Soluble polymers and copolymers with bound tertiary amine groups react at room temperature with halogens and halogen compounds to give crosslinked systems. Crosslinking occurs in solution, emulsion and in polymer mixtures, in ultra-violet and visible light and in the dark. PREVIOUS work cl) has shown that unstable esters of ~-amino alcohols R 1R2NCH(Ra) -OCOR 4 and ~-halogeno-amines R1R2NCH(Ra)hal condense with tertiary amines to give oligomeric amines. Later, in an investigation of the condensation reactions of esters of a-aminocarbinols, t2) gel-chromatographic analysis confirmed qualitatively ta) the formation of oligomeric amines during the reaction of N,N-dimethylaniline and N-N-dimethyl-p-toluidine with tetrachloromethane.
The results of subsequent work t4) showed that soluble polymers and copolymers with bound tertiary amino groups can be crosslinked at normal temperature by reaction with halogens or halogen compounds. This process of binding the macromolecules has been proved in solution, emulsion and in polymer mixtures; it can be accelerated by a simultaneous action of ultra-violet or visible light. The times needed for gel formation after the mixing of amino polymers with a halogen or a halogen compound at room temperature are given in Tables 1234.
The following polymers containing tertiary amino groups were used: poly(pdimethylaminostyrene), 1VI, ~ 2.4 x l0 s (polyDMAS); poly(2-dimethyl aminoethyl acrylate), 1~1. > 1 • 0 x l 0 s (polyDMAEA); poly(2-dimethylaminoethyl methacrylate), 1VI n > 1-10 x l0 s (polyDMAEMA); copolymer of styrene and p-dimethylaminostyrene (polyS + DMAS) (3: l, w/w); copolymer of 2-dimethylaminoethyl acrylate and methyl methacrylate (polyDMAEA + MMA) (l:l, w/w); poly(N-vinylcarbazol) (polyVCZ).
A number of organic and inorganic low-molecular weight compounds (Tables 123) and the following halogen-containing polymers and copolymers prepared in our laboratory (Table 4) were used as halogen compounds: poly(2,2,2-trichloroethyl acrylate), IVI, ~ 3.3 x l0 s ; poly(1,2,2,2-tetrachloroethyl methacrylate), ~1, ~ 4.8 x 10s; poly(styrene-co-2,2,2-trichloroethyl acrylate); poly(styrene-co-l,2,2,2-tetrachloroethyl methacrylate); poly(styrene-co-2,3-dichloropropene); poly(styrene-cotrichloroethylene); poly(styrene-co-vinylidene chloride); poly(vinyl chloride), i~l, 4.6 × 104; and brominated polychloroprene, 1VI~ > 1.0 x 105 and n 2s 1.585.