Effect of monomer ratio of AA to PTA on properties of PBAT copolyesters

doi:10.11949/j.issn.0438-1157.20160888

Abstract

Abstract:

Poly(butyleneadipate-co-terephthalate)(PBAT) copolyesters were synthesized from adipic acid(AA), p-phthalic acid(PTA) and 1, 4-butanediol(BDO) with tetrabutyl titanate as catalyst through a two-step process of esterification and polycondesation.The effects of molar ratio of AA to PTA on the structures, thermal and elastic properties of copolyesters were studied.FTIR and NMR test results showed that PBAT copolyesters were successfully synthesized.GPC test showed the molecular weight(M_w) of copolyesters were between 41000-142000, which was consistent with the result of the intrinsic viscosity.DSC results showed that T_m and T_c were gradually reduced with the increase of adipic acid.WXRD test results indicated that with the increase of adipic acid, the crystal structure copolyesters gradually changed from PBA into PBT.DMA results showed that the T_g of copolyesters trended to decrease with the increase of adipic acid.From TGA curves, the initial decomposition temperature of PBAT copolyesters shifted to the high temperature zone, while the thermal stability of the copolyesters closed at high temperature.It was found from the tensile test that the AA/PTA ratio significantly affected the mechanical properties of copolyesters.PBAT7:3 was of the maximum elongation at break, and PBAT3:7 was of strong and tough tensile properties.

Key words: PBAT, synthesis, monomer ratio, thermal properties, mechanical properties

摘要：

以己二酸（AA）、对苯二甲酸（PTA）和1，4-丁二醇（BDO）为原料，钛酸四丁酯为催化剂，采用先酯化后缩聚的两步聚合法制备了一系列聚（己二酸/对苯二甲酸丁二醇）（PBAT）共聚酯。研究己二酸与对苯二甲酸不同摩尔比对合成共聚酯的结构、热性能和弹性性能的影响。FTIR和NMR测试结果表明本实验成功合成了PBAT共聚酯。GPC测试结果表明共聚酯的重均分子量（M_w）在41000~142000之间，测试结果与特性黏度具有一致性。DSC测试结果表明随己二酸含量的增加，共聚酯的熔融温度和结晶温度逐渐降低；WXRD测试结果表明随着己二酸含量的不断增加，共聚酯的晶型结构逐渐由PBA转变为PBT；DMA结果表明玻璃化转变温度（T_g）基本呈不断降低的趋势；TGA结果表明PBAT共聚酯的初始分解温度随对苯二甲酸含量的增加向高温区移动，而在高温段共聚酯的热稳定性接近。拉伸结果表明，AA/PTA比例的变化显著影响共聚酯的力学弹性，PBAT7：3具有最大的断裂伸长率，而PBAT3：7则表现为强而韧的拉伸特性。

关键词: PBAT, 合成, 单体比例, 热性能, 力学性能

CLC Number:

TQ31.6

ZHAO Caixia, BAI Xiang, ZOU Guoxiang, HE Yingjie, LI Jinchun. Effect of monomer ratio of AA to PTA on properties of PBAT copolyesters[J]. CIESC Journal, 2017, 68(1): 452-459.

赵彩霞, 柏祥, 邹国享, 何英杰, 李锦春. AA/PTA单体比例对PBAT共聚酯性能的影响[J]. 化工学报, 2017, 68(1): 452-459.

References 20

[1]	WITT U, MÜLLER R J, DECKWER W D. Biodegradation behaviour and material properties of aliphatic/aromatic polyesters of commercial importance[J]. J. Environ. Polym. Degrad., 1997, 5(2):81-89.
[2]	PIOTR R, MICHA? K, MICHA? S, et al. Study of aliphatic-aromatic copolyester degradation in sandy soil and its ecotoxicological impact[J]. Biomacromolecules, 2010, 11(4):839-847.
[3]	ABOU-ZEID D M, MÜLLER R J, DECKWER W D. Biodegradation of aliphatic homopolyesters and aliphatic-aromatic copolyesters by anaerobic microorganisms[J]. Biomacromolecules, 2004, 5(5):1687-1697.
[4]	AJIOKA M, SUIZU H, HIGUCHI C, et al. Aliphatic polyesters and their copolymers synthesized through directcondensation polymerization[J].Polymer Degradation and Stability, 1998, 59(1/2/3):137-143.
[5]	NICOLAS J, RENÉ S L, PASCAULT J P, et al. Bio-based alternatives in the synthesis of aliphatic-aromatic polyesters dedicated to biodegradable film applications[J]. Polymer, 2015, 59:234-242.
[6]	MOHANTY S, NAYAK S K.Aromatic-aliphatic poly(butylene adipate-co-terephthalate) bionanocomposite influence of organic modification on structure and properties[J]. Polymer Composites, 2010, 31(7):1194-1204.
[7]	HERRERA R, FNAREO L, GALAN A R, et al. Characterization and degradation behvaior of poly(butylene adipate-co-terephthaiate)s[J]. Polymer Chemistry, 2002, 40(23):4141-4157.
[8]	SAADI Z, CESAR G, BEWA H, et al. Fungal degradation of poly(butylene adipate-co-terephthalate) in soil and in compost[J]. Journal of Polymers and Environment, 2013, 21(4):893-901.
[9]	周承伟, 张玉, 吴智华. 填充复合材料PBAT的降解性能研究[J]. 塑料科技, 2013, 4(19):63-66. ZHOU C W, ZHANG Y, WU Z H. Study on degradation properties of filled PBAT composite[J]. Plastics Technology, 2013, 4(19):63-66.
[10]	JIANG L, WOLCOTT M P, ZHANG J. Study of biodegradable polylactide/poly(butylene adipate-co-terephthalate) blends[J]. Biomacromolecules, 2006, 7(1):199-207.
[11]	JIANG L, LIU B, ZHANG J. Properties of poly(lactic acid)/poly(butylene adipate-co-terephthalate)/nanoparticle ternary composites[J]. Ind. Eng. Chem. Res., 2009, 48(16):7594-7602.
[12]	QUERO E, MÜLLER A J, SIGNORI F, et al. Isothermal cold-crystallization of PLA/PBAT blends with and without the addition of acetyl tributyl citrate[J]. Macromolecular Chemistry and Physics, 2012, 213(1):36-48.
[13]	王垒, 靳玉娟, 孟庆阳, 等. 聚乳酸与聚对苯二甲酸/己二酸/丁二酯共混物增容体系的制备及表征[J]. 高分子材料科学与工程, 2014, 30(1):108-112. WANG L, JIN Y J, MENG Q Y, et al. Preparation and characterization of polylactic acid and polyethylene terephthalate/adipic acid/polybutylene terephthalate blend capacity system[J]. Polymeric Materials Science and Engineering, 2014, 30(1):108-112.
[14]	顾书英, 詹辉, 任杰. 聚乳酸/PBAT共混物的制备及其性能研究[J]. 中国塑料, 2006,20(10):39-42. GU S Y, ZHAN H, REN J. Preparation and properties of poly(lactic acid)/PBAT blend[J]. China Plastics, 2006, 20(10):39-42.
[15]	邹俊, 李芷, 张竞, 等. 生物可降解聚(对苯二甲酸丁二酯/己二酸丁二酯)共聚酯的合成与表征[J]. 江苏科技大学学报(自然科学版), 2013, 27(3):289-294. ZOU J, LI Z, ZHANG J, et al. Synthesis and characterization of the biodegradable poly(butylene adipate-co-butylene terephthalate) copolyesters[J]. Journal of Jiangsu University of Science and Technology(Natural Science Edition), 2013, 27(3):289-294.
[16]	GAN Z, KUWABARA K, YAMAMOTO M, et al. Solid-state structures and thermal properties of aliphatic-aromatic poly(butylene adipate-co-terephthalate) copolyesters[J]. Polymer Degradation & Stability, 2004, 83(3):289-300.
[17]	GAN Z, ABE H, DOI Y. Temperature-induced polymorphic crystals of poly(butylene adipate)[J]. Macromol. Chem. Phys., 2002, 203(16):2369-2374.
[18]	GAN Z H, KUWABARA K, ABE H, et al. The role of polymorphic crystal structure and morphology in enzymatic degradation of melt-crystallized poly(butylene adipate) films[J].Polymer Degradation and Stability, 2005, 87(1):191-199.
[19]	YASUNIWA M, TSUBAKIHARA S, OHOSHITA K, et al. X-Ray studies on the double melting behavior of poly(butylene terephthalate)[J]. J. Polym. Sci. Part B:Polym. Phys., 2001, 39(17):2005-2015.
[20]	ZHAO C, HE X, ZOU G, et al. Biodegradable Poly(butylene succinate-co-butylene dimerized fatty acid)s:synthesis, crystallization, mechanical properties, and rheology[J]. Polymer Science, Series B, 2016, 58(2):183-193.