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。     

降冰片烯与丙烯共聚合的研究进展

继高活性茂金属催化体系成功开发以降冰片烯和乙烯共聚物为代表的高性能环烯烃共聚物以来, 降冰片烯与其他α-烯烃如丙烯的共聚物研究也备受学术界和工业界的重视。本文介绍了降冰片烯与丙烯共聚合的催化剂和聚合机理等方面的最新研究进展, 包括各种不同结构的茂金属催化剂催化降冰片烯与丙烯共聚合的特点及其共聚物的结构分析。C₂-对称和C_s-对称的茂金属催化剂催化降冰片烯与丙烯共聚合时链转移反应较多, 以致催化活性较低, 所得的聚合产物分子量偏低。采用限定几何构型茂金属柄型-二甲基亚甲硅基(芴基)(氨基)二甲基钛催化剂进行降冰片烯与丙烯共聚合时, 催化活性可高达10⁷ g polymer·(mol cat·h)^-1, 所得共聚物的相对分子质量超过20万, 降冰片烯含量可达70%(mol)且玻璃化转变温度高。     

乙丙橡胶催化剂的研发趋势

<正>一、茂金属催化技术优势明显茂金属催化乙丙共聚技术的优点是催化活性效率高,用量少,催化剂残余物极少,不需要脱催处理,可采用高温溶液聚合,聚合反应液中EPDM浓度高(16.4%),热能利用率高,产品颜色浅,聚合物结     

茂金属乙丙弹性体技术进展

论述了茂金属乙丙弹性体的合成、表征、反应机理及工业化进程,着重介绍了茂金属催化体系和茂金属乙丙弹性体的结构和性能。     

茂金属乙丙弹性体技术进展

论述了茂金属乙丙弹性体的合成、表征、反应机理及工业化进程，着重介绍了茂金属催化体系和茂金属乙丙弹性体的结构和性能。     

茂金属催化剂在弹性体合成中的应用

综述茂金属催化剂在弹性体合成中的应用研究进展。茂金属催化剂在聚烯烃弹性体、BR和IIR的合成以及苯乙烯-丁二烯-苯乙烯嵌段共聚物（SBS）和苯乙烯-异戊二烯-苯乙烯嵌段共聚物（SIS）的催化加氢制备氢化SBS（SEBS）和氢化SIS（SEPS）方面具有重要意义。在茂金属存在下，EPR的催化合成和SBS、SIS的催化加氢已经实现工业化，而茂金属在其它领域的应用尚处于技术开发阶段。     

茂金属化合物催化极性烯类单体活性聚合的研究进展

综述了CGC催化剂、单茂催化剂、多核茂金属催化剂、桥联茂金属催化剂,非茂金属催化剂催化极性烯类单体均聚合及极性烯类单体与非极性烯类单体共聚合的研究.茂金属催化剂催化极性烯类单体聚合的机理包括配位聚合机理与活性自由基聚合机理.采用茂金属催化体系可以制备极性烯类单体的均聚物及极性烯类单体与非极性烯类单体的共聚物.不仅拓宽了茂金属催化剂的应用范围,而且可开发出具有新性能的极性聚烯烃树脂.     

茂金属环烯烃聚合物进展

评述了茂金属环烯烃聚合物的最新进展,讨论了环烯烃聚合及其与乙烯共聚合的茂金属催化体系、聚合机理、聚合工艺以及茂金属环烯烃共聚物的性能及应用。     

茂金属环烯烃聚合物技术进展

叙述了茂金属环烯烃聚合物的最新进展,讨论了环烯烃聚合及其与乙烯共聚合的茂金属催化体系、聚合机理、聚合工艺以及茂金属环烯烃共聚物的性能及应用     

茂金属催化剂及烯烃高分子材料研究新进展

介绍茂金属催化剂的一般组成、主要特性及在烯烃聚合催化技术所具有的显著优势和近年研究取得的一些新进展。详细叙述采用茂金属催化工艺技术合成的一些烯烃聚合物,如聚乙烯(PE)、聚丙烯(PP)、间规聚苯乙烯(sPS)、茂金属环烯烃、茂金属乙丙橡胶、茂金属乙烯-辛烯共聚物等。这些茂金属聚合物与传统催化剂合成的聚合物相比,具有更优良的特性和更广阔的应用范围。许多用传统催化剂难以合成的材料,在采用茂金属催化技术后变得容易进行。在烯烃聚合物合成中茂金属催化剂正在替代传统催化剂。茂金属催化剂在全球增长非常迅速,具有广阔的应用和市场前景。     

丙烯/1-丁烯无规共聚物与丙烯/乙烯抗冲共聚物的对比研究

对丙烯/1-丁烯无规共聚物(PPB)与丙烯/乙烯抗冲共聚物(PPE)的结晶行为进行对比,在等温结晶时,通过相对结晶度随时间的变化关系、等温结晶曲线等研究,表明丙烯/1-丁烯无规共聚物结晶速率明显低于丙烯/乙烯抗冲共聚物,同时丙烯/乙烯抗冲共聚物的等温结晶速率随乙烯单元含量增加没有明显降低。根据Avrami方程计算了共聚物的结晶活化能,证明丙烯/1-丁烯无规共聚物的结晶能力较丙烯/乙烯抗冲共聚物低。扫描电镜分析丙烯/1-丁烯无规共聚物在丁烯单元摩尔分数2.39%时没有韧性拉伸,而丙烯/乙烯抗冲共聚物在乙烯单元摩尔分数3%时出现韧性拉伸。     

Influence of copolymerization conditions on the structure and properties of polyethylene/polypropylene/poly(ethylene‐co‐propylene) in‐reactor alloys synthesized in gas‐phase with spherical ziegler‐natta catalyst

A spherical TiCl₄/MgCl₂‐based catalyst was used in the synthesis of polyethylene/polypropylene/poly (ethylene‐co‐propylene) in‐reactor alloys by sequential homopolymerization of ethylene, homopolymerization of propylene, and copolymerization of ethylene and propylene in gas‐phase. Different conditions in the third stage, such as the pressure of ethylene–propylene mixture and the feed ratio of ethylene, were investigated, and their influences on the compositions, structural distribution and properties of the in‐reactor alloys were studied. Increasing the feed ratio of ethylene is favorable for forming random ethylene–propylene copolymer and segmented ethylene–propylene copolymer, however, slightly influences the formation of ethylene‐b‐propylene block copolymer and homopolyethylene. Raising the pressure of ethylene–propylene mixture results in the increment of segmented ethylene–propylene copolymer, ethylene‐b‐propylene block copolymer, and PE fractions, but exerts a slight influence on both the random copolymer and PP fractions. The impact strength of PE/PP/EPR in‐reactor alloys can be markedly improved by increasing the feed ratio of ethylene in the ethylene–propylene mixture or increasing the pressure of ethylene–propylene mixture. However, the flexural modulus decreases as the feed ratio of ethylene in the ethylene–propylene mixture or the pressure of ethylene–propylene mixture increases. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2481–2487, 2006     

Influence of the longest ethylene and isotactic propylene sequences on crystallization elution fractionation of ethylene/propylene copolymers

Crystallization elution fractionation (CEF) is the newest crystallization-based technique for estimating the chemical composition distribution of ethylene/1-olefin copolymers. Understanding the separation mechanism of CEF for ethylene/propylene copolymers over their full compositional range is challenging because the crystallizabilities of the copolymer chains depend on the longest ethylene sequence and on longest isotactic propylene sequence. We developed a mathematical model to describe the CEF mechanism for ethylene/propylene copolymers over the entire compositional range using population balances for the crystallization and dissolution stages. The joint distribution of longest ethylene and isotactic propylene sequences determines how the copolymer populations crystallize and dissolve. The model was validated with experimental CEF profiles of ethylene/propylene copolymers varying from pure ethylene to propylene homopolymers.     

PP/PE blends. IV. Characterization and compatibilization of blends of postconsumer resin with virgin PP and HDPE

The mechanical properties of blends of isotactic polypropylene and high-density polyethylene with a postconsumer resin (recycled dairy containers) were investigated over the entire composition range. Modification of these blends with an ethylene/propylene/diene copolymer or an ethylene/vinyl acetate copolymer was also investigated. Isotactic polypropylene/postconsumer resin blends have satisfactory impact and tensile properties at postconsumer resin contents of less than 50% for certain applications. At higher postconsumer resin contents, the tensile properties were adversely affected. The impact properties remained satisfactory. Addition of an ethylene/propylene/diene copolymer improved the mechanical properties of these blends to levels equal to or greater than those for neat isotactic polypropylene. Ethylene/vinyl acetate copolymers were also able to improve the mechanical properties, but not as efficiently as did the ethylene/propylene/diene copolymer. Blends of high-density polyethylene and a postconsumer resin had poor impact and tensile properties. Although the ethylene/propylene/diene copolymer and ethylene/vinyl acetate copolymers were able to improve these properties, the improvement was insufficient for general recycling, except at lower (≤25%) postconsumer resin contents. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 2081–2095, 1998     

Polymeric proton conducting systems based on commercial elastomers. II. Synthesis and microstructural characterization of films based on HSBR/EPDM/PP/PS/silica

This article reports on the synthesis and structural characterization of films containing hydrogenated poly(butadiene‐styrene) block copolymer/ethylene‐propylene terpolymer/polypropylene, hydrogenated poly(butadiene‐styrene) block copolymer/ethylene‐propylene terpolymer/polystyrene, and hydrogenated poly(butadiene‐styrene block copolymer/ethylene‐propylene terpolymer/silica) crosslinked with peroxides and heterogeneously sulfonated. Sulfonation of the different polymeric systems gives rise to materials with high proton conductivity and great dimensional stability, suited for application in a variety of electronic devices. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2394–2402, 2004     

汽车专用聚丙烯树脂的研制

通过分子设计,确定了共聚聚丙烯中乙丙橡胶质量、乙烯含量、乙丙橡胶和共聚聚丙烯特性粘数等因素对其宏观性能的影响,并确定了各因素的最佳控制指标,在生产能力为40kt/a的工业装置上开发了本体法工艺汽车用共聚聚丙烯树脂。     

Zur radikalisch initiierten Copolymerisation von Ethylen,I. Ethylen-Propylen-Copolymerisate

Waxy copolymerisates of ethylene and vinyl acetate are employed in the oil industry as flow improvers for middle distillates. The objective was to determine whether the same effects could be achieved with other copolymers having an analogous composition. To this end the copolymerisation of ethylene and propylene was examined at pressures of 150 to 200 MPa and at temperatures of 160 and 200°. The initiation of the reaction with peroxides presents no problems. However, an additional amount of initiator is necessary for an increase of the propylene amount in the reaction mixture. The average molar mass of the products depends on the propylene content. It can also be selectively adjusted by the use of chain transfer agents. Compared with the analogous ethylene/vinyl acetate copolymer waxes the ethylene/propylene copolymer waxes exhibited only limited effectiveness as flow improvers in Middeldestillates.     

Cocrystallization and polymer miscibility

Low-density polyethylene was blended in various proportions with an ethylene/propylene/1,4-hexadiene copolymer having an ethylene/propylene mole ratio of 4.5 and a low level of crystallinity. The DSC melting peak of polyethylene was decreased, the unit cell was expanded, and the spherulitic development was disturbed. The temperature of a dynamic mechanical loss peak varied smoothly with composition between the T_g of the copolymer and the β-relaxation of the polyethylene, but the glass temperature of the copolymer measured by DSC was unchanged. These effects were all diminished when the ethylene/propylene ratio of the copolymer was reduced. Blends with highdensity polyethylene showed little depression of the melting point or change in crystal structure and much less effect on the dynamic mechanical behavior. However, the behavior of copolymers of ethylene with low levels of vinyl acetate or methyl methacrylate was similar to that of low-density polyethylene. Therefore, the ability to cocrystallize is an important factor for limiting the tendency of nonpolar polymers to separate, thereby facilitating the preparation of blends with desirable combinations of properties.     

环氧乙烷环氧丙烷嵌段共聚醚应用进展

介绍了环氧乙烷环氧丙烷嵌段共聚醚的生产技术和应用领域,重点叙述了烯丙醇类环氧乙烷环氧丙烷共聚醚在减水剂行业中的应用。     

Structure and properties of impact copolymer polypropylene. I. Chain structure

In this work, impact copolymer polypropylene (ICPP) was fractionated into 4 fractions. ICPP and the 4 fractions were studied using Fourier transform infrared and ¹³C nuclear magnetic resonance analysis. The results demonstrate that fraction A is ethylene–propylene rubber, fraction B is ethylene–propylene (EP) segmented copolymer, fraction C is ethylene–propylene block copolymer, and fraction D is polypropylene with a few ethylene monomers in the chain. The differences in properties between different impact copolymer polypropylenes should be due to their fractions' differences in composition and chain sequence structure. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 93–101, 1999