• •
翟紫航1(), 蒋杰1(
), 李锦锦1,2, 赵玲1,2, 奚桢浩1,2(
)
收稿日期:
2024-06-03
修回日期:
2024-07-04
出版日期:
2024-07-11
通讯作者:
蒋杰,奚桢浩
作者简介:
翟紫航(1998—),女,硕士研究生,zhai_zihang@163.com
基金资助:
Zihang ZHAI1(), Jie JIANG1(
), Jinjin LI1,2, Ling ZHAO1,2, Zhenhao XI1,2(
)
Received:
2024-06-03
Revised:
2024-07-04
Online:
2024-07-11
Contact:
Jie JIANG, Zhenhao XI
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。
中图分类号:
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.
Samples | FDCA/(FDCA+SA) in feed/ %(mol) | FDCA/(FDCA+SA) by NMR (φBF) /%(mol) | Ln,BF | Ln,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 |
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 (φBF) /%(mol) | Ln,BF | Ln,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 |
Samples | Tg by DSC/°C | Tg by DMA/°C | Tm /°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 |
表2 PBF和PBSF-x的热性能表
Table 2 Thermal properties of PBF and PBSF-x
Samples | Tg by DSC/°C | Tg by DMA/°C | Tm /°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 |
Samples | T5%/°C | Tmax/°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 |
表3 PBF和PBSF-x的热分解数据
Table 3 Thermal decomposition data of PBF and PBSF-x
Samples | T5%/°C | Tmax/°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 |
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 |
Samples | O2/barrer | BIFp |
---|---|---|
PBAT[ | 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 |
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[ | 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 |
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