Patent GB-793915-A (GB)
Title: Production of polymeric materials from polyoxyalkylene polyols and organic polyepoxycompounds
IPC: C08L63/00
Filed: 1956-09-05
Abstract: Polymeric compounds of high molecular weight suitable for use as lubricants for moulding and extruding compositions, dispersing agents, thickeners, suspending, coagulating and surface-active agents and for use in coating, textile, sizing, binding, laminating and casting compositions, are obtained by reacting a polyoxyalkylene glycol, having an average m.w. of at least 600 and preferably 1000-10,000, with an organic compound having as sole reactive groups at least two epoxy groups, in the presence of a Friedel-Crafts or alkali metal alcoholate catalyst.  The polyoxyalkylene polyols are obtained by condensation of an alkylene oxide with a compound having at least two primary hydroxyl groups or one primary and one secondary hydroxyl group and having the general formula H-O(RC2H3-O)n-H where R is hydrogen or an alkyl group.  Preferred compounds having at least two epoxy groups are butadiene diepoxide, diglycidyl ether, the diglycidyl ether of 2,2-bis-(4-hydroxyphenyl) - propane, 4 - vinyl - cyclohexene diepoxide dicyclopentadiene diepoxide, bis-(2,3-epoxycyclopentyl) ether, ethylene glycol bis-(3,4 - epoxy - methylcyclohexanecarboxylate), 3,4 - epoxy - methylcyclohexylmethyl 3,4-epoxy - methylcyclohexane - carboxylate.  The polyepoxy compounds serve as chain extenders between the polyoxyalkylene glycol chains and as cross-linking agents.  The linear products are water soluble while cross-linked products are water insoluble solids suitable for moulding and casting.  The reaction is carried out at temperatures from 25-250 DEG  C. in presence of inert diluents and solvents, e.g. dioxane, glycol ethers, toluene, benzene xylene; from 0.2-20 mol. polyepoxy compound per mol. polyoxyalkylene glycol may be used. Friedel-Crafts catalysts specified are halides of B, Al, Zn, Fe or Sn.  The alkali metal alcoholates may be employed as alcoholates of the polyethylene glycols formed in situ, e.g. by addition of NaOH or KOH.  The reaction can be stopped by adding a chain-stopping agent or neutralizing the reaction mixture.  In examples: (1) 1000 gs. of a polyoxyethylene glycol of m.w. 1000 is heated to 65 DEG  C. in nitrogen with 8.873 gs. aqueous NaOH and 109 gs. of the product is heated to 95 DEG  C. with 2.878 gs. diglycidyl ether of 2,2-bis-(4-hydroxyphenyl)-propane; a tan-coloured wax was obtained which dissolves in acetonitrile; (2) as in (1), using butadiene diepoxide; (3) a similar polyoxyglycol ether was reacted with boron trifluoride-diethyl ether complex and the products reacted with a similar glycol which had been reacted with 3,4,6-methylcyclohexane-carboxylate; (6) a diepoxide obtained by epoxidizing bis-(2-cyclopentenyl) ether was reacted with a polyoxyethylene glycol part of which had been pre-reacted with aqueous KOH; (20) a polyoxyethylene polyol was prepared from sucrose and ethylene oxide using sodium methylate as catalyst and benzene as solvent.  The regulating slurry containing unreacted sucrose, benzene and sodium alcoholate was hydroxyethylated in a bomb by addition of ethylene oxide.  After removal of sediment, benzene and unreacted ethylene oxide a light-brown syrup remained which was treated with metallic sodium and additional sucrose and ethylene oxide in an autoclave.  The hydroxyethylated sucrose obtained after treatment with metallic potassium was reacted with butadiene diepoxide to give a yellow hard brittle resin.