PTA酯化缩聚法合成PTT的研究

研究了用精对苯二甲酸 ( PTA )法合成聚对苯二甲酸丙二醇酯 ( PTT)的工艺特点 ,探讨了影响合成工艺的因素 ,并与 PET的合成工艺进行了比较。结果表明 ,PDO质量对 PTT性能有较大影响 ;PTT的合成工艺与 PET的有较大差别 ,合成 PTT采用钛化合物或 X作为酯化和缩聚反应的催化剂较合适 ,酯化反应在 2 2 0～ 2 40℃ ,0 .2 5 MPa以下进行 ,酯化率要达到 98%以上 ,缩聚反应的真空度及反应时间需准确控制     

抗静电PTT及其纤维的研制

采用精对苯二甲酸(PTA)、1,3-丙二醇(PDO)及抗静电剂直接酯化法合成具有抗静电性能的聚对苯二甲酸-1,3-丙二醇酯(PTT)。对合成的PTT切片固相增粘后进行高速纺丝制得165 dtex/36 f抗静电PTTDTY。结果表明:在聚合反应完成前20 min加入抗静电剂,抗静电剂质量分数控制在1.5%～2.5%,聚合得到的切片经过真空固相增粘至其特性粘数达0.950 dL/g,可得到可纺性好、抗静电性好的PTT。制得的PTTDTY纤维手感好,织物表面电阻率达到10~9～10~(10)Ω。     

直接酯化法合成PTT的研究

研究了用直接酯化法合成聚对苯二甲酸丙二醇酯(PTT)的工艺,考察了影响合成工艺的各种因素。结果表明,1,3-丙二醇的醛含量对PTT合成反应有较大影响;实验所选定的复合催化剂能起到较好的催化作用,相对催化剂钛酸四丁酯可使反应速度提高15%,并可提高产品色相;制备PTT切片最佳工艺条件为醇酸量比为1.4:1,缩聚反应温度为270~272℃;固相增黏得到的PTT切片主要物理性能和纺丝性能指标达到美国杜邦公司的同类产品水平。     

聚对苯二甲酸丙二醇酯合成研究

研究了以对苯二甲酸二甲酯(DMT)与1,3 丙二醇(PDO)为原料,采用酯交换、缩聚反应路线合成聚对苯二甲酸丙二醇酯(PTT)。动力学分析表明:酯交换反应在转化率为95%之前,符合二级反应动力学模型。实验结果指出,采用传统催化剂体系当原料配比n(PDO)/n(DMT)=2.2/1时,1gDMT的酯交换催化剂醋酸锌为400～600μg,反应温度为220℃时,酯交换反应速率较快;1gDMT的缩聚催化剂三氧化二锑为500μg,反应温度为265℃,在高真空下,可得较高摩尔质量的PTT。     

Ti/Si系催化剂催化聚酯缩聚反应动力学研究

研究了Sb2 O3 和C 94两种催化剂对于PET缩聚反应的动力学。结果表明 ,在相同条件下C 94的催化活性明显高于常规的Sb2 O3 催化剂 ;C 4的表观活化能明显高于Sb2 O3 催化剂 ;在有效搅拌条件下 ,两种催化剂在高真空阶段仍有较高的催化活性 ,过程是化学反应控制的。     

聚酯高效催化剂缩聚反应动力学研究

研究了常规的Sb2 O3 、复合催化剂和C - 94三种催化剂对于PET缩聚反应的宏观动力学。结果表明 ,在相同条件下复合催化剂和C - 94的催化活性明显高于常规的Sb2 O3 催化剂 ;C -94的表观活化能明显高于复合催化剂和常规催化剂 ,其催化PET缩聚反应过程的温度效应显著 ;在有效搅拌条件下 ,三种催化剂在高真空阶段仍有较高的催化活性 ,过程是化学反应控制的。     

Surface hydrolysis of filaments based on poly(trimethylene terephthalate) spun at high spinning speeds

The surface alkaline hydrolysis of fibers made from poly(trimethylene terephthalate) (PTT) was studied after extruding the polymer at high spinning speeds from 2000 to 6000 m/min and heat setting in the range of temperatures from 100 to 180°C. Fiber weight loss increased with an increasing heat‐setting temperature but it was also dependent on the spinning speed. Some of the partially hydrolyzed fibers had a well‐developed, hydrophilic surface, and pore size in the range of 0.69 to 1.20 μm. The optimum reaction and morphological conditions for increasing porosity in PTT fibers depends on spinning speed and heat‐setting temperature. A temperature of 180°C is the upper limit for heat‐setting PTT filaments but seems to be the most effective for making porous fibers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1724–1730, 2004     

Film reaction kinetics for melt postpolycondensation of poly(ethylene terephthalate)

Melt polycondensation has recently been reported to prepare high-viscosity poly(ethylene terephthalate) (PET), the reaction efficiency is greatly improved in over 10-folds compared with conventional solid state polycondensation (SSP). Melt postpolycondensation of common PET chips was conducted in specified film thickness to obtain industrial PET. Based on the investigation of reaction conditions, film reaction kinetics were determined in the principle of end groups analysis. It was positively regulated that the intrinsic viscosity of PET could be achieved in condition of high vacuum, thin melt film and proper temperature, degradation reaction would be increased at exorbitant temperature. An apparent reaction kinetic model was proposed and was verified by experiments. Results indicated the activation energy of melt postpolycondensation of PET was 88.22 kJ/mol and the reaction rate constant was significant higher than that of solid state polycondensation.     

PTT纤维的加工技术与性能

综述PTT的聚合纺丝、后加工技术及纤维的性能。指出PTT集良好的可加工性、机械性、热塑性、延伸性、高弹性、尺寸稳定性和染色性等性能于一体,优于PET、PA,可广泛应用于工程塑料、薄膜和纤维等领域。可利用现有的PET的缩聚和纺丝设备,加快我国PTT纤维工业化的进程。     

聚对苯二甲酸丙二醇酯的合成及表征

采用直接酯化缩聚合成工艺自制新型树脂—聚对苯二甲酸丙二醇酯（ＰＴＴ） 。详细讨论了聚合条件对合成反应的影响。用红外光谱、核磁共振分析表征了ＰＴＴ 的结构,并将结果同ＰＢＴ和ＰＥＴ 作了比较。研究结果表明在酯化反应转化率达到８０ ％ 左右开始进行缩聚反应有利于减少副产物,同时也不会影响制得合格的ＰＴＴ 树脂：在ＰＢＴ 大分子链节中的（ － ＣＨ２） 数是ＰＥＴ 的２ ．０４ 倍,是ＰＴＴ 的１．３４ 倍;ＰＴＴ 大分子链节中的（ － ＣＨ２） 数是ＰＥＴ 的１ ．５２ 倍。因此ＰＴＴ 大分子链的柔顺性在ＰＢＴ 和ＰＥＴ 之间     

Conversion of polyester into heat‐resistant polyamide by reacting with aromatic diamine compound II. Semibatch reaction by nitrogen gas sweeping process

The conversion of poly(ethylene terephthalate) (PET) into heat‐resistant polyamide was carried out in the solid state polycondensation by applying a nitrogen gas sweeping process. The reaction product obtained by the catalyzed and uncatalyzed batch reaction with the specified reaction condition was used as the starting material in the semibatch reaction process. Nitrogen gas was introduced into the reactor to remove a volatile reaction byproduct from the reaction mixture. Effect of the semibatch reaction variables such as temperature, time, and nitrogen gas sweeping rate on the extent of reaction and the heat‐resistant property of polyamide obtained was investigated. A comparison of the extent of reaction in the semibatch reaction process was made between the catalyzed starting material and the uncatalyzed one. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2223–2232, 2004     

国产生物法1,3-PDO合成PTT研究

以国产生物法1,3-PDO及PTA为原料,采用直接酯化法工艺路线合成了PTT,对缩聚工艺进行了研究,并以IR对PTT进行了表征,结果表明:可以用催化剂A以国产生物法1,3-PDO为原料制备得到PTT,较佳的缩聚工艺为温度:255℃,压力<50 Pa,时间:3.5~4 h。     

Characterization and crystallization behavior of poly(ethylene‐co‐trimethylene terephthalate) copolymers

A series of poly(ethylene‐co‐trimethylene terephthalate) (PETT) copolymers were prepared by polycondensation. The synthesized PETT are block copolymers and the content of poly(trimethylene terephthalate) (PTT) units incorporated into the copolymers are always larger than that fed in the polymerization. The nonisothermal crystallization at the different cooling rates was studied by means of differential scanning calorimetry. The copolymers develop the crystallization later and show the lower melting temperature than the corresponding enriched homopolymers. The modified Avrami analysis fit well the nonisothermal crystallization of these polymers. The overall rate of crystallization of PTT is fastest and that of PET is slowest, whereas the copolymers are between them at the same cooling rate. The minor PET units incorporated into PTT polymer chains reduce the crystallization of PTT segments, but the present minor PTT units in the PET chains seem to accelerate the crystallization of PET segments. The Avrami exponent nvaries in the range of 3 – 4, indicating that the nonisothermal crystallization follows the homogeneous nucleation and two‐ to three‐dimensional growth mechanism. Wide angle X‐ray diffraction analysis explains that the PET and PTT units do not cocrystallize and it is considered as the enriched polymer segments to crystallize during crystallization. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

PTT连续生产工艺设计

重点分析了聚对苯二甲酸丙二醇酯(PTT)直接酯化法连续生产的工艺特点,结合这些特点,详细介绍了PTT直接酯化法连续生产工艺技术的开发及工艺流程的创新点。     

连续式PTT工艺

简要介绍了聚对苯二甲酸丙二酯(PTT)的应用、市场和工艺发展。重点分析了间歇式和连续式聚合物工艺的不同及对产品质量的影响。详细介绍了吉玛公司PTT民用长丝的纺丝工艺——冷态工艺加上改性剂。     

聚酯的固相缩聚增粘

固相缩聚增粘是提高聚酯性能从而拓宽其用途的有效途径。对聚酯固相缩聚的理论和工业生产进行了较全面地介绍     

草酸亚锡催化合成PTT的研究

采用对苯二甲酸(PTA)和1,3-丙二醇(1,3-PDO)为原料,以自制的草酸亚锡为催化剂经酯化、缩聚,制得聚对苯二甲酸丙二醇酯(PTT)。探讨了反应条件对合成反应的影响。结果表明:草酸亚锡的催化活性优于丁基锡酸和辛酸亚锡。1,3-PDO／PTA的摩尔比为1．5／1、草酸亚锡用量为5×10-4mol／mol(相对PTA),酯化反应温度260℃,反应时间2 h;缩聚反应温度260℃,反应时间2 h,可制得PTT,其特性粘数为0．8950dL／g,端羧基含量为15 mol／t。     

The rate acceleration in solid‐state polycondensation of PET by nanomaterials

The effect of nanomaterials on the solid‐state polycondensation (SSP) of PET was investigated using intrinsic viscosity measurement, wide‐angle X‐ray diffraction, differential scanning calorimetry, and polarizing microscope. The results showed that the montmorillonite nanomaterials could greatly increase the rate of solid‐state polycondensation of PET, probably due to the nucleation of montmorillonite nanomaterials for PET crystallization, which resulted in lower crystallinity, more small crystals, and more surfaces of the crystals. The surfaces of microcrystal and richer amorphous regions benefitted the polycondensation reaction of PET and diffusion of volatile by‐products, which led to the higher rate of SSP. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 971–976, 2004     

Crystallization behavior and crystal structure of poly(ethylene‐co‐trimethylene terephthalate)s

A series of random copolymers were synthesized by the bulk polycondensation of dimethyl terephthalate with ethylene glycol (EG) and propane‐1,3‐diol (PDO) in various compositions. Their composition and thermal properties were investigated. The copolymers with 57.7 mol % or more PDO or 14.4 mol % or less PDO were crystallizable, but those with 36–46.2 mol % PDO were amorphous. The nonisothermal crystallization behavior was investigated with varying cooling rates by DSC. Poly(ethylene terephthalate) (PET) and poly(trimethylene terephthalate) (PTT) homopolymers have relatively lower activation energy than their copolymers. PET‐rich copolymers (EG > 85.9%) exhibited PET crystal structure, and exhibited no PTT crystal structure; and PTT‐rich copolymers (PDO > 41.7%) exhibited PTT crystal structure, and exhibited no PET crystal structure. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

聚酯装置终聚釜反应机理及工艺优化探讨

通过对终聚反应机理及工艺优化的探讨,以提高聚酯装置生成熔体的质量。具体方法是根据生产负荷的变化,控制入口液位在适当范围内,并通过调整搅拌转速,使釜内物料达到最佳成膜效果,以保证物料在正常真空度条件下以最低的反应温度、最短的停留时间完成终聚反应,同时最大限度地减少副反应。通过以上措施,有效降低了聚酯熔体的端羧基含量及 b 值。因此终聚反应工艺优化的核心是控制终聚釜入口液位,稳定真空度及真空蝶阀开度。