机械球磨共聚络合剂法制备Zn-Ni双金属催化剂催化环氧丙烷和邻苯二甲酸酐共聚（英文）

机械球磨法是一种快速且环境友好,具有巨大潜力的无溶剂合成双金属氰化物催化剂(DMC)的合成方法。通过共聚络合剂辅助机械球磨法成功制备出了Zn-Ni双金属催化剂,经元素分析和红外光谱结果显示双金属催化剂中掺入了各种共聚络合剂;扫描电镜表明,由此产生的双金属催化剂是纳米级的。双金属催化剂在无溶剂、反应时间为6h、反应温度为110℃的条件下可高效催化环氧丙烷(PO)与邻苯二甲酸酐(PA)的开环聚合,在共聚反应中,催化剂显示相对较高的活性,以高产率得到高分子量和窄分子量分布的聚酯(PO-co-PA)。     

二氧化碳—环氧丙烷—甲苯二异氰酸酯的三元共聚

二氧化碳和环氧丙烷(PO)在阴离子配位催化剂,如二乙基锌和等摩尔的水作用下,可接式(1)发生共聚。但产物聚丙撑碳酸酯(PPC)的热稳定性较差。改进途径之一是在反应中引入甲苯二异氰酸酯(TDI)进行三元共聚。本文报导在双金属阴离子配位催化剂PBM存在下合成一种热稳定性优于PPC的聚碳酸酯聚氨酯(PCPU)的研究结果(式2)。     

有机小分子催化环醚与环状酸酐共聚研究进展

有机小分子催化聚合反应是合成化学领域新的研究方向。有机催化环醚(主要为环氧化物)与环状酸酐共聚制备聚酯的合成路线,由于单体具有来源广泛、有机催化剂低毒、对水和空气不敏感等特点,因而应用前景广阔。本文按有机小分子催化剂、环醚与环状酸酐的种类综述了近年来出现的有机催化共聚合成聚酯的反应,并详细讨论了该共聚反应及其机理,尤其是高催化活性和聚合可控性的Lewis酸碱对催化共聚的机理;提出了利用Lewis酸为增长链阴离子提供结构因素(如基团和电子结构效应)来调控聚合的方法。今后,催化环氧化物与环状酸酐共聚研究的中心任务仍然是发展新的高活性有机催化剂,并实现"活性"的全交替共聚反应,进一步提高共聚物的分子量,并实现共聚反应的化学选择性、区域和立体选择性的精确控制。     

Fe-Al-α,α′-联吡啶催化体系催化马来酸酐与环氧丙烷开环共聚

马来酸酐与环氧丙烷开环共聚,所得聚酯具有功能团（C＝C）,可以通过接技、交联待方法改变其性能,马来酸杆与环氧化物开环共聚合成聚酯,所用催化剂通用有有机金属化合物和稀土 事物等,我们在铁系催化丁二聚合和马来酸酐与苯乙烯共聚的基础上,首次将Fe(acac)3-Al(i-Bu)3-α,α′－联吡啶催化剂用于马来酸酐与环氧化物开环共聚,发现该催化剂催化共聚反应具有时间短、收率高、共聚物交替度高等优点,并测定了共聚合反应动力学的参数。     

冠醚络合高活性双金属氰化物制备及CO2与环氧丙烷共聚

首次在共沉淀过程中添加18-冠-6醚络合生成的钾离子得到了均一的高活性冠醚络合的锌-钴双金属催化剂,并用红外光谱(FTIR)、扫描电镜(SEM)、热重红外(TGA-IR)和X射线衍射(XRD)进行了表征.元素分析发现K含量为1.2%. FTIR表明未加冠醚络合的双金属催化剂离心后上下部分呈现不同的络合状态,而冠醚络合的双金属催化剂仍保持均一. SEM表明冠醚络合的双金属催化剂为均一松散的结构.由于生成的钾离子被冠醚络合,不影响聚合反应效果. TGA-IR表明冠醚不仅络合K离子,还参与对金属活性中心的络合. XRD表明此催化剂具有低的结晶度.所制冠醚络合的锌-钴双金属催化剂能成功催化CO2与环氧丙烷共聚,其中CDMC3催化得到的共聚物碳酸酯含量为47.8%,副产物环状碳酸酯为1.5%,催化效率高达5122 g/g催化剂(32600 g/g Zn),明显优于不添加冠醚以同样工艺制备的DMC1(共聚物碳酸酯含量29.2%,副产物环状碳酸酯3.3%,催化效率4100 g/g催化剂(16300 g/g Zn).与不添加冠醚8次洗涤离心得到的DMC2相当(共聚物碳酸酯含量48.3%,副产物环状碳酸酯含量2.4%,催化效率5073 g/g催化剂(16400 g/g Zn)).基于此结果提出了两步的反应机理假设.     

球磨双金属氰催化剂催化CO_2/环氧丙烷/四氯苯酐三元共聚

由于共聚配合剂的加入有利于提高双金属氰催化剂(DMC)的催化活性,因此本文通过加入不同的共聚配合剂,采用绿色高效的机械球磨法制备了Zn-Co DMC催化剂体系,然后将DMC用于制备CO2、环氧丙烷和四氯苯酐(THPA)的三元共聚物聚碳酸亚丙酯四氯苯酐(PPCPA)。通过傅里叶变换红外光谱(FTIR)、扫描电子显微镜(SEM)、多晶X射线衍射(XRD)、凝胶渗透色谱(GPC)和热重分析(TG)等技术手段表征了催化剂和PPCPA的结构和性能。结果表明,共聚配合剂辅助球磨Zn-Co DMC催化聚合反应转化数25.67~141.80,PPCPA数均相对分子量2.21×10~3~3.15×10~3,多分散指数1.04~1.24,呈现窄分布。PPCPA的热稳定性要高于聚碳酸亚丙酯(PPC),热分解温度提高了129.8℃。     

硫代羧基环内酸酐与丙交酯的可切换共聚

硫代聚酯是一种兼具聚酯材料的优点(降解性、生物相容性和热稳定性等)与含硫聚合物材料的优点(光学性能和金属吸附性能等)的新型材料.本文合成了含硫单体硫代羧基环内酸酐(MDTD),以希夫碱锰(Salen-Mn)为催化剂,在低投料比(50:1)较低温度(60℃)的情况下,抑制了小分子副产物的生成,实现了MDTD的活性聚合.在此基础上,利用Salen-Mn可逆插入氧硫化碳(COS)的性质,设计开发出了一条新的硫代单体控制的自切换共聚路线.通过在丙交酯(LA)聚合的过程中添加MDTD单体以及改变聚合反应气氛的手段实现了MDTD与LA的可切换共聚,并应用核磁、凝胶渗透色谱等方法跟踪反应进程表征反应产物,证实了多嵌段聚酯/聚硫酯(p(LA-b-MDTD-b-LA))的生成.通过该方法最终得到了五嵌段的聚酯/聚硫酯(M_n=12.4 kg/mol,?=1.20)的嵌段共聚物.该方法可以通过改变相应的单体结构合成相应的多嵌段聚酯/聚硫酯,为改善含硫聚酯的物理化学性质打下了基础.     

双金属氰化络合物催化环氧丙烷和邻苯二甲酸酐共聚

采用双金属氰化络合物 (DMC)催化环氧丙烷 (PO)和邻苯二甲酸酐 (PA)共聚 ,探讨了共聚合特征 ,并用IR、1 H NMR和GPC对共聚物的结构和分子量进行了表征 .发现DMC催化剂对该共聚反应速度快 ,转化率高 ,是该反应的有效催化剂 ,催化剂浓度为 6 0mg kg时 ,90℃下 ,以THF作溶剂共聚反应 3h ,转化率可达94 0 % .聚合速度甚至比DMC催化PO均聚还快 .该共聚反应可在多种溶剂中进行 ,极性溶剂更有利于共聚合 ,溶液聚合温度比本体共聚低 ,合适的溶液共聚温度在 90～ 10 0℃之间 .共聚产物的分子量受催化剂用量、反应温度和体系中水份含量的影响 ,数均分子量在数百至数千之间 .考察该共聚体系的动力学表明 ,该共聚反应速率对单体浓度呈一级关系     

钴系催化剂催化丁二烯—苯乙烯共聚动力学研究

合成高顺-1,4-丁苯胶的催化剂主要是镍、钴、钛系3类。钴系催化剂基本上是三元体系,也有加入添加剂(含N,O,S化合物)的多元体系。该体系的特点是,共聚物顺1,4含量高(～98％),分子量大。但苯乙烯的共聚活性低,有均聚苯乙烯和凝胶形成。本文以Co(nap)_2-Al_2Et_3Cl_3进行了丁苯共聚的动力学研究。     

负载型钴二亚胺配合物-TiCl_4复合催化剂制备新型乙烯/1-丁烯共聚产物结构性能研究

合成了三种负载型二亚胺配体钴配合物 TiCl4复合催化剂 (CL1、CL2、CL3催化剂 ) .不用MAO ,以烷基铝为助催化剂 ,用它们催化乙烯 1 丁烯淤浆共聚合制备一系列塑性体和弹性体共聚物 .研究表明 ,复合催化剂性质受二亚胺配体性质影响 ,配体L1制备的复合催化剂具有低聚及原位共聚性能 ,可制得高支化度(36 0～ 6 1 5branchnumber 10 0 0C)低密度和极低密度 (0 885～ 0 910g cm3)塑性体和弹性体共聚物 .在 1 丁烯用量低于 5 %时 ,CL1催化剂制备的共聚产物中 1 丁烯含量超过投料比     

Biodegradable Polycarbonate Synthesis by Copolymerization of Carbon Dioxide with Epoxides Using a Heterogeneous Zinc Complex

As a means for the chemical fixation of carbon dioxide and the synthesis of biodegradable polycarbonates, copolymerizations of carbon dioxide with various epoxides such as cyclohexene oxide (CHO), cyclopetene oxide, 4-vinyl-1-cyclohexene-1,2epoxide, phenyl glycidyl ether, allyl glycidyl ether, propylene oxide, butene oxide, hexene oxide, octene oxide, and 1-chloro-2,3-epoxypropane were investigated in the presence of a double metal cyanide catalyst (DMC). The DMC catalyst was prepared by reacting K₃Co(CN)₆ with ZnCl₂, together with tertiary butyl alcohol and poly(tetramethylene ether glycol) as complexing reagents and was characterized by various spectroscopic methods. The DMC catalyst showed high activity (526.2 g-polymer/g-Zn atom) for CHO/CO₂ (P_CO2 = 140 psi) copolymerization at 80 °C, to yield biodegradable aliphatic polycarbonates of narrow polydispersity (M_w/M_n = 1.67) and moderate molecular weight (M_n = 8900). The DMC catalyst also showed high activities with different CO₂ reactivities for other epoxides to yield various aliphatic polycarbonates with narrow polydispersity.     

Novel type of heterogenized CuCl2 catalytic systems for oxidative carbonylation of methanol

A novel type of heterogenized CuCl₂ catalysts was designed for the oxidative carbonylation of methanol to dimethyl carbonate (DMC) taking account of the plausible reaction mechanism and intermediates. To prevent severe corrosion of the reaction equipment materials due to Cl^? while keeping the catalytic activity of the homogeneous CuCl₂ catalyst, we adopted, as supports (or ligands) of CuCl₂, four polymers, bearing a 2,2′-bipyridine (bpy) or pyridine (py) unit, namely, poly(2,2′-bipyridine-5,5′-diyl) (Pbpy), poly(pyridine-2,5-diyl) (Ppy), poly(N,N′-bisphenylene-2,2′-bipyridine-4,4′-dicarboxylic amide) (Bpya), and poly(4-methyl-4′-vinyl-2,2′-bipyridine) (Pvbpy), together with one chelate compound, 8-quinolinol. The catalytic activity, stability of heterogenized CuCl₂ and their corrosivities to stainless steels were examined in the liquid-phase reaction of the oxidative carbonylation of methanol. These polymer-supported catalysts showed considerable catalytic activity and stability for the DMC synthesis. In particular, the Pbpy-CuCl₂ and Ppy-CuCl₂ catalysts exhibited high DMC yields and selectivity comparable to those of the homogeneous CuCl₂ catalyst. This high activity appears to be associated with the presence of the π-conjugated system in the polymers, which affect the redox reactions of Cu involved in the catalytic reaction. All of the polymer-supported CuCl₂ catalysts could be easily recycled after filtration, and the initial catalytic activity was maintained after three times of use. The corrosive characters of the catalysts were closely related to CuCl₂ leaching from the supports, which reflects the ability of supports to coordinate Cu. These experimental results suggest that both the electronic structure and the coordination ability of the polymer supports are key factors for the development of an effective catalytic system.     

Effect of supercritical CO2 on the copolymerization behavior of cyclohexene oxide/CO2 and copolymer properties with DMC/Salen‐Co(III) catalyst system

The copolymerization of cyclohexene oxide (CHO) and carbon dioxide (CO₂) was carried out under supercritical CO₂ (scCO₂) conditions to afford poly (cyclohexene carbonate) (PCHC) in high yield. The scCO₂ provided not only the C1 feedstock but also proved to be a very efficient solvent and processing aid for this copolymerization system. Double metal cyanide (DMC) and salen‐Co(III) catalysts were employed, demonstrating excellent CO₂/CHO copolymerization with high yield and high selectivity. Surprisingly, our use of scCO₂ was found to significantly enhance the copolymerization efficiency and the quality of the final polymer product. Thermally stable and high molecular weight (MW) copolymers were successfully obtained. Optimization led to excellent catalyst yield (656 wt/wt, polymer/catalyst) and selectivity (over 96% toward polycarbonate) that were significantly beyond what could be achieved in conventional solvents. Moreover, detailed thermal analyses demonstrated that the PCHC copolymer produced in scCO₂ exhibited higher glass transition temperatures (T_g ～ 114 °C) compared to polymer formed in dense phase CO₂ (T_g ～ 77 °C), and hence good thermal stability. Additionally, residual catalyst could be removed from the final polymer using scCO₂, pointing toward a green method that avoids the use of conventional volatile organic‐based solvents for both synthesis and work‐up. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2785–2793     

Highly active double metal cyanide complexes： Effect of central metal and ligand on reaction of epoxide/CO2

Various novel double metal cyanide (DMC) catalysts were successfully prepared by modifying the central metal (M) and one of cyanide ion (CN-) in Zna[M(CN)b]c complex. Such modifications have significant impact on the catalytic efficiency as well as the polymer selectivity for the reaction of PO/CO2. Zn–Ni(Ⅱ) DMC is a potential catalyst for alternating copolymerization of PO/CO2, and DMC catalysts based on Zn3[Co(CN)5X]2 (X = Br-and N3-) exhibit moderate efficiency for the production of polycarbonates. This research presents the preliminary exploration of novel DMC complex via chemical modification of its central metal and ligand.     

Synthesis of dimethyl carbonate from methanol and supercritical carbon dioxide

The synthesis of dimethyl carbonate (DMC) from methanol and supercritical carbon dioxide over various base catalysts has been studied. Compounds of group-I elements (Li, Na and K) were used as base catalysts. The promoter and the dehydrating agent were also used to enhance the yield of DMC. The effects of the catalysts, promoter and dehydrating agent on the yield of DMC were investigated. By-products such as dimethyl ether (DME) and C₁–C₂ hydrocarbons were formed with the DMC as a main product. The yield of DMC with different alkali metal catalysts ranked in the following order: K > Na > Li. The catalysts of the metal-CO₃ compounds were more effective than the metal-OH compounds in DMC synthesis. The maximum DMC yield reached up to about 12 mol% in the presence of K₂CO₃ (catalyst), CH₃I (promoter) and 2,2-dimethoxypropane (dehydrating agent) at 130–140°C and 200 bar. The reaction mechanism of DMC synthesis from methanol and supercritical carbon dioxide was proposed.     

Double metal cyanide catalyst prepared using H3Co(CN)6 for high carbonate fraction and molecular weight control in carbon dioxide/propylene oxide copolymerization

Simple mixing of H₃Co(CN)₆ and ZnCl₂ in methanol resulted in precipitates of [ZnCl]⁺₂[HCo(CN)₆]^2?, constituting a new type of double metal cyanide (DMC) catalyst exhibiting a high performance in carbon dioxide (CO₂)/propylene oxide (PO) copolymerization. High‐molecular‐weight poly(propylene carbonate‐co‐propylene oxide)s [poly(PC‐co‐PO)s] (M_n～40,000) were consistently obtained with high carbonate fractions (～60 mol %) and a high selectivity (>95%) with the new type of DMC catalyst. Conventional preparation of the DMC catalyst using K₃Co(CN)₆ and ZnCl₂ required removing KCl through thorough washing and resulted in lower carbonate fractions (10–40 mol %), which depended on the washing conditions. Feeding hydrophobic diols such as 1,10‐decanediol as chain transfer agent preserved the high carbonate fraction (～60%) and enabled precise control of the molecular weight, including preparation of a low‐molecular‐weight poly(PC‐co‐PO)‐diol (M_n ～2000), which was a flowing viscous liquid with a low T_g (?30 °C) suitable for polyurethane applications. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4811–4818     

Fe/Zn double metal cyanide catalyzed ring-opening polymerization of propylene oxide: 2. Characterization of active structure of double metal cyanide catalysts

Double metal cyanide (DMC) complexes based on Zn₃[Fe(CN)₆]₂ were synthesized using different molar ratios of ZnCl₂ to K₃[Fe(CN)₆] and special complexing agents. IR spectroscopy, electron spectroscopy for chemical analysis, X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, and other analytical techniques were employed to characterize these catalysts. The morphology and structure of these DMC catalysts were attributed to the different complexing agents as well as to the different molar ratios of ZnCl₂ to K₃[Fe(CN)₆]. In addition, the catalytic activity was strongly correlated with the morphology and noncrystalline content of DMC catalysts. High-activity catalysts could be prepared by controlling the structure of DMC catalysts by incorporating complexing agents. The active species of DMC catalysts for ring-opening polymerization are Zn²⁺, [Fe(CN)₆]^3–, Cl^–, and the compound of their ligands.     

Ring‐opening polymerizations of propylene oxide by double metal cyanide catalysts prepared with ZnX2 (X = F,Cl, Br,or I)

Polymerizations of propylene oxide were carried out with double metal cyanide (DMC) catalysts based on Zn₃[Co(CN)₆]₂. Through the control of the type and amount of ZnX₂ (X = F, Cl, Br, or I) during the preparation of the catalyst, the catalytic activity, induction period, and unsaturation level in the polyether polyols could be tuned. The DMC catalysts were characterized by X‐ray photoelectron spectroscopy, infrared spectroscopy, and X‐ray powder diffraction. In general, ZnBr₂ was the most effective zinc halide with respect to the properties of the resulting polymers as well as the activity and induction period. The average rates of polymerizations of DMC catalysts prepared with ZnCl₂, ZnBr₂, and ZnI₂ were 889, 1667, and 784 g of polyoxypropylene/g of catalyst h, respectively, with induction periods of about 53, 5, and 60 min, respectively, at 115 °C. The DMC catalysts produced polyoxypropylenes with an ultralow unsaturation level (0.0025–0.0057 mequiv/g) and a narrow molecular weight distribution (1.07–1.42) without high‐molecular‐weight tails; this resulted in a low viscosity (962–3950 cP). According to the results collected from catalyst characterizations and polymerizations, the active sites of DMC‐catalyzed polymerization had mainly coordinative characters. The presence of free anions accelerated the ring‐opening procedure and thus enhanced the propagation rate and shortened the induction period. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4393–4404, 2005     

Copolymerization of styrene and conjugated dienes with half‐sandwich titanium(IV) catalysts: The effect of the ligand structure on the monomer reactivity,monomer sequence distribution,and insertion mode of dienes

The copolymerization of styrene and 1,3‐butadiene (Bd) or isoprene (Ip) was carried out with half‐sandwich titanium(IV) Cp′TiCl₃ catalysts (where Cp′ is cyclopentadienyl 1 , indenyl 2 , or pentamethylcyclopentadienyl 3 ) with methylaluminoxane as a cocatalyst. For the copolymerization with Bd, catalyst 3 gave the copolymers containing the highest amount of Bd among the catalysts used. The resulting copolymers were composed of a styrene–Bd multiblock sequence. High melting points were observed in the copolymers prepared with catalyst 1 . The structures of hydrogenated poly(styrene‐co‐Bd) were studied by ¹³C NMR spectroscopy, and the long styrene sequence length was detected in the copolymers prepared with catalyst 1 . For styrene/Ip copolymerization, random copolymers were obtained. Among the used catalysts, catalyst 1 gave the copolymers containing the highest amount of Ip. The copolymers prepared with catalyst 1 showed a steep melting point depression with increasing Ip content because of the high ratio of 1,4‐inserted Ip units and/or the low molecular weights of the copolymers. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 939–946, 2003