Crosslinking of unsaturated polyester resins studied by low-resolution 1H-NMR spectroscopy

The curing behavior of five unsaturated polyester resins with different molar ratios of styrene to the double bonds in the polyester chain (MR) was investigated. The gel time was measured according to a standard method by the Society of the Plastic Industry (SPI) and by low-resolution pulse nuclear magnetic resonance (LRP-NMR). The gel and curing times decreased and the maximum temperature of the reaction increased when the MR was decreased. The proton mobilities and populations were measured by LRP-NMR. Three components could be seen in the crosslinking reaction: styrene (very mobile, T₂ ≅ 3 s), free polyester polymers (less mobile, T₂ ≅ 150 ms), and cured resin (immobile, T₂ ≅ 0.04 ms). The third component, cured resin, could be detected at the gel point. At this point, the proton mobilities of styrene and free polyester polymers were rapidly decreasing and the proton populations of the cured resin started to increase. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 77–83, 1997     

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     

影响涂料用DCPD型不饱和聚酯涂料凝胶时间的因素

主要从不饱和聚酯树脂酸值,苯乙烯、促进剂、引发剂的用量,颜填料的选择与用量等方面进行了研究,考察这些因素对气干性DCPD型不饱和聚酯涂料凝胶时间的影响,为不饱和聚酯涂料的实际生产和应用提供参考。     

不饱和脂肪族聚酯生物降解性的研究

以1，4-反丁烯二酸和一缩二乙二醇（DEG）为原料，采用缩聚法合成端羟基不饱和聚酯，并采用红外光谱分析（FT—IR）、羟值、酸值、黏度等对所得聚合物进行表征，确认了其分子结构．对其降解性进行研究，并且与1，4-丁二酸与一缩二乙二醇合成的饱和脂肪族聚酯进行了对比。研究结果表明，不饱和脂肪族聚酯和饱和脂肪族聚酯的生物降解性差别不大，也就是双键的引入对其生物降解性没有大的影响；但是不饱和脂肪族聚酯膜经过高温处理后，双键会打开发生交联，而交联后的不饱和脂肪族聚酯的生物降解性变差，而且交联度越高，生物降解性越差。     

Bis(nitrone) as crosslinking agent for unsaturated polyesters via 1,3‐dipolaric cycloaddition

The microwave‐assisted polycondensation of maleic anhydride and 1,6‐hexanediol was carried out using p‐toluenesulfonic acid as catalyst. The resulting unsaturated polyester was characterized using Fourier transform infrared (FTIR) and ¹H NMR spectroscopy, and the molecular weight determined using gel permeation chromatography. 4,4′‐Decanediyldioxydi(N‐methyl‐p‐phenylenenitrone) was chosen as a model compound for the crosslinking of the unsaturated polyester. The crosslinking, which is known to proceed via 1,3‐dipolaric cycloaddition, was followed using differential scanning calorimetry. Additionally, the kinetics of the cycloaddition was evaluated at 120 °C using FTIR spectroscopy. Copyright © 2012 Society of Chemical Industry     

Effects of microstructures on the viscoelastic and rheological properties of metallocene‐catalyzed cyclo‐olefin copolymers: A preliminary study

We characterized metallocene‐catalyzed cyclo‐olefin copolymers (mCOCs) with similar heat distortion temperatures but dramatic differences in melt‐flow indices to understand how the molecular conformation affected their rheological and viscoelastic properties. The mCOC conformations were identified with ¹³C‐NMR, whereas the viscoelastic and rheological properties were measured with cone‐and‐plate and high‐pressure capillary rheometers. Our preliminary results showed that the mCOC rheological and viscoelastic properties might depend strongly on the conformation rather than the norbornene content, molecular weight, and molecular weight distribution. mCOCs containing ‐NNN‐ locks (where N represents norbornene) exhibited stronger molecular entanglements than those having no ‐NNN‐ blocks, as reflected in lower crossover frequencies and higher crossover torque. Furthermore, the existence of larger rigid ‐NNN‐ blocks resulted in higher molten viscosities and flow activation energies. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3695–3701, 2002     

Cross-linkers control the viscoelastic properties of soybean oil-based biomaterials

Because of environmental concerns, biodegradable materials have been of increasing research interest over the last several years. Previously, we reported on a biobased material developed from epoxidized soybean oil (ESO) that displayed viscoelastic behavior similar to synthetic rubbers or plastics. In this work, the viscoelastic properties of several biomaterials made from ESO cross-linked by different amounts of two different cross-linking agents were investigated. The composites exhibited different glass transition temperatures and viscoelastic behaviors depending on the type and amount of cross-linker used. Higher glass transition temperatures and stronger viscoelastic properties of the materials were found with a greater amount of cross-linker. Comparing agent triethylene glycol diamine (TGD) with agent triethylenetriamine (TETA), we found that the material cross-linked by TETA had a higher glass transition temperature and stronger viscoelastic solid properties than the material cross-linked by the agent TGD.     

Nonlinear viscoelastic properties of molten thermoplastic vulcanisates: An insight on their morphology

A series of thermoplastic vulcanisates (TPVs) in the molten state were submitted to large amplitude oscillating strain tests at different frequencies, to investigate their nonlinear viscoelastic properties. A purposely modified torsional harmonic tester with a closed cavity was used to run such experiments, whose results were treated with a Fourier transform (FT) algorithm to extract main torque and strain components, and harmonics if any. Quarter cycle integrations of (averaged) torque signal were also performed, to supplement FT analysis, namely to distinguish extrinsic and intrinsic nonlinear viscoelasticity. The nonlinear viscoelastic character of TPVs was found substantially differing from the one of a molten polypropylene (PP) used for comparison. Within the strain window investigated, no linear behavior is observed with TPVs, in contrast with the pure PP. However, extrapolated “linear” complex modulus G*₀ tends to decrease with increasing hardness of TPVs, but subtle differences between the various grades are clearly detected, when using simple models to fit experimental data. While the (room temperature) hardness is somewhat related with the viscoelastic behavior in the molten state, the strain sensitivity of TPVs appears essentially affected by the extractible content (mainly oil). TPVs nonlinear viscoelastic character appears to depend on the strain amplitude: mainly intrinsic, i.e., due to their morphology, at low strain, and essentially extrinsic, i.e., due to the large strain amplitude, at high strain, and in this respect, qualitatively similar to pure PP. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4193–4205, 2006     

Block copolymers of unsaturated polyesters and functional elastomers

Block copolymers of unsaturated polyester were prepared by condensation polymerization of hydroxyl or carboxyl terminated liquid rubbers with maleic anhydride, phthalic anhydride, and propylene glycol. The condensate obtained was mixed with styrene monomer to get an unsaturated polyester resin formulation. In this study, copolymers of unsaturated polyesters with hydroxy terminated polybutadiene, carboxy terminated nitrile rubber, and hydroxy terminated natural rubber were prepared. Mechanical properties such as tensile strength, tensile modulus, elongation at break, toughness, impact strength, surface hardness, abrasion resistance, and water absorption were evaluated after the resin was cured in appropriate molds for comparison with the control resin. The fracture toughness and impact resistance of CTBN‐modified unsaturated polyester show substantial improvement by this copolymerization without seriously affecting any other property. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1956–1964, 2004     

苯乙烯对不饱和聚酯树脂性能的影响

本文主要探讨了不饱和聚酯中应用得最广泛的活性稀释剂——苯乙烯，对不饱和聚酯树脂机械性能、电性能、吸水性、耐化学性等的影响，从而为实际生产中采用最佳的苯乙烯含量提供参考。     

Control of gel time and exotherm behaviour during cure of unsaturated polyester resins

The curing behaviour of an unsaturated polyester resin has been studied by gel time and pseudo‐adiabatic exotherm measurements. The gel time corresponded closely with the initial rise in exotherm temperature. Incorporation of tert‐butyl catechol inhibitor increased the gel time in a linear fashion and the exotherm was similarly delayed. An increase in the concentrations of initiator (either methyl ethyl ketone peroxide or acetyl acetone peroxide) or cobalt octoate accelerator decreased the gel time in a reciprocal fashion and increased the rate of polymerization. These results are fitted to a theoretical model for inhibition and initiation. © 2001 Society of Chemical Industry     

Development of unsaturated polyester matrix – carbon nanofibers nanocomposites with improved electrical properties

In this work, the dispersion of carbon nanofibers (CNFs) in an unsaturated polyester (UP) resin was performed by mean of the calendering process. The calendering process allows to obtain good dispersion of the nanoparticles, and, with respect to the other techniques, is also possible to scale it up at the industrial level. Optimization of the calendering conditions for the processing was carried out as a first step of this study. Optimization, in this case, means to reach the best dispersion level, as rapidly as possible and with the lowest amount of styrene evaporation. The dispersion level reached was investigated by the technique of scanning electron microscopy. The investigation on electric conductivity of the nanocomposites at different CNF concentrations has revealed that the electrical percolation threshold exists at around 0.3 wt %, where electrical conductivity switches from 10^?13 to 10^?7 S/cm. The rheological characterization has been performed to verify if the improved electrical properties are obtained at the expense of loss of workability, that is a significant increase of viscosity. Eventually, a mechanical characterization was carried out. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

含水不饱和聚酯的动态流变行为和微观结构

使用三乙醇胺(TEA)和Span80复合乳化剂制备含水不饱和聚酯树脂,改变水/乳化剂的比率(W/E)和TEA∶Span80复合比例,通过动态流变法研究含水不饱和聚酯树脂乳液的流变性质,结合光学显微镜和SEM扫描电镜分析微观结构,并测试固化树脂材料的力学性能。实验表明在一定含水量和乳化剂复合比例下,可以制备出乳胶粒子界面膜强度高,粒子数密度高,分布均匀,且乳液稳定性好的含水不饱和聚酯(WCUP)树脂,得到力学强度高的固化树脂,并得到了复合乳液黏度随应力和频率的流变规律。最佳配比TEA∶Span80=9.0∶1.0,W/E=19.2时,其树脂固化体系的拉伸强度和冲击强度比单使用TEA体系分别提高了34%和67%。     

Synthesis and characterization of new unsaturated polyesters containing cyclopentapyrazoline moiety in the main chain

3‐p‐Hydroxyphenyl‐6‐p‐hydroxybenzylidene cyclopentapyrazoline (III) and 3‐vanillyl‐7‐vanillylidene cyclopentapyrazoline (IV) were used as new starting materials for preparing new unsaturated polyesters. The polyesters were prepared by reacting (III) or (IV) with adipoyl, sebacoyl, isophthaloyl, and terephthaloyl dichlorides utilizing the interfacial polycondensation technique. The polyester samples have been characterized by elemental and spectral analyses. The polyesters have inherent viscosities of 0.55–0.97 dL/g. All the polyesters are semicrystalline and most of them are partially soluble in most common organic solvents but freely soluble in concentrated sulfuric acid. Their glass transition temperatures (T_g) range from 103.34 to 208.81°C, and the temperatures of 10% weight loss as high as 190 to 260°C in air, indicating that these aromatic polyesters have high T_g and excellent thermal stability. Doping with iodine dramatically raised the conductivity and produced dark brown colored semiconductive polymers with a maximum conductivity in the order of 3.1 × 10^?7 Ω^?1 cm^?1. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Thermal and mechanical behavior of unsaturated polyesters filled with phase change material

Samples of commercial unsaturated polyester (UPE) resin, filled with phase‐changeable fillers (PCMs), were prepared, and the thermal and mechanical properties of the cured samples were examined. Fillers chosen were paraffin and Wood's metal. Samples were prepared by making dispersions of these fillers in liquid unsaturated polyester followed by curing with methyl ethyl ketone peroxide (MEKP) and conaphtanate and rigid thermoset samples filled with PCM particles were obtained. The thermal and mechanical behaviors of such a filled composite around the melting points of fillers are very interesting. Effects of varying proportions of PCM on mechanical and thermal properties of final products were examined. The samples show thermal melting behavior without undergoing a change in physical state. Decreases in the maximum working temperature from 75 to 53°C for metal‐filled samples and from 75 to 43°C for paraffin‐filled samples were observed by using dynamic mechanical thermal analysis. Differential scanning calorimetry indicated that heat absorption of paraffin samples were higher than that of metal‐filled samples. For paraffin‐filled samples, heats of fusion were 3.44 cal/g for 10% filled sample and 6.35 cal/g for 20% filled sample. For Wood's metal‐filled samples, heats of fusion were 1.18 cal/g for 10% metal‐filled sample and 1.54 cal/g for 20% metal‐filled sample. Surface hardness was tested with Shormeter D. Surface hardness of metal‐filled composites varied from 86 to 34 shore D at 21°C and 80.6 to 35 shore D at 80°C. For paraffin‐filled samples, surface hardness changed from 86 to 42 shore D at 21°C and from 80.6 to 13 shore D. Morphology of the samples was determined by scanning electron microscopy, of the crack surfaces. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 832–838, 2006     

Modification of unsaturated polyester resin with bismaleimide

The modification of a commercially available unsaturated polyester resin with 4,4′‐bismaleimidodiphenylmethane is presented. The properties of the modified resins were compared with those of the nonmodified resin, and the resins were characterized in the noncured state and after curing. The results indicate that the addition of bismaleimide to unsaturated polyester resin not only improves its properties but also accelerates the curing reactions. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2003–2007, 2001     

不饱和聚酯型人造大理石的力学性能

简述了不饱和聚酯(UPR)型人造大理石的制备工艺。研究了质量比为4∶1的Al(OH)3/Ca(OH)2复合填料用量对不饱和聚酯型人造大理石力学性能的影响,对制得的人造大理石的耐腐蚀性进行了测试,采用光学显微镜观察了试样腐蚀前后的表面形貌。结果表明,在复合填料与UPR质量比为1.86∶1时,弯曲强度、压缩强度达到最大,分别为55.88 MPa和96.04 MPa。甲苯对人造石的腐蚀作用最大,氢氧化钠次之,硫酸腐蚀作用较小,腐蚀介质主要对不饱和树脂聚合物产生腐蚀,从而导致人造石力学性能降低。     

Effect of ambient atmosphere on crosslinking of polysilazanes

The influence of ambient atmosphere on the crosslinking process of two commercially available polysilazanes with different molecular units in the backbone structure (one polysilazane with and one without urea units) was studied at different temperatures using oscillatory rheometry under isothermal conditions. The measurements were performed using cone/plate, plate/plate, and Couette geometries to assess the influence of the contact surface of the samples with air on their crosslinking behavior. The crosslinking process of the investigated polysilazanes in ambient atmosphere was found to occur faster than that in inert atmosphere. DSC and FTIR‐spectroscopic investigations indicate that hydrolysis and polycondensation processes occur in both polysilazanes when crosslinked in air. Interestingly, the effect of moisture was found to be more pronounced in the case of the urea derivative. The evolution of the measured complex viscosity and dynamic moduli supported this finding. Furthermore, the variation of the time derivative of complex viscosity (dη*/dt) emphasizes structural changes during crosslinking of the samples which were ascribed to their contact with the ambient atmosphere. This study emphasizes the high potential of rheometry in investigating the crosslinking behavior of polymers in inert and ambient atmosphere. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Influence of TDI concentration on the properties of unsaturated polyester resins

Three different unsaturated polyester resins were modified by toluene diisocyanate (TDI). All the resins studied were commercially available. One, 2, and 3% additions of TDI caused important changes of the resins properties. With an increase of TDI concentration gelation times increased. Suppression of the exotherm peaks—desired effect from practical point of view—was observed. Unfortunately, increase of TDI concentration caused enormous increase of the resins viscosity. Additionally the resins with 3% of TDI exhibit thixotropic properties. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1201–1206, 2001     

The linear viscoelastic properties of copolypropylene–clay nanocomposites

The linear viscoelastic properties of copolypropylene (cPP)–clay nanocomposites (cPPCNs) prepared by melt intercalating with different amounts of clay were extensively examined by rheological measurements. Meanwhile, the clay effects on the cPP confinements were first estimated by calculating the activation energy of different cPP moving units, including the whole molecular chain, the chain segment, and smaller unit such as chain link. The results showed that the stability of cPPCNs melts wrecked when the clay loading was above 5 wt %. An increase in clay loading of cPPCNs gave rise to a strong low frequency solid‐like response (G′ > G″). Unlike the matrix polymer, cPPCN5 (with 5 wt % clay) exhibited a relaxation plateau as relaxation time prolonged above 100 s, and displayed a maximal linear modulus. The variations of the activation energy of different cPP moving units revealed that the mobility of cPP molecular chains was restricted by clay layers, while these restrictions were not only related to the clay loadings but also largely depended on the clay dispersion status in the matrix. The motions of cPP chain segments were greatly limited at 3–5 wt % loading of clay, but drastically activated with the addition of 7 wt % clay due to the increasing stacks of clay layers within the matrix. However, it was found that the presence of clay had little effect on the mobility of small cPP moving units such as chain links. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1523–1529, 2006