基于2，5-呋喃二甲酸的三元无规共聚酯PBSF的制备与性能

doi:10.11949/0438-1157.20240603

摘要/Abstract

摘要：

利用可再生资源制备新型生物基聚合物可减少对化石资源的依赖，是缓解能源与环境危机的有效手段。以2，5-呋喃二甲酸（FDCA）、丁二酸（SA）和1，4-丁二醇为共聚单体，钛酸四丁酯为催化剂，通过一锅法熔融缩聚制备了不同FDCA和SA比例的系列全生物基聚2， 5-呋喃二甲酸-丁二酸-丁二醇酯（PBSF），探究了PBSF共聚酯的化学结构与组成对其热行为、结晶行为、热机械性能、热稳定性、力学性能、气体阻隔性能和亲水性等影响。结果表明，随FDCA含量的增加，共聚酯的玻璃化转变温度从-23.6 ℃升高至38.6 ℃，杨氏模量先减小后增加，断裂伸长率先增加后减小，氧气阻隔性能先降低再升高，亲水性先增加后降低。当FDCA和SA比例接近时（44：56），共聚酯表现出典型的热塑性弹性体特征。

关键词: 生物质, 2，5-呋喃二甲酸, 聚合物, 共聚酯, 机械性能, 阻隔性能, 构效关系

Abstract:

The sustainable biomass for polymer production has received much attention due to the consumption of fossil resources and the environmental issues associated with the use of petroleum-based polymer materials. Bio-based chemicals can be prepared using biomass and further converted into functional monomers to synthesize high performance polymers, which is an effective way to alleviate the energy and environmental crisis. This work reported a series of fully bio-based poly(butylene succinate/2,5-furandicarboxylate) (PBSF) synthesized by one-pot melt polycondensation using 2, 5-furandicarboxylic acid (FDCA), succinic acid (SA) and 1,4-butanediol (1,4-BD) as the comonomers and titanate titanium(IV) butoxide as the catalyst. The effects of the chemical structures and compositions of the PBSF copolyesters on their thermal behavior, crystalline behavior, thermo-mechanical properties, thermal stability, mechanical properties, gas barrier properties and hydrophilicity were systematically investigated. The results showed that as the FDCA molar content increased from 25 % to 100 %, the glass transition temperature (T_g)of the copolyester increased from -23.6 ℃ to 38.6 ℃; the Young's modulus decreased and then increased; the elongation at break increased and then decreased; the oxygen barrier property decreased and then increased, and the hydrophilicity increased and then decreased. When the molar ratio of FDCA and SA was 44:56, the copolyester shows typical thermoplastic elastomer characteristics with low T_g value, high elongation at break and without yield point. It is expected that the results can provide valuable guide for the development of high-performance furan-based polyester.

Key words: biomass, 2,5-furandicarboxylic acid, polymers, copolyesters, mechanical properties, barrier properties, structure-property relationship

中图分类号:

TQ 324.1

翟紫航, 蒋杰, 李锦锦, 赵玲, 奚桢浩. 基于2，5-呋喃二甲酸的三元无规共聚酯PBSF的制备与性能[J]. 化工学报, DOI: 10.11949/0438-1157.20240603.

Zihang ZHAI, Jie JIANG, Jinjin LI, Ling ZHAO, Zhenhao XI. Synthesis and properties of ternary random copolyester based on 2,5-furandicarboxylic acid[J]. CIESC Journal, DOI: 10.11949/0438-1157.20240603.

图/表 16

图1 PBSF共聚酯的合成路线图

Fig. 1 The synthetic route of PBSF copolyester

图2 PBF和PBSF-x的1H NMR谱图

Fig. 2 1H NMR spectra of PBF and PBSF-x

图3 PBSF的SBS，SBF和FBF链段化学结构

Fig. 3 Chemical structure of SBS, SBF and FBF chain segments

表1 PBF和PBSF-x化学组成、序列结构与特性黏度

Table 1 Composition， sequence and intrinsic viscosity of PBF and PBSF-x

Samples	FDCA/(FDCA+SA) in feed/ %(mol)	FDCA/(FDCA+SA) by NMR (φ_BF) /%(mol)	L_n,BF	L_n,BS	R	[η] /(dL/g)
PBSF-25	25.0	24.8	1.38	3.89	0.98	1.31
PBSF-30	30.0	29.6	1.47	3.27	0.99	0.91
PBSF-37	37.5	37.4	1.61	2.65	1.00	1.15
PBSF-44	45.0	44.0	1.81	2.23	1.00	1.12
PBSF-50	50.0	50.0	1.95	1.95	1.02	1.02
PBSF-60	60.0	60.0	2.43	1.75	0.98	0.70
PBF	—	—	—	—	—	0.96

图4 PBF和PBSF-x的红外光谱图

Fig. 4 FT-IR spectra of PBF and PBSF-x

表2 PBF和PBSF-x的热性能表

Table 2 Thermal properties of PBF and PBSF-x

Samples	T_gby DSC/°C	T_gby DMA/°C	T_m/°C
PBSF-25	-23.6	7.6	-
PBSF-30	-21.7	11.6	-
PBSF-37	-15.8	10.7	-
PBSF-44	-10.3	2.2	-
PBSF-50	-4.9	8.9	-
PBSF-60	2.4	21.9
PBF	38.6	-	169.7

图5 PBF和PBSF-x的DSC曲线

Fig.5 DSC curves of PBF and PBSF-x: (a) 1st cooling; (b) 2nd heating

图6 PBSF-x的Tg与组成的关系

Fig. 6 Relationship of the Tg and composition of PBSF-x

图7 PBSF-x的DMA曲线

Fig. 7 The DMA curves of PBSF-x: (a) storage modulus; (b) loss factor

图8 PBSF-x的XRD衍射曲线

Fig. 8 X-ray diffraction curves of PBSF-x

表3 PBF和PBSF-x的热分解数据

Table 3 Thermal decomposition data of PBF and PBSF-x

Samples	T_5%/°C	T_max/°C
PBSF-25	340.1	393.9
PBSF-30	340.4	391.4
PBSF-37	343.7	393.6
PBSF-44	343.1	390.7
PBSF-50	346.0	392.0
PBSF-60	343.6	387.9
PBF	348.8	376.6

图9 PBF和PBSF-x的热失重曲线:

Fig. 9 Thermal gravimetric curves of PBF and PBSF-x: (a) TGA; (b) DTG

图10 PBF和PBSF-x的拉伸应力-应变曲线

Fig. 10 Tensile strain-stress curves of PBF and PBSF-x

表4 PBF和PBSF-x的力学性能

Table 4 The mechanical properties of PBF and PBSF-x

Samples	杨氏模量/MPa	拉伸强度/MPa	断裂伸长率/%
PBSF-25	175.5 ± 17.1	42.1±3.3	1094.2 ± 37.4
PBSF-30	200.4 ± 9.2	22.7 ±2.3	898.9 ± 128.6
PBSF-37	95.5 ± 13.9	23.0 ± 1.2	1144.7 ± 37.2
PBSF-44	28.0 ± 6.1	25. 2 ± 0.9	1180.5 ± 152.3
PBSF-50	48.2 ± 4.7	22.6 ± 1.5	1069.3 ± 100.4
PBSF-60	143.8 ± 9.9	25.6 ± 1.7	712.5 ± 63.6
PBF	1173.9 ± 86.1	48.8 ± 2.5	504.4 ± 32.2

表5 PBSF-x共聚酯的气体阻隔性能

Table 5 Gas barrier properties of PBSF-x copolyesters

Samples	O₂/barrer	BIFp
PBAT^[34]	0.76	1
PBSF-25	0.32	2.34
PBSF-30	0.36	2.14
PBSF-37	0.42	1.79
PBSF-44	0.62	1.23
PBSF-50	0.57	1.33
PBSF-60	0.33	2.31

图11 PBF和PBSF-x的水接触角

Fig. 11 Water contact angles of PBF and PBSF-x

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