NO152072B - PROCEDURE AND PREPARATION FOR AROMATIZATION OF TEA - Google Patents

Description

Process for the preparation of a graft copolymer.

The present invention relates to a

method for producing a new type of graft copolymer with essentially two components, one of which is butadiene.

The invention thus relates to a method for producing a graft copolymer of butadiene and the peculiarity of the method according to the invention is that a butadiene polymer is made to react with an unsaturated vegetable or marine oil or a derivative thereof by heating to a temperature between 50 and 350°C.

As examples of suitable unsaturated organic oils, mention should be made of vegetable oils

oils such as linseed oil, soya bean oil, palm oil, corn oil, tung oil or olive oil, derivatives thereof such as e.g. dehydrated castor oil and marine oils such as cod liver oil or sperm oil. The term "marine oils" shall here mean oils produced from living organisms in the sea.

. The polymer can be polybutadiene and

preferably a polybutadiene with substantially unbranched molecules and completely gel-free. The polymer can also be a copolymer of butadiene with others

serves as e.g. isoprene or with olefin monomers such as e.g. styrene acrylonitrile etc. where the butadiene portion exceeds 50 mole percent.

The most suitable polybutadiene rubbers are those prepared in solution using lithium alkyl initiators, a typical example of which is a diene type which

is brought to market by Firestone Synthetic Rubber & Latex Co. Limited. Analysis

'shows that this type of polybutadiene is almost

completely unbranched and linear and comprises approximately 6-10% 1,2-structure, 30-60% cis-1,4-structure while the remainder is trans-1,4-. These conditions depend entirely on the conditions under which the polybutadiene is produced, e.g. of the catalyst concentration and the polymerization temperature.

This essentially linear polybutadiene dissolves readily in unsaturated oils. Other polybutadienes, e.g. those produced by emulsification contain a different steric structure and are generally not completely free of gel, so that they do not dissolve quite so easily. Nevertheless, useful graft copolymers can be prepared from such polybutadienes.

The molecular weight of the polybutadiene polymer is preferably in the range 2000-200,000, although higher and lower values are not excluded. The amount of oil and butadiene used in the production of the graft copolymer is normally 5-99 percent oil and 95-1 percent polybutadiene. When the quantity of oil is from 85-95 per cent, it is not necessary to use any additional solvent. Outside this range, however, it may be necessary to use a solvent to lower the viscosity of the mixture. Typical solvents that can be used are hydrocarbons or chlorinated hydrocarbons, e.g. xylene, toluene, white spirit, decalin, tetralin, chlorobenzene, o-dichlorobenzene etc.

In order to graft at a low temperature, it may be beneficial to co-use a catalyst, e.g. a compound that forms free radicals. Suitable catalysts are peroxides or hydroperoxides, e.g. benzoyl peroxide, cumene hydroperoxide, dicumyl peroxide or tertiary butyl hydroperoxide.

The fact that grafting really takes place can be shown by attempting to extract the unsaturated oil, e.g. linseed oil, with acetone after carrying out the method according to the invention.

When it concerns unreacted mixtures with polybutadiene, the linseed oil or other unsaturated oil can be easily extracted, but after the method according to the invention has been carried out, it has been found that the oil cannot be extracted completely. From 5 to 50 percent of the oil used is normally grafted with polybutadiene. Although some excess of oil may be extracted with acetone, as described, such extraction does not normally need to be carried out as the graft copolymer can generally be used with any excess of oil.

Infrared analysis which characterizes different groups present in the reacting compounds also indicates chemical bonding between the two constituents. Another indication that chemical grafting has taken place is obtained by comparing films produced from unreacted polybutadiene-linseed oil mixtures, and mixtures where polybutadiene and linseed oil have reacted with each other. The former, with added driers, produce blurred films, but the latter, prepared from mixtures reacted in the manner described, produce perfectly clear films. The ability to produce clear films is important in the paint and varnish industry. The graft copolymers produced according to the invention can be used in the following important areas: 1. For the production of fillers (mastic), putty and sealing compounds. These are then given improved resistance to water, flexibility, strength and adhesiveness. 2. In surface coatings, e.g. in the manufacture of improved alkyd resins, varnishes and substances for impregnating or treating wood. 3. As manufacturing and processing aids in the rubber and plastics industry. 4. To reinforce synthetic and natural resins, e.g. bitumen, tar and wood resin.

Example 1.

10 parts of "Diene" 35S, which is a commercially available polybutadiene of approximately 35 ML4 Mooney viscosity at 100°C, was dissolved in 90 parts of alkali-refined linseed oil at 100°C to give a solution of viscosity 960 poise at 20°C. This solution was heated to 250°C and held at this temperature for 3y2 hours after which the viscosity was 50 poise. Parts of this mixture were diluted with white spirit and the desiccant was added (0.5 per cent lead and 0.05 per cent cobalt desiccant calculated on non-volatile components). A film formed from this solution was dry to the touch after one night and was completely clear. A similar film was prepared from the mixture before it was heated to 250°C.

A portion of the original solution (from before heating) was treated with a large excess of acetone to extract the linseed oil. After three such extractions, the insoluble fraction was dried and proved to be essentially unchanged "Diene" 35 S. This was demonstrated by infrared analysis, determination of the iodine value and measurements of viscosity.

After the material had been heated for 3y2 hours at 250°C, it was treated with acetone in the same way. After both 6 and 12 such extractions, the insoluble fraction was different from the original polymer. It was an oily material and the infrared spectrum showed that it was a reaction product between linseed oil and the polybutadiene.

Example 2.

10 parts of "Diene" 35 S were dissolved in 90 parts of crude linseed oil at 100°C. The solution was then heated at 250°C for one hour and the mixture dissolved in white spirit. Tøfke agents, 0.5 percent lead and 0.05 percent cobalt desiccants based on non-volatile constituents, were added and a film was formed from the solution. It was touch dry after one night and was completely clear.

Example 3.

Example 2 was repeated using soybean oil instead of linseed oil. Similar results were obtained.

Example 4.

Example 2 was repeated except that the material was held at 250°C until the viscosity increased to 1200 poise, measured at 20°C. This took 15 hours. Similar results were obtained.

Example 5. 10 parts "Diene" 35 S and 90 parts linseed oil were dissolved in 100 parts white spirit, one part cumene hydroperoxide was added and the solution heated at 150°C for 10 hours. After cooling, drying agents were added, 0.5 percent lead and 0.05 percent cobalt driers based on non-volatile components and the solution was poured over a glass plate. The film formed was dry to the touch after one night and was completely clear.

Example 6.

Example 2 was repeated except that "Diene" 35 NF, a non-liquid polybutadiene having a Mooney viscosity of approximately 35 ML4 at 100°C, was used instead of "Diene" 35 S. Similar results were obtained

Example 7.

Example 2 was repeated using a copolymer solution containing 86% butadiene and 14% styrene with an intrinsic viscosity in benzene at 20°C of 1.5. Similar results were obtained.

Example 8.

Example 2 was repeated using a copolymer solution containing 99.95% butadiene and 0.05% divinylbenzene with an intrinsic viscosity measured in benzene at 20°C of 2.6. Results substantially similar to those obtained in Example 6 were obtained.

Example 9.

Example 2 was repeated except that instead of "Diene" 35 S, an emulsion-polymerized styrene-butadiene copolymer of low molecular weight was used, which appears in the trade under the name "Flos-brene" LV. This type of polymer is manufactured by the American Synthetic Rubber Corporation. Similar results were obtained except that the film dried more slowly.

Example 10. 10 parts of "Diene" 35 S were dissolved in 90 parts of oleic acid at 100°C. This solution was heated at 250°C for 6 hours. After cooling, the mixture was poured into a large excess of acetone. The rubber graft copolymer separated as an insoluble fraction.

Claims (1)

Process for producing a graft copolymer of butadiene, characterized in that a butadiene polymer is caused to react with an unsaturated vegetable or marine oil or a derivative thereof by heating to a temperature between 50 and 350°C.