DE1669843B2 - Process for the production of crosslinked polymers - Google Patents

Description

saturated carboxylic acid esters, vinyl acetate, acrylonitrile, acids.

Vinyl chloride, vinylidene chloride, butadiene, isoprene, 20 rubbersLutic products with excellent

Ethylene, propylene, etc. by adding olefinic properties are also obtained when mixed

unsaturated monomers containing more than one gene of such olefinically unsaturated elastomers

Contain double bond in the molecule, with increased copolymers of monoolefins and vinyl esters.

Temperature with radical generator !, to be crosslinked. z. B. a copolymer of ethylene and vinyl

Such polyunsaturated monomers are acetate, with the addition of polymeric allyl or meth-

z. B. divinylbenzene, trivinylbenzene, esters of multiple allyl esters are crosslinked.

Valuable alcohols with olefinically unsaturated car-

carboxylic acids, such as B. glycol dimethacrylate, esters of mers from the series of polyester urethanes or poly-

polybasic acids with olefinically unsaturated ether urethanes, such as. B. the conversion products

Alcohols such as B. phthalic acid diallyl ester, o-silica 3 ° polyesters based on adipic acid, succinic acid or

acid tetra-allyl ester, phosphoric acid triallyl ester, olefi- a phthalic acid and ethylene glycol, propylene glycol,

nically unsaturated ethers, such as B. Di- and Trialhl- 1,3-propanediol, butanediol, 1,6-hexanediol, diethylene

ethers of glycerol, also compounds such as triglycol or dipropylene glycol, with diisocyanates such as

acryloyl perhydro-s-triazine or triallyl cyanurate. Tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate,

It has now been found that particularly advantageous 35 1,5-naphthylene diisocyanate or hexamethylene diisocyanate

Results with regard to the physical cyanate and the polyurethanes from these diisocyanates

properties such as temperature resistance, solvents and polyethylene glycol, polypropylene glycol, poly-

resistance and aging resistance then achieved tetrahydrofuran or polyhexamethylene glycol.

If allyl as crosslinking components, it was also found that products with

or polymers containing methallyl ester groups ₄₀ valuable properties. If the

can be used, such as B. the allyl or methallyl described polymeric allyl or methallyl esters

esters of homopolymers of unsaturated mono-

carboxylic acids, such as acrylic or methacrylic acid, and saturated mono- and dicarboxylic acid esters are used

unsaturated dicarboxylic acids or their anhydrides. For example, polymers are suitable

such as maleic acid, fumaric acid, itaconic acid or their 45 acrylic acid or methacrylic acid alkyl and hydroxy

Copolymers with styrene, methyl styrene, vinyl toluene, alkyl esters with one another and their copolymers

Halostyrene, vinyl ethers, vinyl acetate, isoprenylsate with unsaturated monomers, such as. B. styrene,

acetate, acrylic and methacrylic acid esters ^ vinyl halo-a-methylstyrene, vinyl toluene, acrylonitrile, acrylamide,

nides, such as vinyl chloride and vinylidene chloride, oils, acrylic or methacrylic acid, vinyl esters, such as vinyl

fines, such as ethylene, propylene, butadiene, isoprene, di- 50 acetate.

pentene and / or nitriles, such as acrylonitrile and vinyl, the mixed polymers of mono- and di-

deneyanid. esters of unsaturated dicarboxylic acids and the other

The preparation of the polymeric allyl or methallyl monomers can be carried out according to the invention

esters can be carried out by various processes, the processes according to the invention are crosslinked, as well as

z. B. one can polymers, the anhydride groups 55 the homopolymers of the as Copolymerisationskom-

contain, react with the unsaturated alcohols, components already mentioned vinyl esters, preferred

or one can use allyl esters of easily polymerizing vinyl acetate.

Acids polymerize. Mixtures of the polymers can be used in each

The most suitable are products that are used according to the desired proportions. the

drive the DT-OS 1 720 393 were thereby obtained, 60 combinations can be 0.5 to 99.5 percent by weight

that contain polymers containing carboxyl groups or of polymeric allyl esters.

Copolymers with alkenyl halides, preference is given to using combinations

Allyl or methallyl chloride, which 1.0 to 20% polymeric allyl or methallyl chloride

Such polymeric allyl esters provide particularly containing esters.

favorable results when used as a crosslinking agent 65 The mixing of the components can in itself be

in the processing of elastomers or thermo-known way, z. B. in a Banbury mixer or

Plastics that are both saturated and unsaturated are produced in a rolling mill, with different ones

can be used. Additives such as fillers, pigments, crosslinking

Catalysts, anti-aging agents and other additives can be introduced. The mixing can erfeigen at temperatures of about 20 to 150 ⁰ C, preferably, however, carried out at temperatures of about 50 to 100 ⁰ C. After deforming c. f ilgt crosslinking the polymer mixtures at temperatures between 50 and 250 ⁰ C, preferably between 100 and 200 ⁰ C over a period of 1 to 30 minutes. In contrast to the starting materials, the crosslinked products are insoluble in the usual organic solvents.

It is also possible to carry out the mixing in solution, since some of the polymers are chlorinated Is soluble in hydrocarbons and other solvents.

Suitable crosslinking catalysts are compounds which decompose at elevated temperature with the formation of free radicals, for example azo compounds (such as azodiisobutyronitrile, azodicarboxylic acid esters) or peroxides such as benzoyl peroxide, di- * ° chlorobenzoyl peroxide, tert-butyl hydroperoxide, peroxide, tertiary dicarbonate, cyclohexanone .-Butyl perbenzoate, polyfunctional peroxides, such as polymeric phthalyl peroxide or adipic acid-bis-tert-butyl perester, also persulfates, perborates. Particularly suitable ² S, however, are peroxides which, at temperatures below 100.degree. C., have such a low rate of decomposition that they do not cause crosslinking when incorporated into the polymers, but disintegrate rapidly at higher temperatures of up to 250.degree. Such peroxides are e.g. B. Di-terL-alkyl peroxides, such as di-tert-butyl peroxide, 2,5-bis-tert-butylperoxy-2,5-dimethylhexane, di-tert-amyl peroxide and di (aralkyl) peroxides, such as bis - (A, * - dimethylbenzyl) peroxide.

The free radical formers are preferably used in amounts of 1 to 10 percent by weight and through Rolling or kneading added to the polymers.

In addition to the radical formers mentioned, fillers such as carbon black, silica, calcium silicate, Titanium dioxide, zinc sulfate, zinc oxide, clay, calcium carbonate, pigments, phenol-formaldehyde resins, Plasticizers and anti-aging agents are added.

The mixtures to be crosslinked according to the process of the invention are suitable for Production of elastic shapes, such as seals and profiles or as coating compounds for Textiles, wood and metal.

If rubber elastomers are also used, the ozone resistance in particular is increased.

The parts given in the following examples are parts by weight.

B e i s ρ i e

Vinyl acetate-ethylene copolymer
(Monomer weight ratio: 45:55)

Butadiene-styrene copolymer (monomer weight ratio:
70:30)

Natural rubber
(light crepe)

Active silica

Anti-aging agents ...

Titanium dioxide

Dioctyl phthalate

Dicumyl peroxide

Allyl ester of the copolymer of maleic anhydride and
Dipents

Allyl polyacrylate.

Allyl ester of a styrene maleic anhydride
Copolymer

1 (Tci'-v

100

30 1.0 5.0 5.0 1.5

(Parts)

100

30 1.0 5.0 5.0 1.5

2.0

(Parts)

100

30 1.0 5.0 5.0

1.5

5.0

IV (parts)

30th
1.0

5.0
5.0
1.5

10.0

V Vl VIl VIII IX (Parts) (Parts) (Parts) (Parts) (Parts) 100 100 50 50 ■ - 50 - - -._. - 50 100 30th 30th 30th 30th 30th 30th 30th 30th 30th 30th 30th 30th 30th 30th 30th 5.0 5.0 5.0 5.0 5.0 1.5 1.5 1.5 1.5 1.5 5.0 5.0 5.0 5.0 - _ .. - 5.0

The mixtures listed in the table were produced on a roller mill at room temperature and then crosslinked ^{at 150 ° C. for 25 minutes.}

The test specimens produced were tested for their resistance to solvents. After 24 hours Storage at 30 ° C in toluene or chloroform gave the following ratings:

No.

I.
II

toluene

completely solved partially solved

chloroform

completely resolved
partially resolved

continuation

No.

Ill

IV
V

VI

VII

VIII

IX

toluene

swollen weak swelling

the same

the same. Practically unchanged

the same

the same

chloroform

swollen

practically unchanged

weak swelling

the same
practically unchanged

the same

the same

Example 2

Copolymer of ethyl acrylate

ester 80 Tl.

Acrylic acid 18 Tl.

Acrylamide 2 Tl.

Copolymer of ethyl acrylate

ester 80 tsp

Acrylic acid 15 TI.

Vinyl acetate 5 Tl

Copolymer of ethyl acrylate

ester 80 TI.

Acrylic acid 18 Tl.

Methacrylic acid oxethyl ester .. 2 TI.

Dicumyl peroxide

Allyl ester of the copolymer of maleic anhydride and dipentene (1: 1)

Allyl ester of a styrene-maleic anhydride 1: 1 copolymer ...

Allyl ester of vinyl methyl ether maleic anhydride-l : 1 copolymer

100 Tl.

2.5 TI.

5.0 Tl.

100 Tl.

2.5 TI.

5.0 TI.

100 TI.

2.5 TI.

5.0 Tl.

100 Tl.

2.5 TI.

5.0 TI.

TI.

2.5 Tl.

5.0 TI.

100 TI.

2.5Tl.

5.0 TI.

100 TI.
2.5 TI.

5.0 Tl.

100 tl. 2.5 tl.

5.0 Tl.

100 tl. 2.5 tl.

5.0 TI.

The polymeric allyl esters and dicumyl peroxide were added to the copolymers, which were in the form of 35% methanolic solutions. The mixtures obtained in this way were applied to textile fabrics. After evaporation of the solvent, the thus-coated fabric was not treated with tissue at 150 ⁰ C within 1 to 2 minutes under 2 atmospheric pressure pressed.

The thus joined pieces of tissue were stored for hours at 30 to 4O ⁰ C in trichlorethylene. The bonding was not impaired in the case of the examples given. In analogous tests without the addition of the polymeric allyl esters as crosslinkers, the bonded parts peeled off after a short time (30 minutes to 2 hours).

Claims (1)

As examples of elastomers or thermoplastics Potent claim: are listed: homo- and copolymers of Monoolefins such as ethylene, propylene, iso- Process for crosslinking natural and / or butylene, styrene or vinyl esters, such as. B. vinyl acetate, synthetic crosslinkable homo- and copoly- 5 vinyl chloroacetate, vinyl formate, vinyl benzoate. merisate by mixing the polymers with a suitable olefinically unsaturated elastomer, the Renewed with the addition of radical formers, it is crosslinked by the process according to the invention heats, characterized in that are, for example, natural rubber and elasto- the crosslinking agents used are allyl or methallyl ester groups, polymers of open-chain, conjugated dienes pen containing polymers used. io with 4 to 8 carbon atoms, 1,3-butadiene, isoprene, 2,3-dimethylbutadiene-1,3,3-chloroprene and elastomers Copolymers of conjugated dienes of this type which are copolymerized with one another or copolymers of the mentioned diolefins with monoolefi- 15 nically unsaturated monomers, such as. B. styrene, Λ-methylstyrene, acrylonitrile, acrylic or methacrylic It is known that a wide variety of polymers, acids and their esters, vinylidene chloroJ-i, vinyl such as B. homo- and copolymers of styrene, unpyridine, and monoesters of unsaturated dicarbon