乙酸氧钛催化酯化缩聚法合成聚丁二酸乙二醇酯及其性能研究

李振超; 魏东; 苗庆; 王明亮; 魏忠; 王自庆; 宋晓玲

doi:10.12434/j.issn.2097-2547.20230118

您当前的位置：

首页 >

文章列表页 >

乙酸氧钛催化酯化缩聚法合成聚丁二酸乙二醇酯及其性能研究

低碳分子转化合成

- 乙酸氧钛催化酯化缩聚法合成聚丁二酸乙二醇酯及其性能研究
- Study on synthesis and properties of poly (ethylene succinate) by esterification polycondensation catalyzed by titanyl acetate
- 低碳化学与化工 2024, 49(2): 60-66.
- 作者机构：
  
  1.石河子大学化学化工学院，新疆石河子 832001
  2.新疆天业（集团）有限公司，新疆石河子 832001
- 作者简介：
  
  李振超（1995—），硕士研究生，研究方向为可生物降解聚合物的合成与改性，E-mail：1156869709@qq.com。
  王自庆（1987—），博士，副教授，研究方向为煤基精细化学品和新材料，E-mail：wzq20070420@163.com；
  宋晓玲（1970—），博士，正高级工程师，博士研究生导师，研究方向为化工新材料技术开发与实践，E-mail：xjty39@163.com。
- 基金信息：
  
  新疆生产建设兵团区域创新引导计划(2022BB003);中国博士后科学基金(2022MD713812);八师石河子市揭榜挂帅重大科技计划项目(2022JB02)
- DOI：10.12434/j.issn.2097-2547.20230118
  中图分类号： TQ323.43
- 纸质出版日期：2024-02-25，
  
  收稿日期：2023-04-02，
  
  修回日期：2023-06-20，
- 稿件说明：
扫描看全文
李振超,魏东,苗庆等.乙酸氧钛催化酯化缩聚法合成聚丁二酸乙二醇酯及其性能研究[J].低碳化学与化工,2024,49(02):60-66.

LI Zhenchao,WEI Dong,MIAO Qing,et al.Study on synthesis and properties of poly (ethylene succinate) by esterification polycondensation catalyzed by titanyl acetate[J].Low-carbon Chemistry and Chemical Engineering,2024,49(02):60-66.
李振超,魏东,苗庆等.乙酸氧钛催化酯化缩聚法合成聚丁二酸乙二醇酯及其性能研究[J].低碳化学与化工,2024,49(02):60-66. DOI： 10.12434/j.issn.2097-2547.20230118.

LI Zhenchao,WEI Dong,MIAO Qing,et al.Study on synthesis and properties of poly (ethylene succinate) by esterification polycondensation catalyzed by titanyl acetate[J].Low-carbon Chemistry and Chemical Engineering,2024,49(02):60-66. DOI： 10.12434/j.issn.2097-2547.20230118.

摘要

聚丁二酸乙二醇酯（PES）作为一种脂肪族聚酯，具有良好的力学性能和全生物降解特性，在降解塑料领域具有广阔的应用前景。以溶剂热法制备了一种乙酸氧钛化合物，将其作为催化剂用于催化丁二酸（SA）和乙二醇（EG）酯化缩聚合成高分子量PES。系统考察了催化剂用量（催化剂占反应物料的质量分数，下同）、反应温度和反应时间对PES分子量的影响，采用

H-NMR和

C-NMR对PES的结构进行了表征，并对其热性能、热稳定性和力学性能进行了测试。结果表明，当催化剂用量为0.6%，在230 °C下聚合8 h时，合成的PES的特性黏度[

]

为0.78，数均分子量（

）为47500，对应的聚合物分散性指数（

PDI

）为2.66。合成的PES熔点为102.4 °C，最大热分解温度为420.2 °C，断裂伸长率为505% ± 5%，拉伸应力为(48.3 ± 0.6) MPa，拉伸弹性模量高达358.8 MPa。以煤制乙二醇为单体合成PES不但可以实现全生物降解聚合物的低成本制备，而且对煤化工产业的高质量发展有重要的现实意义。

Abstract

As an aliphatic polyester

poly (ethylene succinate) (PES) has good mechanical properties and full biodegradability

which has broad application prospects in the field of degradable plastics. Titanyl acetate was prepared by solvothermal method and used as a catalyst to catalyze the esterification and polycondensation of succinic acid (SA) and ethylene glycol (EG) to synthesize high molecular weight PES. The effects of catalyst dosage (the mass fraction of catalyst in the reaction material

the same below)

reaction temperature and reaction time on the molecular weight of PES were investigated. The structures of PES were characterized by

H-NMR and

C-NMR

and its thermal properties

thermal stability and mechanical properties were tested. The results show that the intrinsic viscosity coefficient [

]

of the synthesized PES is 0.78

the number average molecular weight (

) is 47500

and the corresponding polymer dispersion index (

PDI

) is 2.66 when the catalyst dosage is 0.6% and the polymerization is carried out at 230 °C for 8 h. The melting point temperature of PES is 102.4 °C

the maximum thermal decomposition temperature is 420.2 °C

the elongation at break is 505% ± 5%

the tensile stress is (48.3 ± 0.6) MPa

and the tensile elastic modulus is as high as 358.8 MPa. The synthesis of PES using coal-to-ethylene glycol as a monomer can not only achieve low-cost preparation of fully biodegradable polymers

but also has important practical significance for the high-quality development of the coal chemical industry.

关键词

乙酸氧钛煤化工全生物降解聚合物乙二醇聚丁二酸乙二醇酯

Keywords

titanyl acetatecoal chemical industrybiodegradable polymersethylene glycolpoly (ethylene succinate)

references

LAI J H, HUANG H Q, LIN M W, et al. Enzyme catalyzes ester bond synthesis and hydrolysis: The key step for sustainable usage of plastics [J]. Frontiers in Microbiology, 2023, 13: 1113705.

PAEK K H, IM S G. Synthesis of a series of biodegradable poly (butylene carbonate-co-isophthalate) random copolymers derived from CO2-based comonomers for sustainable packaging [J]. Green Chemistry, 2020, 22(14): 4570-4580.

林源. 生物降解塑料的发展现状及应用前景[J]. 石油化工, 2019, 48(7): 759-762.

LIN Y. Development and application of biodegradable plastics [J]. Petrochemical Technology, 2019, 48(7): 759-762.

陈芳菊, 冯俊, 李进, 等. 棒状MgO催化草酸二甲酯酯交换法合成草酸二乙酯的研究[J]. 天然气化工—C1化学与化工, 2022, 47(4): 138-144.

CHEN F J, FENG J, LI J, et al. Rod-shaped MgO catalyzed transesterification of dimethyl oxalate to synthesize diethyl oxalate [J]. Natural Gas Chemical Industry, 2022, 47(4): 138-144.

LEE L T, TSAI C Y, WU T Y. Discussions on crystallization behaviors and physical properties of biodegradable poly (ethylene succinate) composites containing PCL-CD-IC [J]. Journal of Polymer Research, 2023, 30(2): 75.

HE Z H, FENG Y B, WANG C, et al. Structure and properties of new biodegradable elastomers composed of poly (ethylene succinate)-based poly (ether ester) s and poly (lactic acid) [J]. Journal of Applied Polymer Science, 2023, 140(7): e53493.

ZHANG F, JIANG Z G, QIU Z B. Biobased poly (ethylene succinate)-b-poly (triethylene terephthalate) multiblock copolyesters with high melting temperature and improved crystallization rate and mechanical property [J]. Polymer, 2022, 254: 125061.

刘伟, 石峰晖, 季君晖, 等. 生物可降解聚丁二酸乙二醇酯的合成与降解性能研究[J]. 塑料, 2008, 37(4): 44-46.

LIU W, SHI F H, JI J H, et al. Synthesis and degradability of poly (ethylene succinate) biodegradable polyester [J]. Plastics, 2008, 37(4): 44-46.

CAO A, OKAURA T, NAKAYAMA K. Studies on syntheses and physical properties of biodegradable aliphatic poly (butylene succinate-co-ethylene succinate)s and poly(butylene succinate-co-diethylene glycol succinate)s [J]. Polymer Degradation and Stability, 2002, 78(1): 107-117.

TSAI C J, CHANG W C, CHEN C H, et al. Synthesis and characterization of polyesters derived from succinic acid, ethylene glycol and 1,3-propanediol [J]. European Polymer Journal, 2008, 44(7): 2339-2347.

郑晓旭,梁建荣,汪子翔, 等. 环保型PET用钛系催化剂的研究进展[J]. 合成纤维工业, 2020, 43(6): 59-63.

ZHENG X X, LIANG J R, WANG Z Z, et al. Research progress of environmentally friendly titanium catalyst for PET [J]. China Synthetic Fiber Industry, 2020, 43(6): 59-63.

陈志伟, 生刚, 黄丽欢, 等. TiO2/SiO2催化酯交换法合成PES的工艺[J]. 工程塑料应用, 2019, 47(1): 55-59.

CHEN Z W, SHENG G, HUANG L H, et al. Synthesis of PES via TiO2/SiO2 catalyzed transesterification route [J]. Engineering Plastics Application, 2019, 47(1): 55-59.

ŠVEC P, HUBENÁ P, RŮŽIČKOVÁ Z, et al. Poly (ethylene terephthalate) synthesis catalysed by chelated Sn, Zn and Mg complexes [J]. Applied Organometallic Chemistry, 2016, 30(1): 20-25.

ZOU X X, LI G D, GUO M Y, et al. Heterometal alkoxides as precursors for the preparation of porous Fe- and Mn-TiO2 photocatalysts with high efficiencies [J]. Chemistry-A European Journal, 2008, 14(35): 11123-11131.

WANG D, YU R, KUMADA N, et al. Hydrothermal synthesis and characterization of a novel one-dimensional titanium glycolate complex single crystal: Ti(OCH2CH2O)2 [J]. Chemistry of Materials, 1999, 11(8): 2008-2012.

唐荣芝, 王松林, 张元卓, 等. 乙酸氧钛对碳酸二甲酯与苯酚酯交换的催化作用[J]. 高等学校化学学报, 2014, 35(11): 2418-2424.

TANG R Z, WANG S L, ZHANG Y Z, et al. The catalytic effect of titanyl acetate on the transesterification of dimethyl carbonate with phenol [J]. Chemical Journal of Chinese Universities, 2014, 35(11): 2418-2424.

WANG J, CHEN W P, BAI L B, et al. Synthesis of high regular poly (ethylene succinate) by adding oxalic acid in poly-condensation system: Suppressing etherification side reaction [J]. Polymer, 2022, 263: 125527.

YANG J, ZHANG S P, LIU X Y, et al. A study on biodegradable aliphatic poly (tetramethylene succinate): The catalyst dependences of polyester syntheses and their thermal stabilities [J]. Polymer Degradation and Stability, 2003, 81(1): 1-7.

王自庆, 杨先贵, 刘绍英, 等. 聚乙烯吡咯烷酮固载卤化锌催化酯交换法合成脂肪族聚碳酸酯[J]. 高分子学报, 2016, (12): 1654-1661.

WANG Z Q, YANG X G, LIU S Y, et al. Synthesis of aliphatic polycarbonate by transesterification catalyzed by polyvinylpyrrolidone supported zinc halide [J]. Acta Polymerica Sinica, 2016, (12): 1654-1661.

王余伟, 王金堂. 聚酯PET稳定剂应用现状[J]. 合成技术及应用, 2007, 80(4): 32-37.

WANG Y W, WANG J T. Application status of polyester PET stabilizers [J]. Synthetic Technology & Application, 2007, 80(4): 32-37.

陈志伟, 张仲帅, 杨守华, 等. 乙二醇铝催化酯化法合成聚丁二酸乙二醇酯[J]. 塑料, 2020, 49(1): 68-71.

CHEN Z W, ZHANG Z S, YANG S H, et al. Preparation of poly (ethylene succinate) via ethylene glycol aluminum catalyzed esterification reaction [J]. Plastics, 2020, 49(1): 68-71.

QIU Z B, IKEHARA T, NISHI T. Crystallization behaviour of biodegradable poly (ethylene succinate) from the amorphous state [J]. Polymer, 2003, 44(18): 5429-5437.

WU L B, MINCHEVA R, XU Y T, et al. High molecular weight poly (butylene succinate-co-butylene furandicarboxylate) copolyesters: From catalyzed polycondensation reaction to thermomechanical properties [J]. Biomacromolecules, 2012, 13(9): 2973-2981.

马楷, 刘绍英, 王公应. 聚丁二酸乙二醇酯合成的研究进展[J]. 中国塑料, 2012, 26(5): 1-6.

MA K, LIU S Y, WANG G Y. Research progress in synthesis of poly (ethylene glycol succinate) [J]. China Plastics, 2012, 26(5): 1-6.

孙桂香, 罗勇, 陆平晔. 生物降解PBS聚酯的改性研究进展[J]. 高分子通报, 2011, 142(2): 102-107.

SUN G X, LUO Y, LU P Y. Research progress in modification of biodegradable PBS polyester [J]. Polymer Bulletin, 2011, 142(2): 102-107.

ZHAO Y, ZHAO B H, WEI B L, et al. Enhanced compatibility between poly (lactic acid) and poly (butylene adipate-co-terephthalate) by incorporation of N-halamine epoxy precursor [J]. International Journal of Biological Macromolecules, 2020, 165: 460-471.

苗庆, 石磊, 王明亮, 等. PHA/PBC聚合物合金的制备及其性能[J]. 工程塑料应用, 2023, 51(3): 28-33.

MIAO Q, SHI L, WANG M L, et al. Preparation of PHA/PBC polymer alloy and its properties [J]. Engineering Plastics Application, 2023, 51(3): 28-33.

WANG X Y, PAN H W, JIA S L, et al. Mechanical properties, crystallization and biodegradation behavior of the polylactide/poly (3-hydroxybutyrate-co-4-hydroxybutyrate)/poly (butylene adipate-co-terephthalate) blown films [J]. Chinese Journal of Polymer Science, 2020, 38(10): 1072-1081.

浏览量

167

下载量

CNKI被引量

文章被引用时，请邮件提醒。

提交

工具集

关联资源

铜镍双金属催化剂用于乙二醇氨化制乙二胺反应性能研究

乙二醇化学氧化制备乙醇酸催化剂研究进展

乙二醇载冷的液化天然气冷能回收换热器传热特性数值模拟