Crystallographic behavior of nascent isotactic polypropylene produced under supercritical conditions

doi:10.3969/j.issn.0438-1157.2013.02.044

CIESC Journal ›› 2013, Vol. 64 ›› Issue (2): 730-734.DOI: 10.3969/j.issn.0438-1157.2013.02.044

Previous Articles Next Articles

Crystallographic behavior of nascent isotactic polypropylene produced under supercritical conditions

QIU Shaolong¹, HUO Zhihong¹, CAO Kun^1,2, DA Wenzhong³, WANG Xingren³, XU Hongbin³

1. Institute of Polymerization and Polymer Engineering, Department of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, Zhejiang, China;
2. State Key Laboratory of Chemical Engineering(Zhejiang University), Hangzhou 310027, Zhejiang, China;
3. Research Institute of Yangzi Petrochemical Co.Ltd., SINOPEC, Nanjing 210048, Jiangsu, China

Received:2012-09-06 Revised:2012-12-04 Online:2013-02-05 Published:2013-02-05
Supported by:
supported by the National Natural Science Foundation of China (20576115).

丙烯超临界聚合中原生晶特征

邱少龙¹, 霍志宏¹, 曹堃^1,2, 笪文忠³, 王兴仁³, 徐宏斌³

1. 浙江大学化工系聚合与聚合物工程研究所,浙江杭州 310027;
2. 化学工程联合国家重点实验室(浙江大学),浙江杭州 310027;
3. 中国石化扬子石油化工有限公司研究院,江苏南京 210048

通讯作者: 曹堃
作者简介:邱少龙(1987—),男,硕士研究生。
基金资助:
国家自然科学基金项目(20576115)。

Abstract

Abstract: The materials used here were isotactic polypropylene (iPP) produced by conventional slurry polymerization and under supercritical conditions.Wide-angle X-ray diffraction (WAXD) patterns of the iPPs obtained under various conditions were recorded to analyze the nascent polymorphic form.The effects of polymerization process, pre-polymerization temperature,particle size and molecular weight of the resultant iPPs on nascent polymorphic form were investigated.The iPP produced by supercritical polymerization was the mixture of α and γ forms while the iPP produced by conventional slurry process was only in the α form, just because, in the supercritical state of high pressure and high temperature, mass and heat transfer should be faster, which would facilitate development of nascent polymorphic form. Furthermore, pre-polymerization temperature, particle size and molecular weight of obtained iPPs were found to have significant effect on nascent crystallographic behavior.

Key words: propylene polymerization, supercritical polymerization, isotactic polypropylene, nascent crystal

摘要： 通过广角X射线衍射(WAXD)对由丙烯超临界聚合和传统本体淤浆法制得的等规聚丙烯原生结晶特征进行了研究,并讨论了聚合工艺、预聚温度、粒径、分子量等对原生晶特征的影响。结果表明,超临界聚合法制备的等规聚丙烯(SC-iPP)呈现出α和γ的混合晶型,而采用传统淤浆法制备的等规聚丙烯(C-iPP)只含有单一α晶型,这是因为超临界的高温高压状态,使得体系传热传质阻力较小,更有利于原生晶型的发展。此外,预聚温度、粒径、分子量等因素也对丙烯超临界聚合所制得的SC-iPP结晶特征有显著影响。

关键词: 丙烯聚合, 超临界聚合, 等规聚丙烯, 原生晶

CLC Number:

TQ325

QIU Shaolong, HUO Zhihong, CAO Kun, DA Wenzhong, WANG Xingren, XU Hongbin. Crystallographic behavior of nascent isotactic polypropylene produced under supercritical conditions[J]. CIESC Journal, 2013, 64(2): 730-734.

邱少龙, 霍志宏, 曹堃, 笪文忠, 王兴仁, 徐宏斌. 丙烯超临界聚合中原生晶特征[J]. 化工学报, 2013, 64(2): 730-734.

References 18

[1]	You Houping(尤侯平), Cao Kun(曹堃),Fan Rong(范荣),Huo Zhihong(霍志宏),Yao Xiaoli(姚小利),Wang Qi(王齐).Advances in supercritical polymerization of olefins(Ⅰ):Polymerization processes and industry applications[J].Polymer Materials Science and Engineering(高分子材料科学与工程), 2005, 21(4):37-41
[2]	Ahvenainen A, Kari S, Henrik A, Jouni T, Ari P.Multi-stage process for producing polyethylene:US, 5326835.1994-07-05
[3]	Ahvenainen A, Kari S, Henrik A.Method for homo- or copolymerizing ethene:US, 5391654.1995-02-21
[4]	Palmroos A, Harlin A, Ahvenainen A, Takakarhu J, Sahila A.Process for preparing polyethylene:US, 5684097.1997-11-04
[5]	Hokkanen H, Salminen H, Kallio K, Knuuttila H, Palmroos A.Process for manufacturing LLDPE polymers:US, 5986021.1999-11-16
[6]	Myhre O J, Nummila-Pakarinen A, Lindroos J, Waldvogel P, Garoff T.Process for producing a homogeneous polyethylene material in the presence of a catalyst:US, 6455642B1.2002-09-24
[7]	Myhre O J, Jansen B, Nummila-Pakarinen A, Aarila J.Process to produce a homogeneous polyethylene material:US, 6642323B1.2003-11-04
[8]	Kallio K, Kinnunen E, Lehtinen A, Malmberg A, Marja O.Two-step polymerization process:WO, 03037941. 2003-08-05
[9]	Hu Bingyong(胡炳慵), Wang Dingsong(王定松).The third generation of polyolefin technology[J].Petrochemical Technology(石油化工), 1999, 28(2):120-124
[10]	Wang Haodong(王皓东).The advances of the third generation of polyolefin technologies[J].Petrochemical Industry Trends(石油化工动态), 1999, 7(3):29-33
[11]	Takakarhu J, Ding Ning(丁宁).Train of thought about development and design of BORSTAR bimodal polyethylene technology[J].Techno-Economics in Petrochemicals(石油化工技术经济), 2001(2):5-9
[12]	Martin U S, Heuchelheim E S, Alsbach-hahnlein R K.Process for producing ethylene copolymers under high pressure:US, 5969062.1999-10-19
[13]	Sugarland T N, La Porte W P, Webster D A D, Humble A G.Method for pressurizing a propylene polymerization reactor:US, 6214944B1.2001-04-10
[14]	Nivelles P M.Process for producing polyolefins:US, 6355741B1.2002-03-12
[15]	Brant P, Luft G F, Shutt G R, Smith L C, Mclain D J, Burkhardt T J.Polymer production at supercritical conditions:EP, 1539841A1.2005-06-15
[16]	Maartje Kemmere,Tjerk de Vries,Marius Vorstman,Jos Keurentjes.A novel process for the catalytic polymerization of olefins in supercritical carbon dioxide[J].Chemical Engineering Science, 2001,56:4197-4204
[17]	Mo Zhishen(莫志深), Zhang Hongfang(张宏放).Structure of Crystalline Polymers by X-ray Diffraction(晶态聚合物结构和X射线衍射)[M].2nd ed.Beijing:Science Press, 2010
[18]	Jones A T, Aizlewood J M, Beckett D R.Crystalline forms of isotactic polypropylene[J].Die Makromolekulare Chemie,1964, 75(1):134-158

Crystallographic behavior of nascent isotactic polypropylene produced under supercritical conditions

丙烯超临界聚合中原生晶特征

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

References 18

Related Articles 11

Recommended Articles

Metrics

Comments

[1]	ZHANG Tianyi, XIA Xianzhi, LIU Yuexiang. Effect of pre-contact temperature on performance of DQC spherical catalyst in propylene polymerization [J]. CIESC Journal, 2017, 68(4): 1434-1441.
[2]	WANG Jiajia, WANG Lixia, BIAN Ning, WANG Dongfang, WANG Yongzhen, ZHANG Yang, LI Qian, SHEN Changyu. Influence of shear history on morphology, microstructure and mechanical properties of micro injection molded parts [J]. CIESC Journal, 2015, 66(5): 1931-1938.
[3]	LOU Haichuan, SU Hongye, XIE Lei. Recurrent neural network integrated with process-priori-knowledge and its application [J]. CIESC Journal, 2013, 64(5): 1665-1673.
[4]	Lou Haichuan. Recurrent neural network integrated with process priori knowledge and its application [J]. , 2013, 64(5): 0-0.
[5]	SHI Yaoqi, XIN Zhong. Crystallization morphologies and non-isothermal crystallization kinetics of isotactic polypropylene modified by α/β compounded nucleating agents [J]. CIESC Journal, 2012, 63(4): 1274-1286.
[6]	XIN Zhong，SHI Yaoqi. Research advance in controlled crystallization of isotactic polypropylene based on α/β compounded nucleating agents [J]. Chemical Industry and Engineering Progree, 2012, 31(01 ): 126-132.
[7]	WANG Feng，GAO Jinji，CAI Jingbo. Construction of knowledge base of abnormal situation self-recovery system for propylene polymerization [J]. , 2009, 28(10): 1712-.
[8]	LIU Xinggao. Modeling and simulation of heterogeneous catalyzed propylene polymerization [J]. , 2007, 15(4): 545-553.
[9]	YANGZhensheng,LIPingli, CHANGHeying, WANGShichang. Effect of Diluent on the Morphology and Performance of IPP Hollow Fiber Microporous Membrane via Thermally Induced Phase Separation [J]. , 2006, 14(3): 394-397.
[10]	LUO Zhenghong, CAO Zhikai, SU Yaotang. Monte Carlo Simulation of Propylene Polymerization (Ⅰ) Effects of Impurity on Propylene Polymerization [J]. , 2006, 14(2): 194-199.
[11]	ZU Xiaojing，LIN Ge，CHEN Wei，JIANG Tao. Novel MgCl2/SiO2 complex support catalyst for propylene polymerization [J]. , 2006, 25(12): 1439-.