Title of Invention

POLYMER DISPERSION IN A REACTIVE ORGANIC MEDIUM, PROCESS OF PREPARATION AND USES

Abstract A polymer dispersion in an organic medium, characterized in that it comprises the product from the polymerization of one vinyl monomer in the presence of a radical initiator in a reactive organic dispersing medium chosen from the silicones comprising one epoxy group, preferably two, in terminal position (s).
Full Text

POLYMER DISPERSION IN A REACTIVE ORGANIC MEDIUM,
PROCESS OF PREPARATION AND USES
The invention relates to a polymer dispersion in a
reactive organic medium obtained by radical dispersion
po1ymerization.
Polymers in solution or in suspension are widely used,
in particular in the field of glass strands intended
for the reinforcing of organic materials of the polymer
type, to produce sizing or coating compositions.
Glass strands used for reinforcing are generally
produced industrially from molten glass streams flowing
from the multiple orifices of a bushing. These streams
are drawn mechanically in the form of continuous
filaments and are then gathered together into base
strands which are subsequently collected, for example
by winding off on a rotating support. Before they are
gathered together, the filaments are coated with a
sizing composition by passing over a suitable device,
such as coating rolls.
The sizing composition is essential for the manufacture
of the glass strands and for the production of the
composite materials incorporating these strands.
During the manufacture of the strand, the sizing
composition protects the glass filaments from the
abrasion which occurs when the latter rub at high speed
over the various members for guiding and gathering
together and gives cohesion to the strand by binding
the filaments together.
During the manufacture of the composite materials, the
sizing composition makes possible the impregnation of
the strand by the matrix to be reinforced, on the one
hand, and improves the adhesion between the glass and
said matrix, on the other hand, thus contributing to

better mechanical properties being obtained.
The glass strands can be used as they are or can be
gathered together prior to their incorporation in the
matrix to be reinforced, for example in the form of
woven fabrics, used in particular for the reinforcing
of polymer matrices, or of grids, when nonpolymer
matrices are to be reinforced. In this case, it is
necessary to apply a coating to the grid which allows
it to withstand the handling operations and to retain
intact its structure up to the final processing stage.
The polymer solutions, emulsions and dispersions
available for producing sizing or coating compositions
are very largely based on water or on volatile organic
solvent (s) .
In point of fact, the presence of water or of organic
solvent in the size or the coating has a harmful effect
on the quality of the reinforcement in the composite
material and consequently has to be avoided.
Water is removed by drying under conditions which vary
according to whether the composition employed is a size
or a coating:
in the case of a size, drying is carried out at a
temperature generally varying from 100 to 130°C
for a period of time which depends on the
presentation of the strarid, from a few seconds for
cut strands to a few hours for wound packages of
strands (rovings). The stage of drying the rovings
is carried out in specific large-scale plants and,
for this reason, it represents a significant part
of the production cost for the strand,
in the case of a coating, drying is carried out on
the production line at a temperature which varies
from 130 to 250°C, in particular with hot air or
infrared radiation, for a period of time not
exceeding a few minutes, preferably 1 to 5

minutes.
The drying is the important stage of the process which
has a direct effect on the speed of: the manufacturing
line. If drying is carried out too quickly, for example
at a high temperature in order to reduce the time,
blistering of the composition may occur at the surface
of the strands .
Some compositions require recourse to organic solvents
in order to dissolve and/or disperse and/or emulsify
all or part of the constituents. The solvents can be
used alone or added to the aqueous solutions, emulsions
and dispersions in order to improve their properties,
for example in order to reduce the viscosity in order
to allow better penetration between the constituent
filaments of the glass strand. The use of organic
solvents, generally volatile organic solvents in order
to remove them more easily, makes it necessary to take
additional precautions due to their higher flammability
and the greater risk to the health of the personnel
handling the size or the coating on the manufacturing
line. In addition, it is necessary to have available plants for the continuous treatment of the effluents in
order to reduce to a minimum their discharge to the
atmosphere. As regulations with regard to discharging
are becoming increasingly restrictive, the treatment
cost, both with regard to the plants themselves and
with regard to their operation, is constantly
increasing .
Even if the solutions, emulsions and dispersions
available on the market are relatively concentrated in
polymer (40 to 80% by weight), they still comprise
water and/or organic solvents, with the result that the
drying stage cannot be avoided.
It is an aim of the present invention to provide a
polymer dispersion devoid of water and of volatile

organic solvent which is capable of being used in a
sizing composition for glass strands or a coating
composition for glass strands and assemblages of such
strands.
Another aim of the invention is to provide a polymer
dispersion comprising a high polymer content which
remains stable under the normal storage conditions.
These aims are achieved by the dispersion according to
the invention, which comprises the product from the
polymerization of at least one vinyl monomer in the
presence of a radical initiator in a reactive organic
dispersing medium.
According to the invention, an organic latex is formed
composed of a polymer resulting from the in situ
polymerization of one or more vinyl monomers capable of
polymerizing by the radical route, this polymer being
dispersed in an organic medium including one or more
reactive groups which can react with other compounds in
a subsequent stage, said groups not, however, being
capable of polymerizing by the radical route. In some
cases, a small proportion of vinyl monomer(s), which
can range up to 10%, is capable of reacting with the
reactive organic medium, giving a grafted product which
helps in the dispersing of the polymer.
The dispersion in accordance with the invention is
obtained as soon as the difference between the
solubility parameter of the polymer (δtp) and the
solubility parameter of the dispersing medium (δtm) is sufficient to make possible the formation of a two-
phase system. Generally, the dispersion is obtained
when the following relationship is satisfied:
|δtP - δtm > 4, preferably > 5
The dispersion is prepared according to the process

which comprises a stage of mixing at least one vinyl
monomer, the radical initiator and the reactive organic
dispersing medium and a stage of reacting the mixture
at a temperature of at least 20°C and lower than the
boiling point of the compound in the mixture having the
lowest boiling point. The vinyl monomer is chosen from
the monomers of formula

in which
• X is a C1-C18 alkyl radical, an aryl radical,
preferably the phenyl radical, which can comprise
one or more C1-C4 alkyl substituents, preferably the
tolyl radical, or a C7-C10 arylalkyl radical,
preferably the benzyl radical, and Y represents a
hydrogen atom or a C1-C4 alkyl radical,
X is the OR group in which R represents a C1-C18
alkyl radical or a C5-C8 cycloalkyl radical,
or a radical of formula

in which
R1 and R2 represent a hydrogen atom, a methyl radical
or an ethyl radical, R1 and R2 being different,
m and n, which are identical or different, are equal
to 1, 2, 3 or 4, preferably 3 or 4,
z and t, which are identical or different, are
greater than 4,
z + t is less than or equal to 80,
and Y represents a hydrogen atom or a C1-C4 alkyl
radical, X is the OCOR1 group in which R1 represents a C1-C12,
preferably C1-C4, alkyl radical, a C5-C8 cycloalkyl
radical, preferably the cyclohexyl radical, or an
aryl radical, preferably the phenyl radical, and Y
represents a hydrogen atom,

X is the COOR2 group in which R2 represents a C4-C20
alkyl radical, a C6-C20, preferably C4-C12, cycloalkyl
radical, an aryl radical, preferably the phenyl
radical, or a C5-C20 arylalkyl radical, preferably
the benzyl radical, and Y represents a hydrogen atom
or a methyl radical,
X is the group of formula

and Y represents a hydrogen atom.
Preferably, the vinyl monomer is chosen from vinyl
acetate, vinyl propionate, butyl acrylate, octyl
acrylate, lauryl acrylate and N-vinylpyrrolidone.
Particularly preferably, the vinyl monomer is vinyl
acetate, butyl acrylate, octyl acrylate or
N-viny1pyrro1idone.
The radical initiator can be any known type of
initiator which makes it possible to initiate the
polymerization reaction by the radical route which can
be activated thermally or by ultraviolet radiation.
Preferably, the initiator can be activated thermally,
that is to say that it can release radicals at the
reaction temperature, preferably at a temperature lower
by at least 10°C than the boiling point of the compound
in the mixture having the lowest boiling point.
Generally, it. is necessary for the initiator to be
soluble preferentially in the vinyl monomer(s) to be
polymerized, that is to say for the partition
coefficient between the constituents of the mixture to
be favorable to said monomer(s). Mention may be made,

as examples of such initiators, of peroxides, hydro-
peroxides, alone or in combination with a reducing
agent of Fe(II), Co (II) or ascorbic acid type (redox
initiators), and azo compounds. The choice is
preferably made of benzoyl peroxide, lauroyl peroxide,
2,2' -azobisisobutyronitrile, 2,2' -azobismethylbutyro-
nitrile and 4,4'-azobis(cyanopentanoic acid), and
advantageously of lauroyl peroxide, 2, 2'-azobisiso-
butyronitrile. and 2,2'-azobismethylbutyronitrile.
The radical initiator is introduced in a proportion of
0.5 to 6% by weight of vinyl monomer, preferably 1 to
4%, advantageously 1 to 3%.
The organic dispersing medium is chosen from the
compounds exhibiting at. least one reactive group below:
silicones comprising at least one epoxy group,
preferably at least two epoxy groups, in terminal
position (s), for example poly(alkylsiloxane)s
comprising glycidyl ending(s). The silicones
exhibiting a molecular weight of between 450 and
4000, preferably between 600 and 3000, are advantageous as they make possible good
dissolution or dispersion of the vinyl monomer
without increasing too significantly the viscosity
of the composition.
Preferably, the silicone corresponds to the
formula

in which
n varies from 3 to 45, preferably 10 to 3 0
m varies from 1 to 20
polyols derived from saturated or unsaturated and
linear, branched or cyclic hydrocarbons.

Preferably, the polyols exhibit a molecular weight
of less than 5000. Advantageously, the number of
hydroxyl groups in the polyol is at most equal
to 6.
Mention may be made, by way of examples, of diols, such
as ethylene glycol, 1,2-propanediol, 1,4-butanediol,
1,6-hexanediol and cyclohexanedimethanol, of triols,
such as glycerol and 1,2,4-butanetriol, of tetrols,
such as erythritol and pentaerythritol, and of the
mixtures of these compounds.
Advantageously, the dispersing medium is an α,ω-di-
glycidylpolydimethylsiloxane preferably having a
molecular weight of the order of 2000 or ethylene
glycol.
If appropriate, when the viscosity of the dispersing
medium is high, a small proportion of an organic
compound which acts as diluent, namely that it is not
capable of reacting with the vinyl monomer and with the
dispersing medium but can optionally polymerize, can be
added. The diluent is chosen, for example, from ethers
of fatty alcohols including at most 20 carbon atoms,
preferably between 6 and 18 carbon atoms and
advantageously between 8 and 16 carbon atoms, in
particular the monoglycidyl ethers and the diglycidyl
ethers of these fatty alcohols. The diluent is chosen
according to the chemical nature of the dispersing
medium; for example, an alcohol, such as 2-propanol, is
chosen when the dispersing medium is a glycol, such as
ethylene glycol. Generally, the proportion of diluent
does not exceed 30% by weight of the dispersing medium
and preferably remains below 15%.
In the mixture, the vinyl monomer and the dispersing
medium are employed in a ratio by volume which does not
exceed 70:30 in order to avoid phase inversion of the
monomer in the dispersing medium. Preferably, the ratio

is between 60:40 and 30:70.
As has already been mentioned, the polymerization
reaction is carried out at a temperature of at least
20°C and lower than the boiling point of the compound
in the mixture having the lowest boiling point. The
reaction conditions, in particular the temperature and
the duration, vary according to the desired degree of
conversion of the vinyl monomer, the final polymer and
the nature and level of initiator. Generally, the
polymerization is carried out at a temperatur of
greater than or equal to 40°C and lower by at least
10 °C than the boiling point of the monomer having the
lowest boiling point, preferably not exceeding 60°C,
for a period of time which varies between 30 minutes
and approximately 10 hours, preferably less than
6 hours. These polymerization conditions make it
possible to obtain a degree of conversion of the vinyl
monomer of greater than 80%, preferably of greater than
8 5%.
According to an alternative embodiment using a redox
initiator as defined above, the reaction temperature
does not exceed 40°C and preferably does not exceed
30°C.
If appropriate, the content of residual vinyl monomer
can be reduced by increasing the duration of the
reaction or by adding an additional amount of radical
initiator at the end of the reaction rather than by
increasing the temperature, which can result in the
evaporation of the residual vinyl monomer.
In the dispersion obtained, the polymer is found
dispersed directly in the reactive organic medium,
which makes it possible to avoid the intermediate stage
of removal of the solvent, as is necessary with the
known dispersions.

The polymer is found in the form of fine' substantially
spherical particles with a size of less than 4 0 urn,
preferably of less than or equal to 15 µm and better
still of less than 3 µm, which form a stable dispersion
in the dispersing medium, even for a high polymer
content. These particles also exhibit a narrow size
distribution centered on a mean diameter of between
0.05 and 3 µm.
The combination of the size and of the distribution of
the abovementioned particles contributes to the
production of a stable dispersion including 20 to 70%
by weight of polymer, preferably 30 to 60% and better
still 4 0 to 60%.
The viscosity of the dispersion is generally less than
or equal to 500 000 mPa.s but it can be adapted
according to the application targeted, for example by
adjusting in particular the amount of vinyl monomer in
the starting mixture, the viscosity of the reactive
organic dispersing medium, the molecular weight of the
polymer and the size of the particles.
Thus, the viscosity is generally chosen to be less than
2000 mPa-s, preferably between 5 0 and 10 00 mPa.s, for
the production of a coating, and to be less than
250 mPa.s, preferably of the order of 30 to 150 mPa-s,
for a size .
The dispersion can additionally comprise a stabilizing
agent which helps in a better dispersion of the polymer
particles in the reactive medium and makes it possible
to avoid separation by settling during storage. The
stabilizing agent generally exhibits a structure
comprising at least one part having an affinity with
the polymer particles and at least one part exhibiting
an affinity with the reactive organic medium.
The stabilizing agent can be chosen from:

alkylene oxide copolymers, for example copolymers
of ethylene oxide and of propylene oxide, in
particular in the form of diblock or triblock
copolymers. Advantageously, the copolymers are
poly(ethylene oxide)/poly(propylene oxide) diblock
copolymers. These copolymers can be grafted and
the pendent groups can include one or more
carboxyl or sulfo functional groups,
polymers of alkylene oxide and of at least one
other polymerizable monomer, for example styrene
and alkyl, in particular methyl, acrylate or
methacrylate. Use is advantageously made of
poly(ethylene oxide)/poly(methyl methacrylate) and
poly (ethylene oxide)/polystyrene block copolymers,
vinyl alcohol polymers preferably having a
molecular weight of between 3000 and 250 000,.
advantageously between 10 000 and 200 000 and
better still between 25 000 and 150 000. These
polymers are obtained in particular by hydrolysis
of the corresponding poly(vinyl acetate)s, the
degree of hydrolysis generally being less than or
equal to 98%. Poly (vinyl alcohol)s are more
particularly employed when the reactive medium is
based on polyol(s),
silicone polymers, for example poly(alkyl-
siloxane)s, such as polydimethylsiloxanes
comprising acrylic or methacrylic ending (s), and
polydimethylsiloxanes grafted by a poly(alkylene
oxd.de), in particular a poly (ethylene oxide).
The stabilizing agent can be added to the mixture of the
starting reactants in a proportion which can range up to
35% by weight of vinyl monomer, preferably up to 20%.
It has been found, entirely unexpectedly, that the
polymerization of vinyl monomer(s) of vinyl acetate
type in a dispersing medium including epoxy functional
groups, in particular glycidyl functional groups, can
be carried out without the addition of a stabilizing

agent for the polymer. It would appear that the vinyl
acetate can react with the epoxy, in particular
glycidyl, functional group or groups of the dispersing
medium under the conditions of the polymerization,
forming a compound which acts as stabilizing agent. The
fact that this compound is formed in situ in the
dispersing medium during the course of the
polymerization is particularly advantageous as it
prevents the need to add an external stabilizing agent.
The polymer dispersion in accordance with the invention
can be satisfactorily stored under normal conditions
for several days, indeed even several months, generally
from 3 to 6 months, at a temperature varying from 20 to
25 °C, with an acceptable level of sedimentation of the
particles.
The dispersion in accordance with the invention
exhibits the following advantages:
it does not comprise water and, consequently, the
• energy-consuming drying stage is avoided,
it does not comprise volatile solvent and the risk
of contaminating emissions harmful to the
environment and to the health of the operators are
greatly reduced,
the content of residual vinyl monomer is very low,
less than 10% of the weight of the dispersion,
preferab1y less than 5%,
the content of polymer in the dispersion is high,
which makes it possible to have low-volume storage
facilities.
The dispersion according to the invention can be used
as has already been indicated for preparing sizing or
coating compositions.
The expression "sizing composition" has the meaning
usually accepted in the field of glass strands: it
denotes a composition capable of being deposited on

glass filaments during drawing, before they are
gathered together into one or more base strands. The
sizing composition serves to protect the, glass
filaments from abrasion during the manufacture of the
strand and to improve the impregnation of the strand by
the matrix to be reinforced and the coupling between
the glass and said matrix.
The expression "coating composition" denotes a
composition which can be applied to the glass strand at
various stages of the process after fiberizing, for
example strands originating from wound packages
(rovings), or to an assemblage of such strands, which
may or may not be intertwined, for example a woven
fabric, a knitted fabric, a grid or a material. The
role of the coating is to bind the strands together and
to improve their strength when they are finally used.
Conventionally, these compositions are prepared by
adding specific additives, in particular at least one
compound which can react with the epoxy or hydroxyl
reactive functional groups of the dispersing medium,
such as amino compounds and isocyanates, to the
dispersion. It is also possible to add cycloepoxide
compounds which can react under the effect of
ultraviolet radiation by catalysis of the Lewis acid
type starting from compounds such as triarylsulfonium
hexafluoroantimona te, triarylsulf onium hexafluoro-
phosphate of antimony, triarylsulfonium tetrafluoro-
borate of antimony, diaryliodonium hexafluoroantimonate
and derivatives of ferrocene type.
The sizing composition is applied to filaments formed of glass of any nature, for example E, C, AR (alkali-
resistant) or with a low level of boron (less than 5%).
Preference is given, to glass E and glass with a low
level of boron.
These filaments have a diameter which can vary to a

large extent, for example 5 to 24 µm, preferably 9 to
17 pm. The final glass strand generally has a count of
between 10 and 4800 tex, preferably 68 to 2400 tex.
The coating composition is for its part applied to a
glass strand or to an assemblage of such strands, in
particular in the grid or woven fabric form, for
example by spraying or immersion in a bath.
The glass strands coated with the size and the strands
or assemblages of such glass strands treated with the
coating are subjected to a treatment, for example a
heat treatment or a treatment under ultraviolet
radiation, in order to obtain the crosslinking of the
size or of the coating.
The examples which follow make it possible to
illustrate the invention without, however, limiting it.

EXAMPLES
The vinyl monomer, the reactive organic dispersing
medium, the radical initiator and, if appropriate, the
stabilizing agent are introduced into a reactor
equipped with a mechanical stirrer, a water-circulation
reflux condenser, a system which ensures circulation of
nitrogen and an oil bath.
The reaction mixture is heated at a temperature lower
by 10°C than the boiling point of the vinyl monomer for
7 hours with stirring (150 rpm) .
The following compounds are used in the contents shown
in table 1:
Vinyl, monomer
• VAC: vinyl acetate
° VP : N-vi nyi.pyrro.i.i.done
° BA: butyl acrylate

OA : octy.l acrylate
Dispersing medium
PDMS-DG: α,ω-diglycidylpolydimethylsiloxane (weight-
average molecular weight (MW): 2500); sold by
Goldschmidt under the reference Tegomer E-SI 2330
EG: ethylene glycol
Radical initiator :
ACPA: 4,4'-azobis(cyanopentanoic acid)
• AIBN: 2,2'-azobisisobutyronitrile
AMBN: 2,2'-azobismethylbutyronitrile; sold by DuPont
under the reference Vazo 67 BP: benzoyl peroxide
• IP: lauroyl peroxide
S t a b i 1 i z i n g a g e n t:
PDMS-MA: polydimethylsiloxane comprising methacrylic
endings; sold by Shin-Etsu under the reference X22-
174 DX (weight-average molecular weight (MW): 4600)
• PDMSgPEO: polydimethylsiloxane grafted with
poly (ethylene oxide); sold by Goldschmidt under the
reference Tegopren 58 42
PMMA-PEO: poly(methyl methacrylate)/poly(ethylene
oxide) block copolymer; sold by Goldschmidt under the
reference ME PS-PEO: polystyrene/poly(ethylene oxide) block
copolymer; sold by Goldschmidt under the reference SE PVAL: poly(vinyl alcohol) derived from poly(vinyl
acetate) (degree of hydrolysis: 88%; molecular
weight: 88 000); sold by Gohsenol under the reference
GL 05
Diluant: LA-MG: lauryl alcohol monoglycidyl ether; sold by
Huntsman Chemicals under the reference Araldite®
DY0391.
The following measurements are carried out starting
from the dispersion obtained:
the mean size of the polymer particles, expressed
in nanometers, is measured by photon correlation
spectroscopy under an incident beam of laser light

and measurement of the light scattered under an
angle of 90° using a Coulter N4 Plus device (for
sizes up to 3000 nm) and an LS 230 device (for
sizes up to 2 x 106 nm) .
the viscosity, in mPa.s, is measured at 25°C using
a rotary viscometer (Rheomat RM 180).
the stability is measured by giving the
sedimentation time under static conditions
corresponding to separation by settling of 25% by
volume of the dispersion (t25, expressed in days).
the degree of conversion of the vinyl monomer(s)
is measured by 1H NMR.
In table 1, it is found that the poly (vinyl acetate)
dispersions are stable without the addition of a
stabilizing agent for at least 30 days (Ex. 6 to 8) and
more than 60 days at a lower content of polymer (Ex. 1
to 5). For the more concentrated dispersions, the
addition of a stabilizing agent is necessary to obtain
a stability of at least 8 days (Ex. 30 to 34) . The
degree of conversion of the vinyl monomer is at least
equal to 90%.
The addition of stabilizing agent to the vinyl-
pyrrolidone and acrylic polymer dispersions makes it
possible to obtain particles which are small in size
(less than 1 µm) and makes it possible to increase the
duration of the storage (Ex. 9 and 1.0; Ex. 23 and 24) .
The solubility parameter of the polymer (δtp) and the
solubility parameter of the dispersing medium (δtm) are
calculated according to the method described by D.W.
Van Krevelen in the work "Properties of polymers";
Elsevier Science Publisher, 1990, pp. 212-213. The
difference |δtP - δtm| for the examples of table 1 is
given below:

|δtp - δtm|
Example 1-8 and 3 0-32 6.8
Examples 9-11 and 25 7.0
Examples 12 to 25 5.7





WE CLAIM :
1. A polymer dispersion in an organic medium, characterized in that it comprises
the product from the polymerization of one vinyl monomer in the presence of

a radical initiator in a reactive organic dispersing medium chosen from the
silicones comprising one epoxy group, preferably two, in terminal position (s).
2. The dispersion as claimed in claim 1, wherein it exhibits a difference between the solubility parameter of the polymer (δtp) and the solubility parameter of the dispersing medium (δtm) which satisfies the relationship:
| δtp_δtm | > 4, preferably > 5
3. The dispersion as claimed in claim 1 or 2, wherein the vinyl monomer is chosen
from the monomers of formula

in which
• X is a C1-C18 alkyl radical, an aryl radical, preferably the phenyl radical,
which can comprise one or more C1-C4 alkyl substituents, preferably the
tolyl radical, or a C7-C10 arylalkyl radical, preferably the benzyl radical, and Y represents a hydrogen atom or a C1-C4 alkyl radical,

• X is the OR group in which R represents a C1-C18 alkyl radical or a C5-C8
cycloalkyl radical, or a radical of formula

in which
R1 and R2 represent a hydrogen atom, a methyl radical or an ethyl radical, R1
and R2 being different, m and n, which are identical or different, are equal to
1, 2, 3 or 4, preferably 3 or 4, Z and T, which are identical or different, are
greater than 4,
z + t is at most equal to 80,
and Y represents a hydrogen atom or a C1-C4 alkyl radical,
• X is the OCOR1 group in which R1 represents a C1-C12, preferably C1-C4, alkyl radical, a C5-C8 cycloalkyl radical, preferably the cyclohexyl radical, or an aryl radical, preferably the phenyl radical, and Y represents a hydrogen atom,
• X is the COOR2 group in which R2 represents a C4-C20 alkyl radical, a C6-C20,
preferably C4-C12, cycloalkyl radical, an aryl radical, preferably the phenyl radical, or a C6-C20 arylalkyl radical, preferably the benzyl radical, and Y
represents a hydrogen atom or a methyl radical,

• X is the group of formula

and Y represents a hydrogen atom.
4. The dispersion as claimed in claim 3, wherein the vinyl monomer is chosen
from vinyl acetate, vinyl propionate, butyl acrylate, octyl acrylate, lauryl
acrylate and N-vinylpyrrolidone.
5. The dispersion as claimed in one of claims 1 to 4, wherein the silicone is a poly-
(alkylsiloxane) comprising glycidyl ending(s).
6. The dispersion as claimed in claim 5, wherein the silicone has the following
formula


in which
n varies from 3 to 45, preferably 10 to 30
m varies from 1 to 20.
7. The dispersion as claimed in claim 5 or 6, wherein the silicone has a molecular weight of between 450 and 4000, preferably between 600 and 3000.

8. The dispersion as claimed in one of claims 1 to 7, wherein the polymer is found
in the form of fine substantially spherical particles with a size of less than 40
µm, preferably of less than equal to 15 µm, and better still of less than 3 µm.

9. The dispersion as claimed in claim 8, wherein the particles exhibit a narrow size
distribution centered on a mean diameter of between 0.05 and 3 µm.
10.The dispersion as claimed in one of claims 1 to 9, wherein it comprises 20 to
70% by weight of polymer, preferably 30 to 60% and better still 40 to 60%.
11.The dispersion as claimed in one of claims 1 to 10, wherein it exhibits a viscosity of less than or equal to 500 000 mPa • s [or above], preferably of less than 2000 mPa • s and advantageously of between 30 and 1000 mPa • s.

12.The dispersion as claimed in one of claims 1 to 11, wherein it additionally
comprises a stabilizing agent chosen from
- alkylene oxide copolymers, such as copolymers of ethylene oxide and of
propylene oxide,
- polymers of alkylene oxide and of one other polymerizable monomer, such
as styrene and alkyl acrylate or methacrylate,
- vinyl alcohol polymers,
- silicone polymers, such as poly(alkyl-siloxane)s comprising acrylic or
methacrylic ending (s).
13. A process for the preparation of the dispersion as claimed in one of claims 1 to
12, comprising the stages consisting in
a) mixing one vinyl monomer, one radical initiator and one reactive organic
dispersing medium, and
b) reacting the mixture at a temperature of 20°C and lower than the boiling point of the compound in the mixture having the lowest boiling point.

14.The process for the preparation of the dispersion as claimed in claim 13,
wherein the initiator can be activated thermally at the reaction temperature,
preferably at a temperature lower by at least 10°C than the boiling point of the ,
compound in the mixture having the lowest boiling point.
15.The process for the preparation of the dispersion as claimed in claim 14,
wherein the radical initiator is chosen from peroxides, hydroperoxides and azo compounds.
16.The process for the preparation of the dispersion as claimed in one of claims 13 ,
to 15, wherein the amount of radical initiator represents 0.5 to 6% by weight
of vinyl monomer, preferably 1 to 4% by weight.
17.The process for the preparation of the dispersion as claimed in one of claims 13 to 16, wherein the vinyl monomer and the dispersing medium are employed in a ratio by volume not exceeding 70:30, preferably between 60:40 and 30:70.
18.The process for the preparation of the dispersion as claimed in one of claims 13
to 17, wherein the reaction temperature is between 40°C to 60°C.
19.The process for the preparation of the dispersion as claimed in claim 13,
wherein a redox initiator is used and in that the reaction temperature does not
exceed 40°C and preferably does not exceed 30°C.

20.The process for the preparation of the dispersion as claimed in one of claims 13
to 19, wherein a stabilizing agent is added to the mixture of stage a in a
proportion which can range up to 35% by weight of vinyl monomer, preferably
up to 20%.
21. A sizing composition intended to coat glass filaments, wherein it comprises a
dispersion as claimed in one of claims 1 to 12.
22. A coating composition intended to coat glass strands or an assemblage of glass strands, wherein it comprises a dispersion as claimed in one of claims 1 to 12.
23.A glass strand comprising glass filaments which are coated with the sizing composition as claimed in claim 21.
24. A glass strand or an assemblage of glass strands, in particular in the grid on
woven fabric form, coated with a coating composition as claimed in claim 22.


ABSTRACT

Title: POLYMER DISPERSION IN A REACTIVE ORGANIC MEDIUM,
PROCESS OF PREPARATION AND USES
A polymer dispersion in an organic medium, characterized in that it comprises the product
from the polymerization of one vinyl monomer in the presence of a radical initiator in a
reactive organic dispersing medium chosen from the silicones comprising one epoxy group,
preferably two, in terminal position (s).

Documents:

04540-kolnp-2007-abstract.pdf

04540-kolnp-2007-claims.pdf

04540-kolnp-2007-correspondence others.pdf

04540-kolnp-2007-description complete.pdf

04540-kolnp-2007-form 1.pdf

04540-kolnp-2007-form 2.pdf

04540-kolnp-2007-form 3.pdf

04540-kolnp-2007-form 5.pdf

04540-kolnp-2007-gpa.pdf

04540-kolnp-2007-international publication.pdf

04540-kolnp-2007-international search report.pdf

04540-kolnp-2007-pct request form.pdf

4540-KOLNP-2007-(06-09-2012)-AMANDED CLAIMS.pdf

4540-KOLNP-2007-(06-09-2012)-ANNEXURE TO FORM 3.pdf

4540-KOLNP-2007-(06-09-2012)-CORRESPONDENCE-1.pdf

4540-KOLNP-2007-(24-04-2012)-ABSTRACT.pdf

4540-KOLNP-2007-(24-04-2012)-AMANDED CLAIMS.pdf

4540-KOLNP-2007-(24-04-2012)-DESCRIPTION (COMPLETE).pdf

4540-KOLNP-2007-(24-04-2012)-EXAMINATION REPORT REPLY RECEIVED.pdf

4540-KOLNP-2007-(24-04-2012)-FORM-1.pdf

4540-KOLNP-2007-(24-04-2012)-FORM-2.pdf

4540-KOLNP-2007-(24-04-2012)-FORM-3.pdf

4540-KOLNP-2007-(24-04-2012)-OTHERS.pdf

4540-KOLNP-2007-(24-04-2012)-PETITION UNDER RULE 137.pdf

4540-KOLNP-2007-(24-08-2012)-CORRESPONDENCE.pdf

4540-KOLNP-2007-CORRESPONDENCE OTHERS 1.1.pdf

4540-KOLNP-2007-CORRESPONDENCE.pdf

4540-KOLNP-2007-EXAMINATION REPORT.pdf

4540-kolnp-2007-form 18.pdf

4540-KOLNP-2007-FORM 18_.pdf

4540-KOLNP-2007-FORM 3.pdf

4540-KOLNP-2007-FORM 5.pdf

4540-KOLNP-2007-GPA.pdf

4540-KOLNP-2007-GRANTED-ABSTRACT.pdf

4540-KOLNP-2007-GRANTED-CLAIMS.pdf

4540-KOLNP-2007-GRANTED-DESCRIPTION (COMPLETE).pdf

4540-KOLNP-2007-GRANTED-FORM 1.pdf

4540-KOLNP-2007-GRANTED-FORM 2.pdf

4540-KOLNP-2007-GRANTED-SPECIFICATION.pdf

4540-KOLNP-2007-OTHERS.pdf

4540-KOLNP-2007-OTHERS1.1.pdf

4540-KOLNP-2007-PRIORITY DOCUMENT.pdf

4540-KOLNP-2007-REPLY TO EXAMINATION REPORT.pdf


Patent Number 254537
Indian Patent Application Number 4540/KOLNP/2007
PG Journal Number 46/2012
Publication Date 16-Nov-2012
Grant Date 14-Nov-2012
Date of Filing 26-Nov-2007
Name of Patentee SAINT-GOBAIN VETROTEX FRANCE S.A.
Applicant Address 130 AVENUE DES FOLLAZ, F-73000 CHAMBERY
Inventors:
# Inventor's Name Inventor's Address
1 DELAITE, CHRISTELLE 5, IMPASSE DE L'ETANG, F-68720 FORENINGEN
2 MOIREAU, PATRICK LIEU-DIT VERNAY, F-73190 CURIENNE
3 RIESS, GERARD 31 RUE DU MEUNIER, F-68200 MULHOUSE
4 HARIRI, KAMAL CLOUS, KMK, STUDIO N° 4422, 44 BOULEVARD CHARLES STOESSEL F-68200 MULHOUSE
PCT International Classification Number C23C 25/28
PCT International Application Number PCT/FR2006/050478
PCT International Filing date 2006-05-24
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 0551386 2005-05-26 France