DE1111391B - Process for the production of graft copolymers - Google Patents

Description

The most important previously known processes for the production of graft and graft copolymers are based on the one hand on the chain transfer reactions worked in particular by P. J. Flory, on the other hand on interpolymerizations of olefinically monomers with olefinically polyunsaturated monomers. In the latter case, side chains can be formed from the double bonds contained in the primary chains or different monomers are grafted on.

It is also known that graft copolymers can be prepared by using linear polymers, which contain peroxidic groups or radical sites generated by high-energy rays, with polymerizable organic compounds or those containing hydroxyl groups with acyl chloride groups containing polymers.

Furthermore, in a scientific work, graft copolymers are described, which are made from copolymers of acetylaminostyrene with methyl methacrylate by nitrosating and converting the in this way obtained polymeric N-nitroso compounds with methyl methacrylate and Acrylonitrile were produced. However, the last-mentioned graft copolymers tend to The reason for the aromatically substituted amide groups contained in them to a particular degree lead to discoloration.

It has now been found that graft copolymers can advantageously be obtained by nitrosating copolymers from olefinically unsaturated aliphatic, cycloaliphatic or heterocyclic acylamines, those monosubstituted on the amide nitrogen by alkyl, alkenyl, aralkyl, cycloalkyl or cycloalkenyl groups are, and olefinically unsaturated monomers and reacting the obtained in this way Can produce nitrosated copolymers with olefinically unsaturated monomers.

Olefinically unsaturated acylamines for the purposes of the invention are, for example, N-methyl-, N-isopropenyl- and N-cyclohexyl acrylamide, N-methyl and N-CyclohexenylmethacrylamidjMethylene-dimethacrylamid, N- (2-ethylhexyl) maleic acid amide, N-benzyl maleic acid amide, Ν, Ν'-dimethyl maleic acid diamide, N-methyl linoleic acid amide, N-isopropyl fumaric acid amide, C-vinylpyrrolidones, 5-vinyl-5-isopropenyl-bar-. bituric acid and S-vinyl-S-cyclöhexenylbarbituric acid, N-oleyl-maleic acid amide, N-allyl-maleic acid amide and its esters and the allyl ester of N-carbamyl maleic acid amide.

Olefinically unsaturated monomers according to the invention for the production of graft copolymers
of graft copolymers

Applicant:

Aniline & Soda Factory in Baden

Corporation,

Ludwigshafen / Rhine

Dr. Hans Craubner, Karlsruhe,

and Dr. Adolf Hrubesch, Ludwigshafen / Rhine,

have been named as inventors

seeds can be used, are z. B. ethylene, propylene, butadiene, acrylic and methacrylic acid and their methyl, ethyl, propyl, isopropyl and dodecyl esters, acrylonitrile, styrene, α-methylstyrene, vinyl acetate and vinyl propionate, vinyl halides such as vinyl chloride and vinylidene fluoride, butyl vinyl ether, Cetyl vinyl ether, vinyl pyrrolidone, vinyl carbazole and acrylamide.

In the first stage of the process, such monomers are copolymerized in the usual way with olefinically unsaturated acylamines of the type mentioned using suitable polymerization catalysts in the block, in solution, in emulsion or in suspension. In general, proportions of 0.01 to 20% ^of such unsaturated acylamines are sufficient, but larger proportions can also be used to achieve special effects. Examples of suitable catalysts are peroxides, such as dibenzoyl peroxide and cumene peroxide, azodiisobutyronitrile or N-nitrosoacylamines.

The carbonamide groups obtained in this way and containing monosubstituted carbonamide groups on the amide nitrogen Copolymers are then, optionally after their isolation, in solid, dissolved or emulsified or dispersed state on these groups wholly or partially nitrosated. For this, the common nitrosating agents such as alkyl nitriles, sodium nitrite and dilute acids, nitrosyl chloride and Appropriately dinitrogen trioxide can be used in the gaseous or liquid state. In the

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3 4

Polymeric N-nitroso merization produced in this stage sets in by itself at room temperature. Bonds contain molecular components of the general After about an hour, quantitative conversion is a formula kicked. A graft copolymer is obtained,

which is insoluble in common solvents.
5

~ ^C - ^C - ^C - ^CC example 2

CO A mixture of 0.5 parts of the in Example 1 below

b) described nitrosated copolymer,

N no ¹⁰ 4 parts of vinyl acetate and 11 parts of methyl methacrylate are ^{polymerized at 60 °} C. for 6 hours.

ο The polymerization rate is 12%

per hour. The copolymer obtained is soluble

in which R is an alkyl, alkenyl, aralkyl, cycloalkyl in benzene, toluene, acetone and butyl acetate and has in

or cycloalkenyl group. You will think 15 benzene at 25 ° C value 19. According to the results

then in the third stage, if necessary after the chemical analysis and the ultra-red analysis

their isolation, in blocks, in solution, in emulsion or the polymer is built up from 74% methacrylic acid

in suspension with olefinically unsaturated monomers methyl ester, 23% vinyl acetate and about 3% styrene. copolymerized as mentioned above. Included

they act as polymeric, radical-forming polymers - Example 3
sation initiators to which the olefinically unsaturated

Monomers in graft reactions with formation of 100 parts of methyl methacrylate are with

growing up from side chains. The suggestion to add 2 parts of N- (2-ethylhexyl) maleic acid amide

In this stage, copolymerization can be carried out thermally and with the addition of 2 parts of N-nitroso-N-benzyl-

or optionally cocatalytically with the addition of phenacetylamide as a polymerization accelerator

Small amounts of alkaline substances, such as 6O ⁰ C for 2 hours in the block polymerized. The PoIy

Potassium carbonate, potassium or sodium hydroxide, merisate is then made from a benzene solution

Triethanolamine and piperazine, or salts by pouring them into a three to four-fold excess

the transition metals precipitated with inorganic or or- mineral spirits. Its k value in benzene at

ganic acids, such as manganese (II) - 30 25 ⁰ C is 64.

chloride, cobalt chloride or cobalt naphthenate, 2 parts of this copolymer are in 30 parts

follow. Dissolved chloroform and dissolved with careful cooling

The quantitative ratio in which the nitrosated 0 to -5 ° C and with the addition of 20 parts of liquid copolymers with olefinically unsaturated mono-N ₂ O ₃ nitrosated on the acylamide groups.
are reacted kidney, A mixture depends on the 35 of 3.6 parts of this nitrosated content of N-nitroso-carboxamide groups of mixing the copolymer and 15 parts Acrylsäurebutylpolymerisats and in the final product ester is polymerized reasonable about 2 hours at 6O ⁰ C . The aimed for degree of branching. The latter is all the greater; the average polymerization rate is approximately the higher the molar proportion of N-nitroso-carbonamide-50% conversion per hour. A graft group of the copolymer produced in the second stage of the process, which is the nitrosated copolymer of the following composition, is obtained. possesses: 64.8% C, 9.5% H, 25.5% O, less than

It is an advantage of this method that it is based on 0.5% N and 43% OC ₄ H ₉ . It dissolves in benzene, in many ways an extensive modification of the toluene, acetone, butyl acetate and other solution properties of plastics produced afterwards can be determined.

possible. For example, the solubility, 45 example4
the softening range, the impact strength, the

Printability and bondability changed. A mixture of 100 parts of acrylonitrile and 2 parts

will. Methylenedimethacrylamide and 2 parts of N-nitroso

The parts mentioned in the examples are N-benzyl-2-ethylhexane-carbonamide as polymer parts by weight. 50 ons accelerator is poly Example 1 merized ^{at 6O 0 C under nitrogen.} The polymerization is terminated after about _{2–2 hours.} Almost quatitative is obtained

a) 100 parts of styrene and 2 parts of N-benzyl-maleic yield a copolymer, which are in Dimethylsäureamid has the addition of 2 parts of N-Ni formamide at 25 ⁰ C the k value 65th
Troso-N-benzyl-succinamide as a polymerization 55 20 parts of this copolymer are polymerized onsbeschleuniger at 6O ⁰ C. After 7V ₂ careful cooling to 0 to -5 ° C and less than every hour, the polymerization is terminated, the gradual addition of 60 parts of liquid distick copolymer is dissolved in benzene and, by precipitating substance trioxide on the acylamide groups, partially nitrosein a benzene solution with the three- up to four.

times the volume of methanol isolated. The k value of the 60 A mixture of 0.3 parts of this nitrosated mixture Copolymer purified in this way is polymer, 9 parts of acrylonitrile and 6 parts 40 (benzene, 25 ^ C). Vinyl acetate is polymerized at 60 ° C for about 3 hours

b) 2 parts of this copolymer are siert under. The mean rate of polymerization careful cooling to 0 to -5 ° C and below all- is 34% per hour. That gradually in the course of the polymer The addition of 2 parts of liquid dinitrogen sationsreaktion formed graft copolymer is trioxide partially nitrosated on the acylamide groups. insoluble in common solvents. It

c) 0.45 part of the nitrosated copolymer (b) has the composition 63.8% C ₅ 6.0% H, 8.1% O are introduced into 15 parts of acrylic acid. The poly and 21.8% N.

Example 5

20 parts of a copolymer of 100 parts of styrene and 2 parts methylenedimethacrylamide are nitrosated with careful cooling to 0 to -5 ⁰ C with 60 parts of liquid dinitrogen trioxide to the acylamide partially.

A mixture of 20 parts of this nitrosated copolymer, 750 parts of styrene and 20 parts of acrylic acid The nitrosation product obtained in this way is then removed from the dinitrogen trioxide still absorbed on it and water at room temperature under reduced pressure. A nitrosated one is obtained Copolymer in which, on average, about every fifth acylamino group is nitrosated.

60 parts of this nitrosated copolymer are added to 40 parts of methyl methacrylate and the mixture is then polymerized ^{at 70 ° C. for 8 hours.}

butyl ester and 20 parts of acrylonitrile at 10. A graft copolymer is obtained which is used for

Polymerized at 70 ^° C. for 15 hours under nitrogen. A graft copolymer is obtained which is insoluble in the usual solvents. It has the composition: 85.8% C, 7.5% H, 4 ° / ₀ O and 1.7% N.

Example 6

70 parts of a conventionally composed of 10 parts of acrylonitrile, 10 parts of N-benzyl-maleic acid monoamide and 50 parts of the copolymer produced in emulsion butadiene are dissolved in 400 parts of benzene. Man cools the colloidal solution obtained to about 5 ° C and adds a solution of 1 part at this temperature Nitrosyl chloride in 20 parts of benzene. The reaction mixture is then kept at room temperature for 1 hour, the nitrosyl chloride reacts completely. Then the benzene is under reduced pressure evaporated at room temperature. 71 parts of a nitrosated copolymer are obtained as the distillation residue, in which, on average, every fourth of the acylamine groups it contains is nitrosated. ;

70 parts of this nitrosated copolymer is added with stirring to 20 parts of methyl methacrylate, the mixture was heated under nitrogen to 60 to 7O ⁰ C and then holds it for 8 hours this temperature. The reaction product obtained is a graft copolymer which is insoluble in the usual organic solvents. It is suitable, for example, as an additive to wood chips for the production of molding compounds.

Example 7

83 parts of a copolymer prepared in a conventional manner from 15 parts of styrene, 50 parts of butadiene and 18 parts of N-stearyl-maleic acid monoamide in emulsion are dissolved in about 400 parts of benzene. A solution of 2 parts of nitrosyl chloride in 20 parts of benzene is added to the solution at a temperature of about 5 ^{° C.} The reaction mixture is then _{kept at about 5 ° C. for about 2} hours and then the benzene is evaporated off at room temperature under reduced pressure. The distillation residue obtained is about 85 parts of a nitrosated copolymer in which, on average, about every second acylamine group it contains is nitrosated.

80 parts of this copolymer nitrosated to wear in 70 parts of acrylonitrile and the mixture polymerized for 12 hours at 7O ⁰ C. This gives about 150 parts of a graft copolymer which is insoluble in common organic solvents.

Example 8

A mixture of 30 parts styrene and 30 parts of N-allyl-propionamide 12 hours at 7O ⁰ C is polymerized in the usual manner in the block with the addition of 2 parts of azobisisobutyronitrile.

60 parts of this copolymer are in a closed vessel for about 1 hour with the addition of Shake parts of nitrous oxide. From that on

Can use production of molding compounds.

Example 9

80 parts of a conventionally composed of 60 parts of methyl methacrylate and 20 parts of N-isopropyl acrylamide produced and then ground copolymer are, as described in Example 8, Shaken for 1 hour in a closed vessel with the addition of 1 part of nitrous oxide. A nitrosated copolymer is obtained in which, on average, about every sixth acylamine group is nitrosated.

80 parts of this nitrosated copolymer are mixed with 80 parts of acrylonitrile and the mixture is ^{polymerized at 70 °} C. for 12 hours. A graft copolymer is obtained which is practically insoluble in the usual organic solvents.

Example 10

In the usual way, a mixture of 60 parts of vinylidene chloride, 60 parts of styrene and polymerized 12 parts of N-lauryl maleic acid monoamide with added of 3 parts of azobisisobutyronitrile for 8 hours at 70 ° C.

21 parts of the copolymer obtained are finely ground and then shaken in a closed vessel at about -5 ° C. with the addition of 1 part of nitrosyl chloride for about ¹ _1/2 hours. A completely nitrosated copolymer is obtained.

20 parts of this nitrosated copolymer are mixed with 30 parts of acrylonitrile and the mixture is ^{polymerized at 70 °} C. for 1 hour. A graft copolymer is obtained which, compared to a copolymer prepared in a conventional manner from vinylidene chloride, styrene and acrylonitrile, can be colored better by acidic and basic dyes and by vat dyes.

Example 11

A mixture of 80 parts of methyl methacrylate is polymerized and 60 parts of Ν ', Ν'-dimethylmaleic acid monoureid in the usual way with addition of 3 parts of azobisisobutyronitrile for 12 hours at 70 ° C.

40 parts of the copolymer obtained are finely ground and then shaken ^{for about 1 hour in a closed vessel at 0 ° C. with the addition of 2 parts of nitrosyl chloride.} A nitrosated copolymer is obtained in which, on average, every third acylamine group is nitrosated.

40 parts of this nitrosated copolymer are mixed with 40 parts of acrylonitrile and 1 part of azobisisobutyronitrile and the mixture for 12 hours at 7O ⁰ C polymerized. A graft copolymer is obtained which is in comparison with conventional

Way produced polyacrylonitrile can be colored better by basic dyes.

Example 12

A mixture of 100 parts of N-cyclohexyl-maleic acid monoamide and 135 parts of styrene is polymerized and 65 parts of one in the usual manner in a molar ratio of 2: 1: 3.1 from phthalic acid, maleic acid and Propylene glycol made polyester, which has the acid number 40, with the addition of 2 parts of dibenzoyl peroxide 6 hours at 60 ° C.

300 parts of the copolymer obtained are finely ground and then with the addition of 15 parts of nitrosyl chloride for about 1 hour at 0 ° C in a closed vessel. You get about 315 parts of nitrosated copolymer, in which, on average, every third acylamine group is nitrosated is.

100 parts of vinylidene chloride and 10 parts of vinylpyrrolidone and 1 part of azobisisobutyronitrile are added to 300 parts of this nitrosated copolymer in an autoclave, and the mixture is polymerized for 8 hours at ^60.degree. C. A graft copolymer is obtained which is insoluble in the usual organic solvents and which is not Can be colored better with acidic, basic and azo dyes compared to cured polyester resins. Its softening point is around 200 ^° C.

Example 13

355 parts of a copolymer prepared in a conventional manner from 600 parts of methyl methacrylate and 40 parts of N-isooctylmaleic acid monoamide are finely ground and the powdered copolymer is suspended in 3000 parts of water. 100 parts of sodium nitrite are added to this suspension and 200 parts of 20% strength hydrochloric acid are ^{then added dropwise at 0 ° C. with stirring.} When the reaction mixture is filtered, about 360 parts of nitrosated copolymer are obtained as filter residue.

350 parts of this nitrosated copolymer are mixed with 1500 parts of acrylonitrile and the Mixture polymerized for 12 hours at 65 ° C under nitrogen. After separating from the unchanged Acrylonitrile is obtained about 1300 parts of a graft copolymer, which in the usual organic Is insoluble in solvents.

Example 14

10 parts of a finely powdered and in a conventional manner, 100 parts of styrene and 2 parts of methylene dimethacrylamide copolymer produced are shaken for about 1 hour in a closed vessel at about 0 ⁰ C with the addition of 1 part of nitrosyl chloride. A completely nitrosated copolymer is obtained.

A mixture of 10 parts of this nitrosated copolymer and 20 parts of acrylic acid is ^{polymerized at 70 °} C. for 8 hours. A graft copolymer is obtained which is insoluble in the usual organic solvents and which can be used as an ion exchange resin.

Example 15

35 parts of finely powdered and made in conventional manner from 15 parts of vinyl chloride, 15 parts vinyl propionate and 5 parts of N-allyl-maleic acid amide copolymer are shaken with the addition of 1 part of nitrosyl chloride for about 1 hour in a closed vessel at about 0 ⁰ C. A nitrosated copolymer is obtained in which, on average, about every second acylamine group is nitrosated.

35 parts of this copolymer nitrosated be added with stirring to 100 parts of acrylonitrile and the mixture polymerized for 10 hours at 6O ⁰ C. About 135 parts of a graft copolymer are obtained which, in comparison with a copolymer prepared in a conventional manner from acrylonitrile, vinyl chloride and vinyl propionate, can be more easily colored with basic dyes.

Claims (1)

PATENT CLAIM: Process for the production of graft copolymers from copolymers of olefinically unsaturated aliphatic, cycloaliphatic or heterocyclic acylamines which are monosubstituted on the amide nitrogen by alkyl, alkenyl, aralkyl, cycloalkyl or cycloalkenyl groups, with other olefinically unsaturated monomers characterized in that these copolymers are nitrosated on the amide nitrogen and the nitrosated copolymers are reacted with olefinically unsaturated monomers to form graft copolymers. Considered publications:
German Auslegeschriften Nos. 1 015 226, 1 047 437; Belgian patents Nos. 565 853, 577 837;
French Patent No. 1,191,318;
PJ Flory, Principles of Polymer Chemistry, 1953. p. 260; Roger K. Graham, Journ. Polymer Sci., 24, pp. 367 to 382 (1957); G. Smets, Ind. Chim. beige, 18, pp. 785 to 794 (1953);
P. Piganiol, Kunststoffe, Vol. 48 (1958), pp. 398f.