PA5T-56低温溶液/固相聚合的制备与表征

游兴华, 陈爽, 杜云慧, 肖茹

PDF(1681 KB)
PDF(1681 KB)
塑料科技 ›› 2025, Vol. 53 ›› Issue (01) : 10-15. DOI: 10.15925/j.cnki.issn1005-3360.2025.01.002
理论与研究

PA5T-56低温溶液/固相聚合的制备与表征

作者信息 +

Preparation and Characterization of PA5T-56 by Low Temperature Solution/Solid Phase Polymerization

Author information +
History +

摘要

半芳香聚酰胺合成方法多样,其中低温溶液聚合法条件温和,易于控制。利用生物基戊二胺、对苯二甲酰氯以及己二酰氯,经低温溶液聚合和固相聚合制备系列组分的聚对苯二甲酰戊二胺-聚己二酰戊二胺(PA5T-56),以聚合产物相对黏度为考察对象,讨论固相聚合温度和时间对固相聚合的影响,并对PA5T-56的化学结构与热性能进行分析。结果表明:随着固相聚合过程中固相聚合温度和时间的增加,PA5T-56/L固相聚合产物的相对黏度得到提高,但进一步增加至240 ℃、8 h以上时,其相对黏度降低;低温溶液聚合所获不同组分PA5T-56/L的初始分解温度和最大分解速率温度分别高于389.8、463.5 ℃,当对苯二甲酰戊二胺链段(5T)摩尔分数高于70%时固相聚合可使其的熔融温度及结晶温度提高近20 ℃,分别高于290.1、240.3 ℃。

Abstract

There are numerous methods for synthesizing semi-aromatic polyamides, among which the low-temperature solution polymerization method provides mild conditions and is easy to control. Polyp-phenyl-glutarylenediamide (PA5T-56) with a series of component ratios were prepared using bio-based pentanediamine, adipyl chloride and terephthalyl chloride by low temperature solution polymerization and solid phase polymerization. The effects of solid-phase polymerization temperature and time on solid-phase polymerization are discussed in terms of the relative viscosities of the polymerization products.Then the chemical structure and thermal properties of PA5T-56/L were studied. The results showed that with the increase of solid phase polymerization temperature and time during solid phase polymerization, the relative viscosity of low temperature polymerization products of PA5T-56/L could be increased, but when the temperature exceeds 240 ℃ and the reaction time exceeded 8 h, the relative viscosity decreased. The initial decomposition temperature and temperature of maximum decomposition rate of series of components PA5T-56/L obtained by low temperature solution polymerization were higher than 389.8,463.5 ℃. The solid-phase polymerization could increase its melting temperature and crystallization temperature by nearly 20 ℃ when the mole fraction of terephthaloyl pentamethylene diamine segment (5T) was higher than 70%, which was higher than 290.1, 240.3 ℃, respectively.

关键词

生物基聚酰胺 / 低温溶液聚合 / 固相缩聚 / 熔融结晶

Key words

Bio-based polyamide / Low temperature solution polymerization / Solid phase polycondensation / Melt crystallization

中图分类号

TQ322.3

引用本文

导出引用
游兴华 , 陈爽 , 杜云慧 , . PA5T-56低温溶液/固相聚合的制备与表征. 塑料科技. 2025, 53(01): 10-15 https://doi.org/10.15925/j.cnki.issn1005-3360.2025.01.002
YOU Xinghua, CHEN Shuang, DU Yunhui, et al. Preparation and Characterization of PA5T-56 by Low Temperature Solution/Solid Phase Polymerization[J]. Plastics Science and Technology. 2025, 53(01): 10-15 https://doi.org/10.15925/j.cnki.issn1005-3360.2025.01.002

参考文献

1
贺爽爽,胡国胜,张静婷,等.半芳香族聚酰胺合成与改性研究进展[J].工程塑料应用,2020,48(10):151-156.
2
WANG Z, TONG X, YANG J C, et al. Improved strength and toughness of semi-aromatic polyamide 6T-co-6(PA6T/6)/GO composites via in situ polymerization[J]. Composites Science and Technology, 2019, 175: 6-17.
3
ZHANG G, YAN G M, YU T, et al. Semiaromatic polyamides containing carboxyl unit: Synthesis and properties[J]. Industrial and Engineering Chemistry Research, 2017, 56(33): 9275-9284.
4
NOVITSKY T, LANGE C, MATHIAS L, et al. Eutectic melting behavior of polyamide 10,T-co-6,T and 12,T-co-6,T copolyterephthalamides[J]. Polymer, 2010, 51(11): 2417-2425.
5
王萍丽,任中来,邹光继,等.半芳香族聚酰胺的发展与应用研究[J].化工新型材料,2016,44(6):233-234, 239.
6
STAVILA E, ALBERDA V E, LOOS K. Enzyme-catalyzed synthesis of aliphatic-aromatic oligoamides[J]. Biomacromolecules, 2013, 14(5): 1600-1606.
7
FENG W T, ZOU G J, DING Y H, et al. Effect of aliphatic diacid chain length on properties of semiaromatic copolyamides based on pa10t and their theoretical study[J]. Industrial & Engineering Chemistry Research, 2019, 58(17): 7217-7226.
8
陶磊.基于生物基壬二酸的聚酰胺合成及结构性能研究[D].上海:东华大学,2020.
9
SHEN T, ZHANG B, WANG Y Y, et al. Production of 100% bio-based semi-aromatic nylon by aerobic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid with bio aliphatic diamine[J]. Chemical Engineering Journal, 2022, DOI :10.1016/j.cej.2022.135361.
10
张海洋,郭小炜,宋云鹤,等.生物基半芳香族共聚酰胺PA5T/56与脂肪族聚酰胺PA56的性能对比[J].东华大学学报:自然科学版,2024,50(3):39-44.
11
刘冰肖,武宇,杨蕾蕾,等.生物基耐热性PA5T和PA5T/510的制备及性能[J].工程塑料应用,2022,50(11):39-43.
12
WANG X, GAO S Y, WANG J, et al. The production of biobased diamines from renewable carbon sources: Current advances and perspectives[J]. Chinese Journal of Chemical Engineering, 2021, 30(2): 4-13.
13
LI Z H, LI S S, YANG P P, et al. The effect of polymorphism on polymer properties: Crystal structure, stability and polymerization of the short-chain bio-based nylon 52 monomer 1,5-pentanediamine oxalate[J]. International Union of Crystallography, 2023, 10(1): 52-65.
14
MENG C H, LIU X C. Synthesis of bio-based semi aromatic high temperature polyamide PA5T/56 and effect of benzene ring on non-isothermal crystallization kinetics[J]. Journal of Polymer Research, 2021, 28(10): 1-10.
15
李鹤飞.半芳香族耐高温尼龙PA6T-66的制备与性能研究[D].上海:东华大学,2022.
16
王建霞.半芳香族耐高温PA6T/11的合成与表征[D].太原:中北大学,2015.
17
王双.半芳香聚酰胺PA6T/66的合成工艺及性能研究[D].郑州:郑州大学,2014.
18
王孝明,张乃恩,杜维元,等.生物基与石油基高温尼龙的热学性能[J].材料科学与工程学报,2022,40(4):674-678.
19
叶耀挺,杨克俭,陈林飞,等.半生物基耐高温尼龙5T/56制备及性能[J].工程塑料应用,2021,49(11):46-50.
20
YANG K J, LIU Y L, ZHENG Z K, et al. Synthesis and thermal degradation mechanism of a semi-aromatic copolyamide from renewable sources[J]. Polymer Degradation and Stability, 2022, DOI: 10.1016/j.polymdegradstab.2022.110089.
21
贾锦波.含芳环聚酰胺的合成及序列结构分析[D].杭州:浙江大学,2019.
22
曹洪铬.耐高温共聚酰胺PA4T/46的合成及热稳定性研究[D].杭州:浙江大学,2020.
23
万利,冯连芳,顾雪萍,等. PA(66-co-6T)固相缩聚[J].浙江大学学报:工学版,2014,48(8):1522-1527.
24
侯文婷.熔融/固相缩聚合成L-聚乳酸[D].上海:华东理工大学,2011.
25
刘培.尼龙6固相缩聚及其结构性能的研究[D].天津:天津工业大学,2017.

基金

国家重点研发计划(2021YFC2101800)

评论

PDF(1681 KB)

Accesses

Citation

Detail

段落导航
相关文章

/