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The advantage of supercritical carbon dioxide used as an environmental medium in polymerization and reactions in supercritical carbon dioxide are described. It includes homogeneous free radical polymerizations, precipitation free radical polymerizations, dispersion free radical polymerizations, emulsion and inverse emulsion free radical polymerizations, cationic polymerizations, ring-opening polymerization, melt-phase condensation polymerizations, sol-gel polymerizations, polymer blend synthesis, catalytic chain transfer polymerizations, oxidative coupling polymerization, nitroxide-mediated radical dispersion, atom-transfer radical polymerization, reversible addition-fragmentation chain transfer polymerization, electrochemical polymerization, simultaneous one-pot combination of enzymatic and chemical polymerization, copolymerization of carbon dioxide used as monomer.

评述了ScCO2作为聚合反应介质的优点,以及在ScCO2中可进行的聚合反应类型,包括均相聚合、沉淀聚合、分散聚合、乳液及反相乳液聚合、阳离子聚合、开环聚合、熔融态缩聚、溶液-凝胶聚合、聚合物混合合成、链催化转移聚合、氧化-偶合反应聚合、氮氧自由基可控活性聚合、原子转移自由基聚合、可逆加成-断裂链转移、电化学聚合、原子转移聚合与酶催化开环聚合两种活性聚合在ScCO2中同时聚合、二氧化碳作为原料共聚合等。

Effect of polymerization by MTGase on the functionalities of sodium caseinate were studied, it showed that the viscosity, thermal stability and hydration property, emulsifying properties of sodium caseinate were improved remarkably, And the emulsifying activity index increased with the time of polymerization, and the emulsifying stability increased with the polymerization time at low degree of polymerization while declined at high degree of polymerization.

研究了MTGase聚合酪蛋白酸钠对其功能特性的影响,结果表明:MTGase聚合酪蛋白酸钠显著地提高或改善了粘度、水化性质、乳化性能,其中乳化指数随聚合时间的增加而增加,而乳化稳定性在相对较低聚合度时随聚合时间的增加而增加,然而在高聚合度时反而会有所下降。

The paper studies AM and DAC as monomer, copolymerize a new type of cationic polymer flocculants through aqueous solution polymerization, inverse emulsion polymerization and inverse microemulsion polymerization, then studies how to improve solid content by aqueous solution polymerization, ascertain the system and kinetics of inverseemulsion polymerization and technological conditions.

本论文探讨了以AM与DAC为单体,通过水溶液聚合、反相乳液聚合、反相微乳液聚合得到新型阳离子高分子絮凝剂,研究了如何提高水溶液聚合的固含量,反相乳液聚合体系的确定、动力学研究及其工艺条件等影响因素。

Dealcoholization temperature markedly influences the surface area and porosity of the resultant MAO-supports. When the support was pretreated at lower or higher temperature, the corresponding MAO-support shows very low surface area; 2.XRD and IR analyses indicate that MAO has reacted with the residual ethanol in the supports, which is an important manner to get MAO fixed on the carrier. Morever, XPS analyse indicates that MAO can also be coordinated with MgCl_2, which is another way to get MAO fixed on the support; 3.ICP and EDX analyses indicate that dealcoholization temperature not only determined the element content on the solid catalyst, but also influences the element distribution on the carrier; 4.The activities of the supported phenoxy-imine catalysts and the properties of resultant polymers are strongly dependent on the dealcoholization temperature. The support (MSP-5) obtained by treating MgCl_2·2.56C_2H_5OH at 160℃for 4 h, then modified by MAO is very effective for immobilizing complex 3, the resultant solid catalyst (MSPC-5) shows very high activity in ethylene polymerization, and its kinetics of polymerization is stable during the reaction process. Finally, PEs with spherical morphology and high bulk density (over 0.35g/ml) were obtained, without reactor fouling; 5.In this work, polymerization conditions such as alkylaluminums, Al/Zr ratio, temperature and H_2 had a pronounced effect on the activity of MSPC-5 and properties of PE;(3). New MgCl_2-Supported Single-Site Catalysts for Ethylene Polymerization In this work, a kind of new MgCl_2 support was obtained by anhydrous MgCl_2 co-milled with solid MAO, and it is a creative contribution. Then some single-site catalysts were supported on the new MgCl_2 support, and the resulted solid catalysts were tested in ethylene polymerization, the results indicated that: 1.XRD and IR analyses indicate that MAO does be coordinated with MgCl_2, which is in good agreement with the results obtained by XPS; 2.co-mlling time had no obvious effect on the texture of support after 12 hours; 3.In this work, MgCl_2 was co-milled with solid MAO for different hours, and then complex 3 was supported on these co-milled supports. It was found that co-milling time markedly influences the activity of solid catalysts, but it had negligible effect on the kinetic profile and the properties of resultant PE.

XPS研究结果表明,MAO不仅仅只和乙醇作用,MAO还与MgCl_2本身有一定的作用,这是一个极为重要的发现; 3、通过ICP和EDX表征,发现载体的脱醇温度直接影响着元素在固体催化剂中的含量及分布; 4、脱醇温度极大地影响着负载苯氧基亚胺类催化剂的活性和聚合物的性能,特别是原始载体经160℃活化4小时制备得到的固体催化剂MSPC-5的活性明显高于其他脱醇温度条件下制得的固体催化,并且催化剂寿命长,表现出稳定的动力学行为,最终获得了高堆密度(大于0.35g/ml)的球形聚乙烯颗粒; 5、本文选择MSPC-5为研究对象,考察了聚合反应参数对催化剂的活性及其聚合物的影响,研究发现:不同的烷基铝对催化剂具有非常重要的影响,特别足TIBA对MSPC-5的助催化活性最高,烷基铝的加入量有一个较佳值,聚合温度为80度时活性最高,H_2的加入使催化剂的活性明显降低且聚合物的分子量也减小;、新型氯化镁载体负载单活性中心催化剂催化乙烯聚合本文创造性采用固体MAO与无水氯化镁直接进行共研磨,制备出了一种的新型的氯化镁载体,并将该载体用于多种单活性中心催化剂的负载化研究,研究表明: 1、通过BET、XRD的表征,再次证实了MAO与MgCl_2之间具有直接作用,与XPS的研究结果相一致; 2、当研磨时间高于12小时时,延长研磨时间对载体的结构没有显著的影响; 3、将配合物3负载于共研磨时间不同的一系列载体上,乙烯聚合结果表明,尽管共研磨时间对负载催化剂的活性具有明显的影响,但是它对聚合物的性能以及催化剂的影响不明显。

The kinetic behaviors of ethylene homo- olymerization and ethylene / l-hexene co-polymerization , catalyzed by the metallocene catalyst PS-DVB-MC in an 0.5 L stainless steel reactor , were studied. The effects of polymerization conditions on ethylene polymerization , such as concentration of catalyst , temperature of polymerization , pressure of ethylene , molar ratio of AI / Z r , etc ., were also investigated . Some leading results were as follows : the activity of the catalyst PS–DVB- MC for ethylene homo-polymerization was high ( 1.053 x 107 gPE / mol Zr·h ), but the molar ratio of AI / Zr was low ( 350:1 ); the catalytic ability for ethyleneα-olefin ( such as l hexene etc .) co-olymerization was great , and the corresponding activity come up to a maximum of 1.753 x 107 gPE / mol Zr·h while concenlration of l-hexene was 0.080 mol / L ; the molecular weight of polyethylene was about 180,000 , meanwhile the molecular weight distribution was narrow ( 2.19 ); the bulk density of polyethylene and ethylene / l-hexene co -polymer were 0.25 and 0.34 respectively .

采用0.5L高压不锈钢反应釜,对催化剂PS–DVB-MC催化乙烯均聚和乙烯/ l-己烯共聚合的动力学行为进行了研究,详细考察了催化剂浓度、反应温度、压力、Al/ Zr比、1-己烯浓度等因素对乙烯聚合反应的影响,得到如下主要结论:催化剂PS-DVB-MC具有催化乙烯均聚的高活性(1.053×107g PE / mo1 zr.hr),低Al / Zr比( 350:1 );具有良好的催化乙烯与α-烯烃(如1-己烯等)共聚的能力,在1-己烯浓度为0.080 mol / L时,催化活性达到最大(1.783×107 g PE / molZr.hr);乙烯均聚产物的分子量在18万左右,分子量分布窄( 2.19 )。

The conclusions were as follows: theνO-H andνC=O IR absorption maxima shifted towards higher wave numbers after imprinting 17β-estradiol on TFMAA-co-TRIM copolymer with the red shift of theνO-H groups being apparent after precipitation polymerization for 16h while that forνC=O groups being observed after polymerization for 24h. A strong interaction between TFMAA and 17β-estradiol was confirmed by the high selectivity for 17β-estradiol, as indicted by the values of the separation factor of isomers of 17β-estradiol/17α-estradiol (2.28) and the imprinted factor (3.01). Particle diameter of TFMAA-co-TRIM polymer was between 300 nm and 1.5μm, which suited well for solid phase sorbent throughout at low column pressure. The recognition of imprinting TFMAA-co-TRIM polymer for sterol molecules was driven by enthalpy eluted with acetronitile, and low temperature was in favor of the separation of sterol structure analogues on imprinting column. TFMAA-co-TRIM polymer possessed of determinate anti-heat stability, with melting point beginning at 255.84℃, Tp=257.40℃, control TFMAA-co-TRIM polymer and imprinting TFMAA-co-TRIM polymer were respectively decompounded at 267.79℃and 343.11℃, and solid micro-extraction noddle prepared by the special polymerization also showed definite recognition for 17β-estradiol by GC/MS detecting at 270℃. By selection of various washing and elution solvents, elution reagents of close polymerization system were of more advantage in template molecules retention and recognition on molecularly imprinted solid phase extraction column. At a certain extent, progesterone, 17α-estradiol, 17β-estradiol and 4-androstene-3, 17-dione could be intercepted on the MISPE column. Especially, MISPE had high selectivity for progesterone, and imprinting TFMAA-co-TRIM polymer could achieve adsorption balance within 50 min by absorption kinetics test for 17β-estradiol. However, MISPE column showed better selectivity and enrichment property for 17β-estradiol than C18 and CSPE columns according to the data from HPLC and GC/MS analyses. Recovery of 17β-estradiol on MISPE column was up to 85.5% while when prime extracting solution of milk powder was sampled, the recovery of CSPE and C18 columns were 43.7% and 30.7%, respectively.

通过研究阐明:紫外聚合产物TFMAA-co-TRIM中的νO-H振动吸收峰在聚合16h后红移,νC=O振动吸收峰在聚合24h后红移;TFMAA-co-TRIM对雌二醇异构体的印迹因子达到了3.01,α为2.28,优于其它功能单体参与得到的聚合物识别特性;TFMAA-co-TRIM聚合物粒径介于300 nm至1.5μm之间,作为色谱固定相具有良好的通量和低的柱压;在乙腈流动相中,TFMAA-co-TRIM分子印迹固定相的分离过程主要被焓驱动,低温有利于分子印迹固定相分离甾醇结构类似物;TFMAA-co-TRIM分子印迹聚合物在255.84℃时开始熔融,Tp=257.40℃,聚合物CP的降解温度在267.79℃,MIP降解温度在343.11℃,制备的固相微萃取头初步经GC/MS 270℃的耐热性测定;不同的洗提溶剂筛选证明了选择接近聚合溶剂的洗脱体系更有利于MISPE发挥识别效应;分子印迹固相萃取柱对孕酮、17α-雌二醇、17β-雌二醇和雄烯二酮都具有不同程度的保留特性,可作为此类化合物的吸附材料,特别对孕酮强保留的富集特性,可作为孕酮的选择性识别吸附剂,其分子印迹聚合物对17β-雌二醇的吸附动力学测定显示在50 min内基本达到吸附平衡,具有作为传感器核心敏感材料的潜力;对比萃取奶粉中17β-雌二醇性能,MISPE柱比非分子印迹固相萃取柱和C18柱具有更高的保留,回收率依次为85.5%,43.7%和30.7%。

This paper contains three parts: 1 Synthesis of novel titanium complexes; 2 Polymerization behaviors of alkoxyl substituted Cp Titanocenes as catalysts for styrene syndiotactic polymerization; 3 Polymerization behaviors of alkenyl substituted Cp Lanthanocenes as Methyl Methacrylate polymerization catalysts.

中文题名新型茂钛、噁唑啉钛络合物的合成、表征以及茂钛、茂稀土络合物催化性能的研究副题名外文题名 Synthesis,characterization of novel Cp,oxazoline titanium complexes and polymerization behaviors of titanocenes and lanthanocenes 论文作者张浩导师钱延龙黄吉玲学科专业应用化学研究领域\研究方向金属有机与均相催化学位级别博士学位授予单位华东理工大学学位授予日期2003 论文页码总数148页关键词金属有机化学稀土络合物噁唑啉类钛络合物茂钛络合物馆藏号BSLW /2003 /O627 /27 本论文包括三部分内容:1)有机金属钛络合物的合成;2)烷氧基取代茂钛络合物催化苯乙烯间规聚合的研究;3)烯基取代茂稀土络合物催化甲基丙烯酸甲酯聚合的研究。

Dealcoholization temperature markedly influences the surface area and porosity of the resultant MAO-supports. When the support was pretreated at lower or higher temperature, the corresponding MAO-support shows very low surface area;2.XRD and IR analyses indicate that MAO has reacted with the residual ethanol in the supports, which is an important manner to get MAO fixed on the carrier. Morever, XPS analyse indicates that MAO can also be coordinated with MgCl_2, which is another way to get MAO fixed on the support;3.ICP and EDX analyses indicate that dealcoholization temperature not only determined the element content on the solid catalyst, but also influences the element distribution on the carrier;4.The activities of the supported phenoxy-imine catalysts and the properties of resultant polymers are strongly dependent on the dealcoholization temperature. The support (MSP-5) obtained by treating MgCl_2·2.56C_2H_5OH at 160℃for 4 h, then modified by MAO is very effective for immobilizing complex 3, the resultant solid catalyst (MSPC-5) shows very high activity in ethylene polymerization, and its kinetics of polymerization is stable during the reaction process. Finally, PEs with spherical morphology and high bulk density (over 0.35g/ml) were obtained, without reactor fouling;5.In this work, polymerization conditions such as alkylaluminums, Al/Zr ratio, temperature and H_2 had a pronounced effect on the activity of MSPC-5 and properties of PE;(3). New MgCl_2-Supported Single-Site Catalysts for Ethylene PolymerizationIn this work, a kind of new MgCl_2 support was obtained by anhydrous MgCl_2 co-milled with solid MAO, and it is a creative contribution. Then some single-site catalysts were supported on the new MgCl_2 support, and the resulted solid catalysts were tested in ethylene polymerization, the results indicated that:1.XRD and IR analyses indicate that MAO does be coordinated with MgCl_2, which is in good agreement with the results obtained by XPS;2.co-mlling time had no obvious effect on the texture of support after 12 hours;3.In this work, MgCl_2 was co-milled with solid MAO for different hours, and then complex 3 was supported on these co-milled supports. It was found that co-milling time markedly influences the activity of solid catalysts, but it had negligible effect on the kinetic profile and the properties of resultant PE.

XPS研究结果表明,MAO不仅仅只和乙醇作用,MAO还与MgCl_2本身有一定的作用,这是一个极为重要的发现;3、通过ICP和EDX表征,发现载体的脱醇温度直接影响着元素在固体催化剂中的含量及分布;4、脱醇温度极大地影响着负载苯氧基亚胺类催化剂的活性和聚合物的性能,特别是原始载体经160℃活化4小时制备得到的固体催化剂MSPC-5的活性明显高于其他脱醇温度条件下制得的固体催化,并且催化剂寿命长,表现出稳定的动力学行为,最终获得了高堆密度(大于0.35g/ml)的球形聚乙烯颗粒;5、本文选择MSPC-5为研究对象,考察了聚合反应参数对催化剂的活性及其聚合物的影响,研究发现:不同的烷基铝对催化剂具有非常重要的影响,特别足TIBA对MSPC-5的助催化活性最高,烷基铝的加入量有一个较佳值,聚合温度为80度时活性最高,H_2的加入使催化剂的活性明显降低且聚合物的分子量也减小;、新型氯化镁载体负载单活性中心催化剂催化乙烯聚合本文创造性采用固体MAO与无水氯化镁直接进行共研磨,制备出了一种的新型的氯化镁载体,并将该载体用于多种单活性中心催化剂的负载化研究,研究表明:1、通过BET、XRD的表征,再次证实了MAO与MgCl_2之间具有直接作用,与XPS的研究结果相一致;2、当研磨时间高于12小时时,延长研磨时间对载体的结构没有显著的影响;3、将配合物3负载于共研磨时间不同的一系列载体上,乙烯聚合结果表明,尽管共研磨时间对负载催化剂的活性具有明显的影响,但是它对聚合物的性能以及催化剂的影响不明显。

After the oxidative polymerization of DMP,styrene was in-situ polymerized under the initiation of dibenzoyl peroxide and dicumyl peroxide,finally thermodynamically compatible PPO/PS alloy was prepared.When styrene content was 50 wt%,for the synthesized PPO/PS alloy the yield and the weight-average molecular weight were determined to be 95%and 1.7×10~5 for PPO,93%and 2.0×10~5 for PS,respectively.The influence of the concentration of DMP and catalyst,molar ratio of N/Cu, oxygen partial pressure,NaOH concentration and temperature on the initial polymerization rate(R_0) of DMP was studied.It was found that the initial polymerization rate of DMP increased with the concentration of DMP and catalyst. The initial polymerization rate increased with the molar ratio of N/Cu at first and then decreased.

通过测定DMP氧化聚合过程中氧气吸收量随时间的变化,研究了DMP和催化剂浓度、N/Cu摩尔比、氧气分压、氢氧化钠浓度及温度对水介质中DMP氧化聚合初始速率的影响,发现DMP氧化聚合初始速率与氧气分压的0.1次方成正比;DMP氧化聚合初始速率随DMP和催化剂浓度及温度的增加而增加;随氢氧化钠浓度和N/Cu摩尔比的增加DMP氧化聚合初始速率先增加后降低。

Based on the pure styrenes polymerization, the inhibited polymerization by inhibitor was studied. The effect of polymerization temperature, the addition of ethylbenzene, the content of inhibitor, and the compound of inhibitors was measured for the bulk thermal polymerization of styrene.

在纯苯乙烯聚合基础上,着重考察了阻聚剂(缓聚剂DNBP和阻聚剂M)阻聚下苯乙烯的聚合行为,并系统研究了聚合温度、乙苯含量、缓聚剂及阻聚剂含量、阻聚剂的复配对苯乙烯本体热聚合动力学的影响规律。

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I can do simple painting, carpentry and plumbing.

我能做简单的油漆、木工和修水管等工作。

The motivations, notations and outline of this work are also given in this chapter.

从这个意义上讲,这些时滞是无害的。然后用实例说明这三个定理的应用和互不包含性。

American writer known for his droll epigrammatic verse,much of which appeared in the New Yorker.

纳西,奥格登1902-1971美国作家,因写没有固定韵律的幽默诗而闻名,其中大多数发表在《纽约人》杂志上