Degradation of Poly(methyl methacrylate) Model Compounds Under Extreme Environmental Conditions

被引:28
作者
Bennet, Francesca [1 ,2 ]
Hart-Smith, Gene [1 ,3 ]
Gruendling, Till [1 ]
Davis, Thomas P. [2 ]
Barker, Philip J. [4 ]
Barner-Kowollik, Christopher [1 ]
机构
[1] Karlsruhe Inst Technol, Inst Tech Chem & Polymerchem, D-76128 Karlsruhe, Germany
[2] Univ New S Wales, Ctr Adv Macromol Design, Sch Chem Sci & Engn, Sydney, NSW 2052, Australia
[3] Univ New S Wales, UNSW Analyt Ctr, Sydney, NSW 2052, Australia
[4] BlueScope Steel Res, Port Kembla, NSW 2505, Australia
基金
澳大利亚研究理事会;
关键词
electrospray ionisation mass spectrometry; polymer degradation; radiation; surfaces; IONIZATION-MASS-SPECTROMETRY; MOLECULAR-WEIGHT DISTRIBUTIONS; SIZE-EXCLUSION CHROMATOGRAPHY; FREE-RADICAL POLYMERIZATIONS; STAR POLYMER FORMATION; END-GROUP ANALYSIS; THERMAL-DEGRADATION; METHYL-METHACRYLATE; POLY(BUTYL ACRYLATE); MECHANISM;
D O I
10.1002/macp.200900625
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
There is a significant knowledge gap in the degradation of poly(methyl methacrylate) (pMMA) under conditions experienced by surface coatings in the harsh Australian environment. In the current study pMMA model compounds were exposed to 95 degrees C temperatures and high UV radiation (1 kW . m(-2)), separately as well as in combination. Contrary to the findings of previous studies, degradation proceeds in these conditions via a non-radical cyclic mechanism. The mechanism was further confirmed by synthesis and degradation of ethylene-oxide-terminated pMMA, an intermediate product in the cycle. Electrospray ionisation mass spectrometry analysis of thermally degraded samples after 155 weeks shows degradation consistent with the proposed cycle in vinyl-terminated pMMA, while saturated pMMA was shown to be stable after the same period. Saturation delayed the UV-induced degradation, yet these compounds still displayed some slight "degradation after 52 weeks, confirming the terminal vinyl bond in pMMA as a weak point. Combined UV and thermal radiation after 56 weeks showed degradation of both pMMA samples, with the vinyl-terminated sample also exhibiting crosslinking. The combination of thermal and UV radiation also caused acceleration of degradation, shown by a comparison of the polymer samples after approximate to 60 weeks.
引用
收藏
页码:1083 / 1097
页数:15
相关论文
共 59 条
[1]   PHOTODEGRADATION OF POLY (METHYL METHACRYLATE) [J].
ALLISON, JP .
JOURNAL OF POLYMER SCIENCE PART A-1-POLYMER CHEMISTRY, 1966, 4 (5PA1) :1209-&
[2]   CHARACTERIZATION OF THE STRUCTURE, PROPERTIES, AND REACTIVITY OF A COBALT(II) MACROCYCLIC COMPLEX [J].
BAKAC, A ;
BRYNILDSON, ME ;
ESPENSON, JH .
INORGANIC CHEMISTRY, 1986, 25 (23) :4108-4114
[3]   Probing mechanistic features of conventional, catalytic and living free radical polymerizations using soft ionization mass spectrometric techniques [J].
Barner-Kowollik, C ;
Davis, TP ;
Stenzel, MH .
POLYMER, 2004, 45 (23) :7791-7805
[4]   Degradation of poly(methyl methacrylate) model compounds at constant elevated temperature studied via high resolution electrospray ionization mass spectrometry (ESI-MS) [J].
Bennet, Francesca ;
Lovestead, Tara M. ;
Barker, Philip J. ;
Davis, Thomas P. ;
Stenzel, Martina H. ;
Barner-Kowollik, Christopher .
MACROMOLECULAR RAPID COMMUNICATIONS, 2007, 28 (16) :1593-1600
[5]   Gas phase oxygen effect on chain scission and monomer content in bulk poly(methyl methacrylate) degraded by external thermal radiation [J].
Brown, JE ;
Kashiwagi, T .
POLYMER DEGRADATION AND STABILITY, 1996, 52 (01) :1-10
[6]   Electrospray ionization mass spectrometric study of end-groups in peroxydicarbonate-initiated radical polymerization [J].
Buback, Michael ;
Frauendorf, Holm ;
Janssen, Olaf ;
Vana, Philipp .
JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY, 2008, 46 (18) :6071-6081
[7]   Electrospray ionization mass spectrometric end-group analysis of PMMA produced by radical polymerization using diacyl peroxide initiators [J].
Buback, Michael ;
Frauendorf, Holm ;
GUnzler, Fabian ;
Vana, Philipp .
POLYMER, 2007, 48 (19) :5590-5598
[8]   Initiation of radical polymerization by peroxyacetates:: Polymer end-group analysis by electrospray ionization mass spectrometry [J].
Buback, Michael ;
Frauendorf, Holm ;
Guenzler, Fabian ;
Vana, Philipp .
JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY, 2007, 45 (12) :2453-2467
[9]  
CACIOLI P, 1984, POLYM BULL, V11, P325
[10]   Living star polymer formation (RAFT) studied via electrospray ionization mass spectrometry [J].
Chaffey-Millar, Hugh ;
Hart-Smith, Gene ;
Barner-Kowollik, Christopher .
JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY, 2008, 46 (05) :1873-1892