高密度聚乙烯粉末的电子束辐射接枝

高密度聚乙烯粉末的电子束辐射接枝王勇，黄劲，李瑞海（成都科技大学纺织工学院，成都６１００６５）（成都科技大学高分子材料系６１００６５）关键词：ＨＤＰＥ粉末，电子束辐射，接枝聚合本文采用电子束予辐射法使聚乙烯粉末表面产生活性中心，然后通过液－固相接枝共...     

PVB存在下PVC化学法脱氯化氢的研究

ＰＶＢ存在下ＰＶＣ化学法脱氯化氢的研究刘恒＊李大成陈朝珍（四川联合大学化工学院成都６１００６５）关键词聚氯乙烯，脱氯化氢，聚乙烯醇缩丁醛１９９６－０９－０８收稿，１９９７－０５－２６修回国家教育委员会留学归国人员资助费资助课题近年来在ＰＶＣ脱氯化氢制...     

X－CT用于材料组成分析

Ｘ－ＣＴ用于材料组成分析旷文峰（中国科学院成都有机化学研究所，６１００４１）林大全，吴大诚（四川联合大学仿真体模中心，四川联合大学纺织学院，成都６１００６５）Ｘ－ＣＴ是用于医学诊断的Ｘ－射线计算机断层图像仪，其基本工作原理是用Ｘ－射线对检测对象进行连...     

偏钛酸型锂离子交换剂固相合成反应动力学

偏钛酸型锂离子交换剂固相合成反应动力学钟辉＊郭灵虹（成都理工学院应用化学系成都６１００５９）（四川联合大学分析测试中心成都）关键词偏钛酸锂，离子交换剂，合成，固相反应动力学１９９７－０８－２５收稿，１９９７－１２－１０修回四川省应用基础研究基金资助项...     

对—叔丁基杯[4]芳烃在环己烷中的激光光解研究

对－叔丁基杯［４］芳烃在环己烷中的激光光解研究＊袁立华１姚思德２庄志豪１林念芸２（１．四川联合大学化学系成都６１００６４）（２．中国科学院上海原子核研究所辐射化学实验室上海２０１８００）关键词对－叔丁基杯［４］芳烃激光光解三线态中图分类号Ｏ６２１．２...     

二苯骈－21－冠－7与12－磷钨酸铯配合物的合成及表征

二苯骈－２１－冠－７与１２－磷钨酸铯配合物的合成及表征陈伟，罗良琼（四川联合大学（东区）化学系成都６１００６４）关键词合成，冠醚配合物，１２－磷钨酸铯二苯骈－２１－冠－７（ＤＢ２１Ｃ７）与含简单阴离子的铯盐配合物已有一些研究［１］，但是ＤＢ２１Ｃ７与...     

醋酸乙烯酯在硅橡胶上的辐射接枝研究

研究了不同溶剂中的醋酸乙烯酯在硅橡胶上的辐射接技状况及接枝后硅橡胶表面结构情况．结果表明：（１）在硅橡胶－乙酸乙酯－醋酸乙烯酯体系中，接枝有自加速效应；（２）适量加入对苯二酚，接枝诱导期延长，接枝速率下降，凝胶效应消失，辐射接技经验关联式为ＲＰ＝０．２７×［Ｄ］（－０．５６０）×［Ｉ］（０．４９０）×［Ｃ］（０．９２０），接核反应为扩散控制反应；（３）不同的溶剂对硅橡胶接枝有不同的影响，如甲醇发生敏化作用，提高接枝速率，而苯发生惰化作用，降低接枝速率；（４）在合适的甲醇和苯配比时，接枝反应几乎恒速进行，用扫描电镜（ＳＥＭ）观察断面，接枝区比较均一，出现微相分离．     

聚苯基膦酸双酚A酯的合成与表征

聚苯基膦酸双酚Ａ酯的合成与表征唐旭东陈晓婷王玉忠杨科珂王波（四川联合大学化学系成都６１００６４）吴大诚（四川联合大学轻纺学院成都６１００６５）关键词聚膦酸酯，阻燃剂，熔融缩聚，热性能聚膦酸酯类化合物是一类重要的磷系阻燃剂［１～３］，与传统的非聚...     

电缆用无纺布堵水带高吸水树脂的研究

电缆用无纺布堵水带高吸水树脂的研究钟安永，陈德本，周宗华，姚文（四川联合大学（东区）化学系成都６１００６４）关键词高吸水树脂，无纺布堵水带，丙烯酸甲酯－醋酸乙烯共聚物塑料绝缘电力电缆、通讯电缆、光纤电缆等在使用中常常因为护套破损而导致水的纵向渗透，使...     

一类活性极高的高分子表面活性剂

一类活性极高的高分子表面活性剂范仲勇，李娜，吴大诚（四川联合大学轻纺学院，成都，６１００６５）ＺｈａｏｈｕｉＳｕ，Ｓ．Ｌ．Ｈｓｕ（ＤｅｐａｒｔｍｅｎｔｏｆｐｏｌｙｍｅｒＳｃｉｅｎｃｅ＆Ｅｎｇｉｎｅｅｒｉｎｇ，ＵｎｉｖｅｒｓｉｔｙｏｆＭａｓｓａｃｈｕｓ...     

Synthesis of well‐defined polymer brushes on the surface of zinc antimonate nanoparticles through surface‐initiated atom transfer radical polymerization

Zinc antimonate nanoparticles consisting of antimony and zinc oxide were surface modified in a methanol solvent medium using triethoxysilane‐based atom transfer radical polymerization (ATRP) initiating group (i.e.,) 6‐(2‐bromo‐2‐methyl) propionyloxy hexyl triethoxysilane. Successful grafting of ATRP initiator on the surface of nanoparticles was confirmed by thermogravimetric analysis that shows a significant weight loss at around 250–410 °C. Grafting of ATRP initiator onto the surface was further corroborated using Fourier transform Infrared spectroscopy (FT‐IR) and X‐ray photoelectron spectroscopy (XPS). The surface‐initiated ATRP of methyl methacrylate (MMA) mediated by a copper complex was carried out with the initiator‐fixed zinc antimonate nanoparticles in the presence of a sacrificial (free) initiator. The polymerization was preceded in a living manner in all examined cases; producing nanoparticles coated with well defined poly(methyl methacrylate) (PMMA) brushes with molecular weight in the range of 35–48K. Furthermore, PMMA‐grafted zinc antimonate nanoparticles were characterized using Thermogravimetric analysis (TGA) that exhibit significant weight loss in the temperature range of 300–410 °C confirming the formation of polymer brushes on the surface with the graft density as high as 0.26–0.27 chains/nm². The improvement in the dispersibility of PMMA‐grafted zinc antimonate nanoparticles was verified using ultraviolet‐visible spectroscopy and transmission electron microscopy. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Grafting of polymethyl methacrylate from poly(ethylene-co-vinylacetate) copolymer using atom transfer radical polymerization

Atom transfer radical polymerization was employed for the first time to prepare graft copolymer having by ethylene-vinyl acetate (EVA) copolymer as backbone and poly(methyl methacrylate) (PMMA) as branches. The polymerization of MMA was initiated by EVA carrying chloropropionate groups as macroinitiator, in the presence of copper chloride (CuCl) and bipyridine (bpy) at 80 °C. The macroinitiator was prepared by esterification of partially hydrolyzed EVA with 2-chloropropionyl chloride. Successful graft copolymerizations were performed both in toluene/γ-butyrolactone mixed solvent and in toluene solution, with grafting efficiency of 12% and 6%, respectively. Molecular weight distribution of the PMMA segments around 1.2 has been achieved with pure toluene solution. The ATRP graft copolymerization was supported by an increase of the molecular weight of the graft copolymers, as compared to that of the macroinitiator and also by their monomodal molecular weight distribution.     

单组分桥联茂基二异丙胺基钕配合物催化甲基丙烯酸甲酯聚合

催化聚合;茂稀土胺化物;单组分桥联茂基二异丙胺基钕配合物催化甲基丙烯酸甲酯聚合     

纳米SiO_2锚固光敏基团引发MMA光接枝聚合研究

对纳米SiO2进行了锚固光引发剂的表面修饰,进而引发甲基丙烯酸甲脂(MMA)光接枝聚合制备有机/无机复合粒子.纳米SiO2粒子首先用氯化亚砜进行表面氯化,再与光引发剂2-羟基-4-(2-羟基乙氧基)-2-甲基苯丙酮(Irgacure2959)反应从而锚固上光引发剂.通过紫外光引发MMA在经过修饰过的纳米SiO2表面上进行表面光接枝聚合.采用IR、TGA和TEM等方法表征了接枝前后纳米粒子的变化,证明了表面接枝物的存在,并研究了不同反应条件对单体转化率、接枝率和接枝效率的影响.研究结果表明,搅拌对接枝过程的影响比较显著.TGA结果显示未搅拌聚合时接枝率只能达到比较小的程度,而在搅拌条件下180min内MMA的接枝率可达到110%.     

The characterization of latex particles prepared by pulsed electron beam induced emulsion polymerization

The emulsion polymerization of styrene (St) and methyl methacrylate (MMA) induced by 10 MeV pulsed electron beams (PEB) was investigated. The monomer conversion of MMA and St was found to be very low so that the final prepared poly(methyl methacrylate) (P(MMA)) and polystyrene (PS) latex particles exhibit porous structures, as verified by TEM and SEM observations. The results of dynamic light scattering (DLS) and gel permeation chromatography (GPC) showed that both the particle size and the molecular weight of PS and PMMA latexes decrease with the increase of the absorbed dose. However, the molecular weights and the particle sizes of the PS and PMMA latexes change differently with the irradiation time. This work indicated that emulsion polymerization induced by high energy electron beam has an advantage over that induced by γ-ray or chemical initiators in the preparation of latex with a low molecular weight and porous structure.     

Effect of amount of monomer on radiation-induced polymerization of styrene adsorbed on silica gel

The effect of amount of monomer on radiation-induced polymerization of styrene adsorbed on silica gel was investigated with the monomer amounting from less than monolayer adsorption to more than the equilibrium adsorption. The rate of graft polymerization and the molecular weight of the polymer changed with the amount of monomer adsorbed on silica gel. Maximum grafting efficiency was obtained at monolayer adsorption. The molecular weight of graft polymer was higher than that of homopolymer in both radical and cationic polymerizations, and the ratio in molecular weight of graft polymer to that of homopolymer tends to be unity with increasing amount of adsorbed monomer. These results can mainly be explained in terms of the number of initiating species (radical and cation) that change in relation to the amount of adsorbed monomer. Propagation and termination change with amount of adsorbed monomer in relation to the molecular mobility of adsorbed monomer. A very high-molecular-weight graft polymer is formed only with a small amount of adsorbed monomer in the initial stage. The grafting percent with a large amount of adsorbed monomer increased after most of the monomer has been polymerized. Secondary effect of radiation on the graft and homopolymers due to energy transfer from silica gel is suggested from the complicated phenomena in the later stage of the reaction.     

可聚合的光引发转移终止剂合成接枝共聚物

采用一种可聚合的光引发转移终止剂 ,2 N ,N 二乙基二硫代氨基甲酰氧基乙酸 β 甲基丙烯酰氧基乙酯 (MAEDCA) ,通过两种途径制备了含有聚甲基丙烯酸甲酯 (PMMA)和聚苯乙烯 (PSt)链段的接枝共聚物 .其一是将MAEDCA作为引发剂 ,在紫外光照射下引发MMA聚合 ,得到大分子单体 ,通过大分子单体与St的共聚合得到 .考察了所用大分子单体的分子量和浓度对共聚合的影响 .其二是将MAEDCA作为单体与MMA共聚得到侧链上含有N ,N 二乙基二硫代氨基甲酰氧基 (DC)基团的无规共聚物 ,P(MMA co MAEDCA) .在紫外光照射下 ,P(MMA co MAEDCA)作为大分子引发剂引发St聚合 ,得到P(MMA co MAEDCA) g PSt的共聚物 ,研究了接枝共聚合过程的活性自由基聚合特征     

正性远紫外抗蚀剂 Ⅰ.聚苯乙烯砜的研究

合成了一种高分辨率的正性远紫外抗蚀剂—聚苯乙烯砜。其灵敏度比PMMA高6.5倍。分辨率达0.75微米,并发现灵敏度与分子量和膜厚有较大的依赖关系,分子量越大,灵敏度越高;膜越薄,灵敏度越高,紫外和红外光谱表明,在光照过程中生成了氢过氧化物和羰基化合物。     

Process parameters and their effect on grafting reactions in core/shell latexes

The grafting of methyl methacrylate (MMA) onto polybutadiene (PB) latexes prepared by seeded emulsion polymerization at 50°C was investigated as a function of: (a) initiator concentration used in the secondary polymerization, (b) monomer-to-polymer ratio, (c) the specific surface area of the seed latex, and (d) the degree of conversion. The thin layer chromatography/flame ionization detection (TLC/FID) technique was used to determine the proportion of graft copolymer in the core/shell latex, It was found that grafting PMMA onto PB depended upon the concentration of initiator, decreasing as the concentration was increased. The amount of grafting increased with increasing specific surface area of the seed latex, while the molecular weight of the acetone-soluble graft copolymer decreased. The amount of graft copolymer was found to decrease concurrently with increasing monomer-to-polymer ratio and degree of conversion. These results suggest a hydrogen abstraction mechanism in the formation of graft PB–PMMA through a chain transfer process.     

Effect of polymerization conditions on the molecular weight of polystyrene grafted onto silica in the radical graft polymerization initiated by azo or peroxyester groups introduced onto the surface

The effect of polymerization conditions on the molecular weight of polystyrene grafted onto silica obtained from the radical graft polymerization initiated by azo and peroxyester groups introduced onto the surface was investigated. The molecular weight of polystyrene grafted onto silica obtained from the radical graft polymerization initiated by surface azo and peroxyester groups decreased with decreasing monomer concentration and polymerization temperature. The molecular weight of polystyrene was found to be controlled to some extent by the addition of a chain transfer agent. The molecular weight of grafted chain on silica surface obtained from the graft polymerization initiated by surface radicals formed by photodecomposition of azo groups was considerably smaller than that by thermal decomposition. The number of grafted polystyrene in photopolymeriztion, however, was much larger than that in thermal polymerization. These results are explained by the blocking of surface radicals formed on the silica surface by previously grafted polymer chain: when the decomposition of surface azo and peroxyester groups proceed instantaneously at the initial stage of the polymerization, the number of grafted polymer chains increased.