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Recent key developments in isotactic polypropylene in-reactor alloy and in-reactor nanocomposite technology

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Science China Chemistry 2016年第10期59卷 1231-1239页

作者： jinyong dong Yawei Qin CAS Key Laboratory of Engineering Plastics Institute of ChemistryChinese Academy of SciencesBeijing 100190China University of Chinese Academy of Sciences Beijing 100049China

Alloying and nanocompositing are two most effective techniques by which isotactic polypropylene(iPP), one of the most promising polymers of the 21 st century, can be endowed with high performance for ever-demanding high-end applications. Thanks to the continuous advancement of catalyst technology, the technological trend for iPP alloy and nanocomposite fabrication has been projected to be in-reactor synthesis, the performance and economic advantages of which are beyond doubt. In this paper, we review two recent key developments in the iPP in-reactor alloy and in-reactor nanocomposite technology in our laboratory that will have profound influence on the continuing development of the prestigious iPP modification art. The first is the simultaneous EPR(ethylene-propylene random copolymer) cross-linking chemistry for controlling its physical growth pattern during in-reactor alloying, which helps to remove the compositional cap on EPR that so far greatly limits the iPP in-reactor alloying technique. The second is the nanofiller support fabrication strategy for simultaneously controlling both the phase morphology of the nanofiller dispersion and the polymer particle granule morphology of synthesized nanocomposites, which resolves the critical scale-up issue surrounding the iPP in-reactor nanocompositing technique. Based on these new developments, new advancements of iPP materials are envisaged.

关键词： isotactic polypropylene in-reactor alloy in-reactor nanocomposite key development

Preparation of nano-compounded polyolefin materials through in situ polymerization technique:status quo and future prospects

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Chinese Science Bulletin 2009年第1期54卷 38-45页

作者： QIN YaWei dong jinyong CAS Key Laboratory of Engineering Plastics and Joint Laboratory of Polymer Science and Materials Institute of Chemistry Chinese Academy of Sciences Beijing 100190 China

Nano-compounding of polyolefins,an economical yet very effective route to high-performance poly-olefin materials,has received considerable attention in recent years. Unlike most of the other polymers,polyolefins are chemically inert,which dictates that nano-compounding of polyolefins has to be con-ducted via in situ polymerization. In this review,a technological progress of the nano-compounding of polyolefins via in situ polymerization technique was summarized thoroughly,with emphasis laid on the current research status of polyolefin/montmorillonite (MMT) nanocomposites. A clear perspective for future researches on this specific family of materials was envisaged.

关键词：聚烯烃纳米复合材料聚合反应蒙脱石

Preparation of polypropylene/montmorillonite nanocomposites by intercalative polymerization:Effect of in situ polymer matrix functionalization on the stability of the nanocomposite structure

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Chinese Science Bulletin 2007年第2期52卷 181-187页

作者： YANG KeFang HUANG YingJuan dong jinyong CAS Key Laboratory of Engineering Plastic Joint Laboratory of Polymer Science and Materials Institute of Chemistry Chinese Academy of Sciences Beijing 100080 China Graduate University Chinese Academy of Sciences Beijing 100039 China

The copolymerization of propylene and 5-hexenyl-9-borabicyclo[3.3.1]nonane (5-hexenyl-9-BBN) has been conducted with an MgCl2/TiCl4 catalyst intercalated in an organically modified montmorillonite (OMMT) with triethylaluminum (AlEt3) cocatalyst and diphenyldimethoxysilane (DDS) external donor. This polymerization process simultaneously results in both the exfoliation of MMT layers to realize the preparation of polypropylene (PP)/MMT nanocomposites and the implantation of reactive borane groups in the formed PP matrix. The polymer-borne borane groups have been able to undergo an effi-cient hydrolysis process under very mild reaction conditions (40℃, 3 h, in THF), introducing hydroxy groups into PP without sacrificing the polymerization-formed nanocomposite structure (the exfoliation of MMT). The resultant hydroxyl-functionalized PP/MMT nanocomposites exhibit enhanced structural stability against processing compared with those based on unfunctionalized PP matrix.

关键词：聚丙烯化合物共聚合反应蒙脱石催化剂稳定性

A comparison study on the melt crystallization kinetics of long chain branched and linear isotactic polypropylenes

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Chinese Science Bulletin 2008年第2期53卷 188-197页

作者： ZENG Wei LIU JiChun ZHOU JunFeng dong jinyong YAN ShouKe Beijing National Laboratory for Molecular Sciences and Joint Laboratory of Polymer Science and Materials Institute of Chemistry Chinese Academy of Sciences Beijing 100080 China State Key Laboratory of Polymer Physics and Chemistry and Key Laboratory of Engineering Plastics Chinese Academy of Sciences Beijing 100080 China Key Laboratory of Polymer Science and Nanotechnology College of Chemical Engineering and Pharmaceutics Henan University of Science and Technology Luoyang 471003 China

The isothermal and non-isothermal crystallization kinetics of LCBPP and linear-iPP was investigated by optical microscopy and differential scanning calorimetry (DSC). The optical microscopy results in the isothermal crystallization process show that the crystals of LCBPP grow slower than the crystals of the linear-iPP. This originates from the low chain mobility, or in other words, the lower chain diffusion rate of LCBPP due to the existence of long side chains. The DSC results in the isothermal crystallization process show that the LCBPP exhibits, however, a higher overall crystallization rate with respect to the linear-iPP. This is related to the higher nucleation ability of LCBPP since the isothermal crystallization process of both LCBPP and linear-iPP are nucleation-dominated. Avrami analysis indicates that the nucleation nature and crystal growth manner of LCBPP and linear-iPP are about the same. The analy- ses of the non-isothermal crystallization processes indicate an increment in crystallization rate with increasing cooling rate. But at any cooling rate, the linear-iPP crystallizes more quickly than the LCBPP. This implies that the non-isothermal crystallization processes of LCBPP and linear-iPP are diffu- sion-dominated, in which the lower chain diffusion rate of LCBPP results in the slower crystallization of it.

关键词：聚丙烯长链分岔线性全规聚丙烯结晶动力学

聚合新方法研究对我国聚烯烃高性能化技术发展的重要性和可行性

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科学通报 2022年第17期67卷 1863-1869页

作者：董金勇中国科学院化学研究所北京100190 中国科学院大学化学科学学院北京100049

以聚乙烯和聚丙烯为主(占整个聚烯烃消费量的90%以上)的聚烯烃是高分子材料的最大品种.近年来,随原料来源的不断丰富以及应用领域的不断扩展,我国聚烯烃的产量和需求量不断增长,产能也随之高速扩张.目前,我国已经是全球第一大聚烯烃生... 详细信息

以聚乙烯和聚丙烯为主(占整个聚烯烃消费量的90%以上)的聚烯烃是高分子材料的最大品种.近年来,随原料来源的不断丰富以及应用领域的不断扩展,我国聚烯烃的产量和需求量不断增长,产能也随之高速扩张.目前,我国已经是全球第一大聚烯烃生产国和消费国,拥有世界上规模最大、工艺最全、原料多元化最突出的聚烯烃产业.随着新型工业化、信息化、城镇化和农业现代化的深入推进和居民消费结构的不断升级,我国聚烯烃市场和聚烯烃产业的发展前景仍然非常广阔.

关键词：高性能化高分子材料居民消费结构原料多元化聚烯烃新型工业化聚乙烯聚丙烯

Recent Key Developments in Isotactic Polypropylene In-Reactor Alloy and Nanocomposite Technology

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Recent Key Developments in Isotactic Polypropylene In-Reacto...

功能分子和纳米粒子主动干预烯烃聚合策略制备高性能聚烯烃材料

中国化学会第30届学术年会

作者： dong jinyong Institute of Chemistry Key Laboratory of Engineering PlasticsCAS

Alloy and nanocomposite are two most effective routes through which isotactic polypropylene(i PP), of low cost, low weight, high durability, and high mechanical and thermal resistance and thus being one of the most promising polymers in the 21 century, is to access high performance for an ever-demanding high-end application. Thanks to the continuous advancement of catalyst technology, the future technological trend for i PP alloy and nanocomposite has been projected, beyond any doubt, to be an in-reactor synthesis, whose performance and economic advantages are out of question. In this paper, we review two recent key developments in i PP in-reactor alloy and nanocomposite technology born to our laboratory, namely, the simultaneous EPR(ethylene-propylene random copolymer) cross-linking chemistry for controlling its physical growth during in-reactor alloy and the nanofiller particle morphology control strategy for controlling in-reactor nanocomposite particle morphology. By resolving the most critical issues in the technology, the two new developments have in effect infused new blood into and provided new opportunities of continuing development for the somewhat non-enchanting technology, which is however of paramount necessity to i PP material advancement.

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石油化工 2017年第6期46卷 660-670页

作者：董金勇中国科学院化学研究所工程塑料重点实验室北京100190

聚烯烃的高性能化与功能化是聚烯烃材料产业可持续发展的基础。不断挑战聚烯烃的材料性能极限、扩展材料性能范围,或赋予其功能性、从而使其超越本身价值,是聚烯烃材料化学研究的核心与目标。从Ziegler K和Natta G发现烯烃配位聚合使聚... 详细信息

聚烯烃的高性能化与功能化是聚烯烃材料产业可持续发展的基础。不断挑战聚烯烃的材料性能极限、扩展材料性能范围,或赋予其功能性、从而使其超越本身价值,是聚烯烃材料化学研究的核心与目标。从Ziegler K和Natta G发现烯烃配位聚合使聚烯烃材料得以快速发展以来,聚烯烃材料化学在多数时间内偏重于化学与物理改性研究。近年来催化技术的巨大进步使对烯烃聚合机理的认识更加深入,对聚合方法的掌握更加主动,促使聚烯烃材料化学与烯烃配位聚合逐渐融和,进而使高性能/功能化聚烯烃材料不断由聚合反应直接制备出来,且结构性能可调节性更强,而制备过程更直接,代表着聚烯烃材料化学的发展前沿。在聚烯烃材料化学发展的大背景下,集中讨论了利用功能分子和纳米粒子主动干预烯烃聚合策略制备高性能聚烯烃材料的研究进展。

关键词：烯烃配位聚合聚烯烃高性能化功能分子纳米粒子

苯乙烯基封端反应性等规聚丙烯的催化合成及其在构筑新型拓扑结构聚丙烯高分子中的应用

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高分子学报 2010年第1期20卷 87-95页

作者：黄华华董金勇中国科学院化学研究所高分子科学与材料联合实验室中国科学院工程塑料重点实验室北京100190

在具有高度等规定向能力的rac-Me2Si(2-Me-4-Ph-Ind)2ZrCl2/MAO催化体系所催化的丙烯聚合反应中,通过控制聚合条件,实现聚合物链选择性地向对双苯乙烯单体的链转移反应,合成出一种新的苯乙烯基封端的反应性等规聚丙烯.以这种苯乙烯基封... 详细信息

在具有高度等规定向能力的rac-Me2Si(2-Me-4-Ph-Ind)2ZrCl2/MAO催化体系所催化的丙烯聚合反应中,通过控制聚合条件,实现聚合物链选择性地向对双苯乙烯单体的链转移反应,合成出一种新的苯乙烯基封端的反应性等规聚丙烯.以这种苯乙烯基封端反应性聚丙烯为结构单元,构筑了两种拓扑结构(接枝和星型)的聚丙烯共聚物,一是在CpTiCl3/MAO催化下,与苯乙烯小分子进行配位聚合,合成了以间规聚苯乙烯为主链、等规聚丙烯为侧链的接枝共聚物(sPS-g-iPP);二是选择性地在链端苯乙烯基上进行氯化和取代反应,定量地将叠氮基团引入等规聚丙烯链端,再与多炔基偶合剂进行点击反应,合成了星型等规聚丙烯.

关键词：烯烃配位聚合链转移反应反应性等规聚丙烯接枝共聚物星型等规聚丙烯

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新一代功能性聚丙烯催化剂的研发进展

石油化工 2010年第2期39卷 116-124页

作者：董金勇牛慧中国科学院化学研究所工程塑料重点实验室北京100190

为适应聚丙烯树脂高性能化和功能化的发展需求,提出了基于MgCl2负载的高效Ziegler-Natta催化剂,借助于茂金属及非茂金属单中心催化剂丰富多样且明确可控的烯烃聚合催化能力,通过多重载体化制备了Ziegler-Natta/(非)茂金属复合型催化剂,... 详细信息

为适应聚丙烯树脂高性能化和功能化的发展需求,提出了基于MgCl2负载的高效Ziegler-Natta催化剂,借助于茂金属及非茂金属单中心催化剂丰富多样且明确可控的烯烃聚合催化能力,通过多重载体化制备了Ziegler-Natta/(非)茂金属复合型催化剂,从而获得兼具高活性、高立体定向性和可调、可控的共聚性能的新一代功能性聚丙烯催化剂,用于以聚丙烯/乙丙多相共聚物、高熔体强度聚丙烯和极性改性的功能化聚丙烯等为代表的高性能聚丙烯树脂的制备。通过对聚丙烯催化剂与聚合物结构性能之间对应关系的分析,及Ziegler-Natta/(非)茂金属复合型催化剂在制备多相共聚聚丙烯和高熔体强度聚丙烯等树脂中的实践,指出了以获得催化功能性为目标的Ziegler-Natta/(非)茂金属复合型催化剂是今后聚丙烯催化剂的发展方向。

关键词：聚丙烯 Ziegler—Natta催化剂单中心催化剂功能性复合型催化剂茂金属催化剂