Patent GB-1078751-A (GB)
Title: Improvements in or relating to reactive end-group polymers and preparation thereof
IPC: C08G18/52
Filed: 1964-08-04
Abstract: Polyethers, polythioethers and polyimines are cleaved to lower molecular weight polymers or monomeric diols by reacting with an organo-metallic compound of an alkali-metal; the polymers to be cleaved contain at least two units of formula <FORM:1078751/C3/1> wherein X is O, S or NR; R, R1, R2, R3, R4, R5 and R6 are each hydrocarbon, hydrocarbonoxyhydrocarbon or haloalkyl groups, or R1 forms a cyclic structure with R, R2, R3 or R4; m is an integer, n is zero or an integer, p is zero or 1, and the sequence of units is such that at least one hydrogen atom is attached to a carbon atom in a beta position to X.  Examples are homopolymers and copolymers of epoxide, episulphides, alkyleneimines and thioaldehydes and copolymers and graft copolymers comprising units derived from the above with other addition and condensation polymers; many are specified. Suitable organo-metal catalysts are listed. The products contain reactive end-groups, viz. XH, X-alkali-metal or alkenyl groups; the latter two groups may be hydrolysed to XH groups.  The polyethers may be extended by reaction with polyisocyanates, polyepoxides, polyaziridines, polycarboxylic-anhydrides, polyimides, alkylene oxides, polyols, styrene, acrylates, methacrylates, acrylonitrile and acrylamides; polythioethers may be reacted with polyisocyanates, phenols, phenol-formaldehyde resins, di-epoxy resins, organic titanates, or quinone dioxime, or oxidized to polymers containing disulphide linkages; the polyimines may be reacted with diisocyanates, polyalkylene glycols, polyesters, polyamides, polyurethanes, polyureas and diacrylates; many suitable reagents are specified.  The end groups of the polymers may also be modified by diisocyanate, sodium azide, N2O4, phosgene or dianhydrides and the products polymerized by reacting with polyfunctional compounds, e.g. water polyols or polyamines.  The examples describe the preparation and subsequent cleaving of polymers derived from trans- and cis-butene-2-oxides, propylene oxide/alkylglycidyl ether, epichlorohydrin, isobutylene oxide, phenyl glycidyl ether, butadiene monoxide, styrene, propylene oxide (isotactic and atactic polymers), cyclohexene oxide, isopropyl glycidyl ether, trimethylene oxide, tetrahydrofuran, trimethylene sulphide, N-n-butyl-ethyleneimine, and propylene sulphide; methylene di-p-phenyl isocyanate is reacted with (30) poly(trans-butene-2-oxide) and (35) poly(propylene glycol); (31) and (32) poly(trans-butene-2-oxide) is reacted with a tolylene diisocyanate/trimethylol propane condensate yielding a tetraisocyanate and a polyurethane respectively; in (33), (34) and (36) poly(transbutene-2-oxide) and poly(propyleneglycol) and mixtures thereof are converted to polyurethane foams by reacting with tolylene disisocyanate, water, triethylene diamine, stannous octoate and a silicone oil.ALSO:Polyethers, polythioethers and polyimines are cleaved to lower molecular weight polymers or monomeric diols by reacting with an organo-metallic compound of an alkali-metal; the polymers to be cleaved contain at least two units of formula <FORM:1078751/C2/1> wherein X is O, S or NR; R, R1, R2, R3, R4, R5 and R6 are each hydrocarbon, hydrocarbonoxy-hydrocarbon or haloalkyl groups, or R1 forms a cycle structure with R, R2, R3 or R4; m is an integer, n is zero or an integer, p is zero or 1; and the sequence of units is such that at least one hydrogen atom is attached to a carbon atom in a beta position to X.  The polymers may be homo- and co-polymers of epoxides, episulphides and alkyleneimines; many are listed.  Suitable organic-metallic catalysts are also listed.  The products contain reactive end-groups, viz. XH, X-alkali-metal or alkenyl groups; the latter two groups may be hydrolysed to XH and OH groups respectively. Typical examples describe the cleaving of polymers to form (16) poly(styreneoxide) (molecular weight of 808), (26) poly(N-n-butylethyleneimine) (molecular weight of 466) and (29) poly (trans-butene-2-oxide) (molecular weight of 507); in (37) meso-2,3-butanediol is prepared by cleaving poly(trans-butene-2-oxide).