茂金属加合物技术的工业应用试验

根据中国石化集团公司开发的茂金属加合物专利技术,进行了活性组分负载化研究,完成了茂金属加合物催化剂催化乙烯以及乙烯与α-烯烃共聚的淤浆、环管淤浆、气相流化床工艺的中试试验.在中试的基础上进行了茂金属加合物催化剂气相流化床聚乙烯工艺的工业应用试验,探索了茂金属催化剂与Ziegler催化剂之间的切换技术,开发了催化剂结构和配方以及聚合工艺参数对聚乙烯树脂牌号的调控技术.得到百吨级薄膜牌号的茂金属聚乙烯树脂,并对工业应用试验产品进行了加工研究.     

新一代低碳烯烃聚合催化剂

对国内外用于烯烃聚合的Z-N催化剂、茂金属催化剂和非茂金属催化剂的发展及趋势进行综述。随着Z-N催化剂的性能不断改进和完善,新型Z-N催化剂继续占聚聚烯烃催化剂的主导地位;茂金属催化剂在今后的10年内将会占领很明显的市场份额;非茂金属催化剂综合了Z-N催化剂所生产树脂的优良加工性能和茂金属催化剂所生产树脂的优良物理性能。     

茂金属加合物技术首次工业试验

采用中国石油化工股份有限公司茂金属加合物技术制备茂金属加合物,并进行负载化研究;完成了茂金属加合物催化剂催化乙烯聚合以及乙烯与α-烯烃共聚合的淤浆、环管淤浆、气相流化床工艺的中试;在中试的基础上,茂金属加合物催化剂于60kt／a气相流化床聚乙烯生产装置上成功进行了工业试验。探索了茂金属催化剂与Ziegler催化剂的切换技术,研究了催化剂组成和聚合工艺参数对聚乙烯树脂性能的影响。用所得茂金属聚乙烯树脂加工成的薄膜具有较好的透明性,并表现出了优异的落镖冲击强度和撕裂强度。     

茂锆金属催化剂催化乙烯聚合研究

主要考察了含锆的茂金属催化剂中催化乙烯反应条件优化研究,在最优条件下催化聚合反应所得的产物与吉林石化公司聚乙烯厂聚乙烯产品进行分析对比.对茂锆金属催化剂催化乙烯聚合反应条件研究表明,适宜的助催化剂[Al]与主催化剂[Cat]的摩尔比在1 500左右,适宜的主催化剂浓度在1.5×10-4 mol/L左右,最佳聚合温度60℃,此时催化剂的活性可达到106 gPE/(molCat·h).从物理性能、热性能、相对支化度、相对分子质量及其分布分析可知,制备出的负载茂锆金属催化剂在最优反应条件下催化乙烯聚合所得的产物与吉林石化公司聚乙烯产品性质基本一致,符合产品的指标,支链分布均匀,分子量分布更窄.同时对茂锆金属催化剂主、助催化剂催化乙烯聚合的作用和机理进行了探讨.     

分子量宽峰分布聚乙烯茂金属催化剂的研究

以复合茂金属催化剂和双载体茂金属催化剂乙烯聚合、考察聚乙烯（ＰＥ）分子量分布变化情况。结果发现两者都使ＰＥ分子量分布加宽,其中复合茂金属催化剂Ｃｐ２ＺｒＣｌ２／ＹＢ３使分子量分布从２．３７增至９．１８。分子量分布增加幅度与不同复合茂经剂、催化剂配比、２载体量之比负载催化剂用量有关。     

国外化工信息

三井石化公司确立先会属聚丙烯技术三井石化公司采用茂金属催化剂确立了下一代聚丙烯（PP）生产技术。由于（用不对称催化剂）成功地开发出茂金属结构的PP而确立了工艺过程，可以非常稳定地生产接近理论值分子量分布的PP。已在中试装置上进入试生产。这是继Exxon、Hoechst公司成功地开发了用茂金属催化剂制的PP后，世界上的第三家公司。该公司开发的新型PP聚合催化剂选择以错为中心金属的金属络合物的茂金属结构，在此结构中组合配位体，是具有独特结构的催化剂。用此茂金属催化剂制的下一代PP的分子量分布（重均分子量与数均分于量之…     

二茂二氯化钛或锆与二茂基氯化钐复合催化乙烯聚合

分别以二茂二氯化钛(Cp2TiCl2)和二茂二氯化锫(Cp2ZrCl2)与钐茂金属催化剂复合组成催化体系，并以甲基铝氧烷为助催化剂，进行宽分子量分布聚乙烯合成研究。研究发现与使用Cp2TiCl2和二(甲基茂基)氯化钐复合体系相比，使用其与二(特丁基茂基)氯化钐[(t—BuCp)2SmCl]复合体系能得到具有较高粘均分子量的聚乙烯。同样，使用Cp2ZrCl2与(t—BuCp)2SmCl复合体系也能得到具有较高粘均分子量的聚乙烯。且使用含(t-BuCp)2SmCl复合体系得到分子量分布指数达3．5以上的聚乙烯。     

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.     

rac-Et(1-Ind)_2ZrCl_2/MAO催化1-癸烯聚合制备高粘度润滑油

茂金属催化体系具有超高活性和单一活性中心,是催化α-癸烯聚合的理想催化剂。用茂金属催化体系rac-Et(1-Ind)2Zr Cl2/MAO对1-癸烯聚合制备高粘度润滑油基础油进行了研究,提出了反应体系可能的聚合机理。考察了催化剂浓度、Al和Zr物质的量之比、反应温度和反应时间对聚合产物性能的影响。结果表明,在Zr和1-癸烯物质的量之比为8×10-5,Al和Zr物质的量之比为100,反应温度为50℃,反应时间为60 min时,1-癸烯的转化率为91.6%。聚合产物的整体性能较为优异,运动粘度(100℃)为393.9 mm2/s,粘度指数为271,数均分子量为9 091,分子量分布为1.691 3。     

负载茂金属催化剂催化乙烯气相聚合

研究了负载茂金属催化剂(n-BuNeCp)_2ZrCl_2/SiO_2的乙烯气相聚合行为及其催化聚合产品的性能。三乙基铝加入聚合体系后可降低负载茂金属催化剂的初始活性,有利于聚合过程中的温度控制。气相聚合产品聚乙烯的重均分子量为(1 42～2.28)×10~5,相对分子质量分布为2.6～3.1,熔点在135℃以上,结晶度约为60%,聚乙烯产物颗粒形态以球形为主.堆密度大于0.35 g/cm~3。     

Si-C型聚醚改性硅油的制备

研究了以烯丙基聚乙二醇甲基醚和低含氢硅油为原料,甲苯为溶剂,自制的催化剂,制备Si-C型聚醚改性聚硅氧烷,较适宜的合成条件为:选择相对分子量为1 000的聚醚,n(硅氢键)∶n(聚醚)=1∶1.2,反应温度90℃,催化剂用量为30×10-6,甲苯用量为总反应体系质量的25%。合成的聚醚改性硅油透明,性能优越,使用范围较广。     

从分子量分布探討均相及非均相丁二烯顺式-1,4聚合的机理

本工作以逐步沉淀法测定了在均相（Et_2AlCl-CoCl_2·4C_5H_5N）及非均相（i-Bu_3Al-TiI_4）Ziegler型催化剂的作用下,丁二烯在各种条件下进行顺式-1,4聚合的分子量分布。结果指出,不论均相或非均相催化聚合得到的分子量分布都比较窄。对于均相体系,升高聚合温度、降低单体浓度、添加链转移剂（如乙硫醚、N-苯基-β-萘胺、庚烷）、减少催化剂钴的浓度和增加Al/Co比,均能使聚合物的分子量分布变窄;而对于非均相体系,则降低聚合温度和减少Al/Ti比均能增加分子量的均一性;单体浓度和催化剂老化对分子量分布无显著影响。 非均相聚合的分子量分布比均相聚合的更窄,前者的微分分布曲线的高峰偏于高分子量部分,而后者的偏于低分子量部分。这可能是由于非均相聚合的链终止速度依赖于链长,而均相聚合的链终止速度与链长无关。     

Supuramolecular structure of self-assembly fabricated with novel aromatic polyether on Si-wafers

A new synthetic polymer of aromatic polyether (APE), having a narrow distribution of molecular weight, formed a specific self-assembly of Langmuir film (L film) on a water surface, which was subjected to surface pressure relaxation when the L film was compressed over 16.5 mN m(-1) at 15 degrees C. This self-assembly was capable of transferring on silicon-wafers as LB films. We found that, because the XRD patterns for fabricated LB films depended on the crystal face of the silicon-wafer used and moreover increased in diffraction intensity with the increasing number of built-up layers in the LB film, the present LB films showed a kind of epitaxy-like phenomenon. We propose the molecular mechanism explaining that the formation of an ionic supuramolecular structure of APE occurs only on a silicon wafer surface.     

树枝状聚酯—聚L-赖氨酸（Z）两嵌段共聚物的合成

由2,2-二羟甲基丙酸与2,2-二甲氧基丙烷经过逐级醇酸缩合、催化加氢和端氨基化后得到端基为氨基的树枝状聚酯分子G3-C3H9N2,以此为引发剂引发ω苄氧羰基L-赖氨酸-N-羧酸酐（ω-Z—L—lysine—NCA）开环聚合得到树枝状聚酯-聚L-赖氨酸（Z）两嵌段共聚物。采用^1H—NMR、IR、GPC方法对产物进行表征。结果表明：G3-C3H9N2能有效引发NCA开环聚合,共聚物的分子量可以通过调节单体引发剂比例来控制,所得产物具有较窄的分子量分布系数。     

UV induced reversible chain extension of 1-(2-anthryl)-1-phenylethylene functionalized polyisobutylene

The synthesis of novel 1-(2-anthryl)-1-phenylethylene (APE) di-telechelic polyisobutylenes is described. Utilization of a difunctional cationic initiator and the in situ addition of the non-homopolymerizable APE lead to the formation of di-anthryl telechelic polyisobutylenes. Products were characterized by ¹H NMR spectroscopy and Size Exclusion Chromatography. The polymers were UV irradiated at 365 and 254 nm and the reversible photocycloaddition of anthryl moieties was investigated. The chain extension of di-anthryl telechelic PIBs through photocoupling at 365 nm produced higher molecular weight products from low molecular weight precursors. The effect of precursor polymer concentration on the degree of chain extension was investigated, and intermolecular interactions leading to the formation of tetramers was observed. The photocoupled products were UV irradiated at 254 nm to induce the reversal of photocycloaddition of anthryl groups and to follow the consequent photoscission of polymers.     

减少DMC催化合成聚醚多元醇中高相对分子质量拖尾部分的研究

以双金属氰化物络合物(DMC)为催化剂,采用间歇法合成了聚醚多元醇,讨论了催化剂用量、反应温度、反应压力等因素对聚醚多元醇相对分子质量分布的影响。结果表明,硫酸质量分数为总量的0.004%、环氧丙烷预投量为起始聚醚质量分数的16%、DMC催化剂质量分数为总量的0.006%、反应温度在120～130℃和反应压力为0.1 MPa时,所制备的聚醚多元醇中高相对分子质量拖尾部分减少,相对分子质量分布窄,且其它物理性能也较好。     

Einfluß des stofftransportes bei der polymerisation von äthylen und 1-okten mit Ziegler-Katalysatoren

The polymerization of ethylene and 1-octene with supported Ziegler-catalysts was investigated with regard to the influence of mass transport of monomers on the kinetics, molecular weight and molecular weight distribution. In the case of the polymerization of ethylene, it was found that for certain conditions of reaction the mass transport of ethylene can influence the kinetics of polymerization respectively the catalyst efficiency strongly. The molecular weight and molecular weight distribution of the polyethylene formed are practically not affected by the conversion as well as particle size of catalyst and polymer. The molecular weight distribution however is affected by the concentration of the catalyst. The polymerization process of ethylene in suspension is distinguished by chemical and physical processes. A continuous chain initiation, for example, is based on the continuous reduction of the catalyst particles to small pieces during the course of polymerization. An apparent chain termination respectively catalyst deactivation can occur when catalyst particles are encapsulated within the growing polymer particles. The polymerization of 1 -octene for similar conditions of reaction gave polymers which were solved completely in the system used. The molecular weight distribution of the polymer formed nevertheless was very broad. This indicates that the mass transport of the monomers through the solid phase of polymer cannot be the main reason for the broad molecular weight distribution of the polymers which are produced by heterogeneous Ziegler-catalysts in suspension.     

离子液体中ATRP法合成聚合物分子量控制

在氯化1-烯丙基-3-甲基咪唑（[AMIM]Cl）离子液体中,采用原子转移自由基聚合（ATRP）技术,以CuBr/乙二胺为催化体系,合成了分子量分布窄的聚甲基丙烯酸甲酯（PMMA）分子。探索了聚合反应条件对PMMA分子量大小及分布的影响。通过GPC对PMMA分子量大小及分布进行测试,结果表明,在[AMIM]Cl离子液体体系中的ATRP反应,反应时间是控制PMMA分子量大小主要因素,而催化体系是控制PMMA分子量分布宽窄的决定性因素。通过优化反应条件可以设计聚合物分子量的大小和分布,可以实现对聚合物分子量的精确控制,使合成的聚合物材料满足在化工医药中的特定应用。     

Synthesis and characterization of the biomaterial poly(lactic acid‐co‐Nε‐carbobenzoyloxy‐L‐lysine) via direct melt copolymerization

With D,L ‐lactic acid and N^ϵ‐carbobenzoyloxy‐L ‐lysine [Lys(Z)] as the starting monomer material and tin dichloride as the catalyst, the drug carrier material poly(lactic acid‐co‐N^ϵ‐carbobenzoyloxy‐L ‐lysine) was synthesized via direct melt polycondensation. The copolymer was systematically characterized with intrinsic viscosity testing, Fourier transform infrared spectroscopy, ¹H‐NMR, gel permeation chromatography, differential scanning calorimetry, and X‐ray diffraction. The influences of different feed molar ratios were examined. With increasing molar feed content of Lys(Z), the intrinsic viscosity, weight‐average molecular weight, and polydispersity index (weight‐average molecular weight/number‐average molecular weight) gradually decreased. Because of the introduction of Lys(Z) with a big aromatic ring into the copolymer, the glass‐transition temperature gradually increased with increasing feed charge of Lys(Z), and all of the copolymers were amorphous. The copolymers, with weight‐average molecular weights from 10,500 to 6900 Da, were obtained and could reach the molecular weight level of poly(lactic acid) modified by Lys(Z) via the ring‐opening polymerization of the cyclic intermediates, such as lactide and morpholine‐2,5‐dione. However, a few terminal carboxyl groups might have been deprotected during the polymerization reaction under high temperatures. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Atom transfer radical polymerization of acrylonitrile

Iron(II) chloride coordinated by succinic acid was first used as the catalyst in 2‐chloropropionitrile‐initiated atom transfer radical polymerization (ATRP) of acrylonitrile. N,N‐dimethylformamide was used as a solvent to improve the solubility of the ligand. An iron(II) chloride to succinic acid ratio of 0.5 not only gives the best control of molecular weight and its distribution but also provides rather rapid reaction rate. Effects of solvent on polymerization of acrylonitrile were also investigated. The induction period is shorter in N,N‐dimethylformamide than in propylene carbonate and toluene and the rate of the polymerization in N,N‐dimethylformamide is fastest. The molecular weight of polyacrylonitrile agrees reasonably well with the theoretical molecular weight of N,N‐dimethylformamide. The rate of polymerization increases and the induction period becomes shorter with increasing polymerization temperature, and the apparent activation energy was calculated to be 56.5 kJ mol^?1. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1050–1054, 2006