聚丁二酸乙二醇酯合成的研究进展

综述了直接酯化聚合法、丁二酸酐开环聚合法、酯交换聚合法、耦合反应法合成聚丁二酸乙二醇酯(PES)的国内外研究进展,着重介绍了丁二酸和乙二醇酯化聚合法合成PES的催化剂和工艺的研究现状,并展望了PES及其合成工艺的发展前景。     

聚丁二酸乙二醇酯及其共聚酯的生物降解性能

通过降解过程的质量损失率、相对分子质量及其分布、热性能、表面形貌等评价手段,重点考察了Aspergillus niger脂肪酶对聚丁二酸乙二醇酯(PES)和聚(丁二酸乙二醇-共-对苯二甲酸乙二醇酯)(PEST)的降解性能。结果表明:PES在脂肪酶溶液中具有较好的生物降解性能,随着对苯二甲酸摩尔含量的增加,PEST的质量损失率呈现先增加后逐渐减少的趋势;随着酶解时间的延长,残留部分的PES、PEST的相对分子质量均呈下降趋势;残留部分的PES、PEST的熔点随降解时间的延长变化不大,熔融热焓有所增加;聚酯薄膜表面产生了不同程度的沟槽、孔洞和裂纹。可以推测,PES及PEST的生物降解首先发生在无定形区,并且大分子链段发生的是随机断裂。     

聚丁二酸丁二酯的酯化反应新判据

在制备聚丁二酸丁二酯(PBS)的聚合过程中,一般包括酯化反应和缩聚反应两个阶段。在酯化反应阶段,通常用酯化聚合度来表征酯化反应进行的程度,但试验中发现酯化聚合度无法与缩聚后PBS的分子量之间建立直接的联系,而PBS的分子量却是衡量聚合反应的最重要的指标。通过建立新的酯化反应判据,可使酯化反应与缩聚后的PBS分子量之间建立直接的联系,并通过试验验证了该酯化反应新判据的可靠性。     

聚对苯二甲酸乙二醇酯合成催化剂研究进展

探讨了各类锑系催化剂、钛系催化剂(包括乙二醇钛)等不同类型的催化剂在聚酯缩聚反应中的催化性能研究的最新成果,指出在各种类型催化剂中,由于具有作为催化剂时不会带入多余的杂质进入反应体系等优点,乙二醇锑和乙二醇钛的应用前景较为广阔。     

杂多酸催化合成丁二酸二丁酯研究

采用均匀设计，以Keggin型磷钨酸为催化剂，甲苯为带水剂，得到了合成丁二酸二丁酯的最佳工艺条件为：醇酸物质的量比3．0：1，催化剂量为酸质量的1．1％，带水剂量为反应体系总质量的22％，反应时间2h，最高酯化率99．47％。     

硅钨酸催化合成丁二酸二丁酯

以Keggin型硅钨酸为催化剂,均相催化合成丁二酸二丁酯,根据单因素实验结果得到的最佳反应条件是:醇酸物质的量比为1∶8,催化剂用量为反应物总质量的1.1%,在130℃,反应时间60 min的条件下,酯化率可达99.3%。     

β-二酮铝和β-二酮酯铝催化合成聚对苯二甲酸乙二醇酯

采用对苯二甲酸(TPA)和乙二醇(EG)为原料,以自制的β-二酮铝和β-二酮酯铝为催化剂经酯化、缩聚,制得聚对苯二甲酸乙二醇酯(PET).探讨了反应条件对合成反应的影响.结果表明:β-二酮酯铝和乙酰丙酮铝优于其他β-二酮铝.EG与TPA的摩尔比为1.2∶1、催化剂的用量为0.5%(与TPA的摩尔比),酯化反应温度为26...     

可降解高分子量聚丁二酸己二醇酯的合成与表征

以丁二酸和1,6-己二醇为原料,以十氢萘为溶剂,进行直接缩合,合成了高分子量的聚丁二酸己二醇酯,产率达到95.5%。用FTIR和1H-NMR对其结构进行表征,GPC测得其数均分子量为46503,DSC测得其熔点为61.3℃,拉伸强度为30.9MPa,断裂伸长率为869.5%。     

酯化法合成丁二酸二乙酯

以丁二酸和无水乙醇为原料,硫酸氢钠为催化剂合成丁二酸二乙酯,考察了影响收率的各种因素,确定了最佳反应条件为:丁二酸用量0.1mol时,无水乙醇与戊二酸的物质的量比为6.0,3.0g催化剂,25mL环己烷作带水剂,反应时间2.0h,收率达85.09%,结果表明,硫酸氢钠是合成丁二酸二乙酯的优良催化剂。     

化学交联聚乙二醇水凝胶的制备方法

对化学交联聚乙二醇基水凝胶的研究进展进行了综述.介绍了该类水凝胶的制备方法,包括几种常见的前体制备方法和常用的交联方法,并讨论了影响水凝胶溶胀性能和力学性能的几种因素.     

聚乙二醇中咪唑与芳基硼酸的N-芳基化反应

N-芳基咪唑类化合物是一类非常重要的结构单元,常见于药物、农药以及生物分子中,因此寻找新的合成N-芳基咪唑类物质的方法成为有机合成化学家关注的热点问题之一。在绿色化学的倡导下,研究发展了一个促进咪唑类底物与芳基硼酸N-芳基化反应的催化体系,它是以Cu_2O(10%)为催化剂,以聚乙二醇400为反应介质,在室温下反应。研究结果表明,该催化体系适用于咪唑类底物与各种具有不同取代基的芳基硼酸的N-芳基化反应,为N-芳基咪唑类化合物提供一个简单、有效、绿色的合成方法。     

Fractional Crystallization Kinetics of Poly(ethylene oxide) in Its Blends with Poly(butylene succinate): Molecular Weight Effects

The fractional crystallization kinetics and phase behavior of PEO with different molecular weights (MWs) in its miscible crystalline/crystalline blends with PBS are studied. Both fractional crystallization kinetics and phase segregation of PEO in PBS/PEO blends are dramatically influenced by its MW. PEO with a medium MW (20 kDa) shows a significant fractional crystallization in the blends with PBS crystallized at a high T_IC,PBS, which, however, is dramatically depressed in the blends with a very low or high MW of PEO. This indicates that the PEO component with a medium MW is more ready to segregate into the interlamellar region of PBS crystals than those with a very low or high MW. The MW‐dependent fractional crystallization kinetics and phase segregation of PEO component in the PBS/PEO blends are discussed.

     

生物可降解聚丁二酸乙二醇酯的合成与降解性能研究

以丁二酸和乙二醇为原料,直接熔融聚合,合成了高相对分子量的聚丁二酸乙二醇酯(PES),用FTIR,1H-NMR表征其结构;考察了不同聚酯反应催化剂对其聚合反应的影响,结果表明:三氧化二锑的催化效果是最佳的。同时,利用酶降解和体外水解的方法,对聚合物降解性能进行研究,结果表明:PES是一种可生物降解的聚合物,且在体外具有一定的降解性。     

环氧乙烷催化法合成乙二醇的研究进展

对环氧乙烷催化法合成乙二醇研究的最新进展作了综述。阐述了用于环氧乙烷催化水合反应中的多羧酸衍生物催化体系、离子交换树脂催化体系、大环螯合物催化体系、季鏻盐催化体系、多相水滑石型催化体系及其他催化体系近年来的研究进展;同时阐述了用于碳酸亚乙酯法合成乙二醇反应中的催化体系的新进展。     

Blends of Poly(hydroxybutyrate) and Poly(ethylene succinate) Prepared in the Presence of Samarium

Blends of the commercial biodegradable polymer poly(hydroxybutyrate) (PHB) with the oligomeric polyester poly(ethylene succinate) (PES) were prepared by melt processing in the presence of Sm(acac)₃. The occurrence of transesterification reactions during blend processing using the samarium catalyst was investigated. ¹H NMR analyses showed no evidence of transreactions, even using high content of catalyst (4 wt%), long reaction times and high temperatures (200°C). Under the drastic reaction conditions employed, chain degradation characterized by a significant decrease in the molecular weight (MW) of PHB has taken place. PHB/PES blends form immiscible systems in which the PHB crystallizes as large spherulites, but its crystallization is significantly influenced by the presence of PES, which does not crystallize at conditions in which the poly(hydroxyalkanoate) is crystallized.     

Crystallization Kinetics and Hydrophilicity Improvement of Biodegradable Poly(butylene succinate) in its Miscible Blends with Poly(ethylene oxide)

The spherulitic morphology and growth, overall isothermal crystallization kinetics and hydrophilicity of PBSU were investigated by POM, DSC and WCA measurements in its miscible blends with PEO. The Hoffman‐Lauritzen equation was employed to analyze the spherulitic growth rates of neat and blended PBSU, which show a crystallization regime transition between regime II and III. The overall crystallization rates of PBSU decreased with increasing crystallization temperature, regardless of blend composition, while the crystallization mechanism does not change. A significant improvement in the hydrophilicity of PBSU can be achieved by blending with different weight fractions of PEO, which may be essential for the practical application of PBSU/PEO blends.

     

Effects of pH and Neutral Salts on the Adsorption of the Poly(ethylene glycol terephthalate) Condensates Toward Poly(ethylene terephthalate) Fiber

This study deals with the effects of pH and neutral salts on the adsorption of PET fiber with four kinds of poly(ethylene glycol terephthalate) condensated from dimethyl terephthalate (DMT) and poly(ethylene glycol) (PEG). The surface properties of the aqueous solution, the contact angle of polyol‐treated PET fabrics, and its parameters were also discussed. The pH of the solution or the adding of neutral salt in the polyol solution largely affected the contact angle of polyol‐treated PET fabrics as well as the surface tension of the solution. A lower pH of the polyol solution or adding neutral salts in the solution showed a lower surface tension and a lower contact angle that resulted in a better adsorption between polyol and poly(ethylene terephthalate) fibers. The lower pH of the solutions and a higher valence of the added neutral salt in the solution showed a largely positive effect on the adsorption parameters, and the order of effectiveness is Al₂(SO₄)₃ > MgSO₄ > Na₂SO₄.