Z-N催化剂用于原位合成球形聚1-丁烯/聚丙烯合金
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摘要
采用球形Ziegler-Natta催化剂,通过原位聚合法制备了聚1-丁烯(PB)/聚丙烯(PP)合金,考察了聚合时间对聚合物形态、结构及性能的影响,并通过差示扫描量热法、扫描电子显微镜、X射线衍射等对合金的形态和物性进行了表征。结果表明:与1-丁烯本体聚合相比,原位聚合可改善PB的形态,有效地降低PB粒子间的粘连,使PB在釜内成为球形颗粒;丙烯聚合时间为40 min时,催化剂活性最高,达11.7 kg/g,PB/PP合金粉料的堆密度为0.44 g/cm3;原位聚合可有效地缩短PB由不稳定晶型Ⅱ向稳定晶型Ⅰ转变的周期。
Poly(1-butene)(PB)/polypropylene(PP)alloy was prepared via in-situ polymerization with spherical Ziegler-Natta catalyst.The effects of the polymerization time on the morphology,structure and properties of the polymers were investigated.The alloy obtained was characterized by means of differential scanning calorimeter,scanning electron microscope and X-ray diffraction.The results indicate that in-situ polymerization can improve the morphology of PB compared with the bulk polymerization of butene-1,it reduces the adhesion between polymer particles and helps to form spherical particles in the reactor.The catalytic activity reaches the highest of 11.7 kg/g and the bulk density of the alloy is 0.45 g/cm3 when the polymerization continues for 40 minutes.Moreover,in-situ polymerization can effectively shorten the transition period of PB from the unstable crystalline form Ⅱ to the stable formⅠ.
Poly(1-butene)(PB)/polypropylene(PP)alloy was prepared via in-situ polymerization with spherical Ziegler-Natta catalyst.The effects of the polymerization time on the morphology,structure and properties of the polymers were investigated.The alloy obtained was characterized by means of differential scanning calorimeter,scanning electron microscope and X-ray diffraction.The results indicate that in-situ polymerization can improve the morphology of PB compared with the bulk polymerization of butene-1,it reduces the adhesion between polymer particles and helps to form spherical particles in the reactor.The catalytic activity reaches the highest of 11.7 kg/g and the bulk density of the alloy is 0.45 g/cm3 when the polymerization continues for 40 minutes.Moreover,in-situ polymerization can effectively shorten the transition period of PB from the unstable crystalline form Ⅱ to the stable formⅠ.
引文
[1]华树森,黄宝琛.小本体聚丙烯装置改造进行1-丁烯聚合[J].科技创新导报,2010(24):108-109.
[2]黄宝琛,郑保永,姚薇,等.高全同聚1-丁烯的本体沉淀合成方法:中国,101020728 A[P].2007-08-22.
[3]贺爱华,王超.高等规度球形聚1-丁烯及其制备方法:中国,103288993A[P].2013-09-11.
[4]He Aihua,Zheng Weiping,Shi Yangwei,et al.In situ synthesis of polybutene-1/polypropylene spherical alloys within a reactor with an Mg Cl2-supported Ziegler-Natta catalyst[J].Polym Int,2012,61(10):1575-1581.
[5]Jiang Baiyu,Shao Huafeng,He Aihua,et al.Sequential twostage polymerization for synthesis of isotactic polypropylene/isotactic polybutene-1 alloys:composition,morphology and granule growing mechanism[J].Polym Chem,2015,6(17):3315-3323.
[6]张晓萌,毕福勇,宋文波,等.高等规聚1-丁烯的制备方法:中国,103772557A[P].2014-05-07.
[7]毕福勇,宋文波,张晓萌.高等规聚1-丁烯的制备[J].石油化工,2014,43(4):441-446.
[8]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:中国,101914172 B[P].2012-07-25.
[9]Cecchin G,Marchetti E,Baruzzi G.On the mechanism of polypropylene growth over Mg Cl2/Ti Cl4 catalyst systems[J].Macromol Chem Phys,2001,202(10):1987-1994.
[10]Resconi L,Camurati I,Malizia F.Metallocene catalysts for1-butene polymerization[J].Macromol Chem Phys,2006,207(24):2257-2279.
[11]Stolte I,Androsch R,Lorenzo M L D,et al.Effect of aging the glass of isotactic polybutene-1 on formⅡnucleation and cold crystallization[J].J Phys Chem B,2013,117(48):15196-15203.
[12]Li Lei,Liu Tao,Zhao Ling,et al.CO2-induced crystal phase transition from formⅡtoⅠin isotactic poly-1-butene[J].Macromolecules,2009,42(6):2286-2290.
[2]黄宝琛,郑保永,姚薇,等.高全同聚1-丁烯的本体沉淀合成方法:中国,101020728 A[P].2007-08-22.
[3]贺爱华,王超.高等规度球形聚1-丁烯及其制备方法:中国,103288993A[P].2013-09-11.
[4]He Aihua,Zheng Weiping,Shi Yangwei,et al.In situ synthesis of polybutene-1/polypropylene spherical alloys within a reactor with an Mg Cl2-supported Ziegler-Natta catalyst[J].Polym Int,2012,61(10):1575-1581.
[5]Jiang Baiyu,Shao Huafeng,He Aihua,et al.Sequential twostage polymerization for synthesis of isotactic polypropylene/isotactic polybutene-1 alloys:composition,morphology and granule growing mechanism[J].Polym Chem,2015,6(17):3315-3323.
[6]张晓萌,毕福勇,宋文波,等.高等规聚1-丁烯的制备方法:中国,103772557A[P].2014-05-07.
[7]毕福勇,宋文波,张晓萌.高等规聚1-丁烯的制备[J].石油化工,2014,43(4):441-446.
[8]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:中国,101914172 B[P].2012-07-25.
[9]Cecchin G,Marchetti E,Baruzzi G.On the mechanism of polypropylene growth over Mg Cl2/Ti Cl4 catalyst systems[J].Macromol Chem Phys,2001,202(10):1987-1994.
[10]Resconi L,Camurati I,Malizia F.Metallocene catalysts for1-butene polymerization[J].Macromol Chem Phys,2006,207(24):2257-2279.
[11]Stolte I,Androsch R,Lorenzo M L D,et al.Effect of aging the glass of isotactic polybutene-1 on formⅡnucleation and cold crystallization[J].J Phys Chem B,2013,117(48):15196-15203.
[12]Li Lei,Liu Tao,Zhao Ling,et al.CO2-induced crystal phase transition from formⅡtoⅠin isotactic poly-1-butene[J].Macromolecules,2009,42(6):2286-2290.