反应挤出原位阴离子聚合尼龙6/石墨烯复合微球的连续制备与表征
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摘要
以己内酰胺(CL)、苯乙烯(St)及氧化石墨烯(GO)为主要原料,首先在熔融的CL中经自由基聚合得到聚苯乙烯(PS)/CL/GO混合熔体,然后在双螺杆挤出机中引发CL阴离子聚合生成尼龙6(PA6),获得PS为连续相、GO选择性分布于球状PA6分散相的PA6/PS/GO三元混合物,最后去除PS相制备PA6/GO复合微球。采用扫描电镜、透射电镜、热失重及差示扫描量热等方法,研究了GO在三元混合物中的选择分布、PA6/GO复合微球的结构及耐热性。结果表明,在三元混合物中GO选择性分布于PA6相中;随着GO含量增加,PA6/GO复合微球的直径减小;与纯PA6微球相比,PA6/GO复合微球具有更高的热稳定性。
In this study,ε-caprolactam,styrene and graphene were used as materials to prepare the polyamide 6/graphene microspheres.Firstly,free radical polymerization of styrene was first carried out in moltenε-caprolactam,and then an anionic polymerization ofε-caprolactam was preceded in the presence of the catalyst and activator in a twin screw extruder to form polyamide 6/polystyrene/graphene composites.At last,the above mixtures were washed with tetrahydrofuran as solvent to etch the PS phase,and polyamide 6/graphene microspheres was obtained.SEM,TEM,TGA and DSC were used to characterize the microspheres.The results show that graphene is selectively dispersed in the polyamide 6phase of the polyamide 6/polystyrene/graphene composites,and the polyamide 6/graphene microspheres have a high thermal resistant.
In this study,ε-caprolactam,styrene and graphene were used as materials to prepare the polyamide 6/graphene microspheres.Firstly,free radical polymerization of styrene was first carried out in moltenε-caprolactam,and then an anionic polymerization ofε-caprolactam was preceded in the presence of the catalyst and activator in a twin screw extruder to form polyamide 6/polystyrene/graphene composites.At last,the above mixtures were washed with tetrahydrofuran as solvent to etch the PS phase,and polyamide 6/graphene microspheres was obtained.SEM,TEM,TGA and DSC were used to characterize the microspheres.The results show that graphene is selectively dispersed in the polyamide 6phase of the polyamide 6/polystyrene/graphene composites,and the polyamide 6/graphene microspheres have a high thermal resistant.
引文
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[2] Liu W,Yang X,Huang W.Catalytic properties of carboxylic acid functionalized-polymermicrosphere-stabilizedgoldmetallic colloids[J].J.Colloid Interface Sci.,2006,304:160-165.
[3] Cheval N,Gindy N,Flowkes C,et al.Polyamide 66 microspheres metallised with in situ synthesised gold nanoparticles for a catalytic application[J].Nanoscale Res.Lett.,2012,7:182-187.
[4] Hou W,Lloyd T B.A new technique for preparing monodisperse polymer particles[J].Colloid Polym.Sci.,2014,292:3311-3318.
[5] Ricco L,Monticelli O,Russo S,et al,Fast-activated anionic polymerization ofε-caprolactam in suspension,1role of the continuous phase on characteristics and properties of powdered PA6[J].Macromol.Chem.Phys.,2002,203:1436-1444.
[6] Crespy D,Landfester K.Anionic polymerization ofε-caprolactam in miniemulsion:synthesisand characterization of polyamide-6nanoparticles[J].J.Polym.Sci.Part A:Polym.Chem.,2010,48:4929-4937.
[7] Cai X X,Wu G Z.Preparation of composite magnetic microspheres by reactive blending[J].Chin.J.Polym.Sci.,2011,29:580-585.
[8] Cai X X,Zhang Y L,Wu G Z.A novel approach to prepare PA6/Fe3O4 microspheres for protein immobilization[J].J.Appl.Polym.Sci.,2011,122:2271-2277.
[9] Pei A H,Liu A D,Xie T X,et al.A new strategy for the preparation of nylon 6 microspheres with designed morphology[J].Macromolecules,2006,39:7801-7804.
[10] Liu Y,Duan J P,Xia H S,et al.Synthesis from molecule into3Dpolyamide 6microspheres stacked polyhedrons via self-assembly[J].Macromol.Mater.Eng.,2018,303:1700546.
[11] Yan D G,Li J,Li J H,et al.Novel polyamide 6/polystyrene in situ microfibrillar blends prepared by anionic polymerization ofε-caprolactam via reactive extrusion[J].Macromol.Mater.Eng.,2016,301:1242-1247.
[12] Chen Y,Li D X,Yang W Y,et al.Enhancement of mechanical,thermal and tribological properties of AAPS-modified graphene oxide/polyamide 6nanocomposites[J].Composites Part B,2018,138:55-65.
[13] Liu M H,Li M,Hou H Y,et al.Thermal properties of PA6nanocomposites by addition of graphene non-covalently functionalized with dendronized polyamide[J].J.Therm.Anal.Calorim.,2015,120:1303-1310.
[14] Salavagione H J,Gomez M A,Martiínez G.Polymeric modification of graphene through esterification of graphite oxide and poly(vinyl alcohol)[J].Macromolecules,2009,42:6331-6334.
[15]张思维,赵文誉,李微长,等.功能氧化石墨烯纳米带/热塑性聚氨酯复合材料薄膜的制备及阻隔性能[J].高分子材料科学与工程,2016,32(1):151-157.Zhang S W,Zhao W Y,Li W C,et al.Preparation and barrier properties of functionalized graphene oxide nanoribbons/thermoplastic polyurethane composite film[J].Polymer Materials Science&Engineering,2016,32(1):151-157.