Patent GB-959902-A (GB)
Title: New telomers and process for their preparation
IPC: C07D303/24
Filed: 1961-08-25
Abstract: The invention comprises telomers of the formula: <FORM:0959902/C2/1> where Y is an inorganic or organic monovalent residue and Z is a hydrogen or halogen atom formed by the scission of a telogen YZ, R1 to R3 each represents a hydrogen atom or a methyl group, R4 to R7 each represents a hydrogen or halogen atom or an organic substituent containing 1 to 13 carbon atoms; R represents an organic residue containing at least one carbocyclic five-membered or six-membered ring containing at least one epoxide group fused to the ring or one epoxidisable group in the ring, and n and m are small whole numbers, the sum [n+(m-1)] is at least 1 and at most 20, preferably at least 2 and at most 10, and in which the order of disposition of the individual structural units [CRR1-CR2R3] and [CR4R5-CR6R7] in the chain may be as desired. The novel compounds may be prepared by reacting one molecular proportion of a telogen YZ with n mols of a monomer of the formula RCR1=CR2R3 and, if desired, further with (m-1) mols of a monomer of the formula CR4R5=CR6R7, preferably in the presence of a catalyst furnishing free radicals and, if desired, epoxidising any epoxidisable groups present in the telomer. Typical taxogens are 1-vinyl-3:4-epoxycyclohexane, alkenyl esters of 3:4-epoxycyclohexanecarboxylic acids, alkenoic esters of a 3,4-epoxycyclohexyl methanol, monoepoxides of the formula: <FORM:0959902/C2/2> where R is hydrogen or a methyl radical and X1 and X2 each represents a hydrogen atom or a methyl group, or of the formula: <FORM:0959902/C2/3> where p=1 or 2, or the corresponding compounds containing a double bond instead of an epoxide ring. Suitable telogens YZ are halogenated hydrocarbons, halogenated esters, haloalkylnitriles, aldehydes, ketones, acetals, carboxylic acids, esters and anhydrides, alcohols, sulphur compounds, phosphorus compounds, silicon compounds and inorganic halogen compounds. The reaction taken place in the range of 0 DEG  to 200 DEG C., and can be performed batchwise or continuously. Suitable catalysts are hydrazine derivatives, organometal compounds, aliphatic azo compounds, and organic peroxides or persalts. In certain cases cationic or anionic catalysts, or actinic rays may be used. The epoxidation of carbon-carbon double bonds is effected conventionally by per acids, a mixture of H2O2 and organic acid or in two stages with hypochlorous acid and a strong alkali. The unsaturated acetal corresponding to formula II, where X1 and X2 are hydrogen, is obtained from acrolein and 1:1-bis-[hydroxymethyl]-cyclohexene-3, and is epoxidized to acetal II. Acetal II, where p is 1, is made from dihydrodicyclopentadienol-8 and allyl chloride or dicyclopentadiene and allyl alcohol to form the allyl dihydrodicyclopentadienyl ether which is epoxidized.  Vinyl dicyclopentadienyl ether is made from dihydrodicyclopentadienol-8 and acetylene. Detailed examples of these starting materials and preparation of telomers with carbon tetrachloride, thiophenol, tetrahydrobenzaldehyde, cyclohexanone, dimethyl phosphite, and acrylonitrile, or styrene and cyclohexanone, are given.ALSO:Curable compositions comprise telomers of the formula: <FORM:0959902/C3/1> where Y is an inorganic or organic monovalent residue and Z is a hydrogen or halogen atom formed by the scission or halogen atom formed by the scission of a telogen YZ, R1 to R3 each represents a hydrogen atom or a methyl group, R4 to R7 each represents a hydrogen or halogen atom or an organic substituent containing 1 to 13 carbon atoms; R represents an organic residue containing at least one carbocyclic five-membered or six-membered ring containing at least one epoxide group fused to the ring, and n and m are small whole numbers, the sum [n+(m-1)] is at least 1 and at most 20, preferably at least 2 and at most 10, and in which the order of disposition of the individual structural units [CCR1-CR2R3] and [CR4R5-CR6R7] in the chain may be as desired, together with conventional curing agents for epoxy compounds. Other curable condensation resins such as aminoplasts, phenoplasts, epoxy resins, and polyacetals may also be present. Suitable curing agents include amino or amides, formaldehyde resins with aniline, urea or melamine, polymers of aminostyrenes, polyamides, isocyanates, isothiocyanates, polyhydric phenols, phenolaldehyde resins, reaction products of aluminium alcoholates or phenolates with tautomeric compounds, Friedel Crafts catalysts, boroxines, metal fluoborates, phosphonic acid, salts of acid reaction, polybasic carboxylic acids and anhydrides thereof, if desired in conjunction with an accelerator, such as a tertiary amine. Detailed examples are given.  Telomers of the above formula where Y is a silicon-containing residue and Z is a hydrogen or halogen atom formed by scission of a telogen YZ which represents a silicon compound such as silicon tetrachloride, trichlorosilane, silane or alkyl silanes, are prepared by reacting one molecular proportion of a telogen YZ with n mols of a monomer of the formula RCR1=CR2R3 and, if desired, with (m-1) mols of a monomer of the formula CR4R5=CR6R7, preferably in the presence of a catalyst furnishing free radicals and, if desired, epoxidising any epoxidisable groups present in the telomer. The reaction takes place in the temperature range of 0 DEG  to 200 DEG C.