Patent GB-948226-A (GB)
Title: Process for the preparation of low molecular weight copolymers
IPC: C08F10/00
Filed: 1962-04-09
Abstract: Hydrocarbons having at least two conjugated double bonds are copolymerized with an ethylenic aldehyde and with mesityl oxide and/or a vinyl cyclohexene in the presence of a free-radical yielding substance, e.g. an organic peroxide, such as di-tert. butyl peroxide or cumene hydroperoxide, or azobisisobutyronitrile. Polyethylenic hydrocarbons specified are butadiene, isoprene, dimethyl butadiene, 2,4-hexadiene and 1,3-heptadiene. Ethylenic aldehydes specified are acrolein and alpha-ethyl, alpha-decyl, alpha-cyclohexyl, alpha-chloro and beta-dodecyl acroleins. The preferred vinyl cyclohexene is the 4-vinyl isomer.  Other monomers which may be present are styrene, alpha-methyl styrene, acrylic and methacrylic esters and nitriles, allyl alcohol and its esters, vinyl and vinylidene chlorides and vinyl esters.  The polymerization is preferably conducted in liquid phase, and an excess of mesityl oxide or vinyl cyclohexene may be used as the reaction medium.  The reaction may be terminated before the complete conversion of the monomers. Additional quantities of monomer and catalyst may be run in as the reaction proceeds.  The resulting copolymers may be further reacted in several ways, e.g. (a) by further polymerization through double bonds, either alone or in combination with monomers such as divinyl benzene, diallyl benzene, divinyl succinate or ethylene glycol diacrylate; (b) by reaction with polyepoxides, e.g. glycidyl ethers of polyhydric alcohols or phenols; (c) by reaction with hydrogen to give saturated copolymers containing alcoholic groups; (d) by reaction with formaldehyde to give methylol-containing derivatives; (e)  by oxime formation with hydroxylamine; (f)  by oxidation to give polymeric polycarboxylic acids which form esters and salts; (g) by reaction with ammonia or amines to give nitrogen-containing products; (h) by reaction with mercaptans to give mercaptals; (i) by reaction with phenol, urea or melamine to give resins; and (j) by cross-linking with polyamines. The examples describe the preparation of copolymers of: (1) butadiene, acrolein and mesityl oxide; (2) butadiene, acrolein, mesityl oxide and styrene; (3) butadiene, acrolein and 4-vinylcyclohexene-1; (4) as in (1)-(3) but using isoprene in place of butadiene; and (5) butadiene, acrolein, mesityl oxide and alphamethyl styrene.ALSO:Surfaces of metal or wood are coated by applying thereto a copolymer of a conjugated di- or poly-olefin, an ethylenic aldehyde, and mesityl oxide and/or a vinyl cyclohexene, together with, if desired, other monomers.  The copolymer, if in liquid form, may be used as such, or may be dissolved in a solvent before application.  The resulting coatings may be cured by heating to 200-450  DEG C.  The examples describe the use of xylene solutions of copolymers of (1) butadiene, acrolein and mesityl oxide, (2) butadiene, acrolein, mesityl oxide and styrene, and (3) butadiene, acrolein and 4-vinyl-cyclohexene-1 to coat tin plates.  The resulting coatings are cured by heating at 400  DEG F., optionally in the presence of cobalt naphthenate.