups chosen from isothiocyanate (NCS),
and the isocyanate and isothiocyanate materials can each
include combinations of isocyanate and isothiocyanate
functional groups.
[0012] In alternate non-limiting embodiments, the
polyureaurethane of the invention when polymerized can produce
a polymerizate having a refractive index of at least 1.55, or
at least 1.56, or at least 1.57, or at least 1.58, or at least
1.59, or at least 1.60, or at least 1.62, or at least 1.65.
In further alternate non-limiting embodiments, the
wo 2007/097798 vrT(\m2mmm\'}
polyureaurethane of the invention when polymerized can produce
a polymerizate having an Abbe number of at least 32, or at
least 35, or at least 38, or at least 39, or at least 40, or
at least 44. The refractive index and Abbe number can be
determined by methods known in the art such as American
Standard Test Method (ASTM) Number D 542-00. Further, the
refractive index and Abbe number can be determined using
various known instruments. In a non-limiting embodiment of
the present invention,' the refractive index and Abbe number
can be measured in accordance with ASTM D 542-00 with the
following exceptions: (i) test one to two samples/specimens
instead of the minimum of three specimens specified in Section I
7.3; and (ii) test the samples unconditioned instead of
conditioning the samples/specimens prior to testing as
specified in Section 8.1. Further, in a non-limiting
embodiment, an Atago, model DR-M2 Multi-Wavelength Digital |
Abbe Refractometer can be used to measure the refractive index
and Abbe number of the samples/specimens.
[0013] In a non-limiting embodiment, the sulfur-containing
polyureaurethane of the present invention can be prepared by
reacting polyisocyanate and/or polyisothiocyanate with active
hydrogen-containing material selected from polyol, polythiol,
or combination thereof, to form polyurethane prepolymer or
sulfur-containing polyurethane prepolymer; and chain extending
(i.e., reacting) said prepolymer with amine-containing curing
agent, wherein said amine-containing curing agent optionally
includes active hydrogen-containing material selected from
polyol, polythiol, or combination thereof.
[0014] In alternate non-limiting embodiments, the amount of
polyisocyanate and the amount of active hydrogen-containing
material used to prepare isocyanate terminated polyurethane
prepolymer or sulfur-containing polyurethane prepolymer can be
selected such that the equivalent ratio of (NCO) : (SH + OH) can
be greater than 1.0:1.0, or at least 2.0:1.0, or at least
2.5:1,0, or less than 4.5:1.0, or less than 5.5:1.0; or the
amount of polyisothiocyeinate and the amount of active
hydrogen-containing material used to prepare isothiocyanate
wo ;i007/09779g' PCT/US2006/0 46619
terminated sulfur-containing polyurethaxie prepolymer can be
selected such that the equivalent ratio of (NCS):(SH + OH) can
be greater than 1.0:1.0, or at least 2.0:1.0, or at least
2.5:1.0, or less than 4.5:1.0, or less than 5.5:1.0; or the
amo\mt of a combination of polyisothiocyanate and
polyisocyanate and the amount of active hydrogen-containing
material used to prepare isothiocyanate/isocyanate terminated
sulfur-containing polyurethane prepolymer can be selected such
I
that the.equivalent ratio of (NCS + NCO):(SH + OH) can be i
greater than 1.0:1.0, or at least 2.0:1.0, or at least
2.5:1.0, or less than 4.5:1.0, or less than 5.5:1.0
[0015] In a non-limiting embodiment, the amount of
isocyanate terminated polyurethane prepolymer or sulfurcontaining
prepolymer and the amount of amine-containing
curing agent used to prepare sulfur-containing
polyureaurethane can be selected such that the equivalent
ratio of (NH + SH + OH) : (NCO) can range from 0.80:1.0 to
1.1:1.0, or from 0.85:1.0 to 1.0:1.0, or from 0.90:1.0 to
1.0:1.0, or from 0.90:1.0 to 0.95:1.0, or from 0.95:1.0 to
1.0:1.0.
[0016] In another non-limiting embodiment, the amount of
isothiocyanate or isothiocyanate/isocyanate terminated sulfurcontaining
polyurethane prepolymer and the amount of aminecontaining
curing agent used to prepare sulfur-containing
polyureaurethane can be selected such that the equivalent
ratio of (NH + SH + OH) : (NCO + NCS) can range from 0.80:1.0
to 1.1:1.0, or from 0.85:1.0 to 1.0:1.0, or from 0.90:1.0 to
1.0:1.0, or from 0.90:1.0 to 0.95:1.0, or from 0.95:1.0 to
1.0:1.0.
[0017] Polyisocyanates and polyisothiocyanates useful in
the preparation of the polyureaurethane of the present
invention are numerous and widely varied. Suitable
polyisocyanates for use in the present invention can include
but are not limited to polymeric and C2-C20 linear, branched,
cycloaliphatic and aromatic polyisocyanates. Suitable
polyisothiocyanates for use in the present invention can
wo 2007/097798 •PCT/UG2006/046649
include but are not limited to polymeric and C2-C20 linear,
branched, cyclic and aromatic polyisothiocyeuiates, Nonlimiting
examples can include polyisocyanates and
polyisothiocyanates having backbone linkages chosen from
urethane linkages (-NH-C(O)-0-), thiourethane linkages (-NHC(
O)-S-), thiocarbamate linkages (-NH-C(S)-0-), dithiourethane
linkages (-NH-C{S)-S-) and combinations ,thereof.
[0018] The molecular weight of the polyisocyanate and
polyisothiocyanate can vary widely. In alternate non-limiting
embodiments, the number average molecular weight (Mn) of each
can be at least 100 grams/mole, or at least 150 grams/mole, or
less than 15,000 grams/mole, or less than 5000 grams/mole.
The number average molecular weight can be determined using
known methods. The number average molecular weight values
recited herein and the claims were determined by gel
permeation chromatography (GPC) using polystyrene standards.
[0019] Non-limiting examples of suitable polyisocyanates
and polyisothiocyanates can include but are not limited to
polyisocyanates having at least two isocyanate groups;
polyisothiocyanates having at least two isothiocyanate groups;
mixtures thereof; auid combinations thereof, such as a material
having isocyanate and isothiocyanate functionality.
[0020] Non-limiting examples of polyisocyanates and
polyisothiocyanates can include but are not limited to those
described in WO 2004/060951 Al at paragraphs [0014] to [0035],
incorporated by reference herein.
[0021] In further alternate non-limiting embodiments, the
polyisocyanate can include raeta-tetramethylxylylene
diisocyanate (1,3-bis(1-isocyanato-l-methylethyl-benzene); 3-
isocyanato-methyl-3,5,5,-trimethyl-cyclohexyl isocyanate; 4,4-
methylene bis(cyclohexyl isocyanate); meta-xylylene
diisocyanate; and mixtures thereof.
[0022] In a non-limiting embodiment, the polyisocyanate
and/or polyisothiocyanate can be reactecl with an active
hydrogen-containing material to form a polyurethane
prepolymer. Active hydrogen-containing materials are varied
and known in the art. Non-limiting examples can include
wo 2007/097790 •rCTAJ02006/046()'
hydroxyl-containing materials such as but not limited to
polyols; sulfur-containing materials such as but not limited
to hydroxyl functional polysulfides, and SH-containing
materials such as but not limited to polythiols; and materials
having both hydroxyl and thiol functional groups.
[0023] Suitable hydroxyl-containing materials for use in
the present invention can include a wide variety of materials
known in the art. Non-limiting examples can include but are
not limited to polyether polyols, polyester polyols,
polycaprolactone polyols, polycarbonate polyols, polyuretheine
polyols, poly vinyl alcohols, polymers containing hydroxy
functional acrylates, polymers containing hydroxy functional
methac3rylates, polymers containing allyl alcohols and mixtures
thereof.
[0024] Polyether polyols and method^ for their preparation
are known to one skilled in the art. Many polyether polyols
of various types and molecular weight are commercially
available from various manufacturers. Non-limiting examples
of polyether polyols qan include but are not limited to those
described in WO 2004/060951 Al at paragraphs [0038] to [0040]
incorporated herein by reference. Compatible mixtures of
polyether polyols can also be used. As used herein,
'"compatible" means that two or more materials are mutually
soluble in each other so as to essentially form a single
phase.
[0025] A variety of polyester polyols and polycaprolactone
polyols suitable for use in the present invention are known in
the art. Suitable polyester polyols and polycaprolactone
polyols can include but are not limited" to those described in
WO 2004/060951 Al at paragraphs [0041] and [0042] ,
respectively, incorporated by reference herein.
[0026] Polycarbonate polyols for use in the present
invention are varied and known to one skilled in the art.
Suitable polycarbonate polyols can include those described in
WO 2004/060951 Al at paragraphs [0043], incorporated by
reference herein.
wo 2007/097790 vcTfimmmmi^} ,
[0027] Further non-limiting examples of active hydrogencontaining
materials can include low molecular weight difunctional
and higher functional polyols and mixtures thereof.
In a non-limiting embodiment, these low molecular weight
materials can have a number average molecular weight of less
than 500 grams/mole. In a further non-limiting embodiment,
the amount of low molecular weight material chosen can be such
to avoid a high degree of cross-linking in the polyurethane.
The di-f\inctional polyols typically contain from 2 to 16, or
from 2 to 6, or from 2 to 10, carbon atoms. Non-limiting
examples of such difunctional polyols can include but are not
limited to ethylene glycol, propylene glycol, diethylene
glycol, triethylene glycol, tetraethylene glycol, dipropylene
glycol, tripropylene glycol, 1,2-, 1,3- and 1,4-butanediol,
2,2,4-triraethyl-1,3-pentanediol, 2-methyl-1,3-pentanediol,
1,3- 2,4- and 1,5-pentanediol, 2,5- and 1,6-hexanediol, 2,4- |
heptanediol, 2-ethyl-l,3-hexanediol, 2,2-dimethyl-1,3-
propanediol, 1,8-octanediol, 1,9-nonaJiediol, 1,10-decanediol,
1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,2-
bis (hydroxyethyl)-cyclohexane and mixtures thereof. Nonlimiting
examples of trifunctional or tetrafvinctional polyols
can include glycerin, tetramethylolmethane, pentaerythritol,
trimethylolethane, trimethylolpropane, alkoxylated polyols
such as but not limited to ethoxylated trimethylolpropane,
propoxylated trimethylolpropane, ethoxylated
trimethylolethane; and mixtures thereof.
[0028] In alternate non-limiting embodiments, the active
hydrogen-containing material can have a number average
molecular weight of at least 200 grams/mole, or at least 400
grams/mole, or at least 1000 grams/mole, or at least 2000
grams/mole. In alternate non-limiting embodiments, the active
hydrogen-containing material can have a number average
molecular weight of less than 5,000 grams/mole, or less than
10,000 grams/mole, or less than 15,000 grams/mole, or less
than 20,000 grams/mole, or less than 32,000 grams/mole.
[00291 In a non-limiting embodiment, the active hydrogencontaining
material can comprise block polymers including
\\Ui007/09779& PCT/US2006/01661fl
blocks of ethylene oxide-propylene oxide and/or ethylene
oxide-but ylene oxide. In a non-limiting ettibodiment, the
active hydrogen-containing material can comprise a block
copolymer of the following chemical formula:
HO- (CHRxCHRa-O)a- (CHR3CHR4-0)b- (CHRsCHRg-Oc-H
(I")
wherein Ri through Rg dan each independently represent hydrogen
or methyl; a, b, and c can each be independently an integer
from 0 to 300. wherein a, b and c are chosen such that the
number average molecular weight of the polyol does not exceed
32,000 grams/mole, as detearmined by GPC. In another nonlimiting
embodiment, a, b, and c can be chosen such that the
number average molecular weight of the polyol does not exceed
10,000 grams/mole, as determined by GPC. In another nonlimiting
embodiment, a, b, and c each can be independently an
integer from 1 to 300. In a non-limiting embodiment, Ri, R2,
Rs, and Rg can be hydrogen, and R3 and R4 each can be
independently chosen from hydrogen and methyl, with the
proviso that R3 and R4 are different from one another. In
another non-limiting embodiment, Rj and R4 can be hydrogen, and
Ri and R2 each can be independently chosen from hydrogen and
methyl, with the proviso that Ri and Rj are different from one
another, and Rs and Rg each can be independently chosen from
hydrogen and methyl, with the proviso that Rg and Rg are
different from one another.
[0030] In further alternate non-limiting embodiments,
Pluronic R, Pluronic L62D, Tetronic R or Tetronic, which are
commercially available from BASF, can be used as active
hydrogen-containing material in the present invention.
Non-limiting examples of suitable polyols for use in the
present invention can include but are not limited to those
described in WO 2004/060951 Al at paragraphs[0050] at page 17
to page 18, line 6, incorporated by reference herein.
[0031] In a further non-limiting embodiment, the polyol can
be a polyurethane prepolytner having two or more hydroxy
j
wo 2007/097798. PCT/US3006/01661{>
functional groups. Such polyurethane prepolymers can be
prepared from any of the polyols and polyisocyanates
previously described herein. In a non-limiting embodiment,
the OH:NCO equivalent ratio can be chosen such that
essentially no free NCO groups are produced in preparing the
polyurethane prepolymer. In alternate non-limiting
embodiments, the equivalent ratio of OH to NCO (i.e.,
isocycinate) present in the polyurethane prepolymer can be an
amount of from 2.0 to less than 5.5 OH/1.0 NCO.
[0032] In alternate non-limiting embodiments, the
polyurethane prepolymer can have a number average molecular
weight (Mn) of less than 50,000 grams/mole, or less than
20,000 grams/mole, or less than 10,000 grams/mole, or less
than 5,000 grams/mole, or greater than 1,000 grams/mole or
greater than 2,000 grams/mole.
[0033] In a non-limiting embodiment, the active hydrogencontaining
material for use in the present invention can
include sulfur-containing materials such as SH-containing
materials, such as but not limited to polythiols having at
least two thiol groups. Non-limiting examples of suitable
polythiols can include but are not limited to aliphatic
polythiols, cycloaliphatic polythiols, aromatic polythiols,
heterocyclic polythiols, polymeric polythiols, oligomeric
polythiols and mixtures thereof. The sulfur-containing active
hydrogen-containing material can have linkages including but
not limited to ether linkages (-0-), suj.fide linkages (-S-),
polysulfide linkages {-S,-, wherein x is at least 2, or from 2
to 4) and combinations of such linkages. As used herein and
the claims, the terms "thiol," "thiol group," "mercapto" or
"mercapto group" refer to an -SH group which is capable of
forming a thiourethane linkage, (i.e., -NH-C(O)-S-) with an
isocyanate group or a dithioruethane linkage (i.e., -NH-C(S)-
S-) with an isothiocyanate group.
[0034] Non-limiting examples of suitable polythiols can
include but are not limited to 2,5-dimercaptomethyl-l,4-
dithiane, dimercaptoethylsulfide, pentaerythritol tetrakis(3-
mercaptopropionate), pentaerythritol tetrakis(2-
•WO2007/0977Q8. -P€T«JSfOOWW
•
mercaptoacetace) , trimethylolpropane tris(3-
mercaptopropionate) , trimethylolpropane tris(2-
mercaptoacetate), 4-mercaptomethyl-3,6-dithia-l,8-
octanedithiol, 4-tert-butyl-l,2-benzenedithiol, 4,4'-
thiodibenzenethiol, ethanedithiol, benzenedithiol, ethylene
glycol di(2-mercaptoacetate) , ethylene glycol di(3- |
mercaptopropionate), poly (ethylene glycol) di(2- I
mercaptoacetate) and poly (ethylene glycol) di(3-
mercaptopropionate), and mixtures thereof.
In a non-limiting embodiment, the polythiol can be chosen from
materials described in-WO 2004/060951 Al at paragraphs [0056]
to [0061], incorporated by reference herein.
The nature of the SH group of polythiols is such that
oxidative coupling can occur readily, leading to formation of
disulfide linkages. Various oxidizing agents can lead to such
oxidative coupling. The oxygen in the air can in some cases
lead to such oxidative coupling during storage of the
polythiol. It is believed that a possible mechanism for the
coupling of thiol groups involves the formation of thiyl
radicals, followed by coupling of said thiyl radicals, to form
disulfide linkage. It is further believed that formation of
disulfide linkage can occur under conditions that can lead to
the formation of thiyl radical, including but not limited to
reaction conditions involving free radical initiation.
[0035] In a non-limiting embodiment, the polythiol for use
in the present invention can include species containing
disulfide linkage formed during storage.
[0036] In another non-limiting embodiment, the polythiol
for use in the present invention can include species
containing disulfide linkage formed during synthesis of said
polythiol.
[0037] In a non-limiting embodiment, the polythiol for use
in the present invention, can include at least one polythiol
described in WO 2004/060951 Al at paragi'aphs [0062] to [0093] ,
incorporated by reference herein.
[0038] In a non-limiting embodiment, polythiol for use in
the present invention can include polythiol oligomer formed by
w o 2007/097798 PCTAJGa006/01CC
the reaction of dithiol with diene, via thiol-ene type
reaction of SH groups of said dithiol with double bond groups
of said diene.
[0039] In a non-limiting embodiment, polythiol for use in
the present invention can include at least one oligomeric
polythiol as follows:
(IV'f)
wherein Ri can be d to Cg n-alkylene; C3 to Cg alkylene
xansubstituted or substituted wherein substituents can be
hydroxyl, methyl, ethyl, methoxy or ethoxy; or Cg to Cg
cycloalkylene; R2 ceui be C2 to Cg n-alkylene, C2 to Cg branched
alkylene, Cg to Ca cycloalkylene, Cg to Cio alkylcycloalkylene or
--[(CHa --)p --0--]q --(--CH2 --)r --; m can be a rational
number from 0 to 10, n can be an integer from 1 to 20, p can I
be an integer from 2 to 6, q can be sm integer from 1 to 5,
and r can be an integer from 2 to 10.
[0040] Various methods of preparing the polythiol of
formula (IV'f) are described in detail in United States Patent
6,509,41881, coluntti 4, line 52 through column 8, line 25,
which disclosure is herein incorporated by reference. In
general, this polythiol can be-prepared by combining reactants
comprising one or more polyvinyl ether monomer, and one or
more polythiol. Useful polyvinyl ether monomers can include
but are not limited to divinyl ethers represented by
structural formula ( V ):
CH2=CH--0--(--Ra --0--)„ --CH=CH2 (V )
•WO200T/097798 -P€TAJS2006/046649
wherein R2 can be C2 to Cg n-alkylene, C2 to Cs branched
alkylene, Cg to CB cycloalkylene, Cg to Cio alkylcycloalkylene or
--[(CH2 --)p --0--], --(--CH2 --)r --/ m is a rational number
ranging from 0 to 10, p is an integer from 2 to 6, q is an
integer from 1 to 5 and r is an integer from 2 to 10.
[0041] In a non-limiting embodiment, m can be two (2).
[0042] Non-limiting examples of suitable polyvinyl ether
monomers for use can include divinyl ether monomers, such as
but not limited to ethylene glycol divinyl ether, diethylene
glycol divinyl ether, butane diol divinyl ether and mixtures
thereof.
[0043] In alternate non-limiting embodiments, the polyvinyl
ether monomer can constitute from 10 to less than 5 0 mole
percent of the reactants used to prepare the polythiol, or
from 30 to less tlian 50 mole percent.
[0044] The divinyl ether of formula (V ) can be reacted
with polythiol such as but not limited to dithiol represented
by the formula {VI'):
HS--R1 --SH (VI')
wherein Ri can be Ca to Cs n-alkylene group; C3 to Cs branched
alkylene group, having one or more pendant groups which can
include but are not limited to- hydroxyl, alkyl such as methyl
or ethyl; alkoxy, or Cs to Cg cycloalkylene.
[0045] Further non-limiting examples of suitable polythiols
for reaction with Formula (V) can include those polythiols
represented by Formula 2^ herein.
[0046] Non-limiting examples of suitable polythiols for
reaction with Formula (V) can include but are not limited to
dithiols such as 1,2-ethanedithiol, 1.2-propanedithiol, 1,3-
propanedithiol, 1,3-butanedithiol, 1,4-butanedithiol, 2,3-
butanedithiol, 1,3-pentanedithiol, 1,5-pentanedithiol, 1,6-
hexanedithiol, 1,3-dimercapto-3-methylbutane,
dipentenedimercaptan, ethylcyclohexyldithiol (ECHDT),
dimercaptodiethylsulfide (DMDS), methyl-substituted
dimercaptodiethylsulfide, dimethyl-substituted
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•
dimercaptodiethylsulfide, dimercaptodioxaoctane, 1,5-
dimercapto-3-oxapentane and mixtures thereof.
[0047] In a non-limiting embodiment, the polythiol for
reaction with Formula (V ) can have a number average molecular
weight ranging from 90 to 1000 .grams/mole, or from 90 to 500
grams/mole. In a further non-limiting embodiment, the
stoichiometric ratio of polythiol to divinyl ether can be less
than one equivalent of polyvinyl ether to one equivalent of
polythiol.
[00481 In a non-limiting embodiment, the polythiol and
divinyl ether mixture can further include one or more free
radical initiators. Non-limiting examples of suitable free
radical initiators can include azo compounds, such as azobisnitrile
compounds such as but not limited to
azo (bis) isobutyronitrile (AIBN) ,- organic peroxides such as but
not limited to benzoyl peroxide and t-butyl peroxide,-
inorganic peroxides and similar free-radical generators.
[0049] In alternate non-limiting embodiments, the reaction
to produce the material represented by Formula (IV'f) can
include irradiation with ultraviolet light either with or
without a photoinitiator.
[0050] In a non-limiting embodiment, the polythiol for use
in the present invention can include materials, their
preparation, and reaction mixture ingredients therefore
described in WO 2004/060951 Al at paragraphs [00102] to
[00108], incorporated by reference herein.
[0051] In a fvirther non-limiting embodiment, "n+1" moles of
dimercaptoethylsulfide can be reacted with *n" moles of 4-
vinyl-l-cyclohexene, as shown above, in the presence of VAZO-
52 radical initiator.
[0052] In a non-limiting embodiment, the polythiol for use
in the present invention can include a material represented by
the following structural formula and reaction scheme:
wo :007.'0977JB rCT/U0a006/016619
o o
o o
R2 R2
(IV J)
wherein Ri and R3 each can be independently Ci to Cg n-alkylene,
Cj to Cg branched alkylene, Cs to Cg cycloalkylene, Cg to Cxo
alkylcycloalkylene, Cg to Cs aryl, Cg to Cio alkyl-aryl, Ci-Cio
alkyl containing ether linkages or thioether linkages or ester
linkages or thioester linkages or combinations thereof, --[(CHj
--)p --X--]q --(--CH2 --)r --1 wherein X can be 0 or S, p can be
an integer from 2 to 6, q can be an integer from 1 to 5, r can
be an integer from 0 to 10; R2 can be hydrogen or methyl; and n
can be an integer from 1 to 20.
[0053] In general, the polythiol of formula (IV'j) can be
prepared by reacting di (meth) acrylate monomer and one or more
polythiols. Non-limiting examples of suitable
di(meth)acrylate monomers can vary widely and can include
those known in the art, such as but not limited to ethylene
glycol diCmeth(acrylate, 1,3-butylene glycol di(meth)acrylate,
1,4-butanediol di(meth)acrylate, 2,3-dimethylpropane 1,3-
di(meth)acrylate, 1,6-hexeuiediol di (meth)acrylate, propylene
glcol di(meth)acrylate, dipropylene glycol di(meth)acrylate,
tripropylene glycol di (meth)acrylate, tetrapropylene glycol
di (meth)acrylate, ethoxylated hexanediol di(meth)acrylate,
propoxylated hexanediol di (meth)acrylate, neopentyl glycol
di (meth)acrylate, alkoxylated neopentyl glycol
di(meth)acrylate, hexylene glycol di(meth)acrylate, diethylene
glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate,
polybutadiene di(meth)acrylate, thiodiethyleneglycol
di (meth)acrylate, trimethylene glycol di(meth)acrylate,
triethylene glycol di(meth)acrylate, alkoxylated hexanediol
wo 2007/097798 PCT/UE2006/016(i1i)
di(Tneth)acrylate, alkoxyolated neopentyl glycol
di{meth)acrylate, pentanediol di (meth)acrylat:e, cyclohexane
dimethanol di(meth>acrylate, ethoxylated bis-phenol A
di(meth)acrylate.
[0054] Non-limiting examples of suitable polythiols for use
as reactants in preparing polythiol of Formula (IV'j) can vary
widely and can include those known in the art, such as but not
limited to 1,2-ethanedithiol, -1,2-propanedithiol, 1,3-
propanedithiol, 1,3-butanedithiol, 1,4-butanedithiol, 2,3-
butanedithiol, 1,3-pentanedithiol, 1,5-pentanedithiol, 1,6- i
hexanedi thiol, 1,3-dimercapto-3-methylbutane,
dipentenedimercaptan, ethylcyclohexyldithiol (ECHDT),
ditnercaptodiethylsulfide (DMDS) , methyl-siibstituted
dimercaptodiethylsulfide, dimethyl-substituted
dimercaptodiethylsulfide, dimercaptodioxaoctane, 3,6-
dioxa,1,8-octanedithiol, 2-mercaptoethyl ether, 1,5-
diraercapto-3-oxapentane, 2,5-dimercaptomethyl-l,4-dithiane
(DMMD),ethylene glycol di(2-mercaptoacetate), ethylene glycol
di (3-mercaptopropionate), and mixtures thereof.
[0055] In a non-limiting embodiment, the di(meth)acrylate
used to prepare the polythiol of formula (IV'j) can be
ethylene glycol di(meth)acrylate.
[0056] In another non-limiting embodiment, the polythiol
used to prepare the polythiol of formula (IV'j) can be
dimercaptodiethylsulfide (DMDS).
[0057] In a non-limiting embodiment, the reaction to
produce the polythiol of formula (IV'j) can be carried out in
the presence of base catalyst. Suitable base catalysts for
use in this reaction cam. vary widely and can be selected from
those known in the art. Non-limiting exan^les can include
but are not limited to tertiary amine bases such as 1,8-
diazeibicyclo [5.4.0]undec-7-ene (DBU) and N,Ndimethylbenzylamine.
The amount of base catalyst used can
vary widely. In a non-limiting embodiment, base catalyst can
be present in an amount of from 0.001 to 5.0% by weight of the
reaction mixture.
•
[0058] Not intending to be bovmd by any particular theory,
it is believed that as the mixture of polythiol,
di (meth) acrylate monomer, ajcxd base catalyst is reacted, the
double bonds can be at least partially consumed by reaction
with the SH groups of the polythiol. In a non-limiting
embodiment, the mixture' can be reacted for a period of time
such that the dotible bonds are substantially consumed and a
pre-calculated theoretical value for SH content is achieved.
In a non-limiting embodiment, the mixture can be reacted for a
time period of from 1 hour to 5 days. In another non-limiting
embodiment, the mixture can be reacted at a temperature of
from 20 °C to 100 °C. In a further non-limiting embodiment, the
mixture can be reacted until a theoretical value for SH
content of from 0.5% to 20% is achieved.
[0059] The number average molecular .weight (M„) of the
resulting polythiol can vary widely. In a non-limiting
embodiment, the number average molecular weight (Mn) of
polythiol can be determined by the stoichiometry of the
reaction. In alternate non-limiting embodiments, the M„ of
polythiol can be at least 400 g/mole, or less than or equal to
5000 g/mole, or from 1000 to 3 000 g/mole.
[0060] In a non-limiting embodiment, the polythiol for use
in the present invention can include a material represented by
the following structural formula and reaction scheme:
o o
o o
(IV k)
wherein Ri and R3 each can be independently Ci t o Cg n-alkylene,
C2 t o Ce branched alkylene, Ce t o Cg cycloalkylene, Cs t o Cio
alkylcycloalkylene, Cg t o Cg a r y l , Cg t o Cio a l k y l - a r y l , Ci-Cio
wo 2007/097798 PCTAJS2006/01CC19
alkyl containing ether linkages or thioether linkages or ester
linkages or thioester linkages or combinations thereof, --[(CH2
__)p --x--]q --(--CH2 --)r -"/ wherein X can be O or S, p can be
an integer from 2 to 6, q can be an integer from 1 to 5, r can
be an integer from 0 to 10; R2 can be hydrogen or methyl, and n
can be an integer from 1 to 20.
[0061] In general, the polythiol of formula (IV'k) can be
prepared by reacting polythio(meth)acrylate monomer, and one
or more polythiols. Non-limiting examples of suitable
polythio(meth)acrylate monomers can vary widely and can
include those ]cnown in the art such as but not limited to
di(meth)acrylate of 1,2-ethanedithiol including oligomers
thereof, di(meth)acrylate of dimercaptodiethyl sulfide (i.e.,
2,2'-thioethanedithiol- di(meth)acrylate) including oligomers
thereof, di(meth)acrylate of 3,6-dioxa-l,8-octanedithiol
including oligomers thereof, di(meth)acrylate of 2-
mercaptoethyl ether including oligomers thereof,
di(meth)acrylate of 4,4'-thiodibenzenethiol, and mixtures
thereof.
[0062] The polythio(meth)acrylate monomer can be prepared
from polythiol using methods known to those skilled in the
art, including but not limited to those methods disclosed in
US 4,810,812, US 6,342,571; and WO 03/011925. Non-limiting
examples of suitable polythiol- for use as reactant(s) in
preparing polythiols can include a wide variety of polythiols
known in the art, such as but not limited to 1,2-
ethanedithiol, 1,2-propanedithiol, 1,3-propanedithlol, 1,3-
butanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,3-
pentanedithiol, 1,5-pentanedithiol", 1,6-hexanedithiol, 1,3-
dimercapto-3-methylbutane, dipentenedimercaptan,
ethylcyclohexyldithiol (ECHDT), dimercaptodiethylsulfide,
methyl-substituted dimercaptodiethylsulfide, dimethylsubstituted
dimercaptodiethylsulfide, dimercaptodioxaoctane,
3,6-dioxa,l,8-octanedithiol, 2-mercaptoethy1 ether, 1,5-
dimercapto-3-oxapentane, 2,5-diraercaptomethyl-l,4-dithiane
(DMMD),ethylene glycol di(2-mercaptoacetate), ethylene glycol
di(3-mercaptopropionate), and mixtures' thereof.
I
w o 2007/097790 -PCT/USaOOO/O'ieCIP ••
[0063] In a non-limiting embodiment, the
polythio (meth) acrylate used to prepare the polythiol of
foimula (IV k) can be di (meth) acrylate of
dimercaptodiethylsulfide, i.e., 2,2'-thiodiethanethiol
dimethacrylate. In another nop-limiting embodiment, the
polythiol used to prepare the polythiol of formula (IV k) can
be dimercaptodiethylsulfide (DMDS).
[0064] In a non-limiting embodiment, this reaction can be
carried out in the presence of base catalyst. Non-limiting
examples of suitable base catalysts for use can vary widely
and can be selected from those known in the art. Non-limiting
examples can include but are not limited to tertiary amine
bases such as 1,8-diazabicyclo[5.4.0] undec-7-ene (DBU) and
N, N-dimethylbenzylamine.
[0065] The amo\ant of base catalyst used can vary widely.
In a non-limiting embodiment, the base catalyst can be present
in an amount of from 0.001 to 5.0% by weight of the reaction
mixture. In a non-limiting embodiment,, the mixture can be
reacted for a time period of from 1 hour to 5 days. In
another non-limiting embodiment, the mixture can be reacted at
a temperature of from 20 °C to 100 °C. In a further nonlimiting
embodiment, the mixture can be heated \intil a
precalculated theoretical value for SH content of from 0.5% to
20% is achieved.
[0066] The number average molecular weight (M„) of the
resulting polythiol cem vary widely. In a non-limiting
embodiment, the number average molecular weight (Mn) of
polythiol can be determined by the stoichiometry of the
reaction. In alternate non-limiting embodiments, the M„ of
polythiol can be at least 400 g/mole, or less than or equal to
5000g/mole, or from 1000 to 3000g/mole.
[0067] In a non-limiting embodiment, the polythiol for use
in the present invention can include a material represented by
the following structural formula and reaction:
w o 2007/09779C PCT/US2006/016C1!)
n ^^^^^^^^^^-"'^ + n+1 HS-^ ^"^SH ^
o
O
(IV I)
wherein Ri can be hydrogen or methyl, and Ra can be Ci to Cg nalkylene,
Ca to Cg branched alkylene, Cg to CB cycloalkylene, Cg
to Cio alkylcycloalkylene, Cg to Ce aryl,. Cs to Cio alkyl-aryl,
Ci-Cio alkyl containing ether linkages or thioether linkages or
ester linkages or thioester linkages or combinations
thereof,or --[(CHj --)p --X--]q --(--CHa --)r --/ wherein X can |
be O or S, p can be an. integer from 2 to 6, q can be an
integer from 1 to 5, r can be an integer from 0 to 10; and n
can be an integer from 1 to 20.
[0068] In general, the polythiol of formwla (IV'l) can be
prepared by reacting allyl(meth)acrylate, and one or more
polythiols.
[0069] Non-limiting examples of suitable polythiols for use
as reactant(s) in preparing polythiols can include a wide
variety of known polythiols such as but not limited to 1,2-
ethanedithiol, I,2-propanedithiol, 1,3-propanedithiol, 1,3-
butanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,3-
pentanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,3-
dimercapto-3-methylbutane, dipentenedimercaptan,
ethylcyclohexyldithiol (ECaiDT), dimercaptodiethylsulfide,
methyl-siabstituted dimercaptodiethylsulf ide, dimethylsubstituted
dimercaptodiethylsulfide, dimercaptodioxaoctane,
3,6-dioxa,1,8-octanedithiol, 2-mercaptoethyl ether, 1,5-
dimercapto-3-oxapentane, 2,5-dimercaptomethyl-l,4-
dithiane,ethylene glycol di (2-mercaptoacetate), ethylene
glycol di(3-mercaptopropionate), and mixtures thereof.
wo 2007/097790 -^CT/US2006/046649
[0070] In a non-limiting embodiment, the polythiol used to
prepare the polythiol of formula (IV' 1) can be
dimercaptodiethylsulfide (DMDS).
[00711 In a non-limiting embodiment, the (meth) acrylic
double bonds of allyl (meth)acrylate can be first reacted with
polythiol in the presence of base catalyst. Non-limiting
examples of suitable base catalysts can.vary widely and can be
selected from those known in the art. Non-limiting examples
can include but are not limited to tertiary amine bases such
as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and N,Ndimethylbenzylamine.
The amount of base catalyst used can
vary widely. In a non-limiting embodiment, base catalyst can
be present in an amount of from 0.001 to 5.0% by weight of the
reaction mixture. In a non-limiting embodiment, the mixture
can be reacted for a time period of from 1 hour to 5 days. In
i
another non-limiting embodiment, the mixture can be reacted at
a temperature of from 20 °C to 100 °C. In a further nonlimiting
embodiment, following the reaction of the SH groups
of the polythiol with substantially all of the available
(meth)acrylate double bonds of the allyl (meth)acrylate, the
allyl double bonds can then bet reacted with the remaining SH
groups in the presence of radical initiator.
[00721 Not intending to be bound by any particular theory,
it is believed that as the mixture is heated, the allyl double
bonds can be at least partially consumed by reaction with the
remaining SH groups. Non-limiting examples of suitable
radical initiators can include but are not limited to azo or
peroxide type free-radical initiators such as
azobisalkylenenitriles. In a non-limiting embodiment, the
free-radical initiator can be azobisalkylenenitrile which is
commercially available from DuPont under the trade name VA20™.
In alternate non-limiting embodiments, VAZO-52, VAZO-64, VAZO-
67, or VAZO-88 can be used as radical initiators.
[0073] In a non-limiting embodiment., the mixture can be
heated for a period of time siich that the dovible bonds are
substantially consumed and a desired pre-calculated
theoretical value for SH content is achieved. In a nonwo
2007/097790 rCT/US3006/0
* ^^
limiting embodiment, the mixture can be heated for a time
period of from 1 hour to 5 days. In another non-limiting
embodiment, the mixture can be' heated at a temperature of from
40*0 to 100°C. In a further non-limiting embodiment, the
mixture can be heated until a theoretical value for SH content
of from 0.5% to 20% is-achieved.
[0074] The number average molecular weight (M„) of the
resulting polythiol can vary widely. In a non-limiting
embodiment, the number average molecular weight (Mn) of
polythiol can be determined by the stoichiometry of the
reaction. In alternate non-limiting embodiments, the Mn of
polythiol can be at least 400 g/mole, or less than or equal to
5000g/mole, or from 1000 to 3000g/mole.
[0075] In a non-limiting embodiment, the polythiol for use
in the present invention can include polythiol oligomer
produced by the reaction of at- least two or more different
dienes with one or more dithiol; wherein the stoichiometric
ratio of the sum of the number of equivalents of dithiol
present to the sum of the number of ecjpaivalents of diene
present is greater than 1.0 : 1.0. As used herein and the
claims when referring to the dienes used in this reaction, the
term "different dienes" can include the following embodiments:
at least one non-cyclic diene and at least one cyclic
diene which can be selected from non-aromatic ring-containing
dienes including but not limited to non-aromatic monocyclic
dienes, non-aromatic polycyclic dienes or combinations
thereof, and/or aromatic ring-containing dienes;
at least one aromatic ring-containing diene and at least
one diene selected from the non-aromatic cyclic dienes
described above;
, at least one non-aromatic monocyclic diene and at least
one non-aromatic polycyclic diene.
[0076] In a furthe"r non-limiting embodiment, the molar
ratio of polythiol to diene in the reaction mixture can be
(n+1) to (n) wherein n can represent an integer from 2 to 30.
[0077] The two or more different dienes can each be
independently chosen from non-cyclic dienes, including
wo 2007/097798- rCT/U02006/046649
#
Straight chain and/or branched aliphatic non-cyclic dienes,
non-aromatic ring-containing dienes, including non-aromatic
ring-containing dienes wherein the doxible bonds can be
contained within the ring or not contained within the ring or
any combination thereof, and wherein said non-aromatic ringcontaining
dienes can contain non-aromatic monocyclic groups
or non-aromatic polycyclic groups or combinations thereof;
aromatic ring-containing dienes; or heterocyclic ringcontaining
dienes; or dienes containing any combination of
such non-cyclic and/or cyclic groups, and wherein said two or
more different dienes can optionally contain thioether,
disulfide, polysulfide, sulfone, ester, thioester, carbonate,
thiocarbonate, urethane, or thiourethane linkages, or halogen
substituents, or combinations thereof; with the proviso that
said dienes contain double bonds capable of xindergoing
reaction with SH groups of polythiol, and forming covalent C-S
bonds, and two or more of said dienes are different from one
another; and the one or more dithiol can each be independently
chosen from dithiols containing straight chain and/or branched
non-cyclic aliphatic groups, cycloaliphatic groups, aryl
groups, aryl-alkyl groups, heterocyclic groups, or
combinations or mixtures thereof, and wherein said one or more
dithiol can each optionally contain thioether, disulfide,
polysulfide, sulfone, ester, thioester, carbonate,
thiocarbonate, urethane, or thiourethane linkages, or halogen
substituents, or combinations thereof; and wherein the
stoichiometric ratio of the sum of the number of equivalents
of all dithiols present to the sum of the number of
equivalents of all dienes present is greater than 1:1. In
non-limiting embodiments, said ratio can be within the range
of from greater than 1:1 to 3:1, or from 1.01:1 to 3:1, or
from 1.01:1 to 2:1, or from 1.05:1 to 2:1, or from 1.1:1 to
1.5:1, or from 1.25:1 to 1.5:1. As used herein and in the
claims, the terra "number of equivalents" refers to the number
of moles of a particular diene or polythiol, multiplied by the
average number of thiol groups or dov±>le bond groups per
molecule of said diene or polythiol, respectively.
wo 2007/997798- -rCT/UD2006/046649 •
[0078] The reaction mixture that consists of the group of
two or more different dienes and the group of one or more
dithiol and the corresponding number of equivalents of each
diene and dithiol that is used to prepare the poly thiol
oligomer can be depicted as shown in Scheme I below:
i
Scheme I.
diDi + daDa + . . . + d^D^ + tiTj + . . . + tyTy •
polythiol oligomer;
wherein Di through Dx represent two or more different dienes, x
is an integer greater than or equal to 2, that represents the
total number of different dienes that are present; di through
dx represent the number of equivalents of each corresponding
diene; Ti through Ty represent one or more dithiol; and ti
through ty represent the number of equivalents of each
corresponding dithiol; and y is an integer greater than or
equal to 1 that represents the total number of dithiols
present.
[0079] In a non-limiting embodiment, a group of two or more
different dienes and the corresponding number of equivalents
of each diene can be described by the term diDi (such as diDj.
through d^Dx, as shown in Scheme I above) , wherein Di represents
the i^" diene aoid di represents the number of equivalents of Di,
i being can be an integer ranging from 1 to x, wherein x is an
integer, greater than or equal to 2, that defines the total
number of different dienes that are present. Furthermore, the
sum of the number of equivalents of all dienes present can be
represented by the term d, defined according to Expression
(I),
X
d = ' S di
i = 1
Expression (I)
wherein i, x, and di are as defined above.
wo 2007/097790- -J»CT/UG2006/0ty
[0080] Similarly, the group of one or more dithiol and the
corresponding number of equivalents of each dithiol can be
described by the term .tjTj (such as tiTj through tyTy, as shovm
in Scheme I above) , wherein Tj represents the j"" dithiol and tj
represents the number of equivalents of the corresponding
dithiol Tj, j being an integer ranging from 1 to y, wherein y
is an integer that defines the total number of dithiols
present, and y has a value greater than or equal to 1.
Furthermore, the sum of the number of equivalents of all
dithiols present can be represented by the term t, defined
according to Expression (II),
y
t = -^ tj
J = 1
• Expression (11)
wherein j, y, and tj are as defined above.
[0081] The ratio of the sum of the number of equivalents of
all dithiols present to the sura of the number of equivalents
of all dienes present can be characterized by the term t : d,
wherein t and d are as defined above. The ratio t : d can
have values greater than 1:1. In non-limiting embodiments,
the ratio t : d can have values within the reuage of from
greater thcin 1:1 to 3:1, or from 1.01:1 to 3:1, or from 1.01:1
to 2:1, or from 1.05:1 to 2:1, or from 1.1:1 to 1.5:1, or from
1.25:1 to 1.5:1.
[0082] As is known in the art, for a given set of dienes
and dithiols, a statistical mixture of oligomer molecules with
varying molecular weights are formed during the reaction in
which the polythiol oligomer is prepared, where the number
average molecular weight of the resulting mixture can be
calculated and predicted based upon the molecular weights of
the dienes and dithiols, and the relative equivalent ratio or
mole ratio of the dienes and dithiols present in the reaction
mixtiore that is used to prepare said polythiol oligomer. As
is also known to those skilled in the art, the above
wo]i)r;r-T"« .rcTmsuMmun
parameters can be varied in order to adjust the number average
molecular weight of the polythiol oligomer. The following is
a hypothetical example: if the value of x as defined above is
2, and the value of y is 1; and dienei has a molecular weight
(MW) of 100, diene2 has a molecular weight of 150, dithiol has
a molecular weight of 200; and dienei , diene2, and dithiol are
present in the following molar amounts:. 2 moles of dienci, 4
moles of dienea, and 8 moles of dithiol; then the number
average molecular weight (Mn) of the resulting polythiol
oligomer is calculated as follows:
Mn = { (moleSdienel X MWdienel) + (moleSdlene2 X MWdienez) + (mOleSaithiol X
MWdichioi) } / m;
wherein m is the number of moles of the material that is
present in the smallest molar amount.
= {{2 X 100) + (4 X 150) + {8 X 200)} / 2
= 1200 g/mole
[0083] As used herein and in the claims when referring to
the group- of two or more different dienes used in the
preparation of the polythiol oligomer, the term "different
dienes" refers to dieries that can be different from one
another in various aspects. In non-limiting embodiments, the
"different dienes" can be different from one ainother as
follows: a) non-cyclic vs. cyclic; b) aromatic ringcontaining
vs. non-aromatic ring-containing; or c) monocyclic
non-aromatic vs. polycyclic non-aromatic ring-containing;
whereby non-limiting embodiments of this invention can include
the following:
a) at least one non-cyclic diene and at least one cyclic
diene selected from non-aromatic ring-containing dienes,
including but not limited to dienes containing non-axomatic
monocyclic groups or dienes containing non-aromatic polycyclic
-A\'0 2007/097798 rCT/UG2006/04664Q
groups, or combinations thereof, and/or aromatic ringcontaining
dienes; or
b) at least one aromatic ring-containing diene and at
least one diene selected from non-aromatic cyclic dienes, as
described above; or
c) at least one non-aromatic diene containing nonaromatic
monocyclic group, and at least one non-aromatic diene i
containing polycyclic non-aromatic group.
[0084] In a non-limiting embodiment, the polythiol oligomer
can be as depicted in Formula (AA') in Scheme II below,
produced from the reaction of Dienci and Dienea with a dithiol;
wherein Rj, R4, Rs, and R, can be independently chosen from H,
methyl, or ethyl, and Ri and Ra can be independently chosen
from straight chain and/or branched aliphatic non-cyclic
moieties, non-aromatic ring-containing moieties, including
non-aromatic monocyclic moieties or non-aromatic polycyclic
moieties or combinations thereof; aromatic ring-containing
moieties; or heterocyclic ring-containing moieties; or
moieties containing any combination of such non-cyclic and/or
cyclic groups; with the proviso that Dienei and Dienej are
different from one another, and contain dovible bonds capable
of londergoing reaction with SH groups of dithiol, and forming
covalent C-S bonds; and wherein Rs can be chosen from divalent
groups containing straight chain and/or branched non-cyclic
aliphatic groups, cycloaliphatic groups, aryl groups, arylalkyl
groups, heterocyclic groups, or combinations or mixtures
thereof; and wherein Ri, R3, and Rs can optionally contain
ether, thioether, disulfide, polysulfide, sulfone, ester,
thioester, carbonate, thiocarbonate, ui^ethane, or thiourethane
linkages, or halogen substituents, or combinations thereof;
and n is an integer ranging from 1 to 20.
wo 2007/097798- PCTAJS3006/Oil66l9
• ^^-^
Scheme II
Diene, Dien^ DithioL
^ Formula (AA')
I
wherein n=m + p
[0085] In a second non-limiting embodiment, the polythiol
oligomer can be as depicted in Formula (AA') in Scheme III
below, produced from the reaction of Dienei and 5-vinyl-2-
norbornene (VNB) with a dithiol; wherein Rj and R4 can be
independently chosen from H, methyl, or ethyl, and Ri can be
chosen from straight chain and/or branched aliphatic noncyclic
moieties, non-aromatic monocyclic ring-containing
moieties; aromatic ring-containing moieties; or heterocyclic
ring-containing moieties; or include moieties containing any
combination of such non-cyclic and/or cyclic groups; with the
proviso that Dienei is different from'VNB, and contains double
bonds capable of reacting with SH groups of dithiol, and
forming covalent C-S bonds; and wherein R3 can be chosen from
divalent groups containing straight chain and/or branched noncyclic
aliphatic groups, cycloaliphatic groups, aryl groups,
aryl-alkyl groups, heterocyclic groups, or combinations or I
mixtures thereof, and wherein Ri and R3 -can optionally contain
ether, thioether, disulfide, polysulfide, sulfone, ester,
thioester, carbonate, chiocarbonate, urethane, or thiourethane
linkages, or halogen substituents, or combinations thereof;
and n is an integer ranging from 1 to 20.
Scheme til
m ^^Pj - ^ + P %^jl\ + 3"+' HS^ ^H ^
Diene, VNB °'^'°'
wherein n = m + p
Formula (AA")
[0086] In a third non-limiting embodiment, the polythiol
oligomer can be as depicted in Formula (AA'') in Scheme IV
below, produced from the reaction of Dienei and 4-vinyl-1-
cyclohexene (VCH) with a dithiol; wherein R2 and R4 can be
independently chosen from H, methyl, or ethyl, and Ri can be
chosen from straight chain and/or branched aliphatic noncyclic
moieties, non-aromatic polycyclic ring-containing
moieties; aromatic ring-containing moieties; or heterocyclic
ring-containing moieties; or moieties containing any
combination of such non-cyclic and/or cyclic groups; with the
proviso that Dienei is different from VCH, and contains double
bonds capable of reacting with SH group of dithiol, and
forming covalent C-S bonds; and wherein R3 caun be chosen from
divalent groups containing straight chain and/or branched noncyclic
aliphatic groups, cycloaliphatic groups, aryl groups,
aryl-alkyl groups, heterocyclic groups, or combinations or
mixtures thereof, and wherein Ri, and R3 can optionally contain
thioether, disulfide, polysulfide, sulfone, ester, thioester,
carbonate, thiocarbonate, urethane, or thiourethane linkages,
or halogen substituents, or combinations thereof; and n is ein
integer ranging from 1 to 20.
Scheme IV
Diene, Dithiol
wherein n = m + p
Rj R4
Formula (AA"')
[0087] In a further non-limiting embodiment, the polythiol
for use in the present invention can include polythiol
oligomer produced by the reaction of at least two or more
different dienes with with at least one or more dithiol, and,
optionally, one or more trifvmctional or higher functional
polythiol; wherein the stoichiometric ratio of the sum of the
number of equivalents of polythiol present to the sum of the
number of equivalents of diene present is greater than 1.0 :
1,0; and wherein the two or more different dienes can each be
independently chosen from non-cyclic dienes, including
straight chain and/or branched aliphatic non-cyclic dienes;
non-aromatic ring-containing dienes, including non-aromatic
ring-containing dienes wherein the doioble bonds can be
contained within the ring or not contained within the ring or
any combination thereof, and wherein said non-aromatic ringcontaining
dienes can contain non-aromatic monocyclic groups
or non-aromatic polycyclic groups or combinations thereof;
aromatic ring-containing dienes; heterocyclic ring-containing
dienes; or dienes containing any combination of such noncyclic
and/or cyclic groups, and wherein said two or more
different dienes can optionally contain thioether, disulfide,
polysulfide, sulfone, ester, thioester, carbonate,
thiocarbonate, urethane, or thiourethane linkages, or halogen
substituents, or combinations thereof; with the proviso that
said dienes contain doiible bonds capable of undergoing
wo 2007/097798- t»CT/US2006/01661S>
reaction with SH groups of polythiol, and forming covalent C-S
bonds, and at least two or more of said dienes are different
from one another; the one or more dithiol can each be
independently chosen from dithiols containing straight chain
and/or branched non-cyclic aliphatic groups, cycloaliphatic
groups, aryl groups, aryl-alkyl groups, heterocyclic groups,
or combinations or mixtvires thereof, and wherein said one or
more dithiol can each optionally contain thioether, disulfide,,
polysulfide, sulfone, ester, thioester, carbonate,
thiocarbonate, urethane, or thiourethane linkages, or halogen
s\ibstituents, or combinations thereof; the trifunctional or
higher functional polythiol can be chosen from polythiols
containing non-cyclic aliphatic groups, cycloaliphatic groups,
aryl groups, aryl-alkyl groups, heterocyclic groups, or
combinations or mixtures thereof, and wherein said
trifxinctional or higher functional polythiol can each
optionally contain thioether, disulfide, polysulfide, sulfone,
ester, thioester, carbonate, thiocarbonate, urethane, or
thiourethane linkages, or halogen substifcuents, or
combinations thereof.
[0088] Suitable dithiols for use in preparing the polythiol
oligomer can be selected from a wide variety known in the art.
Non-limiting examples can include those disclosed herein.
Further non-limiting examples of suitable dithiols for use in
preparing the polythiol oligomer can include but are not
limited to 1,2-ethanedithiol, 1,2-propanedithiol, 1,3-
propanedithiol, 1,3-butanedithiol, 1, 4-butanedithiol, 2,3-
butanedithiol, 1,3-pentanedithiol, 1,5-pentanedithiol, 1,6-
hexanedithiol, 1,3-dimercapto-3-methylbutane,
dipentenedimercaptan, ethylcyclohexyldithiol (ECHDT), 2-
mercaptoethylsulf ide (DMDS), methyl-svibstituted 2-
mercaptoethylsulfide, dimethyl-substituted 2-
mercaptoethylsulfide, 1, 8-dimercapto-3, 6-dioxaoctane and 1,5-
dimercapto-3-oxapentane. In alternate non-limiting
embodiments, the dithiol can be 2,5-dimercaptomethyl-l,4-
dithiane, ethylene glycol di (2-mercaptoacetate), ethylene
glycol di(3-mercaptopropionate) , poly(ethylene glycol) di(2-
-WO^ee7/097798 •rC-T/UG2006/046649
mercaptoacetate), poly(ethylene glycol) di(3-
mercaptopropionate), dipentene dimercaptan (DPDM), and
mixtures thereof.
[0089] Suitable trifunctional and higher-functional
polythiols for use in preparing the polythiol oligomer can be
selected from a wide variety known in the art. Non-limiting
examples can include those disclosed herein. Further nonlimiting
examples of suitable trifunctional and higherfunctional
polythiols for use in preparing the polythiol
oligomer can include but are not limited to pentaerythritol
tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-
mercaptopropionate), trimethylolpropane tris(2-
mercaptoacetate) , trimethylolpropane trisOmercaptopropionate),
thioglycerol bis(2-mercaptoacetate), and
mixtures thereof.
[0090] Suitable dienes for'use in preparing the polythiol
oligomer can vary widely and can be selected from those known
in the art. Non-limiting examples of suitable dienes can
include but are not limited to acyclic non-conjugated dienes,
acyclic polyvinyl ethers, allyl- emd vinyl-acrylates, allyland
vinyl-methacrylates, diacrylate and dimethacrylate esters
of linear diols and dithiols, diacrylate and dimethacrylate
esters of poly{alkyleneglycol) diols, monocyclic aliphatic
dienes, polycyclic aliphatic dienes, aromatic ring-containing
dienes, diallyl and divinyl esters of aromatic ring
dicarboxylic acids, and mixtures thereof.
[0091] Non-limiting examples of acyclic non-conjugated
dienes can include those represented by the following general
formula:
wherein R can represent Ca to C30 linear branched divalent
saturated alkylene radical, or Ca to C30 divalent organic
radical containing at least one element selected from the
group consisting of sulfur, oxygen and silicon in addition to
carbon and hydrogen atoms.
JWO21I07/W77W -PCT/DOiOllMCIIIilili)
[0092] In alternate non-limiting embodiments, the acyclic
non-conjugated dienes can be selected from 1,5-hexadiene, 1,6-
heptadiene, 1,7-octadiene and mixtures thereof.
[0093] Non-limiting examples of suitable acyclic polyvinyl
ethers can include but are not limited to those represented by
structural formula (V ) :
CH2=CH--0--(--R= --0--)„ --CH=CH2 (V )
wherein R' can be Cj to Cg n-alkylene, C^ to Cg branched alkylene
group, or --[(CHj --)p --0--],'--(--CHj --)r --» m can be a
rational number from 0 to 10, p can be an integer from 2 to 6,
q can be an integer from 1 to 5 and r can be an integer from 2
to 10.
[0094] In a non-limiting embodiment, m can be two (2).
[0095] Non-limiting examples of suitable polyvinyl ether
monomers for use can include divinyl ether monomers, such as
but not limited to ethylene glycol divinyl ether, diethylene
glycol divinyl ether, triethyleneglycol divinyl ether, and
mixtures thereof.
[0096] Non-limiting examples of suitable allyl- and vinylacrylates
and methacrylates can include but are not limited to
those represented by the following formulas:
o o
wherein Ri each independently can be hydrogen or methyl.
[0097] In a non-limiting embodiment, the acrylate cind
methacrylate monomers can include monomers such as but not
limited to allyl methacrylate, allyl acrylate and mixtures
thereof.
[0098] Non-limiting examples of diacrylate and
dimethacrylate esters of linear diols can include but are not
limited to those represented by the following structural
formula:
wo 2007/097798 -f CT/U32006/046649
o o
Rj R2
wherein R can represent C^ to C30 divalent saturated alkylene
radical; branched divalent saturated alkylene radical; or C2 to
Cjo divalent organic radical containing at least one element
selected from sulfur, oxygen and silicon in addition to carbon
and hydrogen atoms; and R2 can represent hydrogen or methyl.
[0099] In alternate non-limiting embodiments, the
diacrylate and dimethacrylate esters of linear diols can
include ethanediol dimethacrylate, 1,3-propanediol diacrylate,
1,3-propanediol dimethacrylate, 1,2-propanediol diacrylate,
1,2-propanediol dimethacrylate, 1,4-butanediol diacrylate,
1,4-butanediol dimethacrylate, 1,3-butanediol diacrylate, 1,3-
butanediol dimethacrylate, 1,2-butanediol diacrylate, 1,2-
butanediol dimethacrylate, cind. mixtures thereof.
[00100] Non-limiting examples of diacrylate and
dimethacrylate esters of poly(alkyleneglycol) diols can !
include but are not limited to those represented by the
following structural formula:
O R2
Rj O
wherein R2 can represent hydrogen or methyl and p can represent
an integer from 1 to 5.
[00101] In alternate non-limiting embodiments, the
diacrylate and dimethacrylate esters of• poly(alkyleneglycol)
diols can include ethylene glycol dimethacrylate, ethylene
glycol diacrylate, diethylene glycol dimethacrylate,
diethylene glycol diacrylate, and mixtures thereof.
^ 0 2007/097798 .PCTAJSaOOC/01(1(119
[00102] Further non-limiting examples of suitable dienes can
include monocyclic aliphatic dienes such as but not limited to
those represented by the following structural formulas:
o
wherein X and Y each independently can represent Ci-io divalent
saturated alkylene radical; or Ci-s divalent saturated alkylene
radical, containing at least one element selected from the
group of sulfvir, oxygen and silicon in addition to the carbon
and hydrogen atoms; and Ri can- represent H, or Ci-Cio alkyl; and
wherein X and Ri can be as defined above and R2 can represent
C2-C10 alkenyl.
[00103] In alternate non-limiting embodiments, the
monocyclic aliphatic dienes can include 1,4-cyclohexadiene, 4-
vinyl-1-cyclohexene, dipentene and terpinene.
[00104] Non-limiting examples of polycyclic aliphatic dienes
can include but are not limited to 5-vinyl-2-norbornene; 2,5-
norbomadiene; dicyclopentadiene and mixtures thereof.
[00105] Non-limiting exanples of aromatic ring-containing
dienes can include but are not limited to those represented by
the following structural formula:
wherein R4 can represent hydrogen or methyl.
wo 2007/097790 -rCT/U3200(i/OI66l9
[00106] In. alternate non-limiting embodiments, the aromatic
ring-containing dienes can include monomers such as 1,3-
diispropenyl benzene, divinyl benzene and mixtures thereof.
[00107] Non-limiting examples of diallyl esters of aromatic
ring dicarboxylic acids can include but are not limited to
those represented by the following structural formula:
O (CHj)!!
wherein m and n each independently can be an integer from 0 to
5.
[00108.] In alternate non-limiting embodiments, the diallyl
esters of aromatic ring dicarboxylic acids can include odiallyl
phthalate, m-diallyl phthalate, p-diallyl phthalate
and mixtures thereof.
[00109] In a non-limiting embodiment, reaction of at least
one polythiol with two or more different dienes can be carried
out in the presence of radical initiator. Suitable radical
initiators for use in the present invention can vary widely
and can include those known to one of ordinary skill in the
art. Non-limiting examples of radical initiators can include
but are not limited to azo or peroxide type free-radical
initiators such as azobisalkalenenitriles. In a non-limiting
embodiment, the free-radical initiator can be
azobisalkalenenitrile which is commercially available from
DuPont under the trade name VAZO™. In alternate non-limiting
embodiments, VAZO-52, VAZO-64, VAZO-67, VAZO-88 and mixtures
thereof can be used as radical initiators.
[00110] In a non-limiting embodiment, selection of the freeradical
initiator can depend on reaction temperature. In a
non-limiting embodiment, the reaction temperature can vary
from room temperature to 100°C, In further alternate nonlimiting
embodiments, Vazo 52 can be used at a ten^erature of
ViOiWtmim' PCT/US2006/0i6619
from 50-60 "C, or Vazo 64 or Vazo 67 can be used at a
temperature of 60 °C to 75 °C, or Vazo 88 can be used at a
temperature of 75-100 °C.
lOOlll] The reaction of at least one polythiol and two or
more different dienes can be carried out under a variety of
reaction conditions. In alternate non-limiting embodiments,
such conditions can depend on the degree of reactivity of the
dienes and the desired structure of the resulting- polythiol
oligomer. In a non-limiting embodiment, polythiol, two or
j
more different dienes and radical initiator can be combined
together while heating the mixture. In a further non-limiting
embodiment, polythiol and radical initiator cein be combined
together and added in relatively small amounts over a period
of time to a mixture of two or more dienes.
[00112] In another non-limiting embodiment, two or more
dienes can be combined with polythiol in a stepwise manner
under radical initiation.
[00113] In another non-limiting embodiment, polythiol can be
mixed with one diene and optionally free radical initiator;
the diene and polythiol and optionally free radical initiator
can be allowed to react and then a second diene can be added
to the mixture, followed by addition of the radical initiator
to the mixture. The mixture is allowed to react until the
double bonds are essentially consumed and a pre-calculated
(e.g., by titration based on stoichiometry) theoretical SH
equivalent weight is obtained. The reaction time for
i
completion can vary from one hour to five dayis depending on
the reactivity of the dienes used.
[00114] In a further non-limiting embodiment, the final
oligomeric product of the stepwise addition process can be a
block-type copolymer
[00115] In a non-limiting embodiment, the reaction of at
least one polythiol with two or more different dienes can be
carried out in the presence of a catalyst. Suitable catalysts
for use in the reaction can vary widely and can be selected
from those known in the art. The amount of catalyst used in
the reaction of the present invention can vary widely and can
wo 3007/0il77Pft- PCT/US200(i/01(iC1t>
depend on the catalyst • selected. In a non-limiting
embodiment, the amount of catalyst can be present in an amount
of from 0.01% by weight to 5% by weight of the reaction
mixture.
[00116] In a non-limiting embodiment, wherein the mixture of
dienes can be a mixture of acrylic monomers, the acrylic
monomers can be reacted with polythiol in the presence of a
base catalyst. Suitable base catalysts for use in this
reaction vary widely and can be selected from those known in
the art. Non-limiting examples can include but are not
limited to tertiary amine bases such as 1,8-
diazabicyclo[5.4.0]undec-7-ene (DBU) and N,Ndimethylbenzylamine.
The amount of base catalyst used can
vary widely. In a non-limiting embodiment, the base catalyst
can be present in an amount of from 0.01 to 5.0% by weight of
the reaction mixture. The reaction of the acrylic monomers
with polythiol in the presence of a base catalyst can
sxobstantially minimize or essentially preclude double bond
polymerization.
[00117] In another non-limiting embodiment, in order to
substantially minimize or essentially preclude dotible bond
polymerization, acrylic double bonds can be first reacted with
polythiol tinder basic catalysis conditions and then, electronrich
reactive doxible bond dienes can be added to the
intermediate product and reacted under radical initiation
conditions. Non-limiting examples of electron-rich reactive
double bond dienes can include materials such as but not
limited to vinyl etherfei, aliphatic dienes and cycloaliphatic
dienes.
[00118] Not intending to be boiind by any particular theory,
it is believed that as the mixture of polythiol, dienes and
radical intiator is heated, the double bonds are at least
partially consumed by reaction with the SH groups of the
polythiol. The mixture can be heated for a sufficient period
of time such that the double bonds are essentially consumed
and a pre-calculated theoretical value for SH content is
reached. In a non-limiting embodiment,_ the mixture can be
j^fQ I007/o:>7790 PCT/US2006/0166i9
heated for a time period of from 1 hour to 5 days. In another
non-limiting embodiment, the mixture cem. be heated at a
ten^erature of from 40°C to 100°C. In a further non-limiting
embodiment, the mixture can be heated until a theoretical
value for SH content of from 0.7% to 17% is reached.
[00119] The number average molecular weight (Mn) of the
resulting polythiol oligomer can vary widely. The number
average molecular weight (M„) of polythiol oligomer can be
predicted based on the-stoichiometry of the reaction. In
alternate non-limiting embodiments, the M„ of polythiol
oligomer can vary from 400 to 10,000 g/mole, or from 1000 to
3000 g/mole.
[00120] The viscosity of the resulting polythiol oligomer
can vary widely. In alternate non-limiting embodiments, the
viscosity can be from 40 cP to 4000 cP at 73°C,.or from 40 cP
to 2000 cP at 73°C, or from 150 cP to 1500 cP at 73°C.
[00121] In a non-limiting embodiment, vinyleyelohexene (VCH)
and 1,5-hexadiene (1,5-HD) can be combined together, and 2-
mercaptoethylsulfide (DMDS) and a radical initiator (such as
Vazo 52) can be mixed together, and this mixture can be added
dropwise to the mixture of dienes at a rate such that a
temperature of SO^C is not exceeded. After the addition is
completed, the mixture can be heated to maintain a temperature
of eo^C until the double bonds are essentially consumed and the
pre-calculated theoretical value for SH content is reached.
[00122] In alternate non-limiting embodiments, polythiol
oligomer can be prepared from the following combinations of
dienes and polythiol:
(a) 5-vinyl-2-norbomene (VNB) , diethylene glycol
4ivinyl ether (DEGDVE)and DMDS;
(b) VNB, butanediol divinylether (BDDVE), DMDS;
(c) VNB, DEGDVE, BDDVE, DMDS;
(d) l,3-diisopropenylben2ene (DIPEB), DEGDVE and DMDS;
(e) DIPEB, VNB and DMDS;
(f) DIPEB, 4-vinyl-l-cyclohexene (VCH), DMDS;(g)
allylmethacrylate (AM), VNB, and DMDS;
(h) VCH, VNB, and DMDS;
I
wo 2007/097798. 'PCT/U0200(i/Oil6619-
(i) Limonene{L), VNB and DMDS
(j) Ethylene glycol diraethacrylate (EGDM), VCH and
DMDS ;
(k) Diallylphthalate (DAP), VNB, DMDS;
(1) DivinylbenzeneCDVB), VNB, DMDS; and
(m) DVB, VCH. DMDS
[00123] In an alternate non-limiting embodiment, the
polythiol for use in the present invention can be polythiol
oligomer prepared by reacting one or more dithiol and,
optionally, one or more trifxinctional or higher functional
polythiol with two or more dienes, wherein said dienes can be
selected such that at least one diene has refractive index of
at least 1.52 and at least one other diene has Abbe number of
at least 40, wherein said dienes contain doiible bonds capable
of reacting with SH groups of polythiol, and forming covalent
C-S bonds; and wherein the stoichiometric ratio of the sum of
the number of equivalents of all polythiols present to the sum
of the number of equivalents of all dienes present is greater
than 1.0 : 1.0. In a further non-limiting embodiment, the
diene with refractive index of at least 1.52 can be selected
from dienes containing at least one aromatic ring, and/or
dienes containing at least one sulfur-containing substituent,
with the proviso that said diene has refractive index of at
least 1.52; and the diene with Abbe number of at least 40 can
be selected from cyclic or non-cyclic dienes not containing an
aromatic ring, with the proviso that said diene has Abbe
number of at least 40. in yet a further non-limiting
embodiment, the diene with refractive index of at least 1.52
can be selected from diallylphthalate and 1,3-diisopropenyl
benzene; and the diene with Abbe number of at least 40 can be
selected from 5-vinyl-2-norbornene, 4-vinyl-l-cyclohexene,
limonene, diethylene glycol divinyl ether, and allyl
methacrylate.
[00124] As previously stated herein, tthe nature of the SH
group of polythiols is such that oxidative coupling ccin occur
readily, leading to formation of disulfide linkages. Various
mo 2007/097798- PeT/US2006/046649
oxidizing agents can lead to such oxidative coupling. The
oxygen in the air Ccui in some cases lead to such oxidative
coupling during storage of the polythiol. It is believed that
a possible mechanism for the coupling of thiol groups involves
the formation of thiyl radicals, followed by coupling of said
thiyl radicals, to form disulfide linkage. It is further
believed that formation of disulfide linkage can occur under
conditions that can lead to the formation of thiyl radical,
including but not limited to reaction conditions involving
free radical initiation.
[00125] In a non-limiting embodiment, the polythiol oligomer
for use in the present invention can contain disulfide
linkages present in the dithiols and/or polythiols used to
prepare said polythiol oligomer. In another non-limiting
embodiment, the polythiol oligomer for use in the present
invention can contain disulfide linkage formed during the
synthesis of said polythiol oligomer. In another non-limiting
embodiment, the polythiol oligomer for use in the present
invention can contain disulfide linkages formed during storage
of said polythiol oligomer.
[00126] In another non-limiting embodiment, polythiol for
use in the present invention can include a material
represented by the following structural formula and reaction
scheme:
wo 2007/097798 •I'CT/U32006/046649
JL ^,-v,^ • Radical Initiator
" ^ • • • — • " -
S -^ n (IV'm)
where n can be an integer from 1 to 20.
[00127] In a non-limiting embodiment., the polythiol of
formula (IV'm) can be prepared by reacting "n" moles of 1,2,4-
trivinylcyclohexcm.e with "3n" moles of
dimercaptodiethylsulfide (DMDS), and heating the mixture in
the presence of a suitable free radical initiator, such as but
not limited to VAZO 64.
[00128] In another non-limiting embodiment, the polythiol
for use in the present invention can include a material
represented by the following structural formula:
II ^ O ^ ^ SH ^2
H OEt
- Jn
(IV'i)
wherein n can be an integer from 1 to 20 .
wo 2007/097798 rCT/U3200(i/046649
[00129] Various methods of preparing the poly thiol of the
formula (IV'i) are described in detail in United States Patent
5,225,472, from column 2, line 8 to column 5, line 8.
[00130] In a non-limiting embodiment, "3n" moles of 1,8-
dimercapto-3,6-dioxaooctane (DMDO) can be reacted with "n"
moles of ethyl formate, as shown above, in the presence of
anhydrous zinc chloride.
[00131] In alternate non-limiting embodiments, the active
hydrogen-containing material for use in the present invention
can be chosen from polyether glycols cmfi polyester glycols
having a number average molecular weight of at least 200
grams/mole, or at least 3 00 grams/mole, or at least 750
grams/mole; or no greater than 1,500 grams/mole, or no greater
them 2,500 grams/mole,, or no greater than 4,000 grams/mole.
[00132] Non-limiting examples of suitable active hydrogencontaining
materials having both hydroxyl and thiol groups can
include but are not limited to 2-mercaptoethanol, 3-mercapto-
1,2-propanediol, glycerin bis(2-mercaptoacetate), glycerin
bis (3-mercaptopropionate) , 1-hydroxy-4-mercaptocyclohexane, ,
l,3-dimercapto-2-propanol, 2,3-dimercapto-l-propanol, 1,2-
dimercapto-l,3-butanediol, trimethylolpropane bis(2-
mercaptoacetate), trimethylolpropane bis(3-
mercaptopropionate), pentaerythritol mono(2-mercaptoacetate),
pentaerythritol bis{2-mercaptoacetate) , pentaerythritol
tris(2-mercaptoacetate), pentaerythritol mono(3-
mercaptopropionate), pentaerythritol bis{3-
mercaptopropionate), pentaerythritol tris(3-
mercaptopropionate) , liydroxymethyltris(
mercaptoethylthiomethyl)methane, , dihydroxyethyl sulfide
mono{3-mercaptopropionate, and mixtures thereof.
The sulfur-containing polyureaurethane of the present
invention can be prepared using a variety of techniques known
in the art. In a non-limiting embodiment of the present
invention, polyisocyanate, polyisothiocyanate or mixtures
thereof and at least one active hydrogen-containing material
can be reacted to form polyurethane prepolymer, and the
polyurethane prepolymer can be reacted .with an amineAVO
2007/097798- -rCTAJ3200(i/046649 •
containing curing agent. In a further non-limiting
embodiment, the active hydrogen-containing material can
include at least one material chosen from polyol, polythiol,
polythiol oligomer and mixtures thereof. In still a further
non-limiting embodiment, the polyurethane prepolymer can be
reacted with amine-containing curing agent. In a further nonlimiting
embodiment, said amine-containing curing agent can
comprise a combination of amine-containing material and active
hydrogen-containing material chosen from polyol, polythiol,
polythiol oligomer and mixtures thereof.
[00133] In a further non-limiting embodiment, said active
hydrogen-containing material can further comprise material
containing both hydroxyl and SH groups.
[001341 In a non-limiting embodiment, said polyurethane
prepolymer can contain disulfide linJcages due to disulfide
linkages contained in polythiol and/or polythiol oligomer used
to prepare the polyurethane prepolymer.
[00135] In another non-limiting embodiment, polyisocyanate,
polyisothiocyanate, or mixtures thereof, at least one active
hydrogen-containing material and amine-containing curing agent
can be reacted together in a "one pot" process. In a further
non-limiting embodiment, the active hydrogen-containing
material can include at least one material chosen from polyol,
polythiol, polythiol oligomer and mixtures thereof,
[00136] In further alternate non-limiting embodiments, the
polyisocyanate, can include meta-tetramethylxylylene
diisocyanate (1,3-bis(l-isocyanato-l-methylethyl-benzene); 3-
isocyanato-methyl-3,5,5,-trimethyl-cyclohexyl isocyanate ;
r
4,4 -methylene bis(cyclohexyl isocyeuaate); meta-xylylene
diisocyanate;, and mixtures thereof.
[00137] Amine-containing curing agents for use in the
present invention are numerous, and widely varied. Nonlimiting
examples of suitable amine-containing curing agents
can include but are not limited to those described in WO
2004/060951 Al at paragraphs [00116] to [00125], incorporated
by reference herein.
wo 2007/097798- J€T/US2000/046(i49'
[00138] In another non-limiting embodiment, the aminecontaining
curing agent can include a combination of polyamine
and material selected from polyol, polythiol, polythiol
oligomer, materials containing both hydroxyl and SH groups,
and mixtures thereof. Non-limiting examples of suitable
polyamines, polythiols, polythiol oligomers, polyols, and/or
materials containing both hydroxyl and SH groups
for use in the curing agent mixture can include those
previously recited herein. In a further non-limiting
embodiment, the amine-containing curing agent for use in the
present invention can be a combination of polyamine and
polythiol and/or polythiol oligomer.
[001391 The sulfur-containing polyureaurethane of the
present invention can be polymerized using a variety of
techniques known in the art. In a non-limiting embodiment,
the polyureaurethane can be prepared by combining
polyisocyanate, polyisothiocyanate, or mixtures thereof and
active hydrogen-containing material to form polyurethane
prepolymer, and then introducing amine-containing curing
agent, and polymerizing the resulting mixture.
[00140] In a non-limiting embodiment, the prepolymer and the
amine-containing curing agent each can be degassed (e.g. under
vacuum) prior to mixing them and carrying out the
polymerization. The amine-containing curing agent can be
mixed with the prepolymer using a variety of methods and
equipment, such as but not limited to an impeller or extruder.
[00141] In another non-limiting embodiment, wherein the
sulfur-containing polyureaurethane can be prepared by a onepot
process, the polyisocyanate and/or polyisothiocyanate,
active hydrogen-containing material, amine-containing curing
agent and optionally catalyst can be degassed and then
combined, and the mixture then can be polymerized.
[00142] Suitable catalysts can be selected from those known
in the art. Non-limiting exanples can include but are not
limited to tertiary amine catalysts or tin compounds or
mixtures thereof. in alternate non-limiting embodiments, the
catalysts can be dimethyl cyclohexylamine or dibutyl tin
wo 2007/097790 rCT/U32006/046e49
dilaurate or mixtures thereof. In further non-limiting
embodiments, degassing can take place prior to or following
addition of catalyst.
[00143] In another non-limiting embodiment, wherein a lens
can be formed, the mixture, which can be optionally degassed,
can be introduced into a mold and the mold can be heated
(i.e., using a thermal cure cycle) using a variety of
conventional techniques known in the art. The thermal cure
cycle can vary depending on the reactivity and molar ratio of
the reactants, and the presence of catalyst (s) . In a nonlimiting
embodiment, the thermal cure cycle can include
heating the mixture of polyurethane prepolymer and aminecontaining
curing agent, wherein said curing agent can include
primary diamine or mixture of primary diamine and
trifunctional or higher functional polyamine and optionally
polyol and/or polythiol and/or polythiol oligomer,- or heating
the mixture of polyisocyanate and/or polyisothiocyanate,
polyol and/or polythiol and/or polythiol oligomer, and aminecontaining
material; from room temperature to a temperature of
200°C over a period of from 0.5 hours to 120 hours; or from 80
to IBCC for a period of from 5 hours to 72 hours.
[00144] In a non-limiting embodiment, a urethanation
catalyst can be used in the present invention to enhance the
reaction of the polyurethane-forming materials. Suitable
urethanation catalysts can vary; for example, suitable
urethcination catalysts can include those catalysts that are
useful for the formation of urethane by reaction of the NCO
and OH-containing materials and/or the reaction of the NCO and
SH-containing materials. Non-limiting examples of suitable
catalysts can be chosen from the group of Lewis bases, Lewis I
acids and insertion catalysts as described in Ullmann' s
Encyclopedia of Industrial Chemistry, 5"* Edition, 1992, Volume
A21, pp. 673 to 674. In a non-limiting embodiment, the
catalyst can be a stannous salt of an organic acid, such as
but not limited to stannous octoate, dibutyl tin dilaxirate,
dibutyl tin diacetate, dibutyl tin mercaptide, dibutyl tin
dimaleate, dimethyl tin diacetate, dimethyl tin dilatirate,
wo 2007/097798 PCT/USa006/0166'
l,4-diazabicyclo[2.2.2]octane, and mixtures thereof. In
alternate non-limiting embodiments, the catalyst can be zinc
octoate, bismuth, or ferric acetylacetonate.
[00145] Further non-limiting examples of suitable catalysts
can include tin compounds such as but not limited to dibutyl
tin dilaurate, phosphines, tertiary ammonium salts and
tertiary amines such as but not limited to triethylamine,
triisopropylamine, dimethyl eyelohexylamine, N,NdimethyIbenzylamine
and mixtures thereof. Such suitable
tertiary amines are disclosed in United States Patent
5,693,738 at column 10, lines 6-38, the disclosure of which is
incorporated herein by reference.
[00146] In non-limiting embodiments, sulfur-containing
polyureaurethane of the present invention can be prepared
using the various combinations of ingredients shown in Table A
below:
3ff%^immrrmr PCT/US3006/016619
Table A.
Amine-Contaiziing Curing
Prepolymer Ingredients Agent Ingredients ^
Dithiol I I I Dithiol I
Embodi- Oligome Polyo Diisocyanat Diamin Oligomer Polythio
ment # r 1 es e s Is
1 A 22. Pes W DETDA A --
2 A 21 Pes W PETDA A HITT
HITT,
3 A 21 Pes W PETDA A PTMA
4 B 21 Pes W DETDA D --
5 B 2Z Pes W DETPA 21 HITT
6 B 2:; Pes W 'PETDA D HITT
7 B TMP Des W DETDA B --
8 B TMP Des W DETDA D --
9 C 21 Des W DETDA D --
10 C 21 Des W PETDA C, D --
11 C -- Pes W, IPPI PETDA P --
12 C Des W, IPPI DETPA C, P --
Des W,
13 C 2:: TMXDI DETDA D --
14 C TMP Des W, IPPI DETPA P —
Des W,
15 I C I TMP I TMXDI | DETDA D --
A = dithiol oligomer made from DMDS + VNB + DEGDVE
B = dithiol oligomer made from DMDS + DIPEB + DEGDVE
C = dithiol oligomer made from DMDS + DIPEB + VNB
D = dithiol oligomer made from DMDS + DIPEB
VNB = 5-vinyl-2-norbornene
DEGDVE = di(ethylene glycol) divinyl ether
DIPEB = 1,3-diisopropenylbenzene
DMDS = dimercaptodiethyl sulfide
HITT = polythiol made by reacting »3n" moles DMDS with "n" moles of
1,2,4-trivinylcyclohexane
(formula IV'm)
PTMA •= pentaerythritol tetrakis (2-mercaptoacetate)
TMP = trimethylolpropane
Des W = 4,4'-methylene bis(cyclohexyl isocyanate)
IPDI = 3-isocyanato-methyl-3,5,5-trimethyl-cycolohexyl isocyanate
TMXDI = meta-tetramethylxylylene diisocyanate (l,3-bis(l-isocyanato-
1-methylethyl-benzene))
DETDA =, mixture of 2,4-diamino-3,5-diethyltoluene/2, 6-diamino-3,5-
diethyltoluene
wo 2007/097798 • fCT/U32006/046C49
[00147] In a non-limiting embodiment, wherein the sulfurcontaining
polyureaurethane can be prepared by introducing
together a polyurethane prepolymer and an amine-containing
curing agent, the polyurethane prepolymer can be reacted with
at least one episulfide-containing material prior to being
introduced together with amine-containing curing agent.
Suitable episulfide-containing materials can vary, and can
include but are not limited to materials having at least one,
or two, or more episulfide functional groups. In a nonlimiting
embodiment, the episulfide-containing material can
have two or more moieties represented by the following general
formula:
X
(V) Yn,-(CH2) n- CH - CH2
wherein X can be S or O; Y can be Ci - Cio allcyl, 0, or S; m can
be an integer from 0 to 2, and. n can be "an integer from 0 to
10. In a non-limiting embodiment, the numerical ratio of S is
50% or more, on the average, of the total amount of S and O
constituting a three-member ed ring.
[00148] The episulfide-containing material having two or
more moieties represented by the formula (V) can be attached
to an acyclic and/or cyclic skeleton. The acyclic skeleton
can be branched or unbranched, and it can contain sulfide
and/or ether linkages. In a non-limiting embodiment, the
episulfide-containing material can be obtained by replacing
the oxygen in an epoxy ring-containing acyclic material using
sulfur, thiourea, thiocyanate, triphenylphosphine sulfide or
other such reagents known in the art. In a further nonlimiting
embodiment, alkylsulfide-type episulfide-containing
materials can be obtained by reacting various known acyclic
polythiols with epichlorohydrin in the presence of an alkali
to obtain an alkylsulfide-type epoxy material; and then
replacing the oxygen in the epoxy ring as described above.
wo 2007/097798 rCT/U02006/OI66ll)
[00149] In alternate non-limiting embodiments, the cyclic
skeleton can include the following materials:
(a) an episulfide-containing material wherein the cyclic
skeleton can be an alicyclic skeleton,
(b) an episulfide-containing material wherein the cyclic
skeleton can be an aromatic skeleton, and
(c) an episulfide-containing material wherein the cyclic
skeleton can.be a heterocyclic skeleton including a sulfur
atom as a hetero-atom.
[00150] In further non-limiting embodiments, each of the
above materials can contain a linkage of a sulfide, axx ether,
a sulfone, a ketone, and/or an ester.
[00151] Non-limiting examples of suitable episulfidecontaining
materials having ari alicyclic skeleton can include
but are not limited to 1,3- and l,4-bis(i8-
epithiopropylthio) cyclohexane, 1,3- and l,4-bis(i3-
epithiopropylthiomethyl) cyclohexane, bis [4- (/?-
epithiopropylthio) cyclohexyl] methane, 2,2-bis [4-{;ffepithiopropylthio)
cyclohexyl] propane, bis [4-(/Sepithiopropylthio)
cyclohexyl]sulfide, 4-vinyl-l-cyclohexene
diepisulfide, 4-epithioethyl-l-cyclohexene sulfide, 4-epoxy-
1,2-cyclohexene sulfide, 2,5-bis (;8-epithiopropylthio)-1,4-
dithiane, and 2, 5-bis (jS-epithiopropylthioethylthiomethyl)-1,4-
dithiane.
[00152] Non-limiting examples of suitable episulfidecontaining
materials having an aromatic skeleton can include
but are not limited to 1,3- and l,4-bis"(/3-
epithiopropylthio)benzene, 1,3- and l,4-bis(/3-
epithiopropylthioraethyl)benzene, bis [4- (jSepithiopropylthio)
phenyl] methane, 2,2-bis [4-(iSepithiopropylthio)
phenyl] propane, bis[4-(j8-
epithiopropylthio)phenyl] sulfide, bis[4-(/Sepithiopropylthio)
phenyl] sulfone, and 4,4-biB(/8-
epithiopropylthio)biphenyl.
[00153] Non-limiting examples of suitable episulfidecontaining
materials having a heterocyclic skeleton including
the sulfur atom as the hetero-atom can include but are not
wo 2007/097798 PCT/UC2006/0
#
limited to the materials represented by the following general
formulas:
^cmCH2)m-S-Yn-W
S CHZ
"^CuTcH2)m-S-Yn-W
^(U)-(CH2)m-(CH2CH2S)a-W
S CHZ
(VII) • I f
ZCH -5
"^C(U) - (CH2)m-(CH2CH2S)a-W
U (CH2)m (CH2CH2S)a W
(VII') W (CH2CH2S)a(CH2)m.^^l |
"Tv^g/^t-^ (CH2)m (CH2CH2S) a W
wherein m can be an integer from 1 to 5; n can be an integer
from 0 to 4; a Cein be an integer from 0 to 5; U can be a
hydrogen atom or an alkyl group having 1 to 5 carbon atoms; Y
can be -(CHaCHaS)-; Z Can be chosen from a hydrogen atom, an
alkyl group having 1 to 5 carbon atoms or -(CH2)mSYnW; W can be
an epithiopropyl group represented by the following formula:
/
(VIII) CH2-CH-CH2
wherein X can be O or S.
[00154] Additional non-limiting examples of suitable
episulfide-containing materials can include but are not
limited to 2,5-bis (/8-epithiopropylthiomethyl)-1,4-dithiane;
2,5-bis(j8-epithiopropylthioeth.ylthiomethyl) -1,4-dithiane; 2,5-
bis (/8-epithiopropylthicethyl) -1,4-dithiane; 2,3,5-tri (/8-
epithiopropylthioethyl)-1,4-dithiane; 2,4,6-tris{0-
wo 2067/097796 PCT/US2006/046649 •
^ 53
epithiopropylmethyl) -1,3,5-trithiane; 2,4,6-tris (/5-
epithiopropylthioethyl) -1,3,5-trithiane; 2,4, 6-tris (jSepithiopropylthiomethyl)
-1,3, S-rtrithiane; 2,4, 6-tris (/3-
epithiopropylthioethylthioethyl)-1,3,5-trithiane;
X
^ CHCH2 - S CHa - a i - CHa
S ^CH2
CHCH2-S CH2-CH-6l2
CHCH2-S-CH2CH2-S CH2-CH-CH2
S ^CH2
CHCH2-S-CHCH2-S—CH2-CH-CH2
,x
CHCH2CH2 - S CH2 - CH- CH2
S CH2
(XI) 1 1 X
^^^ / ^ / CHCH2CH2-S CH2 -CH-CH2
X
B CH2-CH-CH2
^CHCH2CH2 A
S CHCH2-S CH2-CH-CH2
CHCH2CH2-S CH2-CH-CH2
[00155] wherein X can be as defined above.In a non-limiting
embodiment, the polyurethane prepolymer can be reacted with an
episulfide-containing material of the structural formula
XXXII:
wo 2007/097790 >PCT/USM06/046(i49 "
#
• / /
(XXXII) C2I2-CH-CH2 S CHa-OI-CHz
[00156] In alternate non-limiting embodiments, various known
additives cam be incorporated into the sulfur-containing
polyureaurethane of the present invention. Such additives can
include but are not limited to light stabilizers, heat
stabilizers, antioxidants, ultraviolet light absorbers, mold
release agents, static (non-photochromic) dyes, pigments and
flexibilizing additives, such as but not limited to
alkoxylated phenol benzoates atid poly(alkylene glycol)
dibenzoates. Non-limiting examples of anti-yellowing
additives can include 3-methyl-2-butenol, organo
pyrocarbonates and triphenyl phosphite (CAS registry no. 101-
02-0). Such additives can be present in an amount such that
the additive constitutes less th2in 10 percent by weight, or
less than 5 percent by weight, or less than 3 percent by
weight, based on the total weight of the prepolymer. In
alternate non-limiting embodiments, the aforementioned
optional additives can be mixed with the polyisocyanate and/or
polyisothiocyanate. In a further non-limiting embodiment, the
optional additives can be mixed with active hydrogencontaining
material.
[00157] In a non-limiting embodiment', the resulting sulfurcontaining
polyureaurethane of the present invention when at
least partially cured can be solid and essentially transparent
such that it is suitable for optical or ophthalmic
applications. In alternate non-limiting embodiments, the
sulfur-containing polyvireaurethane can have a refractive index
of at least 1.55, or at least 1.56, or at least 1.57, or at
least 1.58, or at least 1.59, or at least 1.60, or at least
1.62, or at least 1.65. In further alternate non-limiting
embodiments, the sulfur-containing polyureaurethane can have
an Abbe number of at least 32, or at least 35, or at least 38,
or at least 39, or at least 40, or at least 44.
[00158] In a non-limiting embodiment, the sulfur-containing
polyureaurethane when polymerized and at least partially cured
iHfO lOQimntS -rCT/U32006/046649
can demonstrate good impact resistance/strength. Impact
resistance caji be measured using a variety of conventional
methods known to one skilled in the art. In a non-limiting
embodiment, the impact resistance is measured using the Impact
Energy Test which consists of testing a flat sheet sample of
polymerizate having a thicknes's of 3mm, and cut into a square
piece approximately 4cm x 4cm. The flat sheet sample of
polymerizate is supported on a flat 0-ring which is attached
to top of the pedestal, of a steel holder, as defined below.
The O-ring is constructed of neoprene having a hardness of 40
+_ 5 Shore A durometer, a minimum tensile strength of 8.3 MPa,
and a minimum ultimate elongation of 400 percent, and has an
inner diameter of 25 mm, an outer diameter of 31 mm, and a
thickness of 2.3 mm. The. steel holder consists of a steel
base, with a mass of approximately 12 kg, and a steel pedestal
affixed to the steel base. The shape of said steel pedestal
is approximated by the solid shape which would result from
adjoining onto the top of a cylinder, having an outer diameter
of 75 mm and a height of 10 mm, the frustum of a right
circular cone, having a bottom diameter of 75 mm, a top
diameter of 25 mm, and a height of 8 mm, wherein the center of
said frustum coincides with the center of said cylinder. The
bottom of said steel pedestal is affixed to said steel base,
and the neoprene O-ring is affixed to the top of the steel
pedestal, with the center of said O-ring coinciding with the
center of the steel pedestal. The flat sheet sample of
polymerizate is set on top of the O-ring with the center of
said flat sheet sample coinciding with the center of said Oring.
The Impact Energy Test is carried out by dropping steel
balls of increasing weight from a distance of 50 inches (1.27
meters) onto the center of the flat sheet sample. The sheet
is determined to have passed the test if the sheet does not
fracture. The sheet is determined to have failed the test
when the sheet fractures. As used herein, the term "fracture"
refers to a crack through the entire thickness of the sheet
into two or more separate pieces, or detachment of one or more
pieces of material from the backside of the sheet (i.e., the
AVO 2007/097798" i'CT/US200(i/046(>49-
side of the sheet opposite the side of impact). The impact
strength of the sheet is reported as the impact energy that
corresponds to the highest level (i.e., largest ball) at which
the sheet passes the test, and it is calculated acording to
the following formula:
E=mgd
wherein E represent impact energy in Joules (J), m represents
mass of the ball in kilograms (kg), g represents acceleration
due to gravity (i.e., 9.80665 m/sec') and d represents the
distance of the ball drop in meters (i.e., 1.27 m). In an
alternate non-limiting embodiment, using the Impact Energy
Test as described herein, the impact strength can be at least
2.0 joules, or at least 4.95 joules.
[00159] In another non-limiting emobidment, the sulfurcontaining
polyureaurethane of the present invention when at
least partially cured can have low density. In alternate nonlimiting
embodiments, the density can be at least 1.0, or at
least 1.1 g/cm^, or less than 1.3, or less than 1.25, or less
than 1.2 g/cm% or from 1.0 to 1.2 grams/cm^ or from 1.0 to
1.25 grams/cm^, or from 1.0 to less than 1.3 grams/cra^. In a
non-limiting embodiment, the density is measured using a
DensiTECH instrument manufactured by Tech Pro, Incorporated in
accordance with ASTM D297.
[00160] Solid articles that can be prepared using the
sulfur-containing polyureaurethane of the present invention
include but are not limited to optical lenses, such as piano
and ophthalmic lenses, svm lenses, windows, automotive
transparencies, such as windshields, sidelights and
backlights, and aircraft transparencies.
[00161] In a non-limiting embodiment, the sulfur-containing
polyureaurethane polyirierizate of the present invention can be
used to prepare photochromic articles, such as lenses. In a
further embodiment, the polymerizate can be transparent to
that portion of the electromagnetic spectrum which activates
the photochromic substance(s), i.e., that wavelength of
ultraviolet (UV) light that produces the colored or open form
of the photochromic s\abstance and that portion of the visible
AVO 2007/097798- FCT/US2006/046649
spectrum that includes the absorption maximum wavelength of
the photochromic siibstance in its UV activated form, i.e., the
open form.
[00162] A wide variety of photochromic substances ccoi be
used in the present invention. Suitable photochromic
substances, suitable amoxints thereof, and methods of
incorporation into the polymerizate are described in WO
2004/060951 Al at [00151] to [00161], incorporated herein byreference
.
[00163] In another embodiment, the photochromic svibstance
can be added to the sulfur-containing polyureaurethane prior
to polymerizing and/or.cast curing the material. In this
embodiment, the photochromic substance used can be chosen such
that it is resistant to potentially adverse interactions with,
for example, the isocyanate, isothiocyante and amine groups
present. Such adverse interactions can result in deactivation
of the photochromic siobstance, for example, by trapping them
in either an open or closed form.
[00164] Further non-limiting examples of suitable
photochromic substances for use in the present invention can
include photochromic pigments and organic photochromic
sijbstances encapsulated in metal oxides such as those
disclosed in U.S. Patents 4,166,043 and 4,367,170; organic
photochromic substances encapsulated in an organic
polymerizate such as those disclosed in U.S. Patent 4,931,220.
EXAMPLES
[00165] In the following examples, unless otherwise stated,
the IH NMR and 13C NMR were measured on a Varian Unity Plus
(200 MHz) machine; the Mass Spectra were measured on a Mariner
Bio Systems apparatus; the refractive index and Abbe number
were measured on a multiple wavelength Abbe Refractometer
Model DR-M2 manufactured by ATAGO Co., Ltd.; the refractive
index and Abbe number of lic[uids were measured in accordance
with ASTM-D1218; the refractive index and Abbe number of
solids was measured in accordance with ASTM-D542; the
refractive index (e-line or d-line) was measured at a
wo 2067/097798 ^CT/US2006/046649 '
temperature of 20"C; the density of solids was measured in
accordance with ASTM-D792; and the viscosity was measured
using a Brookfield CAP 2000+ Viscometer.'
EXAMPLE 1- Preparation of Reactive Polyisooyanate Prepolymer 1
(RPl)
[00166] In a reaction vessel equipped with a paddle blade
type stirrer, thermometer, gas inlet, and addition funnel,
11721 grams (89.30 equivalents of NCO) of Desmodur W obtained
from Bayer Corporation, 5000 grams (24.82 equivalents of OH)
of a 400 MW polycaprolactone diol (CAPA 2047A obtained from
Solvay) , 1195 grams (3.22 ecpaivalents of OH) of 750 MW
polycaprolactone diol (CAPA 2077A obtained from Solvay), and
217.4 grams (4.78 equivalents of OH) of trimethylol propane
(TMP) obtained from Aldrich were charged. Desmodur W (4,4'-
methylenebis(cyclohexyl isocyanate) containing 20% of the
trans,trans isomer and 80% of the cis,cis and cis, trans
isomers) was obtained from Bayer Corporation. The contents of
the reactor were stirred at a rate of 150 rpm and a nitrogen
blanket was applied as .the reactor contents were heated to a
temperature of 120'C at which time the reaction mixture began
to exotherm. The heat was removed and the temperature rose to
a peak of 140*'C for 30 minutes and then began to cool. Heat
was applied to the reactor when the temperature reached 120"C
and was maintained at that temperature for 4 hours to form the
prepolymer (Component A) . The reaction mixture was san^led
and analyzed for % NCO according to the method described
below. The analytical result showed 13.1.% NCO groups. Before
pouring out the contents of the reactor, 45.3 g of Irganox
1010 (thermal stsdailizer obtained from Ciba Specialty
Chemicals) and 362.7 g of Cyasorb 5411 (UV stabilizer obtained
from Cytec) were mixed into the prepolymer (Component A) .
[00167] THE NCO concentration of the prepolymer (Component
A) was determined by reaction with an excess of n-dibutylamine
(DBA) to foann the corresponding urea followed by titration of
the unreacted DBA with HCl in accordance with ASTM-2572-97.
4V0 2007/097798 -rCT/US2006/046649
[001681 REAGENTS
1. Tetrahydrofuran (THF), reagent grade.
2. 80/20 THF/propylene glycol (PG) mix. This
s o l u t i o n was prepared i n - l a b by mixing 800
mis PG with 3.2 Liters of THF i n 4 Liter
b o t t l e .
3. DBA certified ACS-
4. DBA/THF solution. 150 mL of dibutylamine
(DBA) was combined with 750 mL
tetrahydrofuran (THF); it was mixed well
and transfered to an'amber bottle.
5. Hydrochloric acid, concentrated. ACS
certified.
6. Isopropanol, technical grade.
7. Alcoholic hydrochloric acid, 0.2N. 75-ml
of concentrated hydrochloric acid was
slowly added to a 4-liter bottle of
technical grade isopropanol, while stirring
with a magnetic stirrer. It was mixed for
a minimum of 3 0 minutes. This solution was
standardized using THAM (Tris hydroxyl
methyl amino methane) as follows: Into a
glass 100-mL beaker, was weighed
approximately O.S g ,(HOCHa) jCNHa primary
standard to' the nearest 0.1 mg and the
weight was recorded. 100-mL DI water was
added and mixed to dissolve and titrated
with the prepared alcoholic HCl. This
procedure was repeated a minimum of one
time and the values averaged using the
calculation below.
(Standard wt., grams)
Normality HCL
(mLs HCl) (0.12114)
wo 2007/097790 P^T/UD200(i/046()i9
[00169] EQUIPMENT
1. Polyethylene beakers, 200-mL, Falcon
specimen breakers. No. 354020.
2. Polyethylene lids for above. Falcon No.
354017.
3. Magnetic stirrer and stirring bars.
4. Brinkmann dosimeter for dispensing or 10-mL
pipet.
5. Autotitrator equipped with pH electrode.
25-mL, 50-mL dispensers for solvents or
25-mL and 50-mL pipets.
[00170] PROCEDURE-
1. Blank determination: Into a 220-mL
polyethylene beaker was added 50 mL THF
followed by 10.0 mL DBA/THF solution. The
solution was capped and allowed to mix with
magnetic stirring for 5 minutes. 50 mL of
the 80/2 0 THF/PG mix was added and titrated
using the standardized alcoholic HCl
solution and this volume was recorded.
This procedure was repeated and these
values averaged for use as the blank value.
2. In a polyethylene beaker was weighed 1.0
gram of the prepolymer sample and this
weight was recorded to the nearest 0.1 mg.
50 mL THF was added, the sample was capped
and allowed to dissolve with magnetic
stirring.
3 . 10.0 mL DBA/THF solution was added, the
sample was capped and allowed to react with
stirring for 15 minutes.
4. 50 tnL 80/20 THF/PG solution was added.
5. The beaker was placed on the titrator and
the titration was started. This procedure
was repeated.
MK) 2007/097798 PCTAJS2006/01(i619
[00171] CALCUIiATIONS -
(mis Blank - mis Sample) x (Normality HCl) x (4.2018)
%NCO = —
Sample weight, g
(Sample wt., grams) x (1000)
lEW =
(mis Blank - mis Sample) x (Normality HCl)
lEW = Isocyanate Equivalent Weight |
EXAMPLE 2- Preparation of Reactive Polyisocyanate Prepolymer 2
(RP2)
[00172] In a reactor vessel containing a nitrogen blanket,
450 grams of 400 MW polycaprolactone, 109 grams of 750 MW
polycaprolactone, 114.4 grams of tritnethylol propane, 3000
grams of Pluronic L62D, and 2698 grams of Desmodur W, were
mixed together at room temperature to obtain NCO/OH equivalent
ratio of 2.86. Desmodur W (4,4'-methylenebis(cyclohexyl
isocyanate) containing 20% of the trans,trans isomer and 80%
of the cis,cis and cis, trains isomers) was obtained from Bayer
Coirporation. Pluronic L62D (a polyethylene oxidepolypropylene
oxide block polyether diol) was obtained from
BASF. The reaction mixture was heated to a temperature of
65°C and then 30 ppm of dibutyltindilaurate catalyst,
(obtained from Aldrich) was added and the heat source was
removed. The resulting exotherm raised the temperature of the
mixture to 112"C. The reaction was then allowed to cool to a
temperature of 100°C, and 131 grams of OV absorber Cyasorb
5411 (obtained from American Cyanamid/Cytec) and 32.56 grams
of Irganox 1010 (obtained from Ciba Geigy) were added with
0.98 grams of one weight percent solution of Exalite Blue 78-
13 (obtained from Exciton) dissolved in Desmodur W (4,4'-
methylenebis(cylohexylisocyanate)). The mixttire was stirred
for an additional two hours at 100»c and then allowed to cool
to room temperature. The isocyanate (NCO) concentration of the
prepolymer was 8.7% as measured using the procedure described
above (see Example 1 ).
wo 2007/00771)8 rCTAJGa006/016619
EXAMPLE 3- Preparation of Reactive Polyisocyanate Prepolymer 3
(RP3)
[00173] In a reactor vessel containing a nitrogen blanket,
450 grams of 400 MW polycaprolactone, 109 grams of 750 MW
polycaprolactone, 114.4 grams of trimethylol propane, 3000
grams of Pluronic L62D, and 3500 grams of Desmodur W, were
mixed together at room temperature to obtain NCO/OH equivalent
ratio of 3.50. Desmodur W (4,4' -methylenebis (cyclohexyl
isocyanate) containing 20% of tlxe trans, trans isomer and 80%
of the cis,cis and cis, trans isomers) was obtained from Bayer
Corporation. Pl-uronic L62D (a polyethylene oxidepolypropylene
oxide block polyether diol and was obtained from
BASF. The reaction mixture was heated to a temperature of
es^C and then 30 ppm of dibutyltindilaurate catalyst (obtained
from Aldrich) was added and the heat source was removed. The
resulting exotherm raised the ten^erature of the mixture to
112"C. The reaction was then allowed to cool to a temperature
of 100°C, and 131 grams of UV absorber Cyasorb 5411 (obtained
from American Cyanaraid/Cytec) and 32.66 grams of Irganox 1010
(obtained from Ciba Geigy) were added with 0.98 grams of one
weight percent solution of Exalite Blue 78-13 (obtained from
Exciton) dissolved in Desmodur W (4,4'-
methylenebis (cylohexylisocyanate)) . The mixture was stirred
for an additional two hours at 100"C and then allowed to cool
to room temperature. The isocyanate (NCO) concentration of
the prepolymer was 10.8% as measured in accordance with the
procedure described above (see Example 1 ).
EXAMPLE 4- Preparation of Reactive Polyisocyanate Prepolymer 4
(RP4)
[00174] In a reactor vessel containing a nitrogen blanket,
508 grams of 400 MW polycaprolactone, 114.4 grams of
trimethylol propane, 3000 grams of Pluronic L62D, and 4140
grams of Desmodur W, were mixed together at room tett5>erature
to obtain NCO/OH equivalent ratio of 4.10. Desmodur W (4,4'-
methylenebis (cyclohexyl isocyanate) containing 20% of the
trans, trans isomer and 80% of the cis,cis and cis, trans
we 2007/097798' PCT/US2006/046649
#
isomers) was obtained from Bayer Corporation. Pluronic LS2D
(polyethylene oxide-polypropylene oxide block polyether diol)
was obtained from BASF. The reaction mixtiire was heated to a
temperature of GB^C and then 30 ppm of dibutyltindilaurate
catalyst (obtained from Aldrich) was added and the heat source
was removed. The resulting exotherm raised the temperature of
the mixture to 112°C. 'The reaction was then allowed to cool
to a temperature of 100°C, and 150 grams of UV absorber Cyasorb
5411 (obtained from American Cyanamid/Cytec) and 37,5 grams of
Irganox 1010 (obtained from Ciba Geigy) were added with 1.13
grams of one weight percent solution of Exalite Blue 78-13
(obtained from Exciton) dissolved in Desmodur W, 4,4'-
methylenebis(cylohexylisocyanate). The mixture was stirred
for an additional two hours at 100°C and then allowed to cool
to room temperature. The isocyanate (NCO) concentration of
the prepolymer was 12.2% as measured in accordance with the
procedure described above (see"Example 1) .
EXAMPLE 5
[001751 30.0 g of RPl and 10.0 g of bis-epithiopropyl
sulfide (formula XXXII) were mixed in a reactor by stirring at
a temperature of 50'C until a homogeneous mixture was obtained.
4.00 g of PTMA, 2.67g of DETDA and 5.94 g of MDA were mixed in
a reactor by stirring at a temperature of 50°C until a
homogeneous mixture was obtained. Both mixtures were degassed
under vacuum at 50°C, Then the mixtures were combined and
mixed at this temperature and homogenized by gentle stirring
for 1-2 minutes. The resulting clear mixture was immediately
charged between two flat glass molds. The molds were heated
at a temperature of 130°C for 5 hours, yielding a transparent
plastic sheet with the refractive index (e-line), Abbe number,
density and impact values shown in Table 1.
EXAMPLE 6
[00176] 24.0 g of RPl and 20.0 g of bis-epithiopropyl
sulfide (formula XXXII) were mixed in a reactor by stirring at
a temperature of 50°C xintil a homogeneous mixture was obtained.
w o 2007/097998- JP€T/U3200(i/046649-
2.00 g of DMDS, 2.14g of DETDA, 4.75 g of MDA and 0.12 g
Irganox 1010 (obtained' from Ciba Specialty Chemicals) were
mixed in a reactor by stirring at a temperature of 50°C until a
homogeneous mixture was obtained. Both mixtures were degassed
under vacuum at 50°C. The mixtures were then combined and'
mixed at this temperature and homogenized by gentle stirring
for 1-2 minutes. The resulting clear mixture was immediately
charged between two flat glass molds. The molds were heated
to a temperature of 13 0°C for 5 hours, yielding a transparent
plastic sheet with the refractive index (e-line), Abbe number,
density and impact resistance values shpwn in Table 1.
EXAMPLE 7
[00177] 30.0 g of RPl and 20.0 g of bis-epithiopropyl
sulfide (Formula XXXII.) were mixed in a reactor by stirring at
a temperature of 50°C until a homogeneous mixture was obtained.
2.40 g of PTMA, 5.34g of DETDA and 3.96 g of MDA were mixed in
a reactor by stirring at a temperature of 50°C until a
homogeneous mixture was obtained. Both mixtures were degassed
under vacuum at 50°C. The mixtures were then combined and
mixed at this temperature and homogenized by gentle stirring
for 1-2 minutes. The resulting clear mixture was immediately
charged between two flat glass molds. The molds were heated
to a temperature of i3 0°C for 5 hours, yielding a transparent
plastic sheet with the refractive index (e-line), Abbe number,
density and impact values shown in Table 1.
EXAMPLE 8
100178] 24.0 g of RPl and 20.0 g of bis-epithiopropyl
sulfide (Formula XXXII) were mixed in a reactor by stirring at
s temperature of SO'C until a homogeneous mixture was obtained.
2.B5g of DETDA and 3.96 g of MDA were mixed in a reactor by
stirring at a temperature of BO^C until homogeneous mixture was
obtained. Both mixtures were degassed under vacuum at 50°C.
The mixtures were then combined and mixed at this temperature
and homogenized by gentle stirring for 1-2 minutes. The
resulting clear mixture was immediately charged between two
wo 3007/097798 rCT/U32006/046649
flat glass molds. The molds were heated to a temperature of
ISO^C for 5 hoxirs, yielding a transparent plastic sheet with
the refractive index (e-line) , Abbe number, density and impact
values shown in Table 1.
EXAMPLE 9
[00179] 30.0 g of RP3 and 25.0 g of bis-epithiopropyl
sulfide (Formula XXXII) were mixed in a reactor by stirring at
a temperature of 50°C until a homogeneous mixture was obtained.
3.75 g of DMDS, 2.45g of DETDA and 4.66 g of MDA were mixed in
a reactor by stirring at a temperature of 50°C until
homogeneous mixture was obtained. Both mixtures were degassed
under vacuum at 50°C. The mixtures were then combined and
mixed at this temperature and homogenized by gentle stirring
for 1-2 minutes. The resulting clear mixture was immediately
charged between two flat glass molds. The molds were heated
to a temperature of ISO^C for 5 hours, yielding a transparent
plastic sheet with the refractive index (e-line), Abbe number,
density and impact values shown in Tablfe 1.
EXAMPLE 10
[00180] 30.0 g of RP4 and 25.0 g of bis-epithiopropyl
sulfide (Formula XXXII) were mixed in a reactor by stirring at
a temperature of SCC until a homogeneous mixture was obtained.
3.75 g of DMDS, 2.71g of DETDA and 5.17 g of MDA were mixed in
a reactor by stirring at a temperatvire of SO^C until
homogeneous mixture was obtained. Both mixtures were degassed
under vacuum at 50°C. The mixtiires were then combined and
mixed at this temperature and homogenized by gentle stirring
for 1-2 minutes. The resulting clear mixture was immediately
charged between two flat glass molds. The molds were heated
to a temperature of 130°C for 5 hours, yielding a transparent
plastic sheet with the refractive index (e-line), Abbe number,
density and impact values shown in Table 1.
wo 2007/0»779» PCTAJ92006/046649
EXAMPLE 11
[00181] 30.0 g Of RP2 and 21.4.0 g of bis-epithiopropyl
sulfide (Formula XXXII) were mixed in a reactor by stirring at
a temperature of 50°C until a homogeneous mixture was obtained.
3.21 g of DMDS, 1.92 g of DETDA and 3.67 g of MDA were mixed
in a reactor by stirring at a temperature of 50°C until
homogeneous mixture was obtained. Both mixtures were degassed
under vacuum at 50°C. The mixtures were then combined and mixed
at this temperature and homogenized by gentle stirring for 1-2
minutes. The resulting clear mixture was immediately charged
between two flat glass molds. The molds were heated to a
temperature of 13Cc for 5 hours, yielding a transparent
plastic sheet with the refractive index (e-line), Abbe number,
density and impact values shown in Table 1.
Table 1.
Experiment Refractive Abbe Density Impact Energy*
# Index Ntunber
(e-line) (g/cm^) (J)
5 1.58 38 1.195 ~ 3.99
6 1.61 36 1.231 2.13
7 1.59 38 1.217 2.47
8 1.60 37 1.222 2.77
9 1.60 38 1.227 >4.95
10 1.59 37 1.211 3.56
11 I 1.59 I 38 I 1.218 I >4.95 j
*The Impact Energy was measured in accordance with the Impact
Energy Test previously described herein. The ball sizes that
I
•wo 2007/097790- JCTAJS300(i/016619
were used in this test and the corresponding impact energies
are listed below.
Ball weight, kg Impact Energy, J
0.016 0.20
0.022 0.27
0.032 0.40
0.045 0.56
0.054 0.68
0.067 . 0.83
0.080 1.00
0.094 1.17
0.110 1.37
0.129 • 1.60
0.149 1.85 j
0.171 2.13
0,198 2.47
0.223 2.77
0.255 3,17
0.286 3,56
0.321 3,99
0.358 4.46
0.398 4,95
EXAMPLE 12 - Synthesis o£ Polythioether (PTE) Dithiol 1
[00182] NaOH (44.15 g, 1.01 mol) was dissolved in 350 ml of
HjO. The solution was .allowed to cool to room temperature and
500 ml of toluene were added, followed by the addition of
dimercaptodiethyl sulfide (135 ml, 159.70 g, 1.04 mol). The
reaction mixture was heated to a temperature of 40°C, stirred
and then cooled to room temperature. 1, 1 -Dichloroacetone
(DCA) (50 ml, 66.35 g, 0.52 mol) was dissolved in 250 ml of
toluene and then added drop-wise to the reaction mixture while
the temperature was maintained at from 20-25°C. Following the
drop-wise addition, the reaction mixture was stirred for an
additional 20 hours at room temperature. The organic phase
was than separated, washed with 2x100 ml of H20, 1x100 ml of
brine and dried over anhydrous MgSO*. The drying agent was
wo 2007/09779» PCTAJS2006/016C
filtered off and the toluene was evaporated using a Buchi
Rotaevaporator. The hazy residue was filtered through Celite
to provide 182 g (96% yield) of PTE Dithiol 1 as a colorless
clear oily liquid.
[00183] The results of the Mass Spectra were ESI-MS: 385 (M
+ Na) and the molecular weight was calculated as 362.
[00184] The results of the NMR were ^H NMR (CDClj, 200 MHz) :
4.56 (s, IH) , 2.75 (m, 16 H) , 2.38 (s, 3H) , 1.75 (m, 1.5H)) .
[00185] The SH groups within the product were determined
using the following procedure. A sample size (0.1 g) of the
product was combined with 50 mL of tetrahydrofuxan
(THP)/propylene glycol (80/20) solution and stirred at room
temperature until the sample was substantially dissolved.
While stirring, 25.0 mL of 0.1 N iodine solution (commercially
obtained from Aldrich 31, 8898-1) was added to the mixture and
allowed to react for a time period of from 5 to 10 minutes.
To this mixture was added 2.0 mL concentrated HCl. The
mixture was titrated potentiometrically with 0.1 N sodium
thiosulfate in the millivolt (mV) mode. The resulting volume
of titrant is represented as "mLs Sample" in the below
equation. A blank value was initially obtained by titrating
25.0 mli of iodine (including 1 mL of concentrated hydrochloric
acid) with sodium thiosulfate in the same manner as conducted
with the product sample. This resulting volume of titrant is
represented as "mLs Blank" in the below equation.
%SH = (mLsBlank - mLsSample)(Normality Ma2S203)(3.307) - 13.4
sample weight, g
[00186] The refractive index was 1.618 (20°C) and the Abbe
niimber was 35.
[00187] The product sample (lOOmg, 0.28 mmol) was acetylated
by dissolving it in 2 ml of dichloromethane at room
temperature. Acetic anhydride (0.058 ml, 0.6 mmol) was added
to the reaction mixture, and triethylamine (0.09 ml, 0.67
mmol) and dimethylaminopyridine (1 drop) were then added. The
wfnwmmn rcT/usaoQ(i/oi66
mixture was maintained at room temperatiore for 2 hours. The
mixture was then diluted with 20 ml of ethyl ether, washed
with aqueous NaHCOs and dried over MgSO*. The drying agent was
filtered off; the volatiles were evaporated off under vacuum
and the oily residue was purified by silica gel flash
chromatography (hexane / ethyl acetate 8:2 volume per volume)
to provide 103 mg (83% yield) of diacetylated product with the
following results:
^H NMR (CDC13, 200 MHz): 4.65 (s, IH), 3.12-3.02 (m, 4H),
2.75-2.65 (m, 4H), 2.95-2.78 (ra, 8 H), 2.38 (s, 3H), 2.35
(s, 6H) .
ESI-MS: 385 (M + Na) .
EXAMPLE 13 - Synthesis of PTE Dithiol 2
[001881 NaOH (23.4 g, 0.58 mol) was dissolved in 54 ml of
H2O. The solution was cooled to room temperature and DMDS
(30.8 g, 0.20 mol) was added. Upon stirring the mixture,
dichloroacetone (19.0 g, 0.15 mol) was added dropwise while
maintaining the temperature from 20-25°C. After the addition
of dichloroacetone was completed, the mixture was stirred for
an additional 2 hours at room temperature. The mixture was
neutralized with 10% HCl to a pH of 9, and 100 ml of
dichlororaethane were then added, and the mixture was stirred.
Stirring was terminated; the mixture was transferred to a
separatory funnel and allowed to separate. Following phase
separation, the organic phase was washed with 100 ml of H2O,
and dried over anhydrous MgSO^. The drying agent was filtered
off and the solvent was evaporated using a Buchi
Rotaevaporator, which provided 35 g (90% yield) of transparent
liquid having a viscosity (73°C) of 38 cP; refractive index (eline)
of 1.622 (20'C), Abbe number of 36, and SH group analysis
of 8.10%.
EXAMPLE 14 - Synthesis of PTE Dithiol 3
[00189] NaOH (32.0 g, 0.80 mol) was dissolved in 250 ml of
HjO. The solution was cooled to room temperature and 240 ml of
wo 2007/097798- rCT/US2006/046(i49
toluene were added followed by the addition of DMDS (77.00 g,
0.50 mol) . The mixture was heated to a temperature of 40°C,
stirred and then cooled vinder nitrogen flow until room
temperature was reached. DCA (50.8 g, 0.40 mol) was dissolved
in 70 ml of toluene and added dropwise to the mixture with
stirring, while the temperature was maintained from 20-25°C.
After the addition was completed, the mixture was stirred for
additional 16 hours at room temperature. Stirring was
stopped, the mixture was transferred to a separatory funnel
and allowed to separate. The organic phase was separated,
washed with 2x100 ml of H2O, 1x100 ml of brine and dried over
anhydrous MgSO*. The drying agent was filtered off and toluene
was evaporated using a Buchi Rotaevaporator to provide 89 g
(90% yield) of transparent liquid having viscosity (73°C)of 58
cP; refractive index (e-line)of 1.622 ^2Q°C) , Abbe niiraber of
36; and SH group analysis of 3.54%.
EXAMPLE 15 - Synthesis of PTE Dithiol 4
[00190] NaOH (96.0 g, 2.40 mol) was dissolved in 160 ml of
H2O and the solution was cooled to room temperature. DMDS
(215.6 g, 1.40 mol), 1,1-dichlproethane' (DCE) (240.0 g, 2.40
mol) and tetrabutylphosphonium bromide (8.14 g, 1 mol. %) were
mixed and added to the NaOH mixture dropwise under nitrogen
flow and vigorous stirring while the temperature was
maintained between 20-'25°C. After the addition was completed,
the mixture was stirred for an additional 15 hours at room
temperature. The aqueous layer was acidified and extracted to
give 103.0 g of unreacted DMDS. The organic phase was washed
with 2x100 ml of H3O, 1x100 ml of brine and dried over
anhydrous MgS04. The drying agent was filtered off and the
excess DCE was evaporated using a Buchi Rotaevaporator to
yield 78 g (32% yield) transparent liquid having viscosity
(73°C) of 15 cP; refractive index (e-line) of 1.625 (20°C) ,
Abbe number of 36; and SH group analysis of 15.74%.
-wo 2007/09779r •rCT/UG2«06/046649
EXAMPLE 16 - Synthesis of PTE Dithiol 5
[00191] NaOH (96.0 g, 2.40 mol) was dissolved in 140 ml of
HjO and the solution was cooled to a temperature of 10°C and
charged in a three necked flask equipped with mechanical
stirrer and, inlet and outlet for Nitrogen. DMDS (215.6 g,
1.40 mol) was then charged and the temperature was maintained
at 10°C. To this mixture was added dropwise solution of
tetrabutylphosphonium bromide (8.14 g, 1 mol. %) in DCE (120
g, 1.2 mol) under Nitrogen flow and vigorous stirring. After
the addition was completed the mixture was stirred for an
additional 60 hours at room temperature. 300 ml of HjO and 50
ml of DCE were then added. The mixture was transferred to a
separatory fvinnel, shaken well, and following phase
separation, 200 ml toluene were added to the organic layer; it
was then washed with 150 ml HaO, 50 ml 5% HCl and 2x100 ml HaO
and dried over anhydrous MgS04. The drying agent was filtered
off and the solvent was evaporated on rotaevaporator to yield
80 g (32% yield) of transparent liquid having viscosity (73°C)
of 56 cP; refractive index (e-line) of 1.635 (20°C) , Abbe
number of 36; and SH group analysis of 7.95%.
EXAMPLE 17 - Synthesis of Polythiourethane Prepolymer (PTUPP)1
[00192] Desmodur W (62.9 g, 0.24 mol) and PTE Dithiol 1
(39.4 g, 0.08 mol) were mixed and degassed under vacuum for
2.5 hours at room temperature. Dibutyltin dilaurate (0.01 %
by weight of the reaction mixture) was then added and the
mixture was flushed with nitrogen and heated for 32 hours at a
temperature of se'C. SH group analysis showed complete
consumption of SH groups. The heating was stopped. The
resulting mixture had viscosity (73°C) of 600 cP refractive
index (e-line) of 1,562 (20'C) , Abbe number of 43; and NCO
groups of 13.2 % (calculated 13.1%). The NCO was determined
according to the procedure described in Example 1 herein.
EXAMPLE 18 - Synthesis of PTUPP 2
[00193] Desmodur W (19.7 g, 0.075 mol) and PTE Dithiol 2
(20.0g, 0.025 mol) were mixed and degassed vinder vacuum for
wo 2007/09779»- PCT/US2006/046649
7172.
2.5 hours at room temperature. Dibutyltin dichloride (O.Ol
weight percent) was then added to the mixture, and the mixture
was flushed with nitrogen and heated for 18 hours at a
temperature of 86°C. SH group analysis showed complete
consumption of SH groups. The heating was stopped. The
resulting mixture had viscosity (at TS^C) of 510 cP refractive
index (e-line) of 1.574 (20°C) , Abbe number of 42; and NCO
groups of 10.5 % (calculated 10.6%).
EXAMPLE 19 - Synthesis of PTUPP 3
[00194] Desmodur W (31.0 g,. 0.118 mol) and PTE Dithiol 3
(73.7 g, 0.039 mol) were mixed and degassed vmder vacuum for
2.5 hours at room temperature. Dibutyltin dichloride was then
added (0.01 weight percent) to the mixture, and the mixture
was flushed with nitrogen and heated for 37 hours at a
temperature of 64'C. SH group analysis showed complete
consumption of SH groups. The heating was stopped. The
resulting mixture had viscosity (at 73°C) of 415 cP, refractive
index (e-line) of 1.596 (20°C) , Abbe number of 39; and NCO
groups of 6.6^ (calculated 6.3%).
EXAMPLE 20 - Chain Extension of Polythiourethane Prepolymer
with Aromatic Amine
[00195] PTUPP 1 (30 g) was degassed under vacuum at a
temperature of 70'C for 2 hours. DETDA (7.11 g) and PTE Dithiol
1 (1.0 g) were mixed and degassed under vacuum at a
temperature of 70°C for 2 hours. The two mixtures were then
mixed together at the .same temperature and charged between a
preheated glass plates mold. The material was cured in a
preheated oven at a temperature of ISO^C for 5 hours. The
cxored material was transparent and had a refractive index (eline)
of 1.585 (20°C) , Abbe number of 39 and density of 1.174
g/cm^.
EXAMPLE 21
[00196] PTUPP 2 (25 g) was degassed under vacuum at a
temperature of 65»C for 3 hours. DETDA (3.88 g) and PTE
wo 2007/097798- i>€TAJS2006/04tf649
Dithiol 1 (3.83 g) were mixed and degassed under vacuum at a
temperature of 65°C for 2 hours. The two mixtures were then
mixed together at the same temperature and charged between a
preheated glass plates mold. The material was cured in a
preheated oven at a temperature of IBO'C for 10 hours. The
cured material was transparent and had refractive index {eline)
of 1.599 {20°C), Abbe number of 39 and density of 1.202
g/cm^.
EXAMPLE 22
[00197] PTUPP 3 (40 g) was degassed xinder vacuum at a
temperature of 65°C for 2 hours. DETDA (3.89 g) and PTE Dithiol
1 (3.84 g) were mixed and degassed under vacuum at a
temperature of 65°C for 2 hours. The two mixtures were then
mixed together at the same temperature and charged between a
preheated glass plates mold. The material was cured in a
preheated oven at a temperature of 130°C for 10 hours. The
cured material was transparent and had refractive index (eline)
of 1.609 (20°C) , Abbe number of 39 and density of 1.195
g/cm'.
EXAMPLE 23 - Synthesis of 2-Methyl-2-Dichloromethyl-l,3-
Dithiolane
[00198] In a three-hecked flask equipped with a magnetic
stirrer and having a nitrogen blanket at the inlet and outlet,
were added 13.27 grams (0.104 mol) of 1,1-dichloroacetone,
11.23 grams (0.119 mol) of 1,2-ethanedithiol, 20 grams of MgS04
anhydrous, and 5 grams of Montmorilonite K-10 (commercially
obtained from Aldrich) in 200 ml toluene. The mixture was
stirred for 24 hours at room temperature- The insoluble
product was filtered off and the toluene was evaporated off
under vacuum to yield 17.2 grams (80% yield) of crude 2-
methyl-2-dichloromethyl-l, 3-dithiolane.
[00199] The crude product was distilled within a temperature
range of from 102 to 112«>C at 12 mm Hg. ^H NMR and "C NMR
results of the distilled product were: ^H NMR (CDC13, 200
wo 2007/097798- •P€T/U32006/04(i(i49
MHz): 5.93 (s, IH) ; 3 . 3 4 (s, 4H) ; 2 . 0 2 .(s, 3H) ; "CNMR (CDC13,
50MHz): 8 0 . 5 7 ; 4 0 . 9 8 ; 2 5 . 6 7.
EXAMPLE 24 - Synthesis of PTE Dithiol 6 (DMDS/VCH, 1:2 mole
ratio)
[00200] Charged into a 1-liter 4-necked flask equipped with
a mechanical stirrer, thermometer and two gas passing adapters
(one for inlet and one for outlet), was dimercaptodiethyl
sulfide (DMDS) (888.53g, 5.758 moles). The flask was flushed
with dry nitrogen and 4-vinyl-l-cyclohexene (VCH) (311.47g,
2.879 moles) was added with stirring during a time period of 2
hours and 15 minutes. The reaction temperature increased from
room temperature to 62'C after 1 hr of addition. Following
addition of the vinylcyclohexene, the temperature was 37°C.
The reaction mixture was then Jieated to a temperature of 60°C,
and five 0.25g-portions of free radical initiator Vazo-52
(2,2'-azobis(2,4-dimethylpentanenitrile) obtained from DuPorit)
were added. Each portion was added after an interval of one
hour. The reaction mixture was evacuated at 60°C/4-5mm Hg for
one hour to yield 1.2 kg (yield: 100%) of colorless licjuid
with the following properties: viscosity of 300 cps ® 25°C
refractive index (e-line) of 1.597 (20°C); Abbe Number of 39;
and SH groups content of 16.7%.
EXAMPLE 25 - Synthesis of PTE Dithiol 7 (DMDS/VCH, 5:4 mole
ratio)
[00201] In a glass jar with magnetic stirrer were mixed 21.6
grams (0.20 mole) of 4-vinyl-l-cyclohexene (VCH) from Aldrich
and 38.6 grams (0.25 mole) of dimercaptodiethyl sulfide (DMDS)
from Nisso Maruzen. The mixture had a temperature of 60 °C due
to the exothermicity of the reaction. The mixture was then
placed in an oil bath -at a temperature of 47 "C and stirred
under a nitrogen flow for 40 hours. The mixture was cooled to
room temperature. A colorless, viscous oligomeric product was
obtained, having the following properties: viscosity of
10860, cps ® 25 "C; refractive index (e-line) of 1.604 (20oc);
Abbe Number of 41; and SH groups content of 5-1%.
wo 2007/097790- .JteT/US2006/04(rt^49--
EXAMPLE 26 - Synthesis of Star Polymer (SP)
[002021 In a glass-lined reactor of 7500 lb capacity, were
added 1,8-dimercapto-3,6-dioxaoctane (DMDO) (3907.54 lb, 21.43
moles), ethyl formate (705.53 lb, 9.53 moles), and anhydrous
zinc chloride (90.45 lb, 0.66 mole). The mixture was stirred
at a temperature of 85°C for 20 hours, then cooled to a
temperature of 52°C. Added to the mixture was 96.48 lb of a
33% solution of 1, 4-diazabicyclo [2 . 2 .2] octajcie (DABCO) (0.28
mole) for one hour. The mixture was then cooled to a
temperature of 49°C, and filtered through a 200-micron filter
bag to provide liquid polythioether with the following
properties: viscosity of 320 cps ® 25 "C; nn'" of 1.553; Abbe
Number of 42; and SH groups content of 11.8% (thiol equivalent
weight. of 280) .
EXAMPLE 27 - Synthesis of 2;1 Adduct of DMDS and Ethylene
Glycol Dimethacrylate
[002031 . Dimercaptodiethyl sulfide (42.64 g, 0.276 mole) was i
charged into a 100 ml, 4-necked flask equipped with a
mechanical stirrer, thesrmometer, and two gas-passing adapters
(one for inlet and the other for outlet). The flask was
flushed with dry nitrogen and charged under stirring with 1,8-
diazabicyclo[5.4.0]undec-7-ene (0.035 g)obtained from Aldrich.
Ethylene glycol dimethacrylate (27.36 g, 0.138 mole) obtained
from Sartomer under the trade name SR-206 was added into
stirred solution of dithiol and base over a period of 12
minutes. Due to exotherm, the reaction temperature had
increased from room temperature to 54°C during the addition
step. Following completion of the addition of dimethacrylate,
the temperature was 42"C. The reaction mixture was heated at
a temperature of 63"C for five hours and evacuated at 63»C/4-5
mm Hg for 30 minutes to yield 70 g (yield: 100%) of colorless
liquid (thiol equivalent weight of 255), having SH groups
content of 12.94%.
wo 2007/097798 -PCT/U92006/e46649'
EXAMPLE 28 - Synthesis of 3:2 Adduct of DMDS and Ethylene
Glycol Dimethacrylate
[00204] Dimercaptodiethyl sulfide (16.20 grams, 0.105 mole)
and ethylene glycol dimethacrylate (13.83 grams, 0.0698 mole)
were charged into a small glass jar and mixed together using a
magnetic stirrer. N,N-dimethylben2ylamine (0.3007 gram)
obtained from Aldrich was added, and the resulting mixture was
stirred and heated using an oil bath at a temperature of 75°C
for 52 hours. A colorless to slightly yellow liquid was
obtained having thiol equivalent weight of 314, viscosity of
1434 cps at 25°C and SH group content of 10.53%.
EXAMPLE 29 - Synthesis of 3:2 Adduct of DMDS and 2,2'-
Thiodiethanethiol Dimethacrylate
[00205] Dimercaptodiethyl sulfide (13.30 grams, 0.0864 mole)
and 2,2'-thiodiethanethiol dimethacrylate (16.70 grams, 0.0576
mole) obtained from Nippon Shokubai under the trade name S2EG
were charged into a small glass jar and mixed together using a
magnetic stirrer. N,N-dimethylbenzylamine (0.0154 gram)
obtained from Aldrich was adde'd, and the resulting mixture was
stirred at ambient temperature (21-25 °C) for 75 hours. A
colorless to slightly yellow liquid was obtained having thiol
equivalent weight of 4.88, viscosity of 1470 cps at 25°C,
refractive index no^" of 1.6100, Abbe Number of 36, and SH group
content of 6.76%.
EXAMPLE" 30 - Synthesis of 4;3 Adduct of DMDS and Allyl
Methacrylate
[00206] Allylmethacrylate (37.8 g, 0.3 mol) and dimercapto
diethyl sulfide (61.6 g, 0.4 mol) were mixed at room
temperature. Three drops of 1,8-diazabicyclo[5.4.0]undec-7-
ene were added upon stirring. The temperature of the mixture
increased to 83°C due to the exothermicity of the reaction.
The reactor containing the reaction mixture was put in an oil
bath at a temperature of 65°C and was stirred for 21 hours.
Irgacure 812 (0.08 g) obtained from Ciba was added and the
mixture was irradiated with UV light for 1 minute. The UV
.We-2007/097798 PCTAJ32006/046649-
light source used was a 300-watt FUSION-SYSTEMS UV lamp, with
a D-Bulb, which was positioned at a distance of 19 cm cibove
the sample. The sample was passed beneath the UV light source
at a linear rate of 30.5 cm / minute using a model no. C636R
conveyor belt system, available commercially from LESCO, Inc.
A single pass beneath the UV light source as described
imparted 16 Joules / cm^ of UV energy (UVA) to the sample. A
SH titration analysis conducted 10 minutes following the UV
irradiation, showed SH group content of 6.4% and SH ecjuivalent
weight of 515 g/equivalent. The viscosity of this product was
215 cps at TB'C the refractive index was HD was 1.5825, and the
Abbe number was 40.
EXAMPLE 31 - Synthesis of PTUPP 4
[00207] 4,4-dicyclohexylmethane diisocyanate (Desmodur W)
from Bayer (20.96g, 0.08 mole), isophorone diisocyanate (IPDI)
from Bayer (35.52g, 0.16 mole) and PTE Dithiol 6 (32.0 g, 0.08
mole) were mixed and degassed under vacuum for 2.5 hours at
room temperature. Dibutyltin dilaurate (0.01%) obtained from
Aldrich was then added to the mixture and the mixture was
flushed with Nitrogen and heated for 15 hours at a temperature
of 90"C. SH group analysis showed complete consumption of SH
groups. The heating was terminated. The resulting clear
mixture had viscosity (73°C) of 1800 cP, refractive index (eline)
of 1.555 (20°C), Abbe number of 44; and NCO groups of
14.02 %.
EXAMPLE 32 - Chain extension of PTUPP 4 "
[00208] PTUPP 4 (30 g) was degassed under vacuum at a
temperature of SD'C for two hours. DETDA (7.57 g) and PTE
Dithiol 6 (2.02g) were mixed and degassed under vacuum at a
temperature of sCC for' 2 hours. The two mixtures were then
mixed together at the same temperature and charged between a
preheated glass plates mold. The material was cured in a
preheated oven at a temperature of 130°C for five hours. The
cured material was clear and had refractive index (e-line) of
1,574 (20*'C) and 7U>be number of 40.
WO4007/097798. rCT/US3006/016619-
EXftMPLE 33 - Synthesis of PTUPP 5
[00209] 4,4-dicycloh.exylmethane diisocyanate (Desmodur W)
from Bayer (99.OOg, 0.378 mole), PTE Dithiol 6 (47.00g, 0.118
mole) and Star Polymer (Example 26, 4.06 g, 0.0085 mole) were
mixed and degassed under vacuum for 2.5 hours at room
temperature. Dibutyltin dilaurate (Aldrich) was then added
(0.01 %) and the mixture was flushed with Nitrogen and heated
for 16 hours at a temperature of 90°C. SH group analysis
showed complete consumption of SH groups. The heating was
stopped. The resulting clear .mixture had viscosity (VS^C) of
1820 cP, refractive index (e-line) of 1.553 (20'>C) , Abbe
number of 46; and NCO groups of 13.65%.
EXAMPLE 34 - Chain extension of PTUPP 5
[00210] PTUPP 5 (30 g) was degassed under vacuum at a
temperature of 60°C for two hours. DETDA (6.94 g) and DMDS
(1.13g) were mixed together and degassed under vacuum at a
temperature of 60°C for two hours. The two mixtures were then
mixed together at the same temperature and charged between
preheated glass plates mold. The material was cured in a
preheated oven at a temperature of ISO'C for five hours. The
cured material was clear and had refractive index (e-line) of
1.575 (20'C) and Abbe number of 41.
EXAMPLE 35 - One pot synthesis of polythiourea/urethane
material
[00211] 4,4-dicyclohexylmethane diisocyanate (Desmodur W)
from Bayer (42.OOg, 0.16 mole) was degassed under vacuum at
room temperature for two hours. PTE Dithiol 6 (32.OOg, 0.08
mole), DETDA (11.40 g, 0.064 mole) and DMDS (2.46 g, 0.016
mole) were mixed together and degassed under vacuum at room
ten^erature for two hours. The two mixtures were then mixed
together at the same ten^erature and charged between a
preheated glass plates mold. The material was cured in a
preheated oven at a temperature of 130°C for 24 hours. The
cured material was clear. The results were as follows:
wo 2007/097798 JCTAJQ2006/04tf()49
refractive index (e-line) of 1.582 (20*'C) and Abbe number of
40.
EXAMPLE 36 - Synthesis of dithiol oligomers
[00212] The starting materials shown in Table 2 were
prepared according to the method specified in Table 2 and
described below to yield a resulting dithiol oligomer having
the properties shown in Table 2 for Entries 1-16.
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•- r i S n l f l J H H H H i - t H H H H H H
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* ^ wrtm >o WO g o > o > - o g o g o > o S o > Q o go
(tiara C-w -*J gu 5 i ) ^ i j S i > g j j Q a j S 4 j g Q 4 j S +j
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:WO 2007/097798 ' , 4^€^¥mm6tmmin
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-^VO lOVfmTTW •PCT/US3006/0rl6619'
Method 1. Synthesis of dithiol oligomer by radical initiated
polymerization.
[00213] Table 2, Entry 8: In a three-necked glass flask
equipped with thermometer, using a magnetic stirrer, were
mixed 48.0 grams (0.4 mole) of VNB and 28.4 grams (0.2 mole)
of (BDDVE). The flask was emersed in an oil bath having a
temperature between 40-'42°C. With slight heating, 0.4O0 grams
(0.5%) Vazo 52 radical initiator (2,2'-azobis(2,4-
dimethylpentanenitrile, obtained from DuPont) was dissolved in
107.8 grams (0.7 mole) of DMDS. This solution was charged in
a dropping funnel and the solution was added drop-wise to the
mixture of two dienes. The reaction was exothermic and the
temperature of the mixture did not exceed 60*'C. After the
addition was completed (total addition time was 4 hours), the
temperature of the oil bath was increased to a temperature of
60°C and the mixture was- stirred at this temperature for 16
hours. The temperature was then increased to 75°C and the
mixture was stirred for another 4 hours. The SH analysis was
conducted and showed SHEW (SH (mercaptan) equivalent weight)
of 894. The mixture was stirred at a temperature of 6Q°C for
another 24 hours. The SH analysis was conducted and showed
SHEW of 896. The M„ for the oligomeric mixture was calculated
based on SHEW as 1792. The measured refractive index nn (at
20'C) was 1.606 and the viscosity of the mixture at 73°C was
993 cP.
[00214] The mixture slowly crystallized upon cooling to room
temperature but melted again upon heating with essentially no
change in the SH content or the viscosity.
£00215] The polythiol oligomers in Entries 2, 6, 7 and 13
were also prepared according to Method 1 as described above,
with the exception that the starting compounds and
corresponding molar ratios as shown in Table 2 were used.
«WQ 3007/097798 PCT/US2006/046649
Method 2. Stepwise synthesis of block-type dithiol oligomer,
using base catalysis eind then radical initiation.
[00216] (Table 2, Entry 4): In a glass jar, equipped with
magnetic stirrer, 63 grams (0.5 mole) of AM were mixed with
192.5 grams (1.25 mole) DMDS. To this mixture, upon stirring
at room temperature, 3 drops of 1, 8-diazabicyclo [5 .4 .0]\andec-
7-ene (DBU, obtained from Aldrich) were added. The
temperature of the mixture increased slightly due to the
exothermic reaction. The mixture was stirred at room
temperature for 2 hours, and then 60 grams (0.5 mole) of VNB
were added drop-wise with a rate such that the temperature of
the reaction did not exceed 70'C. After the addition was
completed (over a time period of 2 hours), 0.180 grams (0.5%)
radical initiator Vazo 64 (2,2'-azobisisobutyronitrile,
obtained from DuPont) was added and the mixture was heated at
70°C for 15 hours. The SH group analysis was conducted and
showed SHEW of 636 and viscosity at TS^C of 291 cP. The mixture
was heated for another 15 hours at 65°C and the SH analysis
then showed SHEW of 646 and.viscosity of 329 cP at IS^C, The M„
for the oligomeric mixture based on SHEW was calculated as
1292. The measured refractive index no (at 20'C) was 1.593 and
the Abbe number was 41.
[00217] The mixture was a clear liquid and did not
crystallize upon cooling.
[00218] The polythiol oligomers in Entries 1, 3, 5 and 14
were also prepared according to Method 2 as described cibove,
with the exception that the starting compounds and
corresponding molar ratios as shown in Table 2 were used.
Method 3. Stepwise synthesis of block-type dithiol oligomers
by radical initiation.
[00219] (Table 2, Entry 9): In a three-necked glass flask
supplied with thermometer, dropping funnel and magnetic
stirrer, were placed 215.6 grams (1.4 mole)of DMDS. The flask
was emersed in an oil bath having a temperature between 40-
42°C, and then 96.0 grams (0.8 mole) of VNB were added dropw
o 3007/097798 PCT/US3006/01(i6iW
wise with a rate such that the temperature of the reaction did
not exceed 70°C. After the addition was completed (total
addition time was 4 hours) , the mixture was stirred until the 1
temperature reached 60°C. The SH group analysis was conducted
and showed SHEW of 250. Then 0.100 grams (0.03%) of Vazo 52
radical initiator was added and the mixture was stirred for 4
hours at a temperature of 60°C. To this'mixture was added dropwise
at the same temperature, 63.2 grams (0.4 mole) of DEGDVE.
After the addition was completed (total addition time was 1
hour). The mixture was stirred at this temperature for 1
hour. Then 0.100 grams (0.03%) of Vazo 52 radical initiator
was added and the mixture was stirred for 15 hours at a
temperature of 60°C. The SH analysis was conducted and showed
SHEW of 943 and viscosity at 73°C of 861 cP. The Mn for the
oligomeric mixture based on SHEW was measured as 1887. The
measured refractive index n,, (at 20°C) was 1.595 and the Abbe
number was 42.
[00220] The mixture was a clear liquid but it slowly
crystallized upon cooling to room temperature.
[00221} The polythiol oligomers in Eiitries 10, 11, 12, 15
and 16 were also prepared according to Method 3 as described
above, with the exception that the starting compounds and
corresponding molar ratios as shown in Table 2 were used.
EXAMPLE 37 - Synthesis of PTE Dithiol 8 (DMDS/VNB 2:1 mole
ratio)
[00222] 308 grams of DMDS (2 moles) were charged to a glass
jar and the contents were heated to a temperature of 60"C. To
the jar was slowly added 120 grams of VNB (1 mole) with
mixing. The addition rate was adjusted such that the
temperature of the mixture did not exceed 70"C. Once the
addition of VNB was completed, stirring of the mixture was
continued at 60°C, and five 0.04 gram portions of VAZO 52 were
added (one portion added once, every hour) . The mixtxire was
then stirred at a temperature of 60«>C for an additional 3
wo 2007/097798 rCT/UG2006/046649
hours, after which time the product was,titrated and found to
have an SH equivalent weight of 214g/equivalent. The
viscosity was 56 cps at 73"C, the refractive index .no*** was
1.605, and the Abbe number was 41.
EXAMPLE 38 - Synthesis of PTE Dithiol 9 (DMDS/DIPEB 2;1 mole
ratio)
[00223] 524.6g of DMDS (3.4 moles) was charged to a glass
jar, and the contents were heated to a temperature of 60°C.
To the jar was slowly added 269 g of DIPEB (1.7 moles) with
mixing. Once the addition of DIPEB was completed, the jar was
placed in an oven heated to ecc for 2 hours. The jar was
then removed from the oven; 0.1 g VAZO 52 was dissolved into
the contents of the jar; and the jar was retuamed to the oven
for a period of 20 hours. The. resulting sample was titrated
for SH equivalents and was found to have an equivalent weight
of 145 g/equivalent. 0.1 g VAZO 52 was dissolved into the
reaction mixture, which was then returned to the oven. Over a
time period of 8 hours, the reaction mixture was kept in the
60 °C oven, and two more additions of 0.2 g VAZO 52 were made.
After 17 hours, the final addition of VAZO 52 (0.2 g) was
made, and the resulting sample was titrated, giving an
equivalent weight of 238 g/equivalent. The viscosity of the
material at 25"C was 490 cps.
EXAMPLE 39 - Synthesis of PTE Dithiol 10 (2;1 DMDS/DIPEB)/VNB
(2:1 mole ratio)
[00224] (Table 2, Entry 16) : At ambient temperature, 285.6
g of PTE Dithiol 9 (0.6 moles)" and 36.1 g VNB (0.3 moles) were
charged to a glass jar and mixed. 0.1 g VAZO 52 was dissolved
into the mixture, and the jar was subsequently placed in an
oven heated to 72°C. .After 16.5 hours the mixture was removed
from the oven and, the resulting sample was titrated for SH
equivalents and had an ec[uivalent weight of 454 g/equivalent.
An additional 0.1 g VAZO 52 was then added to the mixture, and
the mixture was returned to the oven for 24 hours. After this
. - w o 2007/01)7798 PCT/US200C/01C61t>
time the mixture was removed from the oven and the equivalent
weight of the resulting material was titrated and showed 543
g/equivalent. The viscosity at 73°C was 459 cps, the
refractive index ii6'° was 1.614, and the Abbe number was 36.
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[00225] The above Table 3 refers to the following ball sizes
used and the corresponding impact energy.
Ball weight, kg Impact Energy, J
0.016 0.20
0.022 0.27
0.032 0.40
0.045 0.56
0.054 0,68
0.067 0.83
0.080 1.00
0.094 1.17
0.110 1.37
0.129 1.60
0.149 1.85
0.171 . 2.13
0.198 2.47
0.223 2.77
0.255 3.17
0.286 3.56
0.321 3.99
0.358 4.46
0.398 4.95
1.066 13.30
[00226] The isocyanate and the dithiol components shown in
Table 3 in the molar ratios shovm in Table 3 were mixed at
room temperature under a nitrogen atmosphere. The catalyst
identified in Table 3 was then added and the mixture was
stirred at the temperature and for the period of time
specified in Table 3. The SH group smalysis was performed for
monitoring the progress of the reaction. The reaction was
considered completed when the SH groups analysis showed
substeuitially no SH group present in the reaction mixture.
The properties of the prepolymer including NCO content (%) ,
viscosity at 73'C (cP) and refractive index (d-line> were
measured and are shown in Table 3.
-wo 2007/097798- PCT/US2006/016619
[00227] Wherein the -prepolymer was chain extended with
diamine and polythiol, the prepolymer was degassed under
vacuum at a temperature of 60°C for two hours and diamine and
polythiol were mixed and degassed under vacuum at room
temperature for 2 hours. The weight ratio of
diamine/polythiol was as shown in Table 3 for each experiment.
The molar ratio (NHj+SlD/NCO was in all cases 0.95. The two
mixtures were then mixed together at a temperature of 60'C and
charged between a preheated glass plates mold. The material
was cured in a preheated oven at a temperature of 130°C for 16
hours. The cured material had-the appearance, refractive
index, density and impact resistence as shown in Table 3.
Example 41 - Synthesis of HITT (Formula
[00228] HITT material identified in Table 3 was prepared
according to the following procedure. 1,2,4-
trivinylcyclohexane (43.64 g, 0.269 moDand DMDS (124.4 g,
0.808 mol) were mixed at room temperature. The mixture was
heated to a temperature of eo^C and maintained at this
temperature for 1 hour. 50 mg Vazo 64 radical initiator
obtained from DuPont was then added and the mixture was
stirred for 16 hours at sCC. The addition of 50 mg Vazo 64
radical initiator and subsequent heating for 16 hours at 60°C
was conducted two additional times. SH'titration analysis of
the mixture was conducted and showed SHEW=222. This analysis
showed essentially the same value after one more cycle of
catalyst addition and heating at 60 °C for 16 hours. The
product was clear liquid having viscosity of 85 cP (73°C) ,
refractive index n^ of 1.606, Abbe of 39, refractive index ne
of of 1.610, and Abbe of 39. MS(Electrospray) showed signal at
m/e 647 (M* + Na).
[00229] The invention has been described with reference to
non-limiting embodiments. Obvious modifications and
alterations can occur to others upon reading and understanding
the detailed description. It is intended that the invention
be construed as including all such modifications and
wo ioo7/09Twe - vctmsimmmm
alterations insofar as they come within the scope of the
appended claims or the equivalents thereof.
93
^ We Claim:
1. A sulfur-containing polyureaurethane prepared by the reaction of:
(a) a sulfur-containing polyurethane prepolymer; and
(b) an amine-containing curing agent,
the sulfur-containing polyureaurethane having a refractive index of at least 1.57, an
Abbe number of at least 32 and a density of less than 1.3 grams/cm^, when at least
partially cured, wherein the sulfur-containing polyurethane prepolymer comprises the
reaction product of:
(a) a polyisocyanate, polyisothiocyanate, or mixture thereof; and
(b) an active hydrogen-containing material selected from polythiol and mixture of
polyol and polythiol,
wherein said polythiol comprises an oligomer which is the reaction product of at least
two different dienes and at least one dithiol and wherein the stoichiometric ratio of the
sum of the number of equivalents of dithiol to the sum of the number of equivalents of
diene is greater than 1.0 :1.0.
2. The sulfur-containing polyureaurethane as claimed in claim 1, wherein said
prepolymer has a polyisocyanate plus polyisothiocyanate to hydroxyl equivalent ratio
of from 2.0 :1.0 to less than 5.5 :1.0.
3. The sulfur-containing polyureaurethane as claimed in claim 1 wherein said polyol
comprises a polyether polyol.
4. The sulfur-containing polyureaurethane as claimed in claim 1 wherein said sulfurcontaining
polyurethane prepolymer and said amine-containing curing agent are
present such that the equivalent ratio of (NH + SH + OH) to (NCO + NCS) is from 0.80:
1.0 to 1.1:1.0.
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5. The sulfur-containing polyureaurethane as claimed in claim 1 wherein said
polyisocyanate is selected from 4,4'-methylenebis (cyclohexyl isocyanate) and isomeric
mixtures thereof.
6. The sulfur-containing polyureaurethane as claimed in claim 1 wherein said polythiol
comprises an oligomer which is the reaction product of at least two different dienes
and at least one dithiol and at least one trifunctional or higher-functional polythiol;
and wherein the stoichiometric ratio of the sum of the number of equivalents of
polythiol to the sum of the number of equivalents of diene is greater than 1.0 :1.0.
7. The sulfur-containing poljoireaurethane as claimed in claim 1 wherein said aminecontaining
curing agent comprises a polyamine having at least two functional groups
independently chosen from primary amine (-NH2), secondary amine (-NH-), or
combinations thereof.
8. The sulfur-containing polyureaurethane as claimed in claim 1 wherein said polyamine
is represented by the following structural formula and mixtures thereof:
wherein Ri and R2 are each independently methyl, ethyl, propyl, or isopropyl groups,
and each R3 independently is hydrogen or chloride.
9. The sulfur-containing polyureaurethane as claimed in claim 1 wherein said aminecontaining
curing agent comprises 4.4'- methylenebis(3-chloro-2,6-diethylaniline), 2,4-
diamino-3,5-diethyl-toluene; and/or 2,6-diamino-3,5-diethyl-toluene.
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10. A method of preparing a sulfur-containing polyureaurethane comprising:
(a) reacting polyisocyanate with sulfur-containing active hydrogen-containing material,
said sulfur-containing active hydrogen-containing material selected from polythiol
and mixture of polyol and polythiol, wherein said polythiol comprises an oligomer
which is the reaction product of at least two different dienes and at least one dithiol
and wherein the stoichiometric ratio of the sum of the number of equivalents of dithiol
to the sum of the number of equivalents of diene is greater than 1.0 : 1.0 to form
polyurethane prepolymer; and
(b) reacting said polyurethane prepolymer with amine-containing curing agent,
wherein the polyueaurethane has a refractive index of at least 1.57, an Abbe number of
at least 32 and a density of less than 1.3 grams/cm^.
11. An optical article comprising the sulfur-containing polyureaurethane as claimed in
claim 1
12. The optical article as claimed in claim 11 being an ophthalmic lens.
13. The optical article as claimed in claim 11 comprising at least a photochromic amount of
photochromic substance.
Dated this the 27'h day of May 2008. , .
(MOUTUSHIBHOWMIK)
of SUBRAMANI/ad & ASSOCIATES
Attorney for the Applicants |