Patent GB-768748-A (GB)
Title: Process for the preparation of fusible or liquid hydroxy-substituted allylic ethers and derivatives thereof
IPC: C08G65/331
Filed: 1954-12-15
Abstract: Resinous products employed in the manufacture of surface coating compositions, films and infusible castings, thermoplastic polymers, plasticizers, stabilizers, and cross-linking and hardening agents are prepared from fusible or liquid hydroxy allylic ethers obtained by reacting a polyether polyepoxide with such an amount of a beta-gamma ethylenically unsaturated alcohol that at least one of the epoxy groups of the polyepoxide is opened to form a <FORM:0768748/IV(a)/1> group, where R is the radical of the unsaturated alcohol. Polyether polyepoxides are compounds containing at least one ether group and at least one 1:2-epoxy group.  They may be monomeric or polymeric, saturated or unsaturated aliphatic, cycloaliphatic, aromatic or heterocyclic and may be substituted with halogen atoms, hydroxy groups and ether radicals.  Those mentioned are epoxy-alkoxy ethers of di- or polyhydric alcohols or phenols, examples of which include 4:41-bis-(2-hydroxy-3:4-epoxybutoxy)dipheny - dimethyl methane, diglycidyl ether, 1:3 - bis - (4:5 - epoxypentoxy)5 - chlorobenzene, 1:4 - bis - (3:4-epoxybutoxy)2-chlorocyclohexane, 1:2:3:4-tetra - (2 - hydroxy - 3:4 - epoxybutoxy) butane and the glycidyl ethers of the dihydroxy benzenes, bisphenol, 2:2 - bis - (41 - hydroxyphenyl) - butane, 4:41 - dihydroxybenzophenone, 1:5-dihydroxynaphthalene, glycerol, propylene glycol, diethylene glycol, hexanetriol, sorbitol, octane-1:3-diol, 1:4-dihydroxycyclohexane, pentaerythritol, polyglycerol, carbohydrates, glycerol methyl ether, glycerol allyl ether, polyvinyl alcohol and polyallylalcohol, particularly monomeric and polymeric glycidyl polyethers of dihydric phenols such as bisphenol of the general formul  <FORM:0768748/IV(a)/2> where R is the divalent radical of the dihydric phenol and n is an integer, and glycidyl polyethers of polyhydric alcohols such as glycerol.  Other polyether polyepoxides are those obtained by reacting a polyepoxide such as diglycidyl ether with a polyhydric alcohol or phenol such as catechol, resorcinol or glycerol and the polymers of allyl ethers of epoxy alcohols such as poly-(allyl 2:3-epoxypropyl ether) and copolymers of these alcohols with unsaturated monomers such as styrene, vinyl acetate, acrylonitrile, vinyl chloride and diallylphthalate.  Beta-gamma unsaturated alcohols specified include crotyl alcohol, tiglyl alcohol, cinnamyl alcohol, 2:4-hexadien-1-ol, 5-chloro-2-octen-1-ol, and alcohols of the formula <FORM:0768748/IV(a)/3> where X is hydrogen, chlorine or an aliphatic hydrocarbon radical, such as allyl alcohol, methallyl alcohol, beta-chloroallyl and ethallyl alcohols.  The hydroxy allylic ethers may be used as plasticizers and stabilizers in synthetic resin compositions or as cross-linking or hardening agents for unsaturated alkyd resins. Those containing residual epoxy groups may be used as stabilizers for the halogen-containing polymers, such as poly-(vinyl chloride).  They may be polymerized to form hard, infusible castings or copolymerized with ethylenically unsaturated monomers such as styrene and vinyl naphthalene, alkyl esters of mono- and polycarboxylic unsaturated acids such as methyl acrylate and dibutyl fumarate, alkenyl esters of saturated monocarboxylic acids such as allyl acetate, vinylidene halides such as vinyl chloride, vinyl esters of hydrocyanic acids such as acrylonitrile, vinyl ethers such as vinyl ethyl ether, and vinyl ketones such as vinyl ethyl ketone by heating in the presence of peroxide catalysts or potassium persulphate to from 65 DEG  to 250 DEG  C., to form thermoplastic polymers.  The hydroxy allylic ethers may be reacted with monocarboxylic acids such as acetic acid, stearic acid, benzoic acid or p-isopropyl benzoic acid to give esters for use as plasticizers or with polyethylenically unsaturated monocarboxylic acids such as rosin acids and acids from linseed, soya bean, or dehydrated castor oil. The hydroxy allylic ethers may be converted to alkyd resins for use as film-forming components in varnishes and enamels and as additives for surface-coating compositions by heating with polybasic acids or anhydrides such as oxalic, malonic, succinic, glutaric, adipic, sebacic, maleic, fumaric, phthalic, chlorophthalic, terephthalic, tetrahydrophthalic, naphthalenedicarboxylic, diglycollic, dithioglycollic acids and their anhydrides and in particular with aliphatic or mononuclear aromatic dicarboxylic acids of no more than 12 carbon atoms.  Modifying agents, e.g. monocarboxylic acids and acids derived from coconut, castor or cotton-seed oil or unsaturated modifying agents such as acids derived from such drying oils as linseed, soya bean, and oiticica oil and the monoglycerides of the fatty acids of these drying oils may be added in amounts of from 5-70 per cent by weight.  The alkyd resins for use in surface-coating compositions may be used alone or with synthetic or natural drying oils, amide-aldehydetype resins, cellulose derivatives and vinyl polymers, and may be combined in a liquid vehicle such as ethyl acetate, methyl ethyl ketone, ethylene glycol ethyl ether, xylene or n-butyl alcohol. Plasticizers such as dibutyl phthalate, dioctyl phthalate and tricresyl phosphate, additives such as kopal and dammar and pigments or colouring materials such as titanium pigments may be incorporated.  The surface coating compositions are heat-curable. In examples, a diallyl ether of the formula <FORM:0768748/IV(a)/4> is, (2), heated with adipic acid and xylene under nitrogen to form an alkyd resin to which a cobalt drier is added and which forms hard flexible films on drying; (3) heated with adipic acid, p-tert.-butyl benzoic acid and xylene under nitrogen to form an alkyd resin; (4) heated with phthalic anhydride and xylene to form an alkyd resin. Further examples illustrate (6), the preparation of alkyd resins by heating a diallyl ether, obtained by reacting allyl alcohol with a polyether polyepoxide derived from bis-phenol and epichlorhydrin, with adipic acid, phthalic anhydride, succinic anhydride and isophthalic acid; (7) homopolymerization of the ester obtained in Example (2); (8) co-polymerization of the ester of Example (2) with styrene; (9) preparation of a hydroxy allylic ether by heating allyl alcohol with a polyether polyepoxide derived from bisphenol and epichlorhydrin; (10) preparation of a hydroxy methallylic ether by reacting methallyl alcohol with a polyether polyepoxide derived from glycerol and epichlorhydrin; (11) preparation of a hydroxy allylic ether by reacting allyl alcohol with a polymer of allyl glycidyl ether; (12) preparation of resins by heating the compound of the formula <FORM:0768748/IV(a)/5> with styrene or with 2:4:6-tri-(dimethylamino - methyl) - phenol and a polyether polyepoxide derived from bis-phenol and epichlorhydrin.ALSO:Fusible or liquid hydroxy allylic ethers are prepared by reacting a polyether polyepoxide with such an amount of a beta-gamma ethylenically unsaturated alcohol that at least one of the epoxy groups of the polyepoxide is opened to form a <FORM:0768748/IV(b)/1> group, where R is the radical of the unsaturated alcohol.  The polyether polyepoxides used are compounds containing at least one ether linkage and at least one 1 : 2-epoxy group and may be saturated or unsaturated aliphatic, cycloaliphatic, aromatic or heterocyclic and may be substituted by halogen atoms or hydroxy or ether groups. Polyether polyepoxides specified include among others 4 : 41-bis - (2 - hydroxy - 3 : 4 - epoxybutoxy)-diphenyldimethylmethane, 1 : 3 - bis - (4 : 5-epoxypentoxy) - 5 - chlorobenzene, 1 : 4 - bis-(3 : 4 - epoxybutoxy) - 2 - chlorocyclohexane, diglycidyl ether, 1 : 2 : 3 : 4 - tetra - (2-hydroxy - 3 : 4 - epoxybutoxy) - butane and the glycidyl polyethers of polyhydric phenols such as the dihydroxy benzenes, bisphenol, 2 : 2 - bis - (41 - hydroxyphenyl) - butane, 4 : 41 - dihydroxybenzophenone, bis - (4-hydroxyphenyl) - ethane, 1 : 5 - dihydroxynaphthalene, and 4 : 41 - dihydroxydiphenyl ether and glycidyl polyethers of polyhydric alcohols such as glycerol, propylene glycol, diethylene glycol, hexanetriol, sorbitol, octane-1 : 3 - diol, 1 : 4 - dihydroxycyclohexane, pentaerythritol, polyglycerol, carbohydrates glycerol methyl ether, and glycerol allyl ether. Other polyether polyepoxides mentioned include the reaction product of a polyhydric alcohol or phenol with a polyepoxide such as the reaction product of glycerol, resorcinol or catechol with diglycidyl ether, the reaction product of bis-(2 : 3-epoxy-2-methylpropyl)-ether with sorbitol or bisphenol or of pentaerithritol with 1 : 2-epoxy-4 : 5-epoxypentane.  Beta - gamma ethylenically unsaturated alcohols specified include, among others, crotyl alcohol, tiglyl alcohol, cinnamyl alcohol, 2 : 4-hexadien - 1 - ol, 5 - chloro - 2 - octen - 1 - ol, 4 - phenyl - 2 - hepten - 1 - ol and in particular alcohols of the formula <FORM:0768748/IV(b)/2> where X is hydrogen, chlorine or an aliphatic hydrocarbon radical, such as allyl, methallyl, beta-chloroallyl and ethallyl alcohols. The reaction is effected by mixing the reactants at temperatures from 10 DEG  to 125 DEG  C.  Catalysts such as acid-acting fluorine containing compounds, stannic halides, mineral acids, caustic soda, pyridine or active charcoal may be used in amounts from 0.01 to 8 per cent by weight of the reactants.  Solvents or diluents may be used in the reaction and include toluene, benzene and ethylene glycol monoacetate methyl ether or mixtures thereof.  The polyepoxide and unsaturated alcohol may be reacted in chemically equivalent ratios of from 1 : 1 to 1 : 4 to obtain hydroxy allylic ethers, or from 0.5 to 0.75 equivalents of alcohol per equivalent of polyepoxide to obtain hydroxy allylic ethers containing residual epoxy groups.  The reaction product is isolated by removal of the catalyst, solvent and any excess alcohol by conventional means such as neutralization or