1,2-二乙炔基四苯基乙硅烷与1,2-二乙炔基四甲基乙硅烷的共聚及其光解

1,2-二乙炔基四苯基乙硅烷与1,2-二乙炔基四甲基乙硅烷在催化剂铑(Ⅰ)络合物[氯化三-(三苯基膦)铑]的作用下得到一种新的含硅共聚物。实验证明此共聚物的主链是有规交替结构。研究了固体薄膜及其溶液的光解作用,并测定了SbF_5蒸气处理后的共聚物薄膜的导电性。     

1,2-双(四甲基环戊二烯基)四甲基二硅烷与六羰基钼的反应

１,２－双（四甲基环戊二在）四甲基二硅烷与正丁基锂作用生成（四甲基二硅撑）双（四甲基环戊二烯基负离子盐）,后者随即与六羰基钼反应形成１,１＇－（四甲基二硅撑）双（四甲基环戊二烯基钼负离子盐）－－（Ｍｅ２ＳｉＳｉＭｅ２）〖Ｍｅ４ＣｐＭｏ（ＣＯ）３－Ｌｉ＾＋〗２（１）,１与冰醋酸作用,随即分别与ＣＣＩ４,ＮＢＳ及Ｉ２反应,生成相应的钼卤化合物（Ｍｅ２ＳＩＳｉＭｅ２）〖Ｍｅ４ＣｐＭｏ（ＣＯ）３Ｘ〗２〖Ｘ     

从呋喃甲醛制备4－(1,2－亚乙二氧基)环己酮的系列合成

从呋喃甲醛制备４－（１，２－亚乙二氧基）环己酮的系列合成蒋本国，葛树丰，叶秀林（北京大学化学与分子工程学院１００８７１）４－（１，２－亚乙二氧基）环己酮（５）及其脱羧前的母体化合物４－（１，２－亚乙二氧基）环己酮－２－羧酸乙酯（４）都是反应性能很强的...     

合成1，3－二（3－羟丙基）四甲基二硅氧烷的新方法

用二乙氧基二甲基硅烷与３－氯丙醇反应，合成了新化合物３－氯丙氧基乙氧基二甲基硅烷，然后用格氏反应代替Ｗａｌｔｅｒ的钠缩合反应，最后经水解制备了１，３－二（３－羟丙基）四甲基二硅氧烷，总收率为４２．０％。     

顺二羰基2－丁酸甲酯基吡啶铑配合物的合成与性能

顺二羰基２－丁酸甲酯基吡啶铑配合物的合成与性能潘平来，柳忠阳，黄茂开，袁国卿（中国科学院化学研究所，北京１０００８０）含有不同配位基团的共聚物配体与铑形成的配合物，在催化甲醇碳基化制备乙酸和乙酐的反应中具有很高的活性和选择性￣［１１］。本文采用含有Ｎ...     

1,4—双（取代苯乙炔基）苯及反,反—1,4—双（β—取代苯乙…

测定了１，４－双（取代苯乙炔基）苯（Ⅰ）和反，反－１，４－双（β－取代苯乙烯基）苯（Ⅱ）的紫外光谱、荧光光谱。用ＣＮＤＯ／Ｓ－ＣＩ和ＨＭＯ方法对苯乙炔、二苯乙炔和（Ⅰ）及苯乙烯、１，２－二苯乙烯和（Ⅱ）的激发能进行了计算和研究。讨论了化合物结构对光谱的影响。     

（四甲基二硅撑）二（3－三甲硅基环戊二烯基）四羰基二铁及其相关化合物的合成及结构

１，２－二（三甲硅基环戊二烯基）四甲基二硅烷与Ｆｅ（ＣＯ）_５在二甲苯中于１０５～１１０℃反应除分离到少量标题化合物（Ｍｅ_２ＳｉＳｉＭｅ_２）［η－（３－Ｍｅ_３ＳｉＣ_５Ｈ_３Ｆｅ（ＣＯ）］_２（μ－ＣＯ）_２（５）外，主要是生成了脱Ｍｅ_３Ｓｉ基的产物（Ｍｅ_２ＳｉＳｉＭｅ_２）［η－Ｃ_５Ｈ_４Ｆｅ（ＣＯ）］_２（μ－ＣＯ）_２（１）及１的热重排异构体［Ｍｅ_２ＳｉＣ５Ｈ４－Ｆｅ（ＣＯ）_２］_２（２）．将５的二甲苯溶液加热回流１８ｈ，则转化为其异构体［Ｍｅ_２Ｓｉ（Ｍｅ_３ＳｉＣ_５Ｈ_３）Ｆｅ（ＣＯ）_２］_２（６）．脱硅基发生在由相应反应物制备５的过程中。且脱硅基是与反应物中（Ｍｅ_２ＳｉＳｉＭｅ_２）桥的存在有关．５的晶体结构经Ｘ射线衍射测定属单斜晶系，Ｐ２_１／ｍ空间群，晶体学数据：ａ＝０．６７８０（１）ｎｍ，ｂ＝２．２３０３（９）ｎｍ，ｃ＝０．９９８８（１）ｎｎ，；β＝９８．９６（１）°，Ｖ＝１．４９６０ｎｍ~３．Ｚ＝２，Ｄ_ｃ＝１．３６ｇ／ｃｍ~３．     

柄型金属有机化合物（Ⅱ）：硅氧硅桥联二（1—茚基及四氢茚基…

１，３－二（１－茚基）四甲基二硅氧烷相继与丁基锂及ＺｒＣｌ４．２ＴＨＦ作用，生成硅氧桥联二（１－茚基）二氯化锆（Ｍｅ２ＳｉＯＳｉＭｅ２）（Ｉｎｄ）２ＺｒＣｌ２（１）。对其进行催化氢化得到相应的四氢茚基化合物（Ｍｅ２ＳｉＯＳｉＭｅ２）ＩｎｄＨ４）２ＺｒＣｌ２（２）．１和２均含有顺式和反式二种异构体（１和１以及２和２），通过重结晶得到纯的单一异构体，１，２和２，１和２的晶体结构经Ｘ射线衍射测定，二者均     

聚γ-(β-氰乙硫基)两基硅氧烷铑配合物的合成与催化硅氢化性能

γ-巯丙基三乙氧基硅烷与丙烯腈加成，得到γ－（β-氰乙硫基）丙基三乙氧基硅烷，后者依次与气相法二氧化硅、三氯化铑作用，合成了聚γ-（β-氰乙硫基）丙基硅氧烷铑配合物，研究了其催化烯烃与三乙氧基硅烷硅氢加成反应的特性。     

两种[对苯乙炔-2,5-二(十二烷氧基)对苯乙炔]共聚物的合成及性能研究

用含氯前聚物路线和Ｈｅｃｋ反应分别合成［对苯乙炔－２，５－二（十二烷氧基）对苯乙炔］无规共聚物及交替共聚物．由元素分析、凝胶渗透色谱、吸收光谱及ＤＳＣ对其进行表征，研究了共聚物的组成与导电率、溶解性及发光性能的关系．比较了无规共聚物与交替共聚物在性能上的差别．     

SYNTHESIS AND CHARACTERIZATION OF SOLUBLE POLYPHENYLENE COMPOSED OF p-PHENYLENE AND m-PHENYLENE UNITS

NiCl_2(bpy) catalyzed polycondensation between p-dibromobenzene and m-dibromobenzene has been carried outunder vdrious conditions. The polycondensation endows the copolymer with an M_n of 2300 (by GPC, polystyrene standards)and good solubility in organic solvents. The fluorescence spectra of the copolymer measured with tetrahydrofuran solutionshows an emission maximum (λ_(max)) at 372.8 nm, whereas for the film the maximum shifts to 436.6 nm.     

Synthesis and Hydrogenation of 1,2-1,4-1,2-Stereotriblock Polybutadienes and the Study of Their Properties

The effects of various polar modifiers, their concentration, and the polymerization temperature on the microstructure of poly-butadiene obtained during anionic polymerization using lithium α-methyl naphthalene as the bifunctional initiator were studied. 1,2-1,4-1,2-Stereotriblock polybutadiene was synthesized by polymerization in cyclohexane to a certain conversion and polymerization was completed in the presence of diethylene glycol dimethyl ether. The microstructure of the stereotriblock copolymer was characterized by IR and ¹H-NMR. GPC showed that the stereo-block polybutadiene has a narrow MWD. Two T_g's of the copolymer with higher molecular weight exist, as shown by dynamic mechanical test. The stereotriblock copolymer was hydrogenated using cobalt 2-ethyl hexanoate and triisobutyl aluminum as the catalyst. The hydrogenated product was shown to be a (butene-1-ethylene-butene-1) triblock copolymer which consists of more than 30% crystallinity and exhibits the behavior of a thermoplastic elastomer. The relationship between stress-strain properties arid the contents of the blocks was also studied.     

Effect of molecular weight and film thickness on the crystallization and microphase separation in polystyrene-<Emphasis Type="Italic">block</Emphasis>-poly(L-lactic acid) thin films at the early stage

We investigated the effects of molecular weight and film thickness on the crystallization and microphase separation in semicrystalline block copolymer polystyrene-block-poly(L-lactic acid) (PS-b-PLLA) thin films, at the early stage of film evolution (when T _g < T < T _ODT) by in situ hot stage atomic force microscopy. For PS-b-PLLA 1 copolymer which had lower molecular weight and higher PLLA fraction, diffusion-controlled break-out crystallization started easily. For PS-b-PLLA 2 with higher molecular weight, crystallization in nanometer scales occurs in local area. After melting of the two copolymer films, islands were observed at the film surface: PS-b-PLLA 1 film was in a disordered phase mixed state while PS-b-PLLA 2 film formed phase-separated lamellar structure paralleling to the substrate. Crystallization-melting and van der Waals forces drove the island formation in PS-b-PLLA 1 film. Film thickness affected the crystallization rate. Crystals grew very slowly in much thinner film of PS-b-PLLA 1 and remained almost unchanged at long time annealing. The incompatibility between PS and PLLA blocks drove the film fluctuation which subsequently evolved into spinodal-like morphology.     

Synthesis and characterization of indeno[1,2‐b]fluorene‐based white light‐emitting copolymer

An indenofluorene‐based copolymer containing blue‐, green‐, and red light‐emitting moieties was synthesized by Suzuki polymerization and examined for application in white organic light‐emitting diodes (WOLEDs). Tetraoctylindenofluorene (IF), 2,1,3‐benzothiadiazole (BT), and 4,7‐bis(2‐thienyl)‐2,1,3‐benzothiadiazole (DBT) derivatives were used as the blue‐, green‐, and red‐light emitting structures, respectively. The number‐average molecular weight of the polymer was determined to be 25,900 g/mol with a polydispersity index of 2.02. The polymer was thermally stable (T_d = ～398 °C) and quite soluble in common organic solvents, forming an optical‐quality film by spin casting. The EL characteristics were fine‐tuned from the single copolymer through incomplete fluorescence energy transfer by adjusting the composition of the red/green/blue units in the copolymer. The EL device using the indenofluorene‐based copolymer containing 0.01 mol % BT and 0.02 mol % DBT units ( PIF‐BT01‐DBT02 ) showed a maximum brightness of 4088 cd/m² at 8 V and a maximum current efficiency of 0.36 cd/A with Commission Internationale de L'Eclairage (CIE) coordinates of (0.34, 0.32). The EL emission of PIF‐BT01‐DBT02 was stable with respect to changes in voltage. The color emitted was dependent on the thickness of the active polymer layer; layer (～60 nm) too thin was unsuitable for realizing WOLED via energy transfer. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3467–3479, 2009     

Synthesis and characterizations of a novel zwitterionic hybrid copolymer containing both sulfonic and carboxylic groups via sulfonation and zwitterionic process

A novel zwitterionic hybrid copolymer containing both sulfonic and carboxylic groups was synthesized via sulfonation, zwitterionic process and sol-gel reaction. The properties of the step products were characterized by FT-IR spectra, thermal analyses, MALDI measurements and SEM morphologies. FT-IR spectra confirmed the related reactions. TGA and DrTGA analyses showed that their thermal stability enhanced with an increase in the zwitterionic extent. DSC curves revealed that both the glass transition temperature and the melting temperature elevated with the rising content of ion pairs. MALDI measurements suggested that the molecular structure of the zwitterionic hybrid PEG-[Si(OEt)₃]₂SO₃HCOOH was more stable than that of neutral hybrid PEG-[Si(OEt)₃]₂ or that of negatively charged hybrid PEG-[Si(OEt)₃]₂SO₃H. SEM image of the sulfonated polymer film indicated that the pore size was within 2.4-6.1 μm; whereas SEM of the zwitterionized copolymer film displayed that its pore size was less than 1 μm. This shrinkage in pore size can be ascribed to the introduction of carboxylic groups into the copolymer chains. Compared with that observed in the unionized polymer film, the large difference in the morphology of the ionized copolymer films demonstrated that ionization could alter these copolymer’s characteristics. Due to its excellent pore-creating performance, this zwitterionic hybrid copolymer expects to be employed to prepare nanofiltration and ultrafiltration membranes.     

水分散体系中甲基丙烯酸甲酯和丙烯酸八氟戊酯嵌段共聚物的合成与表征

在聚合物链上引入氟元素可以赋予聚合物很多优异的性能 ,如良好的热稳定性、化学稳定性、生物相容性和憎水憎油性等 .含氟单体与一般单体共聚是合成含氟共聚物的重要途径 .通过原子转移自由基聚合 (ATRP)不仅可以实现多种单体的控制 (共 )聚合 ,而且可以合成出具有预定分子量、窄分子量分布以及结构明晰聚合物[1] ,我们曾报道了溶液体系中用ATRP方法合成含氟嵌段共聚物[2～ 4] .众所周知 ,大多数含氟聚合物都是通过乳液或悬浮聚合反应合成的 .然而 ,普通的乳液或悬浮聚合难以合成结构和组成可控的聚合物 ,如嵌段共聚物 ,所以近年来 ,水…     

Improving Damping Properties and Thermal Stability of Epoxy/Polyurethane Grafted Copolymer by Adding Glycidyl POSS

Modified castor oil-based epoxy resin (EP)/polyurethane (PU) grafted copolymer by glycidyl polyhedral oligomeric silsesquioxane (glycidyl POSS) was synthesized. The damping properties, thermal stability, mechanical properties and morphology of the grafted copolymer modified by glycidyl POSS were studied systematically. The results revealed that the incorporation of glycidyl POSS improved the damping performance evidently and broadened damping temperature range, especially when the glycidyl POSS content was0.2%–1%. At the same time, there was a slight increase in thermal stability with the increase of POSS content. The tensile properties changed with the change of the copolymer's Tg, decreased at low POSS contents and increased at high POSS contents. This modified copolymer has the potential to be used as film damping material or constrained damping layer.     

Crystal phase transformations within propylene/hexene-1 copolymers films as induced by direct current discharge treatment

The effect of a direct current discharge on the films of polypropylene and copolymers of propylene and hexene-1 synthesized with an isospecific catalytic system, rac-Me₂SiInd₂ZrCl₂-polymethylaluminoxane, was investigated. The treatment of isotactic polypropylene films by the discharge did not affect the ratio of crystalline phases in the polymer to a measurable extent. However, for the plasma treated films of copolymers of propylene and hexene-1 (the hexene-1 content of 1-2 mol%), a structural transformation of γ-modification into α-modification has been noticed. The observed phase transition has no apparent relation to any changes in microstructure of the copolymer chain because melting temperature values and the stereoregularity parameters of the samples remained practically unchanged. An experimental investigation of the specific influence exerted by individual components of a direct current discharge on the crystalline structure of copolymers has been undertaken. The exposure to a quantum component of the discharge did not induce any changes in the phase composition of the irradiated samples. The heating of the samples led to a negligible change of their phase composition. It has been determined that the surface of polypropylene and propylene/hexene-1 copolymer films facing the cathode in the course of the direct current discharge treatment had an accumulated negative charge Q > 10 nC/cm² which persisted for a long time afterwards. It has been suggested that the electrical field of a negative discharge may be the main cause of the γ-into α-phase transition in propylene/hexene-1 copolymers under the plasma effect. To verify this assumption, a propylene/hexene-1 copolymer film was charged under electron beam with energy of 4 keV. The electron beam treatment of the film resulted to the negative charge value of 11 nC/cm². The electron beam irradiation has induced the phase transition which was quite similar to the transition observed as the result of plasma treatment. So, it may be concluded that the phase transition from crystal γ-modification to α-modification under the effect of direct current discharge which has been investigated for copolymers of propylene and hexene-1 is induced by electric field of the negative charge accumulated at the surface layers of the films of the copolymers.     

SYNTHESIS AND THERMAL PROPERTIES OF A NEW CHOLIC ACIDCONTAINING COPOLYMER

A new copolymer was synthesized by free radical polymerization in solution from methyl 3α-methylacryloyl-7α, 12α-dihydroxy-5β-cholan-24-oate (MACAME) and maleic anhydride (MAN). The copolymer was characterized by FT-IR and functional group analysis. The reactivity ratios of the two monomers were estimated [r_1 = 11.6 (MACAME), r_2 = 0.01(MAN)] by conducting a series of copolymerizations with a variety of monomer feed compositions and analyzing thecopolymer composition. Thermogravimetric and differential scanning calorimetric analyses of the samples indicate that thecopolymer possesses good thermal stability. The temperature at which the copolymer samples experienced a 10% weight loss(T_(WL)) is over 287℃, and the T_g ranged from 174 to 185℃ for the copolymers.