聚丙烯酸酯-纳米二氧化硅接枝复合胶粒在熔融剪切场中的取向重排
|
摘要
以聚丙烯酸酯-硅烷改性二氧化硅(PAcr-MPS-SiO_2)石榴状接枝复合胶粒为分散相,以聚甲基丙烯酸甲酯树脂(PMMA)为连续相,在HAKKA转矩流变仪中进行熔融共混,考察不同交联结构复合胶粒在不同熔融共混条件下的剪切形变行为。发现:微米级复合胶粒在熔融共混过程中既受强力剪切场的诱导作用,同时又受复合胶粒接枝交联结构的约束作用,因而依次会经历球形、椭球形、棒状、微纤状等取向形态,但又不至于出现大规模的撕裂解离现象,从而可在聚合物基体中原位并排生成大量具有较大长径比的微纤状取向结构体。通过改变SiO_2表面MPS改性程度和SiO_2含量调节复合胶粒的交联程度,或通过改变螺杆转速调节熔融剪切场的剪切强度,可在一定范围内调控复合胶粒及其中的接枝SiO_2粒子簇的取向程度。其中,当胶粒凝胶率为40%、共混温度180℃、螺杆转速65r/min、共混时间12min时,可得到平均长径比达到11.8的规则并排取向结构。研究可为聚合物基体中原位构建和有效调控一维取向结构提供一种新途径。
Using guava-like polyacrylate-3-(methacryloyloxy)propyltrimethoxysilane modified silica(PAcr MPSSiO_2)grafted composite particles as the dispersion phase,and polymethylmethacrylate(PMMA)resin as the continuous phase,their mixture was melt blended in a HAKKA torque rheometer,in order to investigate the dispersion and orientation behavior of the grafted composite particles with different crosslinking structures under various melt shear conditions.It is found that due to the induced effect provided by the strong shear force in the melt-mixed field,and also the restraint effect provided by the widespread grafting cross-linking structure formed with SiO_2 particles as the cross-linking point and the grafted polymer chain as the linking line in PAcr-MPS-SiO_2 particles,the guava-like composite particles are likely to be oriented and rearranged.They can be in turn deformed into sphere,ellipsoid,rod-shaped,microfibril and other oriented morphologies without large-scale tear dissociation,and finally in-situ formed a fibrous orientation structure with a large aspect ratio in the polymer matrix.The degree of orientation of the composite particles and the grafted SiO_2 clusters inside could both be controlled within a certain range,by adjusting the degree of crosslinking of the PAcr-MPS-SiO_2 composite particles from changing the degree of MPS modification on the silica surface,or by adjusting the shear strength of the melt shear field from changing the screw speed.When the gel fraction of the composite particles is 40%,the mixture temperature is 180℃,the screw speed fixed at65 r/min and the blending time of 12 minutes,an ordered alongside oriented structure with an average aspect ratio of11.8 can be obtained.Accordingly,we would believe this study could open a new pathway to in-situ construct and effiviently regulate one-dimensional orientation structure in polymer matrix.
Using guava-like polyacrylate-3-(methacryloyloxy)propyltrimethoxysilane modified silica(PAcr MPSSiO_2)grafted composite particles as the dispersion phase,and polymethylmethacrylate(PMMA)resin as the continuous phase,their mixture was melt blended in a HAKKA torque rheometer,in order to investigate the dispersion and orientation behavior of the grafted composite particles with different crosslinking structures under various melt shear conditions.It is found that due to the induced effect provided by the strong shear force in the melt-mixed field,and also the restraint effect provided by the widespread grafting cross-linking structure formed with SiO_2 particles as the cross-linking point and the grafted polymer chain as the linking line in PAcr-MPS-SiO_2 particles,the guava-like composite particles are likely to be oriented and rearranged.They can be in turn deformed into sphere,ellipsoid,rod-shaped,microfibril and other oriented morphologies without large-scale tear dissociation,and finally in-situ formed a fibrous orientation structure with a large aspect ratio in the polymer matrix.The degree of orientation of the composite particles and the grafted SiO_2 clusters inside could both be controlled within a certain range,by adjusting the degree of crosslinking of the PAcr-MPS-SiO_2 composite particles from changing the degree of MPS modification on the silica surface,or by adjusting the shear strength of the melt shear field from changing the screw speed.When the gel fraction of the composite particles is 40%,the mixture temperature is 180℃,the screw speed fixed at65 r/min and the blending time of 12 minutes,an ordered alongside oriented structure with an average aspect ratio of11.8 can be obtained.Accordingly,we would believe this study could open a new pathway to in-situ construct and effiviently regulate one-dimensional orientation structure in polymer matrix.
引文
[1]TANG Z,KOTOV N A.One-dimensional assemblies of nanoparticles:preparation,properties,and promise[J].Advanced Materials,2005,17(8):951-962.
[2]YUN S H,YOO S M,SOHN B H,et al.Electrically anisotropic thin films consisting of polymeric and metallic nanolayers from self-assembled lamellae of diblock copolymers[J].Langmuir,2005,21(8):3625-3628.
[3]GRENARD V,TABERLET N,MANNEVILLE S.Shearinduced structuration of confined carbon black gels:steadystate features of vorticity-aligned flocs[J].Soft Matter,2011,7(8):3920-3928.
[4]MA A W K,MACKLEY M R,RAHATEKAR S S.Experimental observation on the flow-induced assembly of carbon nanotube suspensions to form helical bands[J].Rheol Acta.2007,46(7):979-987.
[5]VERMANT J,SOLOMON M J.Flow-induced structure in colloidal suspensions[J].Journal of Physics:Condensed Matter,2005,17(4):187-216.
[6]SUN X,YU Q,SHEN J,et al.In situ microfibrillar morphology and properties of polypropylene/polyamide/carbon black composites prepared through multistage stretching extrusion[J].Journal of Materials Science,2013,48(3):1214-1224.
[7]HUANG J,ZHU Y,JIANG W,et al.Parallel carbon nanotube stripes in polymer thin film with remarkable conductive anisotropy[J].ACS applied materials &interfaces,2014,6(3):1754-1758.
[8]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):45-53.HOU L C,LIU H H,WANG N et al.Preparation of functionalized carbon nanotubes and functionalization of carbon nanotubes/nylon 6composite fibers[J].Acta Materiae Compositae Sinica,2013,30(1):45-53(in Chinese).
[9]甘舟,曹海琳,晏义伍,等.碳纤维-Ni/尼龙66复合材料的制备与性能表征[J].复合材料学报,2017,34(5),945-951.GAN Z,CAO H L,YAN Y W,et al.Preparation and characterization of carbon fiber-Ni/nylon 66composites[J].Acta Materiae Compositae Sinica,2017,34(5):945-951(in Chinese).
[10]戚栋明,袁艳,张睿,等.高分散性SiO2/PMMA复合材料的制备与表征———接枝与交联[J].高分子学报,2011,(11):1258-1265.QI D M,YUAN Y,ZHANG R,et al.Preparation and characterization of silica/PMMA composites with highly dispersed silica—Grafting and crosslinking[J].Acta Polymerica Sinica,2011,(11):1258-1265(in Chinese).
[11]戚栋明,赵晓丽,陈智杰,等.超声均质微悬浮聚合制备亚微米级聚苯乙烯胶粒[J].化工学报,2014,65(2):744-751.QI D M,ZHAO X L,Chen Z J,et al.Preparation of submicron polystyrene particles by micro-suspension polymerization with ultrasonic homogenization[J].CIESC Journal,2014,65(2):744-751(in Chinese).
[12]QI D M,GAO F,CHEN Z J,et al.preparation of composite films with controlled dispersion state of SiO2,nanoparticles by using polymer/SiO2,nanocomposite particles[J].Colloids&Surfaces A:Physicochemical &Engineering Aspects,2017,523:106-117.
[13]王振,雷中秋,潘忆乐,等.微悬浮聚合法制备的PA/MPSSiO2接枝复合胶粒的溶胀性能研究[J].浙江理工大学学报,2017,37(4):480-484.WANG Z,LEI Z Q,PAN Y L,et al.Study on swelling property of PA/MPS-SiO2graft composites prepared by micro-suspension polymerization[J].Journal of Zhejiang SciTech University,2017,37(4):480-484(in Chinese).
[14]QI D M,LIU C H,CHEN Z J,et al.Formation mechanism of guava-like polymer/SiO2nanocompositeparticles in in situ emulsion polymerization systems[J].Colloids and Surfaces A:Physicochemical and Engineering Aspests,2016,489:265-274.
[15]WANG D,SUN G,CHIOU B S.A high-throughput,controllable,and environmentally benign fabrication process of thermoplastic nanofibers[J].Macromolecular Materials and Engineering,2007,292(4):407-414.
[16]LIU W,NIE M,WANG Q.Biaxial reinforcements for polybutene-1 medical-tubes achieved via flow-design controlled morphological development of incorporated polystyrene:Insitu microfibrillation,alignment manipulation and performance optimization[J].Composites Science and Technology,2015,119(23):124-130.
[17]HUANG J,ZHU Y,JIANG W,et al.Parallel carbon nanotube stripes in polymer thin film with tunable microstructures and anisotropic conductive properties[J].Composites Part A:Applied Science and Manufacturing,2015,69(3):240-246.
[18]MCCARDLE R,BHATTACHARYYA D,FAKIROV S.Effect of Reinforcement Orientation on the Mechanical Properties of Microfibrillar PP/PET and PET Single-Polymer Composites[J].Macromolecular Materials and Engineering,2012,297(7):711-723.
[19]黎学东,陈鸣才,黄玉惠,等.PP/PA6原位成纤复合材料I.形态与力学性能[J].复合材料学报,1998,15(2):58-62.LI X D,CHEN M C,HUANG Y H,et al.PP/PA6in-situ fiber composite I.morphology and mechanical properties[J].Acta Materiae Compositae Sinica,1998,15(2):58-62(in Chinese).
[20]WANG L,FENG L F,GU X P,et al.Influences of the viscosity ratio and Processing Conditions on the formation of highly oriented ribbons in polymer blends by tape extrusion[J].Industrial &Engineering Chemistry Research,2015,54(44),11080-11086.
[21]KASALIWAL G R.,GOLDEL A,POTSCHKE P,et al.Influences of polymer matrix melt viscosity and molecular weight on MWCNT agglomerate dispersion[J].Polymer,2011,52(4):1027-1036.
[22]HE J,ZHANG Z,KRISTIANSEN H,et al.Crosslinking effect on the deformation and fracture of monodisperse polystyrene-co-divinylbenzene particles[J].EXPRESS Polymer Letters,2013,7(4),365-374.
[23]张连斌,王珂,朱锦涛.中国嵌段共聚物受限自组装的研究进展[J].高分子学报,2017,8(8):1261-1276.ZHANG L B,WANG K,ZHU J T.Research progress on restricted self-assembly of Chinese block copolymers[J].Acta Polymerica Sinica,2017,8(8):1261-1276(in Chinese).
[24]XIE L,XU H,NIU B,et al.Unprecedented access to strong and ductile poly(lactic acid)by introducing in situ nanofibrillar poly(butylene succinate)for green PAcrcrckaging[J].Biomacromolecules,2014,15(11):4054-4064.
[25]LIU P,OUYANG Y,XIAO R.Fabrication and morphology development of isotactic polypropylene nanofibers from isotactic polypropylene/polylactide blends[J].Journal of Applied Polymer Science,2012,123(5):2859-2866.
[2]YUN S H,YOO S M,SOHN B H,et al.Electrically anisotropic thin films consisting of polymeric and metallic nanolayers from self-assembled lamellae of diblock copolymers[J].Langmuir,2005,21(8):3625-3628.
[3]GRENARD V,TABERLET N,MANNEVILLE S.Shearinduced structuration of confined carbon black gels:steadystate features of vorticity-aligned flocs[J].Soft Matter,2011,7(8):3920-3928.
[4]MA A W K,MACKLEY M R,RAHATEKAR S S.Experimental observation on the flow-induced assembly of carbon nanotube suspensions to form helical bands[J].Rheol Acta.2007,46(7):979-987.
[5]VERMANT J,SOLOMON M J.Flow-induced structure in colloidal suspensions[J].Journal of Physics:Condensed Matter,2005,17(4):187-216.
[6]SUN X,YU Q,SHEN J,et al.In situ microfibrillar morphology and properties of polypropylene/polyamide/carbon black composites prepared through multistage stretching extrusion[J].Journal of Materials Science,2013,48(3):1214-1224.
[7]HUANG J,ZHU Y,JIANG W,et al.Parallel carbon nanotube stripes in polymer thin film with remarkable conductive anisotropy[J].ACS applied materials &interfaces,2014,6(3):1754-1758.
[8]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):45-53.HOU L C,LIU H H,WANG N et al.Preparation of functionalized carbon nanotubes and functionalization of carbon nanotubes/nylon 6composite fibers[J].Acta Materiae Compositae Sinica,2013,30(1):45-53(in Chinese).
[9]甘舟,曹海琳,晏义伍,等.碳纤维-Ni/尼龙66复合材料的制备与性能表征[J].复合材料学报,2017,34(5),945-951.GAN Z,CAO H L,YAN Y W,et al.Preparation and characterization of carbon fiber-Ni/nylon 66composites[J].Acta Materiae Compositae Sinica,2017,34(5):945-951(in Chinese).
[10]戚栋明,袁艳,张睿,等.高分散性SiO2/PMMA复合材料的制备与表征———接枝与交联[J].高分子学报,2011,(11):1258-1265.QI D M,YUAN Y,ZHANG R,et al.Preparation and characterization of silica/PMMA composites with highly dispersed silica—Grafting and crosslinking[J].Acta Polymerica Sinica,2011,(11):1258-1265(in Chinese).
[11]戚栋明,赵晓丽,陈智杰,等.超声均质微悬浮聚合制备亚微米级聚苯乙烯胶粒[J].化工学报,2014,65(2):744-751.QI D M,ZHAO X L,Chen Z J,et al.Preparation of submicron polystyrene particles by micro-suspension polymerization with ultrasonic homogenization[J].CIESC Journal,2014,65(2):744-751(in Chinese).
[12]QI D M,GAO F,CHEN Z J,et al.preparation of composite films with controlled dispersion state of SiO2,nanoparticles by using polymer/SiO2,nanocomposite particles[J].Colloids&Surfaces A:Physicochemical &Engineering Aspects,2017,523:106-117.
[13]王振,雷中秋,潘忆乐,等.微悬浮聚合法制备的PA/MPSSiO2接枝复合胶粒的溶胀性能研究[J].浙江理工大学学报,2017,37(4):480-484.WANG Z,LEI Z Q,PAN Y L,et al.Study on swelling property of PA/MPS-SiO2graft composites prepared by micro-suspension polymerization[J].Journal of Zhejiang SciTech University,2017,37(4):480-484(in Chinese).
[14]QI D M,LIU C H,CHEN Z J,et al.Formation mechanism of guava-like polymer/SiO2nanocompositeparticles in in situ emulsion polymerization systems[J].Colloids and Surfaces A:Physicochemical and Engineering Aspests,2016,489:265-274.
[15]WANG D,SUN G,CHIOU B S.A high-throughput,controllable,and environmentally benign fabrication process of thermoplastic nanofibers[J].Macromolecular Materials and Engineering,2007,292(4):407-414.
[16]LIU W,NIE M,WANG Q.Biaxial reinforcements for polybutene-1 medical-tubes achieved via flow-design controlled morphological development of incorporated polystyrene:Insitu microfibrillation,alignment manipulation and performance optimization[J].Composites Science and Technology,2015,119(23):124-130.
[17]HUANG J,ZHU Y,JIANG W,et al.Parallel carbon nanotube stripes in polymer thin film with tunable microstructures and anisotropic conductive properties[J].Composites Part A:Applied Science and Manufacturing,2015,69(3):240-246.
[18]MCCARDLE R,BHATTACHARYYA D,FAKIROV S.Effect of Reinforcement Orientation on the Mechanical Properties of Microfibrillar PP/PET and PET Single-Polymer Composites[J].Macromolecular Materials and Engineering,2012,297(7):711-723.
[19]黎学东,陈鸣才,黄玉惠,等.PP/PA6原位成纤复合材料I.形态与力学性能[J].复合材料学报,1998,15(2):58-62.LI X D,CHEN M C,HUANG Y H,et al.PP/PA6in-situ fiber composite I.morphology and mechanical properties[J].Acta Materiae Compositae Sinica,1998,15(2):58-62(in Chinese).
[20]WANG L,FENG L F,GU X P,et al.Influences of the viscosity ratio and Processing Conditions on the formation of highly oriented ribbons in polymer blends by tape extrusion[J].Industrial &Engineering Chemistry Research,2015,54(44),11080-11086.
[21]KASALIWAL G R.,GOLDEL A,POTSCHKE P,et al.Influences of polymer matrix melt viscosity and molecular weight on MWCNT agglomerate dispersion[J].Polymer,2011,52(4):1027-1036.
[22]HE J,ZHANG Z,KRISTIANSEN H,et al.Crosslinking effect on the deformation and fracture of monodisperse polystyrene-co-divinylbenzene particles[J].EXPRESS Polymer Letters,2013,7(4),365-374.
[23]张连斌,王珂,朱锦涛.中国嵌段共聚物受限自组装的研究进展[J].高分子学报,2017,8(8):1261-1276.ZHANG L B,WANG K,ZHU J T.Research progress on restricted self-assembly of Chinese block copolymers[J].Acta Polymerica Sinica,2017,8(8):1261-1276(in Chinese).
[24]XIE L,XU H,NIU B,et al.Unprecedented access to strong and ductile poly(lactic acid)by introducing in situ nanofibrillar poly(butylene succinate)for green PAcrcrckaging[J].Biomacromolecules,2014,15(11):4054-4064.
[25]LIU P,OUYANG Y,XIAO R.Fabrication and morphology development of isotactic polypropylene nanofibers from isotactic polypropylene/polylactide blends[J].Journal of Applied Polymer Science,2012,123(5):2859-2866.