DE1262601B - Process for the preparation of copolymers containing cyano groups - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. α .:

C08f

German class: 39 c -25/01

Number:
File number:
Registration date:
Display day:

1262601
B79058IVd / 39c
October 24, 1964
March 7, 1968

It has been found that copolymers containing cyano groups and having advantageous properties can be obtained can be obtained if 5-cyanbicyclo- [2,2, l] -hepten- (2) with other polymerizable olefinic unsaturated compounds in a molar ratio of 1:99 copolymerized to 35:65.

5-cyano-bicyclo- [2.2, l] -hepten- (2) is an easy one mobile colorless liquid that is produced as a mixture of isomers in the synthesis of cyclopentadiene and acrylonitrile the exocompound (boiling point 19 ° C / 19 mm Hg) and the endocompound (100 ° C / 19 mm Hg) arise. The isomers which can be separated by distillation are in the usual organic solvents soluble. . '. ". ■

Suitable comonomers are, for. B. olefinically unsaturated Carboxylic acids, their esters, amides and methylolamides, vinyl esters, olefinically unsaturated ones aromatic compounds and vinyl and vinylidene halides. Examples of suitable comonomers are Acrylic acid, methacrylic acid, maleic acid, itaconic acid, methyl acrylate, butyl acrylate, propyl methacrylate, acrylic acid amide, Methacrylic acid amide, N-methylol methacrylic acid amide, vinyl acetate, vinyl propionate, styrene, α-methylstyrene, vinyl chloride and vinylidene chloride. Of these, the esters of acrylic acid with alcohols containing 1 to 8 carbon atoms are particularly suitable of the chain, as well as the vinyl esters of straight-chain monocarboxylic acids.

According to the invention, a mixture of 1 to 35 mol percent, in particular 10 to 25 mol percent, 5-cyano-bicyclo- [2.2, l] -hepten- (2) and 65 to 99 mol percent, in particular 75 to 90 mol percent, based on the sum of the monomers, polymerized.

The copolymers can be in a customary manner by the processes of emulsion, solution or Bulk polymerization using the usual catalysts and initiators, such as benzoyl peroxide, Cumene hydroperoxide, potassium peroxydisulfate, hydrogen peroxide or azodiisobutyronitrile, which are also used in Combination with reducing agents such as sodium formaldehyde sulfoxylate, sodium bisulfate, dimethylaniline or ascorbic acids, which can be used as redox systems.

It is an advantage of using the 5-cyano-bicyclo- [2.2, l] -heptens- (2), that there is a moderate regulating effect on the molecular weight during the polymerization of the copolymers and a special regulator addition is not required during the polymerization is. Another advantage of the monomers containing cyano groups used according to the invention is that the polymers produced therewith show a significantly lower tendency to yellow than such Method of manufacture

of copolymers containing cyano groups

Applicant:

Aniline & Soda Factory in Baden

Aktiengesellschaft, 6700 Ludwigshafen

Named as inventor:

Dr. Paul Raff, 6700 Ludwigshafen;

Dr. Hans Georg Peine,

Dr. Gerd Louis, 6710 Frankenthal;

Dr. Gerhard Faulhaber, 6800 Mannheim

Polymers containing cyano groups and containing acrylonitrile as polymerized units.

The copolymers obtainable according to the invention are also distinguished by their very good adhesion on inorganic substrates, such as glass, metals or ceramic materials, and are suitable therefore excellent as adhesives. The fact that bonds produced with them are colorless opened up a particularly broad and interesting area of application for the new copolymers.

The parts and percentages given in the following examples are, unless otherwise stated, Weight units. The specified K values were determined using the method of H. Fikentscher, Cellulosechemie, 13 (1932), p. 58.

example 1

1 part of 5-cyano-bicyclo- [2.2, l] -hepten- (2) (exo-isomer), 19 parts of isobutyl acrylate, 20 parts of butyl acetate and 0.05 part of azodiisobutyronitrile are heated to 80 to 90 ° C. with stirring and after the polymerization reaction has started, a mixture of 4 parts of 5-cyano-bicyclo- [2,2,1] -hepten- (2) (exo-isomer), 76 parts of isobutyl acrylate, 80 parts of butyl acetate and 0.2 parts of azodiisobutyronitrile are added dropwise. After the addition is complete and 2 ¹ I ₂ hours after this point in time, 0.25 parts of azodiisobutyronitrile are added each time. After a total of 10 hours, it is cooled down. A 48.5% strength colorless solution of a copolymer with a K value of 33, which can be used directly as an adhesive, is obtained.

: 809 517/708

Example 2

A mixture of 101.3 parts of distilled water, 0.3 parts of the sodium salt of a sulphurized reaction product of 1 mole of isooctylphenol and 25 moles of ethylene oxide (emulsifier I), 0.15 parts of the sodium salt ■ of ,, sulfonated! Castor oil (emulsifier II) and 0.3 parts potassium peroxydisulfate is introduced into a polymerization vessel and heated to 85 ⁰ C. An emulsion of 153 parts of n-butyl acrylate, 47 parts of 5-cyano-bicyclo- [2.2.1] -heptene- (2) (25 mol percent or 23.5 percent by weight of the total monomers), 3.1 Parts of emulsifier I, 0.45 parts of emulsifier II and 1 part of potassium peroxydisulfate in 403 parts of distilled water. Polymerization is then continued for 1 hour at 90.degree. C. and the polymerization batch for 1 hour at 90.degree. steamed while passing nitrogen over it. A stable, milky dispersion with a solids content of 26% is obtained. The dispersion can be applied directly to substrates and, when dried in the air, gives clear, colorless, highly tacky films that do not yellow even after heating at 130 ° C. for several hours. Copolymers of 75 mol percent butyl acrylate and 25 mol percent acrylonitrile produced under comparable conditions gave almost tack-free surfaces and yellowed to a large extent when heated to 130 ° C.

The strongly regulating effect of 5-cyano-bicyclo- [2.2, l] -heptens- (2) clearly shows a comparison of the copolymer prepared according to Example 2 with that copolymers prepared analogously from n-butyl acrylate and acrylonitrile. While the K value of the copolymer according to the invention measured in dimethylformamide 30.3, the copolymer prepared accordingly from butyl acrylate and acrylonitrile has a K value of 64.4.

Example 3

10 parts of 5-cyano-bicyclo- [2.2, l] -hepten- (2) (endo-

"Isomeres" are mixed with 90 parts of isobutyl acrylate, 100 parts of butyl acetate and 0.25 part of benzoyl peroxide. One third of this mixture is placed in a polymerization vessel and ^{heated to 85 °} C. As soon as the polymerization reaction begins, the remaining amount of the mixture is added dropwise The polymerization batch is then kept at 80 to 90 ° C. and 0.25 parts of benzoyl peroxide are added four times at intervals of 4 to 5 hours. After a total of 18/2 hours, a 48% solution of a copolymer results, which has a K- Has a value of 31. A film produced with the polymer solution on glass is clear, colorless, sticky and has excellent adhesive strength.

Claims (1)

Claim: Process for the preparation of copolymers containing cyano groups, characterized in that that 5-cyano-bicyclo- [2.2, l] -hepten- (2) with other polymerizable copolymerized olefinically unsaturated compounds in a molar ratio of 1:99 to 35:65. 809 517/708 2.68 © Bundesdruckerei Berlin