Title of Invention

"COPOLYMERS PRODUCED FROM REACTING A GLYCIDYL ESTER AND /OR ETHER WITH A POLYOL AND THE USE OF THE COPOLYMERS IN COATING COMPOSITIONS"

Abstract The present invention provides a copolymer and having a molecular weight distribution greater than 1.10 and its process of preparation. The copolymer comprising a reaction product of a glycidyl ester or ether or combination thereof with a polyol comprising a functionality of atleast 2 wherein the molar ratio of glycidyl ester or ether or combination thereof to polyol is atleast 3:1 and wherein atleast 50% by weight of the copolymer comprises a minimum of 3n+X repeating units, wherein n is a monomer unit derived from the glycidyl ester or ether or combination thereof and X is a monomer derived from the polyol.
Full Text COPOLYMERS PRODUCED FROSVI REACTiWG A GLYCIDYL
ESTER ANDTOR ETHER WITH A POLYOL AND THE USE OF THE
COPOLYMERS IN COATING COMPOSITIONS
TECHNICAL FIELD
[0001] The present invention relates to copolymers produced from reacting a
gfycidyl ester and/or ether with a polyoi, to a method for making such copolymers and to the use of the copolymers in coating compositions
BACKGROUND OF THE INVENTION
[0002] In the field of coatings, there has been an increased Interest in
providing high solids coating compositions having low VOC's to comply with environmental controls. In an effort to develop such coatings, reactive diluents having lower molecular weights and Sow viscosity have been used to repiace some of the high molecular weight, high viscosity polymers typically used in coatings. For instance, glycidyl esters have been reacted with polyols to form adducts having a very narrow molecular weight distribution, i.e., SUMMARY OF THE INVENTION
[0003] The present invention is directed to a copolymer produced from
reacting a glycidyl ester and/or ether with a polyoi comprising a functionality of at least 2 wherein at least 50% by weight of the copolymer comprises a minimum of 3n+X repeating units, wherein n is a monomer unit and X is a monomer unit and/or other reactanl
[0004j The present invention is also directed to process for preparing a
copolymer comprising reacting in a molar ratio of at least 3:1, a glycidyl ester and/or ether with a polyoi having a functionality of at least 2 to form a copolymer wherein at
least 50% by weight of the copoiymer comprises a minimum of 3n+X repeating units,
wherein n is a monomer unit and X is a monomer unit and/or other reactant
[0005] Also contemplated by the present invention is a coating
corriposiliorj eiVtpioyiity ihw inveniive copolymer, Sucft a coating composition comprises the inventive'copolymer containing functional groups and a curing agent having functional groups reactive with the functional groups of the copolymer,
DETAILED DESCRIPTION
[0006] The present invention is directed to a copoiymer for use in coating
compositions. The copolymer of the present invention is the reaction product of a giycidyi ester and/or ether with a polyoi.
•[0007] in one embodiment, a giycidyi ester, such as the giycidyi ester of a C5
- C12 aliphatic acid, is used, in another embodiment a giycidyi ether, such as the
giycidyi ether of a C5 - CI 2 aliphatic alcohol, is used, illustrative of a giycidyi ester is
a monglycidyi ester of.a branched cariboxylic acid such aspivalic acid and versatic
add. One such material is commercially available as CARDURA E10.
[0008] The poiyol reacted with the giycidyi ester and/or ether is one that has
a functionality ranging from 2 to 18. in one embodiment, the polyoi functionality is from 2 to 5. Polyois of varying molecular weights may be used. In another embodiment, the polyoi has a number average molecular weight (Win) of less than 300. Some examples of such polyois include neopentyl glycol, 2-ethyl-1, 3 hexane diol, cyciohexane dimethanoi, trimethyoipropane, tris(hydroxyethyl)isocyanurate, and pentaerythritoi.
[0009J In certain embodiments, the molar ratio of giycidyi ester and/or
ethenpolyol is at least 3:1. For instance, ratios of 3:1, 4:1, and 5:1 are typical as well as any variation thereof, i.e., 2.8:0.18.
[00010] The reaction can be carried out in the presence of a catalyst. One
such catalyst is stannous octoate. If the catalyst is used, it is present in an amount sufficient to accelerate the reaction of the giycidyi ester with the polyoi. The catalyst is typically used in an amount ranging from 0.01% to 1.0% based on the total weight of the reactants.
[00011] The copolymers produced by way of the reaction recited above have a
molecular weight distribution, defined as the ratio of the weight average molecular weight, Mw, to the number average molecular weight, Mn. that is greater than 1.10. The molecular weight distribution is dependent on the properties and functionality of
the polyol used in the reaction. The following Table 1 illustrates the relationship between the molar ratios of poiyo! to glycidyl ester and the resultant molecular weight distribution (IViw/Mn) of the copolymer.
TABLE 1

(Table Removed)
[00012] Table 1 above details a particular trend of the foregoing reaction that
the greater the functionality of the polyol and/or the greater the molar ratio of gycidyl ester to polyol, the higher the molecular weight distribution. The polyols shown in Table 1 are specific polyols that may be used in the practice of the invention and are cited for illustrative purposes only. Other poiyols are satisfying the features set forth above are also contemplated.
[00013] in one embodiment of the present invention, the copolymer has a Mn
of at feast 500g/rnoi. in other embodiments, the copolymer may also have a hydroxy!


value of 50 to 300 such thai it can cross-fink with a curing agent when used in a coating formulation, in soma embodiments, a molar ratio of gycidyl ester and/or ethenpolyol is greater than or equal to 3:1 and the poiyoi has a functionality of at least 2. In this embouim«itt, ih« resuiiani copolymer comprises 50% by weight of the copolymer having a minimum of 3n+X repeating units, wherein n is a monomer unit and X is a monomer unit, the same or different from n, and/or other reactant. "Other reactant" Includes such things as adducts and/or tow molecular weight residues formed during the reaction. Determining if the copolymer has a minimum of3n+X repeating units can be accomplished by analyzing its GPC data, for example, consistent with Example 1 below, a copolymer can be formed from the reaction of 3 moles of CARDURA E with 1 mole of neopentyt glycol. In order to achieve greater . than 50% of the copolymer having a minimum of"3n+X repeating units, at least 50% of the reaction product must have a molecular weight greater than 824g/mole which correlates to 3 moles of CARDUA E at a Mw of 240g/m to 1 mole of neopentyi glycol. at a Mw of 104g/m. As shown by GPC data, 9 peaks are present where at least 4 of the peaks have a peak molecular weight greater than 824g/moie. These peaks comprise 60.93% of the total makeup of the copolymer. As such, it is shown that Example 1 satisfies having greater than 50% of the copolymer having a minimum of 3n+X repeating units as described above.
[Q0014J In yet another embodiment, the copolymer has less than 50%
polymeric units having the same molecular weight. That is, there is no single peak in
the GPC result that has an area percentage greater than 50% of the total peaks.
Again, this can also be determined by analysing the GPC data of the copolymer.
Looking to the GPC results of Example 1, for illustrative purposes, of the 9 peaks, the
greatest area percentage peak is at a molecular weight of -804 g/mois. This peak has
an area percentage of 27,73%, which is substantially less than 50%.
[00015| The present invention is also directed to coating compositions
including the inventive copolymer described herein, A coating composition according to the present invention includes the copolymer and a curing agent having functional groups reactive with the copoSymer. in some embodiments, curing agents may be selected from any of s variety of art- recognized curing agents,, provide the curing agent comprises functional groups which are reactive with the functional groups of the copolymer, For example, suitable curing agents can include, but are not iimited to aminopiasfs, poiyisocyanates, including blocked [socyanatss, polyepoddes, beta-frydroxyaikyiarnides. palyacids, anhydrides, organometallic acid-functronaj materials,
polyamines, polyamides, poiyois, polyurea, urea, dicyandiamide, and mixtures of any of the foregoing, it should be understood that the blocked isocyanates can be blocked using any of the blocking agents known in the art for this purpose. For example, the blocking agents can include, out are not limited to suitable monoalcohois, phenolic compounds, glycol ethers, oximes, lactams, heterocyclic amines, imidazoles, and/or amnes. Note that the terms "curing agent" and "crosslinking agent" may be used interchangeably.
[00016] The coating compositions described herein may include an additional
component, such as a form filming resin, having reactive functional groups, which can react with the curing agent. The additional component may be selected from any of a variety of polymers well-known in the art. The additional components may be' selected from, for example, acrylic polymers, polyester polymers, poiyurethane polymers, poiyamide polymers, polyether polymers, poiysiloxane polymers, copolymers thereof, and mixtures thereof. Generally these polymers can be any polymers of these types made by any method known to those skilled in the art. Such polymers may be solvent borne or water dispersibie, emulsifiable, or of limited water solubility. The functional groups on the film-forming resin may be selected from any of a variety of reactive functional groups including, for example!, carboxylic acid groups, amine groups, epoxide groups, hydroxy! groups, thiol groups, carbamate groups, amide groups, urea groups, isocyanate groups (including blocked isocyanate groups) mercaptan groups, and combinations thereof. Appropriate mixtures of additional components is also contemplated for use with the copolymer described herein.
£00017] The coating composition according to the present invention can further
include conventional additives such as pigments, fillers and other coating additives such' as flow agents, uv absorbers and the like.
[00018] In some embodiments, the coatings can include colored pigments and
the like for use as a color coat. In other embodiments, the coatings may be used as a clear coat
[00019] In one embodiment, the coating composition comprises two
components. • Component one includes the copolymer of the present invention and may include any additional component having reactive groups as described above. The second component may include the curing agent. The curing agent in a two component system need not be blocked. The two components are mixed just prior to application of the coating. A catalyst can be added to either the first or second
component. The catalyst enhances the reaction of the first component with the curing agent upon mixing of the components. Such catalysts are well known to those in the art.
[Ouuio] in anotner emDOdiment, the coating comprises one component. In the
one component system, the copolymer and curing agent are mixed as a single component Additional hydroxyl containing polymers may be added and are described above, in the one component system, the curing agent should be one that is not reactive with the copolymer or additional hydroxy! containing polymer at room temperature but is reactive at elevated temperatures. Examples of such curing agents are blocked poiyisocyanates and aminoplasts. A catalyst may also be used in the one component system,
[ooozij The compositions can be applied by conventional means including
brushing, dipping, flow coating, spraying and the like, but they are most often applied by spraying, Further, after application of the compositions to the substrate, the coating is allowed to cure. Curing can be accomplished at room temperature or at elevated temperature. In some embodiments, the compositions are given a solvent flash. Curing techniques will be apparent to one of skill in the art in view of this disclosure.
[00022] Coating compositions according to the present Invention including the
inventive copolymer can be formulated to have low VOC's such as less than or equal to 3.5lb/gal. In addition, the compositions can be formulated to a viscosity suitable for spray applications, in certain embodiments, suitable spray viscosity is typically iess than or equal to 60 cps.
[00023} As used herein, unless otherwise expressly specified, all numbers
such as those expressing values, ranges, amounts or percentages may be read as if prefaced by the word "about", even if the term does not expressly appear. Any numerical range cited herein is intended to include all sub-ranges subsumed therein. Plural encompasses singular and vice versa. For example, the reactants m the present invention are described as "a" glycidyi ester and/or ether and "a" polyol, however, mixtures of giycidyS ester with glycidyi ether as well as mixtures of polyols is also contemplated. Furthermore, as used herein, the term "polymer*1 is meant to refer to prepolyrners, oligomers and both hornopolymers and copolymers; the prefix "poly" refers to two or more.
EXAMPLES
[000241 The following examples are intended to illustrate the invention, and
should not be construed as limiting the invention in any way.
juuuisaj examples 1-16 tnat follow iliustrate various glycidyl-polyol reaction
products, in the following Examples, the GPC data was obtained by analyzing the sample in a Water's Alliance 2695 GPC with a refractive index detector. The column was a PL Gel mixed E column commercially available from Waters Coporation having a principal place of business In Milford, MA 01757. The GPC was used to determined the weight average molecular weight, Mw and the number average molecular weight Mn. The polydispersity was calculated by dividing the Mw by the Mn. The actual data derived from the GPC is supplied for Example 1. The properties for the remaining Examples was calculated in the same manner, however, the GPC data has been omitted.
Example 1
[00026] A reaction vessel equipped with stirrer, thermocouple, condenser and
nitrogen inlet was charged with 104.1 g (1.0 mole) neopentyl glycol, 720.2 g (3.0 moles) CARDURA E10P (from Hexion Specialty Chemicals) and 0.828 g stannous octoate and heated to 130oC. The reaction exotnermed to 141oC. The reaction temperature was raised to 150oC and the contents were stirred until the epoxy equivalent weight was greater than 13,000.
[0002?] The resultant product had an epoxy equivalent of 58,000, a timed
bubble tube viscosity of 61.8 sec, an APHA color of 50 - 60, a hydroxyl value of 192.6 mg KOH/g The following are the results of the GPC data for this copolymer:

(Table Removed)
[00028J The copolymer had a weight average molecular weight (Mw) of 1174,
a number average molecular weight (Mn) of 882 and polydispersity of 1.3 m THF.
Example 2
[00029J A reaction vessel equipped with stirrer,, thermocouple, condenser and
nitrogen inlet was charged with 52.0 g (0.5 mole) neopentyl glycol, 479.4 g (2 moles)
CARDURA E10P and 0.531 g stannous octoafe and heated to 130oC. The reaction
exothermed to 144oC. The reaction temperature was raised to 150oC and the
contents were stirred until the epoxy equivalent weight was greater than 13,000.
[00030] The resultant product had an epoxy equivalent of 223,600, a timed
bubble tube viscosity of 89.6 see, an APHA color of 50 - 60. a hydroxy! value of 155.9 mg KOH/g; had a peak moiecufar weight of 1147, a weight average molecular weight of 1372, a number average molecular weight of 1038 and polydispersity of 1.3 in THF.
Examjafe_3
[00031] A reaction vessel equipped with stirrer, thermocouple, condenser and
nitrogen inlet was charged with 131.8 g (0.9 mole) 2-ethy!-1,3-hexanediol, 647.6 g (2.7 moles) CARDURA E10P and 0.792 g stannous octoate and heated to 130oG. The reaction exothermed to 139oC. The reaction temperature was raised to 150oC and the.contents were stirred until the epoxy equivalent weight was greater than 13,000.
£00032] The resultant product had an epoxy equivalent of 25,873, a timed
bubble tube viscosity of 38.8 sec, an APHA color of 50 - 60, a hydroxyl value of 152.4 mg KOH/g; ; had a peak molecular weight of 835, a weight average molecular weight of 1132, a number average molecular weight of 817 and polydispersity of 1.4 in THF.
Example. 4
[00033J A reaction vessel equipped with stirrer, thermocouple, condenser and
nitrogen inlet was charged with 117.3 g (0.8 mole) 2-ethyl-1,3-hexanediof, 767.4 g (3.2 moles) CARDURA E10P and 0.889 g stannous octoate and heated to 130oC. The reaction exothermed to 145oC. The reaction temperature was raised to 150OC and the contents were stirred until the epoxy equivalent weight was greater than 13,000.
[00034] The resultant product had an epoxy equivalent of 15,948, a timed
bubble tube viscosity of 65.8 sec, an APHA color of 50 - 60, a hydroxy) value of 143.9 mg KOH/g.
Example 5
[00035] A reaction vessel equipped with stirrer, thermocouple, condenser and
nitrogen iniet was charged with 115.3 g (0.8 mole) 1,4-cyclohexane dimethanol,
576.1 g (2.4 moies) CARDURA E10P and 0.691 g stannous octoate and heated to
130oC. The reaction exothermed to 143oC. The reaction temperature was raised to
150oC and the contents were stirred until the epoxy equivalent weight was greater
than 13,000.
[00036] The resultant product had an epoxy equivalent of 35,854, a timed
bubble tube viscosity of 3 min 18.8 sec, an APHA color of 100 - 150, a hydroxy? value of 174.4 mg KOH/g; had a peak molecular weight of 1320, a weight average molecular weight of 1277, a number average moiecular weight of 788 and polydispersity of 1.6 in THF.
Example 8
[00037] A reaction vessel equipped with stirrer, thermocouple, condenser and
nitrogen inlet was charged with 93.8 g (0.65 mote) 1,4-cyclohexane dimethanol,
624.2 g (2.6 moies) CARDURA E10P and 0.721 g stannous octoate and heated to
130oC. The reaction exothermed to 146oC. The reaction temperature was raised to
150oC and the contents were stirred until the epoxy equivalent weight was greater
than 13,000.
[00038] The resultant product had an epoxy equivalent of 18,055, a timed
bubble tube viscosity of 3 min 2.6 sec, an APHA color of 70 - 80, a hydroxy! vaiue of 158.5 mg KOH/g.
Example 7
[000391 A reaction vessel equipped with stirrer, thermocouple, condenser and
nitrogen inlet was charged with 115.2 g (0.8 mole) Unoxof 3,4-diol (a mixture of 1,3-dimethylolcyclohexane and 1,4-dimethylolcyclohexane from Dow Chemical), 576.0 g (2.4 moles) CARDURA E10P and 0.69 g stannous octoate and heated to 130oC. The reaction exothermed to 136oC. The reaction temperature was raised to 150oC
and the contents were stirred until the epoxy equivalent weight was greater than
13,000.
[00040J The resultant product had an epoxy equivalent of 17,161, a timed
bouuls lu'ue vioCGsR>' ui'4 utin 17.6 sec, an APHA color or 60 - 60, a hydroxyl value of
131.2 mg KOH/g.
Example 8
[00041] A reaction vessel equipped with stirrer, thermocouple,, condenser and
nitrogen inlet was charged with 93.4 g (0.65 mole) Unoxoi 3,4-dioi (from Dow
Chemical), 823.8 g (2.6 moles) CARDURA E10P and 0.71 S g stannous octoate and
heated to 130oC. The reaction exoihermed to 141oC. The reaction temperature was
raised to 150oC and the contents were stirred until the epoxy equivalent weight was
greater than 13,000. An additional 0.32 was added to accelerate the reaction.
[00042J The resultant product had an epoxy equivalent of 44,406, a limed
bubble tube viscosity of 2 min 27.5 sec, an APHA color of 200 - 250, a hydroxy! value of 177.3 rng KOH/g.
Example 9
[00043] A reaction vessel equipped with stirrer, thermocouple, condenser and
nitrogen inlet was charged with 114.1 g (0.85 mole) trimethylolpropane, 612.0 g (2.56
moles) CARDURA El OP and 0.0.731 g stannous octoate and heated to 130oC. The
reaction exothermed-to 138oC. The reaction temperature was raised to 150oC and
the contents were stirred until the epoxy equivalent weight was greater than 13,000.
100044] The resultant product had an epoxy equivalent of 18,202, a timed
bubble tube viscosity of 2 min 45.4 sec, an APHA color of 40 - 50, a hydroxy! value of 231.8 mg KOH/g; had a peak molecular weight of 878„ a weight average molecular • weight of 1146, a number average molecular weight of 938 and polydispersity of 1.2 in THF.
Example 10
[00045] A reaction vessel equipped with stirrer, thermocouple, condenser and
nitrogen Inlet was charged with 93.9 g (0.7 mole) trimethylolpropane, 672,2 g (2.8 moies) CARDURA E10P and 0.778 g stannous octoate and heated to 130oC. The reaction exothermed to 141oC. The reaction temperature was raised to 150oC and
the contents were stirred until the epoxy equivalent weight was greater than 13,000.
An additional 0,32 g of stannous octoate was added to accelerate the reaction.
[00046J The resultant product had an epoxy equivalent of 24,023, a timed
bubbie tuoe viscosity or a mm lU.'i sec, an APHA color of 40 •■• 50, a hydroxy! value of 203.4 mg KOH/g.
ExaniBljsJLi
[00047] A reaction vessel equipped with stirrer, thermocouple, condenser and
nitrogen inlet was charged with 195.7'g (0.75 mole) trishydroxyethyl isocyanurate,
540.1 g (2.2S moles) CARDURA E10P and 0.745 g stannous octoate and heated to
130oC. The reaction exothermed to 138oC. The reaction temperature was raised to
165GC and the contents were stirred until the epoxy equivalent weight was greater
than 13,000.
[00048] The resultant product had an epoxy equivalent of 81,182, a timed
bubbie tube viscosity of 17 min 14.1 sec, an APHA color of > 500, a hydroxy! value of 202.7 mg KOH/g.
Example 12 |00049] ' A reaction vessel equipped with stirrer, thermocouple, condenserand nitrogen inlet was charged with 117.5 g (0.6 mole) trishydroxyethyl isocyanurate,
648.2 g (2.4 moles) CARDURA E10P and 0.778 g stannous octoate and heated to
130oC. The reaction exothermed to 138oC. The reaction temperature was raised to
185oC and the contents were stirred until the epoxy equivalent weight was greater
than 13,000.
100050] The resultant product had an epoxy equivalent of 19,203, a timed
bubble tube viscosity of 12 min 34.6 sec, an APHA color of > 500, a hydroxyi value of
178.3 mg KOH/g; had a peak molecular weight of 1370, a weight average molecular
weight of 1436, a number average molecular weight of 1023 and polydispersity of 1.4
in THF.
Example 13
I00051J A reaction vessel equipped with stirrer, thermocouple, condenser and
nitrogen inlet was charged with 115.8 g (0.75 mole) pentaerythritol, 861.3 g (2.55 moles) CARDURA E10P and 0.718 g stannous octoate and heated to 130oC. The reaction exothermed to 138oC. The reaction temperature was gradually raised to
180oC to get the pentSerythritol to dissolve and the contents were stirred until the epoxy equivalent weight was greater than 13,000.
|00052j The resultant product had an epoxy equivalent of 84,833, a timed
buboie tuoe viscosity OT 7 min 14.3 sec, an APHA coior of 100 - 150, a hydroxyl value of 272.9 rng KOH/g.
Example 14
[00053] A reaction vessel equipped with stirrer, thermocouple, condenser and
nitrogen inlet was charged with 88.4 g (0.85 mole) pentaerythritol, 623.3 g (2.4 moles) CARDURA E10P and 0.718 g stannous octoate and heated to 130oC. The reaction exqthermed to 138oC. The reaction temperature was gradually raised to 180oC to get the peniaerythritoS to dissolve and the contents were stirred until the epoxy equivalent weight was greater than 13,000.
[00054] The resultant product had an epoxy equivalent of 88,000, a timed
bubble tube viscosity of 4 min 47.1 sec, an APHA coior of 50 ~ 60, a hydroxyl value of 219.0 mg KOH/g; had a peak molecular weight of 1477, a weight average molecular weight of 1373, a number average molecular weight of 1140 and polvdispersity of 1.2 InTHF.
Examj3tej[5
[000551 A reaction vessel equipped with stirrer, thermocouple, condenser and
nitrogen inlet was Gharged with 36.1 g (0.25 mole) 1,4-cycfohexane dimethanol, 33.5 g (0.25 mole) frimethyiolpropane, 360.2 g (1.50 moies) CARDURA E10P and 0.408 g stannous octoate and heated to 130oC. The reaction exothermed to 133oC. The reaction temperature was raised to 150oC and the contents were stirred until the epoxy equivalent weight was greater than 13,000.
[00056] The resultant product had an epoxy equivalent of 33,018, a timed
bubble tube viscosity of 3 min 45.4 sec, an APHA color of 30 - 40; had a peak molecular weight of 1222, a weight average molecular weight of 1273, a number average molecular weight of 721 and polvdispersity of 1.8 in THF.
Examp!@ 16
10005?) A reaction vessel equipped with stirrer, thermocouple, condenser and
nitrogen inlet was charged with 292.3 g (2.0 mole) 2-ethyl-1, 3-hexanediol, 268.2 g (2.0 mole) trimethylolpropane, 2881.0 g (12.0 moies) CARDURA. E10P and 3.179 g
stannous octoate and. heated to 130oC. The reaction exothermed to I4I0C. The reaction temperature was raised to 150oC and the contents were stirred until the epoxy equivalent weight was greater than 13,000,
[uooaaj The resultant product had an epoxy equivalent of 18,044, a timed
bubble tube viscosity of 88.0 sec, an APHA color of 20 --- 30 and density of 8.29 Sb/ga!; had a.peak molecular weight of 1199, a weight average molecular weight of 1166, a number average molecular weight of 828 and polydispersrty of 1.4 in THF.
Example 1.7
[00059] A reaction vessel equipped with stirrer, thermocouple, condenser and
nitrogen inlet was charged with 312.5 g (0.18 moles) Boitorn H20 dendritic polyol
(from Perstorp Pofyois, Inc.), 711.8 g (2.82 moles) Glydexx N-10 (from Exxon
Chemical) and 1.02 g stannous octoate and heated to 130oC. The reaction
exothermed to 139oC. The reaction temperature was raised to 150oC and the
contents were stirred until the epoxy equivalent weight was greater than 13,000.
COOO603 - The resultant product had a 110oC/1 h solids content of 98.2%, a
Brookfield viscosity of 25680 centipoise, a hydroxy! value of 298.1 mg KOH/g and a weight average molecular weight of 3045 and number average molecular weight of 1281 in THF.
Example 18
{00061J A reaction vessel equipped with stirrer, thermocouple, condenser and
nitrogen inlet was charged with 357.5 g (0.22 moles) Boitorn H20 dendritic polyof
(from Perstorp Poiyois, Inc.), 609.5 g (2.41 moles) Glydexx N-10 (from Exxon
Chemical) and 0.97 g stannous octoate and heated to 130oC, The reaction
exothermed to 139oC. The reaction temperature was raised to 150oC and the
contents were stirred until the epoxy equivalent weight was greater than 13,000.
[00062] The resultant product had a 110oC/1h solids content of 98.7%, a
Brookfield viscosity of 22570 centipoise, a hydroxy! value of 234.4 mg KOH/g and a weight average molecular weight of 2940 and number average molecular weight of 1277 In THF.
£00063] Examples 19-22 that follow illustrate the preparation of various
hydroxyl containing acrylic polymers.
Example 19
[00064] A reaction vessel equipped with stirrer, addition funnels with pumps,
thermocouple, cundensei and nitrogen iniet was charged with 490.0 g PIVI acetate
and heated to reflux { 144oC). Two feeds, identified herein as A and B, were added
gradually and simultaneously over a period of three hours while the contents of the
vessel were maintained at reflux conditions. Feed A consisted of a mixture of 43.3 g
PiVf acetate and 120.1 g of a 50% solution of t-butyl peroctoate in mineral spirits,
Feed B consisted of 250.1 g rnethyi methacrylate, 319.8 g styrene, 138.9 g butyl
methacrylate, 67.1 g butyi acrylate, 100.0 g hydroxyethyl methacrylate, 102.0 g
hydroxypropyi methacrylate, 17.0 g of the monomer from 1/1 mole ratio of acrylic
acid and CARDURA El OP and 7.0 g acrylic acid. After the addition of the two feeds
A and B were complete, the funnels were rinsed with 19.3 g PM acetate, the vessel
contents were allowed to reflux for an additional 15 minutes. Then an additional feed
consisting of 38.5 g PM acetate and t-butyl peroctoate were added over 30 minutes.
The funnel was rinsed with 28.9 g PM acetate and vessel contents were refluxed
another 30 minutes. Thereafter, heating was discontinued, 28,9 g PM acetate added
and the contents of the vessel allowed to cool it to ambient temperature.
100065] The resultant product had a total solids content measured for 1 hour at
1 IOOC of 58.82% by weight; a timed bubble tube viscosity of 24.2 seconds; an acid value of 4.25 mg KOH/g; residua! contents of methyl methacryiate, butyl methacrylate, hydroxyethyl methacryiate and hydroxypropyi methacrylate, respectively, of 0.15%, 0.12%, 0.12% and 0.28% by weight; had a peak molecular weight of 7452, a weight average molecular weight of 7S78 and a number average molecular weight of 2230 in THF.
Example 20
[00066] A reaction vessel equipped with stirrer, addition funnels with pumps,
thermocouple, condenser and nitrogen inlet was charged with 489.28 g CARDURA E10P and heated to 200oG. The feed consisted of 619.86 g styirene, 536.30g hydroxypropyi methacrylate, 484.2 g methyl methacryiate, 123.20 g acrylic acid, 11.46 g triphenyl phosphite and 40.00 g di-t-buty! peroxide was added gradually and simultaneously over a period of two hours while the contents of the vessel were maintained at 205oC. After addition was complete, the vessel contents were stirred
for 15 minutes, cooled to ambient temperature accompanied by the addition of 563.22 g n-propyl propionate.
[00067] The resultant product had a total solids content measured for 1 hour at
11CoC of 7G.CC% by vvtsiyiii, buubie iube viscosity of Z6+; an acia value of 1.13 mg KOH/g; a hydroxy!! value of 112.2 mg KOH/g; an APHA color of 80; residual contents of styrene, hydroxy propyl methacrylate, methyl methacrylate and CARDURA E10P, respectively, of 0.07%e 0.65%, 089% and 1.07% by weight; had a peak molecular weight of 1793, a weight average molecular weight of 256*4 and a number average molecular weight of 910 in THF.
Example 21
[00068] A reaction vessel equipped with stirrer, addition funnels with pumps,
thermocouple, condenser and nitrogen inlet was charged with 620.1 g CARDURA
El OP and heated to 200QC. TWO feeds, identified herein as A and B, were added
gradually and simultaneously over a period of two hours while the contents of the
vessel were maintained at 200 — 205oC. The feed A consisted of 838.9 g styrene,
853.7 g hydroxyethyi methacryiate, 853.7 g methyl methacrylate, 168.3 g acrylic acid
and 15.0 g triisodecyl phosphite. Feed B consisted of 52.1 g di-t-butyl peroxide.
After addition was complete, the vessel contents were stirred for 15 minutes, cooied
to ambient temperature accompanied by the addition of 760.1g n-propyl propionate.
[00089] The resultant product had a total solids content measured for 1 hour at
110oC of 74.94% by weight; a timed bubble tube viscosity of 3 minutes 22.8 seconds; an acid value of 0.21 mg KOH/g; a density of 8.81 ib/gai; an APHA color of 20-30.
Example 22
[000701 A reaction vessel equipped with stirrer, addition funnels with pumps,
thermocouple, condenser and nitrogen inlet was charged with 846.2 g PM acetate and heated to reflux ( 145oC). Two feeds, identified herein as A and B, were added gradually and simultaneously over a period of three hours 35 minutes and three hours, respectively, while the contents of the vessel were maintained at reflux conditions. Feed A consisted of a mixture of 85.0 g PM acetate and 336.3 g of a 50% solution of t-butyl peroctoate in mineral spirits. Feed B consisted of 545.9 g isobornyl methacrylate, 698.2 g styrene, 335.9 g butyl methacrylate, 148.0 g butyl acrylate, 441.1 g hydroxyethyi methacn/late and 15.3 g acrylic acid. After the
addition of the two feeds A and B were compiete, the funnels were rinsed with 42.0 g
and 63.1 g PM acetate, respectively, the vessel contents were, allowed to reflux for
an additional 30 minutes. Thereafter, heating was discontinued, 63.1 g PM acetate
added and the contents of the vessel allowed to cool to ambient temperature.
[00071] The resuitant product had a total solids content measured for 1 hour at
110oC of 65.40% by weight; a timed bubble tube viscosity of 40.25 seconds; an acid value of 5.83 mg KOH/g; an APHA color of 5 •- 10; a density of 8.61 lb/gal; had a peak molecular weight of 5801, a weight average molecular weight of 6424 and a number average molecular weight of 2156 in THF.
COATING COMPOSITION EXAMPLES
[00072] The following Examples 22-37 illustrate coating compositions
employing copolymers of the present invention.
' Example 23
PACK 1 Weight (grams)
BYK 300 0.50
DBTDL 0.26
TINUVIN 292 1.20
CHISORB328 1.00
Propionic Acid 0.46
Hydroxy containing acrylic polymer of Example 19 15.17
Hydroxy containing acrylic polymer of Example 20 24.18
Glycidyl ester/polyol reaction product of Example 1 30.00
Solvent Blend #7 40.00
Pm Acetate 10.15
Sub Total 122.93
PACK 2
DESMODUR N-3400 23.03
DESMODUR Z 4470- BA 24.33
MIBK " 2.72
Sub Total 50.08
Total 173.00

(Table Removed)
Example 25
PACK 1 Weight(qrams)
BYK 300 0.50
DBTDL 0.26
TINUVIN 292 1.20
CHISORB 328 1.00
Propionic Acid 0.46
Hydroxy containing acrylic polymer of Example 19 17.15
Hydroxy containing acrylic polymer of Example 20 27,33
Glycidyi Ester/polyol reaction product of Example 2 30.00
Solvent Blend #7 40.00
Pm Acetate
Sub Total 127.28
PACK 2
DESMODUR N-3400 21.03
DESMODUR 2 4470 BA 22.21
MIBK 2.48
Sub Total ■ 46.72
Total 173.00

Sub Total

127.28

PACK 2

DESMODUR N-3400 DESMODUR Z 4470 BA MIBK

21.03 22.21 2.48



Sub Total Total

45.72 173.00

(Table Removed)

■ Example 28
PACK 1 Weiqhtfqrams)
5YK 300 0.50
DBTDL 0.28
TINUVIN292 1.20
CHISORB 328 1.00
Propionic Acid 0.46
Hydroxy containing acrylic polymer of Example 19 15.17
Hydroxy containing acrylic polymer of Example 20 24.18
Glycidyl ester/polyol reaction' product of Example 5 30.00
Solvent Blend #7 ' 40.00
Pm Acetate 10.15
Sub Total 122.93
DESMODUR N-3400 23.03
DESMODUR Z 4470 BA 24.33
MIBK 2.72
Sub Total 50.08
Total 173.00
Example 29
PACK_i Weiqht(grams)
BYK 300 0.50
DBTDL 0.26
TINUVIN 292 1.20
CHISORB 328 1.00
Propionic Acid 0.48
Hydroxy containing acrylic polymer of Example 19 17,15
Hydroxy containing acrylic polymer of Example 20 27.33
Glycidyl ester/polyol reaction product of Example 8 30.00
Solvent Blend #7 40.00
Pm Acetate 9.39
Sub Total 127.28
PACK 2
DESMODUR N-3400 21 03
DESMODUR Z 4470 BA 22.21
MIBK 2.48
Sub Total 45.72
Total 173.00


(Table Removed)
Example 31
PACK 1 WeigjTtigjgnis)
BYK 300 0,50
DBTDL 0.26
TINUVIN 292 1 ?n
CHISORB 328 1.00
Propionic Acid 0.46
Hydroxy containing acrylic polymer of Example 19 15.17
Hydroxy containing acrylic polymer of Example 20 24.18
Glycidyl ester/polyol reaction product of Example 12 30.00
Solvent Blend #7 40.00
Pm Acetate 10.15
• Sub Total 122.93
PACK 2
DESMODUR N-3400 23.03
DESMODUR Z 4470 BA 24.33
MIBK" ' 2,72
Sub Total 50.08
Total 173.00
(Table Removed)
Example 33
PACK 1 Weiqht(qrams)
BYK 300 0.50
DBTDL 0.26
TINUVIN 292 1.20
CHISORB.328 1.00
Propionic Acid 0.46
Hydroxy containing acrylic polymer of Example 19 9.02
Hydroxy containing acrylic polymer of Example 20 14.38
Glycidyl ester/polyoi reaction product of Example 9 30.00
Solvent Blend #7 40.00
Pm Acetate 12.53
Sub Total ' 109.36
PACK 2
DESMODUR N-3400 28.27
DESMODUR 2 4470 BA 30.92
MIBK 3.46
Sub Total 3.64
Total' 173.00

Example 34
PACK.1 WeigfTtfgrarns)
UYK.3UU 0.50
DBTDL 0.26
TINUVIN29.2 1.20
CHISORB328 1.00
Propionic Acid 0.46
Hydroxy containing acrylic polymer of Example 19 9.02
Hydroxy containing acrylic polymer of Example 20 14.38
Glycidyi ester/polyoi reaction product of Example 10 30.00
Solvent Blend #7 40.. 00
Pm Acetate 12.53
SubTotai 109.-35
PACK 2

(Table Removed)
DESMODUR N-3400 29 ?7
DESMODUR Z 4470 BA 30.92
MIBK 3.46
Sub Total 63.64
Total 173,00
Examg]e_36
PACK 1 ' Weiqhtfqrams)
5YK 300 0.50
DBTDL 0.20
TINUViN 292 1.20
CHISORB328 1.00
Hydroxy containing acrylic polymer of Example 19 31.87
Hydroxy containing acrylic polymer of Example 21 27.58
Glycidyl ester/polyoi reaction product of Example 16 20.99
Solvent Blend #7 30.00
Pm Acetate 15.77
Sub Total 129.11
PACK 2
DESMODUR N-3400 20.18
DESMODUR Z 4470 BA 21.32
MIBK 2.38
Sub Total 43.89
Total 173.00
Example 37
PACK 1 Weiqhtfqrams)
BYK 300 0.50
DBTDL 0.20
TINUVIN 292 1.20
CHISORB328 ' 1.00
Hydroxy containing acrylic polymer of Example 22 40.87
Hydroxy containing acrylic polymer of Example 20 11.58
Glycidy! ester/polyoi reaction product of Example 15 26.73
Solvent Blend #7 29.99
Pm Acetate 16,95
Sub Total 129.02
PACK 2
DESMODUR N-3400 20.23
DESMODUR Z 4470 BA 21.36
MIBK 2.38
Sub Total 43.98
Totai 173.00
[00073] The Examples above include materials that may he cited as a ■
tradename or are otherwise not clear as the nature of the material. The following
definitions are provided to clarify such names:
[GGG74] Asisyi Ffopiunaie (peniyi propionate) solvent is commercially available
from Dow Chemical Co. having a place of business in Midland, Ml.
[00075] BYK 300 flow additive is commercially available from Byk Chemie
having a place of business in Wallingford, CT.
{00076] Butyl Acetate urethane grade solvent is commercially available from
Eastman Chemical Co. having a place of business in Kingsport, TN.
[00077] BUTYL CELLOSOLVE Acetate (EB Acetate) solvent is commercially
available from Eastman Chemical Co. having a place of business in Kingsport, TN
[00078] CHISORB 328 UV absorber is commercially available from CHITEC
Chemical Co. having a place of business in Taiwan, R.O.C.
[00079] Desmodur N-3400 aliphatic polyisocyanate is commercially available
from Bayer having a place of business in Pittsburgh, PA
[00080] Desmodur Z 4470 BA aliphatic polyisocyanate is commercially
available from Bayer having a place of business in Pittsburgh, PA
[00081] DSTDL (dibuty tin dilaurate) DABCO T-12 is commercially available
from Air Products having a place of business in Alientown, PA
[00082] MIBK (methyl isobutyl ketone) solvent is commercially avaiiabie from
Eastman Chemical Co. having a place of business in Kingsport, TN
[00083] Propionic Acid is commercially available from AJdrich Chemical Co.
having a place of business in Milwaukee, Wi
[00084] PM Acetate solvent is commercially available from Eastman Chemical
Co. having a place of business in Kingsport, TN
[00085] Solvent Blend #7 used In the foregoing Examples has the following
formulation:

(Table Removed)
Total 100.00

[00086] SOLVESSO 100, aromatic solvent, is commercially available from
Exxon Mobil Corp. having a place of business in Houston, TX
[00087J TINUVIN 292, hindered amine light stabilizer is commercially available
iiom CiBA Specialty Chemical Corp. having a piace of ousiness in Tarrytown, NY.
[00088] The compositions of Examples #23-37 were sprayed applied with a
DeViibiss GTI Millennium gravity spray gun over the following substrate:
[0008SJ An APR43741 coated metal substrate from ACT Laboratories, Inc.
Hiiisdaie, MI was sanded with 600 grit paper. PPG Global BC color number 3964 basecoat, available from PPG Industries, Pittsburgh PA, was then applied to the sanded substrate and given a solvent flash at room temperature for thirty (30) minutes. The ciearcoat of Examples 23-37 was applied to the basecoat and cured at room temperature. The ciearcoat had a dry film thickness of 2 to 3 mils. The following Table 2 illustrates the physical properties of the coating compositions of the foregoing Examples:
Table 2
(Table Removed)
1 - Viscosity was measured at 60 rpm by a BROOKFiELD Viscometer Model LVT right after
mixing the formula components (initial) and again measured at 1 hour after mixing.
2 - Dust time was measured by placing a cotton ball on the coating at various times after
applying and recording the time the cotton ball cleanly falls off after the pane! is inverted.
3 - Gloss was measured by a BYK-Gardner Micro-TRI-GIossmeter.
4 - Konig hardness was measured by a BYK-Gardner Pendulum Hardness Tester.
[00090] Whereas particular embodiments of this invention have been
described above for purposes of illustration, it will be evident to those skilled in the art that numerous variations of the details of the present invention may be made without departing rrom tne invention as defined in the appended claims.




We claim:
1. A copolymer having a molecular weight distribution greater than 1.10 comprising a reaction product of a glycidyl ester or ether or combination thereof with a polyol comprising a functionality of atleast 2 wherein the molar ratio of glycidyl ester or ether or combination thereof to polyol is atleast 3:1 and wherein atleast 50% by weight of the copolymer comprises a minimum of 3n+X repeating units, wherein n is a monomer unit derived from the glycidyl ester or ether or combination thereof and X is a monomer derived from the polyol.
2. The copolymer as claimed in claim 1 wherein less than 50% of the copolymer includes polymeric units having the same molecular weight.
3. The copolymer as claimed in any of the preceding claims having a number average molecular weight (Mn) of at least 500 g/mol.
4. The copolymer as claimed in any of the preceding claims wherein the glycidyl ester comprises a C5-C12 branched aliphatic acid.
5. The copolymer as claimed in any of the preceding claims wherein the polyol has a number average molecular weight (Mn) of less than 300.
6. The copolymer as claimed in claim 5 wherein said polyol is selected from the group comprising neopentyl glycol, 2-ethyl-lf 3-hexane diol, cyclohexane di-methanol, trimethyolpropane, tris(hydroxyethyl)isocyanurate, and/or pentaerythritol.
7. The copolymer as claimed in any of the preceding claims wherein said polyol comprises a functionality of 2 to 16.
8. The copolymer as claimed in claim 7 wherein said polyol comprises a functionality 2 to
5.
9. The copolymer as claimed in any of the preceding claims having a hydroxyl value of 50 to 300.

10. A process for preparing a copolymer claimed in any of the preceding claims having a
molecular weight distribution greater than 1.10 comprising reacting in a molar ratio of at
least 3:1 a glycidyl ester, or ether or combination thereof with a polyol having a
functionality of at least 2 to form a copolymer wherein at least 50% by weight of the
copolymer comprises a minimum of 3n+X repeating units, wherein n is a monomer unit
derived from the glycidyl ester or ether or combination thereof and X is a monomer unit
derived from the polyol.
11. The process as claimed in claim 10 wherein less than 50% of the copolymer includes polymeric units having the same molecular weight.
12. The process as claimed in claim 10 wherein the copolymer has a number average molecular weight (Mn) of least 500 g/mol.
13. The process as claimed in claim 10 wherein the glycidyl ester is a C5-C12 branched aliphatic acid.
14. The process as claimed in claim 10 wherein the polyol has a Mn of less than 300.
15. The process as claimed in claim 10 wherein said polyol comprises at least one polyol selected from the group comprising neopentyl glycol, 2-ethyl-l, 3-hexane diol, cyclohexane di-methanol, trimethyolpropane, tris(hydroxyethyl)isocyanurate and pentaerythrftol.
16. The process as claimed in claim 10 wherein said polyol comprises a functionality of at least 2 to about 16.
17. The process as claimed in claim 16 wherein said polyol comprises a functionality ranging from at least about 2 to about 5.
18. A coating composition comprising: (a) the copolymer as claimed in claim 1 having reactive functional groups; and (b) a curing agent having functional groups reactive with the functional groups of the copolymer.

19. The coating composition as claimed in claim 18 comprising an additional component having functional groups reactive with the functional groups of the curing agent and/or the copolymer.
20. The coating composition as claimed in claim 19 wherein said additional component comprises a polyester, an acrylic polymer, and/ or a polyurethane.
21. The coating composition as claimed in claim 18 wherein said curing agent comprises a polyisocyanate and/or an anhydride.
22. The coating composition as claimed in claim 18 wherein the composition is a two-component system, wherein one component comprises the copolymer and the second component comprises said curing agent.
23. The coating composition as claimed in claim 18 wherein the curing agent component comprises a blocked polyisocyanate or an aminoplast.
24. The coating composition as claimed in claim 23 wherein the composition is a one-component system.
25. A copolymer comprising a reaction product of a glycidyl ester or ether or combination thereof wherein the polyol comprises a functionality of at least 2 and wherein at least 50% by weight of the copolymer comprises repeating units according to 3n+X wherein n is a monomer unit and X is a monomer unit or other reactant, said copolymer having a molecular weight distribution greater than 1.10.

Documents:

4037-delnp-2008- Form-13 (19-05-2008).pdf

4037-DELNP-2008-Abstract-(18-07-2012).pdf

4037-delnp-2008-abstract.pdf

4037-delnp-2008-Claims-(01-05-2013).pdf

4037-DELNP-2008-Claims-(14-05-2012).pdf

4037-DELNP-2008-Claims-(18-07-2012).pdf

4037-delnp-2008-claims.pdf

4037-delnp-2008-Correspondence Others-(01-05-2013).pdf

4037-delnp-2008-Correspondence Others-(10-05-2013).pdf

4037-delnp-2008-Correspondence Others-(12-06-2012).pdf

4037-delnp-2008-Correspondence Others-(14-05-2012).pdf

4037-DELNP-2008-Correspondence Others-(18-07-2012)..pdf

4037-delnp-2008-Correspondence Others-(18-07-2012).pdf

4037-delnp-2008-correspondence-others.pdf

4037-delnp-2008-description-(complete).pdf

4037-delnp-2008-form-1.pdf

4037-delnp-2008-form-2.pdf

4037-delnp-2008-Form-3-(01-05-2013).pdf

4037-DELNP-2008-Form-3-(18-07-2012).pdf

4037-delnp-2008-form-3.pdf

4037-DELNP-2008-Form-5-(18-07-2012).pdf

4037-delnp-2008-form-5.pdf

4037-delnp-2008-GPA-(01-05-2013).pdf

4037-delnp-2008-pct-101.pdf

4037-delnp-2008-pct-102.pdf

4037-delnp-2008-pct-105.pdf

4037-delnp-2008-pct-132.pdf

4037-delnp-2008-pct-202.pdf

4037-delnp-2008-pct-210.pdf

4037-delnp-2008-pct-220.pdf

4037-delnp-2008-pct-301.pdf

4037-delnp-2008-pct-304.pdf

4037-delnp-2008-Petition-137-(18-07-2012).pdf


Patent Number 257195
Indian Patent Application Number 4037/DELNP/2008
PG Journal Number 37/2013
Publication Date 13-Sep-2013
Grant Date 11-Sep-2013
Date of Filing 12-May-2008
Name of Patentee PPG INDUSTRIES OHIO, INC
Applicant Address 3800 WEST 143RD STREET, COLECELAND, OHIO 44111, USA.
Inventors:
# Inventor's Name Inventor's Address
1 MARTZ, JONATHAN T. 2509 HAMILTON AVENUE, GLENSHAW, PENNSYLVANIA 15116, USA.
2 THOMAS, STEPHEN J. 309 CENTER AVENUE, ASPINSALL, PENNSYLGANIA 15215, USA.
PCT International Classification Number C09D 5/00
PCT International Application Number PCT/US2006/043980
PCT International Filing date 2006-11-13
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 11/286,721 2005-11-23 U.S.A.