乳液共聚反应过程与聚合物结构关系及13C－NMR对聚合物结构的表征

 用间歇法和半连续法进行了丙烯酸丁酯（ＢｕＡ）与醋酸乙烯酯（ＶＡｃ）乳液共聚合．^１３Ｃ－ＮＭＲ对共聚产物分子结构测试表明，在间歇法共聚合中随着反应进行其组成及结构发生很大变化，而半连续法确能制得成份及结构均匀一致的Ｐ（ＢｕＡ－ＶＡｃ）共聚物．由于ＢｕＡ水溶性小于ＶＡｃ，而其竟聚率远大于ＶＡｃ，间歇法共聚合反应初期只有少量ＶＡｃ参加共聚合．通过对间歇法共聚合中不同反应时间聚合物的^１３Ｃ－ＮＭＲ测试，表明反应初期聚合的ＶＡｃ以单链节或二元序列形式存在于主要由ＢｕＡ单元构成的分子链中，而并未形成较长ＶＡｃ链段．对上述试样玻璃化转变温度的测试结果与^１３Ｃ－ＮＭＲ实验结果颇为一致．     

蒙脱土负载聚合催化剂用于乙烯原位共聚制备LLDPE

将蒙脱土 (MMT)负载的聚合催化剂rac Et(Ind) 2 ZrCl2 和均相低聚催化剂 { [(2 ArNC(Me) ) 2 C5H3N]FeCl2 } (Ar=2 ,4 C6 H4 (Me) 2 )组成双功能催化体系用于乙烯原位共聚制备线性低密度聚乙烯 (LLDPE) .通过调节两种催化剂之间的比例和MAO的用量制备了一系列支化度不同的LLDPE产品 .聚合反应动力学曲线表明 ,两种催化剂表现出各自的乙烯吸收特征 ,蒙脱土负载化的共聚催化剂催化乙烯聚合时反应平稳易控制 .DSC曲线表明 ,聚合物的熔点和结晶度随Fe Zr的增大而减小 .用密度梯度法测得的聚合物密度随Fe Zr的增大而降低 .从1 3C NMR谱图上可以看到 ,得到的聚合物是LLDPE ,其支化度随Fe Zr的增大而增大 ,聚合物中仍含有未共聚的α 烯烃 ,这一点从GPC上也能得到验证 .扫描电镜 (SEM)照片表明用这种双功能催化剂共聚得到的LLDPE具有良好的形态     

原位插层聚合制备聚丁二烯/蒙脱土纳米复合材料的结构与性能研究

聚合物 /粘土纳米复合材料由于具有常规复合材料所没有的结构、形态及更优异的力学、热学、阻燃、阻隔等性能 ,自 1 987由日本丰田公司首次报道了制备尼龙 6 粘土纳米复合材料以来 ,立刻引起人们的普遍关注[1～ 17] .目前报道的聚合物 /粘土纳米复合材料主要集中在以树脂为基体 ,例如 ,聚酰胺[1～ 4] 、聚苯乙烯[5～ 8] 、聚甲基丙烯酸甲酯[9,10 ] 、聚丙烯[11,12 ] 等 .制备以橡胶为基体的橡胶/粘土纳米复合材料研究较少 ,采用的方法多为通过橡胶大分子插层 ,如熔融插层法[1 3] 、溶液插层法[14 ] 、乳液法[15,16] 等 ,这些方法均存在插层…     

阳离子改性蒙脱土及对活性翠蓝K-GL染料的吸附性能研究

以十六烷基三甲基溴化铵(CTMAB)作为有机改性剂对钠基蒙脱土(MMT)进行改性得到阳离子化有机改性蒙脱土(CTMAB-MMT)。X-Ray衍射结果表明,随CTMAB用量的增加,MMT的层间距增加。以CTMABMMT为吸附剂,研究了其对活性翠蓝K-GL染料的吸附性能,结果表明,CTMAB-MMT对染料的吸附容量随CTMAB用量的增加或吸附温度的提高而增大;在弱酸性条件下CTMAB-MMT的吸附容量明显优于碱性条件;随着吸附时间的延长,CTMAB-MMT对染料的吸附容增加,一定时间后趋向于平衡。     

氯硅烷改性蒙脱土的制备与性能

基于氯硅烷与羟基的反应性,用氯硅烷对蒙脱土进行化学改性,FTIR证实硅烷已接枝到了蒙脱土上,WAXD表明,在极性分散剂中,硅烷成功地插层到了蒙脱土的片层间;而在非极性分散剂中,硅烷插层到蒙脱土片层间的量少,测定了蒙脱土阳离子交换容量(CEC),改性后其CEC值大幅度降低,分散性实验表明,由于改性后的蒙脱土颗粒以及片层间的相互作用力得到极大降低,其在水中和甲苯中的分散性更好.     

聚合物/蒙脱土纳米复合乳液的制备及其表面施胶性能

采用蒙脱土(MMT)改性聚苯乙烯-丙烯酸酯(PSB)乳液制备了一种新型表面施胶剂。 比较了不同方法合成的乳液在性能上的异同。 采用X射线衍射（XRD）和透射电子显微镜（TEM）测试技术表征了复合材料的结构。 研究了苯丙/蒙脱土纳米复合乳液作为表面施胶剂对纸张的物理性能和抗水性能的影响。 结果表明,聚合法制备的复合乳液中蒙脱土片层已发生剥离并在复合物中呈现纳米级分散。 纳米复合乳液与淀粉以质量比1∶10（绝干）复配进行表面施胶时,纸张的施胶度、挺度和环压强度比纯苯丙施胶剂分别提高1.8倍、45.5%和44%。     

羧甲基纤维素钠/蒙脱土纳米复合膜的制备及性能

用溶液插层法制备出了剥离型羧甲基纤维素钠 蒙脱土纳米复合物 .X射线衍射结果中蒙脱土d0 0 1 峰的消失证实了纳米复合物的生成 ,透射电镜观察表明硅酸盐片层在羧甲基纤维素钠基体中达到了纳米级的分散 .红外测试表明 ,羧甲基纤维素钠分子上的醚键和蒙脱土分子上的硅氧键、铝氧键之间强的作用力是插层的驱动力 .加入蒙脱土后 ,提高了羧甲基纤维素钠膜的拉伸强度、热稳定性 ,降低了其水蒸汽透过系数 .     

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．     

有机硅改性丙烯酸酯共聚乳液合成方法及胶膜性能的研究

用一次投料法、单体乳液滴加法和引发剂滴加法有机硅改性丙烯酸酯共聚乳液，聚合过程、胶粒形态及乳液稳定性的观测结果表明：单体乳液滴加法是合成该类乳液的最佳方法，研究了单体乳液滴加法中有机硅含量与聚合反及胶膜性能的关系，结果表明：有机硅含量在１５％以下时，聚合反应可以顺利进行，胶膜性能不仅依赖于聚合时有机硅单体的总量，而且还依赖于有机硅单体中活性硅氧烷所占的比例。     

有机硅/蒙脱土复合改性聚氨酯弹性体的制备和性能

采用先将聚醚三元醇N330与有机蒙脱土(OMMT)研磨,制得N330/OMMT复合物,再将其与有机硅改性聚氨酯的预聚体混合的方法,以二甲硫基甲苯二胺(DMTDA)为固化剂,制备了有机硅/蒙脱土复合改性聚氨酯弹性体,并用FTIR对产物结构进行了表征.XRD和TEM表明,蒙脱土片层被撑开,并分散在基体中;SEM显示,加入蒙脱土后,有机硅与聚氨酯之间的相容性提高;TGA表明,有机硅和OMMT共同改性聚氨酯后,其耐热性比有机硅单一改性聚氨酯有所提高,并在OMMT含量为5 wt％时提高最大;DSC数据表明,在OMMT含量为5 wt％时,有机硅/蒙脱土复合改性聚氨酯弹性体的Tg明显升高.复合改性材料具有良好的表面性能和力学性能,其拉伸强度、断裂伸长率和硬度在OMMT含量为3 wt％时达到最大值.     

Characterization of particle surface and morphology in vinyl acetate-butyl acrylate emulsion copolymers — Influence of the copolymerization pathway

Surface characterization was investigated in vinyl acetate (VAc) butyl acrylate (BuA) copolymer latexes of various compositions and prepared with four different emulsion polymerization processes: conventionnal batch, composition-controlled batch, core-shell, emulsifier-free semi-continuous. Surface end-groups (sulfate or carboxylic) titration results were first compared and discussed according to the type of process and as a function of conversion. As previously shown [1], it was confirmed that batch latex particles present a heterogeneous structure with a rich VAc outlayer, as in core-shell particles. As expected, semi-continuous and composition-controlled batch particles exhibit surface end-group characteristics revealing a more homogeneous distribution of both monomers within the particles. These differences in particle morphology were corroborated by analyzing water-polymer interface in these latexes using the soap titration method, with the sodium dodecyl sulfate (SDS) or sodium hexadecyl sulfate (SHS) as emulsifier probes. When the BuA was batch-polymerized onto PVAc seed particles, the estimated surface composition seemed to show that probably phase rearrangement occurs in the particle during the synthesis or upon aging. It was also confirmed that SDS displays an abnormal adsorption due to complexation and solubilization in the rich-VAc shell of the particles.     

Semicontinuous seeded emulsion copolymerization of vinyl acetate and methyl acrylate

The semicontinuous seeded emulsion copolymerization of vinyl acetate and methyl acrylate was investigated. The effect of type of process (starved process versus semi-starved process), type of feed (neat monomer addition versus monomer emulsion addition), amount of seed initially charged in the reactor, and feed rate on the time evolution of the overall conversion, copolymer composition, and polymer particle size was analyzed. It was found that, in the case of the starved process, both monomers, but mainly vinyl acetate, accumulated in the reactor. The preferential accumulation of vinyle acetate resulted in a drift of the copolymer composition. Both monomers accumulation and copolymer composition drift were reduced by increasing the amount of seed initially charged in the reactor and by decreasing the feed rate. For the semi-starved process, it was found that a vinyl aceatate rich copolymer was formed when a low methyl acrylate feed was used, whereas a methyl acrylate rich copolymer was obtained at high methyl acrylate feed rates. For both starved process and semi-starved process, the total number of polymer particles, after an initial increase, reached a plateau value which was the same in all of the experiments carried out. These results were analyzed by means of a mathematical model developed for this system.     

Miniemulsion copolymerization of vinyl acetate and butyl acrylate. I. Differences between the miniemulsion copolymerization and the emulsion copolymerization processes

Differences between the emulsion copolymerization and miniemulsion copolymerization processes, in terms of emulsifier adsorption, emulsion stability, polymerization kinetics, copolymer composition and dynamic mechanical properties were studied for the comonomer mixture of 50:50 molar ratio vinyl acetate (VA+)—butyl acrylate (BuA), using sodium hexadecyl sulfate (SHS) as a surfactant and hexadecane (HD) as a co-surfactant. The use of hexadecane with the appropriate SHS initial concentration led to a higher adsorption of surfactant, smaller droplet size, higher stability of the emulsions, lower polymerization rates, and larger latex particle size. The copolymer composition during the initial 70% conversion was found to be less rich in Vac monomer units for the miniemulsion process. The dynamic mechanical properties of the copolymer films showed less mixing between the BuA-rich core and the VAc-rich shell in the miniemulsion latexes compared to the conventional latex films.     

Miscibility of poly(vinyl chloride) with poly(methyl-co-hexyl acrylate) and poly(methyl-co-2 ethyl hexyl acrylate)

The miscibility and phase behavior in blends of PVC with poly(methyl-co-hexyl acrylate)[MHA] and poly(methyl-co-2 ethyl hexyl acrylate)[MEH] were studied. It was found that PVC is miscible with MHA copolymers having a HA volume fraction from 0.30 to 0.92 and MEH copolymers having an EH volume fraction from 0.30 to 0.83 at 100°C. By applying the mean field theory to the phase diagrams of these blend systems, segmental interaction parameters which represent the binary interaction between different monomer units were estimated. The calculated values reflect the fact that the miscibility window observed for PVC/MHA and PVC/MEH blend systems was attributed to the effect of repulsion between different monomer units within the copolymer. To investigate the effect of specific interaction on the miscibility for these blend systems, an attempt was also made to describe the blend interaction parameter as a function of polar group concentration in the acrylate copolymer. The blend interaction parameter values exhibit a u-shaped curve as a function of the weight fraction of C?O group in the copolymer, and the lowest blend interaction parameter value appears at about 0.24 C?O weight fraction.     

Synthesis and emulsion copolymerization of amphiphilic poly(2-oxazoline) macromonomer possessing a vinyl ester group

The present article describes the synthesis and emulsion copolymerization of a block-type amphiphilic poly(2-oxazoline) macromonomer possessing a polymerizable vinyl ester group. The macromonomer was synthesized by one-pot two-stage block copolymerization of 2-oxazolines using vinyl iodoacetate as initiator. 2-Methyl- and 2-n-butyl-2-oxazolines were employed for the construction of hydrophilic and hydrophobic segments, respectively. The surface activities evaluated by the surface tension of the macromonomer in water were fairly good. Emulsion copolymerization of vinyl acetate with the macromonomer was carried out. The macromonomer acted as a polymeric surfactant, as well as a comonomer. The resulting copolymer latex particles were spherical and their diameter was in the sub-micron range. The effects of the composition of the macromonomer on the emulsion copolymerization and the resulting latex particles were examined. © 1993 John Wiley & Sons, Inc.     

The effect of sodium methacrylate on the soapless emulsion copolymerization of methyl methacrylate and n-butyl acrylate

The soapless emulsion polymerization of methyl methacrylate (MMA) and n-butyl acrylate (BA) containing various concentrations of sodium methacrylate (NaMA) or methacrylic acid (MMA) is studied. The hydrosoluble yields in final latexes are not larger than 1.3–5%, depending on the concentration of NaMA used. Below 25% conversion, the change of conversion with reaction time follows the square rule and the particle size is proportional to the 2/3 power of time. Above 25% conversion, serious gel effect occurs, and the conversion follows the seventh power on time and the growth of particle diameter obeys the 2.5 power on time. The multiple glass transition (T_g) occur below 20% conversion, where monomer droplets exist. NaMA added induces more T_gs. The effect of molecular weight of the copolymers obtained on T_g (even the molecular weight distributions were shown to be shouldertype bimodal) is estimated to be insignificant. Thus, the heterogeneity of copolymer compositions for multiple T_gs is ascribed to be caused from neither the molecular weight heterogeneity nor the shifts in compositions due to the difference of the monomer reactivity ratios. Referring to the results mentioned, we assume the sublayer surrounding the particle, rich with SO₄^? and COO^? groups, and the concentration gradients of monomers in particles to illustrate particle morphology. In addition, the relatively hydrophilic sublayer is proposed to be closely relative with the occurrence of the composition heterogeneity in particles.     

Characterization of poly(vinyl alcohol) during the emulsion polymerization of vinyl acetate using poly(vinyl alcohol) as emulsifier

During the emulsion polymerization of vinyl acetate (VAc) using poly(vinyl alcohol) (PVA) as stabilizer and potassium persulfate as initiator, the VAc reacts with PVA forming PVA-graft-PVAc. When the grafted polymer reaches a critical size it becomes water-insoluble and precipitates from the aqueous phase contributing to the formation of polymer particles. Since particle formation and therefore the properties of the final latex will depend on the degree of grafting, it is important to quantify and to characterize the grafted PVA. In this work, the quantitative separation and characterization of the grafted water-insoluble PVA was carried out by a two-step selective solubilization of the PVAc latex, first with acetonitrile to separate PVAc homopolymer, followed by water to separate the water-soluble PVA from the remaining acetonitrile-insoluble material. After the separation, the water-soluble and water-insoluble PVA were characterized by Fourier Transform Infrared (FTIR) spectroscopy and ¹H and ¹³C nuclear magnetic resonance (NMR) analyses, from which the details of the PVA-graft-PVAc structure were obtained. © 1996 John Wiley & Sons, Inc.     

The formation mechanism of poly(vinyl acetate)/poly(butyl acrylate) core/shell latex in two-stage seeded semi-continuous starved emulsion polymerization process

In this paper, the morphological evolution of latex particles on poly(vinyl acetate) (PVAc)/poly(butyl acrylate) (PBA) in two-stage seeded semi-continuous starved emulsion polymerization is studied, and the thermodynamic analysis and a mathematic model are derived to describe the interfacial free energy changes corresponding to various possible thermodynamically unstable morphologies during the polymerization process. The comparisons between the morphological evolution and the related thermodynamic analysis show that the morphological evolution of latex particles is oriented to the thermodynamic preferred morphology which is an inverted core/shell structure with PBA as core and PVAc as shell. Based on the comparisons, the possible morphological developmental pathway of PVAc/PBA core/shell latex is described. The possible morphological developmental pathway suggests that the observed multi-particle morphology in the polymerization process is due to restricted chain mobility related to high internal viscosity. The formation mechanism of PVAc/PBA core/shell latex, based on the experiments as well as the thermodynamic and dynamic analyses, is proposed, which signifies that PBA is first formed outside the PVAc seed and then migrate to the inside of the PVAc seed.     

Gamma radiation induced graft copolymerization of vinyl monomers onto poly(vinyl alcohol)

In an attempt to modify water-soluble synthetic polymers, graft Copolymerization of methylmethacrylate (MMA) and ethyl acrylate (EA) onto poly(vinyl alcohol), PVA, has been studied by using gamma irradiation from a Co⁶⁰ source as initiator. The graft copolymerization was carried out in an aqueous medium by the mutual method in air. The effect of total dose and concentration of vinyl monomers on percentage of grafting has been determined. Water plays a significant role in the enhancement of graft copolymerization and the optimum amount of water to afford maximum grafting has been evaluated. The effect of CH₃OH on aqueous grafting of MMA and EA by radiation method has been studied. The graft copolymer has been characterized by IR spectroscopic and thermogravimetric methods.     

Solution properties of poly(methyl acrylate) and (1:1) poly(styrene-co-methyl acrylate)

Poly(methyl acrylate) (PMA) and 1:1 poly(styrene-co-methyl acrylate) (PSMA) were prepared by solution and bulk polymerization, respectively. The copolymer was analyzed with NMR to ascertain its composition and microstructure. The solution properties of unfractionated PMA and fractionated PSMA in ethyl acetate were investigated by light-scattering and viscosity techniques at 35°C. Narrow composition heterogeneity as revealed from the light-scattering measurements in different solvents justified the use of a single solvent for the copolymer characterization. The equations relating the limiting viscosity number to molecular weight, the molecular dimension to molecular weight, etc., were found for homopolymer and copolymers in ethyl acetate at 35°C. In the evaluation of the Flory constant K for the unperturbed state by methods based on Flory-Fox-Schaefgen, Kurata-Stockmayer, and Stockmayer-Fixman expressions, only the first method gave a value for PMA in ethyl acetate, consistent with that obtained in other solvents, whereas similar values of K were obtained by the three methods for PSMA in ethyl acetate. The studies indicate reduced thermodynamic interaction for PSMA–ethyl acetate compared to PMA–ethyl acetate, but increased steric effect in the copolymer compared with the homopolymer.