双金属氧联醇盐催化环硫丙烷的开环聚合

研究了环硫丙烷以铝锌双金属氧联醇盐为催化剂在甲苯中的聚合动力学及分子量分布。结果表明,环硫丙烷的聚合速度对单体浓度是二级关系,对催化剂浓度是半级关系。聚合系统中催化剂存在缔合,认为环硫丙烷以双分子配位增长。测得聚合活化能为12.2±0.5kcal/mol,计算了单体及溶剂的链转移常数。通过淋洗液中加氯化锂的GPC工作研究了分子量及其分布随转化率的变化。     

RING OPENING POLYMERIZATION OF PROPYLENE SULFIDE BY RARE EARTH COORDINATION CATALYSTS*

Ring opening polymerization of propylene sulfide using rare earth coordination catalysts has been investigated for the first time. It has been found that trinary rare earth coordination catslysts composed of rare earth compounds of phosphonate, naphthenate or acetylacetonate, trialkyl sluminum and water are effective catalysts for the polymerization of propylene sulfide. The polymerization in toluene is a homogeneous reaction. High molecular weight as high as several million poly(propylene sulfide) with high yield can be prepared by these catalysts. Kinetic studies showed that the polymerization rate is of first order with respect to both monomer concentration and catalyst concentration. The activation energy of the polymerization reaction is 61.4 k fJ/mol. The structure of the polymers so obtained has also been characterized by ~(13)C NMR spectroscopy, X-ray diffraction, gel permeation chromatography and differential scanning calorimetry.     

有机氨钙催化聚合脂肪族环酯

分别用经环氧丙烷和环氧丙烷/乙腈处理的氨钙催化剂催化聚合了ε-己内酯和L-丙交酯.研究了催化剂浓度、聚合时间、真空度、聚合温度和陈化温度等对聚合收率和聚合物粘均分子量的影响.结果表明,有机氨钙催化剂对ε-己内酯和L-丙交酯的开环聚合有较高的催化活性,在较低的温度下和较短的时间内,即可获得较高的转化率和较高的分子量,而且具有一些“准活性聚合”的特点,分子量在一定范围内可控.陈化处理和乙腈的加入可以大大提高聚ε-己内酯的分子量,最大分子量达到27×10⁴.     

Synthesis of a telechelic polypropylene with a vanadium-based living polymerization catalyst

The V(acac)₃ (acac = acetylacetonato)/AlEt₂Cl catalyst is known to promote the living polymerization of propylene at low temperature. In the present study, the catalyst was modified by contacting with α,ω-unconjugated diene compounds, and the resulting catalyst was applied to propylene polymerization. The polymer produced shows a bimodal molar mass distribution, where the molecular weight of the higher molecular weight portion is twice that of the lower molecular weight portion. By using the CO quenching technique, it was found that the polymer with the higher molecular weight has a telechelic structure.     

Ring opening polymerization of propylene oxide by chitosan-supported rare earth catalytic system and its kinetics

Ring opening polymerization of propylene oxide in the presence of a new type of catalytic system composed of chitosan-supported rare earth complex, triisobutyl aluminium, and acetylacetone and its kinetics have been studied for the first time. It has been found that the characteristics of this catalytic system are of high catalytic activity, of higher stereoselectivity, and of a high molecular weight polymer of 2 × 10⁶. Kinetic studies show that the polymerization rate is first order with respect to monomer concentration and catalyst concentration, respectively. The apparent activation energy of the polymerization reaction is 37.1 kJ/mol. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2177–2182, 1997     

SIMULATION OF EFFECTS OF REACTIVE IMPURITIES ON PROPYLENE POLYMERIZATION IN LOOP REACTORS THROUGH GENERATION FUNCTION TECHNIQUE

The estimation of the amount of reactive impurities in a loop reactor is of strategic importance to the propylene polymerization industry. It is essential to investigate the level of impurities in order to develop reliable monitoring and control strategies. This paper described one approach based on generation function technique with the following two steps. First, a new mechanism for propylene polymerization was proposed by considering the effects of the reactive impurities in the material on the propylene polymerization. Second, a series of equations of population balance for the propylene polymerization in loop reactors were established based on the proposed mechanism. Accordingly, the equations were transformed into the mathematic matrix through the generation function technique to investigate the effects of the reactive impurities on the propylene polymerization. Significant effects of the reactive impurities were analyzed through computational simulation. The results show that the concentration of active centre on catalysts and the polymerization conversion both decrease with the increase of the initial concentration of any reactive impurity; hydrogen concentration decreases with the increase of the initial concentration of ethylene or butylenes, whereas, it increases with the increase of the initial concentration of propadiene; the simulated weight average molecular weight and the molecular weight distribution index of polymer resins both increase with the increase of the initial concentration of ethylene or butylenes. They decrease with the increase of the initial concentration of propadiene.     

Kinetic features of ethylene polymerization over supported catalysts [2,6‐bis(imino)pyridyl iron dichloride/magnesium dichloride] with AlR3 as an activator

The effects of polymerization temperature, polymerization time, ethylene and hydrogen concentration, and effect of comonomers (hexene‐1, propylene) on the activity of supported catalyst of composition LFeCl₂/MgCl₂‐Al(i‐Bu)₃ (L = 2,6‐bis[1‐(2,6‐dimethylphenylimino)ethyl] pyridyl) and polymer characteristics (molecular weight (MW), molecular‐weight distribution (MWD), molecular structure) have been studied. Effective activation energy of ethylene polymerization over LFeCl₂/MgCl₂‐Al(i‐Bu)₃ has a value typical of supported Ziegler–Natta catalysts (11.9 kcal/mol). The polymerization reaction is of the first order with respect to monomer at the ethylene concentration >0.2 mol/L. Addition of small amounts of hydrogen (9–17%) significantly increases the activity; however, further increase in hydrogen concentration decreases the activity. The IRS and DSC analysis of PE indicates that catalyst LFeCl₂/MgCl₂‐Al(i‐Bu)₃ has a very low copolymerizing ability toward propylene and hexene‐1. MW and MWD of PE produced over these catalysts depend on the polymerization time, ethylene and hexene‐1 concentration. The activation effect of hydrogen and other kinetic features of ethylene polymerization over supported catalysts based on the Fe (II) complexes are discussed. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5057–5066, 2007     

合成高分子量无规聚丙烯的研究 Ⅰ.单茂基钛化合物/MAO催化丙烯聚合

用合成得到的五甲基环戊二烯基三苄氧基钛［ＣｐＴｉ（ＯＢｚ）３］与甲基铝氧烷（ＭＡＯ）组成新型催化体系进行丙烯的均聚合,研究了影响聚合活性及产物分子量的各种因素．结果表明,用甲基取代钛化合物茂环上的氢可使聚合产物分子量增大一个数量级,所制得的聚丙烯为无规聚丙烯,具有高分子量（Ｍｗ＝２０～１００×１０４）．     

Anionic graft polymerization of propylene sulfide on cellulose. I

The anionic graft polymerization of propylene sulfide on cellulose membrane was studied. Alkali cellulosates were used to initiate graft polymerization, and graft polymers of high polypropylene sulfide content were obtained in good yields. The graft polymerization was accompanied by a certain extent of homopolymerization. The effects of reaction solvent, monomer concentration, cellulosate degree of substitution, and type of the alkali metal cellulosate on the graft polymer composition, yield, and on the molecular weight of the grafted side chains were investigated.     

Comparison of the role of new ethers and conventional alkoxysilanes as external donors in the polymerization of propylene using the industrial Ziegler-Natta catalyst

Two new ethers were synthesized using the Williamson reaction from related alcohols and were used as external donors in propylene polymerization in the presence of the industrial diisobutyl phthalate-based MgCl₂-supported Ziegler-Natta catalyst. For comparison the propylene polymerization was carried out in the presence of silane and in the absence of external donors. The produced polymers were characterized by differential scanning calorimetry, xylene extraction, melt flow index, scanning electron microscopy and gel permeation chromatography. The isotacticity, molecular weight and molecular weight distribution, melt flow index, crystallinity degree and thermal properties of polypropylenes were influenced by the type of external donors.     

合成高分子量无规聚丙烯—在烷烃溶剂中聚合及性能初步表征

丙烯聚合;茂金属催化剂;立体结构;合成高分子量无规聚丙烯—在烷烃溶剂中聚合及性能初步表征     

Cp*TiCl2N[Si(CH3)3]2/MAO催化剂合成无规聚丙烯弹性体

合成了Cp TiCl2 N[Si(CH3) 3]2 甲基铝氧烷 (MAO)催化体系 ,以该体系进行丙烯聚合得到无规聚丙烯 ,具有高的分子量及良好的弹性 ,玻璃化温度为 - 8 8℃ .产物经DSC、1 3C NMR、DMA等方法表征 .结果表明 ,催化活性随着丙烯压力的增加 ,有明显的增大 .催化活性在 4 0℃下有最高的催化活性 ,而产物分子量随着温度的下降有明显增大 ,在 0℃～ 5 0℃范围内分子量MW =(2 0～ 6 0 )× 10 4 .     

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     

Synthesis of exfoliated isotactic polypropylene/functional alkyl-triphenylphosphonium-modified clay nanocomposites by in situ polymerization

Diphenyl (4-hydroxyphenyl) hexadecyl phosphonium bromide (POH) -modified montmorillonite (POHMMT) was used to prepare a novel TiCl₄/MgCl₂/POHMMT compound catalyst and exfoliated iPP/POHMMT nanocomposites were prepared by the in situ intercalative polymerization of propylene with the TiCl₄/MgCl₂/POHMMT compound catalyst. The POH surfactants don’t change the catalytic characteristic of the Z-N catalyst and the obtained PP presents high isotacticity, normal molecular weight and molecular weight distribution. The WAXD, SAXS and TEM results demonstrate the highly exfoliated iPP/POHMMT nanocomposites were produced by the in situ polymerization with this novel catalyst, while the intercalated iPP/Na⁺MMT nanocomposites were produced with the TiCl₄/MgCl₂/Na⁺MMT compound catalyst. Through this approach, in situ propylene polymerization can actually take place between the silicate layers and lead not only to PP with high isotacticity and molecular weight, but also to highly exfoliated PP nanocomposites.     

Polymerization of propylene with TiCl3–AlEt2Cl–polymeric electron donor catalyst

Polymeric donors having ether or carbonyl groups were added to the TiCI₃–AlEt₂CI catalyst system as the third component, and the effects on the polymerization of propylene were investigated in comparison with the effect of the electron donors with low molecular weight. The polymeric donors were effective in making the catalyst more active, but the donors of low molecular weight depressed the catalyst activity. In the case of poly(propylene glycol dimethyl ether) (PPG-DME), PPG–DME with a number of propylene oxide units (n) of more than 6.7 was effective in enhancing the catalyst activity. These effects were considered to be due to the different reactivities between TiCI₃ and AlEt₂CI-polymeric donor complexes having various chain lengths.     

甲基丙烯酸甲酯的原子转移自由基悬浮聚合

以 1 苯基氯乙烷为引发剂 ,氯化亚铜为催化剂 ,2 ,2 联吡啶为配体 ,外加搅拌 ,氮气保护下进行了甲基丙烯酸甲酯 (MMA)在 80℃下的原子转移悬浮聚合 .结果表明 ,聚合反应符合对单体浓度为一级的动力学关系 .经计算聚合体系的增长自由基浓度为 5 .74× 10 - 8mol L .聚合物分子量随转化率呈线性增加 ,分子量分布较窄 ,Mw Mn 在 1.37～ 1.40之间 .还以AIBN为引发剂 ,在三氯化铁和三苯基膦存在下进行了MMA的反向原子转移本体和悬浮聚合研究 .结果证明本体聚合具有好的可控特征 ,分子量随转化率呈线性增长 ,分子量分布指数在 1.2 7～ 1.31之间 .聚合反应速率较快 ,聚合体系中的增长自由基浓度较高 ,为 1.6 4× 10 - 7mol L .而在此催化体系下的悬浮聚合则完全失去了活性特征     

Preparation of polypropylene/clay nanocomposites by <Emphasis Type="Italic">in situ</Emphasis> polymerization with TiCl<Subscript>4</Subscript>/MgCl<Subscript>2</Subscript>/clay compound catalyst

TiCl₄/MgCl₂/clay compound catalyst was prepared by chemical reaction.Exfoliated polypropylene（PP）/clay nanocomposites were synthesized by in situ polymerization with this compound catalyst.Effects of polymerization temperature,polymerization time,propylene pressure,solvent consumption and pre-treat time of catalyst on catalyst activity and catalytic stereospecificity were studied.Under optimal conditions,activity of the nano-compound catalyst is about 88.3 kg/（mol Ti·h）.Isotacticity of PP obtained in the nanocomposites is in the range of 89%-99%,and its melting temperature is about 159℃.The weight-average molecular weight of PP can reach 6.7×10⁵ - 7.8×10⁵,and the molecular weight distribution is between 7.7 and 7.9.     

Direct evidence of the second‐order dependence of propagation rate on propene concentration in living polymerization with the [t‐BuNSiMe2Flu]TiMe2/B(C6F5)3 catalyst

Propene polymerization was conducted with the [t‐BuNSiMe₂Flu]TiMe₂/B(C₆F₅)₃ catalyst at –50°C at various concentrations of propene. The polymerization proceeds in a living manner regardless of the propene concentration employed. Molecular weight of polymer obtained in a certain polymerization time with low monomer conversion increases with increasing concentration of propene. The logarithmic plot of molecular weight against propene concentration gives a straight line with a slope of 1.8, which indicates that the propagation rate is almost of second order with respect to propene concentration.     

Mechanism of Ziegler-Natta polymerization of propylene and α-d-propylene

Rates of propylene homopolymerization and α-d-propylene-propylene copolymerization were determined by using constant-pressure polymerization conditions. It could be demonstrated that the rate of propylene homopolymerization was constant under the conditions used. However, the initial rate of copolymerization was faster and decreased with time to the rate obtained for propylene homopolymerizations. The higher initial copolymerization rate was attributed to the stabilization of potentially active centers in solution when the deuterated monomer was present. These active centers are assumed to be formed by reactions of tetravalent titanium with monomer. These active centers, which are formed in solution, are said to be destroyed by isotopically controlled reactions, i. e., abstraction of the hydrogen or the α-deuterium atom from these monomer-alkylated species in solution or at the interface. These active centers are believed to be adsorbed and/or chemisorbed onto the precipitated catalyst surface and to be responsible for a polymer of considerably lower steric order. This scheme predicts a stereoregular polymer of high molecular weight produced by polymerization on a Ti(III) surface and a largely amorphous polymer of lower molecular weight produced by adsorbed and/or chemisorbed species. This prediction was verified by fractionation of the deuterated polymers into crystalline and amorphous portions.     

Living radical polymerization of acrylonitrile catalyzed by copper with a high concentration of radical initiator and its application in removal of Ag(I) after modification

In this study, we reported the synthesis of polyacrylonitrile (PAN) via living radical polymerization in N, N‐dimethylformamide using carbon tetrachloride as initiator, copper(II) chloride (CuCl₂)/hexamethylenetetramine as catalyst system, and 2,2‐azobisisobutyronitrile as a high concentration of thermal radical initiator. The polymerization proceeded in controlled/living manner as indicated by first‐order kinetics of the polymerization with respect to the monomer concentration, linear increase of the molecular weight with monomer conversion and narrow polydispersity. Higher polymerization rate and narrower molecular weight distributions were observed with CuCl₂ less than 50 ppm. The rate of polymerization showed a trend of increase along with temperature. The modified PAN containing amidoxime group was used for extraction of Ag(I) ions from aqueous solutions. The adsorption kinetics data indicated that the adsorption process followed pseudo‐second‐order rate model. The isotherm adsorption process could be described by the Freundlich isotherm model. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013