Photoinitiated alternating copolymerization of dialkyl maleates and fumarates with vinyl ethers

Abstract

A systematic study of the free radical photoinitiated alternating crosslinking copolymerizations of dialkyl maleates and furmarates with multifunctional vinyl ethers was carried out. The photocopolymerizations were fast and highly efficient when carried out using a variety of a-cleavage photoinitiators. The effects of the structures of the both the unsaturated esters and the vinyl ether monomers were examined. Dialkyl maleates were observed to be more reactive than the corresponding fumarate esters. The photopolymerization rates of several of these comonomer pairs were compared with standard diacrylate and dimethacrylate monomers. A range of different physical properties can be obtained by varying the length of the alkyl chain on alcohol portion of the unsaturated ester monomer. Prospects for the use of these comonomer systems in UV curable coatings, adhesives, printing inks, and composites are discussed. V C 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: [4726][4727][4728][4729][4730][4731][4732][4733][4734][4735][4736] 2010

Synthesis of α,β-unsaturated esters of perfluoropolyalkylethers (PFPAEs) based on hexafluoropropylene oxide units for photopolymerization

“…Indeed, in the literature, it was reported for this maleate product a chemical shift for the two protons of the double bond of 6.24 ppm 23,24 whereas the chemical shift for the fumarate product was 6.85 ppm. 24,25 As the cis and trans -products did not show the same reactivity in copolymerization, 2,10 a control of the reaction time is essential.…”

“… 8,9 Under UV-curing, maleates usually showed a faster reactivity than the more thermodynamically stable fumarates. 2 Nonetheless, the opposite effect was observed 10 and another study will be dedicated to the comparison of their kinetics. In comparison to the common (meth)acrylic systems, their polymerization is less sensitive to oxygen.…”

“…a,b-unsaturated esters are very useful in polymer applications. [1][2][3] Two congurations of a,b-unsaturated esters are conceivable: the cis-conguration (maleate) and the trans-conguration (fumarate) (Fig. 1).…”

“…Indeed, the synthesis of the corresponding fumarates can then easily be transposed but the maleates are inclined towards isomerization and consequently their synthesis is more challenging. In the past, maleate monomers have been successfully copolymerized with a variety of monomers such as vinyl acetate, 1,4,5 vinyl ether, 2 epoxy 3 or even hydrophobic types. 6 They have been seen in applications such as latex films, 1,5 polyelectrolytes 6 or cooperative complexation of cyclodextrins.…”

Catalyst‐Free Efficient Synthesis of Alkyl Acetates Bearing Arylsulfide and Quinoxaline Moieties and Stereoselective Synthesis of Dialkyl 2‐Amino‐3‐thiomalates at Room Temperature

“…It is noteworthy that dialkyl maleates are among the most applicable chemicals which have been are used in production of copolymers, inhibitors in industrial curing, coatings with special properties and their medicinal and pharmaceutical importance . In the following, by replacing 1,2‐diamines 1 a‐c with amines 7 a‐c , we got diastereoselectively access to dialkyl 2‐amino‐3‐thiomaleates ( Z )‐ 8 a‐f (Scheme ).…”