Polymerization of methyl methacrylate with iron-ytterbium dinuclear metallocene catalyst

A novel iron-ytterbium dinuclear catalyst, FcB(MeCp) Yb (MeCp) Cl (Fc: ferrocenyl, B: diethylene ether), was synthesized for the polymerization of methyl methacrylate (MMA). Synergistic effects between the ferrocenyl group and the lanthanocene part were investigated regarding their catalytic behaviors. UV, IR, GPC and NMR were used to characterize the structures of the catalyst and polymer. Kinetic study showed that polymerization is first order in monomer concentration and fractional order (0.78) in the catalyst. The bimetallic complex is a good catalyst for the polymerization of MMA, giving high molecular weight PMMA with 78% syndiotactivity. Project (29774021) supported by NSFC and Laboratory of Rare-Earth Chemistry and Physics, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences     

The polymerization of methyl methacrylate with a new Tin-bridged yttrocene/Al(I-Bu)3

A new catalyst composed of Tin-bridged yttrocene Ph₂Sn(MeCp)₂YCI (MeCp=methylcyclopentadienyl) and Al (i-Bu)₃ was successfully developed for the polymerization of methyl methacrylate (MMA). Detailed study of factors (such as the molar ratio of Al/Cat., catalyst concentration, various solvents, temperature and time) influencing polymerization reaction indicated that the catalytic active species may be still somewhat stable at high temperature and still have a long catalytic lifetime.¹H NMR spectrum showed about 65% syndiotactic content in the polymethyl methacrylate (PMMA) prepared. From kinetic studies, the polymerization rate equation may be expressed as Rp=Kp[Cat.]^2.4. The overall activation energy of polymerization is 20.9±3.1 kJ/mol. Project(29774021) supported by the Natural Science Foundation of China and National Laboratory of Element-Organic Chemistry, Nakai, University.     

POLYMERIZATION OF METHYL METHACRYLATE WITH ETHYLENE BRIDGED HETERODINUCLEAR METALLOCENE OF SAMARIUM AND TITANIUM-STUDY ON SYNERGISM AND KINETICS

ＩＮＴＲＯＤＵＣＴＩＯＮＨｅｔｅｒｏｄｉｎｕｃｌｅａｒｃｏｍｐｌｅｘｅｓａｒｅｏｆｇｒｅａｔｉｍ ｐｏｒｔａｎｃｅｆｏｒｔｈｅｓｔｕｄｙｏｆｔｈｅｓｙｎｅｒｇｉｓｔｉｃｅｆｆｅｃｔｓｆｏｕｎｄｉｎｂｉｍｅｔａｌｌｉｃｃａｔａｌｙｓｉｓ (Ａｄａｍｓ,1 988;Ｒｅｄｄｙｅｔａｌ.,1 989;Ｚｈｅｎｇｅｔａｌ.,1 989;Ｗｅｒｎｅｒｅｔａｌ.,1 992 ) ,ｗｈｉｃｈｉｎｄｉｃａｔｅｄｄｉｓｔｉｎｃ ｔｉｖｅｅｌｅｃｔｒｏｎｉｃ ,ｅｌｅｃｔｒｏｃｈｅｍｉｃａｌａｎｄｍａｇｎｅｔｉｃｐｒｏｐｅｒｔｉｅｓａｒｉｓｉｎｇｆｒｏ…     

Polymerization of methyl methacrylate with ethylene bridged heterodinuclear metallocene of samarium and titanium-study on synergism and kinetics

Comparison of MMA polymerization results with samarocene chloride, titanocene chloride and the title heterodinuclear (Sm−Ti) catalyst, respectively, showed synergism in the Sm-Ligand-Ti system, which obviously influenced the polymerization behaviors, for example, of yeilding higher activity and higher molecular weight polymer. Kinetic studies on polymerization of MMA with ethylene bridged samarocene and titanocene chloride/Al(i-Bu)₃ showed that the polymerization rate was first-order on the catalyst concentration, and 1.9-order on the monomer. The overall activation energy measured was 52.8 kJ/mol. Project supported by NSFC (No. 20074028), and SINOPEC(X598037).     

Preparation of poly (methyl methacrylate)/nanometer calcium carbonate composite by in-situ emulsion polymerization

Methyl methacrylate (MMA) emulsion polymerization in the presence of nanometer calcium carbonate (nano-CaCO3) surface modified with (-methacryloxypropyltrimethoxysilane (MPTMS) was carried out to prepare poly (methyl methacrylate) (PMMA)/nano-CaCO3 composite. The reaction between nano-CaCO3 and MPTMS, and the grafting of PMMA onto nano-CaCO3 were confirmed by infrared spectrum. The grafting ratio and grafting efficiency of PMMA on nano-CaCO3 modified with MPTMS were much higher than that on nano-CaCO3 modified with stearic acid. The grafting ratio of PMMA increased as the weight ratio between MMA and nano-CaCO3 increased, while the grafting efficiency of PMMA decreased. Transmission electron micrograph showed that nano-CaCO3 covered with PMMA was formed by in-situ emulsion polymerization.     

双环戊二烯基钛(锆)不饱和羧酸配合物的合成

利用各种取代苯甲醛 ,通过Perkin反应或安息香缩合反应制备取代苯基丙烯酸钠盐配体 ,再与二氯二 (甲基 )茂钛 (锆 )反应 ,得到相应的配合物 .控制配体的加入量 ,可以得到二氯二 (甲基 )茂钛 (锆 )的双分子羧酸配合产物和单分子羧酸的配合物     

实验室制备有机玻璃的影响因素研究

以过氧化苯甲酰（BPO）为引发剂,甲基丙烯酸甲酯（MMA）为单体进行本体聚合制备有机玻璃。探讨了引发剂的用量、不同阶段的反应温度等因素对反应的影响。得出最佳实验条件为：m（BPO）／m（MMA）为0．3％;-N聚水浴温度为90℃,预聚时间为1．5h;烘箱中聚合前期温度为45％,24h后升温至90℃再聚合2h。     

异丁烯酸甲酯/氰酸酯树脂半互穿聚合物的合成与表征

于加热熔融的氰酸酯树脂(BACDy)中加入异丁烯酸甲酯(MMA),在引发剂存在下,引发单体及预聚体MMA发生本体聚合,采用同步合成法和异步合成法分别制备互穿聚合物网络氰酸酯树脂/聚异丁烯酸甲酯(BACDy/MMA-SIPN)高分子材料,研究了几种不同配比的SIPN体系.结果表明,BACDy/MMA-SIPN网络形成的反应条件对体系的力学性能和耐热性能都有较大提高.给出了较合理的制备工艺条件.     

新型二茂铁骨架糖基硫脲催化剂的合成

以天然D－构型葡萄糖和商业易得的二茂铁甲酸为原料,经简单几步反应,设计合成了一种结构新颖的二茂铁骨架糖基硫脲催化剂,该催化剂的结构通过IR,1 H NMR,13 C NMR,和HRMS等物理手段进行了表征。     

Study on surface modification of titanium dioxide using polymethyl methacrylate

ＳｔｕｄｙｏｎＳｕｒｆａｃｅＭｏｄｉｆｉｃａｔｉｏｎｏｆＴｉｔａｎｉｕｍＤｉｏｘｉｄｅＵｓｉｎｇＰｏｌｙｍｅｔｈｙｌＭｅｔｈａｃｒｙｌａｔｅＴａｎＤｉｎｇｓｈｅｎｇ（ＳｈａｎｇｈａｉＵｎｉｖｅｒｓｉｔｙ）ＹａｎＮｉａｎｘｉＸｕｅＱｉｎｇ（Ｓｏｃｈｏｗ...     

DSC法研究MMA/纳米Si3N4体系的聚合过程

利用差示扫描量热仪(DSC)对MMA/纳米Si3N4体系的聚合过程进行研究,着重考察了聚合温度,纳米Si3N4粉体加入量及引发剂AIBN用量对体系聚合速率的影响.结果表明:升高聚合反应温度,增大引发剂用量,均可使体系的凝胶效应提前出现,聚合速率增大;而纳米Si3N4粉体的加入对体系的聚合起到延缓的作用,且随着加入量的增加,聚合速率逐渐降低.     

实验探讨微波辐射合成聚天冬氨酸的反应条件对其产率及分子量的影响

采用L-天冬氨酸（L-ASP）为原料,磷酸作为催化剂,碳酸丙烯酯为溶剂,置于微波反应器中进行微波辐射合成聚天冬氨酸（PASP）,采用正交法比较各实验条件对其产率和分子量的影响。结果表明,合成聚天冬氨酸的最佳条件是：催化剂用量为5‰微波功率455W,反应时间约为4min,溶剂用量为18ml／g。     

Ethylene polymerization with novel silicon bridged homo-dinuclear cyanoethyl cyclopentadienyl

Novel homo-dinuclear silicon bridged cyanoethyl cyclopentadienyl complexes of titanium and zirconium (CH3)2Si((η5-C5H3CH2CH2CN)(C5H5)MCl2)2 (M=Ti(1), Zr(2)) were synthesized and developed for the polymerization of ethylene. Compared with their corresponding mononuclear complexes (η5-C5H4CH2CH2CN)(C5H5)MCl2 (M=Ti(3), Zr(4)), the dinuclear complexes had higher catalytic activity. And the polyethylene produced had a higher molecular weight than that obtained with mononuclear catalysts. Effects of conditions on the ethylene polymerization catalyzed by (2)/MAO (methylaluminoxane) were studied in detail. The catalyst showed a very high activity ( >106g PE/mol Zr*h) under low catalyst concentration and high molar ratio of Al/Zr.     

以碘代乙腈控制丙烯酸酯活性自由基聚合研究

研究了以碘代乙腈退化转移剂的丙烯酸醋活性自由基聚合，实验结果表明：在碘代乙腈的存在下控制甲基丙烯酸甲酯（MMA）的聚合，得到的分子量大（1万-10万），而控制丙烯酸甲醋（MA）、丙烯酸乙醇（EA）、醋酸乙烯醋（VAc）得到的分子量较小（〈1万）．实验得出：[IAN]与EAIBN]之比对控制活性自由基聚合有很大的影响，[IAN]与[AIBN]之比为6：1是有效控制聚合的理想浓度．反应温度为60℃时，转化率随时间的增长而增高，分子量随转化率的增高而增大，成线性关系，分子量的分布较窄（〈1．5）．^1H NMR分析表明，在聚合物主链的末端连有碘，说明碘代乙腈在反应中起退化-转移聚合（IDTP）的作用，通过循环往复的碳-碘键的活化，断裂，再形成而得到最终活性的聚合物。     

Liquid-phase catalytic hydrogenation of furfural in variable solvent media

Water is the most abundant compound inherently existing in bio-oils. Thus understanding the role of water within bio-oils upgrading process is essential for future engineering scale-up design. In this study, furfural was chosen as bio-oils model compound, and the catalytic hydrogenation of furfural over commercial 5%, Ru/C catalyst was firstly investigated in a series of gradient variable water/ethanol mixture solvents. Water had a significant effect on the distribution of product yields. The dominant reaction pathways varied with the water contents in the water/ethanol mixture solvents. Typically, when ethanol was used as the solvent, the main products were obtained by the hydrogenation of carbonyl group or furan ring. When pure water was used as the solvent, the rearrangement reaction of furfural to cyclopentanone should be selectively promoted theoretically. However, serious polymerization and resinification were observed herein in catalytic hydrogenation system of pure water. The catalyst surface was modified by the water-insoluble polymers, and consequently, a relative low yield of cyclopentanone was obtained. A plausible multiple competitive reaction mechanism between polymerization reaction and the hydrogenation of furfural was suggested in this study. Characterizations(TG,FT-IR,SEM)were employed to analyze and explain our experiments.     

辛可宁分子印迹纳米球的制备及药物释放性能研究

以辛可宁为模板分子(T),甲基丙基酸(MAA)为功能单体,甲基丙基酸甲酯(MMA)为调节剂,乙二醇二甲基丙烯酸酯(EDMA)为交联剂,采用沉淀聚合法制备得到均匀球形纳米分子印迹聚合物。当MIP组成为nMAA∶nMMA∶nEDMA=2∶7∶7∶10时,其平均粒径为580 nm,平衡吸附与释放实验表明该聚合物不仅对辛可宁有较好的分子识别性能,而且还具有良好的药物缓释性能。     

N-二茂铁甲酰基-N′-苯甲酰氨基硫脲的合成与杀菌活性

二茂铁甲酸与草酰氯反应得二茂铁甲酰氯,与硫氰酸钾反应生成二茂铁甲酰基异硫氰酸酯,再与苯甲酰肼进行加成反应,合成一种新型二茂铁硫脲衍生物——N-二茂铁甲酰基-N′-苯甲酰氨基硫脲,产物经IR和1H NMR鉴定,与结构相符.初步的生物活性测试结果表明,该化合物对枯草杆菌有抑制作用,而对大肠杆菌无明显的抑制作用.     

Gel time of calcium acrylate grouting material

INTRODUCTION One of the main advantages of chemical groutsis easy control of gel time (Mollamahmutoglu andLittlejohn, 1996; ?nupárek and Soucek, 2000).Calcium acrylate is a chemical grout usually used ingeotechnical engineering (Zelanko and Karfakis,1997), and is a water-soluble monomer that po-lymerizes in an aqueous solution. The rate of po-lymerization is controlled by the concentration ofcatalyst and activator. The polymerization of cal-cium acrylate is free radical chain pol…     

α，α＇-邻苯二甲基桥联双茚基钐二苯胺化物催化丙烯腈聚合

以α,α＇-邻苯二甲基桥联双茚基钐二苯胺化物为催化剂,对丙烯腈聚合反应进行了研究,考察了催化剂用量、反应时间及反应温度对丙烯腈聚合的影响,并且用粘度法对聚合产物的粘均分子量进行了表征。发现α,α＇-邻苯二甲基桥联双茚基钐二苯胺化物对丙烯腈聚合反应具有极高的催化活性。随着催化剂用量增加聚合反应转化率增大,聚合产物的粘均分子量下降;延长反应时间,转化率和分子量都增大。     

提高催化剂活性的几个途径

近年来关于催化剂活性研究认为：中心浓度[C^*]和聚合增长速度常数Kp,都能使活性增加,但通过实验验证,中心浓度[C^*]的活性增加率较Kp明显,依据这一认识,从主催化剂、载体催化剂、助催化剂及第三组分等方面,进一步探讨和验证了提高催化剂活性的途径。