Patent GB-1012791-A (GB)
Title: Vinyl sulphone-group-containing polymers
IPC: C08G75/045
Filed: 1961-11-08
Abstract: The invention comprises sulphone prepolymers of the general formulae <FORM:1012791/C3/1> and a process for the preparation of crosslinkable sulphone prepolymers, which contain at least two vinyl sulphone groups per molecule, by reacting (A) a monosulphone of formula <FORM:1012791/C3/2> or a polysulphone of formula <FORM:1012791/C3/3> with less than a stoichiometric quantity of (B) an active hydrogen containing compound or a donor compound which is water or a polyol, polythiol or amine of the formula R(-2H)n1 or a mixture thereof; the said quantity being such that the ratio of n.X to n1.X1 is greater than unity and wherein n and n1 are integers of 2 to 6, n being 2 when A is a monosulphone, and X and X1 are the respective number of mols. of reactants A and B; the R groups being the same or different and each representing an organic radical of valency 2 to 6 and being free of reactive groups; R1, R2 and R3 representing hydrogen atoms or alkyl or aryl radicals; and Z representing -NH-, oxygen or sulphur.  The reaction, which is exothermic, may be performed in a non-reactant solvent, e.g. dioxane, acetone, chloroform and benzene, or in mass and is preferably effected in the presence of a basic compound as catalyst when the donor reactant B is a polyol or polythiol. Additives and adducts may be employed to stabilize the pre-polymer mixture, e.g. the addition of sufficient acid to neutralize the basic catalyst and of free radical inhibitors to protect the free vinyl groupings.  The invention also comprises a process for the production of cross-linked sulphone polymers by treatment of the pre-polymer with a cross-linking agent.  Four main types of cross-linking are described wherein the pre-polymer is reacted with (a) a polyol, preferably a primary polyol with 2 to 4 hydroxy groups, or water in the presence of a basic polymerization catalyst which is preferably soluble in the pre-polymer; (b) a free radical initiator, preferably a peroxide, in the presence or absence of ethylenically unsaturated co-monomers which are liquid or are soluble in water or organic solvents, e.g. styrene, a -chlorostyrene, vinyl naphthalene, acrylates, methacrylates, acrylic acid, methacrylic acid, acrylonitrile and vinyl toluene and, optionally, in the presence of accelerators, fillers and colouring materials; (c) a primary or secondary sulphonamide containing at least two sulphonamido hydrogens in the presence of a basic polymerization catalyst, preferably a tertiary aliphatic amine, and, optionally, inert fillers and pigments; and (d) a primary, secondary or mixed primary and secondary amine containing at least two amino hydrogens optionally in the presence of solvents, emulsifiers, suspending agents, fillers, pigments and, when aromatic amines are employed, acid polymerization catalysts. In (a), (c) and (d) it is preferred to use 50 to 150% of the stoichiometric equivalent of free vinyl groups in the pre-polymer, of donor. Reactions (a), (c) and (d) also have the proviso that when there are two vinyl-sulphone groups in the prepolymer, the polyol, sulphonamide or amine must contain more than two hydroxyl groups, sulphonamido hydrogens or amino hydrogens, respectively.ALSO:The invention comprises sulphone prepolymers of the general formulae <FORM:1012791/C2/1> <FORM:1012791/C2/2> and a process for the preparation of cross-linkable sulphone pre-polymers, which contain at least two vinyl sulphone groups per molecule, by reacting (A) a monosulphone of formula <FORM:1012791/C2/3> or a polysulphone of formula <FORM:1012791/C2/4> with less than a stoichiometric quantity of (B) an active hydrogen containing compound or donor compound which is water or a polyol, polythiol or amine of the formula R(-ZH)n1, or a mixture thereof; the said quantity being such that the ratio of nX to n1X1 is greater than unity and wherein n and n1 are integers of 2 to 6, n being 2 when A is a monosulphone, and X and X1 are the respective number of moles of reactants A and B; the R groups being the same or different and each representing an organic radical of valency 2 to 6 and being free of reactive groups; R1, R2 and R3 representing hydrogen atoms or alkyl or aryl radicals; and Z representing -NH-, oxygen or sulphur.  The reaction, which is exothermic, may be performed in a non-reactant solvent, e.g. dioxane, acetone, chloroform and benzene, or in mass and is preferably effected in the presence of a basic compound as catalyst when the donor reactant B is a polyol or polythiol. Additives and adducts may be used to stabilize the pre-polymer mixture, e.g. the addition of sufficient acid to neutralize the basic catalyst and of free radical inhibitors to protect the free vinyl groupings.  The pre-polymers may be cross-linked by reaction with, for example, polyols, water, free radical initiators, sulphonamides and amines.ALSO:Surfaces are coated with resins obtained by cross-linking with, for example, a polyol, water, free radical initiator, sulphonamide or amine, a sulphone prepolymer which contains at least 2 vinyl sulphone groups per molecule and is obtained by reacting a monosulphone of the formula <FORM:1012791/B1-B2/1> or a polysulphone of the formula <FORM:1012791/B1-B2/2> with less than a stoichiometric quantity of water or a polyol, polythiol or amine of the formula R(-ZH)n; the R's being the same or different and representing organic radicals of valency 2-6 and being free of reactive groups, R1, R2 and R3 representing hydrogen atoms or alkyl or aryl groups, and Z representing -NH-, oxygen or sulphur.  In the examples, polished metal plates are coated with resins obtained by cross-linking (Example XII) a prepolymer, obtained by reacting piperazine with divinyl sulphone and having 2 vinyl sulphone groups per molecule, with trimethylolpropane; (Example XXI) a prepolymer, obtained by reacting diethylene glycol with divinyl sulphone and having 3 vinyl sulphone groups per molecule, with ethylsulphonamide; and (Example XXXII) the prepolymer of Example XII with 1,4-bis(aminomethyl)cyclohexane.  Example XXXI describes the coating of a glass surface with the resin obtained by cross-linking of a prepolymer, obtained by reacting propanedithiol with divinylsulphone and having 2 vinyl sulphone groups per molecule, with m-xylylene diamine.  Application to the surface may be by dipping and the coatings may be cured by heating.