球形聚丙烯/聚丁烯-1合金粒子制备和性能
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摘要
用原位聚合方法使用球形Ziegler-Natta催化剂制备新型聚丁烯-1合金材料,通过DSC、SEM、XRD和~(13)C NMR等手段对产物的形态、物性和结构进行了表征,考察了丁烯-1加入量对聚合产物形态、结构及聚合性能的影响。结果表明:与丁烯-1本体聚合相比用原位聚合可改善聚丁烯-1产物的形态,降低聚合物粒子之间的粘联,使聚合物在釜内成为球形颗粒,催化活性最高为10.4 kg/g Cat,聚合产物的堆积密度为0.44 g/cm~3,粒径约为500μm;同时,用原位聚合可缩短聚丁烯-1产品由不稳定的晶型II向稳定的晶型I转变周期。聚丁烯-1釜内合金的拉伸强度和弯曲模量都随着丙烯结构单元含量的提高而提高,但是聚合物的密度、冲击强度和断裂伸长率降低。
A new type of polymer alloy of polypropylene/polybutene-1 was prepared by in-situ polymerization with spherical Ziegler-Natta as catalyst. The effect of butene-1 addition on the morphology, structure and the properties of polymer alloy was investigated. The polymers obtained were characterized by means of DSC, SEM XRD and13 C NMR. The results show that compared with the bulk polymerization of butene-1, the in-situ polymerization could improve the morphology of the product made from polybutene-1,and effectively reduce the adhesion between polymer particles. The catalytic activity, stacking density and particle size of the prepared polymer alloy are 10.4 kg/g Cat, 0.44 g/cm3 and 500 μm, respectively.Moreover, the in-situ polymerization could effectively shorten the transition period of the polybutene-1 product from the unstable crystal form II to the stable crystalline form I. The mechanical property test revealed that with the rise of the content of the structural unit in propylene the tensile strength and flexural modulus of the polybutene alloys were increased, however, the density, impact strength and elongation at break were decreased.
A new type of polymer alloy of polypropylene/polybutene-1 was prepared by in-situ polymerization with spherical Ziegler-Natta as catalyst. The effect of butene-1 addition on the morphology, structure and the properties of polymer alloy was investigated. The polymers obtained were characterized by means of DSC, SEM XRD and13 C NMR. The results show that compared with the bulk polymerization of butene-1, the in-situ polymerization could improve the morphology of the product made from polybutene-1,and effectively reduce the adhesion between polymer particles. The catalytic activity, stacking density and particle size of the prepared polymer alloy are 10.4 kg/g Cat, 0.44 g/cm3 and 500 μm, respectively.Moreover, the in-situ polymerization could effectively shorten the transition period of the polybutene-1 product from the unstable crystal form II to the stable crystalline form I. The mechanical property test revealed that with the rise of the content of the structural unit in propylene the tensile strength and flexural modulus of the polybutene alloys were increased, however, the density, impact strength and elongation at break were decreased.
引文
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[18]Cecchin G,Marchetti E,Baruzzi G.On the mechanism of polypropene growth over Mg Cl2/Ti Cl4catalyst systems[J].Macromol.Chem.Phys.,2001,202:1987
[2]Huang B C,Zhang B Y,Yao W,et al.Bulk depositing synthesis process of isotactic polybutylene-1[P].Chin Pat,CN101020728A,2007(黄宝琛,郑保永,姚薇等.高全同聚丁烯-1的本体沉淀合成方法[P].中国专利,CN101020728A,2007)
[3]He A H,Wang C.Spherical polybutylene-1 with high isotacticity and preparation method thereof[P].Chin Pat,CN103288993A,2013(贺爱华,王超.高等规度球形聚丁烯-1及其制备方法[P].中国专利,CN103288993A,2013)
[4]He A H,Zheng W P,Shi Y W,et al.In situ synthesis of polybutene-1/polypropylene spherical alloys within a reactor with an MgCl2-supported Ziegler–Natta catalyst[J].Polym.Int.,2012,61:1575
[5]Jiang B Y,Shao H F,He A H,et al.Sequential two-stage polymerization for synthesis of isotactic polypropylene/isotactic polybutene-1 alloys:composition,morphology and granule growing mechanism[J].Polym.Chem.,2015,6:3315
[6]Zhang X M,Bi F Y,Song W B,et al.Preparation method for high isotactic polybutene-1[P].Chin Pat,CN103772557A,2014(张晓萌,毕福勇,宋文波等.高等规聚丁烯-1的制备方法[P].中国专利,CN103772557A,2014)
[7]Bi F Y,Song W B,Zhang X M,et al.Preparation of high isotactic polybutene-1[J].Petrochem.Technol.,2014,43:441(毕福勇,宋文波,张晓萌等.高等规聚1-丁烯的制备[J].石油化工,2014,43:441)
[8]Liu B Y,Ren H G,Yang M,et al.Spherical catalyst for 1-butene polymerization as well as preparation method and application thereof[P].Chin Pat,CN101914172B,2012(刘宾元,任合刚,杨敏等.1-丁烯聚合用的球形催化剂及其制备方法和应用[P].中国专利,CN101914172B,2012)
[9]Abedi S,Sharifi-Sanjani N.Preparation of high isotactic polybutene-1[J].J.Appl.Polym.Sci.,2000,78:2533
[10]Liu Y P,Cui K P,Tian N,et al.Stretch-induced crystal-crystal transition of polybutene-1:an in situ synchrotron radiation wide-angle X-ray scattering study[J].Macromolecules,2012,45:2764
[11]Resconi L,Camurati I,Malizia F.Metallocene catalysts for 1-butene polymerization[J].Macromol.Chem.Phys.,2006,207:2257
[12]Zhang C Y,Dong B,Zhang X Q,et al.Preparation and characterization of propylene/1-butene alloy with bulk copolymerization[J].Chem.J.Chin.Univ.,2014,35:2014(张春雨,董博,张学全等.本体共聚合制备丙烯/1-丁烯合金及表征[J].高等学校化学学报,2014,35:2014)
[13]Ma Y P,Li L G,Shao H F,et al.Microstructure and its effect on the properties of poly(1-butene)alloys within reactor[J].Chem.World,2016,(5):261(马亚萍,李兰阁,邵华锋等.聚1-丁烯釜内合金的微观结构及其对性能的影响[J].化学世界,2016,(5):261)
[14]Fisch M H,Dannenberg J J.Propylene incorporation in 1-butene copolymers by carbon-13 nuclear magnetic resonance spectrometry[J].Anal.Chem.,1977,49:1405
[15]Wang X F,Zhao Y X,Bi F Y,et al.The structure and properties of polybutene-1—(Ⅰ)the relation between isotacticity and properties of polybutene-1[J].Polym.Mater.Sci.Eng.,2008,24(7):66(王秀峰,赵永仙,毕福勇等.全密度聚丁烯-1的结构与性能—(I)全同含量与聚丁烯-1性能的关系[J].高分子材料科学与工程,2008,24(7):66)
[16]Stolte I,Androsch R,Di Lorenzo M L,et al.Effect of aging the glass of isotactic polybutene-1 on form II nucleation and cold crystallization[J].J.Phys.Chem.B,2013,117:15196
[17]Li L,Liu T,Zhao L,et al.CO2-induced crystal phase transition from form II to I in isotactic poly-1-butene[J].Macromolecules,2009,42:2286
[18]Cecchin G,Marchetti E,Baruzzi G.On the mechanism of polypropene growth over Mg Cl2/Ti Cl4catalyst systems[J].Macromol.Chem.Phys.,2001,202:1987