Chemical modification of unsaturated polyesters influence of polyester's structure on thermal and viscoelastic properties of low styrene content copolymers

In this study, the chemical modification of unsaturated polyesters and the influence of polyester's structure on thermal and viscoelastic properties have been presented. The structure of unsaturated polyesters obtained in polycondensation of cyclohex-4-ene-1,2-dicarboxylic anhydride (THPA), maleic anhydride and only one suitable symmetrical glycol: ethylene glycol or 1,4-butanediol (BDO) or 1,6-hexanediol has been modified by peracetic acid. The selective oxidation of unsaturated polyesters conducted in mild time and temperature conditions was a successful and effective method to prepare new materials/unsaturated epoxy polyesters/containing epoxy groups in cycloaliphatic rings and carbon–carbon double bonds in polyester chain. The unsaturated epoxy polyesters were capable of both copolymerization with vinyl monomer and polyaddition reactions with suitable curing agent. Therefore, they were successfully used as a component of low styrene content copolymers. As was confirmed by DSC, DMA, and TGA analyses, polyester's structure had significant influence on thermal and viscoelastic properties of styrene copolymers. The properties of styrene copolymers prepared from unsaturated epoxy polyesters were considerably better compared with those obtained for styrene copolymers from unsaturated polyesters.© 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

[1]  M. Worzakowska Synthesis and characterization of the new unsaturated epoxyoligoester suitable for further modification , 2008 .

[2]  M. Alagar,et al.  Thermo mechanical behaviour of unsaturated polyester toughened epoxy–clay hybrid nanocomposites , 2007 .

[3]  P. Penczek,et al.  Photocationic-curable powder coatings , 2006 .

[4]  Martin P. Ansell,et al.  Modified polyester resins for natural fibre composites , 2005 .

[5]  R. Jeng,et al.  Expandable graphite systems for phosphorus-containing unsaturated polyesters. I. Enhanced thermal properties and flame retardancy , 2004 .

[6]  W. Cook,et al.  Dynamic mechanical thermal analysis of thermally stable and thermally reactive network polymers , 2004 .

[7]  C. Bowman,et al.  The effect of primary cyclization on free radical polymerization kinetics: experimental characterization , 2003 .

[8]  K. Jaszcz,et al.  Studies on hydrolytic degradation of epoxy‐polyester resins cured with glutaric anhydride , 2002 .

[9]  P. Penczek,et al.  Epoxypolyesters as film-forming materials , 2002 .

[10]  A. P. Costa,et al.  Dynamic mechanical and thermal behavior of epoxy resins based on soybean oil , 2002 .

[11]  H. Chiu,et al.  Curing reaction of unsaturated polyester resin modified by dicyclopentadiene , 2001 .

[12]  Sang-wook Kim,et al.  Reaction mechanism of an unsaturated polyester system containing thickeners , 2001 .

[13]  Z. Mathys,et al.  Post-fire mechanical properties of marine polymer composites , 1999 .

[14]  W. Park,et al.  Epoxidation of bacterial polyesters with unsaturated side chains V. Effect of crosslinking on thermal degradation of epoxidized polymers , 1999 .

[15]  W. Park,et al.  Epoxidation of bacterial polyesters with unsaturated side chains: IV. Thermal degradation of initial and epoxidized polymers , 1999 .

[16]  P. Penczek,et al.  Aliphatic-Cycloaliphatic Epoxy Compounds and Polymers , 1999 .

[17]  K. Jaszcz,et al.  The synthesis of multifunctional polyester-epoxy resins , 1999 .

[18]  C. Bowman,et al.  A study of the evolution of mechanical properties and structural heterogeneity of polymer networks formed by photopolymerizations of multifunctional (meth)acrylates , 1998 .

[19]  J. Pascault,et al.  Modeling of unsaturated polyester prepolymer structures. I. Chain branches and overall chain end numbers , 1997 .

[20]  E. Martuscelli,et al.  A polymer network of unsaturated polyester and bismaleimide resins: 1. Kinetics, mechanism and molecular structure , 1996 .

[21]  L. J. Lee,et al.  Thickening behaviour and shrinkage control of low profile unsaturated polyester resins , 1996 .

[22]  R. Tsiang,et al.  Epoxidation of partially hydrogenated styrene‐butadiene block copolymers using peracetic acid in a cyclohexane/water heterogeneous system , 1996 .

[23]  P. Guerrero,et al.  Influence of cure schedule and stoichiometry on the dynamic mechanical behaviour of tetrafunctional epoxy resins cured with anhydrides , 1996 .

[24]  Jong Keun Lee,et al.  Cure Behavior of an Epoxy-Anhydride-Imidazole System , 1996 .

[25]  P. Allen,et al.  Dynamic-mechanical properties and cross-polarized, proton-enhanced, magic angle spinning 13C-NMR time constants of urethane acrylates—1. Homopolymer networks , 1993 .

[26]  J. Pascault,et al.  Influence of processing conditions on shrinkage behavior of low profile unsaturated polyester resins. I: Systems without fillers , 1993 .

[27]  A. Coutsolelos,et al.  Metalloporphyrins catalyse cis-polybutadiene to polyepoxide , 1992 .

[28]  A. S. Hay,et al.  Catalytic epoxidation of polyisobutylene-co-isoprene with hydrogen peroxide , 1991 .

[29]  G. Simon,et al.  Properties of dimethacrylate copolymers of varying crosslink density , 1991 .

[30]  J. Charlesworth Effect of crosslink density on molecular relaxations in diepoxide-diamine network polymers. Part 2. The rubbery plateau region , 1988 .

[31]  M. Ochi,et al.  Mechanical relaxation mechanism of epoxide resins cured with acid anhydrides. II. Effect of the chemical structure of the anhydrides on the β relaxation mechanism , 1986 .

[32]  M. Ochi,et al.  Mechanical relaxation mechanism of epoxide resins cured with acid anhydrides , 1984 .

[33]  P. Holmes,et al.  The thermal degradation of poly(-(d)-β-hydroxybutyric acid): Part 2—Changes in molecular weight , 1984 .

[34]  A. Tobolsky,et al.  Rubber elasticity and chain configuration , 1961 .

[35]  J. W. Pearce,et al.  Epoxidation of polyesters of tetrahydrophthalic acid and unsaturated alkyd resins , 1957 .

[36]  F. Greenspan,et al.  A Modified Peracid Process for Making Epoxy Compounds from Unsaturated Fatty Acid Esters , 1955 .

[37]  C. Marvel,et al.  The Effect of cis and trans Olefinic Groups on the Properties of Polyurethans and Polyesters1 , 1951 .