DE1025148B - Process for the production of resinous copolymers of monoolefinic unsaturated esters of epoxy fatty acids - Google Patents

Description

According to the invention, a monomeric epoxy ester of the formula

XCH ₉ COY

(1)

in which X is an epoxyalkyl group having 8 to 16 carbon atoms and 1 or 2 epoxy oxygen atoms and Y represents a monoolefinic alkyl group with another polymerizable monomeric unsaturated group Substance in the presence of a peroxide polymerization catalyst with the formation of high resins Molecular weight polymerized.

The molecular weight of a polymer in this regard can be determined in various ways. In the present case, the increase in viscosity of a thin solution of the polymer compared to that of the solvent itself was measured. A standard Ubbelohde viscometer was used for this measurement. The times for the thin solution of the resin T ₂ and for the solvent itself, T ₁ , were determined. The reduced viscosity / ,. is then defined by the following equation:

Yes

- 1

in which C is the concentration of the resin in the solution, expressed in g per 100 ecm. In the present case, the concentration of the resin was kept at 0.2 g per 100 ecm of the solvent. So a very thin solution was used. In the present case, the calculated reduced viscosity corresponds completely to the Staudinger intrinsic viscosity.

Copolymers produced by the process of the invention have as an essential component one Esters with the structure of the following formula:

Method of manufacture

of resinous copolymers

monoolefinic unsaturated ester

of epoxy fatty acids

Applicant:

Union Carbide Corporation, New York, N.Y. (V. St. A.)

Representative: Dr. phil. Dr. rer. pole. K. Köhler, patent attorney, Munich 2, Amalienstr. 15th

Claimed priority: V. St. v. America November 26, 1954

John Robert Kilsheimer, South Charleston, W.Va.,

and Bruce R. Thompson, Charleston, W. Va. (V. St. A /

have been named as inventors

R ₁ CHCHR ₂ COR.

(Q ₁ H ₂ ^ ₁ O) CH ₂ COR

(2)

CH ₃ (CH ₂ ) ₄ CHCHCH ₂ CHCH (CH ₂ ) ₇ COR (3)

in which R is an unsaturated alkyl group, especially an alkylene group which is the residue of an α-β-monoolefinic aliphatic monohydric alcohol or a β-γ-monoolennic unsaturated aliphatic monohydric alcohol, e.g. B. a vinyl group or an allyl group, or the formula in which R _{1 is} a hydrogen atom or an alkyl group having 1 to 14 carbon atoms and R _{2 is} an alkylene chain having 1 to 15 carbon atoms, the total number of carbon atoms in R ₁ and R ₂ is between 7 and 15, and R has the meaning given above. For interpolymerization with the esters indicated above, organic polymerizable substances such. B. unsaturated aliphatic or aromatic monomers are suitable. If desired, the unsaturated aliphatic monomer can be a vinyl ester of an inorganic or organic acid, such as vinyl or vinylidene fluoride, chloride or bromide, acrylonitrile, methacrylonitrile, methyl acrylate, methyl methacrylate, ethyl acrylate, vinyl acetate, vinyl butyrate, vinyl chloroacetate, vinyl formate or vinyl caproate. Unsaturated monomers with conjugated double bonds, such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1-acetoxybutadiene, piperylene, 2-cyano-1,3-butadiene, 2-meth-

709 907/446

3 4

Use oxy-1,3-butadiene or 2-fluoro-1,3-butadiene. The vessel was flushed with nitrogen, sealed

Another suitable class of polymerizable mono- and in a water bath at 50 ° for 64 hours

merer are those with an acetylene bond, e.g. B. acetylene, rolled. 80 g of the polymer were obtained (89 ° / "

Alkylacetylenes and dialkyl acetylenes, also dimer conversion). This resin had diminished and trimers of acetylene having one or more viscosity in benzene of 0.167. Analysis of the resin

acetylenic bonds or mixed olefinic gave 59.4% carbon and 8.2% hydrogen what

and acetylenic bonds. 81% polyvinyl acetate corresponds. From a methyl iso-

Another class of polymerizable monomers butyl ketone solution of this resin with 1% phosphoric acid

if the unsaturated aliphatic esters are more saturated (based on the resin weight) a film was cast, and unsaturated polybasic aliphatic acids i ° The film was cured for 20 minutes at 150 °; thereafter

or aromatic polybasic acids such as divinyl, it was insoluble to 67% ^m of methyl isobutyl ketone.
Diallyl and dimethallyl esters of oxalic, maleic, malonic,
Citric and tartaric acid; and the divinyl, diallyl and

Dimethallyl esters of phthalic, isophthalic, terephthalic, Example 3

Naphthalenedicarboxylic acid, also styrene, chlorostyrene or mixed polymerization of acrylonitrile with

Allyl styrene. ", ._,. Allyl 9,10-epoxystearate in emulsion

(If desired, a glycidyl polyether can be one

polyhydric phenol with the unsaturated ester. 21 g acrylic-

an epoxy fatty acid mixed and copolymerized nitrile, 9 g allyl-9,10-epoxystearate, 0.3 g potassium persulfate, will. These products can tert to hard, tough resins 20 0.9 g. Hexadecyl mercaptan, 150 ecm distilled

are cured, as protective coatings, adhesives water, 15 cc of a 5 ° / _o aqueous solution of

and dioctyl esters of the sodium salt of sulfosuccinic acid suitable for press mixes or molding mixes.

are. The vessels were flushed with nitrogen,

Copolymers with three or more components closed and placed in a water bath at 45 ° during can rolled by copolymerizing two different 25 17 hours. 40 g of polymer were recovered

polymerizable materials with the unsaturated ester (67% conversion); the analysis showed 86% poly-

an epoxy fatty acid. acrylonitrile. The resin had a reduced viscosity

The starting materials for the process of the invention in dimethylformamide of 4.65. From a dimethyl

Serving unsaturated ester of epoxy fatty acids formamide solution of this resin with a content of

can be obtained by epoxidizing an un- 30 1% phosphoric acid (based on the resin weight)

saturated ester, e.g. B. Treating an unsaturated film was cast. This was 20 minutes

Esters hardened with peracetic acid at temperatures between 10 177 °; after this time he was 90% in dimethyl

and 90 °. formamide insoluble.

Typical starting materials for the process of

Invention are allyl-5,6-epoxy laurate, vinyl-5,6-epoxy-35 Example 4

laurate, allyl-910-epoxymyristate, vinyl-9,10-epoxymy- mixed polymerisation of ethyl acrylate and

nstat allyl-9 10-epoxypalmitate vinyl-9,10-epoxypal-allyl-9,10-epoxystearate in solution

mitate or allyl and vinyl 9,10,12,13-diepoxystearate. j rj o

The allyl and vinyl esters can also be epoxidized. 12 g of allyl-9,10-

Fatty acids from soybean oil, linseed oil, safflower oil, cotton epoxystearate, 8 g ethyl acrylate, 1 ecm of a 25% strength

seed oil, tall oil, and mixtures can be used. The solution of acetyl peroxide in dimethyl phthalate, 10 g

Manufacture of unsaturated esters of epoxy fatty acids acetone.

is known. The tube was flushed with nitrogen, sealed and in a water bath at 50 ° during

Example 1 45 shaken for 18 hours. The recovered polymer was

Copolymerization of vinyl chloride and JJf ₁ (90% conversion); the analysis showed 68.40 /

Allyl 910 epoxystearate carbon and 10.6% hydrogen; This matches with

43% polyethyl acrylate. From a benzene solution this

A pressure vessel was filled with 18 g of vinyl chloride, resin containing 1% phosphoric acid (based on the weight

12gAUyl-9,10-epoxystearate, 2 ecm of a 25% solution 50 of the resin), a film was cast. The film

of acetyl peroxide in dimethyl phthalate, 150 ecm acetone. was cured at 177 ° for 20 minutes; he was then closed

The vessel was flushed with nitrogen, 77% insoluble in benzene,
closed and in a water bath at 50 ° for 17 hours

rolled. The polymer was obtained by precipitation in isopropanol Example 5

won. The dry precipitation weighed 33 g (55% strength 55 ,,.,. ... ".,. ,,,,,

Conversion). Analysis of the resin showed 84% poly copolymerization of methyl methacrylate and

vinyl chloride, the reduced viscosity in cyclohexanone allyl-9, 10-epoxystearate

was 0.325. From a methyl isobutyl ketone solution In a Pyrex tube 14 g of allyl-9,10-

this resin with 1% phosphoric acid (calculated on the epoxystearate, 6 g methyl methacrylate, 10 g acetone,

Resin weight) a film was cast and this then 60 1.0 ecm of a 25% solution of acetyl peroxide in

cured at 150 ° for 20 minutes; after that time were dimethyl phthalate.

93% insoluble in methyl isobutyl ketone. The tube was purged with nitrogen, sealed

and in a water bath at 50 ° for 10 ¹ ₂ hours

Example 2 shaken. 4.3 g of polymer (21%

",. ,, .. _TT . ,, 65 conversion). The resin had a viscosity in benzene

Copolymerization of vinyl acetate and of _{023; the analysis ergafe 6O6} “ _{/ o} carbon and

Allyl 9,10-epoxystearate Q ^ ₀ ^ hydrogen; this corresponds to 96% polymethyl

72 g of vinyl acetate, methacrylate were placed in a pressure vessel. From a benzene solution of this resin that

18 g allyl-9,10-epoxystearate, 3 ecm of a 25% solution 1% phosphoric acid (based on the resin weight)

of acetyl peroxide in dimethyl phthalate, 150 ecm acetone. 70 contained a film was cast. The movie was

5 6

Cured at 177 ° for 20 minutes; then 64% was in solution of this resin in dimethylformamide, the 1%

Benzene insoluble. Contained phosphoric acid (based on resin weight),

Example 6 a film was cast. The film was at 177 °

,,. ,, ·, · An in in + j. Cured for 20 minutes; thereafter it was 95% insoluble

Copolymerization of AUy-9,10-epoxystearate _{5 in dimethyl formamide} .

with vinyl chloride and vinyl acetate

54 g of vinyl chloride, Example 10, were poured into a Pyrex vessel

18 g vinyl acetate, 18 g AUyl-9,10-epoxystearate, 3 ecm.

a 25% solution of acetyl peroxide in dimethyl mixed polymer of Vmyl-9,10-epoxystearate and

phthalate, 150 ecm acetone. * io chlorostyrene

The vessel was flushed with nitrogen, sealed. 18.0 g of vinyl-9,10- were poured into a Pyrex tube.

and in a water bath for 64 hours at 50 ° epoxystearate, 2.0 g chlorostyrene, 20.0 g acetone, 1.5 ecm

rolled. 73 g of the polymer were obtained (81% of a 25% solution of acetyl peroxide in dimethyl

Conversion); the analysis showed 44.7% polyvinyl phthalate.

chloride. The polymer had a reduced viscosity. The tube was flushed with nitrogen, sealed

in cyclohexanone of 0.246. From a methyl isobutyl and in a water bath at 50 ° for 80 hours

ketone solution of this resin, the 1% phosphoric acid shaken. 12 g of polymer (60% conversion

(based on resin weight) was a film conversion); the analysis showed 15.9% polychlorostyrene.

poured. The film was cured at 150 ° for 20 minutes; The polymer had a reduced viscosity of

thereafter, 92.5% was insoluble in methyl isobutyl ketone. 20 0.11 in benzene. From a benzene solution of this resin,

the 1% phosphoric acid (based on the resin weight)

Example 7 contained a film was cast. The movie was

, ..,. ..., ", _, hardened for 20 minutes at 177 °; after that he was 52% in

Mixed polymer of allyl-9,10-epoxystearate with benzene insoluble vinyl chloride by suspension polymerization ₂ _

A pressure vessel was filled with 24.0 g of vinyl example

chloride, 6.0g allyl-9,10-epoxystearate, 0.5g lauroyl-. ,. . _A " , _n , ~. ~ <",.

peroxide, 130.0 ecm of distilled water, 10.0 ecm of a copolymerization of AUy1-9 10,12,13-diepoxy-

9% aqueous solution of HydroxyäthylceUulose. stearate with vinyl chloride

The vessel was flushed with nitrogen and sealed. 15 g of vinyl chloride were poured into a Pyrex tube,

and in a water bath at 50 ° for 22 hours 5 g of AUyl-9,10,12,13-diepoxystearate, 1 ecm of a 25% strength

emotional. 4 g of polymer (13.4% solution of acetyl peroxide in dimethyl phthalate, 15 g

Conversion); analysis showed 80% polyvinyl chloride. Acetone.

The polymer had a reduced viscosity of The tube was purged with nitrogen, sealed

0.13 in cyclohexanone. From a cyclohexanone and 35 in a water bath at 50 ° for 6 ¹ ₂ hours J

of this resin, which contains 1% phosphoric acid (based on shaken. 5% polymer (25% conversion

Resin weight), a film was cast. The change); analysis showed 83.5% polyvinyl chloride.

Film was cured at 177 ° for 20 minutes; thereafter the resin had a reduced viscosity of 0.47

it is 36% insoluble in cyclohexanone. in cyclohexanone. From a solution of this resin in

40 cyclohexanone, the 1% phosphoric acid (based on the

Example 8 containing weight of resin) a film was cast.

, ..,. . .. _Tr . , _n ._ ^. The film was cured at 177 ° for 20 minutes; thereafter

Copolymerization of Vin _y l-9,10-epoxystearate with _{he was too g4 0 / cyclohexanone in un} i i _{i ös.}

Vinyl chloride ^{/ u}

15 g of vinyl chloride, 45 Example 12, were poured into a Pyrex tube

5 g vinyl 9,10-epoxystearate, 1ccm of a 25% solution ",. ,,. . ".,,", »."., ",.

of acetyl peroxide in dimethyl phthalate, 10 g of acetone. Interpolymerization of ally 9,10 12,13-diepoxystearate

The tube was flushed with nitrogen, sealed ^{with acrylic lnitnl}

and shaken in a water bath at 50 ° for 19 hours. 10 g of acrylonitrile were poured into a Pyrex tube,

Recovered 17 g (85% conversion) polymer; 5 ° 10 gAUyl-9,10,12,13-diepoxystearate, 1 ecm of a 25%

analysis showed 68% polyvinyl chloride. The polymer solution of acetyl peroxide in dimethyl phthalate, 10 g

had a reduced viscosity of 0.47 in cyclohexa-acetone.

non. From a solution of this resin in cyclohexanone, The tube was purged with nitrogen, closed, and the 1% phosphoric acid (based on the resin weight) in a water bath at 50 ° for 5 ¹ Z ₂ hours geenthielt, a film was cast. The film was 55 shakes. 5 g of polymer were obtained (25% um-20 minutes cured at 177 °; after this time it was conversion); the analysis showed 85% polyacrylonitrile. 75% insoluble in cyclohexanone. Polymers had a reduced viscosity in dimethylformamide of 5.1. From a solution of this resin in Example 9 dimethylformamide containing 1% phosphoric acid (based on

,,. , ... Tr 1 η in. ^6o the resin weight), a film was cast. Of the

_? Copolymerization of ymyl-9,10-epoxystearate _{Füm WUR} ^s _{de 2Q} ^^ ₀ f _{cured at 17} | _{afterwards was}

with acrylonitrile _{it is insoluble in} dimethylformamide.

In a Pyrex glass were poured 15 g of vinyl-9,10-

epoxystearate, 5g acrylonitrile, 1ccm of a 25% example 3

Solution of acetyl peroxide in dimethyl phthalate, 10 g 65
Aceton jrj Jf t, mixed polymer of AUyl-lO ^ l-epoxyundecanoate and

The tube was purged with nitrogen, vinyl chloride sealed by solvent polymerization

and shaken in a water bath at 50 ° for 19 hours. 7.0 g of vinyl chloride were poured into a Pyrex tube,

7 g of the polymer were obtained (35% conversion 3.0 g of allyl 10,11-epoxy undecanoate, 0.1 g of acetyl peroxide,

lung); the analysis showed 48% polyacrylonitrile. From a 70 10.0 ecm acetone.

The tube was flushed with nitrogen, sealed and shaken in a water bath at 50 ° for 7 ^{1 1} ₂ hours. Recovered 3.6 g (36% conversion) of polymer; analysis found 79.2% polyvinyl chloride. The polymer had a reduced viscosity of 0.45 in cyclohexanone. Three films were cast from cyclohexanone solutions of this resin, the first containing 1% phosphoric acid, the second 1% diethylenetriamine (based on the resin weight) and the third containing no catalyst. The films were cured at 177 ° for 20 minutes; thereafter they were 81, 80 and 42% insoluble in cyclohexanone.

Example 14

Mixed polymer of allyl-10, II-epoxy undecanoate and acrylonitrile

A Pyrex tube was filled with 1.0 g of acrylonitrile, 9.0 g of allyl 10, ll-epoxy undecanoate, 10.0 ecm of acetone, 0.1 g acetyl peroxide.

The tube was purged with nitrogen, sealed and shaken in a water bath at 50 ° for 20.7 hours. Recovered 0.59 g of polymer (5.9% conversion); the analysis showed 51% polyacrylonitrile. The polymer had a reduced viscosity of 0.15 in dimethylformamide. From a dimethylformamide solution a film was cast of this resin containing 1% phosphoric acid (based on the weight of the resin). The film was cured at 177 ° for 20 minutes; thereafter it was 82% insoluble in dimethylformamide. royl peroxide, 150.0 ecm distilled water, 15 ecm one 9% aqueous solution of hydroxyethyl cellulose.

The jar was purged with nitrogen, sealed and rolled in a water bath at 45 ° for 36 hours. Recovered 27 grams of polymer (90% conversion); analysis showed 78% polyvinyl chloride.

To demonstrate the technical progress achieved with the present invention, two comparative tests were carried out.

ίο It was a vinyl chloride-allyl ^ .lO-epoxystearate copolymer with a polyvinyl chloride resin of correspondingly reduced viscosity, which with sufficient Dioctyl phthalate had been plasticized to obtain a resin with a corresponding stiffness modulus, compared to each other. The resin in each case was granulated and then pressed into samples for each test.

Example 15

20th Resin No. 1,
containing 65% Vi
nyl chloride and 35%
Allyl-9,10-epoxy-
stearate *) Resin # 2
Polyvinyl chloride,
containing 42%
Dioctyl phthalate Decreased vis-
^a 5 kosity des
Resin
tensile strenght
kg / cm ^{2 2} )
30 modulus of stiffness
kg / cm ^{2 2} )
Hardness ³ ) 0.9
123
58
64 0.9 **)
129
58
63

Copolymer of allyl 10, ll-epoxyundecanoate vinyl chloride by emulsion polymerization

15.0 g of allyl-10yl-epoxyundecanoate, 15.0 g of vinyl chloride, 0.5 g were placed in each of two pressure vessels Potassium persulfate, 150.0 ecm distilled water, 15 ecm a 5% aqueous solution of the dioctyl ester of the sodium salt of sulfosuccinic acid.

The jars were purged with nitrogen, sealed and rolled in a water bath at 45 ° for 36 hours. There was obtained 32 g of polymer (53% conversion); analysis showed 61.2% vinyl chloride.

Example 16

Mixed polymer of vinyl 10, ll-epoxy undecanoate with vinyl chloride and acrylonitrile

A Pyrex tube was filled with 12 g of vinyl chloride, 4 g of acrylonitrile, 4 g of vinyl 10 ^ l-epoxy undecanoate, 10 g Acetone, 2 ecm of a 25% solution of acetyl peroxide in dimethyl phthalate.

The tube was purged with nitrogen, sealed and ^{shaken in a water bath at 50 ° 4 x} / ₂ hours. Recovered 2.5 grams of polymer (12.5% conversion); analysis found 36% vinyl chloride, 60.8% acrylonitrile; oxygen analysis showed about 4% vinyl 10,11-epoxy undecanoate. The polymer had a reduced viscosity in dimethylformamide of 1.33. A film was cast from a dimethylformamide solution of this resin which contained 1% phosphoric acid (based on the resin weight). The film was cured at 177 ° for 20 minutes. It was then 83% insoluble in dimethylformamide.

Example 17

Mixed polymer of vinyl lQ.II epoxy undecanoate and Vinyl chloride by suspension polymerization

A pressure vessel was filled with 24.0 g of vinyl chloride, 6.0 g of vinyl-lOjll-epoxyundecanoate, 0.5 g of lau- *) 2 percent by weight aconitic acid was added to this resin as a crosslinking agent.

**) The value obtained relates to the not plasticized " Resin.

^a ) The tensile strength was determined with a Scott L-6 tensile strength meter, which operates at a uniform elongation of 122 cm per minute.

^a ) The stiffness modulus was determined according to ASTM test D 747-50 (American Society for Testing Materials). ³ ) The hardness was determined according to ASTM test D 785-51 using a hardness meter with an “A” head.

The polyvinyl chloride resin plasticized with dioctyl phthalate is completely soluble in hot methyl isobutyl ketone, while a sample of the molded polyvinyl chloride epoxy resin was 91% in hot methyl isobutyl ketone was insoluble. Thus, although the two resins originally had about the same stiffness, the vinyl chloride-allyle epoxystearate polymer becomes due to the pliable polymer's resistance to solvents can be used in a much wider range.

The polyvinyl chloride-allyl epoxystearate copolymers have a better thermal stability than the usual vinyl chloride copolymers. This increase in thermal stability is due to the epoxy component, epoxy stabilizers are in themselves customary. In the present invention, however, the epoxy component is in the polymer molecule built in and therefore cannot bloom. This stabilizing effectiveness can be seen, for example in the following comparative experiment in which a vinyl chloride allyl ^ .lO-epoxystearate copolymer with a commercially available vinyl chloride-vinyl acetate copolymer with respect to the reflection of blue light was compared. This test results in a value of 100 with a completely clear, non-colored material. The time at which a Resin can retain high reflectivity is a measure of its stability.

9 Decreased Vis
kosity of
Resin Resin No. 3
A polyvinyl chloride
rid-allyl-9,10-epoxy ~
stearate-copoly-
merisat with 86 ° / "
Vinyl chloride Resin # 4
A polyvinyl
chloride vinyl
acetate-copoly- '
merisat with 86 ° / "
Vinyl chloride Original
Colour blue
reflection ¹ ) .... 0.5 0.5 Minutes up to 75%
Blue reflection .. 87 82 Minutes up to 60%
Blue reflection .. 14th 7th 79 24

10

¹ J The color stability was determined in such a way that the samples (0.762 ram thick) were heated at 135 ° with air circulation in an oven and the discoloration with the aid of a photovoltaic reflectance meter, model 610, which was equipped with a Wratten C-5 blue object, was measured. The color was reported in percent blue light reflection against the reflection, which was obtained with a transparent, mounted on a Magnesiumcarbonatblock film which 100% of the reflected beam at one- ₂ g covered blue light.

Claims (13)

Patent claims: 1. Process for the production of resinous copolymers monoolefinically unsaturated ester of epoxy fatty acids, characterized in that a monomeric epoxy ester of the formula XCHXOY 35 in which X is an epoxyalkyl group having 8 to 16 carbon atoms and 1 or 2 epoxy oxygen atoms and Y is a monoolefinic alkyl group with a monomeric, unsaturated, organic, polymerizable Substance that is polymerized in the presence of a peroxide polymerization catalyst. 2. The method according to claim 1, characterized by the polymerization of an organic epoxy ester the formula i; R ₁ CHCHR ₂ COR in which R _{1 is} hydrogen or an alkyl group having 1 to 14 carbon atoms and R _{2 is} an alkylene chain having 1 to 15 carbon atoms, the total number of carbon atoms in R ₁ and R _{2 being} between 7 and 15, and R is an alkylene group. 3. The method according to claim 1 or 2, characterized in that the polymerizable substance is a is unsaturated aliphatic or aromatic monomer. 4. The method according to claim 3, characterized in that the unsaturated aliphatic monomer is a vinyl ester of an inorganic acid or an aliphatic carboxylic acid. 5. The method according to claim 4, characterized in that the vinyl ester of an inorganic acid Vinyl chloride, vinyl bromide, vinyl fluoride, acrylonitrile, methacrylonitrile, vinylidene chloride, vinylidene bromide or vinylidene fluoride "is used. 6. The method according to claim 4, characterized in that the vinyl ester of an organic acid Methyl acrylate, methyl methacrylate or ethyl acrylate is used. 7. The method according to claim 3, characterized in that the unsaturated aliphatic monomer a monomer with a conjugated system of double bonds or with an acetylenic Binding is used. 8. The method according to claim 3, characterized in that that the unsaturated aliphatic monomer is an unsaturated aliphatic ether of an unsaturated one polyhydric alcohol or polyalcohols is used. 9. The method according to claim 3, characterized in that the unsaturated aromatic monomer a glycidyl ether of a polyhydric phenol is used. 10. The method according to claim 3, characterized in that the unsaturated aromatic monomer Styrene, chlorostyrene or allyl styrene is used. 11. The method according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, characterized in that as a catalyst Acetyl peroxide, benzoyl peroxide, lauroyl peroxide or potassium persulfate is used. 12. The method according to claim 11, characterized in that the catalyst in an amount between 0.1 and 5% of the weight of the material to be polymerized is used. 13. The method according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, characterized in that the Polymerization at a temperature between 0 and 150 °, preferably between 40 and 60 °, carried out will. Considered publications:
U.S. Patent No. 2,680,109. © 709 607/446 2.