Patent GB-867461-A (GB)
Title: Process for the production of organic compounds of high molecular weight from an organic compound contanining at least one linear or cyclic acetal group, an alkylene oxide and a compound containing at least one reactive carbon-to-carbon double bond
IPC: C08G4/00
Filed: 1959-04-03
Abstract: High molecular weight organic compounds are prepared by reacting a compound containing at least one linear or cyclic acetal group with an alkylene oxide and with a compound containing at least one carbon-to-carbon double bond in the presence of a catalyst.  Suitable acetal compounds are reaction products of formaldehyde, acetaldehyde, benzaldehyde or glyoxal with hydroxy compounds, e.g. methanol, ethanol, b -chloroethanol, propanol, benzyl alcohol, propyl alcohol, cyclohexanol, allyl or oleyl alcohol, pentanediols, hexanediols, 7, 18, -dihydroxyoctadecane, 2-butane-1, 4-diol, 2-butyne-1, 4-diol, trimethylol propane, glycerine, sorbitol, 4, 41-dihydroxy dycyclohexyl methane, ethylene glycol, propane-1, 2- or 1, 3-diol, butane or butene-diols, condensates of alkylene oxides with such alcohols or phenols, glycerine monomethyl methacrylate, trimethylol propane monoallyl ether, castor oil, phthalic acid diglycol ester, hydroxyl-containing polyesters, polythioethers with terminal OH groups, polyvinyl alcohol, and adipic acid-bishydroxyethyl methylamide.  Other suitable polyacetals can be prepared from condensates of formaldehyde with xylene, phenols, urea or melamine. Suitable alkylene oxides are ethylene, trimethylene, propylene, butylene or styrene oxide, oxides as described in Specification 758,450, epichlorhydrin, 3-ethyl-3-hydroxymethyl trimethylene oxide, 1-allyl-hydroxy-2, 3-epoxypropane, reaction products of unsaturated carboxylic acids with peroxidic compounds, vinyl cyclohene oxide, dioxaspiroheptane, butadiene dioxide, and glycidyl ethers obtained by reacting epichlorhydrin with a polyhydric compound.  Some olefins mentioned are ethylene, propylene, butylene, styrene, butadiene, isoprene, divinyl benzene, cyclopentadiene, vinyl chloride, allyl chloride, acrylonitrile, maleic or cinnamic acid esters, and chloroprene. Suitable catalysts are boron trihalides and their ether adducts, acid chlorides of chlorosulphonic acid type, ferric chloride, AlCl, SbCl3 and others usual for ionic polymerization. Reaction may be in solvents, e.g. hydrocarbons, chlorinated hydrocarbons, esters, ethers, ketones.  Polymerization inhibitors, e.g. hydroquinone may also be present.  In Examples (1) trimethylene glycolformaldehyde polyacetal and propylene oxide are reacted in presence of boron trifluoride diethyl ether etherate and the product reacted with styrene; (2) Styrene and propylene oxide are reacted with a mixture of dimethyl formal, boron trifluoride diethyl ether etherate and hydroquinone; (3) is similar to (2) but uses a polyacetal from trioxyethylated trimethylol propane and formaldehyde; (4) Butane-1, 4-diol methylene ether is treated with boron trifluoride and the viscous product, after addition of hydroquinone is reacted with propylene oxide and chloroprene; (5) A styrene-propylene oxide mixture is reacted with 4-phenyl-1, 3-dioxane in presence of hydroquinone and boron trifluoride diethyl ether etherate; (6) Boron trifluoride-tetrahydrofuran etherate, hydroquinone, and butane-1, 4-dioxethyl glycol formaldehyde polyacetal were mixed, and butadiene and propylene oxide were added dropwise to react; (7) is similar to (3) with epichlorhydrin replacing the propylene oxide; (8) Boron trifluoride-tetrahydrofuran etherate is mixed with the polyacetal of Example 1, and the mixture reacted with styrene, propylene oxide and a polyglycidyl ether from butane diol and epichlorhydrin; (9) Diethylene glycolformaldehyde polyacetal, hydroquinone and boron trifluoride-tetrahydrofuran etherate are reacted with 3-ethyl-3-hydroxymethyl trimethylene oxide and styrene; (10) The polyacetal of Example 6, hydroquinone and FeCl3 are reacted with propylene oxide and styrene; (11) Boron trifluoride is mixed with the polyacetal of Example 1 and 1-allyloxy-2, 3-epoxypropane; (12) The polyacetal of Example 1 is reacted with ethylene oxide in presence of boron trifluoride-tetrahydrofuran etherate and the product reacted with styrene; (13) The polyacetal of Example 1 is mixed with boron trifluoride-di-ethyl ether etherate and hydroquinone.  The mixture is reacted with isobutylene and propylene oxide; (14) The polyacetal of Example 1 is used with AlCl3, hydroquinone, styrene and styrene oxide; (15) The polyacetal of Example 6 is reacted with propylene oxide in presence of FeCl3 and the product reacted with propylene oxide and isobutylene.  By choosing reactants to give products with reactive groups, e.g. hydroxyl, terminal halogen or double bonds the products may be subjected to further reactions, e.g. for modifying polyesters or epoxide resins or for making plastics by the polyisocyanate polyaddition process.  The products also find uses as plasticisers or emulsifiers.