DE1268396B - Process for the preparation of a graft copolymer - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY GERMAN S / MTW> PATENT OFFICE

EDITORIAL

Int. Cl .:

C08f

German class: 39 c - 25/05

Number: 1268 396

File number: P 12 68 396.4-44

Filing date: February 18, 1964

Opening day: May 16, 1968

It is known that certain unsaturated organic oils are polymerizable and that conjugated drying oils such as tung oil, together with monomeric dienes, are very highly viscous reaction products result. It is also known for the production of high-impact polystyrene to use the monomeric Styrene with 1 to 15 parts of a rubbery polymer of a conjugated diolefin for heating and 0.5 to 5 percent by weight of a higher fatty acid to distribute the heat of reaction produced or to add an ester thereof. This creates resin-like thermoplastic solids. aside from that it is known that sodium-butadiene polymers graft polymerization with over 10% of unsaturated Monomers, including esters, can be subjected to modification, the Use of a maleic acid-castor oil-glycol condensation product shown together with styrene monomers. This results in largely solvent-free Lacquer systems for insulating wire enamels.

However, these processes do not allow for increased rebound resilience or improved flow properties high molecular weights, improved aging resistance of vulcanized films, better solubility in common solvents and oils, extensive use in rubber tracks and excellent Recognize vulcanization features.

The object of the invention is now the production of graft copolymers with the specified properties, suitable for mastic compounds, surface coatings, rubber and plastic auxiliaries and useful for reinforcing resins by co-heating a mixture containing a polymer of butadiene and an unsaturated organic oil or a derivative thereof.

The process of the invention consists in that 95 to 1 percent by weight of a gel-free polymer of butadiene with unbranched linear structure containing at most 10% 1,2-bonds with 5 to 99 percent by weight of an unsaturated organic vegetable or animal oil or a derivative thereof heated ⁰ C in the presence or absence of a solvent and / or a catalyst to a temperature of 50 to 35O.

Preferred embodiments consist of heating in the range from 50 to 290, in particular 150 to 290, makes a vegetable oil, especially linseed oil, soybean oil, as unsaturated oil, Olive oil, coconut oil, corn oil or wood oil, or an oil from the sea, especially cod liver oil or whale oil, begins.

If the proportion of oil is below 85 or above 95% process for the production of a
Graft copolymers

Applicant:

The International Synthetic Rubber Company

Limited, Southampton, Hampshire

(Great Britain)

Representative:

Dr. W. Müller-Bore, Dipl.-Ing. H. Gralfs
and Dr. G. Manitz, patent attorneys,
3300 Braunschweig, Am Bürgerpark 8

Named as inventor:

Edward William Duck,

Paul Simmons,

Dibden Purlieu, Hythe, Hampshire

(Great Britain)

Claimed priority:

Great Britain 19 February 1963 (6723)

a solvent is preferably used.

A catalyst is expediently used at a low temperature.

Suitable unsaturated organic oils also include derivatives thereof, in particular dehydrated castor oil is preferred. The expression

"Oil from the sea" means oils made from organisms living in the water.

The polymer can be polybutadiene, and it is preferably a polybutadiene that is essentially has unbranched molecules and is completely free of gel. The polymer can also be a mixed polymer of butadiene with other dienes, such as isoprene, or with olefinic monomers, such as styrene, Acrylonitrile, etc., the butadiene content exceeding mole percent.

The most suitable polybutadiene rubber is made in solution with the aid of lithium alkyl as a catalyst manufactured. A typical example of this is one made by Firestone Synthetic Rubber & Latex Co. Limited sold polybutadiene, the analysis of which shows that it is almost completely unbranched and is linear and has approximately 6 to 10% 1,2 configuration, 30 to 60% cis-1,4 configuration and im

809 549/431

contains remaining trans-1,4-configuration. The relationship depends entirely on the conditions under which the polybutadiene has been produced, e.g. B. from the concentration of the catalyst used and the polymerization temperature. This essentially linear polybutadiene dissolves easily in unsaturated oils.

The molecular weight of the polybutadiene polymer is preferably in the range from 2,000 to 2,000,000, but higher and lower molecular weights are also not excluded. The one used to form the Graft copolymers used proportions of oil and butadiene are 5 to 99% oil and 95 to 1% Polybutadiene. If the proportion of oil is 85 to 95%, no additional solvent needs to be used to become. Outside this range, however, there may be a need to use a solvent exist to reduce the viscosity of the mixture. Hydrocarbons are suitable as solvents or chlorinated hydrocarbons, such as ao z. B. xylene, toluene, heavy gasoline, decalin, tetralin, Chlorobenzene, o-dichlorobenzene.

To form the graft polymer at low temperature the presence of a catalyst, e.g. A free radical donor compound, useful be. Suitable catalysts are peroxides or hydroperoxides, such as benzyl peroxide, cumene hydroperoxide, Dicumyl peroxide or tert-butyl hydroperoxide.

The fact that the formation of a graft polymer occurs can be demonstrated by trying to the unsaturated oil, e.g. B. the linseed oil, after performing the method according to the invention Extract acetone. In the case of unreacted mixtures with polybutadiene, the linseed oil or the other unsaturated oil can be easily extracted, but it was found that after performing the method according to the invention, the oil cannot be extracted completely. Usually put 5 to 50% of the oil used is around the polybutadiene. Though all excess oil with it With the help of acetone can be extracted as described, such an extraction normally needs not to be carried out because the graft polymer is generally in the presence of excess Oil can be used.

Also the infrared analysis, which provides information about the various present in the reacting mixtures Groups indicates a chemical link between the two components. Another indication that chemical grafting has occurred is provided by comparison of the films supplied, which are made from unreacted polybutadiene-linseed oil mixtures and poured from converted polybutadiene-linseed oil mixtures. the the first with added siccatives produced cloudy films, while the last, made in the manner described reacted mixtures had been produced, gave perfectly clear films. The ability to Formation of clear films is of concern in the surface coating industry. The graft copolymers, the preparation of which is the subject of the invention, can be used in the following important fields will:

1. for mastic compositions and for putty and sealant mixtures; there will be improved water resistance, Elasticity, strength and adhesion achieved,

2. for surface coatings, e.g. B. for the production of improved alkyd resins, paints and Wood treatment agents,

3. as an aid in the manufacture and processing of rubber and plastics,

4. to reinforce synthetic and naturally occurring resins, e.g. B. bitumen, tars and resin.

example 1

10 parts of a polybutadiene with a Mooney viscosity ML ₄ at 100 ° C. of about 35 were dissolved in 90 parts of alkaline refined linseed oil at 100 ° C. to give a solution with a viscosity of 960 poise at 20 ° C. This solution was increased to 250 C. and _{held at this temperature for 3V for 2} hours, whereupon the viscosity was 50 poise. Part of this mixture was diluted with heavy fuel and added siccatives (siccatives with 0.5% lead and 0.05% cobalt, based on the content of non-volatile components). A film cast from this solution felt dry to the touch overnight and was perfectly clear. A similar film made from the mixture before heating to 250 ° C was cloudy.

A part of the starting solution, which had not yet been heated, was used with a large excess Treated acetone to extract the linseed oil from it. After three extractions, the one became insoluble Fraction dried, it was found to be essentially unchanged starting polybutadiene. Proven This fact could be confirmed by infrared analysis, determination of the iodine number and viscosity measurements.

The substance, which _{had been heated at 250 ° C. for 3Y for 2} hours, was treated with acetone in the same way. After six and also after twelve such extractions, the insoluble fraction did not resemble the starting polymer. An oily substance was obtained, and the infrared spectrum showed that it was a reaction product of linseed oil with polybutadiene.

Example 2

10 parts of the polybutadiene used in Example 1 were added to 90 parts of crude, unprocessed linseed oil 100 ° C dissolved. The solution was then heated to 250 ° C. for 1 hour and the substance in heavy gasoline solved. Siccatives were added (siccatives with 0.5% lead and 0.05% cobalt, based on the Non-volatile content) and a film was cast of the solution. This felt dry overnight and was perfectly clear.

Example 3

Example 2 was repeated, but using soybean oil instead of linseed oil. It similar results were obtained.

Example 4

Example 2 was repeated, but the reaction was held at 25O ⁰ C, was increased until the viscosity at 1200 poises (measured at 20 ° C). That took 15 hours. Similar results were obtained.

Example 5

10 parts of the polybutadiene used in Example 1 and 90 parts of linseed oil were dissolved in 100 parts of heavy gasoline, 1 part of cumene hydroperoxide was added and the solution was heated to 150 ° C. for 10 hours. Upon cooling driers were added (siccatives with 0.5% lead and 0.05 ° / ₀ cobalt, based on the content of nichtfiüchtigen ingredients), and the solution was applied to a glass plate. The film felt dry overnight and was perfectly clear.

Example 6

Example 2 was repeated, but using a partially crosslinked, non-flowing type of polybutadiene with a Mooney viscosity ML ₄ at 100 ° C. of about 35. Similar results were obtained.

Example 7

20th

Example 2 was repeated, but using a solution of a mixed polymer of 86 ° / ₀ butadiene and 14 ° / ₀ styrene with an intrinsic viscosity of 1.5 (in benzene at 20 ° C.). Similar results were obtained in this case as well.

Example 8

Example 2 was repeated except that a solution was used a mixed polymer of 99.95 ° / ₀ ° butadiene and 0.05 / ₀ divinylbenzene having an intrinsic viscosity of 2.6 (in benzene at 20 ° C). Results similar to those in Example 6 were obtained.

Example 9

10 parts of the polybutadiene used in Example 1 were dissolved in 90 parts of oleic acid at 100.degree. The solution was heated to 250 ° C. for 6 hours. At the To cool the mixture was poured into a large excess of acetone. The rubber graft copolymer separated out as an insoluble fraction.

Claims (2)

Patent claims: 1. Process for the preparation of a graft copolymer by heating together a mixture containing a polymer of butadiene and an unsaturated organic oil or derivative contains thereof, characterized in that that 95 to 1 percent by weight of a gel-free polymer of butadiene with unbranched linear structure, which contains at most 10% 1,2 bonds, with 5 to 99 percent by weight an unsaturated organic vegetable or animal oil or a derivative thereof in the presence or absence of a solvent and / or a catalyst heated to a temperature of 50 to 350 ° C. 2. The method according to claim 1, characterized in that there is used as a derivative of an unsaturated Oil's dehydrated castor oil is used. Considered publications:
German Patent No. 932,986;
German Auslegeschrift No. 1 079 328;
French patent specification No. 1,061,959.