United States Patent (19) (11) 4,161,571 Yasui Et Al
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United States Patent (19) (11) 4,161,571 Yasui et al. 45 Jul. 17, 1979 (54) PROCESS FOR PRODUCTION OF THE 4,080,493 3/1978 Yasui et al. .......................... 260/879 MALE CANHYDRDE ADDUCT OF A 4,082,817 4/1978 Imaizumi et al. ...................... 526/46 LIQUID POLYMER 4,091,198 5/1978 Smith ..................................... 526/56 75 Inventors: Seimei Yasui, Takarazuka; Takao FOREIGN PATENT DOCUMENTS Oshima, Sonehigashi, both of Japan 2262677 2/1975 France ....................................... 526/56 73) Assignee: Sumitomo Chemical Company, 44-1989 1/1969 Japan ......................................... 526/56 Limited, Osaka, Japan Primary Examiner-William F. Hamrock Attorney, Agent, or Firm-Birch, Stewart, Kolasch and 21 Appl. No.: 843,311 Birch 22 Filed: Oct. 18, 1977 57 ABSTRACT Related U.S. Application Data A process for production of the maleic anhydride ad duct of a liquid polymer having a maleic anhydride 62 Division of Ser. No. 733,914, Oct. 19, 1976, Pat, No. addition amount of 2 to 70% by weight, which com 4,080,493. prises reacting a liquid polymer having a molecular 51 Int. C.’................................................ CO8F 8/46 weight of 150 to 5,000 and a viscosity of 2 to 50,000 cp (52) U.S. C. ...................................... 526/90; 526/192; at 30 C. in the presence of at least one compound, as a 526/209; 526/213; 526/193; 526/195; 526/226; gelation inhibitor, selected from the group consisting of 526/233; 526/237; 526/238; 526/272; 525/285; imidazoles, thiazoles, metallic salts of mercapto 525/249; 525/251; 525/255; 525/245; 525/248 thiazoles, urea derivatives, naphthylamines, nitrosa (58) Field of Search ................. 526/56, 46, 48.1, 48.2, mines, iron, iron compounds and specific halogen com 526/24, 27, 40, 47; 260/879, 880 R pounds, said liquid polymer being selected from the (56) References Cited group consisting of liquid polybutadienes, liquid poly U.S. PATENT DOCUMENTS isoprenes and liquid copolymers comprising units of butadiene or isoprene and units of at least one com 2,388,477 11/1945 Fryling ................................. 526/205 2,388,514 11/1945 Zwicker et al. .... 526/205 pound selected from the group consisting of other diole 3,546,184 12/1970 Heidel et al. ... ... 526/56 fins, olefins and aromatic vinyl compounds. 3,778,418 12/1973 Nakayama ...... ... 526/56 3,937,677 2/1976 Broecker et al. ...................... 526/56 16 Claims, No Drawings 4,161,571 1. 2 the use of a complex-forming agent such as acetylace PROCESS FOR PRODUCTION OF THE MALEC tone in such a reaction. ANHYDRIDE ADDUCT OF A LIQUID POLYMER As result of an extensive study seeking a gelation inhibitor which exerts a sufficient effect for preventing This application is a divisional, of copending applica the formation of gels in the addition reaction of maleic tion Ser. No. 733,914, filed on Oct. 19, 1976 now U.S. anhydride to give conjugated diene polymers even Pat. No. 4,080,493. when employed in a small amount, it has been found The present invention relates to a process for produc that imidazoles, thiazoles, metal salts of mercapto tion of the maleic anhydride adduct of a liquid polymer thiazoles, urea derivatives, naphthylamines, nitrosa having a maleic anhydride addition amount of 2 to 70% 10 mines, iron and its compounds, and specific halogen by weight. compounds have such an effect and are utilizable as the Hitherto, it is well known to prepare the important gelation inhibitor. materials for paints by reacting natural unsaturated oils The present invention is based on the above finding such as soybean oil, linseed oil or castor oil with maleic and provides a process for production of the maleic anhydride. Many attempts have been made to use sub 5 anhydride adduct of a liquid polymer having a molecu stitutes for the natural unsaturated oils in production of lar weight of 150 to 5,000 and a viscosity of 2 to 50,000 the said materials. For example, Japanese Patent Publi cps at 30° C. in the presence of at least one compound, cation No. 21193/1961 discloses the production of the as a gelation inhibitor, selected from the group consist materials for alkyd resins by reacting cyclododecatriene ing of imidazoles, thiazoles, metal salts of mercapto with maleic anhydride. Japanese Patent Publication No. 20 thiazoles, urea derivatives, naphthylamines, nitrosa 954/1971 discloses the production of a modified poly mines, iron and its compounds and specific hydrogen mer by the addition reaction of maleic anhydride to compounds, said liquid polymer being selected from the give low molecular weight polybutadiene having the group consisting of liquid polybutadienes, liquid poly 1,2-structure in an amount of not less than 80%. Japa isoprenes and liquid copolymers comprising units of nese Patent Publication No. 7269/1971 discloses a 25 butadiene or isoprene and units of at least one com method for the preparation of a water-soluble resin by pound selected from the group consisting of other diole neutralizing the said modified polymer or its esterified fins, olefins and aromatic vinyl compounds. product with ammonia or an amine. Compared with the said gelation inhibitors as dis In the reaction wherein maleic anhydride adds to the closed in Japanese Patent Publication Nos. 26870/1968 polymers resulting from conjugated diolefins, the ad 30 and 44557/1972, the gelation inhibitors used in the pres ducts are generally prepared by heating and, in this ent invention have various advantages. For instance, reaction, there is usually observed a tendency that, the gelation inhibitors of this invention can reduce suffi while the addition reaction proceeds, the double bonds ciently and satisfactorily the viscosity of the reaction of the polymers are crosslinked with other molecules mass by the use of a smaller amount than that of the according to the radical addition, whereby the viscosity 35 known gelation inhibitors. This is advantageous in pro of the reaction mass increases. When the viscosity is duction of resinous materials to be used for paints since further increased, the reaction mass in the reaction ves the influence by the gelation inhibitor can be sup sel completely forms a gel to make the after-treatment pressed. Further, for instance, the coloration of the very troublesome. Even if the gel is not formed, the maleinized product caused by the gelation inhibitors of increase of the viscosity in the maleinization causes the invention is much less than that caused by the various difficulties. For instance, the paints prepared by known gelation inhibitors. This apparently contributes the use of the resulting maleinized products form a to the production of resinous materials of higher qual coating film having inferior physical properties. Fur ity. ther, for instance, the controls of the conversion of The working mechanism of the gelation inhibitors maleic anhydride and of the viscosity of the reaction 45 according to the present invention is still unclear. How mass for obtainment of the maleinized products having ever, it is presently assumed that they are effective in a suitable viscosity for paints are quite difficult. decomposition and elimination of such radicals as hy Various trails have been made to overcome the said droperoxy groups, oxy radicals and polymer radicals difficulties. For example, Japanese Patent Publication present in the molecules of the liquid polymer and/or No. 3547/1973 proposes to use cyclic ethers, aldehydes 50 molecular oxygen existing in the liquid polymer. or ketones as a gelation inhibitor in the maleinization As the liquid polymer, there are utilizable liquid poly reaction. Further, as such gelation inhibitor, there are butadienes, liquid polyisoprenes, liquid butadiene co proposed the uses of amides (Japanese Patent Publica polymers and liquid isoprene copolymers, which may tion No. 3544/1973), catechols (Japanese Patent Publi have a molecular weight of 150 to 5,000 and a viscosity cation (unexamined) NO. 7895/1975), naphthols (Japa 55 of 2 to 50,000 cp at 30 C, irrespective of the proportion nese Patent Publication (unexamined) No. 87491/1975), of the cis-, trans-, vinyl- and 3,4-structures constituting phenothiazines (Japanese Patent Publication (unexam the micro structure of the liquid polymer. In case of the ined) No. 132013/1974), etc. liquid polymer being a low molecular weight copoly On the other hand, Japanese Patent Publication No. mer of butadiene or isoprene with styrene, it may con 26870/1968 discloses the preparation of maleinized tain styrene units in a proportion of not more than 40% products by heating a liquid polybutadiene having the by weight. The said liquid polymer can be prepared in cis-1,4 structure in an amount of not less than 50% and a conventional procedure, for instance, as disclosed in a viscosity of 30 to 30,000 cp (centipoise), particularly U.S. Pat. No. 3,428,699. 80 to 10,000 cp, at 50 C. with maleic anhydride in the The addition reaction of maleic anhydride to the presence of a copper compound. This method is charac 65 liquid polymer in the presence of the gelation inhibitor terized in that the viscosity in maleinization is reduced may be carried out by charging the liquid polymer, by the existence of the copper compound. Further, maleic anhydride and the gelation inhibitor into a reac Japanese Patent Publication No. 44557/1972 proposes tion vessel in an optional order and then heating at an 4,161,571 3 4. elevated temperature until the maleinization is com halogen atom, a mercapto group, a hydroxyl group or a pleted. Practically, for instance, the liquid polymer and hydroxymethyl group, or a group of the formula: the gelation inhibitor are first charged into a reaction -SNR7R8 in which R7 and R8 are each a hydrogen vessel and kept at a temperature of 10 to 270° C.