Patent GB-1086314-A (GB)
Title: Polymerization of cyclic carbonates
IPC: C08G64/02
Filed: 1964-09-25
Abstract: New unsaturated polycarbonates are made by copolymerizing a mixture of a saturated cyclic carbonate and an unsaturated cyclic carbonate. The cyclic carbonates contain 6 or more atoms in a ring composed solely of carbon and oxygen, the oxygen present in the ring being present as the carbonate group and possibly, also, as etheric oxygen. The carbon atoms on the ring may be substituted by up to 4 hydrocarbyl, hydrocarbyloxymethyl, acyloxymethyl, nitro, tertiary amino, cyanoalkyl or cyanoalkoxy methyl groups and two of these substituents may be linked together to form a carbocyclic nucleus or a heterocyclic nucleus (e.g. containing oxygen or sulphur).  The substituents on the saturated cyclic carbonates must be free from ethylenic or acetylenic unsaturation, but those on the unsaturated cyclic carbonates must contain at least one ethylenic double bond. Polymerization is effected at - 20 DEG  to 250 DEG  C. in the presence of a catalyst. Preferred catalysts are (a) those of formula Ra-M-Rb, where M is a Group II metal, Ra is a hydrocarbyl, pyridyl or furyl radical and Rb is hydrogen, halogen, hydrocarbyl, secondary amino, hydrocarbyloxy, pyridyl or furyl; (b) compounds of formula R1-M-R112, where M is a Group III metal, R1 is hydrocarbyl and R11 is hydrogen, halo, hydrocarbyloxy or hydrocarbyl; (c) compounds of formula M(R)y, where M is a Group II or Group III metal, R is hydrocarbyloxy and y is 2 or 3; (d) compounds of formula MR1, where M is an alkali metal and R1 is hydrocarbyl, pyridyl or furyl; (e) compounds of formula H2N-M-OR1, where M is Mg, Ca, Zn, Sr, Cd or Ba and R1 is hydrocarbyl; (f) reaction products of an alkaline earth hexanmoniate, an olefin oxide and an organic nitrile.  Catalysts of type (a) and (b) may be used together with alkanols, phenols, ketones, water, molecular oxygen, polyols, diketones, ketoesters, ketoacids, ketoaldehydes and oximes. Polymerization may be by a bulk, suspension polymerization or solution polymerization process.  The polymers may be cured to elastomeric products by means of sulphur, organic sulphur compounds or radiation, possibly in the presence of the usual accelerators and accelerator activators. Vulcanization may also be effected in the presence of (i) antioxidants or anti-ozonants, e.g. amines, phenols, quinolines or phosphites (ii) plasticizers, softeners, lubricants, tackifiers, dispersing aids, plasticizers, freezing point depressants, reinforcing agents or extenders, e.g. vegetable or mineral oils, waxes, coal tars, pitches or natural or synthetic resins; (iii) pigments, e.g. carbon blacks, calcium carbonate, hard clays, calcium silicate, silicon dioxide, zinc oxide, zinc sulphide, lithophone or titanium dioxide; (iv) fillers, e.g. soft clays, barytes, talc, asbestos fibre, cellulosic material and ebonite dust.  In examples, the following cyclic carbonates are copolymerized (1) 4,4-dimethyl-2,6-dioxacyclohexanone and 4-ethyl-4-allyloxymethyl - 2,6 - dioxacyclohexanone; (2) 4,4 - dicyanomethyl - 2,6 - dioxacyclohexanone and 4 - ethyl - 4 - allyloxymethyl - 2,6 - dioxacyclohexanone; (3) 4,4 - dichloromethyl - 2,6 - dioxacyclohexanone and 4 - ethyl - 4 - allyloxymethyl - 2,6 - dioxacyclohexanone; (4) 4,4 - di-(cyanoethoxymethyl) - 2,6 - dioxacyclohexanone and 4 - ethyl - 4 - propenoyloxymethyl - 2,6 - dioxacyclohexanone (5) 4,4 - dimethyl - 2,6 - dioxacyclohexanone and 4,4-diallyloxymethyl - 2,6 - dioxacyclohexanone; (6) 4 - nitro - 4 - ethoxymethyl - 2,6 - dioxacyclohexanone and 4 - ethyl - 4 - vinyloxymethyl - 2,6 - dioxacyclohexanone; (7) 4 - nitro - 4 - ethoxymethyl-2,6-dioxacyclohexanone, 4,4 - dimethyl - 2,6 - dioxacyclohexanone, 4,4 - dimethyl - 2,6 - dioxacyclohexanone, and 4 - ethyl - 4 - allyloxymethyl - 2,6 - dioxacyclohexanone; (8) triethylene glycol carbonate and 4-nitro-4-allyloxymethyl - 2,6 - dioxacyclohexanone; (9) 3 - oxo - 2,4,7 - trioxaspiro [5, 5] undecane and 4 - allyl - 4 - ethoxymethyl - 2,6 - dioxacyclohexanone; (10) 4,4 - dimethyl - 2,6 - dioxacyclohexanone, 4,4 - dichloromethyl - 2,6-dioxacyclohexanone and 4 - ethyl - 4 - allyloxymethyl - 2,6 - dioxacyclohexanone; (11) 3,4,5-trimethyl - 2,6 - dioxacyclohexanone and 4 - ethyl - 4 - oleoyloxymethyl - 2,6 - dioxacyclohexanone; (12) 4,4 - di - (cyanoethoxymethyl)- 2,6 - dioxacyclohexanone and 4,4 - di - (allyloxymethyl) - 2,6 - dioxacyclohexanone; (13) 4,4 - dimethyl - 2,6 - dioxacyclohexanone, 4,4-di - (chloromethyl) - 2,6 - dioxacyclohexanone and 4 - ethyl - 4 - allyloxymethyl - dioxacyclohexanone; (14) 4,4 - di - (acetoxymethyl)-2,6-dioxacyclohexanone and 4,4 - di - (3 - butenyloxymethyl) - 2,6 - dioxacyclohexanone. The products of Examples (1)-(5) were vulcanized using mixtures of two or more substances selected from benzothiazyl disulphide, tetramethylthiuram disulphide, 2-mercaptobenzothiazole and sulphur.  Vulcanization was effected in the presence of various substances selected from carbon black, zinc oxide and stearic acid.