聚(丁二酸丁二醇-co-二苯醚二甲酸丁二醇)酯/聚对苯二甲酸丁二醇酯复合材料的制备及性能

赵彩霞; 余苗苗; 许愿; 李锦春; 戴钧明; 潘小虎; 李乃祥

doi:10.13801/j.cnki.fhclxb.20210726.002

聚(丁二酸丁二醇-co-二苯醚二甲酸丁二醇)酯/聚对苯二甲酸丁二醇酯复合材料的制备及性能

doi: 10.13801/j.cnki.fhclxb.20210726.002

赵彩霞^1,,
余苗苗^1,,
许愿^1,,
李锦春^1, ,,
戴钧明^2,,
潘小虎^2,,
李乃祥^2,

1.
常州大学材料科学与工程学院资源循环利用与创新材料产业研究院，常州 213164
2.
中国石化仪征化纤有限责任公司，仪征 211900

基金项目: 中国石油化工技术开发项目(420039-4)

详细信息

通讯作者:
李锦春，硕士，教授，博士生导师，主要从事生物降解材料及阻燃材料的研究　E-mail：lijinchun88@163.com

中图分类号: TQ323.4
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出版历程
- 收稿日期: 2021-05-10
- 修回日期: 2021-07-01
- 录用日期: 2021-07-09
- 网络出版日期: 2021-07-26
- 刊出日期: 2022-03-23

Preparation and properties of poly(butylene succinate-co-butylene diphenyl ether dicarboxylate)/polybutylene terephthalate composites

ZHAO Caixia^1
,,
YU Miaomiao^1
,,
XU Yuan^1
,,
LI Jinchun^{1
, ,},
DAI Junming^2
,,
PAN Xiaohu^2
,,
LI Naixiang^2
,

1.
Industrial Institute of Resource Recylcling and Innovative Materials, School of Materials Science and Engineering, Changzhou University, Changzhou 213164, China
2.
Sinopec Yizheng Chemical Fibre Limited Liability Company, Yizheng 211900, China

摘要

摘要: 聚对苯二甲酸丁二醇酯 (PBT) 是半结晶热塑性聚合物，具有出色的尺寸稳定性、高的刚度和硬度、良好的耐化学性、力学性能和可加工性等优良特点。但其抗冲击性较低、韧性较差。采用将PBT与具有优异韧性的聚(丁二酸丁二醇-co-二苯醚二甲酸丁二醇)酯 (PBSO) 进行熔融共混以改善PBT的韧性。首先以二苯醚二甲酸 (OBBA)、丁二酸 (SA) 和丁二醇 (BDO) 为单体，以钛酸四丁酯为催化剂，采用先酯化后缩聚的两步法合成了PBSO。然后将不同质量比的PBSO与PBT 进行熔融挤出共混，研究复合材料的力学韧性、PBSO与PBT的相容性、结晶行为、热稳定性以及流变性能等。FT-IR、¹H NMR、GPC测试分析了所合成PBSO的结构。力学性能测试表明，20wt%PBSO/PBT复合材料的拉伸强度为40.3 MPa，断裂伸长率达到82.1%，断裂能增加到24.7 MPa，冲击强度达到较大值23.2 kJ/m²，具有较高的拉伸强度和良好的韧性。动态热机械分析 (DMA) 和SEM结果发现，PBSO对PBT具有增容效果，PBSO/PBT是部分相容共混体系。差示扫描量热 (DSC) 和广角X射线衍射(WAXD) 结果显示，非晶聚合物PBSO的加入，降低了PBT的结晶度，但未改变PBT的晶体结构。热重分析 ( TGA)分析可知，PBSO/PBT复合材料具有良好的加工热稳定性。
- 聚(丁二酸丁二醇-co-二苯醚二甲酸丁二醇)酯 /
- PBT /
- 增韧 /
- 相容性 /
- 结晶行为
Abstract: Polybutylene terephthalate (PBT) is a semi-crystalline thermoplastic polymer with excellent dimensional stability, high stiffness and hardness, good chemical resistance, mechanical properties and processability. But its impact resistance is low and toughness is poor. PBT was melt blended with poly(butylene succinate-co-butylene diphenyl ether dicarboxylate) (PBSO), which has excellent toughness, to improve the toughness of PBT. Firstly, PBSO was synthesized by a two-step method of esterification and polycondensation, using diphenyl ether dicarboxylic acid (OBBA), succinic acid (SA) and butanediol (BDO) as monomers, and tetrabutyl titanate as catalyst. Then, PBSO/PBT with different mass ratios of PBSO and PBT were blended by melt-extrusion to study the toughening effect of PBSO on PBT. The mechanical toughness of blends, the compatibility of PBSO and PBT, crystallization behavior, thermal stability and rheological properties were studied. The structure of PBSO was characterized by FT-IR, ¹H NMR and GPC. The mechanical performance test show that the tensile strength of the 20wt%PBSO/PBT composite material is 40.3 MPa, the elongation at break reach to 82.1%, the breaking energy increas to 24.70 MPa, and the impact strength is 23.2 kJ/m², indicating a higher tensile strength and good toughness. Dynamic mechanical analysis (DMA) and SEM results indicate that PBSO has a compatibilizing effect on PBT, and PBSO/PBT is a partially compatible blend system. DSC and wide-angle X-ray diffraction (WAXD) results show that the addition of amorphous polymer PBSO reduce the crystallinity of PBT, but do not change the crystal structure of PBT. Thermogravimetric analysis (TGA) analysis demonstrated that the PBSO/PBT composite has a good processing thermal stability.
- poly(butylene succinate-co-butylene diphenyl ether dicarboxylate) ester /
- PBT /
- toughening /
- compa-tibility /
- crystallization behavior

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图 1 先酯化后缩聚法合成脂肪族-芳香族共聚酯(PBSO)

Figure 1. Synthesis of poly(butylene succinate-co-butylene diphenyl ether dicarboxylate) (PBSO) via two-step process of esterification and polycondensation

OBBA—Diphenyl ether dicarboxylic acid; BDO—Butanediol; PBSO—Poly(butylene succinate-co-butylene diphenyl ether dicarboxylate); SA—Succinic acid; m, n—Degree of polymerization

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图 2 PBSO的红外图谱 (a) 和核磁共振氢图谱 (b)

Figure 2. FTIR spectrum (a) and ¹H NMR spectrum (b) of PBSO

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图 3 PBT、PBSO及PBSO/PBT应力-应变曲线

Figure 3. Stress-strain curves of PBT, PBSO and PBSO/PBT

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图 4 PBT、PBSO及PBSO/PBT的储能模量 (a) 和损耗因子 (b) 与温度的关系曲线

Figure 4. Dependence of storage modulus (a) and tanδ (b) on temperature for PBT, PBSO and PBSO/PBT

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图 5 PBT和PBSO/PBT的SEM图像对比

Figure 5. Comparison of SEM images for PBT and PBSO/PBT

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图 6 PBT、PBSO及PBSO/PBT的冷却 (a) 和二次加热 (b) DSC曲线

Figure 6. DSC curves of cooling (a) and second heating (b) of PBT, PBSO and PBSO/PBT

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图 7 PBT、PBSO及PBSO/PBT的X射线衍射图谱

Figure 7. X-ray diffraction patterns of PBT, PBSO and PBSO/PBT

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图 8 PBT、PBSO及PBSO/PBT的TGA (a) 和DTG (b) 曲线

Figure 8. TGA (a) and DTG (b) curves of PBT, PBSO and PBSO/PBT

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图 9 PBT、PBSO及PBSO/PBT的黏度与剪切速率的关系曲线

Figure 9. Relationship curves of viscosity and shear rate for PBT, PBSO and PBSO/PBT

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表 1 不同PBSO含量的聚(丁二酸丁二醇-co-二苯醚二甲酸丁二醇)酯/聚对苯二甲酸丁二醇酯(PBSO/PBT)复合材料

Table 1. Poly(butylene succinate-co-butylene di-phenyl ether dicarboxylate)/polybutylene terephthalate (PBSO/PBT) composites with different content of PBSO

Samples	Mass fraction of PBSO/wt%	Mass fraction of PBT/wt%
PBT	0	100
10%PBSO/PBT	10	90
20%PBSO/PBT	20	80
30%PBSO/PBT	30	70

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表 2 PBSO的分子量及其分子量分布

Table 2. Molecular weight and its distribution of PBSO

Sample	M_n/(10⁴ g·mol⁻¹)	M_w/(10⁴ g·mol⁻¹)	PDI
PBSO	2.29	4.35	1.90
Notes: M_n—Number average molecular weight; M_w—Weight average molecular weight; PDI—Polydispersity index.

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表 3 PBT、PBSO及PBSO/PBT力学性能数据

Table 3. Mechanical properties of PBT, PBSO and PBSO/PBT

Samples	Tensile strength/MPa	Elongation at break/%	Fracture energy/MPa	Impact strength/(kJ·m⁻²)
PBSO	1.3	1523.4	7.86	—
PBT	52.1	4.4	1.52	4.8
10%PBSO/PBT	49.0	24.6	11.62	12.7
20%PBSO/PBT	40.3	82.1	24.70	23.2
30%PBSO/PBT	28.4	110.2	25.07	24.9

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表 4 PBT和PBSO/PBT的热性能和结晶度

Table 4. Thermal properties and percentage crystallinity of PBT and PBSO/PBT

Samples	First cooling			Second heating
Samples	T_c/℃	ΔH_c/(J·g⁻¹)	T_m-1/℃	T_m-2/℃	ΔH_m/(J·g⁻¹)	X_c-1/%	X_c-2/%
PBT	194.2	52.2	215.9	225.5	50.7	35.6	44.4
10%PBSO/PBT	189.9	48.4	214.7	223.7	42.8	33.5	41.2
20%PBSO/PBT	189.2	42.9	214.8	222.8	37.1	32.7	38.8
30%PBSO/PBT	186.9	37.9	215.0	222.5	30.7	30.9	36.9
Notes: T_c—Crystallization temperature; ΔH_c—Enthalpy of crystallization; T_m-1—First melting temperature；T_m-2—Second melting temperature；ΔH_m—Melting enthalpy；X_c-1—First crystallinity；X_c-2—Second crystallinity.

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表 5 PBT、PBSO及PBSO/PBT的热重分析数据

Table 5. Thermogravimetric analysis data of PBT, PBSO and PBSO/PBT

Samples	T_5%/℃	T_max/℃
PBSO	367.4	435.7
PBT	396.3	429.5
10%PBSO/PBT	387.0	428.6
20%PBSO/PBT	384.0	427.9
30%PBSO/PBT	382.6	427.6
Notes: T_5%—5% Decomposition temperature；T_max—Maximum decomposition temperature.

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