Polymers from multifunctional isocyanates, 12. Alternating copolymers from isocyanatoalkenes and electron deficient 1,2‐disubstituted alkenes

Abstract

The free radical copolymerization of the electron rich monomers vinyl isocyanate, isopropenyl isocyanate, trans-I-propenyl isocyanate, and trans-P-styryl isocyanate with maleic anhydride has been investigated. The copolymerization behaviour of different electron deficient monomers like maleic anhydride, citraconic anhydride, N-phenylmaleimide and fumaronitrile with isopropenyl isocyanate or vinyl isocyanate has also been studied. Polymerization in benzene is accompanied by precipitation of polymer, while the polymerization proceeds in solution in 2-butanone. Alternating copolymers were obtained in all cases. The alternating behaviour is favoured by the very low tendency of all monomers except maleimides to undergo homopolymerization. From the reaction with maleic anhydride the reactivity of electron donating monomers was found to be vinyl isocyanate = isopropenyl isocyanate % P-styryl isocyanate = > I-propenyl isocyanate, while the reactivity of electron accepting monomers with isopropenyl isocyanate was: maleic anydride > N-phenylmaleimide > fumaronitrile.

Synthesis and Characterization of Novel Multifunctional High-Tg Photorefractive Materials Obtained via Reactive Precursor Polymers

“…AIBN was used as radical initiator for the copolymerization of the maleimides M1 − M7 and methyl vinyl isocyanate MVI . The copolymerization of maleic anhydride with vinyl isocyanate as well as MVI is known to be alternating . The same tendency has been found for the copolymerization of maleimide derivatives with vinyl isocyanate or MVI .…”

Sequential and alternating RAFT single unit monomer insertion: model trimers as the guide for discrete oligomer synthesis

“…The FCN and DMF monomers meet the basic requirements of the SUMI process; the propagation rate constants (k p ) are relatively low but they can copolymerize with many other monomers. [52][53][54][55][56] Furthermore, these monomers have been used to prepare special polymer materials which exhibit unique mechanical or thermal properties such as high glass transition temperature when copolymerized with divinylbenzene. [57][58][59][60] The other electron-accepting monomer, PMI, has been demonstrated to be a good monomer for discrete oligomer synthesis through sequential and alternating SUMI, which is used for comparison with FCN and DMF.…”

Polymers from Multifunctional Isocyanates, 15

“…[1] Their synthesis from two different monomers enables the introduction and combination of different functional groups and functionalities. In previous papers we have described alternating copolymers containing anhydride and isocyanate groups, [2][3] imide and isocyanate groups and their polymer analogous reactions. [4] Zentel and his group used the imide function to vary the glass transition temperature and the isocyanate group for reaction with a NLO-chromophore to achieve temperature stable orientation after poling.…”