牛物法PDO合成PTT结构与性能的研究

采用生物法1，3-丙二醇（PDO）直接酯化缩聚合成聚对苯二甲酸丙二醇酯（PTT），通过IR、^1H NMR、DSC和TG方法对其进行了表征，并与化学法PDO合成的PTT进行比较。结果表明，生物法PDO合成的产物是PTT；生物法PDO合成的肿比同一纯度的化学法PDO合成的肿色泽好、粘度大、摩尔质量高，且随PDO纯度提高，肿粘度、摩尔质量增大；生物法PDO合成的肿熔点与化学法PDO合成的肿相差不大，熔融峰比化学法PDO合成的肿尖锐，熔融热大，结晶度高；不同PDO合成的肿树脂热失重相差不大，表明PDO不同对肿热分解行为影响不大。     

1,3-丙二醇中残留羰基对PTT切片色相的影响

阐述了 1,3-丙二醇 ( PDO)的主要杂质之一残留羰基的来源、分析方法及其纯化 ,并探讨了降低残留羰基含量对改善聚对苯二甲酸丙二醇酯 ( PTT)切片色相的作用。结果表明 :用 PTA法合成 PTT时 ,切片的 b* 值较高 ,且合成较难 ;PDO中残留羰基含量是影响 PTT色泽的一个重要因素 ,经碱化减压蒸馏 ,可降低其残留羰基着色度、水分等。     

生物法1,3-丙二醇工艺技术分析

1,3-丙二醇（1,3-PDO）是生产聚对苯二甲酸丙二醇酯（PTT）的主要原料,生物法工艺技术比化学法更具竞争优势,国内已形成多条工艺路线,多家企业拟进行大规模产业化生产,工艺路线的技术经济性是企业的关注要点.文章从原料选择、发酵工艺、菌体及蛋白质去除、除盐、蒸发及PDO精制等工序进行工艺技术经济性分析,在此基础上,对目前国内采用的3种千吨级PDO工艺路线进行分析,提出了发展建议.     

聚酯新星PTT

聚对苯二甲酸丙二醇(PTT)是1941年美国壳牌化工公司(Shell)首次威功合成的树脂．是以对苯二甲酸(TPA)和1.3一丙二醇(PDO)通过缩聚反应制备的聚酯。壳牌公司是目前唯一能供应挤出级和吹塑级PTT基础树脂的厂家。由于该公司合成PDO的催化剂取得了突破性进展，PDO的生产威本大幅下降。     

均匀试验设计法对PTT合成工艺的优化研究

使用钛酸四丁酯作为聚对苯二甲酸丙二醇酯(PTT)合成催化剂,以对苯二甲酸(TPA)和1,3-丙二醇(PDO)为原料,通过直接酯化法合成得到纤维级PTT;运用均匀实验设计方法,对PTT合成的工艺条件进行了优化,得到了各个工艺条件与产品特性黏数的作用关系。结果表明:PTT合成优化工艺条件为PDO和TPA的摩尔比1.345 9,催化剂与TPA的摩尔比9.0×10-4,不加抗氧剂,反应温度262℃,拟合方程预测产品特性黏数最优结果为1.049 1 dL/g,实验验证结果为1.031 3 dL/g;拟合方程的预测性较好。     

具有自主知识产权的生物法1,3-丙二醇成功投产

<正>我国具有完全自主知识产权的生物法1,3-丙二醇(PDO)项目于2013年12月在张家港成功投产,这一生产线的投产打破了美国企业在这一领域的长期垄断。据介绍,由PDO方法合成的聚对苯二甲酸丙二醇酯(PTT)被称为"智能型"聚合物,是21世纪初推出的最先进的聚合物平台,PTT纤维具有比涤纶和锦纶更优异的性能以及更广泛的应用。     

PTT的工业开发及 1,3丙二醇的合成

介绍了聚对苯二甲酸丙二醇酯 (PTT)的性能和 1,3-丙二醇 (1,3- PDO)的合成方法 ,并讨论了其市场前景、技术经济比较等。指出我国已具备开发 PTT及其纤维的条件 ,应独立开发成套技术。     

Davy和Samsung合作开发丙二醇工艺

Davy工艺技术公司和Samsung公司已达成协议,合作开发将环氧乙烷转化为1,3-丙二醇(PDO)的钴基催化剂催化工艺。PDO为生产聚对苯二甲酸亚丙基酯(PTT)的前体。按照该协议,Samsung公司拟将其专利转让给Davy公司,进行进一步工艺开发和发放许可证。Samsong公司的专利涉及EO加氢酯化为羟酯中间体;Davy公司的专利则涉及将粗PDO加氢精制为PTT生产所需纯度。     

具有自主知识产权的生物法PDO成功投产

<正>我国具有完全自主知识产权的生物法PDO(1,3-丙二醇)项目2013年12月在张家港成功投产,这一生产线的投产打破美国企业在这一领域的长期垄断。据介绍,由PDO方法合成的PTT被称为"智能型"聚合物,是21世纪初推出的最先进的聚合物平台,PTT纤维具有比涤纶和锦纶更优异的性能以及更广泛的应用。专家认为,此次华美PTT的正式投产,是我国第一次有机会掌握特种聚合物上游原材料的核心技术和     

有机胺催化一缩二丙二醇合成工艺研究

以有机胺AEDA为催化剂,环氧丙烷(PO)和丙二醇(PDO)为原料合成了一缩二丙二醇,对其合成工艺条件进行了初步研究。通过正交实验得出最佳工艺条件为:反应温度100℃,反应压力202.64 kPa,反应时间90 min,n(PDO)∶n(PO)为2.0,催化剂用量为环氧丙烷摩尔质量的0.10。此时,一缩二丙二醇的收率可达83.8%,选择性91.2%以上。产品薄层色谱图和标准品图谱吻合。     

1,3-丙二醇钛催化合成PTT的工艺研究

以自制的1,3-丙二醇钛为催化剂,采用对苯二甲酸(PTA)和1,3-丙二醇(PDO)为原料,通过直接酯化法制得聚对苯二甲酸丙二醇酯(PTT);研究了催化剂用量、反应物配比、酯化和缩聚温度、缩聚时间等对反应结果的影响.结果表明:以1,3-丙二醇钛为催化剂制备PTT是可行的;在酯化反应温度为230～235℃,PDO/PTA...     

聚对苯二甲酸丙二醇酯的热性能研究

研究了聚对苯二甲酸丙二醇酯 (PTT) ,PET ,CDP在不同温度和时间下的特性粘数和端羧基含量的变化。结果表明 ,一定温度下 ,PTT熔体特性粘数随熔融时间的延长而下降 ,一定时间下 ,随温度的升高而下降。PTT端羧基含量随温度升高而增大 ,PTT的热稳定性较PET明显下降。     

Melt Crystallization Behavior and Spherulitic Morphology of Poly(Trimethylene Terephthalate)/Poly(Propylene Glycol) Copolymers with Different Poly(Propylene Glycol) Molecular Weights

Poly(trimethylene terephthalate)/poly(propylene glycol) (PTT/PPG) copolymers with different PPG molecular weights (400–4,000?g?/mol) were successfully synthesized and characterized. Double melting endotherms during isothermal melt crystallization were observed by differential scanning calorimetry. Middle-temperature melting endotherms in all copolymers were stronger than that in PTT homopolymer and became smaller with the increasing PPG molecular weight. Nonisothermal crystallization kinetics of all samples were analyzed by Ozawa and Mo models. Polarized optical microscopy micrographs revealed that ring-banded spherulitic morphology was relatively easier to be observed in copolymers with higher PPG molecular weight at lower crystallization temperature, and PPG molecular weight nearly had no influence on the band spacing.     

Synthesis and characterization of poly(ethylene‐co‐trimethylene terephthalate)s

Taking advantage of a melt polycondensation process, a series of copolyesters composed of pure terephthalate acid (PTA), ethylene glycol (EG), and 1,3‐propanediol (1,3‐PDO) were synthesized. The component, molecular weight, molecular weight distribution, and thermal properties of the copolymers were characterized. The results show that the contents of trimethylene terephthalate (TT) units in the resulting copolyesters are higher than PDO compositions in original diol. Oligomer content in the copolyesters varies with the compositions and attains a minimum value when the TT ingredient is 49.52 mol %. The glass transition temperature (T_g) of the copolyesters varies from 78.5°C for PET (polyethylene terephthalate) to 43.5°C for PTT (polytrimethylene terephthalate) and decreases monotonically with the components. The copolyesters are amorphous copolymers when TT content is in the range of 32.4–40.8 mol %, as calculated from the melting enthalpy (ΔH_m) measured via differential scanning calorimetry. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1511–1521 2006     

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。     

Lower purity dimer acid based polyamides used as hot melt adhesives: synthesis and properties

Hot melt polyamides exhibit high adhesive strength. The polyamides synthesized from dimer fatty acids and diamines can present low crystallinity and a broad range of melting temperatures. In this work, polyamides with different compositions of dimer fatty acids, piperazine, ethylenediamine, sebacic acid and stearic acid and different content of secondary diamine (piperazine) and primary diamine (ethylenediamine) were synthesized. Polyamides with higher purity of dimer acids showed greater molecular weight, adhesion performance and a better mechanical resistance evaluated in stress/strain test. Softening point increased with increase in monomers content. By differential scanning calorimetry analysis, it was observed that polyamides with low percentage of monomer content show only one narrow melting peak in 100 °C. The increase in the acids monomer content leads to a larger temperature range of melting peak. The use of dimer fatty acid with a low content of monomers (up to 6%) in the polyamides synthesis promotes the formation of hot melt adhesives with good adhesion performances. The lowest monomer content leads to an increase in molecular weight, viscosity and mechanical properties of polyamide. Increase in the content of primary amines in polyamides increases crystallinity, viscosity and mechanical properties due to the higher number of hydrogen bonds formed by amide groups.     

PET/PTT共聚酯的序列结构

采用TPA生产路线合成一系列PET/PTT共聚物,发现在不改变其他条件的情况下,改变单体配比,所获得的共聚物特性黏度值都在0.6dL/g以上。对共聚物进行核磁共振测试来表征其序列结构,发现1H-NMR和13C-NMR所测试的结论一致,所得共聚酯无规度值均接近1,表明所得共聚酯均接近无规共聚物。     

PTT相对分子质量对结晶性能的影响

选取了不同相对分子质量的聚对苯二甲酸丙二醇酯 (PTT)试样 ,进行差热扫描量热 (DSC)分析 ,采用特性粘度与 Mark-H ouwink关联的方法表征相对分子质量。比较试样的结晶度 ,认为 PTT相对分子质量大于 5 .5× 10 4 时 ,相同热处理条件下相对分子质量对结晶度的影响不大。比较几种试样的半结晶期 ,认为 PTT相对分子质量低时结晶速度快 ;高时结晶速度慢 ,但是在相对分子质量达到 5 .5× 10 4时影响已不明显。根据经验关系式和 DSC谱图 ,估算出 PTT的最大结晶度约为 5 8% ,最大结晶速度的温度约 14 0℃。     

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