聚(丁二酸丁二醇-co-二苯醚二甲酸丁二醇)酯的合成及性能
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Synthesis and Properties of Poly(butylene succinate-co-oxybisbenzoic)
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    摘要:

    以4,4-二苯醚二甲酸(OBBA)、丁二酸(SA)和1,4-丁二醇(BDO)为原料,以钛酸四丁酯(TBOT)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(丁二酸丁二醇-co-二苯醚二甲酸丁二醇)酯(PBSO),研究了二元酸单体SA与OBBA的摩尔比(10∶0、9∶1、7∶3、5∶5、3∶7、1∶9、0∶10)对聚酯的结构、热性能、流变性能和力学性能的影响。红外光谱和核磁共振氢谱分析表明成功地制备了脂肪族-芳香族共聚酯,Mw在22070~43530之间,多分散性指数(PDI)在2.0左右。差示扫描量热分析和X射线衍射结果表明PBS和PBSO(9∶1)为结晶聚合物,结晶度分别为43%和24%,其它共聚酯均为无定形聚合物。随着共聚酯中OBBA单体含量的增加,共聚酯的Tg逐渐升高。热重分析结果表明共聚酯初始分解温度均高于275 ℃。流变性能分析表明,共聚酯均属于典型的假塑性流体,其中,PBSO(5∶5)的黏度对剪切具有较高的敏感性。拉伸测试结果表明,随着OBBA单体含量增加,聚酯拉伸强度先下降后上升,断裂伸长率先增加后降低。其中,PBSO(5∶5)的拉伸强度为1.2 MPa,断裂伸长率最大为1523.2%,表现出良好的韧性,且循环拉伸测试表明PBSO(5∶5)的拉伸永久变形在10~30 ℃内对温度具有敏感性。

    Abstract:

    A series of poly(butylene succinate-co-oxybisbenzoic) (PBSO) were synthesized by two-step process of esterification and polycondensation using oxybisbenzoic acid (OBBA), succinic acid (SA), and 1,4-butanediol (BDO) as raw material, and tetrabutyl titanate (TBOT) as catalyst. The effects of different mole ratios of SA to OBBA (10∶0, 9∶1, 7∶3, 5∶5, 3∶7, 1∶9, 0∶10) on the structure, thermal, rheological and mechanical properties of polyesters were studied. The structure and composition of the copolyesters were characterized by FT-IR and 1H-NMR, which prove that the aliphatic-aromatic copolyesters were successfully synthesized. The Mw the polyesters is between 22070 and 43530 and the polydispersity index (PDI) is about 2.0. DSC and WAXD test results show that PBS and PBSO(9∶1) are semi-crystalline polymers, and other copolyesters are amorphous polymers. The crystallinity of PBS and PBSO(9∶1) calculated by WAXD is 43% and 24%, respectively. As increase of the OBBA monomer content, Tg of the copolyesters gradually increases. According to the TGA test results, the initial decomposition temperature of the synthesized copolyesters is greater than 275 ℃. Rheological properties analysis show that the copolyesters are typical pseudoplastic fluids, and the viscosity of PBSO(5∶5) is highly sensitive to shear. The tensile test results show that with the increase of OBBA monomer content, the tensile strength of polyester decreases first and then increases, and the elongation at break increases first and then decreases. Among them, the tensile strength of PBSO(5∶5) is 1.2 MPa, and the elongation at break is 1523.2%, showing good toughness. The cyclic tensile test indicate that the tensile permanent set of PBSO(5∶5) is sensitive to temperature within 10~30 ℃.

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赵彩霞,李 鑫,范期程,邹国享,李锦春.聚(丁二酸丁二醇-co-二苯醚二甲酸丁二醇)酯的合成及性能[J].高分子材料科学与工程,2019,35(12):36-43.

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