改性纤维素纳米晶对聚酰胺6结晶行为的影响

doi:10.19491/j.issn.1001-9278.2020.06.001

中国塑料 ›› 2020, Vol. 34 ›› Issue (6): 1-6.DOI: 10.19491/j.issn.1001-9278.2020.06.001

• 材料与性能 • 下一篇

改性纤维素纳米晶对聚酰胺6结晶行为的影响

张静, 王洪, 邹威, 杜中杰, 张晨()

北京化工大学材料科学与工程学院，碳纤维及功能高分子教育部重点实验室，北京 100029

收稿日期:2020-01-02 出版日期:2020-06-26 发布日期:2020-06-26

Effect of Modified Cellulose Nanocrystals on Crystallization Behavior of Polyamide 6

Jing ZHANG, Hong WANG, Wei ZOU, Zhongjie DU, Chen ZHANG()

Key Laboratory of Carbon Fiber and Functional Polymers, Ministry of Education，College of Materials Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China

Received:2020-01-02 Online:2020-06-26 Published:2020-06-26
Contact: Chen ZHANG E-mail:zhangch@mail.buct.edu.cn

摘要/Abstract

摘要：

通过表面基团反应制备了异氰酸酯改性纤维素纳米晶（IPDI?CNC)，将其与聚酰胺6（PA6）共混后研究了有机纳米晶对PA6结晶行为的影响。利用差示扫描量热仪（DSC）对比分析了纤维素纳米晶（CNC）和IPDI?CNC对PA6的结晶度、结晶动力学参数及结晶速率的影响。结果表明，由于IPDI的引入，IPDI?CNC在PA6中的分散性更好，可以有效提高PA6的结晶度；采用 Jeziorny法研究非等温结晶过程，发现IPDI?CNC起到了异相成核作用，提高了PA6的结晶速度和结晶度；由于PA6的结晶能力提高了，IPDI?CNC的加入使PA6的吸水率降低了71.4 %。

关键词: 聚酰胺6, 改性纤维纳米晶, 异氰酸酯, 结晶度, 吸水性

Abstract:

A surface chemical reaction was conducted to prepare the isocyanate?modified cellulose nanocrystals (IPDI?CNC), and the resulting product was blended with polyamide 6 (PA6) to improve its crystallinity. The effects of pristine CNC and IPDI?CNC on the crystallization degree, crystallization kinetic parameters, and crystallization kinetics of PA6 were investigated by differential scanning calorimetry. The results indicated that IPDI?CNC exhibited better dispersibility in PA6 than CNC due to a significant improvement in crystallinity of PA6 as a result of the surface modification by IPDI. The non?isothermal crystallization process was studied by the Jeziorny’s method, and the results demonstrated that IPDI?CNC could act as a heterogeneous nucleating agent to improve the crystallization speed and crystalli?nity of PA6. Moreover, the addition of IPDI?CNC reduced the water absorption of PA6 by 71.4 % due to the increase of crystallization degree.

Key words: polyamide 6, modified?cellulose nanocrystals, isocyanate, crystallinity, water absorption

中图分类号:

TQ323.6

张静, 王洪, 邹威, 杜中杰, 张晨. 改性纤维素纳米晶对聚酰胺6结晶行为的影响[J]. 中国塑料, 2020, 34(6): 1-6.

Jing ZHANG, Hong WANG, Wei ZOU, Zhongjie DU, Chen ZHANG. Effect of Modified Cellulose Nanocrystals on Crystallization Behavior of Polyamide 6[J]. China Plastics, 2020, 34(6): 1-6.

图/表 9

图1 CNC和IPDI?CNC的FTIR谱图

Fig.1 FTIR spectra of CNC and IPDI?CNC

图2 CNC和IPDI?CNC的TEM照片

Fig.2 TEM images of CNC and IPDI?CNC

名称	元素含量/%
名称	C	O	H	N
IPDI?CNC	43.96	48.68	6.63	0.73
CNC	40.93	52.72	6.35	—

表1 CNC和IPDI?CNC的元素分析结果

Tab.1 Elemental analysis of CNC and IPDI?CNC

图3 PA6/CNC和PA6/IPDI?CNC的断面SEM照片

Fig.3 SEM images of PA6/CNC and PA6/IPDI?CNC

样品名称	结晶度/%	T_m/℃
PA6	30.2	220.3
PA6/1 %CNC	43.6	221.5
PA6/5 %CNC	41.4	219.8
PA6/10 %CNC	35.6	219.4
PA6/1 % IPDI?CNC	43.9	220.5
PA6/5 % IPDI?CNC	47.8	221.4
PA6/10 % IPDI?CNC	43.8	221.7

表2 不同PA6/CNC和PA6/IPDI?CNC样品的熔点和结晶度

Tab.2 Melting temperature and crystallinity of PA6, PA6/CNC and PA6/IPDI?CNC

图4 PA6、PA6/CNC和PA6/IPDI?CNC在不同冷却速率下的DSC曲线

Fig.4 DSC curves for PA6, PA6/CNC and PA6/IPDI?CNC at different cooling rate

样品	φ/℃?min^-1	T_p/℃	n	t_1/2/min	Z_c
PA6	5	190.44	5.043	3.30	0.261
	10	185.78	5.962	2.03	0.616
	15	179.85	4.996	1.73	0.789
	20	176.01	5.214	1.47	0.884
PA6/1 %CNC	5	198.61	5.546	1.67	0.476
	10	195.54	5.354	1.15	0.834
	15	191.92	4.388	0.98	0.937
	20	190.62	3.475	0.71	1.001
PA6/1 %IPDI?CNC	5	199.17	4.074	1.85	0.456
	10	196.32	3.858	1.03	0.864
	15	193.73	4.923	0.87	0.965
	20	192.41	4.98	0.70	1.028

表3 Jeziorny法得到的不同样品的非等温结晶动力学参数

Tab.3 Kinetic parameters of nonisothermal crystallization obtained from Jeziorny method

图5 PA6、PA6/CNC和PA6/IPDI?CNC在不同冷却速率下的相对结晶度随时间变化曲线

Fig.5 The curves of relative degree of crystallinity versus time for PA6, PA6/CNC and PA6/IPDI?CNC

样品名称	吸水率/%
PA6	51.12
PA6/1 %CNC	19.35
PA6/5 %CNC	22.04
PA6/10 %CNC	26.59
PA6/1 %IPDI?CNC	16.52
PA6/5 %IPDI?CNC	14.61
PA6/10 %IPDI?CNC	17.99

表4 PA6、PA6/CNC和PA6/IPDI?CNC的吸水率

Tab.4 Water absorption of PA6,PA/CNC and PA6/IPDOCNC

参考文献 13

1	PAGE I B. Polyamides as Engineering Thermoplastic Materials[M]. iSmithers Rapra Publishing, 2000.
2	OUYANG C, XUE W, ZHANG D, et al. Influence of a Synthetic Ureido Nucleating Agent on Crystallization Behavior and Mechanical Properties of Polyamide 6[J]. Polymer Engineering & Science, 2015, 55(9): 2 011⁃2 017.
3	RAJESH J J, BIJWE J, VEKATARAMAN B, et al. Effect of Water Absorption on Erosive Wear Behaviour of Polyamides[J]. Journal of Materials Science, 2002, 37(23): 5 107⁃5 113.
4	吕励耘, 朱诚身, 何素芹. 成核剂对聚酰胺结构与性能影响的研究进展[J]. 工程塑料应用, 2003, 31(5): 69⁃72.
	LV L G, ZHU C S, HE S Q. Research Progress on The Effects of Nucleating Agents on The Structure and Properties of Polyamides[J]. Engineering Plastics Application, 2003, 31 (5): 69⁃72.
5	季翔,于斌,苏娟娟,等.氧化石墨烯的表面改性及对尼龙6纤维的力学增强作用[J].高分子材料科学与工程,2019,35(8):49⁃54.
	JI X, YU B, SHU J J, et al. Surface Modification of Graphene Oxide and Its Mechanical Strengthening Effect on Nylon 6 Fiber[J]. Polymer Materials Science and Engineering, 2019,35 (8): 49⁃54.
6	HABIBI Y, LUCIA L A, ROJAS O J. Cellulose Nanocrystals: Chemistry, Self⁃assembly, and Applications[J]. Chemical Reviews, 2010, 110(6): 3 479⁃3 500.
7	AITHA S, VASANTHAN N. Effect of Cellulose Nanocrystals on Crystallization, Morphology and Phase Transition of Polyamide 6[J]. Composite Interfaces, 2019: 1⁃14.
8	LIN N,HUANG J, DUFRESNE A. Preparation, Properties and Applications of Polysaccharide Nanocrystals in Advanced Functional Nanomaterials: A Review[J]. Nanoscale, 2012, 4(11): 3 274⁃3 294.
9	ESPINO⁃PEREZ E, BRAS J, DUCRUET V. Influence of Chemical Surface Modification of Cellulose Nanowhiskers on Thermal, Mechanical, and Barrier Properties of Poly (lactide) Based Bionanocomposites[J]. European Polymer Journal, 2013, 49(10): 3 144⁃3 154.
10	SHAHEEN T I, EMAM H E. Sono⁃chemical Synthesis of Cellulose Nanocrystals from Wood Sawdust Using Acid Hydrolysis[J]. International Journal of Biological Macromolecules, 2018, 107: 1 599⁃1 606.
11	SHI J, YANG X, HAN Q, et al. Polyurethane Grafted Attapulgite as Novel Fillers for Nylon 6 Nanocomposites[J]. Journal of Wuhan University of Technology⁃Mater Sci Ed, 2011, 26(4): 615⁃619.
12	ZHANG T, ZHAO Y, LI H, et al. Effect of Polyurethane Sizing on Carbon Fibers Surface and Interfacial Adhesion of Fiber/Polyamide 6 Composites[J]. Journal of Applied Polymer Science, 2018, 135(16): 46111.
13	RUSU G, RUSU E. Nylon 6/TiO₂ Composites by In Situ Anionic Ring⁃opening Polymerization of ε⁃caprolactam: Synthesis, Characterization, and Properties[J]. International Journal of Polymer Analysis and Characterization, 2011, 16(8): 561⁃583.

[1]	魏思淼, 邵路山, 许准, 刘艳婷, 赵思衡, 许博. 次磷酸盐⁃环四硅氧烷双基化合物复配二乙基次磷酸铝对PA6的阻燃性能研究[J]. 中国塑料, 2022, 36(7): 129-135.
[2]	陈胜, 梁颖超, 吴方娟, 方辉, 范新凤, 陈晖, 王永刚. 聚酰胺6/双向经编玻璃纤维复合材料的制备及其界面改性研究[J]. 中国塑料, 2022, 36(5): 24-28.
[3]	许荣霞, 魏刚, 魏莉岚, 吴洁萃, 蒋雨江. Nano⁃SiO₂及PA6复合改性PE⁃UHMW的摩擦磨损性能研究[J]. 中国塑料, 2022, 36(4): 47-52.
[4]	张九夫, 罗开强, 徐军, 郭宝华. 长玻璃纤维增强PA66复合材料的综合性能及其影响因素研究[J]. 中国塑料, 2022, 36(3): 1-8.
[5]	于志省, 李应成, 王洪学, 庞馨蕾, 王宇遥. PA6/PC基激光直接成型材料研究及其立体结构制件制备[J]. 中国塑料, 2022, 36(2): 8-12.
[6]	杨正, 王振华, 鲁世科, 柳妍, 房晓敏, 李建通, 刘保英, 丁涛. 硼酸锌协效二乙基次膦酸铝阻燃PA6[J]. 中国塑料, 2022, 36(1): 120-127.
[7]	张周雅, 白世建, 张玉霞, 周洪福, 宫芳芳, 唐雪古丽, 王斌. 高分子材料导热性能影响因素研究进展[J]. 中国塑料, 2021, 35(9): 156-165.
[8]	司晓闯, 袁端鹏, 李凯, 郝留成, 陈蕊, 张娜娜. 玻璃纤维增强PA66复合材料作为高压开关设备绝缘件材料的可行性分析[J]. 中国塑料, 2021, 35(9): 75-80.
[9]	陆伟鑫, 陆冲, 王斌, 胡晶, 吴菁菁, 周秦鹏. 环氧改性剂对PA6/EVOH共混物性能的影响[J]. 中国塑料, 2021, 35(9): 8-14.
[10]	刘耀, 丁剑峰, 夏浙安, 李欣欣. 聚酰胺6/短切碳纤维/铜盐复合材料抗热氧老化机理的研究[J]. 中国塑料, 2021, 35(7): 12-17.
[11]	吕强. 无卤阻燃永久抗静电玻璃纤维增强聚酰胺6材料的研制[J]. 中国塑料, 2021, 35(7): 58-62.
[12]	段婧婷, 张效林, 王哲, 李少歌, 迪静静, 吕金燕, 朱晓凤, 王毅. 矿物填料填充聚乙烯/麦秸杆复合材料性能比较[J]. 中国塑料, 2021, 35(3): 1-7.
[13]	张静, 李小晴, 周海瑛, 江文正, 钟金环, 李文珠, 张文标. PP/EVA复合发泡材料的制备与性能研究[J]. 中国塑料, 2021, 35(3): 23-29.
[14]	李胤, 周松, 鲁超飞, 罗玉梅, 白小东. PE⁃g⁃MAH对聚酰胺6/导电炭黑复合材料性能的影响[J]. 中国塑料, 2021, 35(3): 44-49.
[15]	胡慧廉, 施嘉亮, 郎蕾, 施超欧, 姚建磊. 热裂解气质联用鉴别PA56、PA66和PA6[J]. 中国塑料, 2021, 35(11): 120-124.

改性纤维素纳米晶对聚酰胺6结晶行为的影响

Effect of Modified Cellulose Nanocrystals on Crystallization Behavior of Polyamide 6

RichHTML

PDF

可视化

摘要/Abstract

引用本文

使用本文

图/表 9

参考文献 13

相关文章 15

编辑推荐

Metrics

本文评价