合成氯醇橡胶催化剂——三异丁基铝-磷酸-叔胺催化体系

我们曾报导过三异丁基铝-磷酸-噻唑亚磺酰胺组成的催化体系对环氧氯丙烷均聚及环氧氯丙烷与环氧乙烷的共聚有相当高的催化活性,比一般常用的三异丁基铝-水-乙醚体系的催化效率高达十倍左右。后来我们进一步做了些工作,发现三异丁基铝-磷酸-叔胺组成的体系对环氧氯丙烷均聚及共聚也具有很高的催化活性。叔胺的成本一般较噻唑亚磺酰胺为低,而且是液体,在催化剂配制上较为方便。在我们工作的后期,看到日本专利中也有报导三异丁基铝-磷酸-叔胺催化体系的,但催化剂的配制方法有所不同,所举例子活性显得较我们的工作结果为低。     

开环共聚法合成热可逆共价交联聚醚橡胶

以烷基铝为催化剂,双环戊二烯二甲酸双缩水甘油酯为交联单体,与环氧氯丙烷、环氧乙烷、环氧丙烷进行离子型开环共聚,制得了热可逆共价交联的聚醚橡胶．研究了聚合方法、聚合配方和工艺条件对单体转化率、共聚物组成的影响．通过 Ｉ Ｒ 和 Ｄ Ｓ Ｃ 测定及反应溶解性和高温成型实验,证明了共聚物的结构及共价交联的热可逆转化特性．     

用简易凝胶渗透色谱柱研究氯醇橡胶

用简易GPC柱研究了三种类型氯醇弹性体的分子量分布。装柱填料是多孔硅胶球。理论塔板数2000块/米以上。用三异丁基铝-磷酸-水-二甲基苯胺催化剂制得的均聚氯醇胶比用三异丁基铝-磷酸-苯并噻唑亚磺酰胺所得氯醇胶分子量分布宽,宽度指数在3—6之间。均聚氯醇胶在素炼过程中,分子量分布变窄,分子量变低。转化率增加,单体浓度增加或温度降低使分布变宽。催化剂中的二甲基苯胺对三异丁基铝克分子比影响二元共聚胶的分布宽度。     

氯醚橡胶扩试成功

环氧氯丙烷橡胶(简称氯醚橡胶)是一类综合平衡性能良好的特种橡胶。它具有优良的耐热、耐油、耐寒、耐臭氧老化和耐气体透过等性能。 1973年以来,我们与沧州市合成橡胶实验厂协作,采用烷基铝-水-乙酰丙酮;烷基铝-乙酰丙铜锌(或烷基锌)-水;烷基铝-磷酸-路易士碱等催化体系,先后进行了环氧氯丙烷均聚;环氧氯丙烷和环氧乙烷共聚;以及环氧氯丙烷、环氧乙烷和环氧丙烷三元共聚的扩大试验。扩试结果表明:上述三个品种的氯醚橡胶均具有良好的综合平衡性能,且各具有不同的特色。其中三     

以氯代钒酸酯-三异丁基铝催化体系合成丁二烯-丙烯交替共聚物的研究

本文比较了各种氯代钒酸酯-三异丁基铝体系催化丁二烯、丙烯交替共聚的活性,得出氯代钒酸二新戊酯-三异丁基铝体系催化活性最高。能制得高分子量的交替共聚物。研究了该催化体系的特点和聚合规律及提高共聚物[η]的途径。在-76--45℃温度范围内可以制得正[η]为1.7-2.6dl/g的丁丙交替共聚物,单体转化率在80％以上。通过分析鉴定,证明产物交替度在95％左右,反式1,4丁二烯组分含量在95％以上。     

稀土配位催化环硫氯丙烷与环氧氯丙烷共聚合研究

研究了稀土配位催化剂对难以开环均聚和共聚的环硫氯丙烷（ＣＭＴ）与环氧氯丙烷（ＥＣＨ）的共聚合。发现稀土乙酰丙酮盐、环烷酸盐等与异丁基铝、水组成的络合催化剂有良好的催化活性，能制备得到类交替共聚物，产率高达６０％以上，分子量频高（［η］＝０．１５ｄＬ／ｇ）。应用ＩＲ、＾１３Ｃ ＮＭＲ、ＧＰＣ、ＶＰＯ等测试手段对共聚物的结构和分子量进行了表征。测定ＣＭＴ（１）与ＥＣＨ（２）共聚合的竞聚率分别为ｒ１＝０     

DL－丙交酯与2－氢－2－氧－1，3，2－二氧磷杂环己烷的开环共聚合研究

在三异丁基铝催化下ＤＬ－丙交酯与２－氢－２－氧－１，３，２－二氧磷杂环己烷开环共聚，制备了一类新型水溶性共聚物Ｐ（ＬＡ－ｃｏ－ＴＭＰ）。用１ＨＮＭＲ、ＩＲ谱对其结构进行了表征，并研究了催化剂用量及不同单体配比对总转化率、共聚物组成及特性粘度的影响。     

DL—丙交酯与2—氢—2—氧—1,3,2—氧磷杂环己烷的开环共聚合研究

在三异丁基铝催化下ＤＬ－丙交酯与２－氢－２－氧－１，３，２－二氧磷杂环已烷开环共聚，制备了一类新型水溶性共聚物Ｐ（ＬＡ－ｃｏ－ＴＭＰ），用ＨＮＭＲ、ＩＲ谱对其结构进行了表征，并研究了催化剂用量及不同单体配比对总转化率、共聚物组成及特性粘度的影响。     

环氧化合物以三异丁基铝-水-双(2,4-戊二酮基)锌水合物为催化剂的共聚

本文以i-Bu_3Al-H_2O-Zn(acac)_2为催化剂,对环氧氯丙烷、环氧乙烷和环氧丙烷的三元共聚进行了研究。结果表明,这种三元共聚橡胶具有良好的性能,其耐寒性可与丁腈-18相媲美,耐油性比丁腈-18为佳,而耐臭氧老化性是丁腈橡胶所不能比拟的。     

环氧乙烷及其同系物开环聚合的一些特点及其高聚物的某些性质

二十世纪五十年代以来,环氧乙烷及其同系物的聚合物的分子量从几万发展到几十万甚至几百万.Hill,Furukawat 及 Millert 等先后报道了用碱土金属碳酸盐、烷基锌及烷基铝等作为催化剂,使环氧乙烷聚合得到高分子量的聚合物.1952年 Pruittt 等用 FeCl_3与环氧丙烷作用所得的反应物作为催化剂使环氧丙烷聚合成为高分子量的产物.1965年 Vandenberg 报道了用烷基铝的水解产物作为催化剂成功地得到以环氧氯丙烷为     

Reaction of chlorine-containing polymers with living polymers

A graft polymer was prepared by means of the coupling reaction of chlorinated ethylene–propylene terpolymer with living polystyrene, obtained with a sodium–naphthalene complex as initiator, under various conditions; the grafting efficiency and the percentage of grafting are discussed. Poly(chloroprene), chlorinated butyl rubber, poly(vinyl chloride), poly(epichlorohydrin), and epichlorohydrin–ethylene oxide copolymer were also used as chlorine-containing polymers. The grafting efficiencies were found to be in the following order: chlorinated butyl rubber > poly(epichlorohydrin) > epichlorohydrin-ethylene oxide copolymer > chlorinated ethylene-propylene terpolymer > poly(chloroprene) > poly(vinyl chloride). A graft polymer was obtained from the reaction between chlorinated ethylene–propylene terpolymer and living poly(isoprene), with butyllithium in benzene. The undesirable metal–halogen interchange reaction was considerable.     

二氧化碳-环氧乙烷-氧化环己烯三元共聚物的制备与性能

采用稀土三元催化剂实现了二氧化碳、氧化环己烯与环氧乙烷的三元共聚,当环氧乙烷和氧化环己烯等摩尔投料时催化活性达到690 g/(mol Zn h),所得三元共聚物的数均分子量达到7.9×104,远程异核多量子相关核磁谱证明所得共聚物主要是无规三元共聚物,其中环氧乙烷-二氧化碳结构单元与氧化环己烯-二氧化碳结构单元相连的全交替结构占26.9%.二氧化碳-氧化环己烯共聚物的脆性导致其熔体加工十分困难,引入环氧乙烷为第三单体进行三元共聚,实现了二氧化碳-氧化环己烯共聚物的增韧,解决了其熔体加工难题,而且改变环氧单体比率能够调节三元共聚物的耐温性能和力学性能,当环氧乙烷与氧化环己烯等摩尔投料时,所得三元共聚物在20℃下的杨氏模量达到(900±17)MPa,拉伸强度为(38±2)MPa,断裂伸长率为(26.3±9.2)%.     

Synthesis of poly(carbon monoxide-co-ethylene-co-hexene) with supported palladium catalysts

The effect of conditions of carbon monoxide terpolymerization with ethylene and 1-hexene on the yield and composition of the terpolymer is investigated. The reaction is first carried out in toluene with the use of a supported palladium catalyst at different molar ratios of the olefins in the reaction solution. An increase in the hexene-to-ethylene molar ratio from 0.2 to 2.9 is accompanied by a decrease in the yield of the terpolymer by a factor of 2.8 and by a small increase in the molar fraction of hexene units in the terpolymer from 0.02 to 0.005?C0.06. The dependence of the amount of hexene units in the terpolymer on the olefin ratio differs from that obtained earlier in terpolymerization with propylene.     

氧化环己烯连续进料下二氧化碳-环氧丙烷-氧化环己烯三元共聚物的合成

由于氧化环己烯（CHO）与二氧化碳的共聚反应速度比其与环氧丙烷（PO）快,这种竞聚率的差异导致一锅法所得的二氧化碳-环氧丙烷-氧化环己烯三元共聚物的组成难以稳定控制。 为此本文在稀土三元催化剂下,采用氧化环己烯单体连续进料的方法合成了二氧化碳-环氧丙烷-氧化环己烯三元共聚物,催化效率可达575 g/(mol Zn h)。 三元共聚物的玻璃化转变温度随CHO含量升高而增大,当CHO的摩尔投料比从0.19增加到0.59时,玻璃化温度从44.3 ℃提高到70.1 ℃。 CHO连续进料合成的三元共聚物的组成与投料比基本相近,且连续进料法所合成的三元共聚物只有一个玻璃化转变温度,而普通的一锅法所得的三元共聚物通常存在两个玻璃化转变温度,因此连续进料法是制备组成稳定的二氧化碳-环氧丙烷-氧化环己烯三元共聚物的有效方法。     

稀土三元催化剂催化二氧化碳/环氧丙烷/环氧环己烷的三元共聚合研究

在稀土三元催化剂(三氯乙酸稀土配合物/二乙基锌/甘油)催化下实现了二氧化碳、环氧丙烷及环氧环己烷的三元共聚合.该催化剂对二氧化碳与环氧环己烷共聚的催化活性比对二氧化碳与环氧丙烷共聚的高.增加反应单体中环氧环己烷的比例可提高共聚物中环己撑碳酸酯的含量,大幅度改善共聚物的耐热性.     

以丙烯为主体的二元及三元共聚研究──丙烯与乙烯和丁烯－1的共聚合

研究了ＭｇＣｌ２载体高效催化剂用于丙烯为主体的与乙烯和丁烯－１的二元及三元共聚合反应：选择了最佳的共聚合条件；实验测定了共聚单体配比对共聚合活性、共聚物分子量和物理性能的影响；并用１３Ｃ—ＮＭＲ分析了共聚物组成、序列分布和支链结构等微观结构信息．     

三元共聚物聚甲基乙撑-环己撑碳酸酯的合成与表征

报道了三元共聚物聚甲基乙撑-环己撑碳酸酯的制备与性能研究. 实验采用高活性的负载戊二酸锌作为催化剂, 在不添加任何溶剂的情况下, 以二氧化碳和环氧丙烷、环氧环己烷为原料, 制备了不同环己撑碳酸酯含量的三元共聚物, 并对其结构和热性能、力学性能进行了表征和分析. 结果表明这些三元共聚物具有较高的分子量, 且玻璃化转变温度随着主链上的环己撑碳酸酯含量增加而逐渐升高. 同时三元共聚物表现出比二元共聚物更好的力学性能.     

Terpolymerization of carbon monoxide, ethylene and styrene in the presence of supported palladium catalyst

Terpolymers of carbon monoxide with ethylene and styrene are synthesized in the presence of supported palladium catalyst in toluene and heptane medium for the first time. The terpolymerization rate exceeds the rate of carbon monoxide and ethylene copolymerization. The maximum terpolymer yield amounts 7.9 g per g of supported catalyst per hour or 321 g per g of palladium per hour. The influence of reaction temperature, pressure, 1.4-benzoquinone amount and co-monomers mole ratio on the yield and the composition of terpolymer have been studied. The NMR ¹³C data obtained testify to a distribution of ethylene and styrene units in terpolymer with the predominance of short blocks at equal contents of comonomer units.     

Course of the terpolymerization of ethylene,propylene, and dicyclopentadiene. I. Single initial addition of dicyclopentadiene

Detailed studies were made of the course of the terpolymerization of ethylene, propylene, and dicyclopentadiene to form unsaturated elastomers. All the dicyclopentadiene was added at the start of a polymerization, but the monoolefins were added continuously throughout the run. Under these conditions, unsaturation of the initial polymer is fairly high but decreases steadily as the reaction progresses. From analyses of the initial samples from each run, the catalyst of VCl₄ (with Al₂Et₃Cl₃ cocatalyst), with heptane as the polymerization solvent, was most efficient for introducing unsaturation into terpolymer. This system also produces gel in the terpolymer in the latter stages of reaction, however. Catalysts of VCl₄, VOCl₃, or V(C₅H₇O₂)₃, with Al₂Et₃Cl₃ cocatalyst, in benzene solvent gave terpolymers of quite similar unsaturations. With all systems, terpolymer yield increases very rapidly in the first few minutes of reaction, then very slowly for the remainder of the 30-min. reaction time, reflecting the rapid loss of activity of the vanadium catalysts. Molecular weight growth of the terpolymer prepared in heptane was extremely rapid, reaching a high value in a few minutes. When prepared in benzene, the terpolymers showed a steady increase in molecular weight throughout the reaction but reached only a moderate final value (as expressed by inherent viscosity).