用可溶性催化剂合成顺式聚丁二烯的研究——Ⅰ.用CoCl2·4C5H5N-(C2H5)2AlCl作催化剂

本文研究了催化剂的用量、单体的浓度、聚合温度等聚合条件对聚丁二烯的转化率、分子量以及链结构的影响。试验结果表明:这个催化剂的特点是催化剂用量极少,1,4-顺式含量高而且稳定,聚合速度太快,高聚物的分子量过大,因此进一步研究了聚合速度的控制和高聚物分子量的调节。已得到的结果是:(1)在不同溶剂中聚合的速度相差甚大。其快慢的顺序是,苯>甲苯>二甲苯>三甲苯。(2)添加一些如苯基-β-萘胺、N,N′-二苯基对苯二胺等胺类,既可减慢聚合速度,又能降低高聚物的分子量。(3)调节体系中水分的含量,控制高聚物的分子量。(4)利用二种溶剂混合的不同比例,调节高聚物的分子量。(5)加入少量的萘、蒽等稠环芳烃于庚烷溶剂中,则大大提高高聚物的分子量。对上述结果进行了讨论。     

球笼烯（C_（60）／C_（70）载体钕系催化丁二烯聚合的研究

球笼烯（Ｃ_（６０）／Ｃ_（７０）载体钕系催化丁二烯聚合的研究赵春英，陈滇宝，仲崇祺，董文寰，徐玲，唐学明（青岛化工学院高分子材料系青岛２６６０４２）杨海滨，李明辉，邹广田（吉林大学超硬材料国家重点实验室长春１３００２３）关键词球碳载体钕系催化剂，聚丁...     

钼体系催化丁二烯聚合动力学——链转移

本文考察了MoCl_4OC_8H_(17)-(i-Bu)_2Alo催化体系在加氢汽油中催化丁二烯聚合过程中的链转移情况,提出了比较聚合体系中各组分对链转移的贡献大小的方法和计算链转移次数的公式及链转移次数与聚合温度的函数关系式。发现本体系中单体和主催化剂是主要的链转移剂,向烷基铝的链转移占10％,向杂质的链转移仅占6％。在链转移反应中,单体和主催化剂的级数为1,烷基铝的级数为1/2。     

BF_3·OEt_2对钼体系催化合成1,2-聚丁二烯的影响

在以加氢汽油为溶剂,MoCl_3(C_7H_(15)COO)_2(Mo)为主催化剂,(i-Bu)_2AlO〈O〉(Al)为助催化剂合成1,2-聚丁二烯的二元催化体系中,添加BF_3CH3·OEt_2等,对体系的催化活性影响显著。以的混合物为第三组份加入催化体系,较大幅度提高了钼系催化体系的活性。在Mo/Bd=8.0×10~(-5)(摩尔比),聚合5小时,丁二烯转化率可达到70％。初步搞清了钼催化体系合成的1,2-聚丁二烯中产生凝胶的条件,推测了凝胶的生成原因,考察了聚合条件对催化活性、分子量及微观结构含量的影响。     

A STUDY OF POLYBUTADIENE SYNTHESIS WITH MoCl_n(OR)_(4-n)-(i-Bu)_2AlOPh AS A CATALYST

The catalytic effect of Mo Cl_n (OR)_(4_n)-(i-Bu)_2AlOPh on the polymerization of butadiene inhydrogenated gasoline is studied (R is alkyl, cycloheptyl, phenyl of C_(4_16)). In this system, the solu-bility and the catalytic activity of the catalyst do not depend on whether the number of carbon atomsin R group is odd or even. The R group with the primary and secondary carbon atom has a fairlygreat influence on the catalytic activity. When R is an alkyl, the catalytic activity increases and therange of Al/Mo values that keeps higher conversion of butadiene is broadened as the size of the Rgroup increases. The content of 1,2-units in the polymer hardly varies with the size of the R group.     

1H和19F NMR研究镍系催化丁二烯聚合中醇类对BF3·Oet2的增溶作用

The solubility of BF₃OEt₂ in hydrogenated gasoline was improved greatly by means of premixing BF₃OEt₂ with C₃H₁₇OH in nickel catalyst system, so that the effeciency of fluorine in the system was increased markedly. It is confirmed that there was a intermolecular hydrogen bond between alcohol and BF₃OEt₂ molecules by using ¹H NMR, which was a vital factor to lead the solubilization of BF₃OEt₂ in hydrogenated gasoline. Otherwise, the caculation formula of the chemical shift ofproton in hydroxy, ¹H = xipi,was suggested in hydrogen bond system.     

BF_3·OEt_2在镍体系催化丁二烯聚合中的作用

本文借助于紫外可见光谱、磁化率法和聚合活性测定等方法,研究了BF_3·OEt_2在镍体系催化丁二烯聚合中的作用。初步探明了BF_3·OEt_2与Ni(naph)_2作用会形成“F-B-Ni”配合物,对形成活性中心不利。     

钨系催化丁二烯聚合动力学的研究——聚合速率方程的建立及活化能的确定

本文研究了WCl_6-C_4H_9OH-Al(i-Bu)_2 OPhCH_3体系催化合成1,2-聚丁二烯的动力学特征,测定了单体、主催化剂和助催化剂的反应级数,建立了稳态期聚合速率方程,求得其表现活化能及Arrhenius因子,并对其反应动力学机理作了初步讨论。     

STUDY ON SYNTHESIS OF HIGH VINYL POLYBUTADIENE WITH TETRAVALENT MOLYBDENUM CATALYST SYSTEM

In this paper the catalytic behaviour of tetravalent molybdenum catalyst system in polymeriza-tion of butadiene is dealt with. The effects of the variety of apions combined with molybdenumatom, the pattern of the substituent R in (i-Bu)_2AlOR and the polymerization conditions on thebutadiene conversion, the molecular weight and its distribution and the microstructure of the polymeralso are studied. It has been found that the catalyst system is significantly active when anions com-bined with the molybdenum atom are acetoxy (CH_3COO-),or ethoxy (C_2H_5O-). Obviously, thevariety of substituent R in (i-Bu)_2 AlOR has a great influence on the catalytic activity. The catalystsystem is inactive if the R group is--COR' (R'is alkyl or aromatic group) or alkyl, whereas the activityof the catalyst system increases if the R group is phenyl or tolyl. With the rise of polymerizationtemperature the polymer molecular weight decreases, the distribution index of molecular weight in-creases and the content of 1,2-unit in polybutadiene reduces.     

镍催化体系合成顺式聚丁二烯的研究——Ⅶ.紫外可见光谱法探讨镍系各组分间的相互作用

环烷酸镍的汽油或甲苯溶液呈亮绿色,根据自旋允许d-d跃迁,在光谱的红和兰区有三个吸收带,其峰值分别是403、680和1170nm,络合物具有八面体构型。在Ni-Al体系中,当Al/Ni摩尔比<0.53,只发生配位体的交换反应,Al/Ni≥0.53,体系中发生还原反应,Ni(II)→Ni(I)→Ni(O)。在Ni-B体系中,只发生配位体交换反应,生成的氟-硼-镍络合物具有和环烷酸镍相类似的d-d吸收带,络合物也具有八面体构型。以上结论与磁化率法的结果一致。