CS255461B1 - N-aryl-4-substituted-4-cyclohexene-1,2-dicarboximide copolymers and processes for their preparation - Google Patents

Abstract

The essence of the solution is copolymers of N-aryl-4-substituted 4-cyclohexene-1,2-dicarboximide in which the aryl is phenyl, bromophenyl, chlorophenyl, tribromophenyl, pentabromophenyl and pentachlorophenyl and the substituent is a hydrogen atom, chlorine or CH2 group, with vinyl or pulp monomers selected from the group consisting of esters of acrylic or methacrylic acid with 1 to 2 carbon atoms in the alcoholic residue, 2-chloro-1,3-butadiene, styrene and N-phenylmaleimide, wherein the molar ratio of the substance of general formula I to the comonomer can vary from 0.01 to 50. They can be produced by treating the appropriate mixture of monomers with a radical polymerization initiator at the temperature of decomposition of the initiator into initiating polymerization centers.

Description

The invention relates to copolymers of N-aryl-4-substituted-4-cyclohexene-1,2-dicarboximide.

The present invention provides copolymers of the N-aryl-substituted 4-cyclohexene-1,2-dicarboximide of formula I

wherein the aryl is phenyl, bromophenyl, chlorophenyl, tribromophenyl, pentabromophenyl and pentachlorophenyl and X is hydrogen, chlorine or CH 2 with vinyl or pith monomers selected from the group consisting of acrylic or methacrylic esters of 1 to 2 carbon atoms in the alcoholic 2-chloro-1,3-butadiene (chlorprene), styrene and N-phenylmaleimide, wherein the molar ratio of the compound of formula I to the comonomer can vary from 0.01 to 50.

Copolymers of compounds of formula I have not been prepared. The process according to the invention can be prepared by mixing a monomer of the formula I with vinyl or pith monomers selected from the group consisting of esters of acrylic or methacrylic acid having 1 to 2 carbon atoms in the alcohol residue, 2-chloro-1,3-butadiene , styrene, and N-phenylmaleimide act as initiators of radical polymerization at initiator decomposition temperatures to initiate polymerization centers. In general, all known compounds known to be radically homopolymerized or copolymerized with other unsaturated compounds, e.g. with esters of acrylic or methacrylic acid, with styrene, butadiene, acrylonitrile, 2-methyl-1,3-butadiene, 2-chlorobutadiene, acrylamide, vinyl chloride, vinylidene chloride, vinyl acetate.

Because of the high molecular weight of the monomers of formula (X) and their relatively high melting point, their homogeneous mixing with other monomers is usually achieved by the addition of a solvent such as a chlorinated or aromatic hydrocarbon, alcohol, ether, acetone, N, N-dimethylformamide, dimethylsulfoxide, tetrahydrofuran or tetrahydrofuran. 1,4-dioxane, into the polymerization mixture.

Any conventional initiator or initiator system used in the free radical polymerization of known monomers with olefinic C = C bonds in the molecule can be used to initiate copolymerization of the monomers of formula (I). Depending on the nature of the initiator or initiator system used, the polymerization temperature is chosen such that the initiator decomposes into free radicals at a sufficiently rapid rate.

Methods for copolymerizing compounds of formula I are illustrated in the following examples.

Example 1

Polymerization batch containing 1.79 g of N- (2,4,6-tribromophenyl) -4-methyl-4-cyclohexene-1,2-dicarboximide, m.p. 144 [deg.] C., 0.65 g of N-phenylmaleinimide and 0.02 g of 2,2'-azobis (iso3 butyronitrile) in 7.5 cm of chloroform are dehumidified in a glass dilatometer by alternate evacuation and flushing with nitrogen, the dilatometer is sealed and leave in a thermostat at 50 ° C for 50 hours. A five-fold amount of ethanol then precipitates a white powder copolymer (0.85 g, i.e. 34.8% conversion) in solution. This, after precipitation with ethanol from the chloroform solution, contains 55.86% C, 3.54% H, 6.01% N and 20.19% Br, corresponding to 42.60% by weight (21% by mol) of substituted 4-cyclohexene -1,2-dicarboximide in copolymers (calculated from the determined C content).

Example 2

A solution of 2.11 g of N- (2,4,6-tribromophenyl) -4-methyl-4-cyclohexene-1,2-dicarboximide, 0.42 g of methyl methacrylate and 0.03 g of 2 was polymerized in the same manner as in Example 1. 2'-azo-bis (isobutyronitrile) in 8.8 cm @ 3. chloroform. The prepared white copolymer (1.19 g, i.e. 47% conversion) was precipitated with hexane from a chloroform solution. Found composition 54.37% C, 7.41% H, 0.70% N and 16.91% Br corresponds to 25.2% (6.59% mole) of substituted 4-cyclohexene-1,2-dicarboximide in copolymers .

Example 3

A solution of 1.99 g of N- (2,4,6-tribromophenyl) -4-methyl-4-cyclohexene-1,2-dicarboximide, 1.30 g of styrene and 0.03 g of 2 is polymerized in the same manner as in Example 1. Of 2'-azobis (isobutyro nitrile) in 8.3 cm @ 3 of chloroform. The white copolymer obtained (0.70 g, i.e. 21.3% conversion) contains 86.06% C, 7.25% H and 0.29% N after ethanol precipitation from tetrahydrofuran solution, corresponding to 11.36% by weight (2%). 71 mole% of substituted 4-cyclohexene-1,2-dicarboximide in copolymers.

Example 4

A mixture of 1.52 g of N- (2,4,6-trichlorophenyl) -4-chloro-4-cyclohexene-1,2-dicarboximide, m.p. 150 DEG C., 0.72 g of N-phenylmaleimide and 0.03 g

2.2 ^1- azo-bis (isobutyronitrile) in 8.3 cm @ 3 of chloroform. 0.83 g of white copolymers (37% conversion) is obtained, which is precipitated with ethanol from a chloroform solution. According to the amount of carbon found (57.52%), it contained 50.86% by weight of substituted 4-cyclohexene-1,2-dicarboximide (32.93% by mole).

Example 5

A solution of 1.42 g of N- (2,4,6-trichlorophenyl) -4-chloro-4-cyclohexene-1,2-dicarboximide (0.41 g styrene and 0.03 g 2) was polymerized in the same manner as in Example 1, 2'-azobis (isobutyronitrile) in 7.8 cm @ 2; chloroform. The copolymer was precipitated with ethanol from a chloroform solution. Conversion: 0.23 g ie 12.6%. The found content of 73.43% C corresponds to 40.76% by weight (16.41% by mol) of the substituted 4-cyclohexenedicarboximide.

Example 6

In the same manner as in Example 1, a batch of 1.52 g of N- (2,4,6-trichlorophenyl) -4-chloro-4-cyclohexene-1,2-dicarboximide was polymerized with 0.42 g of methyl methacrylate and 0.03 g of 2, Of 2'-azobis (iso3 butyronitrile) in 8.3 cm @ 3 of chloroform. The copolymer obtained (1.50 g, i.e. 77.3% conversion) contains, after hexane precipitation from a chloroform solution, 49.01% C, which corresponds to 78.81% (50.5% by weight) of substituted 4-cyclohexene-1. Of 2-dicarboximide in the copolymer.

Example7

A mixture of 1.72 g of N- (2,3,4,5,6-pentachlorophenyl) -4-methyl-4-cyclohexene-1,2-dicarboximide, m.p. 174 DEG C., 0.72 g of N-phenylmaleinimide and 0.04 g of benzoyl peroxide in 8.3 cm @ 3 of chloroform. 1.36 g of white copolymers (55.7% conversion) are obtained, which, after precipitation with ethanol from a chloroform solution, contains 52.05% C, i.e. 67.12% by weight of substituted 4-cyclohexene-1,2-dicarboximide (46, 09 mole%).

Example 8

A solution of 0.64 g of N- (2,3,4,5,6-pentabromophenyl) -4-methyl-4-cyclohexene-1,2-dicarboximide, m.p. 187 [deg.] C., 0.52 g of N-phenylmaleinimide 3 and 0.016 g of 2,2 ' -azzo-bis (isobutyronitrile) in 5 cm chloroform in a glass ampoule. The obtained white copolymer (0.60 g, i.e. 51.7% conversion) contains 57.37% C after ethanol precipitation from chloroform solution, corresponding to 29.23% (10.11% by mole) of substituted 1-cyclohexene-1. , 2-dicarboximide.

Example 9

In the same manner as in Example 1, a batch of 0.76 g of N- (2,4,6-trichlorophenyl) -4-chloro-4-cyclohexene-1,2-dicarboximide, 0.55 g of chloroprene and 0.33 g of 2 are polymerized. Of 2'-azobis (isobutyro nitrile) in 7.2 cm of chloroform. The white copolymer (0.94 g, m.p. 71.8% conversion) was precipitated with ethanol from a chloroform solution. The content of 48.9% C found corresponds to 65.85% (31.9% by weight) of substituted 4-cyclohexene-1,2-dicarboximide in the copolymer.

The copolymers of N-aryl-4-substituted-4-cyclohexene-1,2-dicarboximide burn in the flame of the gas burner, but extinguish outside the flame. They can therefore be used for polymer articles with the desired reduced flammability.

Claims (3)

Copolymers of N-aryl-4-substituted 4-cyclohexene-1,2-dicarboximide of the general formula I in which the aryl is phenyl, bromophenyl, chlorophenyl, tribromophenyl, trichlorophenyl, pentabromophenyl and pentachlorophenyl and the substituent X is H, Cl or CH with vinyl or diene monomers selected from the group consisting of an ester of acrylic or methacrylic acid having 1 to 2 carbon atoms in the alcohol residue, 2-chloro-1,3-butadiene, styrene and N-phenylmaleimide, wherein the molar ratio of the compound of the formula It can also vary from 0.01 to 50 to the comonomer. 2. A process for the preparation of copolymers according to claim 1, characterized in that the monomer of the formula I is mixed with vinyl or diene monomers selected from the group consisting of esters of acrylic or methacrylic acid having 1 to 2 carbon atoms in the alcohol residue, 2-chloro-1. 3-butadiene, styrene, and N-phenylmaleinimide act to initiate radical polymerization at initiator decomposition temperatures to initiate polymerization centers. 3. Process according to claim 2, characterized in that the homogenization of the reactants is facilitated by the addition of a solvent to the polymerization mixture.