苯乙炔直接成膜聚合

本文首次应用六种过渡金属(V、Cr、Mn、Fe、Co、Ni)环烷酸盐-三异丁基铝配合催化体系, 在室温下, 于加氢汽油-甲苯混合溶剂中, 使苯乙炔直接聚合成膜。研究了成膜聚合反应特征, 动力学行为及溶剂的影响。比较了不同催化体系的活性(Fe>Cr>Co>Mn>V>Ni)。表征了所制备的聚苯乙炔膜。聚苯乙炔膜可为黄、橙、红或褐色, 具有高顺式、高分子量、高稳定性及较好结晶性和半导体特性(电阻率为10^9Ω·cm)。     

聚合脂质体

本文综述了聚合脂质体的结构类型、制备及应用前景。     

Ziegler-Natta 型催化剂NdCl3·3I-PtOH-AlEt3 两组分间的反应及其反应产物对双稀烃聚合的催化活性

The reactions between the two components of the rare-earth coordination catalyst, NdCl3.3i-PrOH and AlEt3, were studied. It was found that the activated solid product was a mixture containing alkylated neodymium compounds, but no alkyl chloride was formed during the reaction. The alkyls bounded to neodymium or to the bridge between neodymium and aluminium atoms are thermally less stable than those bonded to the aluminium atom. Two possible structures of alkylated neodymium compounds were postulated. The catalytic activity in the isoprene polymerization increases with the increase of degree of alkylation and decreases in the presence of alkyl aluminium chloride.     

新一代高活性后过渡金属烯烃聚合催化剂

介绍了近几年发展起来的新一代后期过渡金属(Fe,Co,Ni,Pd)烯烃聚合催化剂,对催化剂的结构、性能及催化烯烃聚合进行了阐述。     

六氟丙烯等离子体聚合的研究

求得了六氟丙烯等离子体聚合物(PPHFP)膜的热裂解反应活化能为101.6 kJmol~(-1),半分解温度为322℃。讨论了不同条件下聚合速率的变化,找出了反应器内各点的聚合速率与压力的关系曲线,同时也证实了N_2作等离子气体时,N可以化学键的形式进入PPHFP膜结构。     

Nd(OR)3-nCln-AlEt3催化体系对丁二烯的聚合 II.聚合物微观结构和催化剂诱导效应指数的关系

With a new series of binary catalyst Nd(OR)3-nCln-AlEt3 prepared in our laboratory, the effect to catalyst composition on the microstructure of polybutadiene was studied in detail. A linear relationship is found between the variation of the microstructure of the polymer obtained and the iductive effect index (I) which reprepresents the magnitude of the displacement of paired valence electrons on transition metal-halogen bond (MT-X) of the catalyst. This linear relationship also holds in dealing with the data published in the literature.     

三水合稀土氯化物RECl3·3H2O的热化学研究

本文报道了一套化学反应绝热式热量计的设计和建立,用(HOCH_2)_3CNH_2与0.1mol·dm~3HCl的反应焓检验标定了热量计装置,测得ΔH_(208.15)=-245.41J·g~(-1),sdm=±0.24,与IUPAC的推荐值-245.76±0.26J·g~(-1)十分吻合,证明热量计和操作手续是可靠的。用这样的热量计测定了十一种三水合稀土氯化物RECl_3·3H_2O(RE=La,Ce,Nd,Sm,Eu,Gd,Tb,Dy,Er,Yb,Y)298.15K时在水中的积分溶解热(终浓度-0.01541mol·kg~(-1))。计算了这些水合物的标准生成焓和脱水焓。     

烯烃聚合中金属化合物间的链转移反应

烯烃聚合过程中, 金属化合物之间快速可逆的链转移反应是一个重要和有用的反应, 它不仅影响催化剂的活性和实现对聚合物分子量的控制, 还可以得到长链烷基金属化合物, 进而通过后续转化得到特种聚烯烃材料, 如官能团化聚烯烃和多嵌段聚烯烃共聚物. 综述了这一方面的主要发展情况.     

酚化合物的酶催化聚合研究进展

酶催化聚合反应条件温和,具有绿色化学的特点,其中过氧化物酶催化酚类化合物的聚合反应是一种制备无醛酚聚合物的新方法,引起众多学者的关注.本文作者综述了各类酚化合物的酶催化聚合研究进展,并对一些聚合产物的性能进行了分析.酚化合物的酶催化聚合反应具有良好的应用前景,但仍存在一些制约因素,本文作者对此也进行了总结.     

Nd(OR)3-mClm-AlEt3 catalyst system in the polymerization of butadiene: I. The general feature of polymerization

Homopolymerization of butadiene has been carried out with a new series of binary catalyst system Nd(OR)_3-mG_m-AlEt₃. The catalytic activity as well as the microstructure of the resulting polymer have been studied. The results indicate that the stereospecificity of the polybutadiene obtained with these binary catalyst system (when m = 2) is similar to that prepared with ternary system Nd(OR)₃-Al₂Et₃Cl₃-AlEt₃, yet the catalytic activity of the former is somewhat higher. Thus possibly, the present simpler binary system is preferable to the ternary system when applied to the polymerization of butadiene.     

MgCl2载体对Nd(OiPr)3-nCln-HAl(i-Bu)2催化剂性能的影响

对不含ｆ 电子的过渡金属 (Ｔｉ、Ｃｏ、Ｎｉ等 )的Ｚｉｅｇｌｅｒ Ｎａｔｔａ催化剂 ,载体化是提高催化活性的一种重要方法 ,并已经取得了成功[1,2 ] 。而对具有许多独特优点[3] 的稀土Ｚｉｅｇｌｅｒ Ｎａｔｔａ催化剂的载体化 ,虽然人们也做了一些研究[4 ,5] ,并在一定程度上提高了催化效率 (约 2～ 3倍 ) ,但与高效载体催化剂相比 ,其催化效率还是比较低 ,因此有必要进行进一步探索 ,以助于寻找提高催化活性和定向性的途径。1　实验部分1 1　催化剂的制备1 1 1　ＭｇＣｌ2 载体的制备[6] 　将 2 0 0ｇＭｇＣｌ2 ·6Ｈ2 Ｏ与 5 5ｇＮ…     

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...     

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...     

氯化稀土乙二醇二甲醚配合物催化丁二烯聚合

以Nd2O3、(CH3)3SiCl和乙二醇二甲醚(DME)为原料,合成了NdCl3·2DME配合物,并将其用于催化丁二烯聚合。 考察了助催化剂种类与用量、陈化温度和聚合时间对聚合的影响。 结果表明,以烷基铝与MAO共同作为助催[JP2]化剂时具有高聚合活性,而单独以烷基铝或甲基铝氧烷(MAO)为助催化剂时聚合活性很低。 当n(Nd)∶n(AlR3)∶n(MAO)=1∶30∶45时,催化活性最高。 陈化温度对聚合活性、聚合物结构及相对分子质量均有较大的影响。 陈化温度过低或者过高,聚合活性、聚丁二烯cis-1,4含量和相对分子质量均降低;陈化温度为50 ℃时,具有最高聚合活性和最高cis-1,4含量。 NdCl3·2DME催化体系所得聚丁二烯的cis-1,4含量高达98.7%（IR）,而1,4-结构总含量高达99.6%（1H NMR）。     

聚合物载体-稀土金属配合物的研究IV.含亚硫酰基聚合物载体-稀土金属配合物的合成,表征及其催化活性

Styrene-2-(methylsulfinyl)ethyl methacrylate copolymer-supported MCl3 complexes, where M = La, Pr, Nd, Eu, Ho, Er, Tm, and Yb, were prepared and characterized by IR spectroscopy. The catalytic activity of the polymer-supported NdCl3-(iso-Bu)3Al system towards stereospecific polymerisation of butadiene was 2-3 times higher than that of NdCl3-(iso-Bu)3Al-DMSO system. The cis-1,4 content of polybutadiene formed was >98%.     

镍系催化丁二烯聚合条件的新探索

通过改变环烷酸镍─三异丁基铝─三氟化棚乙醚络合物［（Ni（naph）2－Al（i－Bu）3－BF3OEt2）］体系中催化剂的配比，丁二烯浓度，聚合温度等聚合条件，考察了它们对适宜Al／B比活性范围的影响，结果表明：采用固定Ni变Al或者固定Al变Ni两种方式改变Al／Ni摩尔比，都能有效地调节适宜Al／B比范围，并认为目前工业生产顺丁橡胶的配方中Al／Ni＝4是太低的，有必要适当加以提高；丁二烯浓度太低时，适宜Al／B比范围很窄，从提高聚合活性和聚合速率来看，适当地提高丁二烯浓度是有益的；在一定范围内改变聚合温度，对适宜Al／B比范围没有明显影响。     

Nd（OPr~i）_（3－n）Cl_n－AIR_3二元体系催化异成二烯聚合的研究

Ｎｄ（ＯＰｒ￣ｉ）＿（３－ｎ）Ｃｌ＿ｎ－ＡＩＲ＿３二元体系催化异成二烯聚合的研究蔡小平，龚志，王佛松，朱行浩（中国科学院长春应用化学研究所，长春１３００２２）（吉林化学工业公司研究院，吉林１３２０２１）关键词聚异成二烯，二元钕催化剂，定向聚合，稀土催...     

Neodymium alkoxides: synthesis,characterization and their combinations with dialkylmagnesiums as unique systems for polymerization and block copolymerization of ethylene and methyl methacrylate

The synthesis and characterization (NMR and X-ray) of a variety of neodymium alkoxides derived from simple and functionalized tertiary monoalcohols, and their application as inorganic precursors in combination with dialkylmagnesium reagents for ethylene and methyl methacrylate (MMA) (co)polymerization have been investigated. Salt metathesis reactions between NdCl(3) and sodium alkoxides in THF led to the formation of trinuclear complexes [Nd(3)(mu(3)-OR)(2)(mu(2)-OR)(3)(OR)(4)(thf)(2)] with R=tBu (1), tAm (2), while aggregate structure [Nd(12)(OtAm)(26)(HOtAm)(2)Cl(11)Na].(OEt(2))(2) (3) was obtained when the synthesis was performed in Et(2)O. [Nd(3)(mu(3)-OtBu)(2)(mu(2)-OtBu)(3)(OtBu)(4)(HOtBu)(2)] (4), prepared by aminolysis of Nd[N(SiMe(3))(2)](3) in hexane, slowly decomposed in toluene into oxo complex [Nd(5)(mu(5)-O)(mu(3)-OtBu)(4)(mu(2)-OtBu)(4)(OtBu)(5)] (5). Finally, the dimer [Nd(2)(mu(2),eta(2)-OR)(2)(eta(2)-OR)(2)(eta(1)-OR)(2)] (OR=OCMe(2)CH(2)CH(2)OMe) (6) was synthesised by aminolysis reaction from the corresponding gamma-donor-functionalized alcohol. Some of these neodymium alkoxides, in particular homoleptic complex 1, when associated in situ to one equivalent of a dialkylmagnesium, allow the formation of an active catalyst for ethylene polymerization. Under mild conditions (0 degrees C, 1 bar), the latter catalyst system exhibited a moderate activity (5-10 kg mol(-1) h(-1) bar(-1)). Effective transfer reactions were observed in the presence of H(2) or PhSiH(3) and renewal/improvement of activity occurred upon extra addition of dialkylmagnesium. The most outstanding feature of this catalytic system lies in the precipitation of the active "Nd-polyethylenyl" species during the ethylene polymerization course as solid S which could be isolated. This heterogeneity was turned to good account, enabling to achieve heterogeneous solid-gas ethylene polymerization and to prepare diblock PE-PMMA copolymers with high diblock efficiency and high molecular weights (M(n) > 200 000). A catalytic cycle for this unique system is proposed based on the isolation of a transmetallation product (7) from a neodymium alkoxide/dialkylmagnesium combination and NMR studies of the latter.