N,N—二乙基二硫代氨基甲酸聚氯乙烯酯引发甲基丙烯酸甲…

用铜试剂（Ｎ，Ｎ－二乙基二硫代氨基甲酸钠）取代聚氯乙烯中的部分氯原子制备了Ｎ，Ｎ－二乙基二硫代氨基甲酸聚氯乙烯酯（ＰＶＣ－ＳＲ），研究了紫外光照下ＰＶＣ－ＳＲ引发甲基丙烯酸甲酯（ＭＭＡ）的聚合反应，考察了光照时间、单体浓度、ＰＶＣ－ＳＲ用量及官能度的影响。结果表明，ＰＶＣ－ＳＲ能有效地引发ＭＭＡ聚合，其产物是交联型接枝聚合物，且具有高接枝率和接枝效率。     

2-(N,N-二乙基二硫代氨基甲酰氧基)乙酸苄酯存在下苯乙烯光聚合

研究了２ Ｎ, Ｎ 二乙基二硫代氨基甲酰氧基乙酸苄酯（ Ｂｚ Ｄ Ｃ Ａ） 引发的苯乙烯光聚合反应,发现单体转化率和数均分子量（ Ｍｎ） 都随反应时间而增加,在反应时间相同时随着 Ｂｚ Ｄ Ｃ Ａ 浓度的增加单体转化率升高而 Ｍｎ 降低．聚苯乙烯（ Ｐ Ｓ） 的 Ｍｎ 同单体转化率成线性关系并同理论计算值符合得较好．以２ 甲基 ２ 亚硝基丙烷（ Ｍ Ｎ Ｐ） 为捕捉剂用（ Ｅ Ｐ Ｒ） 技术对聚合反应机理进行了研究．认为 Ｂｚ Ｄ Ｃ Ａ 引发的 Ｓｔ 光聚合是一个“活性”聚合过程     

N－丙烯酰基－N＇－苯基脲及其衍生物的合成与聚合反应

以三种合成路线分别合成了含有脲键的一类单体，Ｎ－丙烯酰基－Ｎ’－苯基脲（ＡＰＵ）、Ｎ－甲基丙烯酰基－Ｎ’－苯基脲（ＭＰＵ）、Ｎ－甲基丙．烯酰基－Ｎ’－对甲苯基脲（ＭＴＵ），通过单体的自由基聚合与共聚合，制备了均聚物和共聚物，经ＩＲ、１Ｈ—ＮＭＲ表征和ＴＧＡ、ＤＳＣ测定．     

THE CHIRAL SELECTIVITY IN ACROSS－MEMBRANE TRANSPORT OF 1，2－DIAMINOCYCLOHEXANE PLATINUM（II）COMPLEXES AND THE CONTRIBUTION OF LEAVING GROUPS

ＴＨＥＣＨＩＲＡＬＳＥＬＥＣＴＩＶＩＴＹＩＮＡＣＲＯＳＳ－ＭＥＭＢＲＡＮＥＴＲＡＮＳＰＯＲＴＯＦ１，２－ＤＩＡＭＩＮＯＣＹＣＬＯＨＥＸＡＮＥＰＬＡＴＩＮＵＭ（ＩＩ）ＣＯＭＰＬＥＸＥＳＡＮＤＴＨＥＣＯＮＴＲＩＢＵＴＩＯＮＯＦＬＥＡＶＩＮＧＧＲＯＵＰＳ￥...     

STUDY ON THE SORPTION BEHAVIOR OF N－METHYL－2－THIO－IMIDAZOLE RESIN FOR Rh（Ⅲ）AND SEPARATION OF Rh（Ⅲ）WITH COMMON METAL IONS BY USING MTIR

ＳＴＵＤＹＯＮＴＨＥＳＯＲＰＴＩＯＮＢＥＨＡＶＩＯＲＯＦＮ－ＭＥＴＨＹＬ－２－ＴＨＩＯ－ＩＭＩＤＡＺＯＬＥＲＥＳＩＮＦＯＲＲｈ（Ⅲ）ＡＮＤＳＥＰＡＲＡＴＩＯＮＯＦＲｈ（Ⅲ）ＷＩＴＨＣＯＭＭＯＮＭＥＴＡＬＩＯＮＳＢＹＵＳＩＮＧＭＴＩＲＣｈｅｎＹｉｙｏｎ...     

SYNTHESIS, CHARACTERIZATION OF 2-[2-(3-NITRO-4-METHOXYLPHENYL) VINYLI-1-ME

ＳＹＮＴＨＥＳＩＳ，ＣＨＡＲＡＣＴＥＲＩＺＡＴＩＯＮＯＦ２－［２－（３－ＮＩＴＲＯ－４－ＭＥＴＨＯＸＹＬＰＨＥＮＹＬ）ＶＩＮＹＬＩ－１－ＭＥＴＨＹＬＰＹＲＩＤＩＮＩＵＭＰＥＮＴＡＡＮＤＨＥＸＡＮＩＴＲＡＴＯＲＡＲＥＥＡＲＴＨ（Ⅲ）ＣＯＭＰＬＥＸＥＳＨ...     

甲壳胺接枝聚合反应的研究

本文是以过硫酸钾为引发剂，研究甲基丙烯酸甲酯（ＭＭＡ）与甲壳胺的接枝聚合反应．通过对不同脱乙酰度（ｄａ）甲壳胺（ＣＴＳ）的接枝聚合反应条件实验，研究了反应时间，温度，引发剂浓度和单体浓度对接枝聚合反应的影响，从中得到优选的反应条件．在相同条件下，比较不同脱乙酰度甲壳胺及Ｎ－取代甲壳胺的接枝聚合反应结果，表明：甲壳胺中氨基参与了接枝聚合反应的引发过程．     

LASER-ENHANCED ELECTROCHEMICAL DOPING OF POLY (N-VINYLCARBAZOLE)

ＬＡＳＥＲ－ＥＮＨＡＮＣＥＤ　ＥＬＥＣＴＲＯＣＨＥＭＩＣＡＬ　ＤＯＰＩＮＧ　ＯＦ　ＰＯＬＹ　（Ｎ－ＶＩＮＹＬＣＡＲＢＡＺＯＬＥ）ＬＡＳＥＲ－ＥＮＨＡＮＣＥＤＥＬＥＣＴＲＯＣＨＥＭＩＣＡＬＤＯＰＩＮＧＯＦＰＯＬＹ（Ｎ－ＶＩＮＹＬＣＡＲＢＡＺＯＬＥ）Ｙａ...     

IN－SITU FTIR AND UV－VISIBLE－NEAR－IR SPECTROELECTROOHEMICAL STUDIES OF MIXED－VALENCE ISOPOLYANION Mo＿6O＿（19）￣（3－） IN APROTIC MEDIA

ＩＮ－ＳＩＴＵ　ＦＴＩＲ　ＡＮＤ　ＵＶ－ＶＩＳＩＢＬＥ－ＮＥＡＲ－ＩＲ　ＳＰＥＣＴＲＯＥＬＥＣＴＲＯＯＨＥＭＩＣＡＬ　ＳＴＵＤＩＥＳ　ＯＦ　ＭＩＸＥＤ－ＶＡＬＥＮＣＥ　ＩＳＯＰＯＬＹＡＮＩＯＮ　Ｍｏ＿６Ｏ＿（１９）￣（３－）　ＩＮ　ＡＰＲＯＴＩＣ　Ｍ...     

RUTHENIUM COORDINATION COMPOUNDS WITH POLYPYRIDINES V．DNA－BINDING STUDIES OF Ru（Ⅱ）COORDINATION COMPOUNDS WITH（2－PHENYL－）IMIDAZO［f］1，10－PHENANTHROLINE

ＲＵＴＨＥＮＩＵＭＣＯＯＲＤＩＮＡＴＩＯＮＣＯＭＰＯＵＮＤＳＷＩＴＨＰＯＬＹＰＹＲＩＤＩＮＥＳＶ．ＤＮＡ－ＢＩＮＤＩＮＧＳＴＵＤＩＥＳＯＦＲｕ（Ⅱ）ＣＯＯＲＤＩＮＡＴＩＯＮＣＯＭＰＯＵＮＤＳＷＩＴＨ（２－ＰＨＥＮＹＬ－）ＩＭＩＤＡＺＯ［ｆ］１，１０－...     

可交联PVC的合成及其交联反应

N,N-二乙基二硫代氨基甲酸钠(铜试剂,简称NasR)取代PVC链中的部分氯原子,制得不同官能度的功能高分子PVC-SR.在热的作用下,实现了PVC-SR的自交联和PVC-SR/NBR共混体系的共交联.研究了温度、铜试剂用量对取代反应的影响及PVC-SR官能度对交联反应硫化曲线、产物的凝胶含量、玻璃化温度、拉伸性能和压缩永久变形的影响,并初步探讨了交联反应机理.     

丙烯酰胺在以N,N-二乙基二硫代氨基甲酰基修饰聚氯乙烯上的紫外光非均相接枝聚合

丙烯酰胺在以Ｎ，Ｎ 二乙基二硫代氨基甲酰基修饰聚氯乙烯上的紫外光非均相接枝聚合杨文君王永祥管建均（青岛化工学院橡塑工程研究所青岛２６６０４２）沈家骢（吉林大学化学系长春１３００２３）关键词聚氯乙烯，聚丙烯酰胺，功能高分子，接枝聚合反应，铜试剂以聚氯...     

Vinyl polymerization. CCCXXXIX. Effect of chain length of nylon 3 on the polymerization of methyl methacrylate initiated with the system of nylon 3, copper(II) ion,and water

It was found recently that the system of nylon 3, copper(II) ion, and water could initiate a radical polymerization of methyl methacrylate(MMA). In the present paper, the effect of average chain length of the molecules of nylon 3 on the rate of polymerization of MMA was studied. The rate increased with the chain length of nylon 3. This result was explained well by the fact that the shorter nylon 3 forms a complex with copper (II) ion more easily than longer nylon 3. It was assumed that the shorter nylon 3 fills three or four coordination sites of copper(II) ion and loses the ability to initiate the polymerization. The efficiency of grafting of MMA and the degree of polymerization of MMA homopolymer were independent of the chain length of nylon 3.     

CuX2络合物催化甲基丙烯酸甲酯的氧化聚合

研究了高氧化态过渡金属卤化物络合物催化甲基丙烯酸甲酯(MMA)的氧化聚合.首先在叔胺类聚合物存在条件下以CuBr2/2,2′-联吡啶(bPy)络合物催化MMA在不同溶剂中的氧化聚合,结果在环己酮中得到PMMA均聚物,CuBr2/bPy同叔胺的氧化还原引发可以忽略.随后在环己酮中分别以不同络合物催化MMA的氧化聚合.结果...     

Structure of reactively extruded rigid PVC/PMMA blends

A novel route for producing polymer blends by reactive extrusion is described, starting from poly (vinyl chloride)/methyl methacrylate (PVC/MMA) dry blend and successive polymerization of MMA in an extruder. Small angle X‐ray scattering (SAXS) measurements were applied to study the monomer's mode of penetration into the PVC particles and to characterize the supermolecular structure of the reactive poly(vinyl chloride)/poly(methyl methacrylate) (PVC/PMMA) blends obtained, as compared to the corresponding physical blends of similar composition. These measurements indicate that the monomer molecules can easily penetrate into the PVC sub‐primary particles, separating the PVC chains. Moreover, the increased mobility of the PVC chains enables formation of an ordered lamellar structure, with an average d‐spacing of 4.1 nm. The same characteristic lamellar structure is further detected upon compression molding or extrusion of PVC and PVC/PMMA blends. In this case the mobility of the PVC chains is enabled through thermal energy. Dynamic mechanical thermal analysis (DMTA) and SAXS measurements of reactive and physical PVC/PMMA blends indicate that miscibility occurs between the PVC and PMMA chains. The studied reactive PVC/PMMA blends are found to be miscible, while the physical PVC/PMMA blends are only partially miscible. It can be suggested that the miscible PMMA chains weaken dipole–dipole interactions between the PVC chains, leading to high mobility and resulting in an increased PVC crystallinity degree and decreased PVC glass transition temperature (T_g). These phenomena are shown in the physical PVC/PMMA blends and further emphasized in the reactive PVC/PMMA blends. Copyright © 2005 John Wiley & Sons, Ltd.     

2-芳基苯并噁唑的荧光猝灭和光诱导电子转移研究

本工作对两种不同的2-芳基苯并 唑化合物溶液荧光被四氯化碳所猝灭的机理进行了详细研究,通过多种途径研究表明该猝灭过程具有光诱导电子转移性质,工作还利用此电子转移所形成的活泼自由基来引发烯类单体的聚合,得到了有一定聚合度的聚甲基丙烯酸甲酯。     

新型的香豆素染料/碘鎓盐光敏引发系统的研究

在实际应用中,大部分光敏引发系统只对紫外光敏感．近年来,随着Ａｒ＋（４８８ｎｍ）、ＹＡＧ（５３２ｎｍ）以及ＨｅＮｅ（６３３ｎｍ）激光技术的不断发展,高效的长波长光敏引发体系成为研究的重点．其中之一的方法是使引发剂直接感可见光,然而取得的结果并不显著．所以染料敏化又一次成为焦点．其中最重要的技术是使光敏引发系统的吸收波长移向长波长,并且具有高的灵敏度．大部分的光敏引发系统是由二个或三个组分组成,长波长的光引发聚合是通过以下两种不同过程得到实现［１］：（１）光敏系统直接吸收光并激发,（２）光引发系…     

衣康酸系铜离聚体引发下的甲基丙烯酸甲酯聚合反应

本文报道了衣康酸系铜离聚体引发下的甲基丙烯酸甲酯(MMA)聚合反应,对影响反应的各种因素、反应机理及反应动力学进行了研究。     

Living Radical Polymerization in Homogeneous System by Using Iniferter: Design of Block Copolymers

Benzyl N-ethyldithiocarbamate(BEDC) and xylylene bis(N-ethyl-dithiocarbamate)(XEDC) were prepared, and used as mono- and bi-functional photoiniferters, respectively, of the polymerization of styrene and methyl methacrylate. These photopolymerizations were performed via a living radical polymerization mechanism in homogeneous system. The polymers obtained by BEDC and XEDC still contained one and two reactive N-ethyldithiocarbamate end groups, respectively, bonded at their chain ends. When these polymers were reacted with nucleophiles and copper(n) ion, the chain extension reactions were observed to occur depending on their functionality. By using the polymers obtained by BEDC and XEDC as mono- and bi-functional polymeric photoiniferters, the AB and ABA block copolymers were also obtained, respectively. Similar results were obtained by using benzyl N,N-diethyldithiocarbamate(BDC) and xylylene bis(N,N-diethyldithiocarbamate)(XEDC) as mono- and bifunctional photoiniferters, respectively. These results were also compared and discussed.     

Catalytic aerobic radical polymerization in typical redox-non-innocent solvents as potential low-efficiency initiators

Abstract

Certain complexes of some transition metal cations in the high oxidation state could oxidize some organic substrates with labile C-H moieties, leading to the corresponding cations in the lower" oxidation state and some carbon-centered radicals. The former would form oxidative complexes with molecular dioxygen to continuously oxidize organic substrates, while the latter would initiate polymerization of vinylic monomers. Such catalytic oxidation is adopted to initiate radical polymerization of methyl methacrylate (MMA) and styrene (St) with cyclohexanone (CyHO) and benzylic hydrocarbons as both the solvent and the substrate. Although, a large array of complexes could trigger the polymerization, Cu^II/2,2′-bipyridine complexes display a maximum turnover frequency above 200?h^–1 during the catalytic aerobic radical polymerization of MMA in CyHO at 70–80?°C, but only less than 0.4% of CyHO is involved in chain formatting. Cu^II/ligand-catalyzed aerobic radical polymerization of St in CyHO exhibit comparable behaviors. Only Co^II complexes could catalyze the aerobic radical polymerization of MMA in para-xylene and cumene at 90?°C, but only 0.1% of PX and 0.3% of cumene are involved in chain forming.