Patent GB-1000389-A (GB)
Title: New telomers containing epoxy groups and process for their preparation
IPC: C07F9/655
Filed: 1961-09-25
Abstract: The invention comprises telomer epoxides of formula <FORM:1000389/C3/1> where Y is an inorganic or organic monovalent residue and Z is hydrogen or halogen, being residues of a telogen YZ; R1 to R3 are hydrogen or methyl; R4 to R7 are hydrogen, halogen or organic substituents of 1-13 carbon atoms; and R is an aliphatic, araliphatic or aromatic residue containing at least one group of formula <FORM:1000389/C3/2> where R1 is hydrogen or an aliphatic or aromatic hydrocarbon residue, R11 and R111 are hydrogen or methyl, and p is 1 or 2; and m and n are small whole numbers, the sum m+n - 1 being 2-20, and the disposition of the units CRR1-CR2R3 and CR4R5-CR6R7 within the chain being optional; and their production from YZ and CRaR1=CR2R3 and, if desired, CR4R5=CR6R7 (where Ra is the same as R or a residue that can be converted to R by formation of an epoxy ring) in the presence of octinic radiation or of a catalyst capable of furnishing free radicals, and, if necessary, converting Ra to R.  Thus, Ra can contain a double bond, or OH and halogen an adjacent carbon atoms.  Specified telogens YZ are CCl4, CBr4, CHCl3, CH2ClI, CH2Cl2, CH2I2, CH3I, CF2ClBr, CF2Br2, CHBrCl2, CF3I, C2H2Cl4, C2Cl6, C2HCl3, hexachlorocyclohexane, benzotrichloride, methyl mono- and dichloroacetate, diethyl bromomalonate, CCl3COCl, CCl3CN, a -chloronitroalkanes, isopropylbenzene, CH2O, CH3CHO, benzaldehyde, D 3-tetrahydrobenzaldehyde, mesityl oxide, cyclohexanone, dimethyl formal, dioxolane, acetic acid, isobutyric acid, methyl formate, ethyl formate, methanol, ethanol, isopropanol, lauryl alcohol, H2S, mercaptans, thiophenols, NaHSO3, aromatic sulphonyl chlorides, dialkyl phosphites, SiCl4, SiHCl3, SiH4, alkyl silanes, Cl2, I2, CNCl and HCl.  Specified taxogens CRaR1 = CR2R3 are allyl glycidyl ether, allyl 2,3-epoxy-butyl -1 ether, allyl 9,10-epoxystearyl ether, allyl glycidyl formal, bisphenol A allyl glycidyl ether, allyl, 2,3-epoxy-3-phenylpropyl-1 ether, o-allylphenyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, glycidyl crotonate, allyl glycidyl maleate and allyl glycidyl phthalate; diallyl ether, allyl crotyl ether, allyl methallyl ether, allyl oleyl ether, diallyl formal, diallyl phthalate, allyl cinnamyl ether and allyl 3 - chloro - 2 - hydroxy - 1 - propyl ether. Specified cotaxogens CR4R5 = CR6R7 include olefines, halogenated olefines, vinyl ethers, vinyl aryl compounds, acrylic and methacrylic esters and nitriles and corresponding derivatives of haloacrylic, crotonic, maleic and fumaric acids; and epoxy compounds such as monoepoxybutadiene and monoepoxydivinylbenzene.  Many telomerization catalysts are specified.  The telomers of the formula given can be cured with conventional curing agents for epoxy compounds and many such curing agents are listed.  The products of the invention may be used with other epoxy resins, or in combination with methylolated acrylamide copolymers to form coating compositions (see Division B2).  Other materials.-Polyglycidyl ethers are obtained by reacting epichlorohydrin with bis-(4 - hydroxyphenyl) - dimethylmethane in the presence of an alkali.  A methylolated acrylamide copolymer is prepared by refluxing a mixture of styrene, butyl acrylate and acrylamide with cumene hydroperoxide and dodecyl mercaptan in butanol, and refluxing the product with formaldehyde and maleic anhydride in butanol; some butanol is distilled off and xylene added. Specification 1,000,390 is referred to.ALSO:The invention comprises telomer epoxides of formula <FORM:1000389/C2/1> where Y is an inorganic or organic monovalent residue and Z is hydrogen or halogen, being residues of a telogen YZ; R1 to R3 are hydrogen or methyl; R4 to R7 are hydrogen, halogen or organic substituents of 1-13 carbon atoms; and R is an aliphatic, araliphatic or aromatic residue containing at least one group of formula <FORM:1000389/C2/2> where R1 is hydrogen, or an aliphatic or aromatic hydrocarbon residue, R11 and R111 are hydrogen or methyl, and p is 1 or 2; and m and n are small whole numbers, the sum m+n-1 being 2-20, and the disposition of the units CRR1-CR2R3 and CR4R5-CR6R7 within the chain being optional; and their production from YZ and CRaR1 = CR2R3 and, if desired, CR4R5 = CR6R7 (where Ra is the same as R or is a residue that can be converted to R by formation of an epoxy ring) in the presence of actinic radiation or of a catalyst capable of furnishing free radicals, and, if necessary, converting Ra to R.  Thus Ra can contain a double bond, or OH and halogen on adjacent carbon atoms.  Specified telogens YZ are CCl4, CBr4, CHCl3, CH2CLI, CH2Cl2, CH2I2, CH3I, CF2ClBr, CF2Br2, CHBrCl2, CF3I, C2H2Cl4, C2Cl6, C2HCl3, hexachlorocyclohexane, benzotrichloride, mono- and dichloroacetic acid methyl ester, diethyl bromomalonate, trichloroacetyl chloride, CCl3CN, a -chloronitroalkanes, isopropylbenzene, CH2O, CH3CHO, benzaldehyde, D 3 - tetrahydrobenzoldehyde, mesityl oxide, cyclohexanone, dimethyl formal, dioxolane, acetic acid, isobutyric acid, methyl formate, ethyl formate, methanol, ethanol, isopropanol, lauryl alcohol, H2S, mercaptans, thiophenols, NaHSO3, aromatic sulphonyl chlorides, dialkyl phosphites, Cl2, I2, CNCl and HCl. Specified taxogens CRaR1 = CR2R3 are allyl glycidyl ether, allyl 2,3-epoxybutyl-1 ether, allyl 9,10-epoxystearyl ether, allyl glycidyl formal, bisphenol A allyl glycidyl ether, allyl 2,3-epoxy-3-phenylpropyl-1 ether, o-allyl phenyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, glycidyl crotonate, allyl glycidyl maleate and allyl glycidyl phthalate; diallyl ether, allyl crotyl ether, allyl methallyl ether, allyl oleyl ether, diallyl formal, diallyl phthalate, allyl cinnomyl ether and allyl 3-chloro-2-hydroxy-1-propyl ether.  Specified cotaxogens CR4R5 = CR6R7 include olefines, halogenate olefines, vinyl ethers, vinyl aryl compounds, acrylic and methactylic esters and nitriles and corresponding derivatives of haloacrylic, crotonic, maleic and fumaric acids; and epoxye compounds such as monoepoxybutadiene and monoepoxydivinylbenzene. Many telomerization catalysts are specified. The telomers of the invention can be cured (see Division C3). Examples react (1) CCl4 with allyl glycidyl ether; (2) CCl4 with allyl glycidyl formal; (3) CCl4 with o-allyl phenyl glycidyl ether; (4) CCl4 with allyl 3-chloro-2-hydroxy-1-propyl ether, followed by dehydrochlorination; (5) CCl4 with diallyl phthalate, followed by epoxidation; (6) dimethyl phosphite with allyl glycidyl ether; (7) cyclohexanone with allyl glycidyl ether; (8) dimethyl phosphite with diallyl phthalate monoepoxide; (9) cyclohexanone with allylphenyl glycidyl ether; (10) diethyl phosphite with allyl glycidyl ether; and (11) dimethyl phosphite with allyl glycidyl ether and tetrachloroethylene.  The compound <FORM:1000389/C2/3> is obtained (Example 16) from the diglycidyl ether of 1,1-bis-hydroxymethyl-cyclohexene-3 and hexahclorocyclopentadiene. Specification 1,000,390 is referred to.ALSO:In Examples 17 and 18, sheet aluminium is coated with a composition containing diacetone alcohol, butyl acetate, methyl ethyl ketone and ethylene glycol monoethyl ether, a xylene solution of a methylolated acrylamide copolymer (see Division C3) and a telomer obtained from (i) allyl glycidyl phthalate and dimethyl phosphite, or (ii) allyl phenyl glycidyl ether and cyclohexanone (see Division C2), and the coating is cured by heating.  Specification 1,000,390 is referred to.