EMULSION COPOLYMERIZATION OF VINYL ACETATE IN PRESENCE OF ACID COMONOMERS

The interaction of acid comonomers, crotonic acid, maleic monoesters, maleic acid with the surfactant, the sodium salt of sulfosuccinic acid semiester with nonyl phenol etoxylated with 25 moles ethylene oxide (NPEO₂₅SS) depends on the hydrophilicity of comonomers. The rate of initiator splitting reaction (potassium persulfate - KPS) in presence of NPEO₂₅SS and of comonomers decreases with the increasing of acid comonomer concentration. This rule is valid in copolymerization of acid comonomers with vinyl acetate (VAc) below a small comonomer concentration, then the rate increases. The presence of some more hydrophobic comonomers maleic diesters, lowers the decomposition rate of KPS. These results are the effect of the stronger interaction of NPEO₂₅SS with more hydrophobic polymer particles. In their presence the concentration of free NPEO₂₅SS is lower and it can participate in the KPS - surfactant reaction and rise its rate to a lesser extent. Owing to some secondary acid comonomer - KPS reactions the productivity of initiator splitting decreases with acid comonomer concentration The glass transition temperatures of the thin films obtained in presence of acid comonomers, may increase or decrease, depending on the volume of the substituents of these comonomers.     

醋酸乙烯酯的辐射乳液聚合

本文研究了各种因素对醋酸乙烯酯(VAc)辐射乳液聚合反应速度、胶乳粒子数、分子量、分子量分布及支化度的影响,在Friis导出的VAc化学引发乳液聚合的动力学和分子量公式的基础上,修改了K′_α等参数表达式,对VAc辐射乳液聚合曲线、分子量等随转化率变化的曲线作了理论计算,与实验结果较吻合。     

蒙脱土负载型引发剂的制备及在苯乙烯乳液聚合中的应用

通过正离子交换将引发剂AIBA负载在蒙脱土上制得负载型引发剂V50-MMT.进而采用原位乳液聚合方法引发苯乙烯聚合制备PS/MMT纳米复合材料.采用XRD、TGA、DSC、TEM和抽提等方法对负载型引发剂和纳米复合材料进行了表征.结果表明,负载过程中引发剂AIBA进入了MMT的片层之间;聚合过程中介于片层间的引发剂因发生分解一方面产生自由基引发St聚合,另一方面MMT发生了剥离分散;由此法制备的PS/MMT纳米复合材料,MMT片层无规、均匀地分散于PS基体中,片层厚度在几个纳米至十几个纳米之间,长度为几十至几百个纳米不等;大量的PS链段以化学键接枝在MMT的片层上,接枝在MMT片层上的PS的分子量及其分布与游离的PS不同.     

HOMOPOLYMERIZATION AND COPOLYMERIZATION OF VINYL ACETATE IN NON-IONIC ICROEMULSIONS. I. A STUDY OF HOMOGENEITY DOMAINS

Abstract

The homogeneity ranges of the systems consisting of the monomer (vinyl acetate or vinyl acetate + di-2-ethyl hexil maleate), cosurfactant (ethanol, n-propanol, n-butanol), surfactant (nonylphenol ethoxylate with 25 moles of ethylene oxide) and water were studied. Addition of the more hydrophobic comonomer requires utilization of a more hydrophobic cosurfactant. The increase of surfactant concentration entails the widening of the homogeneity range. The effect of the cosurfactants mentioned is accounted for by the modification of the cluster structure of water. Therefore the refractive indexes and the signals of protons in NMR spectra vary non-linearly with the composition of homogeneous systems. DSC analysis of the systems obtained has come out with two crystallization temperatures of water undercooled to ?60°C in systems of concentrations close to those of organic and aqueous phases. The results plead for the existence of a structure which differs from that of the ideal solutions of the systems studied.     

在阳离子乳化剂的存在下八甲基环四硅氧烷的乳液聚合

研究了八甲基环四硅氧烷(D_4)在十二烷基二甲基苄基卤化铵及碱存在下乳液聚合的反应机理。聚合分二步进行:D_4先开环生成具有端羟基的聚二甲基硅氧烷,然后再缩合。反应终点有二个平衡反应;不同分子量的羟基封头的聚二甲基硅氧烷的平衡,以及羟基封头的线型聚硅氧烷和环硅氧烷的平衡。平衡时羟基封头的聚硅氧烷的量为87％并提出了主要反应位置是在胶束表面并逐渐转移到随后形成的聚合物颗粒表面,单体液滴是次要反应区。     

硅氧烷乳液聚合的研究——Ⅰ.环硅氧烷在阳离子乳化剂存在下的乳化与聚合

<正> 有机硅乳液早已得到广泛应用,但关于有机硅乳液聚合以及反应机理的文献却很少。我们对此做了较为系统的研究,本文首先讨论了单体转化率的测定方法,探讨了乳液的形成过程,比较了不同的环硅氧烷向水相扩散及聚合的速度。     

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.     

丙烯酸丁酯-醋酸乙烯酯共聚物胶乳粒子的结构和性能

电镜观察表明,丙烯酸丁酯-醋酸乙烯酯共聚物胶乳粒子均为核-壳结构,若配料比不同,含量大者为核,而加料方式不同,则先加者先聚合成核.微观结构不同,可明显地影响胶膜的力学性能、T_g和耐水性.根据胶乳粒子微观结构的观察结果,认为当醋酸乙烯酯>50mol%时,共聚的引发和成核是在水相中进行的.     

醋酸乙烯酯-丙烯酸丁酯乳液聚合成核机理

本工作研究了醋酸乙烯酯(VA)和丙烯酸丁酯(BA)乳液共聚合.通过对不同共聚单体配比下共聚合时胶乳粒径及胶粒数密度随转化率变化的分析,对VA/BA乳液共聚合成核及粒增长机理进行了探讨,指出水相成核是高VA含量时胶粒数密度较大的主要原因并解释了胶粒数密度及胶乳粒径与单体转化率的关系,同时也讨论了该共聚体系一步法聚合时反应机理与胶粒形态的关系.     

在18-冠-6存在下苯乙烯无乳化剂乳液聚合

本文研究了在苯乙烯不外加乳化剂的乳液聚合体系中,加入王冠醚18-冠-6对聚合反应及其产物的影响。发现18-冠-6能起到相转移催化作用,并提出两相粒子成核机理,对实验结果作出了合理的解释。     

THE KINETICS OF THE DECOMPOSITION OF CYCLOHEXYL HYDROPEROXIDE IN THE PRESENCE OF VANADYL DIBENZOYLMETHANE

The kinetics of the decomposition of cyclohexyl hydroperoxide(CHHP) in benzene catalyzed by vanadyl dibenzoylmethane[V0(DBM).,] has been studied.It was found that the products of decomposition of CHHP were cyclohexanol and cyclohexanone,which are produced in about equimolar amount,and the product cyclohexanol obviously inhibited the decomposition of CHHP.The kinetics data can be satisfactorily described by the following equation (with [CHHP]0>>[VO(DBM)2]0)R0=kK[CHHP]0[VO(DBM)2]0/(1+k[CHHP]0)This is the kinetic evidence for the formation of a catalyst-hydro-peroxide intermediate.In the equation K is the stability constant of the catalyst-hydroperoxide intermediate complex;k is the rate constant for the decomposition of the complex.The rate constant K at 500℃ may be expressed as follows:k=1.9×108exp(-53.7×103/RT)S-1 with the activation energy Ea=53.7kJ mol-1     

配位催化苯乙烯乳液聚合的动力学研究

以Ni(COD)2和含磷、氧配体为催化剂,利用乳液聚合法合成了间规聚苯乙烯.对产物进行了13C-NMR、1H-NMR、GPC、TEM、DSC、TG等表征.在此反应体系下,最佳聚合条件为:乳化剂用量为1.50 g,[St]0=1.79 mol·L-1,T=60℃,t=2h,[Ni(COD)2]=1.102 mmol·L-...     

INVERSE EMULSION POLYMERIZATION OF ACRYLAMIDE: POLYMERIZATION KINETICS AND PROCESS DEVELOPMENT

Inverse emulsion polymerization confers the benefits of emulsion polymerization kinetics — rapid polymerization rates combined with high polymer molecular weights — on water-soluble polymers, particularly polyacrylamide and its copolymers and derivatives, and allows easy dissolution of the polymer in water by inversion of the latex. The mechanism and kinetics of the inverse emulsion polymerization of acrylamide in o-xylene containing Tetronic 1102 emulslfier and benzoyl peroxide initiator are described, particularly the formation of 10-200nm multiple emulsion droplets resulting from the particulate emulsifier, and their effect on the polymerization process     

调节剂存在下双金属氰化络合催化剂催化环氧丙烷聚合的动力学

研究了双金属氰化络合催化剂DMC催化环氧丙烷调节聚合的动力学 .通过测定反应过程体系压力的变化来决定聚合的起始速率 ,发现聚合反应速率与分子量调节剂浓度Tr的线性函数的 - 1次方成正比 .考察了DMC催化剂在反应不同阶段的远红外吸收变化 ,提出了聚合反应可能的反应历程 ,并推导出调节聚合的动力学方程 .研究结果表明调节聚合的动力学特点在于链引发是发生在催化剂与单体之间 ,而不是催化剂与调节剂之间     

KINETICS OF VINYL CHLORIDE (CO) POLYMERIZATION AT HIGH CONVERSION

This paper provides a summarized review on the kinetics of vinyl chloride homopolymerization inthe absence and presence of chain transfer agents, of VC/DAP(diallyl phthalate) copolymerization with chainextension and/or slightly crosslinking functions, and of vinylidene chloride/VC random copolymerization.Models of rate, degree of polymerization or molecular weight, copolymer composition, gel fraction andcrosslinking density were proposed and interpreted mechanistically.     

在四官能团引发剂存在下的自缩合乙烯基聚合反应制备丙烯酸酯类超支化共聚物

超支化聚合物具有特殊的结构和性能 ,可通过一步法聚合直接制得 ,具有大规模工业应用前景 .近年来 ,超支化聚合物的研究已成为高分子科学的热门课题之一[1～ 3 ] .超支化聚合物的一个主要缺点是它的分子量分布比较宽 .Ｍ櫣ｌｌｅｒ[4] 等通过理论计算指出 ,在聚合体系中加入ｆ个功能基团的分子Ｂｆ[对自缩合乙烯基聚合反应 (ＳＣＶＰ) ,Ｂｆ为ｆ个引发基的引发剂 ;对ＡＢｘ 型单体的缩聚反应 ,为有ｆ个Ｂ官能团的分子 ],可以降低超支化聚合物的分子量分布 ,这一结果已被实验证实[5～ 7] .我们用ＭｏｎｔｅＣａｒｌｏ方法模拟了在多官能团引…     

极性介质中醋酸乙烯酯的辐照引发分散聚合

用钴 60γ射线引发醋酸乙烯酯的分散聚合 ,通过选择各种极性溶剂体系 ,确立了醋酸乙烯酯在极性介质中稳定的分散聚合体系 .对异丙醇 水体系 ,聚合物分子量随剂量率的降低、稳定剂含量的增加、单体浓度的增大、反应温度的升高以及醇水比的降低而增加 .运用XPS、元素分析等表征聚合物粒子 ,及通过辐射接枝理论的分析 ,可以判断稳定剂所起的稳定作用主要是以物理吸附为主     

大分子引发剂-乳化剂的合成及其乳液聚合动力学的研究

 本文用偶氮二异丁腈、聚乙二醇400合成了聚偶氮酯,再与α-甲基丙烯酸聚合得到了具有引发剂和乳化剂双重作用的含偶氮基的聚甲基丙烯酸预聚体,将它用于苯乙烯的乳液聚合,得到稳定性优异的聚苯乙烯乳液,对它的乳液聚合动力学行为进行了研究,发现这种大分子引发剂-乳化剂有着经典乳液聚合的动力学特征,聚合中期动力学方程与Smith-Ewart关于经典乳液聚合中期的动力学方程是一致的.     

大分子引发剂-乳化剂的合成及其乳液聚合动力学的研究

本文用偶氮二异丁腈、聚乙二醇400合成了聚偶氮酯,再与α-甲基丙烯酸聚合得到了具有引发剂和乳化剂双重作用的含偶氮基的聚甲基丙烯酸预聚体,将它用于苯乙烯的乳液聚合,得到稳定性优异的聚苯乙烯乳液,对它的乳液聚合动力学行为进行了研究,发现这种大分子引发剂-乳化剂有着经典乳液聚合的动力学特征,聚合中期动力学方程与Smith-Ewart关于经典乳液聚合中期的动力学方程是一致的.     

醋酸乙烯酯-丙烯酸丁酯乳液共聚乳胶粒形态演化过程的模拟

将簇迁移动力学拓展应用到共聚形态的研究中，对醋酸乙烯酯 丙烯酸丁酯从间歇到不同加料速率下的半连续乳液共聚实验的乳胶粒形态演化过程进行了模拟，模拟从共聚 均聚转折点开始．结果说明：半连续加料时，随着加料速率加快，相分离程度增加，间歇反应时形成了核壳结构．乳胶粒形态模拟结果与文献对此共聚乳胶粒形态的实验表征结果类似．