乙烯丙烯共聚的负载型钛催化剂的研究

用高效的负载型钛催化剂催化制备乙丙共聚物,近年来国外已有报道.徐筠等也早作过探索性的研究.负载型钛催化剂用于乙丙共聚时,虽具有高效特点,但产物中往往含有结晶的溶剂不溶物(含量高达30％以上),不能成为无规弹性体.作者研究了用负载型钛催化剂进行乙丙共聚的规律,用X射线衍射,DSC,IR等方法剖析了共聚     

不同催化体系对乙丙共聚物序列分布的影响

<正> 乙丙橡胶的性能不仅取决于共聚物的组成、分子量及其分布,而且依赖于共聚物的微结构。Natta等认为共聚物中乙烯和丙烯单体链节呈无规分布时可获得性能最好的弹性体。但因催化剂及聚合条件不同,共聚物的单体链节总是存在不同程度的无规、交替及长序列分布。本文采用红外吸收光谱研究了乙丙共聚物的组成及不同催化体系和加入添加剂后对乙丙共聚物序列分布的影响。     

等规聚苯乙烯与聚(乙烯/丙烯)嵌段共聚物的研究(Ⅰ)──一步法嵌段共聚合反应

用自制的稀土化合物改性的高效钛系载体催化剂(SN－1),以顺序加料一步法进行苯乙烯与乙烯/丙烯混合单体的嵌段共聚合反应．通过实验找出典型的共聚合条件为：甲苯为溶剂;催化剂浓度为1．5～1．6mmol/L;铝钛摩尔比为20;聚合温度65℃．先使苯乙烯预聚一定时间,然后连续通入乙丙混合气体．共聚合产物中iPS链段的含量随苯乙烯单体预聚合时间的延长而增加．     

氢气对负载型Z-N高效催化剂的乙烯-丙烯共聚产物链结构影响

用球形的负载型Ziegler-Natta（Z-N）高效催化剂，经丙烯均聚一乙烯丙烯气相共聚两段串联反应工艺制备的聚丙烯／乙丙共聚物（PP／EPR）合金具有优良的抗冲击性能，是聚丙烯的重要高性能化改性品种，已实现大批量生产，对这类反应器合金的结构表征和结构性能关系的研究表明，其共聚物组分中既有起弹性体作用的乙丙无规共聚物，也含有相当量的乙丙多嵌段共聚物．这种多嵌段共聚物既与无规共聚物（EPR）相容，又与PP基体相容，在合金中起相容剂作用，对材料高抗冲性能的形成起着重要作用．然而，负载型Z-N高效催化剂催化乙丙共聚合的产物结构及其影响因素至今鲜见系统的研究，调控PP／EPR合金中共聚物结构的原理尚不明确．氢气在聚烯烃生产中广泛用作分子量调节剂，在PP／EPR合金的生产中同样要用氢气调节PP和EPR组分的分子量．但是，加氢对共聚物的链结构有何影响则鲜见系统的研究．本文初步研究了用Z—N高效催化剂合成的乙丙共聚物的结构特征，着重考察了聚合体系中加入链转移剂氢气对共聚物结构的影响．     

MgCl_2/AlEt_n(OEt)_(3-n)负载单茂钛催化剂催化乙烯聚合研究

以MgCl2/AlEtn(OEt)3-n为载体,分别负载五甲基茂基三氯化钛(Cp*TiCl3)和五甲基茂基三苄氧基钛(Cp*Ti(OBz)3),得到两种负载催化剂,在较廉价的AlEt2Cl为助催化剂常压下可以高效地催化乙烯聚合.报道了载体的制备、聚合条件(不同的烷基铝助催化剂、聚合温度、铝钛摩尔比)对催化剂的聚合行为以及聚合物结构的影响.研究结果表明,两种负载催化体系对乙烯聚合具有较高的催化活性,可达105g PE/(molTi·h)数量级,所得聚乙烯的黏均分子量在105以上.经过13C-NMR和DSC分析,两种负载催化剂得到的均为线型聚乙烯.与均相催化剂相比,负载后的单茂钛催化体系的聚合反应动力学表现高效而平稳.这表明载体的微孔结构使活性中心得到了有效的分散,有效地提高了催化剂的活性,同时载体的受限空间有效抑制了聚乙烯增长链的β-H消除反应.     

环烯烃聚合物的合成和应用研究进展

综述了近年来环烯烃均聚物及其与A2烯烃共聚物的合成和应用的研究情况, 讨论了不同聚合体系(包括开环易位聚合和加成聚合) 的研究发展, 对各种催化剂的结构、催化聚合的机理, 以及所得聚合物、共聚物性能进行了详尽的描述, 同时报道了有关聚合产物应用的现况与前景。     

等规聚苯乙烯与聚（乙烯／丙烯）嵌段共聚物的研究（I）——一…

用自制的稀土化合物改性的高效钛系载体催化剂（ＳＮ－１），以顺序加料一步法进行苯乙烯与乙烯／丙烯混合单体的嵌段共聚合反应。通过实验找出典型的共聚合条件为：甲苯为溶剂；催化剂浓度为１．５￣１．６ｍｍｏｌ／Ｌ，铝钛摩尔比为２０；聚合温度６５℃，先使苯乙烯预聚一定时间，然后连续通入乙丙混合气体，共聚合产物中ｉＰＳ链段的含量随苯乙烯单体预聚合时间的延长而增加。     

乙丙共聚高效负载型催化剂的改进

我们曾报道过将负载型钛系催化剂用于乙丙共聚制取粘度添加剂的初步结果.这在当时是负载型钛系催化剂用于乙丙共聚的首次尝试,结果是催化剂的活性很高,寿命比传统用的钒系催化剂长,腐蚀性也小,共聚物用作润滑油的粘度调节剂性能良好.它的缺点是所得共聚物中有小部分不溶于烃类溶剂,将可溶部分调入机械油,数日后有微量絮状     

嵌段共聚物sPS-b-Poly(S-co-E)的合成与表征

用主催化剂茂基三苄氧基钛和茂基三呋喃甲氧基钛与助催化剂甲基铝氧烷(MAO)组成的催化体系研究了先预聚苯乙烯(S)再引入乙烯(E)进行的嵌段共聚合反应,发现总的催化效率随苯乙烯预聚合时间的延长而增加.对嵌段共聚合产物用丁酮、四氢呋喃和氯仿进行顺序萃取分离,得到四氢呋喃中的可溶级分即嵌段共聚物sPS-b-Poly(S-co-E),占总嵌段共聚合产物的30%～50%,其中乙烯链节的含量占总嵌段共聚物的9%～14%.对嵌段共聚物用DSC、WAXD、FTIR、13CNMR和偏光显微等方法进行了表征.     

丁氧基氯化钛载体型催化体系用于乙烯/丁烯-1共聚合的研究

<正> 近十几年来有关载体型高效齐格勒-纳塔催化体系用于乙烯共聚合反应有了不少报道,其中尤以氯化镁为载体的体系居多。本文系统地研究了以氯化镁为载体的一系列正丁氧基氯化钛催化体系,在催化乙烯与丁烯-1共聚合反应的动力学行为,以及催化剂     

Melting behavior of ethylene copolymers and branched polyethylenes

Prior research on the melting behavior of ethylene copolymers and branched polyethylenes could not be effectively evaluated since there were large differences in the levels of comonomer contents. The present research was undertaken to determine additional data so that an overall evaluation could be made. A consideration of the experimental data of the present work and earlier research data showed that methyl side groups caused less diffuse melting and less melting point depression than either ethyl groups or polyethylene branches. In addition, it was found that the Flory equation can be used to describe the relation of melting point depression to foreign group concentration for propylene copolymers. The equation did not hold for 1-butene-ethylene copolymers or branched polyethylenes. For these materials the Wunderlich modification of the Flory equation applied. Activity values for both 1-butene-ethylene copolymers and branched polyethylenes gave a common correlation with foreign groups. Enthalpy and entropy fusion data for ethylene copolymers and branched polyethylenes were also determined. It was also shown that good agreement was found between crystallinities for these materials determined independently by differential thermal analysis and x-ray analysis.     

单茂钛/MAO体系催化乙烯/丙烯共聚合研究Ⅲ.乙烯/丙烯共聚物的表征与结构分析

采用合成的催化剂五甲基环戊二烯基三烯丙氧基钛 [Cp Ti(OAllyl) 3]与改性甲基铝氧烷 (mMAO)组成催化体系制备乙烯 /丙烯共聚物 .红外分析显示 ,乙醚可溶和己烷可溶两个级分的化学结构几乎相同 .GPC测试结果表明共聚物分子量高 ,分子量分布窄 .X 射线衍射分析 ,大多数样品的图谱为宽的弥散峰 ,表明它们是无规共聚物 ;只有当乙烯含量很高时 ,样品的谱图才有较为尖锐的结晶峰 ,结晶度不高 .经热分析(DSC、TG) ,大多数样品没有出现明显的熔点 ,只有当乙烯含量很高时才显示出熔点 ;共聚物的热稳定性较高 .DMA分析表明 ,共聚物样品中乙烯含量多的 ,其储能模量 (E′)大一些 ;共聚物的玻璃化转变温度随着丙烯链节的增多而升高 .     

单茂钛/MAO体系催化乙烯/丙烯共聚合研究Ⅱ.乙烯/丙烯共聚物的核磁共振分析

用13C NMR测定了由单茂基钛化合物 /mMAO催化体系制备的乙烯 /丙烯共聚物大分子链的立体结构和单体序列分布 ,计算了单体的竞聚率r1=7 91± 0 0 6 ,r2 =0 135± 0 0 3 ,其乘积r1r2 ≈ 1.Fineman Ross计算得到的单体竞聚率与13C NMR测定值相近 ,即r1=7.94,r2 =0 .134,其乘积r1r2 =1 0 4.这表明共聚物是立构无规的 .共聚物经溶剂萃取后 ,乙醚可溶和己烷可溶两个级分中单体的序列分布和竞聚率略有不同 .乙醚可溶级分中丙烯链段稍长 ,而己烷可溶级分中乙烯链段稍长     

Fusion of homopolymers and ordered copolymers containing ethylene sebacate structural units

The melting temperatures of homopolymers of poly(ethylene sebacate) possessing a most probable molecular weight distribution and ordered copolymers of ethylene sebacate/propylene adipate were studied by slow heating processes and by the analysis of the dependence of the melting temperature on the crystallization temperature utilizing rapid heating rates. For the ordered copolyesters, where the composition of the crystallizing co-units ranged from 0.8 to 0.2 mole fraction the latter method gave results which were similar to those that have been obtained for the other polymer systems that have been studied. Extrapolated equilibrium melting temperatures could be obtained in a straightforward manner and were found to be independent of the copolymer composition in accord with theoretical expectations. On the other hand, a unique set of results were obtained for the homopolymers. A plot of the relationship between the melting temperature and the crystallization temperature for all the molecular weights studied gave a slope close to unity. This made it operationally impossible to extrapolate to the equilibrium melting temperature for this system.     

Molecular‐Weight‐Dependence on Domain Formation of Grafted Poly(ethylene‐co‐propylene) in a Poly(propylene) Matrix

Several novel poly(propylene)‐graft‐poly(ethylene‐co‐propylene) copolymers with isotactic poly(propylene) (PP) backbones and ethylene/propylene rubber (EPR) branches were synthesized. The thermomechanical properties of these samples were investigated using a dynamic mechanical analyzer. There appeared to be a critical EPR molecular weight above which a two‐phase system developed with EPR domains dispersed in a PP matrix. This domain formation gave an enhanced loss modulus compared to a commercial high impact PP product below 40°C.     

Separation of ethylene‐propylene copolymers and ethylene‐propylene‐diene terpolymers using high‐temperature interactive liquid chromatography

Ethylene‐propylene‐diene terpolymers (EPDM) are generally amorphous and, therefore, do not crystallize from solution. Consequently, fractionation techniques based on crystallization, such as crystallization analysis fractionation or temperature rising elution fractionation, cannot be used to analyze their chemical composition distribution. Moreover, no suitable chromatographic system was known, which would enable to separate them according to their chemical composition. In this study, two different sorbent/solvent systems are tested with regard to the capability to separate EPDM‐terpolymers and ethylene‐propylene (EP)‐copolymers according to chemical composition. While porous graphite/1‐decanol system is selective towards ethylene and ethylidene‐2‐norbornene, carbon coated zirconia/2‐ethyl‐1‐hexanol is preferentially selective towards ethylene. Consequently, the earlier system enables to separate both EP copolymers and EPDM according to the chemical composition and the latter mainly according to the ethylene content. The results prove that the chromatographic separation in both sorbent/solvent systems is not influenced by molar mass of a sample or by its long chain branching. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Melting behavior of ethylene oxide–propylene oxide (sym-PEP) block copolymers

Melting points and lamellar thicknesses have been measured for ethylene oxide–propylene oxide block copolymers (sym-PEP) with central poly(ethylene oxide) block lengths of 70–100 chain units and end poly(propylene oxide) block lengths of 0–30 chain units. Melting points of the block copolymers are lower than those of the corresponding poly(ethylene oxide) homopolymer by an amount (up to 15°C) which increases as the poly(propylene oxide) block length increases. Most samples have more than one melting transition, which can be assigned to variously folded chain crystals. End interfacial free energies σ_e for the various crystals have been estimated by use of Flory's theory of melting of block copolymers. For a given crystal type (e.g., once-folded-chain) σ_e is higher the longer the chain length of the end poly(propylene oxide) blocks. For a given copolymer σ_e is lower, the more highly folded the poly(ethylene oxide) chain.     

Molecular heterogeneity of ethylene‐propylene rubbers: New insights through advanced crystallization‐based and chromatographic techniques

For a long time ethylene‐propylene rubber (EPR) copolymers with high comonomer contents were believed to be amorphous materials with a random copolymer composition. This is not completely correct as has been shown by temperature rising elution fractionation (TREF) combined with differential scanning calorimetry (DSC), crystallization analysis fractionation (CRYSTAF), and high temperature–high‐performance liquid chromatography (HT‐HPLC). When using only conventional crystallization‐based fractionation methods, the comprehensive compositional analysis of EPR copolymers was impossible due to the fact that large fractions of these copolymers do not crystallize under CRYSTAF conditions. In the present work, HT‐HPLC was used for the separation of the EPR copolymers according to their ethylene and propylene distributions along the polymer chains. These investigations showed the existence of long ethylene sequences in the bulk samples which was further confirmed by DSC. The results on the bulk samples prompted us to conduct preparative fractionations of EPR copolymers having varying ethylene contents using TREF. Surprisingly, significant amounts of crystallizing materials were obtained that were analyzed using a multistep protocol. CRYSTAF and DSC analyses of the TREF fractions revealed the presence of components with large crystallizable sequences that had not been detected by the bulk samples analyses. HT‐HPLC provided a comprehensive separation and characterization of both the amorphous and the crystalline TREF fractions. The TREF fractions eluting at higher temperatures showed the presence of ethylene‐rich copolymers and PE homopolymer. In order to obtain additional structural information on the separated fractions, HT‐HPLC was coupled to Fourier transform‐infrared (FT‐IR) spectroscopy. The FT‐IR data confirmed that the TREF fractions were separated according to the ethylene contents of the eluted samples. Preparative TREF analysis together with a combination of various analytical methods proved to be useful tools in understanding the complex molecular composition of these rubber samples. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 863–874     

Modeling random methyl branching in ethylene/ propylene copolymers using metathesis chemistry: synthesis and thermal behavior

The structure of random ethylene/propylene (EP) copolymers has been modeled using step polymerization chemistry. Six ethylene/propylene model copolymers have been prepared via acyclic diene metathesis (ADMET) polymerization and characterized for primary and higher level structure using in-depth NMR, IR, DSC, WAXD, and GPC analysis. These copolymers possess 1.5, 7.1, 13.6, 25.0, 43.3, and 55.6 methyl branches per 1000 carbons. Examination of these macromolecules by IR and WAXD analysis has demonstrated the first hexagonal phase in EP copolymers containing high ethylene content (90%) without the influence of sample manipulation (temperature, pressure, or radiation). Thermal behavior studies have shown that the melting point and heat of fusion decrease as the branch content increases. Further, comparisons have been made between these random ADMET EP copolymers, random EP copolymers made by typical chain addition techniques, and precisely branched ADMET EP copolymers.     

Improved chemical composition separation of ethylene–propylene random copolymers by high-temperature solvent gradient interaction chromatography

High-temperature solvent gradient interaction chromatography (HT-SGIC) is a fast and efficient fractionation technique for the chemical composition analysis of olefin copolymers. The separation of ethylene–propylene random copolymers (EPRs) was achieved on a graphitic stationary phase, Hypercarb, at 160 °C by using linear solvent gradient elution from 1-decanol to 1,2,4-trichlorobenzene (TCB). In the present work, the solvent gradient profile was modified to improve the chromatographic separation of EPRs. With the aim to obtain a better resolution in separation, a slow increase in the volume fraction of TCB was applied. This allowed for a relatively large retention region for linear polyethylene (PE) chains on the column; thereby, a broader elution volume zone between the start of the gradient and the PE elution was achieved. The efficiency of this new gradient profile was demonstrated by analysing two fully amorphous EPR samples. Clear differences in the chemical composition of these EPR samples with similar ethylene contents have been proven by using this modified solvent gradient. The comprehensive chemical composition and microstructure analysis of the SGIC-separated fractions by FTIR revealed that ethylene/propylene (EP) copolymer chains were eluted according to their ethylene/propylene contents and E or P sequence lengths, even though they are distributed in a random manner. These results showed that the solvent composition is an important factor to affect the interactive adsorption or desorption behaviour of EP chains on Hypercarb. In this way, for the first time, the determination of the complex composition and chain structure of EPR samples was achieved within short analysis time, which is not possible till now using other fractionation techniques reported.