以反丁烯二酸合成的不饱和脂肪族聚酯的生物降解性研究

以反丁烯二酸、一缩二乙二醇和1,4-丁二醇为原料,采用熔融缩聚法合成了不饱和脂肪族聚酯和共聚酯,在37℃下,用含有脂肪酶的磷酸缓冲溶液对聚酯的生物降解性进行了研究,讨论了聚酯结构、组成及C=C双键的交联度对生物降解性的影响。结果表明,对于粘稠液体状的聚酯,C=C双键的引入,没有明显的改变其生物降解性;对于固体状的聚酯,C=C双键引入后,熔点(Tm)和结晶度增加;聚酯部分降解后,其热力学性能(Tm、-ΔHm)和结晶度都升高;对于交联后的聚酯,交联度越高,生物降解性越差。     

聚氨酯粘合剂的制备及其在层压织物中的应用

采用端羟基不饱和脂肪族聚酯,2,4-甲苯二异氰酸酯(TDI)和1,4-丁二醇为原料制备了含有CC双键的聚氨酯,研究了该聚氨酯制备的层压织物的剥离强度,并与以饱和脂肪族聚酯制备的聚氨酯进行了对比。结果表明,该含有CC双键的聚氨酯作为粘合剂使用时,织物剥离强度可达到27.1 N,而以端羟基饱和脂肪族聚酯制备的聚氨酯不能将多层织物粘结在一起。     

聚（反丁烯二酸丁二醇-CO-衣康酸丁二醇）酯的合成及性能研究

用不饱和脂肪族二元酸反丁烯二酸（FA）、衣康酸（IA）和1,4-丁二醇（BD）为原料,用熔融缩聚法合成了舍有c=c双键的聚（反丁烯二酸丁二醇-co-衣康酸丁二醇）酯（PFBI）,并采用红外光谱（FT—IR）、DSC、羟值、酸值及特性黏度测定对其进行结构和性能的表征,在37℃下,用含有脂肪酶的磷酸缓冲溶液对PFBI的生物降解性进行了研究,讨论了各组分对其性能的影响。     

聚己二酸己二醇酯的酶催化合成及其结构表征

选用脂肪族二元酸己二酸（AA）和二元醇1，6-己二醇（HD）为原料，对N435固定化酶催化酯化合成饱和脂肪族聚酯P（AA—co—HD）进行了研究，并对体系pH、酶催化时间、酶浓度、醇酸比例等因素对酶催化聚合的影响进行了探索，利用红外、核磁对合成的饱和脂肪族聚酯P（AA-co—HD）进行了表征。     

功能化可降解脂肪族聚酯的研究进展

对生物可降解脂肪族聚酯进行功能化改性可以有效设计并裁剪分子结构,调控材料的生物相容性、生物降解性以及改善聚酯的反应活性,是目前生物医用材料和食品包装材料领域研究的热点。从聚酯的分子设计、化学结构、合成方法以及性能等方面综述了近年有关生物可降解脂肪族聚酯的研究进展,重点阐述了功能基团为羟基、氨基、不饱和键和叠氮基等的脂肪族聚酯的研究现状。并对可降解脂肪族聚酯未来的发展趋势及应用前景进行了展望。     

不饱和聚酯树脂的制备

不饱和聚酯树脂是用不饱和二元酸、饱和二元酸或酐和二元醇经熔融缩聚而成的一种线形聚合物，用苯乙烯为溶剂交联而成的一种产品所用的二元醇，可以是乙二醇、丙二醇、一缩二乙二醇及新戊二醇等。不饱和羧酸为含碳碳双键的两个羧基的酸或酸酐，通常采用邻苯二甲酸酐或对苯二甲酸及顺丁烯二酸酐等。     

脂肪族聚酯的合成及降解性能研究

通过熔融和溶液结合法合成了脂肪族聚酯—聚丁二酸丁二醇酯(PBS)、丁二酸丁二醇酯-己二酸丁二醇酯共聚物(P(BS-co-BA))和丁二酸丁二醇酯-癸二酸丁二醇酯共聚物(P(BS-co-BSe)),并对其进行了生物降解实验。采用GPC测定了脂肪族聚酯的分子量及其分布,并采用熔点仪测定了聚酯的熔点。得到脂肪族聚酯分子量、熔点以及分子结构对称性和降解之间的关系。     

聚酯树脂及其涂料

可生物降解的含聚酯的防潮涂料组合物及其制备：JP2005—105 134，带烯属不饱和基团的超支化聚酯的制备：WO2005-37 893，不饱和聚酯、其共聚物、组合物、贮存稳定凝胶涂料、防污固化材料及其制法：JP2005—68 167，叔碳酸酯改性聚酯树脂制通用色浆的研究，粉末型紫外光固化饱和聚酯的合成研究     

含乳酸酯链节的不饱和聚酯

用丙交酯（由乳酸脱水得到）与顺丁烯二酸酐及1，2-丙二醇含成了不饱和聚酯树脂，树脂能与苯乙烯、甲基丙烯酸甲酯相溶混，能用一般不饱合聚酯的交联方法固化，固化后的拉伸强度与普通不饱和聚酯相当，且透明性良好。树脂的合成机理在文中进行了讨论。此研究着眼于树脂的环境降解及资源可再生性考虑。     

生物降解脂肪族聚酯合成技术进展

介绍了生物降解脂肪族聚酯的合成方法,重点讨论了聚羟基脂肪酸酯、聚乳酸的合成工艺路线、工艺条件和聚合机理,指出生物降解脂肪族聚酯具有广阔的发展前景。     

Preparation and biodegradation of hydroxyl terminated poly(fumaric acid‐co‐diethylene glycol) and its segmented polyurethane

Hydroxyl terminated poly(fumaric acid‐co‐diethylene glycol), poly(FA‐co‐DEG) was prepared by melt polycondensation. The resultant unsaturated aliphatic polyester was characterized by Fourier transform infrared (FTIR) spectroscopy, hydroxyl value, acid value, and intrinsic viscosity. Its enzymatic degradation and crosslinking behavior as well as the effect of crosslinking degree on enzymatic degradation were also investigated. The crosslinking degree and reduction of carbon–carbon double bonds revealed excellent self‐crosslinking nature of poly(FA‐co‐DEG) at high temperature. The results of enzymatic degradation showed that poly(FA‐co‐DEG) has excellent biodegradability and that the biodegradation can be controlled by the crosslinking degree. Polyurethane was prepared by the reaction of poly(FA‐co‐DEG), 2,4‐toluene diisocyanate (TDI), and 1,4‐butanediol (BD). It was found that the biodegradation of the obtained polyurethane was slower than that of the original unsaturated aliphatic polyester poly(FA‐co‐DEG). The peeling strength of the polyurethane was very high, supporting better adhesion property with enhanced crosslinking. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and properties of UV-curable waterborne unsaturated polyester for wood coating

UV-curable waterborne unsaturated polyesters for wood coatings were prepared. The effects of different polyols and acids on the properties of the UV-curable waterborne unsaturated polyesters were investigated. Several different unsaturated polyester prepolymers were prepared from three different polyols [ethylene glycol (EG), diethylene glycol (DEG), and propylene glycol (PG)] and three different acids [tetrahydrophthalic anhydride (THPAn), terephthalic acid (TPA), and trimellic anhydride (TMAn)]. UV-curable coating materials were formulated from the prepolymers and 2-hydroxy-2-methylphenyolpropane-1-one as a photoinitiator with distilled water as a diluent. Trimethylolpropane diallyl ether was used as an air inhibitor of cure. The dynamic mechanical studies showed the properties of those unsaturated polyesters were well correlated with their glass transition temperature behaviors. It was found that the unsaturated polyester prepared with 60/40 (mol %) TMAn/THPAn and the equimolar mixture of EG, DEG, and PG showed balanced coating properties such as good tensile properties and weatherability, as well as proper viscosity (ca. 2500 cps) when using distilled water as a diluent. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 695–708, 1998     

Synthesis and characterization of some novel unsaturated polyester resins containing amide groups

Summary An ethylenically dibasic acid amide was prepared by reacting anthranilic acid with maleic anhydride and characterized by various methods. The unsaturated dibasic acid amide was used for preparing three novel unsaturated polyesters with ethylene glycol (EG), diethylene glycol (DG) and tetraethylene glycol (TG), respectively. The molecular weights of the prepared polyesters were determined by the end group analysis. These polyesters were diluted with styrene / acrylonitrile (AN) mixture to prepare curable resins with inhibited premature gelation. The effect of the structure of the resins on their curing behavior and mechanical properties has been investigated.     

Unsaturated polyesters based on bis(2-hydroxyethyl)terephthalate

A series of unsaturated polyesters based on bis(2-hydroxyethyl)terephthalate, ethylene glycol, propylene glycol, diethylene glycol, maleic anhydride and styrene were prepared. Properties of these castings were investigated and compared with those analogues based on dimethyl terephthalate or polyester oligomers formed by depolymerization of poly(ethylene terephthalate). It is found that properties of castings based on bis(2-hydroxyethyl)terephthalate are superior to those based on polyester oligomer. When compared with those based on dimethyl phthalate, the castings have higher hardness and heat distortion temperature, but lower tensile strength and elongation; other properties are very similar.     

路标涂料用韧性不饱和聚酯树脂的合成及应用

用一缩二乙二醇增韧不饱和聚酯树脂,在二月桂酸二丁基锡的催化作用下制备出路标涂料用不饱和聚酯树脂。其最优原料配比为：顺酐与苯酐物质的量比为2∶1,一缩二乙二醇占醇总量的物质的量为15%,催化剂的用量为0.5%,阻聚剂的用量为0.025%~0.030%。其最佳合成工艺为采用两步法合成工艺,最高反应温度为225℃,树脂的酸值应处于25~35 mgKOH/g的范围内。     

不饱和聚酯树脂的增韧

用不同摩尔比的己二酸,一缩二乙二醇合成不饱和和聚酯树脂,并对增韧效果进行研究。结果表明己二酸或一缩二乙二醇增韧不饱和聚酯树脂具有相似的增韧效果;而用己二酸和一缩二乙二醇共同增韧不饱和聚酯树脂具有更显著的增韧效果。     

Zusammenhänge zwischen molekulargewicht und elutionsvolumen bei der gelchromatographie von verschiedenen polyestern

The gel chromatograms of the low-molecular linear polyesters of adipic acid and hexanediol, butanediol, dimethyl propanediol, propanediol, diethylene glycol, and ethylene glycol, as well as those of polyhexamethylenecarbonate give on plotting log M against the elution volume a number of parallel calibration curves. The chromatograms obtained from the polyesters can be interpreted by a common calibration curve, if the logarithm of the number of atom equivalents is plotted against the elution volume. The number of atom equivalents results from the number of carbon atoms in the molecules and the number of oxygen atoms in the chain, taking into account the increments for carbon = 1 and for oxygen = 0,6. This common calibration relation applies to polystyrene gels in the solvent and swelling agent tetrahydrofuran, but not to polyvinylacetate gels. The number of atom equivalents obtained for every elution volume can be converted to the molecular weight of the corresponding polyesters. This makes it possible to use the calibration curve prepared for one type of polyester for evaluating the gel chromatograms of the other aliphatic polyesters.     

SYNTHESIS OF UNSATURATED POLYESTER RESIN—EFFECT OF CHOICE OF REACTANTS AND THEIR RELATIVE PROPORTIONS

Unsaturated polyesters are synthesized in the laboratory by the condensation of saturated and unsaturated anhydrides with glycols. The condensate obtained is mixed with styrene monomer to get an unsaturated polyester resin formulation. The properties of the polyester resin synthesized are affected by the synthesis parameters. In this study, the parameters investigated are the effect of choice of reactants and their relative proportions. Properties such as tensile strength, tensile modulus, elongation-at-break, toughness, impact strength, surface hardness, abrasion resistance, and water absorption were tested after curing the resin. Various combinations of (a) maleic anhydride and phthalic anhydride, (b) propylene glycol and ethylene glycol, and (c) propylene glycol and diethylene glycol were used to investigate the effect on the properties of the synthesized resin. The combinations of the anhydrides and glycols that give optimum properties are identified. The results show that most of the properties are maximum at 60% maleic anhydride composition in a mixture of maleic anhydride and phthalic anhydride. Similarly, a better balance of properties is obtained when propylene glycol is mixed with 30% ethylene glycol or 20% diethylene glycol.     

Unsaturated polyester resins from poly(ethylene terephthalate) waste for polymer concrete

Depolymerization of poly(ethylene terephthalate), PET, textile waste was performed with a manganese acetate catalyst. Different ratios of diethylene glycol (DG) to propylene glycol (PG) were used for glycolysis. The weight ratio of PET to the glycol mixture was 1:0.65. The glycolyzed products were analyzed for hydroxyl value and the amount of free glycol. These glycolyzed products were reacted with mixtures of sebacic acid (SE) and maleic anhydride (MA) to prepare a series of unsaturated polyesters having different molecular weights. The molecular weights of the unsaturated polyesters produced were determined by the end group analysis. The obtained polyesters were dissolved in styrene (Sty) monomer and their curing behavior was investigated. Polymer concretes (PC) made with these resins were investigated for their compressive strength. The data revealed that the properties of the PC based on recycled PET are comparable to PC made from virgin materials. We concluded that recycling of PET waste may provide a potentially lower cost source of resin, and its recycling in PC will also help reduce an environmental problem.     

生物降解性脂肪族聚酯改性的研究进展

综述了脂肪族聚酯改性制备生物降解性聚酯的研究进展.在聚酯中引入刚性链段(即将脂肪族聚酯与芳香族、液晶基元共聚合)可改善聚酯的加工性能;在聚酯中引入亲水基大分子(即将脂肪族聚酯淀粉共混或与聚乙二醇共聚合)可改善聚酯的亲水性能.今后脂肪族聚酯改性研究的重点将解决功能化基团的引入、合成路线的简化、成本的降低及改性的效果等方面的问题.