Patent GB-1029037-A (GB)
Title: Curable mixtures of epoxy resins and polyanhydrides or polycarboxylic acids
IPC: C08G59/42
Filed: 1963-02-28
Abstract: Bis-(methyl)-cyclopentadienyl hydrocarbons are obtained by condensing (methyl) cyclopentadienyl sodium or potassium with a dichloro-or dibromo-hydrocarbon.  Examples describe the preparations of bis-methylcyclopentadienyl-1,4 - butene - 2, bis - cyclopentadienyl - 1,3 - propane, -1,4 - butene - 2, -1,5-pentane, -1,8-octane, -1,10-decane, -1,4-cyclopentene-2 and -a ,a 1-para-xylene and bis-cyclopentadienylmethyl - 4,6 - (1,3 - dimethylbenzene) and 1,3-(2,4,6-trimethylbenzene).ALSO:Dianhydrides of bis{dicarboxybiccyclo(2,2,1)-heptenyl) compounds are prepared by the DielsAlder reaction of the corresponding biscyclopentadienyl compound with an unsaturated dicarboxylic anhydride selected from maleic, citraconic and itaconic anhydrides.  Compounds prepared in the examples are those of the formulae <FORM:1029037/C2/1> and the adducts of maleic anhydride with 1,3-biscyclopentadienylpropane ; 1,10 - biscyclopentadienyldecane; 1,4 - biscyclopentadienylcyclopent - 2 - ene; 4,6 - bis(cyclopentadienylmethyl) - 1,3 - dimethylbenzene; 1,3 - bis(cyclopentadienylmethyl) - 2,4,6 - trimethylbenzene; bis(cyclopentadienylmethyl) ether; bis(cyclopentadienylpentenyl) ether and 1,8-biscyclopentadienylactone.  The biscyclopentadienyl compounds are prepared from cyclopentadienyl sodium or methylcyclopentadienyl sodium and the corresponding dichlorides or dibromides (e.g. 1,5-dibromopentane).  An organotin compound of the formula <FORM:1029037/C2/2> is prepared by the Diels-Alder reaction of tetrakiscyclopentadienyl tin (IV) with maleic anhydride. Tetrakiscyclopentadienyl tin (IV) is prepared by the reaction of SnCl4 with cyclopentadienyl sodium.ALSO:Heat curable mixtures contain (1) a polyepoxide, and (2) as curing agent, a polyanhydride obtained by reacting at most n molecular proportions of an unsaturated dicarboxylic acid anhydride of the formula <FORM:1029037/C3/1> in which X1 and X2 each represent a hydrogen atom or a methyl group, with 1 molecular proportion of a compound of the formula <FORM:1029037/C3/2> in which R1 represents a hydrogen atom or a methyl group, n=2 or 4 and R is =Si=, =Si(alkyl)2, =Si(aryl)2, =Sn=, =Sn(alkyl)2 or a bivalent aliphatic, cycloaliphatic, oraliphatic or aromatic hydrocarbon residue which may be interrupted by oxygen atoms or substituted by hydroxy groups or halogen atoms, or a polycarboxylic acid obtained by hydrolysing such a polyanhydride, or both.  The mixtures may also contain an unsaturated dierophilic compound, (3) having a non-aromatic carbon - to - carbon double - bond equivalence and/or carbon-to-carbon triple band equivalence greater than 2 and/or (4) a conventional curing agent and/or accelerator, and/or (5) extenders or fillers and/or (6) solvents, and/or (7) monoepoxides and/or (8) dimerized or polymerized dicyclopentadienyl compounds of the general formula <FORM:1029037/C3/3> in which R and R1 are as hereinbefore defined and y is an integer >1.  Many reactants and components of the mixtures are specified components, (3) being (a) unsaturated polyesters, (b) esters of monobasic unsaturated monocarboxylic acids with tri- or higher polyhydric alcohols, (c) esters of unsaturated di- or polycarboxylic acids with unsaturated monohydric alcohols, (d) ethers of unsaturated monohydric alcohols and tri- or higher polyhydric compounds, (e) polymers and copolymers of dienes and (f) compounds derived from acetylenic acids.  Organosilicon compounds of formulae <FORM:1029037/C3/4> and <FORM:1029037/C3/5> are prepared by reacting tetrakiscyclopentadienylsilane or biscyclopentadienyldimethylsilane, in solution in xylene, with maleic anhydride and isolating the resinous product. Tetrakiscyclopentaienylsilane is prepared by adding SiCl4 to a cooled solution of cyclopentadienyl sodium in xylene, heating the mixture at 17 DEG  C. and neutralizing it with acetic acid. Biscyclopentadienyldimethylsilane is prepared by adding SiCl2Me2 to a cooled solution of cyclopentadienyl sodium in xylene, adding water and separating the xylene solution of the product (see Examples 8, 10 and 21).ALSO:Surfaces of, e.g. metal sheets of aluminium, iron or stainless steel are coated by spraying or brushing with adhesive compositions or lacquers which are heat curable mixtures comprising (1) a polyepoxide and (2) a curing agent obtained by reacting at most n molecular proportions of an unsaturated dicarboxylic acid anhydride of the formula <FORM:1029037/B1-B2/1> <FORM:1029037/B1-B2/2> in which X1 and X2 each represents a hydrogen atom or a methyl group, with 1 molecular proportion of a compound of the formula <FORM:1029037/B1-B2/3> in which R1 represents a hydrogen atom or a methyl group, n = 2 or 4 and R is =Si=, =Si(alkyl)2, =Si(Aryl)2, =Sn=, =Sn(alkyl)2, or a bivalent hydrocarbon radical which may be interrupted by oxygen atoms or substituted by hydroxy groups or halogen atoms, or a polycarboxylic acid obtained by hydrolysing such a polyanhydride or both.  The mixtures may also contain (3) a monomeric or polymeric unsaturated dienophilic compound having a non-aromatic carbon-to-carbon double and/or triple bond equivalence greater than 2, and/or (4) a conventional curing agent and/or accelerator, and/or (5) extenders or fillers and/or (6) solvents.  Many components are specified and/or exemplified.