Patent GB-1043671-A (GB)
Title: Tertiary alkoxyalkyl esters and polymers thereof and their manufacture
IPC: C07C29/00
Filed: 1963-03-04
Abstract: The invention comprises tertiary alkoxyalkyl esters <FORM:1043671/C2/1> where R is a saturated or unsaturated hydrocarbon radical of 1-40 C, or preferably 2-20 C, R1 is a saturated or unsaturated divalent aliphatic hydrocarbon radical or 2-12 C, R2 is a monovalent tert.-alkyl radical of 4-10 C, R3 is hydrogen or a hydrocarbon radical, x is a number from 1-25, preferably 1-5, or is at least 1, m+n is 1-6 and where m+n is 1 R is a saturated hydrocarbon only in particular, bis - (2 - tertiary - butoxyethyl) terephthalate, maleate, fumarate and itaconate.  Examples also describe the preparation of bis-(2-tertiary-butoxyethyl) 2,2,5,5 - tetramethyl adipate, bis - (2 - tertiarybutoxyethyl) isophthalate, methyl t-butoxyethyl itaconate, bis-(3-methyl-5-tertiary amyloxypentyl) terephthalate, bis-(1 - tertiarybutoxy - 2 - propyl maleate.  The esters are prepared by esterifying a carboxylic acid <FORM:1043671/C2/2> or its halide, anhydride or ester derivative, with n moles of tertiaryalkoxyalkanol <FORM:1043671/C2/3> which may in turn be prepared by the etherification of a glycol H-(OR1)x-OH with a tertiary olefine in the presence of a cation exchange resin in the hydrogen form.  Hydroxy esters <FORM:1043671/C2/4> are prepared by heating the tertiary alkoxyalkyl esters above to 50-200 DEG  C. in the presence of an acid catalyst, and removing the tertiary olefine. These hydroxy esters may be further heated, 175-300 DEG  C. to prepare a solid polyester resin. The tertiaryalkoxy-alkyl esters in which R is an unsaturated hydrocarbon radical are polymerized or copolymerized with olefinic monomers.ALSO:Polymers or copolymers of tertiaryalkoxy alkyl esters of formula <FORM:1043671/C3/1> where R is an unsaturated hydrocarbon (1-40 C, preferably 2-20 C), R1 is a saturated or unsaturated divalent aliphatic hydrocarbon radical (2-12 C), R2 is a monovalent tertiary alkyl (4-10 C), is 1-25, preferably 1-5, n is at least 1 and m+n is 2-6 (see Division C2) are prepared by conventional methods including irradiation, and alternating, block, or graft copolymers are included.  Compounds mentioned are methyl 2-tertiarybutoxyethyl maleate, bis-(2-tertiarybutoxyethyl) itaconate, methyl 2-tertiarybutoxyethyl itaconate, bis-(2-tertiarybutoxyethyl fumarate and bis-(2-tertiarybutoxyethyl) maleate and comonomers may be vinyl or vinylidene chlorides, chloroprene, methyl or lauryl methacrylate, octyl or methyl acrylates, methacrylonitrile and acrylonitrile, a -chloroacrylonitrile, dimethyl acrylamide, isobutylene butadiene, styrene, p-chlorostyrene, 3,5-dichlorostyrene, p-methoxystyrene, vinyl acetate, benzoate, pyridine and carbazole. Examples describe the solution copolymerization of styrene and methyl 2-tertiarybutoxyethyl fumarate in methyl ethyl ketone and in the presence of benzoyl peroxide and the preparation of a styrene-methyl 2-hydroxyethyl fumarate copolymer therefrom by heating in methyl ethyl ketone in the presence of phosphotungstic acid; the solution copolymerization of vinylidene chloride with bis-(2-tertiarybutoxyethyl) maleate; bulk copolymerization of styrene and bis-(2-t-butoxyethyl) maleate or bis-(2-t-butoxyethyl itaconate; the bulk copolymerization of vinyl acetate and bis-(2-t-butoxy ethyl) maleate; the emulsion copolymerization of vinyl chloride with bis (2-t-butoxyethyl) itaconate, maleate and fumarate in the presence of water, sodium lauryl sulphate, sodium bisulphite, and ammonium persulphate; emulsion copolymerization of butadiene with bis-(2-t-butoxyethyl) maleate in the presence of water, sodium stearate, potassium persulphate and dodecyl mercaptan; emulsion copolymerization of 3,3-dimethyl-1-butene with bis-(2-tert-butoxyethyl) fumarate; bulk copolymerization of acrylonitrile and bis-(2-tert-butoxyethyl itaconate; and the polymerization by gamma radiation from a cobalt 60 source of bis (2-t-butoxyethyl) fumarate, bis-(2-t-butoxyethyl) itaconate and the copolymerization of these monomers with styrene.  Polyesters are prepared from hydroxy compounds <FORM:1043671/C3/2> prepared by heating (50-200 DEG  C.) the tertiary alkoxyalkyl esters above in the presence of a said catalyst.  The polyester is prepared by heating in the presence of an ester-interchange catalyst at between 175-300 DEG C.  Examples describe the preparation from various bis-(2-tertiary butoxyethyl) dicarboxylates, with liberation of isobutylene and ethylene glycol of polyethylene terephthalate; polyethylene maleate; polyethylene isophthalate; polyethylene fumarate; polyethylene 2,2,5,5-tetramethyl adipate; and polyethylene itaconate.  Another example describes the preparation of the polyester of terephthalic acid and 3-methyl-1,5-pentanediol from bis-(3-methyl-5-tertiaryamyl-oxypentyl) terephthalate.