US2833733A

US2833733A - Manufacture of interpolymers of styrene with drying oil fatty acids and derivatives of such interpolymers

Info

Publication number: US2833733A
Application number: US366608A
Authority: US
Inventors: Cottrell Jack Andrews; Booth Ernest; Richard H Buckle
Original assignee: Sherwin Williams Co
Current assignee: Sherwin Williams Co
Priority date: 1947-02-11
Filing date: 1953-06-24
Publication date: 1958-05-06
Anticipated expiration: 1975-05-06

Description

United States Patent Office 2,833,733 Patented May 6, 1958 MANUFACTURE or INTERPOLYMERS F STYRENE wrrn DRYING OIL FATTY ACIDS ANES DERIVATIVES OF SUCH INTERPOLY- ME No Drawing. Original application February 11, 1947, Serial No. 727,950, now abandoned. Divided and this application June 24, 1953, Serial No. 366,608

Claims. (Cl. 26023) This invention is for improvements in or relating to heating styrene with one or more drying oil fatty acids.

The reaction may be carried outin the presence of substances known to act as polymerisation catalysts for vinyl compounds, amongst which may be mentioned the percompounds such as benzoyl peroxide.

The reaction may be carried out in the presence of solvents and in one embodiment of the invention the monomeric styrene may be used in excess so as to function as the solvent in the reaction mixture.

The reaction may, if desired, be carried out in emulsion in which case thevstyrene and theidrying oil fatty acids form the dispersed phasein an aqueous medium as the continuous phase. g The invention also comprises a modification of the process above described, namely, heating styrene with a drying oil fatty acid ester, saponifying thecopolymer, acidifying the reaction mixture and extracting the styrenat'ed fatty acids with a solvent. The drying oil used in this modification of the process may be a partially polymerised polyhydric alcoholic mixed ester such as is referred to in prior British Patents Nos. 573,809 and 573,835 and also in copending British application Serial No. 580,912

and British application No. 4,907/ 46; or ,a raw drying oil.

2 The styrenated unsaturated fatty acids may be reacted with a polyhydric alcohol to form esters, in which case the product may be used as a coating or impregnating composition. These esters may be transformed into hard, tough coatings either on air-drying or on stoving.

The following examples illustrate various ways in which the invention may be carried into effect, references to parts of the ingredients being references to parts by weight and the percentage figures quoted are, unless otherwise stated, calculated as percentages by weight:

Example I.-200 parts'of wood oil fatty acids, 400 parts of monomeric styrene were heated together under reflux with 4 parts of benzoyl peroxide for eight hours until the solution of unrea-cted and styrenated fatty acids in excess styrene had a viscosity of 87 sees. in a Ford No. 4 Cup at 25 C. Removal of excess styrene in vacuo yielded a mobile mixture of unreacted fatty acids and styrenated fatty acids of an acid value 69 which'could be separated into its components by extraction with industrial alcohol.

. 2 I The mixture as obtained above may be reacted unde reflux with 5% of ethylene glycol for two hours to give an elastic substance of an acid value of 13 which is soluble in xylol to yield a slightly cloudy solution which dries by solvent evaporation in thin films and stoves to a hard mar-proof coating in one hour at 125 C.

In place of the wood oil fatty acids referred to in the foregoing example, the fatty acids of oiticica oil can be used without any substantial modification of the procedure to yield products which are similar in character to those obtained from the wood oil fatty acids. In addition, in place of the ethylene glycol used in the foregoing esterification step, there may be used any other polyhydric alcohol or mixture ofpolyhydric alcohols, for example there may be used glycerol, pentaerythritol, mannitol or sorbitol or any other convenient polyhydric alcohol and the process, being a simple esterification process, proceeds in normal manner to give products which are analogous to those obtainable from ethylene glycol. 7

Example II.82 parts of a copolymer solution in xylol obtained in accordance with Example II of British Patent No. 573,809 was diluted with 325 volumes of benzene and volumes of hot saturated ethyl alcoholic potassium hydroxide were added. The whole was then refluxed for 4 hours and the solvents were removed in vacuo. vOn pouring the residue into a large excess of water there was no unsaponifiable residue and a typical soap solution was formed. After acidification, the insoluble acids were extracted with diethyl ether. The residue, after distillation of the ether, comprises a white solid and a brown oily material which were further separated by extracting the latter in petroleum ether in which the whitesolid was insoluble.

The solid product had an acid value of 14 and a molecular weight of 3900 approximately. The liquid prodnot had an acid value of 183.

Example llI.-400 parts of a 3-poise blown linseed oil were heated under reflux with 400 parts of monomeric styrene for 8% hours until the temperature reached 250 C. The condenser was then removed and the product" ing 55% of the original copolymer, being a thick syrupy liquid, and the other representing 40% of the original, copolymer, a hard brittle solid. The acid values of the a, two portions were 98 and 36 respectively,; The former;

was insoluble in ethyl alcohol Example lV.-300 parts of elaeostearicgacid parts of monomeric styrene were dissolved in 600 parts of xylene and the mixture was heated under reflux for 40 hours. At the end of this time the solution produced had a solids content of 37% and yielded a clear film when poured on to a glass slide.

Example V.--350 parts of elaeostearic acid were dissolved in 350 parts of monomeric styrene and the solu-' tion heated under reflux for 50 hours. At the end of this period the condenser was removed and unreacted monomeric styerne was distilled away, 162 parts of styrene being recovered. The product remaining behind was clear.

Example VI.50 parts of dehydrated castor oil fatty acids were mixed with 10 parts of monomeric styrene and the mixture heated under reflux for 2 hours until thetemperature had risen to 165 C. At this point a further 10 parts of monomeric styrene were added to the. reaction mixture and heating under reflux was contained for a further hourand a quarter by which time the temperature had risen to 200 C. Thereupon a further 10 parts of monomeric styrene were added and the mixture heated tinder refluxfoi' a further period of 2 hours, the temperatui'e again attaining 200 C. whereafter a final further portion of, 10 parts of monomeric styrene was added and the mixture refluxed for a further 2 /2 hours to produce a product which was a slightly cloudy soft balsam.

In place of the dehydrated castor oil fatty acids referred to above, linseed oil fatty acidsmay be used. The details of operationremain substantially unaltered and the product produced by the use of linseed oil fatty acids is closely similar to that produced from the dehydrated cas-' tor oil fatty acids.

Example VII.The styrenated fatty acids produced in accordance with Example VI were used in the production of a modified alkyd resin as follows: 63 parts of the styrenated fatty acids produced in accordance with Example VI were mixed with 7.5 parts of phthalic anhydride and 10 parts of glycerol. The reaction mixture was heated to a temperature of 240 C. and was maintained at this temperature for 8 hours, carbon dioxide being blown through the reaction mixture throughout the whole of this period. The reaction product was then dissolved in xylol to produce a solution which, on the addition of metallic driers, yielded, on pouring, a film which dried by oxidation to a slightly opalescent state.

It will be appreciated that the details as to technique and as to raw materials referred to in the foregoingexamples are not exhaustive of the possible variations in the process within the scope of the present .in'vehtion.'

For example, the technique of reacting thewood oil fatty acids or oiticica oil fatty acids with the styrene referred to in Example 1 may be applied to other fatty acids or, alternatively, the technique illustrated in Examples '11 and III of reacting the styrene with a partially peiymep' ised drying oil and thereafter saponifying the product to produce the'styrenated fatty acids may be applied to the oils containing the fatty acids of Examples 1, IVanjd In fact, it is to be understood that the application of the technique of any of the foregoing examples maybe applied to the raw materials of, any of the examples and any modification of the process either as to technique or as to raw material which would be apparent to a chemist skilled in the art from a study of the specification'aiid the foregoing examplesis to be deemed to fall within. the scope of the present invention.

Thestyrenated acids described above may be reacted with polyhydric alcohls,.monomeric or polymeric primary or secondary. According to the degree of modification with styrene, the esters will be soluble or insoluble in drying oils and aliphatic hydrocarbons. Such acids may also be used to modify polyhydric alcohol-polybasic acid condensates in the manufacture of alkyd resins. Such esters are much more resistant to water and dry much more quickly than similar esters made with unmodified fatty acids.

The styrenated fatty acids may be converted into the soaps of the alkali and alkaline earth metals and of the heavy metals by any convenient method. In the American Chemical Society Monograph No. 103 The Alkaline Earth and Heavy Metal Soaps, published in New York in 1946, S. B. Elliott described two methods of preparing such soaps, namely the precipitation and the fusion methods;v the precipitation method is preferred owing to the tendency of the styrenated fatty acids to decompose at the temperatures used for soap-making by the fusion method.

The alkali metal and ammonium soaps of the styrenated fatty acids may be used as detergents; the cobalt, manganese and load soaps may be used as driers in drying oil compositions, particularly the'styrene-drying oil interpolymers described in the above-mentioned patents and copending applications, and the zinc, calcium and aluminum soaps may be used as wetting and dispersing agents or as paint and varnish ingredients.

The present application is a divisional application of our U. S. application Serial No. 727,950, filed February 11, 1947, now abandoned.

What we claim is:

l. A process for the production of liquid styrenated drying oil fatty acids comprising heating a styrene-partially polymerized drying oil copolymer with an alkali metal hydroxide under reflux to saponify said copolymer, acidifying said saponified copolymer with a dilute mineral acid, and separating the styrenated drying oil fatty acids from the reaction mixture.

2. A process as claimed in claim 1 wherein the copolymer comprises partially polymerized dehydrated castor oil and styrene.

3. A process as claimed in claim 1 wherein the copolymer comprises 3-poise blown linseed oil and styrene.

4. A process as claimed in claim 1 wherein the saponification of the styrene-partially polymerized drying oil copolymer is carried out in the presence of benzene.

5. A process as claimed in claim 1 whereinthe styrenated-drying oil fatty acids are separated from the acidification reaction mixture by extraction with diethyl ether.

References Cited in the file of this patent OTHER REFERENCES Lewkowitsch: Chem. Technology and Analysis of Oils, Fats and Waxes, 1909, vol. I, pages 88 and 89.

Bradley et 211.: Ind. and Eng. Chem., May 1940, pages 694-697.

Petit et al.: Ofiicial Digest, August 1950, pp. 609-614.

Claims

1. A PROCESS FOR THE PRODUCTION OF LIQUID STYRENATED DRYING OIL FATTY ACIDS COMPRISING HEATING A STYRENE-PARTIALLY POLYMERIZED DRYING OIL COPOLYMER WITH AN ALKALI METAL HYDROXIDE UNDER REFLUX TO SAPONIFY SAID COPOLYMER ACIDIFYING SAID SAPONIFIED COPOLYMER WITH A DILUTE MINERAL ACID, AND SEPARATINGA THE STYRENATED DRYING OIL FATTY ACIDS FROM THE REACTION MIXTURE.