Ethylene copolymerization with cyclic dienes using rac‐Et[Ind]2ZrCl2–Methylaluminoxane

The effect of the copolymerization temperature and amount of comonomer in the copolymerization of ethylene with 1,3‐cyclopentadiene, dicyclopentadiene, and 4‐vinyl‐1‐cyclohexene and the rac‐Et[Ind]₂ZrCl₂–methylaluminoxane metallocene system was studied. The amount of comonomer present in the reaction media influenced the catalytic activity. Dicyclopentadiene was the most reactive comonomer among the cyclic dienes studied. In general, copolymers synthesized at 60 °C showed higher catalytic activities. Ethylene–dicyclopentadiene copolymers with high comonomer contents (>9%) did not show melting temperatures. 1,3‐Cyclopentadiene dimerized into dicyclopentadiene during the copolymerization, giving a terpolymer of ethylene, cyclopentadiene, and dicyclopentadiene. A complete characterization of the products was carried out with ¹H NMR, ¹³C NMR, heteronuclear chemical shift correlation, differential scanning calorimetry, and gel permeation chromatography. © 2002 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 471–485, 2002; DOI 10.1002/pola.10133     

Synthesis of Various Functional Propylene Copolymers Using rac‐Et[1‐Ind]2ZrCl2/MAO as the Catalyst System

Propylene copolymers with different polar groups were synthesised using rac‐Et[1‐Ind]₂ZrCl₂/MAO as the catalyst system. 10‐Undecen‐1‐ol, 10‐undecenoyl chloride, 10‐undecenoic acid, 2‐(9‐decen‐1‐yl)‐1,3‐oxazoline, 2‐(9‐decen‐1‐yl)‐4,4‐dimethyl‐1,3‐oxazoline, and 2‐[4‐(10‐undecene‐1‐oxy)phenyl]‐1,3‐oxazoline were used as comonomers. The addition of water to the 10‐undecenoyl chloride copolymer solution led to an acid‐functionalised copolymer. In the case of 2‐(9‐decen‐1‐yl)‐1,3‐oxazoline and its homopolymers, polymerisation temperature was varied. Up to 0.61 mol‐% comonomer were incorporated into the poly(propylene)s. The catalyst activities for 10‐undecen‐1‐ol, 10‐undecenoyl chloride and 10‐undecenoic acid were much higher than for the oxazoline comonomers.     

载体化Et(Ind)2ZrCl2催化乙烯-苯乙烯共聚

用均相亚乙基二(1-茚基)二氯化锆(Et(Ind)₂ZrCl₂)催化乙烯和苯乙烯共聚时,所得共聚物中苯乙烯链节含量和聚合活性不能同时满足聚乙烯功能化的要求^[1,2].因此我们用SiO₂对Et(Ind)₂ZrCl₂进行载体化.     

Insights into propylene/ω‐halo‐α‐alkenes copolymerization promoted by rac‐Et(Ind)2ZrCl2 and (pyridyl‐amido)hafnium catalysts

This article discussed the root causes of the interesting differences between rac‐Et(Ind)₂ZrCl₂ and dimethyl (pyridyl‐amido)hafnium in catalyzing the propylene/ω‐halo‐α‐alkene copolymerization. Confirmed by density functional theory (DFT) calculations, the larger spacial opening around the active center of rac‐Et(Ind)₂ZrCl₂ contributes to the coordination and insertion of the monomers, resulting in the higher catalytic activity, while the narrow spacial opening around the Hf center retards the chain transfer reaction, leading to the much higher molecular weights (M_ws) of the copolymers. The superior tolerability of Zr catalyst toward halogen groups might be attributed to that the dormant species generated from halogen coordination could be promptly reactivated. DFT calculations indicated the higher probability for the ω‐halo‐α‐alkene vinyl to coordinate with the Hf catalyst leading to the better ability to incorporate halogenated monomers. The high M_ws and the outstanding isotacticity achieved by the Hf catalyst determined the higher melting temperature values of the copolymers with a certain amount of halogen groups. In addition, the chain transfer schemes were employed to analyze why the presence of halogenated monomers greatly decreased the M_ws of the copolymers when rac‐Et(Ind)₂ZrCl₂ was used, while had no or little effect upon the M_ws in the copolymerization by the Hf catalyst. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3421–3428     

Copolymerization of propylene with 1‐octene catalyzed by rac‐Me2Si(2,4,6‐Me3‐Ind)2ZrCl2/methyl aluminoxane

The copolymerization of propylene with 1‐octene was carried out with rac‐dimethylsilylbis(2,4,6‐trimethylindenyl)zirconium dichloride as a catalyst activated by methylaluminoxane (MAO) and an MAO/triisobutylaluminum mixture. The copolymerization conditions, including the polymerization temperature, Al/Zr molar ratio, and 1‐octene concentration in the feed, significantly influenced the catalyst activity, 1‐octene incorporation, polymer molecular weight, and melting temperature. The addition of 1‐octene to the polymerization system caused a decrease in the activity, whereas the melting temperature and intrinsic viscosity of the polymer increased. The microstructure of the propylene–1‐octene copolymer was characterized by ¹³C NMR, and the reactivity ratios of the copolymerization were estimated from the dyad distribution of the monomer sequences. The amount of regioirregular structures arising from 2,1‐ and 1,3‐misinserted propylene decreased as the 1‐octene content increased. The influence of the propagation chain on the polymerization mechanism is proposed to be the main reason for the changes in the reactivity ratios and regioirregularity with the polymerization conditions. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4299–4307, 2000     

Copolymerization of propylene with various higher α‐olefins using silica‐supported rac‐Me2Si(Ind)2ZrCl2

The copolymerization of propylene with 1‐hexene, 1‐octene, 1‐decene, and 1‐dodecene was carried out with silica‐supported rac‐Me₂Si(Ind)₂ZrCl₂ as a catalyst. The copolymerization activities of the homogeneous and supported catalysts and the microstructures of the resulting copolymers were compared. The activity of the supported catalyst was only one‐half to one‐eighth of that of the homogeneous catalyst, depending on the comonomer type. The supported catalyst copolymerized more comonomer into the polymer chain than the homogeneous catalyst at the same monomer feed ratio. Data of reactivity ratios showed that the depression in the activity of propylene instead of an enhancement in the activity of olefinic comonomer was responsible for this phenomenon. We also found that copolymerization with α‐olefins and supporting the metallocene on a carrier improved the stereoregularity and regioregularity of the copolymers. The melting temperature of all the copolymers decreased linearly with growing comonomer content, regardless of the comonomer type and catalyst system. Low mobility of the propagation chain in the supported catalyst was suggested as the reason for the different polymerization behaviors of the supported catalyst with the homogeneous system. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3294–3303, 2001     

Copolymerization of Ethylene and Propylene Using Silicon Tetrachloride‐Modified Silica/MAO with Et[Ind]2ZrCl2 Metallocene Catalyst

For the copolymerization of ethylene with propylene or a higher α‐olefin, using Et[Ind]₂ZrCl₂ metallocene catalyst, modification of silica with silicon tetrachloride prior to MAO adsorption can increase the activity, which is more pronounced for ethylene/1‐hexene copolymerization at higher pressure and temperature. The molecular weight of the copolymer produced was lower and the polydispersity tends to be decreased. No significant effect of SiCl₄ addition on the microstructure and the chemical composition distribution of the copolymer produced was observed.     

Synthesis of ethylene‐1‐hexene copolymers from ethylene stock by tandem action of bis(2‐dodecylsulfanyl‐ethyl) amine‐CrCl3 and Et(Ind)2ZrCl2

In this work, ethylene‐1‐hexene copolymers were synthesized with a tandem catalysis system that consisted of a new trimerization catalyst bis(2‐dodecylsulfanyl‐ethyl) amine‐CrCl₃/MAO ( 1 /MAO) and copolymerization catalyst Et(Ind)₂ZrCl₂/MAO ( 2 /MAO) at atmosphere pressure. Catalyst 1 trimerized ethylene with high activity and excellent selectivity in the presence of a relatively low amount of MAO. Catalyst 2 incorporated the 1‐hexene content and produced ethylene‐1‐hexene copolymer from an ethylene‐only stock in the same reactor. Adjusting the Cr/Zr ratio and reaction temperature yielded various branching densities and thus melting temperatures. However, broad DSC curves were observed when low temperatures and/or high Cr/Zr ratios were employed due to an accumulation of 1‐hexene component and composition drifting during the copolymerization. It was found that a short pretrimerization period resulted in more homogeneous materials that gave unimodal DSC curves. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3562–3569, 2007     

Ethylene/hexene copolymerization with the heterogeneous catalyst system SiO2/MAO/rac‐Me2Si[2‐Me‐4‐Ph‐Ind]2ZrCl2: The filter effect

The main focus of this study is the ethylene/hexene copolymerization with the silica supported metallocene SiO₂/MAO/rac‐Me₂Si[2‐Me‐4‐Ph‐Ind]₂ZrCl₂. Polymerizations were carried out in toluene at a reaction temperature of 40°C–60°C and the cocatalyst used was triisobutylaluminium (TIBA). The kinetics of the copolymerization reactions (reactivity ratios r_E/H, monomer consumption during reaction) were investigated and molecular weights M_w, molecular weight distributions MWD and melting points T_m were determined. A schematic model for the blend formation observed was developed that based on a filtration effect of monomers by the copolymer shell around the catalyst pellet.     

Stopped‐flow polymerizations of ethene and propene in the presence of the catalyst system rac‐Me2Si(2‐methyl‐4‐phenyl‐1‐indenyl)2ZrCl2/methylaluminoxane

The kinetics of ethene and propene polymerization at 20–60°C in the presence of the homogeneous catalyst system rac‐Me₂Si(2‐methyl‐4‐phenyl‐1‐indenyl)₂ZrCl₂/methylaluminoxane was investigated by means of stopped‐flow techniques. The specific rate of chain propagation, measured at the very short reaction times typical of this method, turned out to be ≈10² times higher for ethene than for propene; this suggests that diffusion limitations through the poly(ethylene) precipitating at longer reaction times may be responsible for the fact that the two monomers polymerize instead at comparable rates under “standard” conditions. It was also found that the concentration of active sites is significantly lower than the analytical Zr concentration.     

rac-Me_2Si(Ind)_2ZrCl_2负载型催化剂催化丙烯等规聚合的研究

将rac Me2 Si(Ind) 2 ZrCl2 与甲基铝氧烷 (MAO)预络合后负载于SiO2 上得到了高活性的负载型茂金属催化剂 ,并用于丙烯等规聚合 ,研究了 [Al]/ [Zr]比、聚合温度对聚合活性、产物分子量、聚合动力学的影响 ,同时与相应的均相体系进行比较 .结果表明 ,负载化后 ,活性中心的稳定性提高 ,所得聚合物的分子量也明显高于均相体系 .同时用13 C NMR测定了两种催化体系所制备的等规聚丙烯的微结构 .结果发现 ,负载型茂金属催化剂制得的聚丙烯立构选择性高于均相体系 ,其五元组立构序列 [mmmm]从均相的 82 0 %提高到负载的 86 3 % .同时区域选择性也有所改进 ,2 ,1 插入、1 ,3 插入分别从均相体系的 4 4‰和 1 9‰降到负载体系的 3 7‰和 0 5‰ .     

COPOLYMERIZATION OF ETHYLENE WITH 1-OCTENE USING Et(Ind)2ZrCl2/MAO CATALYST

Copolymerization of ethylene/1-octene was carried out in toluene withvarious concentrations of comonomer in the feed using Et(Ind)_2ZrCl_2/MAO (methyl alu-minoxane) as catalyst. It was found that with the increase of 1-octene concentration in thefeed the content of 1-octene in the copolymer increases, while the density, melting point,crystallinity and intrinsic viscosity of copolymer decrease. A copolymer with very lowdensity, containing 11.5 mol% of 1-octene (VLLDPE) can be produced with this catalystsystem. The effect of temperature and zirconium aluminum mole ratio of the catalyst onthe copolymerization was also investigated. The results of ~(13)C NMR determination of thecopolymer showed that the 1-octene units in the copolymer are principally isolated.     

UV‐Visible Spectroelectrochemical Detection of Side‐Reactions in the Hexacyanoferrate(III)/(II) Electrode Process

Hexacyanoferrate(III)/(II) system has been studied by UV‐visible long‐pathway spectroelectrochemistry. Three different methodologies, based on potentiodynamic techniques, have been successfully used in the thermodynamic characterization of the system. Formation of soluble Prussian Blue has been detected during the electrode process. The values of the formal potential (E^0′=0.200 V) and the electron stoichiometry of this side‐reaction (n=0.5) have been obtained.     

MgCl_2负载双金属复合催化剂制备宽分子量分布聚乙烯

聚乙烯的分子量和分子量分布对其熔体的流变性能和产品的力学性能有显著影响．分子量分布的变化,尤其是分子量分布末端部位的变化,都会对材料的注塑行为产生大的影响［１］．为了控制Ｚｉｅｇｌｅｒ催化剂制备的聚乙烯分子量分布而改善聚合工艺的报道很多［２～４］,工业生产中可利用多步聚合工艺来获得宽分子量分布的聚乙烯［５,６］,但这种方法工艺复杂,成本高．美国ＵＣＣ公司利用复合的ＴｉＶ和ＺｒＶ催化剂在气相法Ｕｎｉｐｏｌ工艺装置上首次成功的合成出了双峰高分子量聚乙烯产品［７,８］,由于采用Ｕｎｉｐｏｌ生产工艺…     

球形MgCl2负载的MAO/rac-Et[Ind]2ZrCl2催化剂催化丙烯 聚合

采用只在球形MgCl2上负载MAO,聚合前再同rac--Et[Ind]2ZrCl2预混的负载方式进行丙烯聚合。在少量AlEt3的活化下,很低的Al(MAO)/Zr摩尔比时即可获得比均相催化剂高一个数量级的活性,考察了温度、压力、Al(MAO)/Zr摩尔比和催化剂浓度对聚合的影响,同时用13^CNMR测定了均相和载体催化体系所制备的聚丙烯的微结构,发现负载型茂金属催化剂制得的聚丙烯立构规整性高于均相体系,其五元组立构序列[mmmm]可从均相的52.6%提高到负载催化剂的79.5%。扫描电镜观察表明,聚合物颗粒可较好地复制球形催化剂的颗粒形态。     

Ind2ZrCln(OC6H3-3,5-Me2)2-n/一氯二乙基铝催化乙烯齐聚的研究

合成了 Ind2 Zr(OC6 H3- 3,5 - Me2 ) 2 (A)、 Ind2 Zr Cl(OC6 H3- 3,5 - Me2 ) (B)和 Ind2 Zr Cl2 (C) 3个化合物 ,并在不同反应温度、陈化温度、反应时间等条件下 ,分别考察了每个化合物与 Et2 Al Cl所组成的催化体系对乙烯齐聚活性和选择性的影响 .在相同条件下 ,催化剂活性顺序为 A>B>C;在最佳反应条件下 ,Ind2 Zr(OC6 H3- 3,5 - Me2 ) 2的催化活性为 195 1g齐聚物 / (g Zr· h) ,C4～ 1 0 烯烃选择性为 95 .0 % ,1- C4～ 1 0 =(直链 α-烯烃 )选择性为 85 .5 % .     

Propene polymerization catalyzed over MCM-41 and VPI-5-supported Et(ind)2ZrCl2 catalysts

Et(ind)₂ZrCl₂ (C₂H₅(indenyl)₂ZrCl₂) confined inside regular pores of molecular sieves MCM-41 and VPI-5 were prepared and used to polymerize propene with high activity. Stereoregularity, melting point and molecular weight of polypropene obtained were increased and the polymerization behavior was quite different from that prepared with homogeneous Et(ind)₂ZrCl₂. The small, regular and cylindrical pores of MCM-41 and VPI-5 suppress the formation of inactive binuclear complexes between metallocene and metallocene, or between metallocene and methylaluminoxane, resulting in stable active sites and high activity in propene polymerization.