Vinyl ethers, radiation

Complexation of the initiator and/or modification with cocatalysts or activators affords greater polymerization activity (11). Many of the patented processes for commercially available polymers such as poly(MVE) employ BE etherate (12), although vinyl ethers can be polymerized with a variety of acidic compounds, even those unable to initiate other cationic polymerizations of less reactive monomers such as isobutene. Examples are protonic acids (13), Ziegler-Natta catalysts (14), and actinic radiation (15,16). 

Table 9. Properties of Vinyl Ether-Based Formulations for Radiation-Curing Coating ...

In general the nitroso rubbers also suffer from a poor resistanee to ionising radiation, sensitivity to degradation by organie bases, highly toxic degradation products and an exceptionally high cost. The advent of the rubbers based on perfluorofmethyl vinyl ether) considered above and of the phosphonitrilic elastomers considered below would appear to put the commercial future of these materials in extreme doubt. 

The objective of the present work was to determine the influence of the light intensity on the polymerization kinetics and on the temperature profile of acrylate and vinyl ether monomers exposed to UV radiation as thin films, as well as the effect of the sample initial temperature on the polymerization rate and final degree of cure. For this purpose, a new method has been developed, based on real-time infrared (RTIR) spectroscopy 14, which permits to monitor in-situ the temperature of thin films undergoing high-speed photopolymerization, without introducing any additive in the UV-curable formulation 15. This technique proved particularly well suited to addressing the issue of thermal runaway which was recently considered to occur in laser-induced polymerization of divinyl ethers 13>16. 

A number of publications purport to give values for the absolute propagation rate constant kp for the polymerization of isobutyl vinyl ether (Table 2). The values of Okamura et ah, are derived by techniques and arguments which are of doubtful validity [54a] and they seem much too small. Eley s value, derived from an analysis of non-stationary kinetics, is four orders of magnitude smaller than the kp deduced from studies of radiation... 

This paper is about a reinterpretation of the cationic polymerizations of hydrocarbons (HC) and of alkyl vinyl ethers (VE) by ionizing radiations in bulk and in solution. It is shown first that for both classes of monomer, M, in bulk ([M] = niB) the propagation is unimolecular and not bimolecular as was believed previously. This view is in accord with the fact that for many systems the conversion, Y, depends rectilinearly on the reaction time up to high Y. The growth reaction is an isomerization of a 7t-complex, P +M, between the growing cation PB+ and the double bond of M. Therefore the polymerizations are of zero order with respect to m, with first-order rate constant k p]. The previously reported second-order rate constants kp+ are related to these by the equation... 

It seems that these essential differences between alkenes and vinyl ethers were ignored when the kinetic interpretation of the polymerizations of alkenes by ionizing radiations were extended to the vinyl ethers, but any or all of them may help us to understand the behavioural differences between hydrocarbons and hetero-atomic monomers (see Section 4c). 

The first member of the series, methyl vinyl ether (MVE) provided an interesting lesson, because although it can be polymerised cationically by chemical initiators, its exposure to ionising radiations produces only a radical polymerisation. Desai et al. 

The author s theory which has been used here was developed in detail to explain the polymerisations by ionising radiations of some alkyl vinyl ethers, the polymerisations of which proceed by secondary ions. Although it was shown that the theory is also perfectly serviceable for the tertiary carbenium ions considered here, it must be realised that there is a fundamental difference between these two types of carbenium ions. When one of the bonds of the carbenium ion is a C—H bond, the solvators, especially of course an ion, can get much closer to the positive centre, and they are therefore correspondingly more firmly held to which effect is added that of a smaller steric hindrance. The most researched monomer propagating by secondary cations, apart from the alkyl vinyl ethers, is, of course, styrene. Thus, Mayr s many studies with diaryl methylium cations are directly relevant to the polymerisation of styrene. 

A variety of alternating copolymers based on H-allyl- and N-(3-ethynylphenyl)maleimides, with substituted styrenes and vinyl ethers, have been prepared and their response to x-ray irradiation studied. Broadband and monochromatic x-ray exposures were conducted at the Stanford Synchrotron Radiation Laboratory. Sensitivities were observed to correlate with mass absorption coefficients of the copolymers and were found to be as high as 5-10 mJ/cm2. Preliminary fine line lithographic studies indicate 0.5 ion resolution capabilities. 

TABLE 5-8 Effect of Solvent on kp in Radiation Polymerization of Isopropyl Vinyl Ether at 30° C ... 

Epoxy-functional polydimethylsiloxane oligomers are another group that can be cured by UV radiation. Epoxysilicone block copolymers exhibit a good photoinitiator miscibility, high cure rate, and compatibility with epoxy and vinyl ether monomers. These block copolymers form flexible films with excellent release properties and are therefore used as release coatings. ... 

Although radical cations are generated in some electron-irradiated monomers (e.g., vinyl ethers or epoxies), efficient cationic polymerization is not observed. Under certain conditions (addition of iodonium, sulfonium, or sulfoxonium salts, cationic polymerization with the use of electron beam irradiation can be induced. Several studies on radiation cross-linking of elastomers support the concept of ionic mechanism. ... 

When vinyl monomers such as isobutene, styrene, a-methylstyrene, and vinyl ethers are irradiated by ionizing radiation, the polymerizations of these mono-... 

The evidence in the case of styrene, where both modes of radiation-induced polymerization can be conveniently studied, is quite convincing that reduction of the concentration of water changes the predominating mode of propagation from purely free radical to essentially ionic. Evidence for an ionic propagation initiated by radiation has also been obtained in pure a-methylstyrene (3, 24), isobutylene (12, 32), cyclopenta-diene (5), / -pinene (2), 1,2-cyclohexene oxide (II), isobutyl vinyl ether (6), and nitroethylene (38), although the radical process in these monomers is extremely difficult, if not impossible, to study. 

---