Patent GB-1007842-A (GB)
Title: Process for the production of cured resins and curable resin mixtures of use therein
IPC: C08K5/01
Filed: 1962-12-12
Abstract: A dimeric or low polymeric bis-(cyclopentadienyl) compound of formula <FORM:1007842/C4-C5/1> where R is a bivalent radical, n is a whole number from 2 to 20 and R1 and R11 each are hydrogen or methyl, is prepared by reacting an alkali metal or Grignard compound of cyclopentadiene or of methylcyclopentadiene with dihalogen compounds of formula X-R-X where R is the bivalent radical and X is a halogen atom and then heating the mixture. In Examples (I) polymeric 1 : 5-bis-(cyclopentadienyl) pentane is prepared by adding 1 : 5-dibromopentane at 50 DEG  to 55 DEG  C. to a cyclopentadiene sodium xylene suspension cooled to room temperature, methanol and water added, neutralized, the xylene layer separated and the xylene distilled off; (II) dimeric 1 : 4-bis-(cyclopentadienyl) - butene - 2, as described in Specification 1,007,843; (III) polymeric 4 : 6 - bis - (cyclopentadienylmethyl) - 1 : 3-dimethyl benzene from a suspension of cyclopentadienyl sodium in xylene-ethyleneglycol diethylether and a solution of 4 : 6-bis-(chloromethyl)-1 : 3-dimethylbenzene in xylene, mixed at 50 DEG  C., then heated to 130 DEG  C. and the solvent evaporated; (IV) polymeric 1 : 3-bis-(cyclopentadienyl - methyl) - 2: 4: 6 - trimethyl-benzene from 1 : 3 - bis - (chloromethyl) -2:4:6-trimethyl benzene and cyclopentadienyl sodium in a similar manner; (IX) oligomeric bis-(cyclopentadienyl methane by heating methylene chloride with a suspension of cyclopentadienyl sodium and neutralizing with glacial acetic acid; (X) oligomeric 1 : 4-bis-(cyclopentadienyl) butine-(2) by heating a mixture of 1 : 4-dichlorobutine-(2) in tetrahydrofuran with a suspension of cyclopentadienyl sodium in xylene and neutralizing with glacial acetic acid; (XI) oligomeric bis-(cyclopentadienyl) phenylmethane by replacing the butine-(2) above by benzalchloride; and (XV) oligomeric 1 : 4-bis-(cyclopentadienyl) cyclopentene-(2) from cyclopentadienyl sodium and 1 : 4-dibromocyclopentene-(2).  Hexamethylolmelamine penta-alkyl ether is prepared by mixing hexamethyolamine, allyl alcohol and hydrychloric acid, neutralizing, washing and dehydrating when a water-clear syrup of an allyl ether containing about five allyl ether groups per molecular proportion of melamine is produced. Specification 1,007,841 also is referred to.ALSO:A cured resin is obtained by heating (1) a dimeric or low-polymeric bis-(cyclopentadienyl) compound of formula <FORM:1007842/C3/1> where R is a bivalent radical, n is a whole number from 2 to 20 and R1 and R11 each are hydrogen or methyl with (2) an unsaturated drenophilic compound having a non-aromatic carbon - to - carbon double bond equivalence, or carbon-to-carbon triple bond equivalence, or both, exceeding 2.  The bivalent radical may be <FORM:1007842/C3/2> or <FORM:1007842/C3/3> or a bivalent aliphatic cycloaliphatic, araliphatic or aromatic hydrocarbon residues which may be interrupted by oxygen atoms or substituted by hydroxyl or halogen.  The compound (1) includes dimeric or polymeric 1 : 5-bis - (cyclopentadienyl) - pentane, dimeric or polymeric 1 : 4 - bis - (cyclopentadienyl) - butene-2, dimeric or polymeric 4 : 6-bis-(cyclopentadienyl - methyl) - 1 : 3 - dimethyl - benzene, dimeric or polymeric 1 : 3-bis-(cyclopentadienyl) - methyl) - 2 : 4 : 6 - trimethyl benzene and dimeric or polymeric dicyclopentadienyl - dimethylsilane. Compound (2) includes unsaturated polyesters, triglycerides of unsaturated fatty acids, esters from monobasic unsaturated monocarboxylic acids with trihydric or polyhydric alcohols, e.g. glycerol trisacrylate, esters from unsaturated dicarboxylic or polycarboxylic acids with unsaturated monohydric alcohols, e.g. diallyl maleate, ethers from unsaturated monohydric alcohols and compounds containing three or more hydroxyl groups, e.g. hexamethylolmelamine pentaallyl ether, esters of acetylene-dicarboxylic acids with monohydric unsaturated alcohols, esters of propargylic acid with trihydric alcohols and polymers or copolymers of butadiene and of isoprene.  Unsaturated polyesters specified are those from (A) isophthalic acid, phthalic acid, and 1: 2-propylene glycol, which mixture is esterified and then reacted with maleic anhydride; (B) maleic anhydride and neopentyl-glycol; (C) hexachloroendomethylene - tetrahydrophthalic anhydride, maleic anhydride and 1: 2-propylene glycol; (D) fumaric acid and 1: 2-propylene glycol; (E) acetylene-dicarboxylic acid and bis(2-hydroxy-ethyl) isophthalate; and (F) ethylene glycol, diethylene glycol, maleic anhydride, phthalic anhydride and adipic acid.  The polymerization may take place in the presence of a catalyst, e.g. a metal drier or tertiary butyl-perbenzoate and oxygen, while additives such as kaolin, titanium dioxide and large amounts of glass fibres may be present in solution in e.g., ethylene chloride.  The dimeric or polymeric bis-(cyclopentadienyl) compounds are obtained by reacting alkali-metal or Grignard compounds of cyclopentadiene or of methyl cyclopentadiene with dihalogen compounds of formula X-R-X where R is the bivalent radical and X a halogen atom.  The preparation of the following is disclosed:-(VII) dimeric dicyclopentadienyldimethyl silane from cyclopentadienyl sodium and dimethyldichlorosilane; (VIII) dimeric di-(#c - methylcyclopentadienyl) - dimethyl silane from methylcyclopentadiene sodium and dimethyldichloro silane; (XIV) dimeric dicyclopentadienyl-diphenyl dichlorosilane from cyclopentadienyl sodium and diphenyldichlorosilane and (XVI) the copolymer of 1:4-bis-)cyclopentadienyl) butene-2 and 2: 21-bis-(cyclopentadienyl)-diethyl ether.  Specifications 1,007,841 and 1,007,843 are referred to.ALSO:A dimeric or low polymeric bis-(cyclopentadienyl) compound of formula <FORM:1007842/C2/1> where R is a bivalent radical, n is a whole number from 2 to 20 and R1 and R11 each are hydrogen or methyl is prepared by reacting an alkali metal or Grignard compound of cyclopentadiene or of methylcyclopentadiene with dihalogen compounds of formula X-R-X, where R is the bivalent radical and X is a halogen atom and then heating the mixture. In Example (V) a mixture of isomers of polymeric bis-(cyclopentadienyl-pentenyl)-ethers is made by mixing with external cooling, a mixture of isomers of bis-(chloropentyl) ethers [bis-(5 - chloro - 3 - pentenyl) ether and bis-(3-chloro - 4 - pentenyl) ether] in xylene with a sodium cyclopentadienyl suspension; (VI) dimeric 1:3-bis-(cyclopentadienyl)-propanol-2 by adding epichlorhydrin to a xylene suspension of cyclopentadienyl sodium; (XII) oligomeric 2 : 21 - bis - (cyclopentadienyl) diisopropyl ether is made from cyclopentadienyl sodium and 2 : 21 - dichlorodiisopropyl ether; and (XIII) polymeric 2 : 21-bis-(cyclopentadienyl - methyl) - spiro - bimetadioxane is made from cyclopentadienyl sodium and pentaerythritol - bis - (chloroacetaldehyde) acetal. Hexamethylolmelamine penta-allyl ether is prepared by mixing hexamethylolmelamine, allyl alcohol and hydrochloric acid, neutralising, washing and dehydrating when a water-clear syrup of an allyl ether containing about five allyl ether groups per molecular proportion of melamine is produced.  Specifications 1,007,841 and 1,007,843 are referred to.ALSO:A curable mixture which is applied as a lacquer and then cured comprises (1) a dimeric or low polymeric bis(cyclopentadienyl) compound of formula <FORM:1007842/B1-B2/1> where R is a bivalent radical, n is a whole number from 2 to 20 and R1 and R11 each are hydrogen or methyl with (2) an unsaturated dienophilic compound having a non aromatic carbon-to-carbon double bond equivalence, or carbon-to-carbon triple bond equivalence, or both, exceeding 2 (see Division C3). In Examples (4) an unsaturated polyester or linseed oil is mixed with (a) polymeric 1 : 5-bis(A) pentane (A is cyclo-pentadienyl), (b) dimeric 1:4-bis(A)-butene-(2), (c) polymeric 4 : 6-bis(A-methyl-1:3-dimethyl-benzene, (d) dimeric di-(A)-methyl-silane, (e) dimeric di-(x-methyl-A)-dimethyl-silane in chloroform, coated on aluminium sheets and then dried and cured; (5) a lacquer solution of (b) with a butadiene styrene copolymer on benzene is coated on to aluminium sheets and cured, and (6) an unsaturated polyester or hexamethylol melamine pentaalkyl ether in lacquer solution with (a) polymeric 2 : 21-bis(A-methyl)-spiro-h-metadioxane or dimeric di-(A)-diphenylsilane are coated on to aluminium sheet, dried and cured.  Specifications 1,007,841 and 1,007,843 are referred to.