PA6/磺化石墨烯功能微球的制备及性能研究

王钒丞, 温兴翰, 李明沛, 李玉林, 吴波震

doi:10.19817/j.cnki.issn 1006-3536.2021.03.019

化工新型材料 >

2021 , Vol. 49 >Issue 3: 83 - 89

DOI: https://doi.org/10.19817/j.cnki.issn 1006-3536.2021.03.019

新材料与新技术

PA6/磺化石墨烯功能微球的制备及性能研究

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1.浙江工业大学材料科学与工程学院,杭州310014;
2.华东理工大学材料科学与工程学院,上海200237

王钒丞(1994-),硕士研究生,主要研究方向为聚酰胺微球复合材料。

收稿日期: 2019-11-05

修回日期: 2020-12-27

网络出版日期: 2021-05-10

基金资助

国家自然基金面上项目(51873193);国家重点研发计划重点项目(2017YFB0307503);国际合作专项(2016YFE0133200)

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Preparation and characterization of PA6/SG functional microsphere

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1. College of Materials Science and Engineering,Zhejiang University of Technology, Hangzhou 310014;
2. School of Materials and Science and Engineering,East China University of Science and Technology,Shanghai 200237

Received date: 2019-11-05

Revised date: 2020-12-27

Online published: 2021-05-10

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摘要

以己内酰胺(CL)、聚苯乙烯(PS)、磺化石墨烯(SG)为主要原料,通过阴离子聚合反应诱导相分离的方法,制备得到了一系列粒径可控的PA6/SG杂化微球。SG在PS的存在下,选择性分散在CL单体中,形成CL/PS/SG悬浮液;再通过CL原位阴离子聚合制备PA6/PS/SG合金,利用甲苯除去PS相后可以获得粒径分布在10～50μm的PA6/SG微球。扫描电镜及粒径测试结果表明,PS及SG含量可以影响PA6微球的形貌及尺寸。通过透射电镜可确定SG选择性分散在了PA6相中,同时SG的加入可有效地改善PA6的热稳定性、结晶性、熔融性能和烧结性能,并且适用于3D打印激光烧结领域。

关键词： 尼龙6; 微球; 阴离子聚合; 反应诱导相分离; 磺化石墨烯

本文引用格式

王钒丞, 温兴翰, 李明沛, 李玉林, 吴波震 . PA6/磺化石墨烯功能微球的制备及性能研究[J]. 化工新型材料, 2021 , 49(3) : 83 -89 . DOI: 10.19817/j.cnki.issn 1006-3536.2021.03.019

Abstract

Nylon is one of the most widely used engineering plastics due to their combinative merits,including light density,good strength and durable toughness,chemical resistance.These advantages make nylon as an ideal candidate for 3D printing through selective laser sintering technology (SLS).In this case,how to develop nylon microspheres with controllable size and good processability is determinant for their SLS 3D printing application.A kind of sulfonated graphene-hybridized polyamide 6 (PA6/SG) functional microspheres with adjustable diameters were fabricated via reaction induced phase separation technique.SG was firstly dispersed in caprolactam monomer (CL) in the presence of polystyrene (PS) to form CL/PS/SGsolution.CL was then in-situ polymerized into PA6/PS/SG composite.Scanning Electron Microscopy (SEM) images indicated that the shape and morphology of the PA6 microspheres in the PA6/PS/SG alloy can be mediated through controlling the degree of phase inversion and content of SG.After PS removal by toluene,PA6/SG microspheres with controllable size (10～50μm) and narrow size distribution were obtained.Transmission Electron Microscopy (TEM) images shown a successful incorporation of SG in PA6/SG microspheres,which improved the crystallization and melting properties,as well as thermal stability,enabling a wide sintering window which was good for selective laser sintering 3D printing applications.

Key words： polyamide 6; microsphere; anionic polymerization; reaction induced phase separation; sulfonated graphene

参考文献

[1] 黄树槐,张祥林,马黎,等.快速原型制造技术的进展[J].中国机械工程,1997,5(8):8-12.
[2] 杜宇雷,孙菲菲,原光,等.3D打印材料的发展现状[J].徐州工程学院学报,2014,1(29):20-24.
[3] 史玉升,闫春泽,魏青松,等.选择性激光烧结3D打印用高分子复合材料[J].中国科学信息科学,2015,2(45):204-211.
[4] Goodridge R D,Tuck C J,Hague R J M.Laser sintering of polyamides and other polymers[J].Progress in Materials Science,2012,57:229-267.
[5] Kenzari S,Bonina D,Dubois J M,et al.Quasicrystal-polymer composites for selective laser sintering technology[J].Materials and Design,2012,35:691-695.
[6] Zhu W,Yan C,Shi Y,et al.Study on the selective laser sintering of a low-isotacticity polypropylene powder[J].Rapid Prototyping Journal,2016,22:621-629.
[7] 许恩惠,郑强,王彩红,等.尼龙6/有机锂皂石纳米复合材料的制备及性能研究[J].高分子学报,2015,5:515-523.
[8] 胡孝迎,郑强,辜婷,等.Ca₃(Si₃O₉)的含量对尼龙6结构与性能的影响[J].高分子材料科学与工程,2017,33(2):44-49.
[9] 李姝喆,王伟,夏浙安,等.增韧剂对尼龙6/碳纤维复合材料性能的影响[J].功能高分子学报,2018,31(6):595-601.
[10] Li H,Wu Y,Sato H,et al.A new facile method for preparation of nylon-6 with high crystallinity and special morphology[J].Macromolecules,2009,42:1175-1179.
[11] Wang G X,Liu P,Zhang W,et al.Preparation and characterization of novel PA6/SiO₂ composite microsphere applied for selective laser sintering[J].Polymer Letters,2018,12:13-23.
[12] Wu B Z,Li L,Xie T X,et al.Preparation of micron-sized PA6/12copolymer microspheres via successive in-situ polymerization[J].Materials Letters,2011,65(14):2174-2177.
[13] Kuilla T,Bhadra S,Yao D,et al.Recent advances in graphene-based polymer composites[J].Progress in Polymer Science,2010,35:1350-1375.
[14] 陈一,陈文旗,成群林,等.纳米钛酸钡负载还原氧化石墨烯/PBO纳米复合材料的制备和性能[J].功能高分子学报,2019,31(6):569-577.
[15] Li R G,Shi K H,Lin Y,et al.Intercalation structure and enhanced thermal oxidative stability of polyamide 6/graphene nanocomposites prepared through in situ polymerization[J].Industrial & Engineering Chemistry Research,2017,56:13715-13724.
[16] Muhammad T M,Evie L P,Jose A,et al.Graphene and polytetrafluoroethylene synergistically improve the tribological properties and adhesion of nylon 66 coatings[J].Carbon,2017,123:26-33.
[17] 潘鸽,吴广峰,李欣鹤,等.磺化聚苯乙烯纳米微球-聚苯稀酰胺杂化水凝胶的制备及性能[J].功能高分子学报,2017,4(30):457-463.
[18] Huang W,Ouyang X,Lee L J.High-performance nanopapers based on benzenesulfonic functionalized graphenes[J].ACS Nano,2012,6(11):10178-10185.
[19] 张娜,赵大江,杨桂生.聚酰胺微球的研究进展[J].高分子通报,2019,2:126-136.
[20] Ma M,Zhu Z D,Wu B Z,et al.Preparation of highly conductive composites with segregated structure based on polyamide-6 and reduced graphene oxide[J].Materials Letters,2017,190:71-74.
[21] Pei A H,Liu A D,Xie T X,et al.Preparation of polyamide-6 sub micrometer-sized spheres by in situ polymerization[J].Macromolecules,2006,39:7801-7804.
[22] 李娜娜,尹巍巍,刘峰.聚偏氟乙烯含量对共混微孔膜结构与性能的影响[J].天津工业大学学报,2019,38(4):13-23.
[23] 周强,郝军正,祝琳华,等.泡沫相相分离制备多孔聚合物微球连续化工艺[J].化工学报,2019,70(3):1208-1219.
[24] Goodridge R D,Dalgarno K,Wood D J.Indirect selective laser sintering of an apatite-mullite glass-ceramic for potential use in bone replacement applications[J].Proceedings of the Institution of Mechanical Engineers,Part H:Journal of Engineering in Medicine,2006,220:47-68.
[25] 杨旭生,汪艳,陈亚武.选择性激光烧结用尼龙6粉末的性能研究[J].塑料工业,2018,46(3):135-138.
[26] Li R G,Shi K H,Ye L,et al.Intercalation structure and enhanced thermal oxidative stability of polyamide-6/graphene nanocomposites prepared through in situ polymerization[J].Industrial & Engineering Chemistry Research,2017,56:13715-13724.
[27] Roy S,Tang X Z,Das T,et al.Enhanced molecular level dispersion and interface bonding at low loading of modified graphene oxide to fabricate super nylon 12 composites[J].Applied Materials and Interfaces,2014,7:3142-3151.
[28] Wang C H,Hu F,Yang K J,et al.Preparation and properties of nylon 6/sulfonated graphene composites by an in-situ polymerization process[J].RSC Advances,2016,6:45014-45022.
[29] 李姝喆,王伟,夏浙安,等.增韧剂对尼龙6/碳纤维复合材料性能的影响[J].功能高分子学报,2018,31(6):595-601.
[30] 符博支,高洋洋,冯予星,等.聚合物纳米石墨烯复合材料导热性能研究进展[J].功能材料,2019,8(50):8065-8075.
[31] 杨坤好,姚盼,肖海刚,等.石墨烯纳米片/环氧树脂的导热性能研究[J].热固性树脂,2019,34(4):40-44.

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