Vulcanizable compositions based on elastomeric copolymers of vinylidene fluoride, process for vulcanization thereof utilizing phosphorous metal coordination complex and vulcanized compositions obtained thereby

Vulcanizable compositions comprising:

• 1. 100 parts by weight of an elastomeric copolymer of (a) vinylidene fluoride, and (b) at least one fluorinated or chloro-fluorinated ethylenically unsaturated monomer selected from 1-hydropentafluoropropene, 2-hydropentafluoropropene, 1,1-dihydrotetrafluoropropene, hexafluoropropene, tetrafluoroethylene, trifluorochloroethylene, and fluorinated alkyl and aryl vinyl ethers;
• 2. 1-40 parts by weight of an inorganic acid acceptor selected from magnesium oxide, calcium oxide, lead monoxide, zinc oxide and basic lead phosphite as such or in the form of a complex or cationic chelate;
• 3. 0.5-10 parts by weight of at least one basic compound selected from calcium, strontium or barium hydrate, the alkali metal or alkaline earth metal salts of weak acids as such or in the form of complexes with chelating agents or cationic complexants;
• 4. 0.5-15 parts by weight of a vulcanizing agent selected from polyhydroxy and polythiol compounds of the formulae:
• A(BC).sub.n and CB--R--BC
• wherein
• A is an arylene radical;
• n is a whole number equal to or greater than 2;
• B is oxygen or sulfur;
• C is hydrogen, an alkali metal or an alkaline earth metal;
• R is an organic radical selected from the group consisting of alkylene, cycloalkylene, mono- or polyalkylenecycloalkyl, alkylenediaryl, bis-aryl sulfone, bis-arylsulfide, bis-aryl ether and bis-aryl ketone;
• and
• 5. 0.1-5 parts by weight of at least one phosphorus complex of the formulae:
• a(MX).sub.m.b[(R.sub.1 R.sub.2 R.sub.3)P] (I)
• a(MX.sub.m).b[(R.sub.1 R.sub.2 R.sub.3)P].c(R.sub.4 Y) (II)
• wherein
• M is an element or oxygen containing group capable of forming coordination complexes with phosphorus and capable of yielding cations with a valence m of of from 1 to 4 and being selected from the group consisting of Cu, Hg, Zn, Cd, Fe, Co, Ni, Pd, VO.sup.+2 and TiO.sup.+2 ;
• a, b and c are whole numbers of from 1 to 4;
• R.sub.1, r.sub.2, r.sub.3 and R.sub.4 are the same or different and are selected from hydrogen, alkyl, aralkyl, alkylaryl, cycloalkyl, aryl, oxyalkyl, carbomethoxy alkyl or linear or cyclic polyoxyalkyl radicals with the hydroxyl group either free or etherified, or alkyl, cycloalkyl, aralkyl, alkylaryl, oxyalkyl, or linear or cyclic polyoxyalkyl radicals substituted by halogen groups;
• R.sub.1, r.sub.2 and R.sub.3 may also be selected from alkoxyl, cycloalkoxyl, aryloxyl, or alkylenearyloxyl radicals;
• R.sub.1, r.sub.2, r.sub.3 and R.sub.4 when not hydrogen, have from 1 to 18 carbon atoms;
• and X and Y are organic and inorganic monovalent anions independently selected from the group consisting of halides, perchlorates, nitrates, acetates, haloacetates and benzoates.