给电子体对VOCl_3/Al_2Et_3Cl_3催化的乙丙橡胶结构和性能的影响

采用VOCl_3/Al_2Et_3Cl_3体系催化乙烯-丙烯共聚合合成乙丙橡胶(EPR),考察了给电子体苯甲酸乙酯和邻苯二甲酸二异丁酯对EPR结构和性能的影响。结果表明,少量给电子体的加入可以明显提高VOCl_3/Al_2Et_3Cl_3催化乙烯-丙烯共聚合的催化活性,随着给电子体加入量的增大,催化活性反而下降; 给电子体的加入并未引入结晶的长序列乙烯嵌段,仅提高了产物的相对分子质量; 给电子体的加入提高了丙烯单体的共聚能力,使EPR的丙烯结合量增加。     

以钕系催化剂催化月桂烯与丁二烯高顺式1,4-共聚合（英文）

首先以Nd(P_(204))_3/Al(i-Bu)_2H/Al_2Et_3Cl_3体系合成了分子量分布较窄的聚丁二烯,利用该体系的活性聚合特征,在聚合体系中加入月桂烯单体,制备了丁二烯与月桂烯的嵌段共聚物。结果表明,该催化体系在50℃下具有较高的催化活性。当共聚单体丁二烯与月桂烯的摩尔比(n_(Bd)/n_(MY))从3/1下降至1/2时,共聚物分子量从3700g/mol增加到7800g/mol,而凝胶渗透色谱(GPC)曲线仍然呈现单峰窄分布,说明形成了月桂烯与丁二烯共聚物;当nBd/nMY为1/3时,部分月桂烯发生了均聚,GPC曲线变成双峰,分子量分布变宽。     

Spheripol工艺生产高抗冲聚丙烯

介绍了Spheripol工艺生产高抗冲聚丙烯产品的方法,采用两步复合工艺生产嵌段聚丙烯,第1步采用环管反应器进行丙烯液相均聚反应,第2步采用流化床反应器进行丙烯均聚物与乙烯单体气相共聚反应,即在气相反应器中,利用来自环管反应器中的均聚物的残余活性,加入乙烯和补充的丙烯及氢气实现乙-丙共聚,共聚物的生成使最终产品的抗冲性能大大提高,尤其是低温下的抗冲性能。     

不同内给电子体催化剂对乙烯和丙烯共聚合的影响

研究了MgCl2/TiCl4/邻苯二甲酸二异丁酯和MgCl2/TiCl4/9,9-二甲氧基甲基-芴两种催化剂体系催化乙烯和丙烯共聚合的规律、共聚物的热性能及动态力学性能。两种催化剂在40℃催化乙烯和丙烯共聚合时,催化剂活性随着乙烯含量的增加先增后降。对于含有二酯型内给电子体的催化剂,n(C2H4)为10%时,催化剂活性最大;对于含有二醚型内给电子体的催化剂,n(C2H4)为30%时,催化剂活性最大,且二醚型催化剂的活性高于二酯型催化剂。在乙烯含量较低时,用二酯型催化剂催化合成的共聚物中含有更多的嵌段结构,而二醚型催化剂催化合成的共聚物更趋于无规结构。当反应气中乙烯占多数时,共聚物不再具有长的聚丙烯链段,而出现长的聚乙烯链段。     

丙烯与极性单体嵌段共聚合的研究进展

综述了近年来聚丙烯基嵌段共聚物合成方法的研究进展。通过选用合适的Ti催化剂能够直接催化丙烯与降冰片烯和/或甲基丙烯酸甲酯进行聚合,从而通过活性聚合的方式直接得到聚丙烯基嵌段共聚物。合适的聚合条件下,链转移剂的加入能够在聚合过程中产生金属―C键,再经氧化酸化后得到末端羟基,实现聚丙烯的端基功能化。将端基功能化与可控自由基反应、点击反应、偶联反应相结合能够得到聚丙烯基嵌段共聚物。通过催化剂的结构优化设计,配合合适的链转移剂,能够调控聚丙烯基嵌段共聚物的结构。     

膦氮配体半茂钛体系催化乙烯均聚合及乙烯与丙烯共聚合

合成了两种配合物中含有膦、氮的半茂钛催化剂,研究了甲基铝氧烷、四(五氟苯基)硼酸盐为助催化剂,不同n(Al)∶n(Ti)对乙烯均聚合及聚合物相对分子质量及其分布的影响。研究了催化剂用量、原料配比、反应压力、反应时间对乙烯与丙烯共聚合及共聚物组成、相对分子质量及其分布的影响。结果表明:合成的膦氮配体半茂催化剂可有效催化乙烯均聚合,在常压下,聚合活性可达0.62×10~6 g/(mol·h),也可以有效催化乙烯与丙烯共聚合,与高活性茂金属催化剂催化效率相近;用该催化剂制备的高相对分子质量乙丙共聚物的相对分子质量分布窄,符合单活性中心催化剂的特点;共聚物的序列结构研究表明,乙烯与丙烯竞聚率之积接近1,共聚物无规性好。     

茂金属催化剂使α-高碳烯和环烯成为新聚烯烃的共聚单体

90年代聚烯烃技术的最大突破是茂金属催化剂的开发和利用。人们使用茂金属催化剂开发了从前不能合成的新的烯烃共聚物,它使α-高碳烯(HAO)和环烯与乙烯和丙烯的有效共聚成为可能,在其活性反应中心和共聚单体几乎能百分之百地聚合,这是传统齐格勒催化剂做不到的,因为后者只能使乙烯或丙烯比其它较重的共聚单体聚合速度更快。     

丙烯/1-丁烯聚合物合金的单体组成切换法制备：动力学及聚合器模型

采用球形负载型Ziegler-Natta催化剂和单体组成周期性切换的丙丁淤浆共聚合技术,原位制备了聚丙烯/丙丁共聚物合金。将共聚动力学的矩模型与物料衡算相结合,首次建立了单体组成切换的共聚反应器模型。依据实验所得的丙烯实时消耗速率拟合得到模型参数,并模拟计算了不同单体组成切换频率下的聚合反应活性和聚合产物的组成。结果表明,模型能很好地描述各切换频率下丙烯的聚合速率曲线、催化聚合活性,以及合金中1-丁烯的总含量、丙丁无规共聚物的含量和“嵌段”共聚物的含量等。结果还显示,共聚过程中丙烯的脉冲进料有利于提高单体向活性中心的扩散,进而提高聚合速率和聚合活性。     

抗冲聚丙烯结构与性能研究

对部分国内外抗冲聚丙烯(PP)产品进行了微观形态和结构分析，研究其对材料宏观力学性能的影响。实验结果表明：抗冲PP是一个含有PP均聚物、丙烯与乙烯-丙烯两嵌段共聚物、乙丙橡胶(EPR)、聚乙烯均聚物等的多相体系。EPR的分子序列结构对聚合物抗冲击性能起主要作用。在序列结构中，丙烯、乙烯单体在分子链上的位置交换越频繁，抗冲击性能越得到提高。丙烯序列平均长度的增大对抗冲击性能有一定的削弱作用。     

酚氧基单茂钛／MAO体系催化乙烯／丙烯共聚合反应规律研究

采用合成的催化荆环戊二烯基-(2,6-二畀丙基)幕氧基-二氯化钛{Cp[OC6H3(iPr)2]TiCl2}与甲基铝氧烷(MAO)组成的新型催化体系进行了乙烯/丙烯共聚合,考察了气体配比、聚合温度、助催化剂浓度、聚合压力等因素对共聚合活性及产物相对分子质量、组成的影响.结果表明.CpTi [OC6H3(iPr)2]Cl2/MAO体系是引发乙烯/丙烯共聚合适宜的催化体系.     

Influence of the catalyst matrix structure of the supported Ziegler-Natta catalysts on the homo- and copolymerization of olefins

The vanadium catalytic complexes immobilized on the same support (aluminium hydroxide, AH) and distinguished by structure and composition have been compared for ethylene and propylene homo- and copolymerization to find relationship between the polymerization activity, copolymerization relative reactivity of comonomers and the supported catalyst structure. The catalytic complexes of vanadium with supported aluminoxanes (II) and catalysts with dispersed solid phase of vanadium compounds on the support surface (III) are more active than catalyst (I) in which vanadium has the covalent bond with surface of support. The relative reactivity of comonomers in copolymerization also depends on type of supported catalyst. The catalysts III unlike I and II can produce the ethylene and propylene copolymers with high content of propylene. The promoting effect of propylene on ethylene polymerization rate takes place only in the presence of catalysts III. Received: 2 October 1996/Revised: 17 January 1997/Accepted: 23 January 1997     

Influence of the nature of monomers on the activity of supported titanium catalysts in the α-olefin polymerization

Summary Ethylene and propylene co-polymerization and sequential polymerization with high activity supported titanium catalysts were studied. Specific rate of homopolymerization and copolymerization constants for ethylene and propylene were determined by using the derived values of the solubility constants for monomers in nascent polymers. The reason of the increased rate of co-polymerization upon enriching the monomers mixture with propylene, the effect of activation of ethylene polymerization upon preliminary polymerization of propylene may be in the increasing number of active sites due to enlarged content of amorphous phase in the nascent polymer product.     

Hydrogen effect on the molecular weight distribution of polymers obtained by polymerization of ethylene and α-olefins over supported titanium-magnesium catalysts

Comparative data on the molecular weight distribution of polymers obtained by polymerization of ethylene, propylene and 1-hexene, and copolymerization of ethylene with α-olefins over the titanium-magnesium catalysts (TMC) in the absence and presence of hydrogen are presented. In contrast to the ethylene polymerization, in the cases of propylene and 1-hexene polymerization and copolymerization of ethylene with α-olefins, the hydrogen addition is characterized by noticeable narrowing of the molecular weight distribution (MWD) due to lower contribution of the MWD component with high molecular weight. This result is an evidence of the increased reactivity of TMC active sites producing high molecular weight poly-α-olefins and copolymers of ethylene with α-olefins in the chain transfer reaction with hydrogen. It is suggested that the increased reactivity of these sites in the transfer reaction with hydrogen appears after the 2,1-addition of α-olefin to the growing polymer chain.     

Comparative study of copolymerization and terpolymerization of ethylene/propylene/diene monomers using metallocene catalyst

(Ind)₂ZrCl₂ catalyst was synthesized and used for copolymerization of ethylene and propylene (EPR) and terpolymerization of ethylene propylene and 5‐ethyldiene‐2‐norbornene (ENB). Methylaluminoxane (MAO) was used as cocatalyst. The activity of the catalyst was higher in copolymerization of ethylene and propylene (EPR) rather than in terpolymerization of ethylene, propylene and diene monomers. The effects of [Al] : [Zr] molar ratio, polymerization temperature, pressure ratio of ethylene/propylene and the ENB concentration on the terpolymerization behavior were studied. The highest productivity of the catalyst was obtained at 60°C, [Al] : [Zr] molar ratios of 750 : 1 and 500 : 1 for copolymerization and terpolymerization, respectively. Increasing the molar ratio of [Al] : [Zr] up to 500 : 1 increased the ethylene and ENB contents of the terpolymers, while beyond this ratio the productivity of the catalyst dropped, leading to lower ethylene and ENB contents. Terpolymerization was carried out batchwise at temperatures from 40 to 70°C. Rate time profiles of the polymerization were a decay type for both copolymerization and terpolymerization. Glass transition temperatures (T_g) of the obtained terpolymers were between ?64 and ?52°C. Glass transition temperatures of both copolymers and terpolymers were decreased with increased ethylene content of the polymers. Dynamic mechanical and rheological properties of the obtained polymers were studied. A compounded EPDM showed good thermal stability with time. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Influences of copolymerization conditions on the structure and properties of isotactic polypropylene/ethylene–propylene random copolymer in situ blends

A spherical TiCl₄/MgCl₂‐based catalyst was used in the synthesis of in situ isotactic polypropylene/ethylene–propylene random copolymer blends by propylene bulk polymerization and subsequent gas‐phase copolymerization of ethylene with propylene. Different copolymerization conditions, such as the reaction time, monomer pressure, and composition, were investigated, and their influences on the structure and properties of the products were studied. Raising the monomer pressure was the most effective way of speeding up the copolymerization, but it caused more increases in the random copolymer than the block copolymer fractions. Increasing the ethylene content of the monomer feed also resulted in higher reaction rates and copolymer contents, but the ethylene contents of both the random and block copolymer fractions were also raised. In situ blends that contain more than 50 wt % copolymer were prepared. The mechanical properties of the blends, including the impact strength and flexural modulus, were regulated in a rather broad range with changes in the copolymerization conditions. The properties were highly dependent on the amount, distribution, and chain structure of the copolymer fractions. The impact strength was influenced by both the random copolymer and block copolymer portions in a complicated way, whereas the flexural modulus was mainly determined by the amount of random copolymer. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 445–453, 2002; DOI 10.1002/app.10415     

新型Ziegler-Natta催化剂用于丙烯多段聚合制备抗冲聚丙烯

聚丙烯（PP）质轻、价廉,具有良好的加工性能,应用范围广泛．PP的很多应用领域要求它应具有较好的韧性．均聚PP在低温时变脆,抗冲PP是通过在均聚PP中加入橡胶制备的．对PP以提高其抗冲击强度为目的的改性大多用共混的方法,将PP和两种或两种以上的其他聚合物以机械共混的方法进行混合,得到一种宏观上均匀的聚合物共混物,其性能有一定的提高．     

Radiation-induced copolymerization of α,β,β-trifluoroacrylonitrile with α-olefin

Homopolymerization and copolymerization of α,β,β-trifluoroacrylonitrile (FAN) with γ-olefins were carried out in bulk by γ-ray irradiation at 25°C. FAN gives very small quantities of brown and greasy low molecular weight polymer. Cyano groups in FAN polymer were found to be readily hydrolyzed to acid amide groups in the atmosphere. FAN was found to copolymerize with ethylene, propylene, and isobutylene via a radical mechanism to form equimolar copolymers in a wide range of monomer compositions. The polymerization rate increases linearly with FAN fraction in the monomer mixture. These copolymers are also hydrolyzed in the atmosphere, and the hydrolysis proceeds with more difficulty for the copolymer with higher α-olefin. The reactivity ratios r₁ (FAN) and r₂ (α-olefin) were determined to be 0.01 and 0.12 for the FAN/ethylene copolymerization and 0.01 and 0.07 for the FAN/propylene copolymerization. These results confirm that an alternating copolymerization takes place in the FAN/α-olefin system.     

Dynamic modeling and experimental evaluation of olefin copolymerization with vanadium‐based catalysts

In this study, we developed a mathematical model for olefin copolymerization using soluble Ziegler–Natta catalysts in a semibatch reactor to predict the reaction rate and polymer characteristics (i.e., molecular weight, polydispersity, and ethylene content) as functions of the reaction parameters (i.e., time, temperature, pressure, concentrations, and so on) accurately. The proposed model differs from others because it considers the olefin copolymerization as a dynamic process and applies double moments for two reactants (ethylene and propylene) in the presence of hydrogen. To establish the model validity, the copolymerization was performed with VOCl₃? Al₂Et₃Cl₃ systems with hydrogen as a molecular weight controlling agent. The dynamic model was able to reproduce the experimental data within experimental accuracy and accurately demonstrated the fundamental importance of the polymerization variables on the final properties of the polymer material in the copolymerization of ethylene and propylene with Al/V ratios of up to 28 before synthesis. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3101–3110, 2006     

茂金属催化乙丙共聚进展

综述了茂金属催化乙丙共聚的研究 ,包括乙丙共聚物的合成、表征、反应机理及工业化进展。着重介绍了茂金属催化乙丙共聚物的结构和性能的研究成果。