DE1216546B - Process for the production of 1,3-diene polymers in aqueous emulsion - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. α .:

C08d

German class: 39 c - 25/05

Number:
File number:
Registration date:
Display day:

1216 546
B76185IVd / 39c
April 4, 1964
May 12, 1966

The subject of patent 1187 800 is a method for the production of elastomeric 1,3-diene polymers by polymerizing 1,3-dienes, in the 1,3-dienes in aqueous emulsion using catalysts

a) Chelate complex compounds of trivalent chromium, manganese and / or cobalt and or or of tetravalent cerium and / or of divalent copper with 1,3-dicarbonyl compounds and

b) organic halogen compounds indifferent to water are polymerized.

Copolymers of 1,3-dienes with up to 50 percent by weight can also be prepared using this process other ethylenically unsaturated compounds, such as especially esters «, ^ - unsaturated Carboxylic acids, acrylonitrile, methacrylonitrile, vinyl aromatic compounds and vinyl ethers are produced will. Butadiene, isoprene and 2,3-dimethylbutadiene are used as 1,3-dienes for this process and 2-vinylbutadiene alone or in any desired mixing ratios with one another, and Butadiene is preferred.

It has now been found that elastomeric 1,3-diene polymers can be produced by polymerization of 1,3-dienes in aqueous emulsion using catalysts

a) Chelate complex compounds of trivalent chromium, manganese and / or cobalt and or or of tetravalent cerium and / or of divalent copper with 1,3-dicarbonyl compounds and

b) organic halogen compounds indifferent to water according to patent 1187 800 with special Can produce advantage by carrying out the polymerization in the presence of ammonia and / or water-soluble amines. As chelate compounds and halogen compounds, the same substances are suitable as also for the process of the patent 1187 800 come into question, and the catalyst components are used in the same proportions.

The water-soluble amines suitable for the process can optionally be hydrophilic and hydrophobic Carry substituents. Suitable are e.g. B. straight-chain, branched and cycloaliphatic amines, such as ethanolamine, triethylamine, tripropylamine, trin-butylamine, diethylamine, dipropylamine, di-tert.-butylamine, Methylamine, ethylamine, hexamethylene

Process for the production of
1,3-diene polymers in aqueous emulsion

Addendum to the patent: 1187 800

Applicant:

Aniline & Soda Factory in Baden

Aktiengesellschaft, Ludwigshafen / Rhein

Named as inventor:

Dr. Herbert Naarmann, Ludwigshafen / Rhine;

Dr. Ernst-Günther Kastning, Assenheim

diamine and ethylenediamine, aromatic amines such as aniline, dimethylaniline, toluidines, xylidines, benzylamine, Phenylethylamine, ephedrine and p-oxyphenylethylamine.

The amount of ammonia or water-soluble amines can be used in the process within wide limits can be varied. In general, from 2 to 50 percent by weight, based on the amount, is used of monomers. The amount range from 5 to 25 percent by weight, based on the amount of monomers, proven. The ammonia and amines of the type mentioned can be used in the Process can be used alone or in any mixtures with one another.

The method makes it possible in the polymerization of the 1,3-dienes using the aforementioned Catalysts, the Defo value and the elastic content of the diene polymers, in particular of polybutadiene to regulate reproducibly.

In addition, if the process is worked up in the customary manner, polymers are obtained which are very little contaminated by catalyst residues. The process enables the production of polymers whose elastic content (measured in accordance with DIN 53 514) is from about 8 to 30 ° / ₀ . The higher the amine and / or ammonia concentration during the polymerization, the higher the Defo value of the polymers obtained. It can be reduced to around 150 with the new process. Polybutadienes that have such a low Defo value have no stability and flow.

609 568/589

The parts mentioned in the following examples are parts by weight. The K values given therein were based on H. Fikentscher "Cellulose Chemie", Vol. 13 (1932), p. 58, determined in benzene.

example 1

To a mixture of 40 parts of water, 3 parts of a 10% aqueous Kaliumstearatlösung and 5 parts of 25 ° / ₀ aqueous ammonia solution are to 0.5 parts of cobalt (III) acetylacetonate and 0.5 part carbon tetrachloride. The mixture is heated to 60 ° C. and 20 parts of butadiene are added with stirring. After 10 hours of polymerization at 60 ° C., a polybutadiene dispersion having a dry content of 15.7 percent by weight is obtained. The polybutadiene has a K value of 82.5, the Def o-value of 725 and an elastic component of 36. The resulting by 1,4-addition of the polymer is about 90 ° / _0th

If 10 parts of the 25% strength aqueous ammonia solution are used in the polymerization, this gives a polybutadiene dispersion is made under otherwise identical conditions, whose dry content is 14.2 percent by weight. The polybutadiene then has a K value of 80.5, a Defo value of 650 and a elastic proportion of 27.

Example 2

To a mixture of 40 parts of water, 3 parts of 10 ° / ₀ aqueous Kaliumstearatlösung and 5 parts of 25 ° / ₀ aqueous ammonia solution are to 0.5 parts KobaltillQ acetylacetonate and 0.5 parts carbon tetrachloride. The mixture is heated to 60 ° C. and a mixture of 20 parts of butadiene and 5 parts of styrene is added. After 10 hours of polymerization, a copolymer dispersion is obtained which has a dry content of 16.3 percent by weight. The K value of the butadiene-styrene copolymer obtained is 78, its glass transition temperature -60 ° C.

The procedure is as above, but the ammonia solution is replaced by 5 parts of a 10% aqueous tri-butylamine -Solution, a product with the same properties is obtained.

Example 3

To a mixture of 50 parts of water, 3 parts of 10% aqueous sodium ^outputs solution and 10 parts of 2O ° / cent aqueous methylamine solution, 0.1 parts of copper (II) acetylacetonate, 0.4 parts of manganese (III ) acetylacetonate and 0.2 parts of amyl chloride. Man

ίο then heated to 40 ° C and added a mixture of 3 parts of butadiene and 10 parts of acrylic acid n-butyl ester. After 20 hours of polymerization at 40 ° C., a copolymer dispersion is obtained whose dry content is 29 percent by weight. The copolymer has a K value of 73, the Defo value 875 and an elastic portion of 36. Its glass transition temperature is -62 ⁰ C.

Work as above, but instead of the methylamine solution, 1 part aniline and 2 parts ethanolamine added, a polymer with a K value of 84.5, a Defo value of 950 and an elastic one Received share of 37.

Claims (1)

Claim: Process for the production of elastomeric 1,3-diene polymers by polymerization of 1,3-dienes in aqueous emulsion using catalysts a) Chelate complex compounds of trivalent chromium, manganese and / or cobalt and / or of tetravalent cerium and / or of divalent copper with 1,3-dicarbonyl compounds and b) organic, water-indifferent halogen compounds according to patent 1187 800, d adurch characterized in that the polymerization in the presence of ammonia and / or of water-soluble amines is carried out. 609 568/589 5.66 © Bundesdnickerei Berlin