Synthesis and ultraviolet‐curing behaviors of vinyl ether functionalized polyurethane oligomers

Abstract

The vinyl ether functionalized oligomer is one of the most basic components of vinyl ether functionalized materials for cationic UV-curable coatings. In this study, three types of vinyl ether functionalized polyurethane oligomers (i.e., polyether, polyester, and polydimethylsiloxane) were synthesized with diisocyanate, diol, and hydroxyethyl vinyl ether. These oligomers were characterized by IR, 1 H-NMR, and 13 C-NMR spectroscopy. The effect of the raw material ratio on the oligomer, UV-curing behaviors, and thermal properties of these oligomers were investigated. The UV-curing behavior was analyzed by real-time Fourier transform infrared spectroscopy. The vinyl ether terminated polyester urethane oligomer exhibited better UV curing, with a higher final conversion and maximum UV-curing rates. In addition, the light intensity was enhanced for oligomers with better UV-curing properties. Research on these vinyl ether functionalized oligomers is essential to the development and applications of cationic vinyl ethers systems. V C 2014Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40501.

Unique Curing Properties through Living Polymerization in Crosslinking Materials: Polyurethane Photopolymers from Vinyl Ether Building Blocks

“…13 It was found that interactions with urethane groups can lead to reduced polymerization rates or yield products with reduced molecular weight and broadened polydispersity, thus indicating that transfer reactions cannot be completely prevented. Vinyl ether terminated urethane prepolymers9, 14 with cationic curing ability were synthesized but they still require blending with multifunctional reactive diluents to obtain higher crosslinking densities and a more distinct mechanical modulus increase upon polymerization. Recently, the first polymer systems bearing vinyl ether moieties along the backbone were reported, prepared as biocompatible polyether15 and polyphosphorester16 templates for post‐polymerization modification through thiol–ene “click” reactions.…”

Preparation of liquid polycarbosilane containing vinyl ether group and its rapid curing through thiol‐ene click reaction

“…After the chlorination of LHBPCS, a new absorption peak corresponding to Si–Cl group appeared at 460–490 cm −1 . 16–30 After incorporating the 2‐HEVE, the absorption peak corresponding to Si–Cl group disappeared, and the absorption peaks corresponding to vinyl ether group appeared at 3116 cm −1 (=C–H stretching), 1616 cm −1 (C=C stretching), and 1219 cm −1 (=C–O stretching) 31,32 . In addition, compared with the raw LHBPCS, the intensity of peaks at 2930 and 2880 cm −1 (C–H stretching of linkage structure –CH 2 –CH 2 –O–) increased significantly 33 .…”

“…[16][17][18][19][20][21][22][23][24][25][26][27][28][29][30] After incorporating the 2-HEVE, the absorption peak corresponding to Si-Cl group disappeared, and the absorption peaks corresponding to vinyl ether group appeared at 3116 cm −1 (=C-H stretching), 1616 cm −1 (C=C stretching), and 1219 cm −1 (=C-O stretching). 31,32 In addition, compared with the raw LHBPCS, the intensity of peaks at 2930 and 2880 cm −1 (C-H stretching of linkage structure -CH 2 -CH 2 -O-) increased significantly. 33 Meanwhile, the absorption peak corresponding to the hydroxy group of 2-HEVE did not exist and the absorption peak corresponding to Si-O stretching at 1100-1050 • cm −1 appeared in the FT-IR spectrum of VE-LHBPCS, indicating the condensation reaction between chlorinated LHBPCS and 2-HEVE proceeded.…”

Einzigartige Härtungseigenschaften durch lebende Polymerisation in vernetzenden Materialien: Polyurethan‐Photopolymere aus Vinylether‐Synthesebausteinen

“…13 Dabei wurde festgestellt, dass Übertragungsreaktionen nicht vollkommen vermieden werden können und die Anwesenheit von Urethangruppen teilweise zu reduzierten Polymerisationsgeschwindigkeiten oder Produkten mit vermindertem Molekulargewicht und breiteren Molekulargewichtsverteilungen führt. Auch endständig vinyletherfunktionalisierte Urethanpräpolymere wurden hergestellt,9, 14 benötigen aber multifunktionelle Reaktivverdünner, um hohe Vernetzungsdichten und einen deutlicheren Anstieg des mechanischen Moduls durch kationische Polymerisation hervorzurufen. Kürzlich wurden erstmals Polymere mit Vinylethern entlang des Polymerrückgrats beschrieben.…”