City Research Online

Abstract

The electron beam induced polymerisation of dialkyltin diacrylates, as well as the UV and electron beam induced polymerisation of some novel silicon containing acrylates are discussed. The reactivity and film forming properties of these materials are compared with that of some commercial diluents such as, tripropyleneglycol diacrylate, TPGDA and trimethylolpropane triacrylate, TMPTA. Mechanistic studies concerning the initiation of free radical polymerisation of the acrylate ester, isodecylacrylate, IDA on electron beam irradiation are presented. Addition of electron and hole scavengers revealed that slow electrons contribute significantly to the initiation of electron beam induced polymerisation of acrylate esters. The film forming properties of phenyl acrylate and mono-, di- and tri- halophenyl acrylates on exposure to electron beam irradiation are evaluated in terms of their ability to produce tackfree films. The sensitivity of catechol diacrylate compared with t-butyl catechol diacrylate is also presented. Mechanistic studies concerning the initiation of both UV and electron beam induced cationic polymerisation of 3,4-epoxycyclohexylmethyl-31,41 -epoxycyclohexanecarboxylate, with the aid of diphenyliodonium hexafýuorophosphate, triphenylsulphonium hexafluorophosphate and (n -2,4-cyclopentadien- I-yl) [(I, 2,3,4,5,6-n) (-I-methylethyl) benzene] -iron(I+) hexafluorophosphate, as well as the radiolysis of 6,7-epoxy- 3,7-dimethyloctylacrylate in the presence of diphenyliodonium hexafluorophosphate are presented. The decomposition of the salts was monitored in situ by infrared and UV spectroscopy and hydrogen fluoride is credited as the true initiator of the cationic polymerisation of epoxides in an open system. The UV photolysis of the aforementioned onium salts led to the production of volatiles, resulting in the polymerisation of thin films of 3,4-epoxycyclohexylmethyl-31,41 - epoxycyclohexanecarboxylate, providing further evidence of hydrogen fluoride evolution. The use of FTIR- photoacoustic spectroscopy was proven to be an invaluable tool in monitoring the polymerisation of thin epoxide or acrylate films on an opaque substrate.

Publication Type:	Thesis (Doctoral)
Subjects:	Q Science > QD Chemistry
Departments:	School of Science & Technology

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