苯乙烯间规空间定向聚合

综述国外近年来苯乙烯间规定向聚合的进展,包括高活性催化剂和聚合规律的研究;介绍间规聚苯乙烯(s-PS)主要特性、应用和结构表征情况。     

苯乙烯间规聚合过程的搅拌功耗研究

采用新型均相茂金属催化剂体系[Cp*Ti(OPh)3／MAO／TIBA]催化苯乙烯间规聚合,研究了主催化剂浓度、惰性介质种类及加入量对聚合过程的影响,尤其是聚合中搅拌功耗的变化,并分析了搅拌功耗、结晶和聚合之间的关系。研究表明,问规聚苯乙烯在聚合过程中不断结晶,当固相质量分数高于第一临界点(XC1≈15％)后聚合体系的搅拌功耗迅速上升,在第二临界点(Xc2≈40％)处搅拌功耗出现峰值;决定搅拌功耗最本质的因素是体系的固相体积分数,产物颗粒形态的规整性直接影响了体系的固相体积分数。     

间规聚苯乙烯的合成与工业化研究

本文评述了间规聚苯乙烯（ｓＰＳ）的联合机理与工业化研究,介绍了茂金属催化剂和聚合反应器。强调要实现ｓＰＳ的工业化,尚需加强以聚合反应工艺和反应器开发为目标的聚合反应工程研究。     

Syndiospecific styrene polymerization with CpTiCl3/MAO: Effects of the order of reactant addition on polymerization and polymer properties

Syndiospecific styrene (St) polymerization, catalyzed by the CpTiCl₃/methylaluminoxane (MAO) system, was investigated using two different activation procedures. The polymerization parameters included polymerization time, temperature (～25–100°C), ratio of [Al]/[Ti] (～100–1000), and catalyst precursor concentration (～0.5–10.0 × 10^?4 mol Ti/L). It was found that adding reactants in the order of (CpTiCl₃ + MAO) + St (Injection of Styrene mode) gave much higher monomer conversion rates, higher weight‐average molecular weights, and narrower molecular weight distributions than for the (St + MAO) + CpTiCl₃ (Injection of Catalyst mode). The former also yielded significantly higher syndiotacticity fractions. Differential scanning calorimetry measurements showed multiple peaks exhibiting polymorphism in crystalline syndiotactic polystyrene samples. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1449–1455, 2004     

Preparation of syndiotactic polystyrene/montmorillonite nanocomposites via in situ intercalative polymerization of styrene with monotitanocene catalyst

Syndiotactic polystyrene (sPS)/montmorillonite nanocomposites were prepared via in situ intercalative coordination polymerization using mono‐(η⁵‐pentamethylcyclopenta‐ dienyl) tribenzyloxy titanium [Cp*Ti(OBz)₃] complex activated by methylaluminoxanes (MAO) and triisobutylaluminum (TIBA). The influences of polymerization conditions, such as the weight ratio of montmorillonite and styrene, temperature, and monomer concentration, on the preparation of sPS/montmorillonite nanocomposites was investigated. The intercalation spacing in the nanocomposites, as well as the exfoliation of the montmorillonite interlayers, was characterized with wide angle X‐ray diffraction (WAXD) and transmission electron microscopy (TEM). The dispersibility of the nanoscale elements depended on the polymerization conditions and the surfactant treatment. The crystallizability and thermal properties of these nanocomposites were determined by differential scanning calorimetry (DSC) analysis and thermogravimetric analysis (TGA). Experimental results indicated that the degree of crystallinity of the sPS nanocomposite increased with increasing montmorillonite content and with higher T_g and thermal decomposition temperature than pure sPS. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1412–1417, 2005     

茂钛催化剂合成及苯乙烯间规聚合

介绍了茂钛催化剂ＣｐＴｉ（ＯＰｈ）３（Ｃｐ为环戊二烯基）的合成。使用ＣｐＴｉ（ＯＰｈ）３／ＭＡＯ均相催化体系,研究了工艺条件对苯乙烯间规聚合的影响。初步探讨了以带有反应性功能基团的聚苯乙烯为载体,负载ＣｐＴｉＣｌ３后进行的苯乙烯间规聚合。同时采用了不同配体的ＣｐＴｉ（ＯＲ）３催化剂用于苯乙与乙烯或丙烯共聚合,得到的共聚产物是一类应用前景良好的工程塑料。     

Full‐range kinetic study on bulk syndiotactic polymerization of styrene with homogeneous metallocene catalysis

By choosing a proper agitator and reinforcing its stirring shear, powdery syndiotactic polystyrene (sPS) is prepared in a bulk precipitation process with two homogeneous metallocene catalyst systems [Cp*TiX₃/MAO/TIBA (X = Cl or OPhOMe)]. A full‐range kinetics study of the heterogeneous polymerization is performed in detail to produce this kind of powdery sPS in an industrial process. A typical curve of conversion versus time takes an S shape and an obvious acceleration phenomenon occurs in the middle stage of the polymerization, although the polymer–monomer gel is avoided. The viscous‐average molecular weight of sPS goes through a peculiar increasing–decreasing–increasing change during the bulk polymerization process. These phenomena are viewed in terms of the two‐phase polymerization mechanism and the overheating in particles during polymerization. The influence of the metallocene catalyst type and concentration, MAO/Ti ratio, triisobutyl aluminum (TIBA)/Ti ratio, and polymerization temperature on the polymerization kinetics are investigated. TIBA has dual effects on the polymerization. A small amount of TIBA in the catalyst system promotes polymerization, but more TIBA leads to a low molecular weight sPS. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2635–2643, 2002     

新型茂钛间规聚苯乙烯催化剂的研究

间规聚苯乙烯具有低比重、优良的电气特性、耐水解性、易成型以及良好的耐热性、耐化学药品性、尺寸稳定性,在未来的许多领域具有应用价值。上海石油化工研究院和中山大学已经完成了新型茂钛间规聚苯乙烯催化剂的研究,创制出具有自己专利技术的产品,产品性能已达到国外同类催化剂的先进水平,同时,还对聚合物的加工做了更深入的研究。     

A kinetic study of novel bimetallic titanocene catalyst for syndiospecific styrene polymerization

A kinetic study of a syndiospecific polymerization was performed with two kinds of catalysts: Cp*Ti(O(C₆H₄)CMe₂(C₆H₄)O)TiCp* [bimetallic system] and Cp*Ti(OMe)₃ [monometallic system]. The purpose of this study was to determine the reasons behind the high activity of a bimetallic catalyst system. The active site structures of the two kinds of catalysts appears to be similar to the cationic Ti [III] species having η⁵‐pentamethylcyclopentadienyl ligand, while the rate of the activation process of the bimetallic catalyst was found to be higher than that of the monometallic catalyst. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Investigation of ethylene and styrene copolymerization initiated with dinuclear constrained geometry catalysts holding polymethylene as a bridging ligand and indenyl as a cyclopentadienyl derivative

A series of polymethylene‐bridged dinuclear constrained geometry catalysts (CGC) [Me₂Si(Ind)(N^tBu) TiCl₂]₂[(CH₂)_n] ( 1 , n = 6; 2 , n = 9; 3 , n = 12) were synthesized to study the copolymerization of ethylene and styrene. The experiments display that the polymerization activity of the dinuclear catalysts increased in the order of 1 < 2 < 3 , which indicated that the dinuclear CGC with the longest methylene units as a bridge showed the greatest activity. According to the activity correlation with the monomer ratio, all the catalysts exhibited maximum polymerization activity at the monomer ratio of ([styrene]/[ethylene]) of 2. The dinuclear CGC 2 and 3 represented excellent characteristics of styrene reactivity while catalyst 1 represented considerably low styrene reactivity. The relation between the molecular weights of the polymers and the catalysts used in the polymerization is not straightforward. The steric interference in catalyst 1 , containing just six methylene bridges, can be applied to explain not only the strikingly decreased activity but also the very low styrene content in the copolymer. In contrast, the electronic effect seems to be more pronounced in manipulating the polymerization properties of catalysts 2 and 3 having nine and 12 methylene bridges, respectively. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2469–2474, 2003     

Poly(pent‐1‐ene) Synthesized with the Syndiospecific Catalyst i‐Pr(Cp)(9‐Flu)ZrCl2/MAO

1‐Pentene was polymerized with the syndiospecific catalyst system i‐PrC(Cp)(9‐fluorenyl)ZrCl₂/MAO. The molar mass of the resulting polymers depends strongly on the reaction temperature and decreases from M̄_w = 126 000 at 0°C to M̄_w = 46 000 at 100°C, but is more or less independent of the monomer and the MAO concentration. The influence of reaction temperature and concentrations of MAO and monomer on the type of end‐groups generated during the chain termination, as well as on the type of stereoerror, was investigated. The degree of tacticity was dependent on the polymerization temperature with [rrrr] > 0.99 at 0°C and [rrrr] = 0.75 at 100°C.     

Melting Properties of Syndiotactic Polystyrenes and Effect of Hydrogen on Molecular Weight Distribution

Summary: The melting properties of syndiotactic polystyrenes are significantly affected by the structural molecular properties of the polymers. The most important influences on the melting behavior are stereoregularity, molecular weight and molecular weight distribution of the polymers. The melting temperature is increased by an enhanced syndiotacticity at sufficiently high molecular weights and at narrow molecular weight distributions. The degree of syndiotacticity obtained primarily depends on the kind and structure of the cyclopentadienyl ligand of the transition metal catalyst, whereas the effect of the other ancillary ligands on stereoregularity is negligible at the same cyclopentadienyl ligand. At narrow molecular weight distributions with below 2.8 and at constant stereoregularities, the molecular weight has a remarkable effect on the melting behavior at weight‐average molecular weights lower than about 80 000 g · mol^?1, resulting in a significant decrease of the melting temperature until below 230 °C. The presence of hydrogen during polymerization leads to a significant shift to lower molecular weights at comparably small amounts of hydrogen, but results in the occurrence of an additional peak in the molecular weight distribution at larger hydrogen concentrations giving evidence for the formation of a second active polymerization site producing lower molecular weight polymers. At constant stereoregularity, the broadening of the molecular weight distribution leads to decreased melting temperatures and to improved flow properties of the syndiotactic polystyrenes with increasing shear rates at moderate molecular weight distributions.

Detailed molecular weight distributions of syndiotactic polystyrenes in dependence on the hydrogen concentration.     

Pressure effects on polymerization of syndiotactic polystyrene

Polymerization pressure has a direct effect on the synthesis of syndiotactic polystyrene (s-PS) with metallocene as a catalyst. The polymerization rate, yield rate, and average molecular weight show a linear relationship with pressure, that is, they all increase with increased polymerization pressure. However, under 1000 psi, the yield of s-PS increases with polymerization duration while the yield rate decreases. As a whole, this syndiotactic polymerization proceeds relatively fast in comparison with ordinary vinyl polymerization. Optimal conditions (pressure, temperature, and duration) for the synthesis of s-PS have been explored. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1747–1752, 1998     

Preparation and characterization of styrene/styryl–polyhedral oligomeric silsesquioxane hybrid copolymers

BACKGROUND: Organic–inorganic nanocomposites were prepared by copolymerization of various monomers and polyhedral oligomeric silsesquioxane (POSS) derivatives. Preliminary results showed that styrene/styryl–POSS copolymers could be obtained using CpTiCl₃ catalyst. In the work reported here, the copolymerization of styrene and styryl‐substituted POSS was studied in detail for a more effective catalyst, Cp*TiCl₃. RESULTS: The glass transition temperature (T_g) of the copolymers prepared increased with increasing POSS content. The degradation temperature (T_d) of the copolymers was 60 °C higher than that of syndiotactic polystyrene under nitrogen. Although the thermal properties were improved by incorporation of POSS, the catalytic activity decreased with POSS content. The racemic triad and syndiotactic index of the copolymers decreased with increasing POSS content. Gel permeation chromatograms of the copolymers exhibited multimodal distribution due to the presence of multi‐active centres, which were formed by interaction of Ti with the POSS siloxane linkage. CONCLUSION: With the incorporation of POSS, the thermal properties of polystyrene were improved. The styrene/styryl–POSS copolymers are formed through the various active sites arising from the interactions of Ti with POSS. Copyright © 2008 Society of Chemical Industry     

茂金属聚乙烯催化剂工业应用研究

北京化工研究院合成了50余种新型茂金属化合物,在茂金属催化剂均相乙烯聚合的系统研究基础上,深入研究了载体茂金属催化剂的制备方法和制备条件等因素与载体催化剂性能的关系,研制出性能优异的载体茂金属催化剂。采用载体茂金属催化剂进行了浆液法和气相法乙烯聚合中试研究,还进行了茂金属聚乙烯树脂的加工应用研究,树脂性能与国外同类产品相当。     

Influence of montmorillonite on syndiotactic polymerization behavior of styrene

The influence of montmorillonite (MMT) on the syndiotactic polymerization behavior of styrene was studied. To avoid the hydrophilic surface of the MMT coming into contact with the catalyst, which could poison it, SAN was introduced between the MMT and Cp*Ti (OCH₃)₃. MMT was introduced into the catalytic system as a supporter for the Ti catalyst (supported catalytic system) or just dispersed in the polymerization solvent directly (in situ polymerization system). The polymerization results showed that surface modification of MMT dramatically affected the catalytic activity as well as the syndiotacticity of the polymers. This is mainly explained by the insulator SAN preventing the formation of the inactive/little active species Si? O? Ti and other atactic active species resulting from the reaction of the ? OH on the MMT layer surface with Cp*Ti(OCH₃)₃. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

均相茂金属催化剂催化苯乙烯间规聚合中搅拌的作用

在不同搅拌型式的聚合反应器中使用均相茂金属催化剂（Cp^*Ti(OR)3/MAO/TIBA催化苯乙烯本体间规聚合。研究搅拌桨型式、反应器以及搅拌速度对聚合物形态以及聚合过程的影响,并分析了搅拌、结晶和聚合之间的关系。研究表明,良好的搅拌剪切对避免凝胶、促进粉状间规聚苯乙烯的生成至关重要。聚合动力学的研究表明,搅拌转速不仅能影响聚合物的颗粒形状,也能通过改变聚合物原生晶的结晶速率从而影响聚合速率。     

Investigation of styrene/1‐hexene copolymerization by homogeneous and heterogeneous bisindenyl ethane zirconium dichloride catalyst system

Homogeneous copolymerization of styrene and 1‐hexene was carried out in toluene at room temperature using bisindenyl ethane zirconium dichloride/methylaluminoxane (MAO). The supported catalyst was prepared with immobilization of Et(Ind)₂ZrCl₂/MAO on silica (calcinated at 500°C) with premixed method. Heterogeneous copolymerization of styrene/1‐hexene with different mole ratios was carried out in the presence of supported catalyst system. The copolymers obtained from homogeneous and heterogeneous catalyst system were characterized by ¹H NMR and ¹³C NMR. Composition of the resulting copolymers was determined by ¹H NMR data. Analysis of ¹³C NMR spectra of obtained copolymers by homogeneous and heterogeneous catalyst systems present isotactic olefin‐enriched copolymers. Molecular weight and thermal behavior of resulting copolymers was investigated. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 4008–4014, 2007     

Styrene/substituted styrene copolymerization by Ph2Zn–metallocene–MAO systems: homo‐ and copolymerization of p‐methoxystyrene with styrene

BACKGROUND: The present work is part of a general study regarding the homo‐ and copolymerization of styrene using diphenylzinc–additive initiator systems, with the aim of improving the properties of commercial atactic polystyrene. The study is focused on syndiotactic polystyrene and/or copolymers of styrene (S) with substituted styrene, styrene derivatives or various α‐olefins. This research has been ongoing over the last 15 years. RESULTS: The reported experiments show that binary metallocene–methylaluminoxane (MAO) and ternary Ph₂Zn–metallocene–MAO, depending on the metallocene employed, are capable of inducing both homo‐ and copolymerization of styrene and p‐methoxystyrene (p‐MeOS). The results indicate that for a styrene/p‐MeOS mole ratio with p‐MeOS > 25% the product obtained has only a minor incorporation of styrene units. The efficiency of the metallocenes studied follows the order bis(n‐butylcyclopentadienyl)titanium dichloride ((n‐BuCp)₂TiCl₂) > indenyltitanium trichloride (IndTiCl₃) > Cp₂TiCl₂. CONCLUSION: Metallocenes (n‐BuCp)₂TiCl₂, Cp₂TiCl₂ and IndTiCl₃ in binary systems combined with MAO, as well as in ternary systems combined with Ph₂Zn and MAO, induce the homopolymerization of p‐MeOS and its copolymerization with styrene. The styrene/p‐MeOS copolymer obtained was enriched in p‐MeOS with respect to the initial feed, in agreement with the I+ inductive effect of the methoxy group in the para position of styrene. As already reported, the role of Ph₂Zn was nullified by its complexation with the p‐MeOS comonomer. Copyright © 2008 Society of Chemical Industry     

Modeling of Ethylene‐Norbornene Copolymer Microstructure in Solution Polymerization with Homogeneous Metallocene Catalysts

Summary: The microstructure of ethylene‐norbornene copolymer produced in solution polymerization is analyzed through kinetic modeling and experiments using homogeneous rac‐Et(1‐indenyl)₂ZrCl₂/methylaluminoxane catalyst in toluene at 70 °C. The sequence distribution function and average chain length equations are derived for terminal model and penultimate model. The model simulations show that both models provide similar predictions of average copolymer composition, especially at low norbornene concentration in the copolymer. However, at higher norbornene concentrations the penultimate model yields much better predictions of norbornene sequence length distribution than the terminal model. The terminal model has been inadequate in describing the copolymerization rate, whereas the penultimate model yields excellent predictions of rate behavior. The model calculations also indicate that at norbornene concentration in the copolymer larger than about 10 mol‐%, the maximum ethylene block length is smaller than 70, prohibiting the formation of crystalline copolymer.

Ethylene sequence distribution curves at different mol‐% of norbornene in copolymer.