Synthesis and properties of unsaturated polyester diol–polyurethane hybrid polymer network

This article deals with the synthesis and properties of poly[(propylene glycol maleate)-co-(propylene glycol phthalate)] diol (PGMPD)/polyester–urethane or polyether–urethane hybrid polymer networks (HPNs). The polyurethane type and the molar ratio of NCO/OH have an effect on their properties. The structure–property relationship is discussed as well. © 1994 John Wiley & Sons, Inc.     

聚氨酯型不饱和聚酯涂料的研究

通过对反应过程中和涂膜酸值和粘度测定以及涂膜性能测定和红外光谱分析研究了聚氨酯型不饱和聚酯树脂的反应温度、反应时间、醇酸比、TDI用量、饱和酸与不饱和酸配比、交联剂聚苯乙烯用量等对涂料性能的影响。研究表明:反应温度170℃,反应时间3 h,乙二醇、邻苯二甲酸酐与顺丁烯二酸酐物质的量比为1.4:3:7,—NCO与—OH物质的量比为1:1,每15 g树脂中加入交联剂苯乙烯5 g,固化体系0.3 g,填料10 g,可制得物理力学性能较好的聚氨酯型不饱和聚酯涂料,涂膜硬度为5 H,附着力1级,柔韧性0.5 mm,抗冲击性50 cm。     

Toughened interpenetrating polymer network materials based on unsaturated polyester and epoxy

Simultaneous interpenetrating polymer networks (IPNs) based on epoxy (diglycidyl ether of bisphenol A) and unsaturated polyester (UP) were prepared by using m‐xylenediamine and benzoyl peroxide as curing agents. A single glass transition temperature for each IPN was observed with differential scanning calorimetry, which suggests good compatibility of epoxy and UP. This compatibility was further confirmed by the single damping peak of the rheometric dynamic spectroscopy. Curing behaviors were studied with dynamic differential scanning calorimetry, and the curing rates were measured with a Brookfield RTV viscometer. It was noted that an interlock between the two growing networks did exist and led to a retarded viscosity increase. However, the hydroxyl end groups in UP catalyzed the curing reaction of epoxy; in some IPNs where the hydroxyl concentration was high enough, such catalytic effect predominated the network interlock effect, leading to fast viscosity increases. In addition, the entanglement of the two interlocked networks played an important role in cracking energy absorption and reflected in a toughness improvement. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 585–592, 1999     

Processing of polyurethane–polyester interpenetrating polymer network (IPN)

The kinetics and heat transfer during the curing of a polyurethane–polyester interpenetrating polymer network (IPN) were investigated experimentally and theoretically. A model based on the additivity rule of constituent ingredients was used to predict the IPNs reaction kinetics and heat transfer. Compared with the adiabatic temperature rise measured during reaction injection molding and the temperature profiles measured during a casting process, the model prediction is close to the experimental data. Deviations of model prediction from experimental results were found in the comparison of reaction rate profiles measured by differential scanning calorimetry. This suggests that reaction interactions may exist in the polymerization system.     

Temperature dependence of the tensile strength of glass fiber–epoxy and glass fiber–unsaturated polyester composites

Epoxy and unsaturated polyester resins reinforced with random-planar orientation of short glass fibers were prepared and the temperature dependence of their tensile strength was studied. The tensile strength decreases as the temperature increases, and this tendency can be expressed in terms of critical fiber length l_c and apparent interfacial shear strength τ: where σ_cs is the tensile strength of composite reinforced with random-planar orientation of short fibers, L is the fiber length, d is the fiber diameter, σ_f is the tensile strength of fiber, σ_m is the tensile strength of matrix, u_f is the volume fraction of fiber, v_m is the volume fraction of matrix, and σ′_m is the stress of the matrix at fracture strain of the composite. The experimental strength values at room temperature are considerably smaller than the theoretical values, and this difference can be explained by the thermal stress produced during molding due to the large difference in the thermal expansion coefficient between glass fiber and matrix resin.     

Kinetic study on simultaneous interpenetrating polymer network formation of epoxy resin and unsaturated polyester

Simultaneous interpenetrating polymer networks (SIN) based on diglycidyl ether of bisphenol-A (DGEBA) and unsaturated polyester (UP) in weight ratios of 100/0, 50/50, and 0/100 were blended and cured simultaneously by using cumene hydroperoxide (CHP) and m-xylenediamine (MXDA) as curing agents. A kinetic study during SIN formation was carried out at 43, 53, 58, and 64°C. Concentration changes for both epoxide and C?C bond were monitored with Fourier transform infrared (FTIR). Rate expressions for epoxide polymerization were established with model reactions for phenyl glycidyl ether (PGE) and benzylamine in dichloroethane containing benzyl alcohol. Experimental results revealed that a lower cure rate constant for the C?C bond during SIN formation was found, compared with pure UP network formation. A model of network interlock is proposed to account for this phenomenon. During simultaneous cure of DGEBA and UP, the network interlock should provide a sterically hindered environment, which subsequently retards cure rate for UP. On the other hand, epoxide cure during SIN formation indicates higher rate constants for both uncatalyzed and catalyzed reactions, compared with those of pure DGEBA cure. Presumably the catalytic effect of hydroxyl end groups in UP overcomes the effect of network interlock. Kinetic parameters were calculated and are discussed. © 1995 John Wiley & Sons, Inc.     

DSC study on simultaneous interpenetrating polymer network formation of epoxy resin and unsaturated polyester

A kinetic study on simultaneous interpenetrating polymer network formation of epoxy resin based on diglycidyl ether of Bisphenol A (DGEBA) and unsaturated polyester (UP) was performed by means of differential scanning calorimetry (DSC). Isothermal DSC characterizations of neat resins and their mixture (in a weight ratio of 50/50) were performed at different temperatures. Dynamic DSC characterization of the systems were performed at three different heating rates. A lower total heat of reaction developed during simultaneous polymerization in dynamic DSC tests was found, compared to the total heats developed during pure resins network formation. This phenomenon can be interpreted as an effect of network interlock that could not be compensated for completely by an increase in curing temperature. The kinetics of the reactions was described by empirical models. The DGEBA, in a 50/50 UP/DGEBA blend, indicated a higher rate constant than the pure DGEBA. The obtained results suggests that the hydroxyl end group of UP in the blend provided a favorably catalytic environment for the DGEBA cure. The results are in good agreement with the literature data. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2689–2698, 2002     

聚氨酯改性不饱和聚酯的徽观结构与性能

利用与天然纤维具有良好亲和性的聚酯聚氨酯(PU)改性不饱和聚酯(UP),通过扫描电镜（SEM）、傅里叶红外光谱（FT-IR）、接触角和力学性能等,研究了改性不饱和聚酯的微观结构、反应程度和主要性能.研究结果表明,引入PU提高了不饱和聚酯树脂的韧性,增加了与天然纤维的界面浸润性,降低了不饱和聚酯树脂的固化收缩率.所得改性不饱和聚酯的冲击断裂截面表现为韧性断裂;与天然纤维的接触角随着聚氨酯添加量的增加而降低,表明改性不饱和聚酯与天然纤维的浸润性增强.力学性能测试表明,当PU含量为5%时,其冲击强度可提高80%,弯曲模量降低小于20%,固化收缩率低于4%.     

混合大二醇基聚氨酯弹性体/环氧树脂互穿网络聚合物的研究

以α,ω-双(γ-羟丙基)聚二甲基硅氧烷(BHPDMS)和聚氧四甲基二醇(PHMO)混合大二醇作为软链段,首先通过两步溶液聚合法合成了-NCO封端的混合大二醇基聚氨酯(PU)弹性体预聚物(PUT);然后以PUT和环氧树脂(EP)预聚物为原料、1,3-双(γ-氨丙基)-1,1,3,3-四甲基二硅氧烷(BATS)为交联剂,采用同步溶液聚合法合成了PUT/EP互穿聚合物网络(PUT/EP I PN)。使用傅里叶红外光谱(FT-I R)法、动力学分析(DMA)法和扫描电子显微镜(SEM)法,对PUT和PUT/EP I PN进行分析和表征,并对其力学性能和表面疏水性进行测试。实验结果表明,PUT/EP I PN中不存在宏观相分离状态,仅发生微观相分离状态;当PUT/EP I PN中w(PUT)=50%时,PUT/EP I PN具有优异的综合力学性能和表面疏水性。     

Temperature dependence of impact fracture energies of short glass fiber–epoxy and unsaturated polyester composites

The temperature dependence of the impact fracture energies of composites reinforced with random-planar orientation of short fibers was studied theoretically and experimentally. The theoretical values of the impact fracture energy of these composites is described by the sum of the fracture energy of the matrix and the fibers and the energy necessary to pull out the fibers on the crack surface, taking into consideration the temperature dependence of the critical fiber length and the breaking probability of fibers. The impact fracture energies were studied experimentally for epoxy and unsaturated polyester resins reinforced with random-planar orientation of short glass fibers. The theoretical values of the impact fracture energy were in good agreement with the experimental values. It was found that in any composite, the impact fracture energy of the fibers in a composite mainly contributes to the impact fracture energy of the composite at room temperature. At higher temperatures, fiber pull-out energy is more significant.     

不饱和聚酯/丙烯酸酯封端聚氨酯/改性蒙脱土复合材料的制备、结构与性能

制备了不饱和聚酯(UPR)／丙烯酸酯封端聚氨酯(ATPU)／改性蒙脱土(OMMT)复合材料,研究了其结构与性能。结果表明,ATPU／OMMT杂化物的比例与用量对UPR／ATPU／OMMT复合材料的结构与性能有很大的影响。当ATPU用量为15份、OMMT用量为2份时,复合材料的综合性能最佳。ATPU／OMMT杂化物对UPR具有增韧增强的协同效应。     

玻璃纤维布/苎麻纤维布混杂增强不饱和聚酯树脂的研究

采用玻璃纤维布与苎麻纤维布混杂增强不饱和聚酯(UP)树脂制备复合材料,研究玻纤布与苎麻布的相对比例及偶联剂处理对复合材料力学性能的影响,研究了不同复合材料的吸水性并与玻璃纤维复合材料和苎麻纤维复合材料二者进行了比较。结果表明,混杂纤维增强复合材料的拉伸强度、拉伸模量随混杂纤维中苎麻布含量的增加而下降,弯曲强度及弯曲模量在混杂纤维中苎麻布与玻纤布的比例为10∶20和15∶15时分别达到最大值188.09 MPa和1.56 GPa;所有偶联剂处理均可明显改善复合材料的拉伸模量及弯曲模量,硅烷类偶联剂的效果更佳,NDZ401可使复合材料的拉伸强度得到最大幅度(37.66%)的提高,而KH570及NDZ401对改善弯曲强度效果最佳;复合材料吸水后,厚度变化率大于宽度变化率,温度升高,复合材料吸水后尺寸变化率及吸水率均增大,混杂纤维复合材料的吸水率与玻纤布复合材料的吸水率相近,远低于苎麻布复合材料的吸水率。     

Dynamic mechanical,mechanical and morphological properties of reactive thermotropic liquid crystalline polymer/unsaturated polyester/glass fibre hybrid composites

Abstract

Unsaturated polyester (UP) reinforced with self-synthesised reactive thermotropic liquid crystalline polymer (TLCP)–methacryloyl copolymer (LCMC) and glass fibre (GF), the hybrid composites of UP/GF/LCMC were prepared by moulding technology. The dynamic mechanical analysis indicated that storage modulus and glass transition temperature (T _g) of hybrid composites increased significantly because of the addition of LCMC. The effect of LCMC content on the mechanical properties of LCMC/UP/GF hybrid composites such as impact strength, specific strength and modulus and load–displacement relationship were also investigated through static mechanical tests. The mechanical properties of hybrid composites increased significantly because of the addition of LCMC. The crystal behaviour analysis of LCMC/UP blend was investigated by X-ray diffraction and polarising optical microscopy. The results showed that the crystal phase and texture structure of LCMC still existed in the blends after blending with UP. The morphology of fracture surfaces of hybrid composites containing different TLCP contents was observed by scanning electron microscopy. The present paper discussed the mechanism for the improvement of dynamic mechanical and mechanical properties.     

Effect of a styrene–butadiene copolymer on the phase structure and impact strength of polyethylene/high‐impact polystyrene blends

The effect of a styrene–butadiene block copolymer on the phase structure and impact strength of high‐density and low‐density polyethylene/high‐impact polystyrene blends with various compositions was studied. For both the blends, the type of the phase structure was not affected by addition of a styrene–butadiene compatibilizer. The localization and structure of the compatibilizer in the blends were dependent on their composition. Addition of the compatibilizer improved impact strength of the blends in the whole concentration range. The improvement was the largest for blends with a low amount of the minor phase. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 570–580, 2001     

Polyurethane acrylate/epoxy–amine acrylate hybrid polymer networks

New classes of hybrid polymer networks (HPNs), having variable polyurethane acrylate (PUA) and epoxy–amine acrylate (EAA) compositions, were prepared using initially miscible systems in methyl methacrylate (MMA). The initial systems were based on PUA prepolymer and EAA monomer solutions in MMA. HPNs were a result of epoxy–amine and radical polymerization competition. Phase separation occurred during the course of HPN formation. Mechanical dynamic analysis of the prepared HPNs showed good affinity between the PUA and PMMA phases and lower affinity between the EAA and PMMA phases. Mechanical property evolution and transmission electronic microscopy showed that, for all the composition ranges used in this study (PUA/EAA/PMMA 15/45/40–45/15/40 wt %), the PUA‐rich phase was the continuous phase. EAA‐rich phases, 20–50 nm, in the PUA‐rich matrix were obtained for HPNs containing up to 30 wt % EAA. For higher EAA concentration (45 wt %), 2 μm EAA‐rich phases were obtained in the PUA‐rich matrix. A substructure was also observed in each phase. PUA/EAA copolymers were prepared and used successfully for the compatibilization of the different phases of the HPNs. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2711–2717, 2000     

不饱和聚酯树脂微乳液的研究(Ⅰ)不饱和聚酯树脂的微乳化

合成了不同磺酸盐含量的三种不饱和聚酯，通过拟三元相图分析磺酸盐含量、苯乙烯、不同正构醇和水组成的体系对微乳区域的影响。研究结果表明，磺酸盐不饱和聚酯同苯乙烯互溶的前提下，磺酸盐含量越大，其微乳液增溶的水量越大；磺酸盐含量一定时，苯乙烯含量越小，其微乳液增溶的水量越大；正构醇质量分数为在2％～10％范围内，其微乳液增溶的水量最多；三种醇相比较，正丁醇体系的微乳区是W／O型向O／W型过渡的连续区域，正丙醇体系的O／W型微乳液区明显不同于正丁醇体系，正戊醇体系不能形成水包油型的微乳区。     

聚酯／聚醚型聚氨酯胶粘剂合成与性能研究

用不同的聚酯和聚醚为原料合成双组分聚氨酯胶粘剂,找到合成该胶粘剂的最佳工艺条件、工艺配方、考察了异氰酸酯及环氧树脂改性剂含量对胶粘剂机械性能的影响。实验结果表明,加入扩链剂可明显提高胶粘剂的机械强度;加入少量环氧树脂可明显提高胶粘剂的拉伸剪切强度,但使剥离强度降低了许多。     

Reaction-induced phase separation during the formation of a polyurethane-unsaturated polyester interpenetrating polymer network

In this study, an interpenetrating polymer network (IPN) based on a polyurethane (PU) and a partially end-capped unsaturated polyester (UPE) was prepared. The reaction-induced phase separation process of the IPN was studied using a phase contrast optical microscope and a transmission electron microscope (TEM), while reaction kinetics and onset of gelation were determined by a differential scanning calorimeter and a rheometer respectively. Except at low temperatures, the phase separation patterns were found to follow the spinodal decomposition mechanism. An interconnected phase developed quickly and was followed by coalescence of the periodic phase to form droplet/matrix type of morphology. A second level of phase separation also occurred within both the droplet and the matrix phases in some cases. The domain sizes resulting from both levels of phase separation gradually increased until the structure was locked by chemical gelation. Reaction temperature, PU reaction rate, and UPE reaction rate all had significant effects on the final morphology of the formed IPNs.     

不饱和聚酯树脂微乳液的研究(Ⅲ) 磺酸盐不饱和聚酯树脂微乳化的表征

研究了4种正构醇(正丙醇、正丁醇、正戊醇和正己醇)对磺酸盐不饱和聚酯树脂的粘度和电导率的影响,聚酯树脂中醇含量增加,溶液的电导率增大,粘度下降;聚酯树脂中的醇含量相同时,醇的碳链越短,溶液的粘度越低,电导率越大。在一定的温度和搅拌速度下,将含有一定量醇的磺酸盐不饱和聚酯树脂加水微乳化,用微乳化过程中体系粘度和阻抗的变化表征了微乳化相反转过程,发现粘度比电导表征相转变更好。用差示扫描量热法的吸收热焓和吸收峰的温度判断了不同含水量时体系的相态。     

Vapour–phase Dyeing of Synthetic–polymer Fibres

Absorption isotherms at high temperatures for some disperse dye vapours and secondary cellulose acetate film have been determined and found to be linear. In order to calculate dye vapour concentrations, two methods have been used for the determination of vapour pressures, and from the results it is shown that disperse dye molecules can associate in the vapour phase. The absorption of dye vapour by polyester fibre in the form of small packages over the range 180–220°C, as well as a laboratory machine that can be used for this purpose, are described. Package dyeing on a larger scale with dye vapour is considered to be possible.