GHD室温自交联乳液的聚合及贮存稳定性

采用半连续种子乳液聚合技术合成了含甲基丙烯酸缩水甘油酯(GMA)、甲基丙烯酸羟乙酯(HEMA)和甲基丙烯酸二甲氨基乙酯(DMAEMA)的室温自交联乳液(GHD).实验结果表明,在甲基丙烯酸甲酯(MMA)-丙烯酸丁酯(BA)-GMA种子乳液存在下,聚合温度升高,聚合过程稳定性下降,但乳液的贮存稳定性提高;乳化单体滴加速度加快,种子聚合物的玻璃化温度升高,可减少聚合过程的交联凝聚作用,提高聚合过程的稳定性;而HEMA和DMAEMA用量增加对聚合过程的稳定性没有明显影响,但使乳液的贮存稳定性下降.官能团间的交联凝聚作用可能是影响室温自交联乳液聚合及贮存过程稳定性的关键因素.     

反应性乳化剂存在下半连续苯丙乳液共聚合表观动力学

研究了在反应性乳化剂SE-10N存在下,采用半连续滴加工艺进行苯丙乳液共聚合的表观动力学.首先利用间歇法研究了引发剂、乳化剂用量、单体总量和温度对聚合反应速率的影响,得到了相应的聚合反应速率方程为Rp =k[M]0.30[I]0.18[E]0.97,并计算得到聚合反应的表观活化能为90.8 kJ·mol-1.然后采用半连续滴加法,讨论了不同滴加速率对聚合表观速率Rp的影响,结果表明,随滴加速率Ra 的增加,反应速率Rp也增加,但增加的幅度逐渐减少,且聚合过程的状态不断远离饥饿态.要使该聚合过程的状态保持在稳定的饥饿态,单体滴加时间应控制在140 min 以上.     

丁苯胶乳的合成研究

以丁二烯和苯乙烯为单体、十二烷基硫醇为乳化剂,通过一步法合成了大粒径丁苯胶乳（SBR）.结果表明：乳化剂浓度、电解质浓度、固含量及单体加入方式是控制丁苯胶乳粒径大小的关键因素.通过适时补加乳化剂,选取适宜的电解质浓度、固含量及采用种子半连续加料方式有利于控制SBR粒径大小及分布.     

氧化-还原低温引发甲基丙烯酸甲酯/丙烯酸丁酯超浓乳液聚合研究

以乳化剂十二烷基硫酸钠 (SDS)和共乳化剂十六烷醇 (HD)作为复合乳化体系 ,过氧化二苯甲酰(BPO)和N ,N 二甲基苯胺 (DMA)作为氧化还原引发体系 ,甲基丙烯酸甲酯 丙烯酸丁酯 (MMA BA)作为混合单体 ,制备了分散相占 83 %以上的稳定的超浓乳液 ,然后在低温下引发聚合 .探讨了引发剂浓度、氧化剂与还原剂的摩尔比、乳化剂的浓度、液膜增强剂的种类、聚合温度等因素对聚合稳定性和聚合速率的影响 ,测定并计算得到了聚合速率的公式 ;用激光散射粒度分布仪测定了聚合物乳胶粒子的大小及粒径分布 ,用透射电子显微镜观察了聚合物乳胶粒的形态 ,讨论了乳化剂浓度、聚合温度等对乳胶粒形态、大小的影响     

苯丙水溶胶的合成与性能研究(I) 聚合工艺和反应组分对聚合稳定性和胶体性能的影响

用一次投料法、半连续滴加法和单体预乳化法三种聚合工艺，合成了苯丙乳液聚合物，并加氨微细化，转化成水溶胶，考察了聚合工艺和反应组分（乳化剂，功能单体等）对苯丙乳液及其水溶胶反应稳定性和粒子大小及分布等胶体性能的影响。     

丙烯酰胺双水相聚合体系稳定性研究

通过浊点滴定法测定了不同温度下PAAmPEGH2O双水相体系相图,发现分相浓度随着温度的升高先增后降,55℃时分相浓度最低.双水相聚合体系微观结构显示,分散相以砾状液滴形式均匀分散在连续相中.研究了聚合过程中聚合体系粘度的变化,以及聚合温度、分散介质、单体、引发剂及乳化剂等对聚合体系最终粘度的影响,聚合体系最终粘度在一定范围内随分散介质和单体浓度增加变化不大,但是超过某一浓度后聚合体系粘度急剧增加;聚合体系中加入少量乳化剂对体系粘度影响不大,但加入大量乳化剂后体系稳定性变差,聚合体系粘度急剧增加;聚合体系最终粘度随着聚合温度升高先降后增,与相图的预测结果一致.     

八甲基环四硅氧烷正离子细乳液开环聚合动力学

以十二烷基苯磺酸钠(SDBS)为乳化剂,硫酸或盐酸为催化剂,八甲基环四硅氧烷(D4)为单体,十六烷为共稳定剂,超声预乳化,制备了聚硅氧烷细乳液,研究了超声时间、催化剂用量、乳化剂用量和温度对聚合动力学的影响.结果表明,在一定酸度范围内,聚合速度与硫酸浓度0.81次方、与盐酸浓度1.02次方、与乳化剂浓度-0.66次方成正比,反应的表观活化能为40.56kJ/mol.     

可聚合乳化剂合成苯乙烯-丙烯酸丁酯-α-烯烃磺酸钠共聚物乳液

以工业原料α-烯烃磺酸钠(AOS)作为可聚合乳化剂,苯乙烯(St)和丙烯酸丁酯(BA)为单体,采用预乳化种子乳液聚合合成了St-BA-AOS共聚物乳液.通过测定AOS与两种单体的竞聚率确定了半连续加料法的聚合方式.探讨了单体的加料方式、反应温度、反应时间、AOS用量等工艺条件对胶乳的影响,获得了最佳聚合条件.IR,NMR和DSC测试结果分析表明:St,BA与AOS发生了自由基共聚反应,形成的P(St-BA-AOS)共聚物结构中含有磺酸基等亲水性基团有利于乳液的稳定.在此基础上考察了AOS用量对乳液的固含量及乳胶粒粒径等的影响.结果表明:随着AOS用量的增加,乳液的固含量增加、乳胶粒的平均粒径减少.当AOS含量为2%时乳液的固含量为45.01%,平均粒径为74 nm,粒径分布指数为0.08,玻璃化温度为23.17℃.TEM测试结果显示,用相同量的AOS代替十二烷基硫酸钠可得到粒径更小和粒径分布更为均匀的乳液体系.     

聚合物基纳米微球制备及抗腐蚀性能评价

采用对苯乙烯磺酸钠（SSS）和改性SiO₂替代常规非反应型乳化剂,苯乙烯（St）、丙烯酸羟乙酯(HEA)、甲基丙烯酸甲酯(MMA)为单体,通过半连续种子乳液预乳化法制备丙烯酸类聚合物微球(PSAC)。探究了单体配比、乳化剂用量对纳米微球粒径、玻化温度、电位、黏度、亲水性及稳定性等性能的影响,其结构经 FTIR、 TEM及SEM等确证,抗CO₂腐性能同时进行初步探讨。      

苯乙烯在阴离子型聚氨酯纳米水分散液中聚合过程的研究

采用自乳化法制备出阴离子聚氨酯纳米水分散液,以其作为乳化剂使苯乙烯单体在其中进行聚合,制备出不同聚苯乙烯与聚氨酯质量比的阴离子型PS/PU纳米复合物水分散液;对苯乙烯单体的聚合过程进行了研究;采用光子相关谱仪和透射电镜对其微观结构、粒径及其分布进行了测试,结果表明,该方法能够制备出稳定的具有核壳结构的PS/PU纳米复合物水分散液,但当苯乙烯单体浓度增大到一定程度(PS/PU质量比为50∶100)时,粒子不稳定而发生聚集.     

反应性乳化剂对有机硅-丙烯酸酯乳液共聚合的影响

有机硅改性丙烯酸酯;乳液聚合;反应性乳化剂对有机硅-丙烯酸酯乳液共聚合的影响     

Suspended Emulsion Copolymerization of Acrylonitrile with Methyl Acrylate: Effects of Reaction Parameters on the Polymerization

Acrylonitrile/methyl acrylate copolymers were synthesized by suspended emulsion polymerization with water as dispersed phase and monomers as continuous phase, potassium peroxydisulphate (KPS) as initiator, Span-80 as emulsifier, and poly(vinyl alcohol) (PVA) as suspending agent. Effects of reaction parameters such as water/monomer mass ratio, concentration of initiator, polymerization temperature and agitation rate on polymerization conversion and the particle size distribution of acrylonitrile/methyl acrylate copolymers were studied. It was found that polymerization conversion increased with an increase of water/monomer mass ratio, concentration of initiator and polymerization temperature, while the agitation rate had no significant effect on the polymerization conversion. Particle size distribution became narrower with an increase of water/monomer mass ratio and agitation rate. Under the same initiator concentration and polymerization temperature, particle size distribution became wider along with polymerization time. The differential scanning calorimetry (DSC) results indicated that the peak temperature of the copolymers decreased with increasing MA content.     

The preparation of sterically stabilized polymer dispersions

The emulsion polymerizations of styrene (St) and butyl acrylate (BA) stabilized by nonionic polyoxyethylene type emulsifiers did not show the long stationary rate interval. This was discussed in terms of two opposing effects: 1) the decreased monomer concentration at the reaction loci due to the depletion of monomer droplets or depressed monomer droplet degradation and 2) the increased number of polymer particles with increasing conversion. The continuous particle nucleation is attributed to the continuous release of emulsifier from the emulsifier saturated monomer droplets and/or the presence of monomer swollen micelles (microdroplets). The limited particle flocculation operative at lower emulsifier concentrations increases the nonstationary-state polymerization. The particle agglomeration is accompanied by the increased reaction order x (N_p vs. [E]^x) above 0.6. The increased uniformity of monomer emulsion stabilized by Tween 20 by homogenization of monomer emulsion increased the final conversion and the polymerization rate as well. The polymerization rate vs. conversion curve of the homogenized emulsion characterized with broader stationary rate interval reminds the four rate intervals system typical for miniemulsion. The accumulation of polymer and nonionic emulsifier within the monomer phase preserves the monomer droplets up to high conversion. The decreased monomer droplet degradation rises the monomer-starved condition or the depressed transport of both monomer and emulsifier to the reaction loci.     

On the emulsion polymerization of styrene in the presence of a nonionic emulsifier

The batch emulsion polymerization kinetics of styrene (St) initiated by a water-soluble peroxodisulfate in the presence of a nonionic emulsifier was investigated. The polymerization rate versus the conversion curves showed two nonstationary rate intervals, two rate maxima, and Smith–Ewart Interval 2 (nondistinct). The rate of polymerization and number of nucleated polymer particles were proportional to the 1.4th and 2.4th powers, respectively, of the emulsifier concentration. Deviation from the micellar nucleation model was attributed to the low water solubility of the emulsifier, the low level of the micellar emulsifier, and the mixed modes of particle nucleation. In emulsion polymerizations with a low emulsifier concentration, the number of radicals per particle and particle size increased with increasing conversion, and the increase was more pronounced at a low conversion. By contrast, in emulsion polymerizations with a high emulsifier concentration, the number of radicals per particle decreased with increasing conversion. This is discussed in terms of the mixed models of particle nucleation, the gel effect, and the pseudobulk kinetics. The formation of monodisperse latex particles was attributed to coagulative nucleation and droplet nucleation for the polymerizations with low and high emulsifier concentrations, respectively. The effects of the continuous release of the emulsifier from nonmicellar aggregates and monomer droplets, the close-packing structure of the droplet surface, and the hydrophobic nature of the emulsifier on the emulsion polymerization of St are discussed. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4422–4431, 1999     

Structure and properties of novel fluorinated polyacrylate latex prepared with reactive surfactant

The novel fluorinated polyacrylate latex was successfully prepared by emulsion polymerization of perfluorononylene allyl ether, butyl acrylate and methyl methacrylate initiated by potassium persulfate in water and emulsified with the reactive surfactant. Films of the novel fluorinated polyacrylate latex were prepared by coating the latex directly on the clean glass sheet and allowed to dry at 80°C in the bake oven. The characteristics of the film such as hydrophobicity and glass transition temperature were studied; its structure was investigated by FTIR spectrometry and NMR. The influence of the fluorinated monomer content on the emulsion polymerization and performance of the latex were also studied. It was shown that the hydrophobicity and glass transition temperature of the latex are improved when the fluorinated monomer is introduced to copolymerize with other monomers, however, the stability of emulsion polymer and the conversion rate is decreased with the increase of its content.     

苯丙乳液合成反应条件优化

以苯乙烯、丙烯酸、丙烯酸丁酯、甲基丙烯酸甲酯等为单体,采用乳液聚合制备了苯丙乳液,研究了合成温度、引发剂用量、乳化剂用量、功能性单体丙烯酸用量等反应条件对苯丙乳液性能的影响,并探讨了丙烯酸单体对乳液耐酸碱稳定性的影响,确定了合成反应条件.结果表明,随着合成温度的提高,混合单体的转化率迅速增加,78℃时转化率最大(达到97.1%),而后随温度继续提高基本保持不变.混合单体转化率随过硫酸钾引发剂用量的增加呈现先增加后逐渐降低的趋势,当过硫酸钾与混合单体质量比为0.010时转化率最大,此时单体转化完全.此外,随着乳化剂用量增加,乳液的外观、钙离子稳定性、凝胶等性能都有所提高,但吸水率也相应增加.最佳合成反应条件为:合成温度为78℃,混合单体组成为15g苯乙烯、2g丙烯酸、18g丙烯酸丁酯、8g甲基丙烯酸甲酯,引发剂和乳化剂与单体质量比分别为0.010和0.035.得到的苯丙乳液在酸性条件下具有良好的稳定性.     

Sterically and electrosterically stabilized emulsion polymerization. Kinetics and preparation

The principal subject discussed in the current paper is the radical polymerization in the aqueous emulsions of unsaturated monomers (styrene, alkyl (meth)acrylates, etc.) stabilized by non-ionic and ionic/non-ionic emulsifiers. The sterically and electrosterically stabilized emulsion polymerization is a classical method which allows to prepare polymer lattices with large particles and a narrow particle size distribution. In spite of the similarities between electrostatically and sterically stabilized emulsion polymerizations, there are large differences in the polymerization rate, particle size and nucleation mode due to varying solubility of emulsifiers in oil and water phases, micelle sizes and thickness of the interfacial layer at the particle surface. The well-known Smith-Ewart theory mostly applicable for ionic emulsifier, predicts that the number of particles nucleated is proportional to the concentration of emulsifier up to 0.6. The thin interfacial layer at the particle surface, the large surface area of relatively small polymer particles and high stability of small particles lead to rapid polymerization. In the sterically stabilized emulsion polymerization the reaction order is significantly above 0.6. This was ascribed to limited flocculation of polymer particles at low concentration of emulsifier, due to preferential location of emulsifier in the monomer phase. Polymerization in the large particles deviates from the zero-one approach but the pseudo-bulk kinetics can be operative. The thick interfacial layer can act as a barrier for entering radicals due to which the radical entry efficiency and also the rate of polymerization are depressed. The high oil-solubility of non-ionic emulsifier decreases the initial micellar amount of emulsifier available for particle nucleation, which induces non-stationary state polymerization. The continuous release of emulsifier from the monomer phase and dismantling of the non-micellar aggregates maintained a high level of free emulsifier for additional nucleation. In the mixed ionic/non-ionic emulsifiers, the released non-ionic emulsifier can displace the ionic emulsifier at the particle surface, which then takes part in additional nucleation. The non-stationary state polymerization can be induced by the addition of a small amount of ionic emulsifier or the incorporation of ionic groups onto the particle surface. Considering the ionic sites as no-adsorption sites, the equilibrium adsorption layer can be thought of as consisting of a uniform coverage with holes. The de-organization of the interfacial layer can be increased by interparticle interaction via extended PEO chains--a bridging flocculation mechanism. The low overall activation energy for the sterically stabilized emulsion polymerization resulted from a decreased barrier for entering radicals at high temperature and increased particle flocculation.     

二甲基二烯丙基氯化铵反相乳液聚合动力学及机理的研究

研究以异构烷烃混合物为连续相,以丁二酸二(2-乙基)己酯磺酸钠(Sodium-di-2-ethylhexylsulfosuccinate,CH~3CH~2CH~2CH~2CH(C~2H~5)CH~2OCOCH(SO~3Na)CH~2COOCH~2CH(C~2H~5)-CH~2CH~2CH~2CH~3,AOT)和山梨糖醇单油酸酯(SMO)为乳化剂,以偶氮二异庚腈(ADVN)为引发剂的二甲基二烯丙基氯化铵的反相乳液聚合,得到了R~P~,~0=kc^0^.^4~Ⅰ~,~0c^0^.^5~A~O~Tc^-^0^.^4~S~M~Oc^3^.^0~M~,~0的表观动力学表达式。首次提出并研究了反相乳液聚合中单体在单体液滴和胶束中的分配系数对聚合动力学的影响,成功地解释了初始聚合反应速度和单体浓度三次方成正比的原因。通过对胶粒(latex)直径、单体在油相中的溶解度、聚合反应速度与AOT浓度及搅拌速度间的关系的测定,证明聚合反应是通过胶束(micelle)成核机理而进行的。通过对不同单体浓度下的^1H NMR盐效应的研究,证明溶液聚合的速度和单体浓度二次方成正比不是由于生成双分子π配合物,而是由静电屏蔽效应和粘度的改变引起的。     

Radical polymerization in homogenized butyl acrylate emulsion

The addition of a small amount of monomer strongly decreased the clouding temperature of nonionic emulsifier (Tween 20). The clouding temperature of the Tween 20 aqueous solution was independent of emulsifier concentration but it strongly varied in the presence of monomer. The decreased cloud temperature was attributed to the penetration of monomer molecules into the interfacial layer that increased the flocculation of microdroplets (monomer-swollen micelles). The surface tension of homogenized ((mini)emulsion) butyl acrylate aqueous emulsion was much smaller than that estimated at or above CMC of Tween 20. The polymerization rate vs. conversion curve of the (mini)emulsion deviates from the three rate intervals typical for the emulsion polymerisation. The shape of the rate-conversion curve reminds more the four rate intervals curve. Interval 2 is overlapped with the initial maximal rate and rate shoulder at higher conversion. The initial maximal polymerization rate (R_p,max,1) is attributed to the abrupt increase in polymer particles, the polymerization under monomer saturated condition and emulsifier containing peroxide groups (Tw_peroxid 20). The rate of emulsion polymerization of BA initiated by ammonium peroxodisulphate (APS) is ca. by one order of magnitude larger than that of blank polymerization (without APS). The second maximal rate (rate shoulder) can result from the gel effect. The more pronounced increase in R_p,max,1 with Tw 20 concentration supports the presence of peroxide groups. The slight dependence of R_p,max,2 on [Tw 20] for both APS and DBP (dibenzoyl peroxide) is discussed in terms of the depressed radical entry rate into the close packed surface later of polymer particles. The low activation energy is attributed to the decreased barrier for entering radicals into the polymer particles with increasing temperature. This is more pronounced with the accumulation of covalently bound emulsifier moieties (resulting from Tw_peroxid 20) at the particle surface. The ratio of the final number of polymer particles to the initial number of monomer droplets (N_p/N_drop) promotes the partial monomer droplet nucleation. The dye approach indicates that the degree of depletion of monomer droplets decreases from the classical emulsion polymerization to the polymerization in pre-homogenized emulsions and the emulsion polymerization with a prolonged-emulsification interval.