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材料研究学报  2014, Vol. 28 Issue (10): 781-786    DOI: 10.11901/1005.3093.2014.227
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催化剂对PBT/PTMG聚醚酯结构与性能影响*
张成,张群朝,郝同辉,蒋涛()
湖北大学材料科学与工程学院 武汉 430062
Effect of Catalyst on Preparation and Properties of PBT / PTMG Poly(ether ester)
Cheng ZHANG,Qunchao ZHANG,Tonghui HAO,Tao JIANG()
Faculty of Materials and Engineering, Hubei University, Wuhan 430062
引用本文:

张成,张群朝,郝同辉,蒋涛. 催化剂对PBT/PTMG聚醚酯结构与性能影响*[J]. 材料研究学报, 2014, 28(10): 781-786.
Cheng ZHANG, Qunchao ZHANG, Tonghui HAO, Tao JIANG. Effect of Catalyst on Preparation and Properties of PBT / PTMG Poly(ether ester)[J]. Chinese Journal of Materials Research, 2014, 28(10): 781-786.

全文: PDF(3120 KB)   HTML
摘要: 

以对苯二甲酸二甲酯(DMT)、1, 4-丁二醇(BG)、聚四氢呋喃(PTMG)为原料, 分别选用钛酸四丁酯, 钛酸四丁酯/醋酸镁, 四丙基锆, 三氧化二锑/醋酸锌为催化剂合成系列PBT/PTMG聚醚酯。通过GPC、SEM、DSC与TG等方法对PBT/PTMG聚醚酯进行结构表征和性能测试, 研究催化剂对其酯交换率、分子量分布、结晶行为、力学性能和耐热性能的影响。结果表明:以钛酸四丁酯/醋酸镁为催化剂, 随着其用量的增加, 聚醚酯酯交换率升高, 分子量和结晶度提高, 分子量分布指数降低, 韧性增强, 热分解温度在390℃以上。

关键词 有机高分子材料PBT/PTMG聚醚酯结构表征性能测试催化剂    
Abstract

Taking dimethyl terephthalate (DMT), 1, 4 - butylene glycol (BG) and polytetrahydrofuran (PTMG) as main raw materials, a series of PBT/PTMG poly(ether ester) thermoplastic elastomers were prepared with catalysts of tetrabutyl titanate, tetrabutyl titanate/magnesium acetat, tetrapropyl-zirconium and zinc acetate/antimony trioxide respectively. The effect of catalysts on the transesterification rate of the synthesis process, the molecular weight distribution, crystallinity, mechanical properties and heat resistance of the synthesized materials were mainly concerned. The synthesized thermoplastic elastomers were characterized by means of SEM, GPC, DSC, TG and mechanical testing. The results show that: while taking tetrabutyl titanate/magnesium acetate as catalyst, with the increasing amount of the catalyst, the transesterification rate increased, and the molecular weight and crystallinity increased, the molecular weight distribution index decreased, the toughness enhanced and the thermal decomposition temperature was above 390℃ for the synthesized thermoplastic elastomer.

Key wordsorganic polymer materials    PBT /PTMG poly(ether ester)    structural characterization    performance test    catalyst
收稿日期: 2014-05-06     
基金资助:* 国家高技术研究发展计划2012AA06A111资助项目。
Cat. Tetrabutyl titanate(‰) Zinc acetate/antimoy trioxide(‰) Tetrapropyl zirconium(‰) Tetrabutyl titanate/ magnesium acetate(‰) Transesterification rate(%) Mn (104) PDI
1 1 82.0 3.0 2.2
2 1 80.4 2.7 2.6
3 1 68.3 1.4 3.3
4 0.8 71.4 2.0 2.7
5 1 91.7 6.7 1.6
表1  催化剂的选用及对PBT/PTMG聚醚酯合成的影响
图1  PBT/PTMG聚醚酯合成流程图
图2  PBT/PTMG聚醚酯的结构示意图
图3  PBT/PTMG聚醚酯的断面扫描电镜图
图4  PBT/PTMG聚醚酯的DSC曲线
Cat. Tm(℃) ΔHPBT (J/g) Tc (℃) WcPBT (%)
1 204.2 30.5 151.7 21.1
2 202.3 28.6 150.0 19.8
3 195.3 20.5 147.6 14.2
4 203.2 21.9 149.2 15.1
5 211.0 38.1 157.7 26.4
表2  PBT/PTMG聚醚酯的DSC分析结果
图5  PBT/PTMG聚醚酯的TG和DTG曲线
Cat. [η]/(dL/g) Tensile strength /MPa Elongation /% Notched Impact Strength / (J/m) Yield Strength /MPa
1 0.91 26.7 487 121 14.6
2 0.84 24.3 415 112 13.8
3 0.70 18.2 324 76 11.3
4 0.79 20.4 383 86 10.5
5 1.26 40.1 713 No break 18.3
表3  PBT/PTMG聚醚酯的力学性能
图6  钛酸四丁酯/醋酸镁催化反应机理
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