Dehydrochlorination of poly(sulfonyl‐co‐2‐chloroethylene)

Cais, R. E.; O’Donnell, James H.

doi:10.1002/macp.1975.021761201

Cited by 8 publications

(4 citation statements)

References 28 publications

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“…Thus, for the butene, chlorobutene and hexene polymers the principle hydrocarbon fragment having the same number of carbon atoms as does the polymer repeat unit (i.e., four or six) corresponds to no hydrogen atoms being lost, while for the chlorohexene polymer a single hydrogen atom is lost, leading to the formation of a fragment of mass 82, i.e., C8H1,-,. The loss of hydrogen atom for this material is in accord with a dehydrochlorination mechanism, a reaction known to be significant in the decomposition of PVC (12) and poly(chloroethy1ene sulfones) (13).…”

Section: Referring Again Tomentioning

confidence: 66%

X‐ray photochemistry: ω‐Chloro olefin sulfones

Kaplan

1983

Polymer Engineering & Sci

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To be efficacious 8s an x-ray resist, a material must efficiently undergo a desirable chemical change upon being irradiated with x-rays. The probability of such a change taking place is given by the product of the fractional x-ray absorption and the "inherent sensitivity," which we define as the yield per unit energy absorbed. Increasing the absorption of the polymer, as, for example, by chlorinating an olefin sulfone thereby increasing the absorption at wavelengths just below the chlorine absorption edge will result in improved usefulness if, and only if, this increased energy absorbed can be used by the polymer to enhance the desired chemical reaction. The "usefulness" of chlorinating is thus dependent on the efficiency of intramolecular energy transfer. We have studied the efficiency of this transfer by monitoring the loss of SO2 from the main-chain backbone as a function of absorbed x-ray energy, using x-ray wavelengths both above and below the chlorine absorption edge. The polymers studied were 1-olefin sulfones, with and without the chlorine atom in the a-position. Through the use of this series of polymers it was hoped to observe an effect due to the changing separation of the chlorine atom from the backbone. The experiments indicate that (a) the inherent sensitivity is independent of irradiating wavelength, for both the chlorine-containing and the non-chlorine-containing polymers; (b) the hexene polymers are considerably more sensitive than the lower members of the series (which exhibit a sensitivity which is approximately independent of the side chain length); and (c) the chlorine-containing polymers are less sensitive than the non-chlorine-containing species. At this time the explanation for these observations is speculative.

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Section: Referring Again Tomentioning

confidence: 66%

X‐ray photochemistry: ω‐Chloro olefin sulfones

Kaplan

1983

Polymer Engineering & Sci

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“…The resonance was at higher field and the resolution was better in THF than in acetone. The doublet splitting (6 Hz in THF, 4.5 Hz in acetone) can be assigned to S/S (R/R) and S/R (R/S) "across-SCV' diad stereosequences.…”

Section: Resultsmentioning

confidence: 98%

“…5 The relationship between copolymer and comonomer compositions does not obey first-order Markoff statistics (Lewis-Mayo copolymerization model) at any temperature above -78 °C. 6 The copolymerization therefore follows a more complex mechanism, which may include participation of comonomer complexes, depropagation, or penultimate unit effects. Several of these models have been suggested for the copolymerization of styrene with SO2 in the formation of a variable-composition copolymer.7 "10 The relationship between macroscopic copolymer composition and comonomer composition cannot always be used to unambiguously distinguish between the various models.…”

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confidence: 99%