Thermal polymerization of thiol–ene network‐forming systems

Polymer International - Tập 56 Số 12 - Trang 1572-1579 - 2007
Wayne D. Cook1, Fei Chen1, Derek W Pattison1, Peyton Hopson2, Mathieu Beaujon3
1Department of Materials Engineering, PO Box 69M, Monash University, Victoria 3800, Australia
2University of Southern Mississippi, Hattiesburg, MS 39406, USA
3University of Nantes, France

Tóm tắt

AbstractThe thermal polymerization of a tetrafunctional thiol (PETMP) and divinyl ether (TEGDVE) was monitored by temperature‐ramping differential scanning calorimetry (DSC) and the effects of inhibitor type and concentration, oxygen inhibition and initiator type were studied. The incorporation of inhibitors was required to produce a stable system at room temperature. Butylated hydroxytoluene (BHT) inhibited polymerization at low temperatures, but was inefficient at high temperatures and polymerization rates, and hence BHT is an ideal stabilizer. In contrast, a nitroxide inhibitor (NO‐67) was a very effective inhibitor and no polymerization occurred until all of the nitroxide was depleted. The presence of oxygen retarded the onset of polymerization but did not change the final conversion significantly. Polymerization with initiators having higher half‐life temperatures shifted the DSC peak to higher temperature because the rate of initiator decomposition and thus initiation was slower. Rheological investigations of the cure at different temperatures revealed that the gel time decreased significantly with increasing cure temperature, and the calculated apparent activation energy for PETMP/TEGDVE was 54 kJ mol−1. Dynamical mechanical thermal analysis of the cured material was undertaken and frequency‐superposed results revealed that the glass transition region of PETMP/TEGDVE/azobisisobutyronitrile was much narrower than that of free‐radically cured dimethacrylate, but was similar to that of an epoxy resin cured with an aromatic diamine. This behaviour could be attributed to PETMP/TEGDVE network homogeneity, or to the less constrained crosslinks in the PETMP/TEGDVE network. Copyright © 2007 Society of Chemical Industry

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Tài liệu tham khảo

10.1021/ma0200672

10.1021/ma034667s

10.1002/pola.20366

10.1002/pi.821

10.1002/apmc.1987.051500113

10.1021/ma9708656

10.1002/apmc.1993.052120111

10.1021/jo00385a014

10.1002/macp.1991.021921205

10.1002/pola.1314

10.1021/ma034072x

10.1002/masy.200450228

10.1002/pola.20181

Chong YK, 1999, Macromolecules, 32, 6897

10.1021/ma00186a037

10.1021/ma010438z

Ferry JD, 1970, Viscoelastic Properties of Polymers

10.1016/B978-0-12-703780-6.50010-9

Shostakovskii MF, 1942, J Appl Chem Russ, 15, 249

Moad G, 1995, The Chemistry of Free Radical Polymerization

10.1002/pola.20181

10.1016/S0032-3861(02)00766-8

10.1002/pi.1518

CookWD ChenF PattisonDW HopsonPandBeaujonM Photopolymerization of thiol‐ene network forming systems (in preparation).

10.1002/pen.760272209

10.1021/ma960287d

10.1021/ma9602886

10.1021/ma00001a008

McCrum NG, 1967, Anelastic and Dielectric Effects in Solid Polymers

10.1002/app.12995

10.1002/app.20569

10.1002/(SICI)1099-0488(199710)35:14<2297::AID-POLB10>3.0.CO;2-7

10.1016/S0032-3861(97)00585-5

10.1021/ma970721r

Ueberreiter K, 1950, Chem Phys, 18, 399

10.1016/0032-3861(64)90212-5

Ferry JD, 1970, Viscoelastic Properties of Polymers

Wako Chemical Company Japan product details. [Online]. Available:http://www.wako‐chem.co.jp/specialty/oilazo/ index.htm[22 March 2007].

Sigma‐Aldrich Applications: Free radical Initiators. [Online]. Available:http://www.sigmaaldrich.com/Area_of_Interest/ Chemistry/Materials_Science/Polymerization_Tools/Free_ Radical_Initiators.html[22 March 2007].

Dupont Chemicals Vazo Free Radical Initiators. [Online]. Available:http://www.dupont.com/vazo/grades.html[22 March 2007].

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Polymer International

Tập 56 Số 12

1572-1579

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