The Synthesis Of Epoxide And Hybrid Monomers Derived From Dicycloheptadiene And The Study Of Their UV Curing Activity

In this paper, 6 kinds of epoxy monomers (CPD-02, CPD-04, CPD-16, CPD-20, CPD-22, CPD-23) and 5 kinds of hybrid monomers (CPD-07, CPD-10, CPD-12, CPD-14, CPD-18), which can photopolymerize easily, were synthesized from dicyclopentadiene. 7 kinds of them (CPD-04, CPD-10, CPD-14, CPD-16, CPD-20, CPD-22, CPD-23) are new, in addition there are 6 kinds of new intermediates (CPD-08, CPD-09, CPD-13, CPD-15, CPD-19, CPD-21). Their structures were confirmed by FTIR and 1HNMR spectrum.The main conclusions are following.(1) The optimum conditions of synthesizing CPD-01 (table 1) were: using ammonium tetrabutyl iodine as catalyst, using sodium hydroxy powder to close cycle under 40-45#. Under the optimum condition, the yield of CPD-01 was 77.7% (based on dicyclopentadiene) and the epoxide number was 0.58. (2) Orthogonal experiments showed that the optimum conditions of synthesizing CPD-05 were: using 98% sulfuric acid as catalyst, with the ratio of dicyclopentadiene to sulfuric acid being 3.6, reacting at 81-82#. Under the optimum condition, the yield of CPD-05 was 76.8% after being heated for 9.5h. (3) The esterific optimum conditions of CPD-06, CPD-15, CPD-19 and CPD-21 were: p-toluenesulfonic acid as catalyst, methylbenzene as dehydrator, the yield of them was over 90%. (4)漏 The yield of CPD-10,CPD-12,CPD-14, CPD-16, CPD-18, CPD-22 and CPD-23 which used benzoyl hydroperoxide as epoxidizing reagent was higher than that of CPD-02, CPD-04 andCPD-07 which used peroxypropanoic acid, but the latter was more applicable to being industrialized. (5) The monomer of CPD-10, CPD-12, CPD-14, CPD-16, CPD-18, CPD-22 or CPD-23 containing photoinitiators was coated respectively on salt plate. A series of FTIR spectrum were obtained by combining radiation of UV light with FTIR. The UV curing activity of these monomers was prescribed quantitatively by the curves of conversions of epoxide (836 cm-1) or acrylate (1637 cm-1) to curing time. The figures showed that the conversions of double bonds in acrylate were higher than those of epoxides at the same curing time, which told us that the speed of radical photopolymerization was faster than that of cationic photopoly- merization. The speed of hybrid's photoplymerization was faster than the radical's, and the epoxide group on five-member cycle was more reactive than one on the six-member cycle. (6) The films formed from most of these monomers after UV radiation have pencil hardness 6H and cross cut test 0 grade.