球形聚丙烯/聚丁烯-1合金粒子制备和性能

doi:10.11901/1005.3093.2017.486

材料研究学报

2018, Vol. 32

Issue (7): 518-524 DOI: 10.11901/1005.3093.2017.486

研究论文

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球形聚丙烯/聚丁烯-1合金粒子制备和性能

任合刚¹(

), 李振友², 闫义彬¹, 王斯晗¹, 崔晓鹏³, 刘宾元³

1 中国石油石油化工研究院大庆化工研究中心大庆 163714
2 中国石油天然气股份有限公司炼油与化工分公司北京 100007
3 河北工业大学化工学院高分子科学与工程研究所天津 300130

Preparation and Properties of Spherical Particles of Polymer Alloy Polypropylene/Polybutene-1

Hegang REN¹(

), Zhenyou LI², Yibin YAN¹, Sihan WANG¹, Xiaopeng CUI³, Binyuan LIU³

1 Daqing Petrochemical Research Center, Petrochemical Research Institute of CNPC, Daqing 163714, China
2 Refining and Chemical Branch of CNPC, Beijing 100007, China
3 Institute of Polymer Science and Engineering, Hebei University of Technology, Tianjin 300130, China

引用本文:

任合刚, 李振友, 闫义彬, 王斯晗, 崔晓鹏, 刘宾元. 球形聚丙烯/聚丁烯-1合金粒子制备和性能[J]. 材料研究学报, 2018, 32(7): 518-524.
Hegang REN, Zhenyou LI, Yibin YAN, Sihan WANG, Xiaopeng CUI, Binyuan LIU. Preparation and Properties of Spherical Particles of Polymer Alloy Polypropylene/Polybutene-1[J]. Chinese Journal of Materials Research, 2018, 32(7): 518-524.

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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¹³C 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/gCat,聚合产物的堆积密度为0.44 g/cm³,粒径约为500 μm;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。

关键词 ：有机高分子材料, Ziegler-Natta 催化剂, 原位聚合, 釜内合金

Abstract：

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 and ¹³C 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/gCat, 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.

Key words： organic polymer materials Ziegler-Natta catalyst in-situ polymerization reactor alloy

收稿日期: 2017-08-15

ZTFLH:

TQ325

作者简介:

作者简介任合刚,男,1981年生,博士生

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https://www.cjmr.org/CN/10.11901/1005.3093.2017.486 或 https://www.cjmr.org/CN/Y2018/V32/I7/518

表1 MgCl2负载型Ziegler-Natta催化剂催化丙烯/丁烯-1连续聚合结果

图1 聚丁烯-1合金典型的DSC曲线

表2 聚丁烯-1合金的结晶性能

图2 聚丁烯-1合金的13C NMR谱图

图3 聚合物的XRD谱图

图4 室温下晶型I和II含量与老化时间的关系

图5 催化剂和聚合物的SEM照片

图6 聚丁烯-1合金颗粒的生长模型

表3 聚丁烯-1合金的力学性能

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