用原位聚合法制备的<strong>PA6/GO</strong>纳米复合材料的结构和性能

doi:10.11901/1005.3093.2018.698

材料研究学报

2019, Vol. 33

Issue (8): 621-628 DOI: 10.11901/1005.3093.2018.698

研究论文

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用原位聚合法制备的PA6/GO纳米复合材料的结构和性能

黄欢¹,陈宇哲¹,郭怡¹,蔺海兰¹,王丽君¹,马素德¹,卞军¹(

),谷志杰²

1. 西华大学材料科学与工程学院成都 610039
2. 日本国立东京农工大学生物应用与系统工程研究生院东京 184-8588 日本

Structure and Properties of PA6/GO Nanocomposite by In-situ Polymerization

Huan HUANG¹,Yuzhe CHEN¹,Yi GUO¹,Hailan LIN¹,Lijun WANG¹,Sude MA¹,Jun BIAN¹(

),Zhijie GU²

1. College of Materials Science and Engineering, Xihua University, Chengdu 610039, China
2. Graduate School of Bio-Applications and Systems Engineering, Tokyo University of Agriculture and Technology, Tokyo, 184-8588, Japan

引用本文:

黄欢,陈宇哲,郭怡,蔺海兰,王丽君,马素德,卞军,谷志杰. 用原位聚合法制备的PA6/GO纳米复合材料的结构和性能[J]. 材料研究学报, 2019, 33(8): 621-628.
Huan HUANG, Yuzhe CHEN, Yi GUO, Hailan LIN, Lijun WANG, Sude MA, Jun BIAN, Zhijie GU. Structure and Properties of PA6/GO Nanocomposite by In-situ Polymerization[J]. Chinese Journal of Materials Research, 2019, 33(8): 621-628.

全文: PDF(7888 KB) HTML

摘要:

以己内酰胺(CL)和6-氨基己酸(ACA)为聚合反应单体，用Hummers法制备氧化石墨烯(GO)，再以GO为纳米填料用原位开环聚合法制备了GO改性PA6纳米复合材料(PA6/GO)，并对PA6/GO纳米复合材料的结构及性能进行了研究。结果表明，PA6的黏均分子量达到10⁴数量级，但加入过多的GO使PA6的分子量降低。形貌分析表明，GO均匀地分散在PA6基体中，并诱导了PA6基体的晶型由α晶型转变成γ晶型。同时，GO作为异相成核剂促进了PA6/GO复合材料中PA6基体的结晶，提高了PA6/GO复合材料的结晶度。拉伸测试结果表明，随着GO的加入PA6/GO纳米复合材料的拉伸强度先提高后降低，GO加入量为0.4份时拉伸强度达到最大值61.72 MPa，比纯PA6(48.52 MPa)提高了27.21%。导热性能分析表明含1.0份GO的PA6/GO纳米复合材料其50℃和100℃的热导率分别为0.317 W/(m·K)和0.280 W/(m·K)，较纯PA6分别提高了33.19%和33.23%。

关键词 ：复合材料, 尼龙6(PA6), 氧化石墨烯(GO), 力学性能, 导热性能

Abstract：

Graphene oxide (GO) modified polyamide 6 nanocomposites (PA6/GO) were prepared by in-situ ring-opening polymerization with caprolactam (CL) and 6-aminocaproic acid (ACA) were used as polymerization monomers and GO as nano-filler. The structure and morphology of PA6/GO nanocomposites were characterized. The results shows that GO was uniformly dispersed in the PA6 matrix. The viscosity average molecular mass of PA6 reached 10⁴ orders of magnitude, but the excessive addition of GO would decrease the molecular mass of synthesized PA6. The addition of GO induced the transformation of crystallographic structure of the PA6 matrix from α-type to γ-type. At the same time, as a heterogeneous nucleating agent, GO promotes the crystallization of PA6 matrix in PA6/GO composites, and increases the crystallinity of PA6/GO composites.. Tensile strength of PA6/GO composites increased first and then decreased with the addition of GO. When the amount of GO was 0.4% (in mass fraction), the tensile strength of PA6/GO nanocomposites reached a maximum of 61.72 MPa, which was superior to that of pure PA6 (48.52 MPa) by 27.21%. When the GO content was 1.0% the thermal conductivity of PA6/GO nanocomposites reached 0.317 W/(m·K) and 0.280 W/(m·K) at 50℃ and 100℃, which were 33.19% and 33.23% higher than that of pure PA6, respectively.

Key words： composites Nylon 6 (PA6) graphene oxide (GO) mechanical properties thermal conductivity

收稿日期: 2018-12-10

ZTFLH:

TQ332

基金资助:国家教育部春晖计划(Nos. Z2018088);国家教育部春晖计划(Nos. Z2017070);西华大学大健康管理促进中心开放课题基金(No. DJKG2019-002);国家级大学生创新创业训练计划(Nos. 201910623XXX);国家级大学生创新创业训练计划(Nos. 201810623007);四川省青年科技创新研究团队项目(No. 2019JDTD0024)

作者简介: 黄欢，女，1995年生，硕士生

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https://www.cjmr.org/CN/10.11901/1005.3093.2018.698 或 https://www.cjmr.org/CN/Y2019/V33/I8/621

图1 用原位聚合法制备PA6/GO纳米复合材料的示意图

图2 GO存在下己内酰胺开环聚合反应示意图

图3 PA6/GO纳米复合材料的红外光谱图

表1 PA6/GO纳米复合材料的黏均分子量

图4 PA6/GO纳米复合材料的XRD图谱

图5 PA6/GO纳米复合材料的结晶曲线和熔融曲线

表2 PA6/GO纳米复合材料的DSC熔融-结晶参数

图6 PA6/GO纳米复合材料的拉伸强度

图7 PA6/GO纳米复合材料拉伸断面的SEM照片

图8 PA6/GO纳米复合材料的热导率

[1]	Hee K, Chae D Y, Siberio P, et al. A route to high surface area, porosity and inclusion of large molecules in crystals [J]. Nature, 2004, 427(6974): 523
[2]	Lee C, Wei X, Kysar J W, et al. Measurement of the elastic properties and intrinsic strength of monolayer graphene [J]. Science, 2008, 321(5887): 385
[3]	Chen J H, Jang C, Xiao S, et al. Intrinsic and extrinsic performance limits of graphene devices on SiO2 [J]. American Physical Society, 2008: 206
[4]	Schadler L S, Giannaris S C, Ajayan P M. Load transfer in carbon nanotube epoxy composites [J]. Applied Physics Letters, 1998, 73(26): 3842
[5]	Balandin A A, Ghosh S, Bao W, et al. Superior thermal conductivity of single-layer graphene [J]. Nano Letters, 2008, 8(3): 902
[6]	Geim A K, Novoselov K S. The rise of graphene [J]. Nature Materials, 2007, 6(3): 183
[7]	Stankovich S, Dikin D A, Dommett G H B, et al. Graphene based composite materials [J]. Nature, 2006, 442, 282
[8]	Li Y C, Huang X R, Zeng L J, et al. A review of the electrical and mechanical properties of carbon nanofiller reinforced polymer composites [J]. Journal of Materials Science, 2019, 54(2): 1036
[9]	Nie G D, Zhu Y, Tian D, et al. Research progress in the electrospun nanofiber based supercapacitor electrode materials [J]. Chemical Journal of Chinese Universities Chinese, 2019, 39(7): 1349
[10]	Bian J, Wang G, Zhou X, et al. Preparation and properties of functionalized graphene-carbon nanotube synergistic toughening HDPE nanocomposites [J]. Chinese Journal of Materials Research, 2017, 31(2): 1
[10]	卞军, 王刚, 周醒等.功能化石墨烯-碳纳米管协同强韧化HDPE纳米复合材料的制备和性能 [J]. 材料研究学报, 2017， 31(2): 1
[11]	Yousefi N, Lin X Y, Zhang Q B, et al. Simultaneous in situ reduction, self-alignment and covalent bonding in graphene oxide/epoxy composites [J]. Carbon, 2013, 59(7): 406
[12]	Sengupta R, Bhattacharya M, Band-yopadhyay S, et al. A review on the mechanical and electrical properties of graphite and modified graphite reinforced polymer composites [J]. Progress in Polymer Science, 2011, 36(5): 638
[13]	Si J, Li J, Wang S, et al. Enhanced thermal resistance of phenolic resin composites at low loading of graphene oxide [J]. Composites Part A, 2013, 54(4): 162
[14]	Zhou Q, Bian J, Wang G, et al. Preparation and properties of functionalized nano-graphene oxide/POE-g-MAH polystyrene composites [J]. Journal of Composite Materials, 2016, 33(2): 1
[14]	周强, 卞军, 王刚等. 功能化纳米氧化石墨烯/POE-g-MAH聚苯乙烯复合材料的制备与性能 [J]. 复合材料学报, 2016, 33(2): 1
[15]	O'Neill A, Bakirtzis D, Dixon D. Polyamide 6/graphene composites: the effect of in situ polymerization on the structure and properties of graphene oxide and reduced graphene oxide [J]. European Polymer Journal, 2014, 59(1): 353
[16]	Lu H M, Li X H, Xu X M, et al. Research progress in nylon nanocomposites [J]. Polymer Bulletin, 2006(11): 63
[16]	卢会敏, 李小红, 徐翔民等. 尼龙纳米复合材料研究进展 [J]. 高分子通报, 2006(11): 63
[17]	Huang L D, Lin Z Y, Qian H, et al. Research progress of nylon 6 na-nocomposites [J]. Engineering Plastics Application, 2005, 33(2): 64
[17]	黄丽丹, 林志勇, 钱浩等. 尼龙6纳米复合材料研究进展 [J]. 工程塑料应用, 2005, 33(2): 64
[18]	Liu W. Preparation and properties of grafted nylon 6 on nano-silica surface [D]. Changsha: Hunan University, 2010: 1
[18]	刘玺. 纳米二氧化硅表面引发接枝尼龙6的制备及性能研究 [D]. 长沙: 湖南大学, 2010: 1
[19]	Hou L C, Liu H H, Wang N, et al. Preparation and functionalization of functionalized carbon nanotubes/carbon nanotube/nylon 6 composite fiber [J]. Journal of Composite Materials, 2013, 30(1): 45
[19]	侯立晨, 刘海辉, 王宁等. 功能化碳纳米管的制备及功能化碳纳米管/尼龙6复合纤维 [J]. 复合材料学报, 2013, 30(1): 45
[20]	Liu C M, You Y L, Dai J Y, et al. Study on properties of polyamide 6/montmorillonite composites [J]. Journal of Hunan City University, 2017, 26(1): 76
[20]	刘晨明, 游一兰, 代佳洋等. 聚酰胺6/蒙脱土复合材料的性能研究 [J]. 湖南城市学院学报, 2017, 26(1): 76
[21]	Wang G, Wang B, Park J. Synthesis of enhanced hydrophilic and hydrophobic graphene oxide nanosheets by a solvothermal method [J]. Carbon, 2009, 47(1): 68
[22]	Nguyen L, Choi S M, Kim D H, et al. Preparation and characterization of nylon 6 compounds using the nylon 6-grafted GO [J]. Macromolecular Research, 2014, 22(3): 257
[23]	Zhang X Q, Fan X Y, Li H Z, et al. Facile preparation route for graphene oxide reinforced polyamide 6 composites via in situ anionic ring-opening polymerization [J]. Journal of Materials Chemistry, 2012, 22(45), 24081
[24]	Hummers J W S, Offeman R E. Preparation of graphitic oxide [J]. Journal of the American Chemical Society, 1958, 80(6)： 1339
[25]	Peng Z H, Shi Z P. Handbook of Polyamide Industry [M]. Beijing: Chemical Industry Press, 2001: 78
[25]	彭治汉, 施祖培. 聚酰胺工业手册 [M]. 北京: 化学工业出版社, 2001: 78
[26]	Cai Y, Huang F, Wei Q, et al. Structures, thermal stability, and crystalline properties of polyamide 6/organic-modified Fe-montmorillonite composite nanofibers by electrospinning [J]. Journal of materials science, 2008, 43(18): 6132
[27]	Gu W X, Wu P Y, Yang Y L. Two dimensional infrared correlation analysis of nylon 6 heating process [J]. Acta Chimica Sinica, 2004(20): 2123
[27]	顾伟星, 武培怡, 杨玉良. 尼龙6升温过程的二维红外相关分析研究 [J]. 化学学报, 2004(20): 2123
[28]	Flory P J. Principles of Polymer Chemistry [M]. New York: Cornell University Press, 1953
[29]	Fu X B. Preparation, structure and properties of graphene/PA6 nanocomposites[D]. Hefei: Hefei University of Technology, 2016: 1-157
[29]	付绪兵. 石墨烯/PA6纳米复合材料的制备、结构与性能 [D]. 合肥: 合肥工业大学, 2016: 1-157
[30]	Zhang P P. Preparation and structural properties of polyamide 6 nanofibers and graphene composites [D]. Shanghai: Donghua University, 2013: 1-85
[30]	张培培. 聚酰胺6纳米纤维及石墨烯复合材料的制备和结构性能研究 [D]. 上海: 东华大学， 2013： 1-85
[31]	Cheng S, Chen X, Hsuan Y G, et al. Reduced graphene oxide-induced polyethylene crystallization in solution and nanocomposites [J]. Macromolecules, 2012, 45(2): 993
[32]	Zhang X Q, Fan X Y, Li H Z, et al. Facile preparation route for graphene oxide reinforced polyamide 6 composites via in situ anionic ring-opening polymerization [J]. Journal of Materials Chemistry, 2012, 22, 24081
[33]	Fang M. Preparation and properties of graphene-based nanocomposites [D]. Shanghai: Fudan University, 2011
[33]	方明. 石墨烯基纳米复合材料的制备及性能 [D]. 上海: 复旦大学, 2011

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