微悬浮法氯乙烯-醋酸乙烯酯共聚树酯的热降解反应动力学研究

用热重分析技术对微悬浮法氯乙烯-酷酸乙烯酯共聚树脂的热降解反应进行了研究,结果表明氯乙烯-醋酸乙烯共聚树脂在热分解过程中,HCl和HAc同时脱出;在静态空气和静态氮气,升温速率为5、10℃min-1的条件下,共聚树脂的热降解均为二级反应,热降解表观活化能Ea为160.82～183.77KJ·mol-1;ln[A/s]为28.64～34.74.     

醋酸乙烯—二乙烯基苯共聚反应动力学

根据文献查得的Ｑ，ｅ值，计算了醋酸乙烯－二乙烯基二元共聚的竞聚率，预测其共聚的可能性。以甲苯为汽油为致孔剂，采用悬浮聚合方法合成该二元大孔共聚物。红外光谱分析跟踪共聚反应过程中乙酰氧基和苯环相对比例的变化，并测定共聚反应过程中比表面积，孔率和平均孔径的变化。     

离子型表面活性单体存在下的MMA/BA乳液聚合(Ⅰ)——表面活性单体的合成及其(共)聚合活性

合成了两种离子型表面活性单体(Surfmer)磺化-十二醇-烯丙基甘油-丁二酸酯钠盐(ZC-L)和磺化-十二醇-甲基丙烯酰甘油-丁二酸酯钠盐(ZD-L).着重研究了ZC-L的结构、表面张力行为、均聚及共聚能力.实验结果表明,不同Surfmer用量以及不同固含量下,MMA/BA/Surfmer,MMA/Surfmer及BA/Surfmer共聚乳液的表面张力较高,说明Surfmer已通过共聚结合在乳胶粒上,乳液中残留甚少.对MMA/BA体系,ZC-L的共聚性能比ZD-L好.     

丙烯酸酯-苯胺共聚乳液的制备及防腐蚀性能

采用两步乳液聚合法制备丙烯酸酯-苯胺共聚乳液.通过红外光谱(FT-IR)、X射线衍射(XRD)、热重分析(TGA)和透射电镜(TEM)等表征手段对产物的结构进行了研究.将共聚乳液涂覆在Q235低碳钢表面,利用电化学交流阻抗谱(EIS)、塔菲尔(Tafel)曲线和平衡开路电位(OCP)考察共聚乳液涂层对Q235低碳钢的腐蚀防护性能.结果表明:丙烯酸酯与苯胺之间形成了化学键,丙烯酸酯乳液有效地起到了掺杂酸的作用;共聚乳液具有良好的成膜性;共聚乳液涂层具有较高的交流阻抗值(3.0×105Ω·cm2),降低了金属的腐蚀电流密度(10-8 A/cm2),显著提高了腐蚀电位(-0.44 V),防腐蚀性能较好.     

基于Maple软件辅助绘制自由基二元共聚曲线的研究

运用数据处理软件(maple)对经典的自由基二元聚合公式进行图形绘制,得到了二元单体之间共聚关系的三组图。一是二元单体的自由基共聚曲线图F1-f1,二是聚合物中单体平均组成(Fp)与投料单体浓度(f1)的关系曲线图,三是聚合物转化率(C)与投料单体(f1)的关系曲线图。通过二组具有代表性的共聚实例,分别是有恒比点的非理想共聚(苯乙烯-丙烯腈共聚物)和非理想非恒比共聚(苯乙烯-乙酸乙烯酯共聚物)展现了绘图步骤和分析了不同竞聚率情况下的聚合物转化过程。     

2-甲基-7-亚甲基-1,4,6-三氧螺[4,4]壬烷与丙烯腈、丙烯酸甲酯的共聚合反应及竞聚率的测定

用高效液相色谱跟踪2-甲基-7-亚甲基-1,4,6-三氧螺[4,4]壬烷(MMTN)与丙烯腈(AN),丙烯酸甲酯(MA)的共聚合反应。根据Lowry-Meyer共聚积分方程式,采用插值法进行数据拟合测定单体的竞聚率。对于体系MMTN(M_1)-AN(M_2),r_1=0.048;r_2=0.213;MMTN(M_1)-MA(M_2)r_1=0.025,r_2=0.764。说明两组共聚体系均有较强的交替共聚趋势。     

三烯丙基异氰酸尿酯－二乙烯苯－醋酸乙烯大孔共聚物的合成及其醇解反应

根据文献查得的Ｑ、ｅ值，计算了三烯两基异氰酸尿酯－二乙烯苯－醋酸乙烯三元共聚体系的竞聚率，预测了它们进行共聚的可能性．以甲苯和汽油为致孔剂，采用悬浮聚合的方法合成了此三元大孔共聚物，并研究了致孔剂用量、交联度等对共聚物孔性能的影响。实验发现，此共聚体系在适当条件下，可以制得很高比表面积的大孔共聚体，比表面积可高达１２１４ｍ２／ｇ。对合成的共聚物又进行了醇解反应，得到了含羟基的共聚体。     

乙烯-甲基丙烯酸甲酯共聚物结构的~1H NMR和~(13)C NMR表征

采用核磁共振(1H NMR、13C NMR)技术对由双[N-(2,6-二异丙基苯基)-3-异丙基水杨醛亚胺]镍(Ⅱ)配合物/甲基铝氧烷(Methylaluminoxane,MAO)催化乙烯-甲基丙烯酸甲酯共聚得到的共聚物(EMMA-a)的微观结构和组成进行了详细的分析与表征,同时对自由基聚合制得的乙烯-甲基丙烯酸甲酯共聚物(EMMA-b)作了相应的分析与表征。通过1H NMR数据,计算得到两种共聚物样品中共聚单体甲基丙烯酸甲酯(MMA)的插入率分别为14.10%和10.26%(摩尔百分数)。基于13C NMR数据,分析比较了由配位共聚与自由基共聚所得共聚物样品在微观结构上的区别,结果发现,在共聚物的乙烯链段部分,由配位共聚得到的共聚物样品EMMA-a主要含有甲基型支链,而由自由基共聚所得共聚物样品EMMA-b具有长链型支链。另外,在共聚物的MMA链节部分,EMMA-a中的MMA单元的羰基(C‖O)碳的化学位移为177.27,而EMMA-b中的MMA单元的羰基(C‖O)碳的化学位移为175.96。     

磺酰基亚胺类给电子体聚丙烯催化剂的性能

以N-(3-氯苯)-二(三氟甲基磺酰基)亚胺为内给电子体的聚丙烯催化剂具有较好的氢调敏感性,随着加氢量的增加,聚丙烯的熔融指数较大幅度地增加。丙烯共聚实验表明,该催化剂还具有较好的丙烯共聚性能。用升温梯度淋洗分级(TREF)的方法对样品进行分级处理的结果表明,所生成的共聚聚丙烯样品与对比样品SP179(市场上的共聚聚丙烯牌号)具有十分相似的TREF分级图。宏观力学性能测试表明,所得共聚聚丙烯非常符合工业上作为汽车保险杠专用树脂的使用要求。     

可用于尾矿库区污染控制的生态修复剂的制备及性能研究

采用种子乳液聚合法,以水性聚氨酯为分散液,醋酸乙烯酯(VAc)、马来酸二丁酯(DBM)、丙烯酸(AA)为主单体,2-丙烯酰胺基-2-甲基丙磺酸(AMPS)为功能单体,成功制备了羧基型共聚乳液,进一步考察了AMPS用量对乳液基本性能的影响,并首次将其用于尾矿库区的生态修复。实验结果表明:当AMPS用量在3%时,该共聚乳液用于尾矿库区固定尾砂的效果最好,且该共聚乳液形成胶膜的拉伸强度与固定尾砂时抗压强度呈现正相关性。另外,通过共聚乳液对尾砂的抗热老化、抗冻耐温、保水性及固定重金属离子稳定性等研究发现,羧基型共聚乳液能够有效实现尾矿库区的污染控制。微生物实验说明,羧基型共聚乳液作为尾矿库区修复剂使用时,具有良好的生态效应。这表明所制备的羧基型共聚乳液能够用于尾矿库区的污染控制与生态修复。     

Effect of solvent on the copolymerization of ethylene and vinyl acetate

The ethylene (M₁)–vinyl acetate (M₂) copolymerization at 62°C and 35 kg/cm² with α,α′-azo-bisisobutyronitrile as initiator has been studied in four different solvents, viz., tert-butyl alcohol, isopropyl alcohol, benzene, and N,N-dimethylformamide. The experimental method used was based on frequent measurement of the composition of the reaction mixture throughout the copolymerization reaction by means of quantitative gas chromatographic analysis. Highly accurate monomer reactivity ratios have been calculated by means of the curve-fitting I procedure. The observed dependence of the r values on the nature of the solvent is surprisingly large and can be correlated with the volume changes (= excess volumes) observed on mixing vinyl acetate (VAc) with the relevant solvent. An increased hydrogen bonding or dipole–dipole interaction through the carbonyl moiety of the acetate side group of VAc, induces a decreased electron density on the vinyl group of VAc, which in turn leads to a decreased VAc reactivity. The differences among the overall rates of copolymerization in the various solvents can be interpreted in terms of a variable chain transfer to solvent and the rate of the subsequent reinitiation by the solvent radical. In the case of benzene, complex formation is believed to play an important part.     

乙烯基乙酸酯合成钯-金催化剂中金的助催化作用

硅胶负载的钯-金双金属催化剂是乙烯乙酰氧基化制乙烯基乙酸酯(VA)的高选择性催化剂,本文应用平面和负载纳米颗粒模型催化剂体系研究金的助催化作用,应用低能离子散射谱、低能电子衍射、X射线光电子能谱、反射红外吸收光谱及程序升温脱附等技术表征这些模型催化剂.结果表明,金的主要助催化作用是隔离催化剂表面的催化活性钯原子,形成孤立的钯活性中心,从而大大抑制或消除反应物和/或产物在毗邻多原子钯中心上的深度分解,提高VA合成的选择性及活性.同时由于形成了孤立的钯原子活性中心,反应副产物或中间物之一的一氧化碳吸附较弱,避免了催化剂表面的一氧化碳中毒,进而提高催化活性.     

反应诱导相分离制备新型温度敏感光学材料

反应诱导相分离制备新型温度敏感光学材料李兴林陈文杰江明（复旦大学高分子科学系和国家教委聚合物分子工程实验室上海２００４３３）关键词高分子合金，旋节线相分离，光散射，温度敏感光学性能温度敏感光学材料是一种具有广泛用途的功能材料，可用作记录材料、显...     

Miscibility behavior of ethylene/vinyl acetate and C5 petroleum resin by FTIR imaging.

FTIR microscopic imaging was used to investigate the miscibility behavior of ethylene/vinyl acetate copolymer (EVA) and C5 petroleum resin. Images with an area of 500 x 500 microm(2) were collected in the reflection mode. The miscibility was characterized by probing the spatial distribution of the carbonyl group (C=O) of EVA in the whole images. It was found that a 1:1 hot-melt mixture of EVA and C5 resin showed a good miscibility behavior. For two different EVA copolymers, one with 18% vinyl acetate (VAc) content showed a better miscibility behavior than that with 28% VAc content. Our results demonstrated that this method allowed a direct, convenient and nondestructive visualization. This developed technique promises to become a powerful tool for studying the miscibility behavior of composite materials.     

Synthesis and properties of all solid polymer electrolytes based on poly(vinyl acetate‐co‐acetyl ethylene oxide acrylate)

Poly(acetyl ethylene oxide acrylate‐co‐vinyl acetate) (P(AEOA‐VAc)) was synthesized and used as a host for lithium perchlorate to prepare an all solid polymer electrolyte. Introduction of carbonyl groups into the copolymer increased ionic conductivity. All solid polymer electrolytes based on P(AEOA‐VAc) at 14.3 wt% VAc with 12wt% LiClO₄ showed conductivity as high as 1.2 × 10^?4 S cm^?1 at room temperature. The temperature dependence of the ionic conductivity followed the VTF behavior, indicating that the ion transport was related to segmental movement of the polymer. FTIR was used to investigate the effect of the carbonyl group on ionic conductivity. The interaction between the lithium salt and carbonyl groups accelerated the dissociation of the lithium salt and thus resulted in a maximum ionic conductivity at a salt concentration higher than pure PAEO‐salts system. Copyright © 2010 John Wiley & Sons, Ltd.     

Studies on pyrazines. Part 28 . Deoxydative acetoxylation of pyrazine N-oxides

Deoxydative acetoxylation of 3-methoxy-, 3-phenyl-, 3-methyl-, 3-chloro-, and 3-methoxycar-bonylpyrazine 1-oxides furnished predominantly 2-acetoxy-6-substituted pyrazines, some of which were more selectively prepared by addition of zinc bromide and triethylamine to the reaction. Regioselectivity of the acetoxylation is discussed based upon heat of formation by AMI and AMI-COSMO for all possible isomers of each set.     

Iodine-Transfer Polymerization (ITP) of Ethylene and Copolymerization with Vinyl Acetate

Controlled radical polymerization of ethylene using different commercially available, cheap, and non-toxic iodo alkyls is performed by iodine transfer polymerization (ITP) under mild conditions (≤100 °C and ≤200 bar). The formed well-defined iodo end-capped polyethylene (PE−I) species is very stable upon storage. Narrow molar-mass distributions (dispersities around 1.6) were obtained up to number average molar masses of 7300 g mol⁻¹. The ethylene copolymerization by ITP (ITcoP) with vinyl acetate allowed to form a broad range of poly(ethylene-co-vinyl acetate) (EVA) containing from 0 to 85 mol % of VAc unit. In addition, EVA-b-PE block copolymers or EVA-b-EVA gradient block copolymers with different content of VAc in the blocks were obtained for the first time using ITP. Finally, reactivity trends were explored by a theoretical mechanistic study. This highly versatile synthetic platform provides a straightforward access to a diverse range of well-defined PE based polymer materials.     

Iodonium salts are key intermediates in Pd-catalyzed acetoxylation of pyrroles

A mild, room-temperature Pd-catalyzed acetoxylation of pyrroles with phenyliodonium acetate is described. The acetoxylation was found to proceed via the initial formation of pyrrolyl(phenyl)iodonium acetates, which were converted to acetoxypyrroles in the presence of Pd(OAc)(2). The acetoxylation could also be carried out as a one-pot sequential procedure without the isolation of the intermediate iodonium salts.     

POLYVINYLACETATE-SiO2 GELS OBTAINED IN HOMOGENEOUS MEDIA

Polyvinylacetate-SiO₂ gels have been obtained by radical polymerization of vinyl acetate (VAc) in the presence of tetraethoxysilane (TEOS). The reaction system was: VAc:TEOS:EtOH:H₂O:S (nonylphenol ethoxylated with 25 moles ethylene oxide) in different ratios. The reaction was performed at 65°C. The initiator of radical polymerization was benzoyl peroxide and a crosslinking agent of sol-gel process bis maleate of diethylene glycol. Traces of acetic acid, maleic acid or acrylic acid catalyze the polymerization of TEOS. The presence of the surfactant (S) ensures the homogeneity of the initial system. The conditions of obtaining homogeneous gels have been selected. Ternary diagrams containing TEOS:EtOH:H₂O or (VAc+TEOS):EtOH:H₂O:S were used in order to establish the domains of homogeneous compositions in the systems. Refractometric and conductometric measurements have shown that the mentioned systems are microemulsions. X-ray diffraction, surface area measurements, DTA/TGA method, as well as IR spectrometry have been used in the characterization of the gels obtained.     

DDQ catalyzed benzylic acetoxylation of arylalkanes: a case of exquisitely controlled oxidation under sonochemical activation

Acetoxylated arylalkanes are selectively obtained via sonochemical activation of DDQ catalyzed benzylic oxidation of arylalkanes in the presence of anhydrous acetic acid. The method gives an exquisite control of benzylic acetoxylation under ultrasound, in contrast to the uncontrolled oxidation observed under conventional heating or microwave activation. In addition, the developed method could be a useful strategy for the synthesis of industrially important enantiopure benzyl alcohols due to the easy amenability of obtained acetoxylated products toward chiral resolution.