固相缩聚共聚酯的熔融行为和结晶速率研究

通过固相缩聚合成了两种不同结构的高分子量共聚酯，研究了样品的熔融行为和结晶速率。研究发现，共聚酯的熔融峰随着固相聚合温度和时间的变化而与纯ＰＥＴ有明显的差别，共聚酯泊结晶速率与慢于纯ＰＥＴ的结晶速率。     

New polymer syntheses: 59. Homo-and copolyesters of 4-(4′-hydrophenoxy)benzoic acid

The homopolyester of 4-(4′-hydroxyphenoxy)benzoic acid (poly(4-HPBA)), was prepared under two different reaction conditions and compared with a sample provided by another research group. Depending on the synthetic route, different melting points, d.s.c. traces and crystal lattices were found. However, after repeated heating and cooling, one thermodynamically stable modification with a melting point of 370–375°C can be obtained. Copolyesters of 4-hydroxybenzoic acid and 4-(4′-hydroxyphenoxy)benzoic acid were prepared with various molar ratios either in the melt (condensation in bulk) or in solution. These copolyesters were characterized by elemental analyses, ¹H n.m.r. spectroscopy, d.s.c. measurements, wide-angle X-ray scattering measurements at various temperatures, and optical microscopy. Whereas copolyesters prepared in solution do not melt below 500°C, those prepared by polycondensation in bulk show melting points down to approximately 260°C and form a nematic melt.     

Thermal cross-linking and anti-meltdrop properties of copolyester containing phosphorus/magnesium salt composites by in situ polymerization

Polyester is widely used in household products because of its good mechanical properties and wears resistance, but polyester is easy to ignite and inclined to produce droplet, so its application range is limited. The cross-linkable magnesium hydroxide nanoparticles were incorporated into flame-retardant polyester, which enables the phosphorus-containing copolyester with thermal cross-linking and anti-meltdrop properties. The nanoparticles were achieved by in situ polymerization and acted as a nucleating agent for improving the crystalline properties of the copolyester. Furthermore, the nanoparticles also enhanced anti-meltdrop properties and reduced the heat and gas release during the combustion process of the copolyester. The maximum heat release rate and total smoke release reduced by 39.8% and 74.4% compared with pure polyester. Specifically, the combustion products of the nanoparticles and phosphorus flame retardant could act a barrier role by covering the carbon layer to isolate air and heat, thereby resulting in excellent anti-meltdrop properties. The simple modification method reported here realizes the collaborative modification of flame retardant and anti-meltdrop properties of phosphorous flame-retardant copolyesters by thermal cross-linking.     

低熔点快固化聚酯热熔胶的合成与性能研究

在对苯二甲酸二甲酯(DMT)和1,4-丁二醇(BD)合成聚酯体系中引入其它共聚组分,制备了快速结晶的低熔点共聚酯热熔胶,其熔点约为70～120℃。由于熔点越低结晶性能越差,因此在合成聚酯热熔胶的基础上,进一步对其进行改性,且对组成与性能的关系进行了研究。结果表明,聚酯热熔胶的熔点和结晶性能随DMT含量的增加而升高;二元醇体系的配比和含量对熔点和结晶性能有很大影响,当混合二元醇物质的量比为1时具有最低的熔点,BD/HD(1,6-己二醇)体系比EG(乙二醇)/HD体系的结晶速率快,BD/HD体系中结晶速率随HD含量的增加而加快。     

Plane stress fracture toughness of physically aged plasticized PETG as assessed by the essential work of fracture (EWF) method

The plane stress fracture toughness of amorphous copolyester (PETG) sheets plasticized by various amount of neopentylglycol dibenzoate (NPGDB in 0, 5, 10 and 20 wt%) was studied in as-received (AR) and rejuvenated (RJ) states by adopting the essential work of fracture (EWF) method. EWF tests were performed on deeply double-edge notched tensile loaded (DDEN-T) specimens at various deformation rates (2,10 and 100 mm/min) at room temperature. It was established that physical aging strongly affected the EWF terms. The specific yielding-related EWF increased with increasing deformation rate and decreased with increasing plasticizer content. The specific non-essential work and its necking-related constituent, which changed parallel to each other, remained constant up to 10 wt% NPGDB content and decreased afterwards. The plastic zone in the DDEN-T specimens was formed by cold drawing which is governed by the entanglement structure. This was demonstrated by the shape recovery of the plastic zone in the broken DDEN-T specimens after heating them above the T_g of the related PETG compound.     

原位插层聚合法制备共聚酯/蒙脱土纳米复合材料

采用原位插层聚合法,制备了蒙脱土含量较高的共聚酯/蒙脱土纳米复合材料,意在做母料使用,含有该母料的聚合物复合材料的染色性能、吸湿浸润性能、抗静电性能及抗紫外性能等都有所改善。阐述了合适的共聚酯/蒙脱土纳米复合材料的制备工艺,讨论了制备过程中的影响因素,结果发现:在采用酯交换-缩聚反应釜进行原位插层聚合制备共聚酯/蒙脱土纳米复合材料的过程中,蒙脱土在缩聚釜中加入更符合生产实际;缩聚反应的实际过程证明了蒙脱土中含有的金属离子对缩聚反应有催化作用;另外,控制聚合的最终温度不超过278℃。最后,对共聚酯/蒙脱土纳米复合材料的结构进行了表征。     

Epoxidized soybean oil modified using fatty acids as tougheners for thermosetting epoxy resins: Part 2—Effect of curing agent and epoxy molecular weight

A series of bio-rubber (BR) tougheners for thermosetting epoxy resins was prepared by grafting renewable fatty acids with different chain lengths onto epoxidized soybean oil at varying molar ratios. BR-toughened samples were prepared by blending BRs with diglycidyl ether of bisphenol A resins, Epon 828 and Epon 1001F, at different weight fractions and stoichiometrically cured using an amine curing agent, 4, 4′-methylene biscyclohexanamine (PACM). Fracture toughness properties of the unmodified and BR toughened polymer samples—including critical strain energy release rate (G_Ic), and critical stress intensity factor (K_Ic)—were measured to investigate the toughening effect of prepared BRs. It was found that the degree of phase separation and toughening were more controllable relative to similar polymers cured using the aromatic curing agent Epikure W, and the use of higher molecular epoxy resins produces a synergistic effect increasing the toughness much more than similar polymers made with lower molecular weight epoxy resins. Average BR domain sizes ranging from 200 to 900 nm were observed, and formulations with G_Ic, values K_Ic as high as 1.0 kJ/m² and 1.4 MPa m^1/2 were attained respectively for epoxy systems with T_g greater than 130°C.     

聚砜类原位复合材料加工流变性

合成了含4,4'-二羟基联苯和4,4'-二羟基二苯基甲烷结构的两种液晶共聚酯BP-LCP和BPM-LCP,将其与聚砜共混制备原位复合材料。探讨了共混物在Haake转矩流变仪中密炼时转矩的变化;通过毛细管挤出考察了液晶共聚酯分子结构、分子量及含量变化对原位复合材料流变性能的影响,由流动曲线获得这一类原位复合材料熔体大部分表现为假塑料性非牛顿型流体,但含低分子量BP-LCP20%和BPM-LCP30%的两种原位复合熔体均表现出特殊的流变性:较低剪切速率时为胀塑性流体,较高剪切速率时为假塑性流体。分析了这种现象与液晶共聚酯结构形态的关系。并讨论了增强组份和基体的相容性对原位复合材料流变性的影响。     

高收缩共聚酯合成性能与成纤性能研究

通过共聚酯PEIT(间苯二甲酸、对苯二甲酸、乙二醇共聚物)的合成及其全拉伸丝(FDY)纺丝的成功实验,研究了高收缩PEIT共聚物合成工艺中共聚组分间苯二甲酸(IPA)的摩尔百分数对共聚酯PEIT的玻璃化温度、熔点的影响,探讨了该PEIT共聚物的结晶性能及其纺丝工艺条件对高收缩纤维性能的影响。     

含磷阻燃共聚酯的热降解动力学及耐热性能研究

采用不同的升温速率,用Kissinger法研究了聚对苯二甲酸乙二酯(PET)和侧基含磷共聚酯(FR-PET)在氮气气氛中的热降解动力学;采用时-温等效原理对其耐热性能进行了深入研究,确定了动力学参数与材料寿命方程之间的关系,为直接估算材料的使用寿命提供了捷径。结果表明,阻燃剂的引入降低了PET整个热降解过程的平均活化能、指前因子及反应级数,并使PET的不同失重率所对应的时间延长,即FR-PET的耐热性能有所提高;在同一温度下,360℃以前FR-PET失重一半的时间要短于纯PET,在360℃以后则长于纯PET,说明在高温下相对于纯PET要难于点燃。利用Kissinger法确定的寿命与动力学关系式可较准确地预测材料的寿命。