含三苯基乙基苯氧基聚氧乙烯醚甲基丙烯酸酯功能单体的缔合型乳液增稠剂的制备及增稠机理

采用半连续法乳液聚合以甲基丙烯酸、丙烯酸乙酯、邻苯二甲酸二烯丙酯和不同量的功能单体三苯基乙基苯氧基聚氧乙烯醚甲基丙烯酸酯(SEM-25)为原料合成了疏水改性碱溶性增稠剂乳液. 测定了增稠剂乳液的粘度、透光率、pH、粒径及其分布, 结果表明随着pH值的增加, 乳液的粘度和透光率首先迅速升高, 然后缓慢下降. 随着SEM-25用量的增加, 乳胶粒的粒径先增大后减小. 与不含SEM-25的乳液增稠剂相比较, SEM-25低含量增稠剂的增稠效果和抗剪切性没有提高, 只有当SEM-25用量提高至单体质量的12%, 且乳液固含量大于0.65%时, 所制备缔合型增稠剂乳液的粘度和流变性比不含SEM-25的增稠剂才有明显提高. 在此基础上研究了增稠剂对苯丙乳液的增稠性. 含有增稠剂的苯丙乳液的粘度和透光率随pH值的变化与纯增稠剂乳液的变化类似. 只有当加入0.34 wt%苯丙乳液固体质量的增稠剂, 并且增稠剂中SEM-25含量达到5 wt%时苯丙乳液的粘度与使用不含SEM-25的增稠剂增稠的粘度相比才有明显增高. 在此基础上对增稠剂的增稠机理进行了探讨.     

P（MMA—co—AA）乳液的制备及pH响应特性

以过硫酸钾(KPS)为引发剂、十二烷基硫酸钠(SDS)为乳化剂,利用正相乳液聚合制备(甲基丙烯酸甲酯-co-丙烯酸)共聚物(P(MMA-co-AA))乳液.通过测定聚合转化率和观察聚合过程稳定性,探讨了AA与MMA不同质量比时制备稳定的共聚物乳液的工艺条件;通过黏度法测定了乳液在不同pH时的相对黏度η,利用粒度分析仪分析了乳胶粒子在不同pH时的平均粒径和粒径分布.结果表明:AA含量较高时,控制聚合时间是得到稳定聚合物乳液的关键,当m(AA)/m(MMA)=12.5/100,65 ℃下反应120 min时,所制得的乳液稳定性最好.随着pH增大,乳液黏度先增大后降低;随着m(AA)/m(MMA)增加,制得的乳液pH敏感性增大;随着乳液从酸性(pH=5.17)变到碱性(pH=8.61),聚合物乳胶粒子平均粒径减小,粒径分布变窄.     

含二十二烷基聚氧乙烯醚甲基丙烯酸酯功能单体的缔合型乳液增稠剂的制备及表征

以甲基丙烯酸、丙烯酸乙酯、邻苯二甲酸二烯丙酯和不同量的功能单体二十二烷基聚氧乙烯醚甲基丙烯酸酯(BEM)为原料,采用半连续乳液聚合方法合成了疏水改性碱溶性缔合型增稠剂乳液.测定了增稠剂乳液的粘度、透光率、乳胶粒粒径及其分布等性能,考察了不同固含量下乳液粘度和透光率随pH的变化情况.结果表明随着BEM用量的增加,乳胶粒粒径逐渐增大.随着pH值的增加,乳液的粘度首先迅速升高,然后缓慢下降.与不含BEM的增稠剂乳液相比,当乳液固含量大于0.5%,BEM含量占单体量低于5.0wt%时,该缔合型增稠剂的增稠效果和抗剪切性有显著提高,BEM含量较高(8.0wt%或更高)时反而使增稠效果和抗剪切性变差.在此基础上研究了增稠剂对苯丙乳液的增稠效应,结果显示BEM含量占单体量的2.5wt%时,对苯丙乳液的增稠作用最好.与使用功能单体三苯乙基苯酚聚氧乙烯醚甲基丙烯酸酯改性的增稠剂相比,含BEM的增稠剂在BEM用量较少的情况下就能起到明显的增稠效果.     

温度、pH敏感性核壳结构微凝胶的制备及性质

以无皂乳液分步聚合的方法, 将N-异丙基丙烯酰胺(NIPAM)与N,N-亚甲基双丙烯酰胺(MBA)交联反应3 h, 制得种子乳液, 再向种子乳液中加入甲基丙烯酸(MAA)功能性单体继续反应2 h, 制备了具有温度、pH敏感性的核壳结构微凝胶. 通过透射电子显微镜(TEM)、红外光谱(IR)等表征了微凝胶外貌形态及结构组成, 动态光散射(DLS)测定了微凝胶粒径响应热、pH的变化及微凝胶Zeta电位的变化. 结果表明凝胶形貌为异型核壳结构; Zeta电位与微凝胶粒径随温度、pH变化相关.     

pH响应性阳离子型微凝胶的制备及性质研究

以甲基丙烯酸-(N,N-二甲氨基)乙酯(DMAEMA)和丙烯酸乙酯(EA)为共聚单体, 二甲基丙烯酸乙二醇酯(EGDMA)为交联剂, 采用半连续乳液聚合法, 制备了具有pH响应性的阳离子型微凝胶, 并研究不同聚合条件对所合成的微凝胶性质的影响. 利用透射电子显微镜(TEM)、激光粒度分析仪和流变仪对微凝胶进行一系列表征. 研究了介质pH值对微凝胶的形态、平均粒径、zeta电位、溶液浊度(透光率)的影响, 以及NaCl盐溶液对微凝胶分散体系稳定性的影响. 结果表明, 这类阳离子型微凝胶体系具有良好的pH响应性, 在pH＝7左右发生相转变. 此外, 研究表明不同浓度NaCl溶液对微凝胶的稳定性有一定影响, 临界絮凝浓度约为1.3 mol•L－1.     

新型γ-聚谷氨酸吸水树脂的合成

以γ-聚谷氨酸(γ-PGA)为原料,乙二醇缩水甘油醚为交联剂,采用溶液聚合法合成了新型γ-PGA吸水树脂(1),其结构经IR表征.研究了反应体系的pH,反应温度和反应时间对1吸水率和透光率的影响.结果表明,在反应体系pH 4.3,于70℃反应36 h的最佳反应条件下合成1,吸水率220 g·g-1,透光率99.6％,分解温度334.9℃.     

用混合乳化剂UE20/PVA制备的水包油型生漆乳液的性能

以漆酚基乳化剂(UE20)和聚乙烯醇(PVA)为混合乳化剂制备了水包油(O/W)型生漆乳液(RLE), 研究了UE20与PVA的质量比、混合乳化剂质量分数(wME)、水与天然生漆(RL)的质量比、温度和贮存时间对RLE性能的影响, 并用透射电镜观察了wME对RLE粒子的大小及形态的影响. 结果表明, RLE的黏度随着PVA的增加而增大; 当wME≤6.7%时, RLE表现出假塑性流体的特征, 其黏度随着wME的增大而增大, 乳液的稳定性增强; 而当wME≥10.0%时, RLE则表现出膨胀型流体的特征, 乳液的黏度较低; 随着温度的升高及水的用量增加, RLE粒子间相互作用减弱, 乳液的稳定性降低. 正交实验结果表明, 影响RLE的黏度及稳定性的顺序为wME＞mH2O∶mRL＞mUE20∶mPVA＞乳化温度. 随着wME的增大, RLE粒子的粒径减小, 其形态也由不规则的形状转变为球形粒子.     

高固含量低黏度聚氨酯微乳液的制备及性能研究

以聚(四氢呋喃-co-氧化丙烯)二醇(Ng210)为软段,异佛尔酮二异氰酸酯(IPDI)为硬段,以1,2-二羟基-3-丙磺酸钠(DHPS)和二羟甲基丙酸(DMPA)作为亲水扩链剂,采用自乳化法合成了一系列了高固含量低黏度稳定聚氨酯微乳液,分析了DHPS和DMPA质量配比对乳液性能的影响,结果表明,所得乳液粒径呈多元分布,乳胶粒子呈球形;乳液为假塑性流体,表观黏度小于250mPa.s(剪切速率为25s-1)且随切变速率的变化规律呈现一定的切力变稀特征;随着DHPS/DMPA比值的增大,胶粒平均粒径逐渐减小,多分散性增强;当DHPS/DMPA值为4/10～6/10时,乳液中大小粒子粒径比为6～8,且大乳胶粒子的体积分数约为70%～75%,乳液的固含量均大于70%.另外,乳液具有较好的低温和高温以及贮存稳定性,具有较低的表面张力,相对于常规的聚氨酯乳液,所制备的高固含量聚氨酯乳液胶膜具有更好的力学性能.     

高固含量低黏度丙烯酸酯乳液的制备及在密封胶中的应用

利用过硫酸铵-亚硫酸氢钠氧化还原引发体系制备了固含量为55%的丙烯酸乙酯、丙烯酸异辛酯、丙烯酸、甲基丙烯酸甲酯的共聚物种子乳液;以上述乳液为种子,十二烷基硫酸钠和辛基酚聚氧乙烯醚为乳化剂、碳酸氢钠为缓冲剂,过硫酸钾为引发剂80℃下制备固含量在70%~74%的高固含量、低黏度稳定乳液。种子乳液呈现多元分布、乳胶粒粒径约为150~300nm,增长后高固含量乳液仍保持宽分布、平均粒径大小在350~600nm,黏度在剪切速率20s-1时为600~900mPa·s。此乳液做成的密封胶固化时间短,收缩率小,强度大。     

阴离子型表面活性剂所组成微乳液的异常流变性

对以正十六烷、油酸钾、正己醇和水所组成的微乳液进行研究,对其流变性和机理作了探讨.微乳液粘度和水油比变化的关系可用相转化来说明.层形结构区显示出有高粘度特征,并具有明显的负触变性现象.对此进行了讨论,并研究了pH值和盐类的影响.     

A novel associative latex thickener using ethoxylated behenyl methacrylate as functional monomer

<正>Alkali-soluble associative latex thickeners modified with hydrophobic long chain alkyl groups were prepared using common acrylics and varying amount of a functional monomer,ethoxylated behenyl methacrylate(BEM),through emulsion polymerization.It was found that the size of the emulsion particle became larger with addition of BEM.The light transmittance of the thickener latex sharply increased with pH varied from 6 to 7.The associative latex thickener manifested a higher viscosity when solids in the latex thickeners were kept at 0.5 wt%or higher,and the optimal amount of BEM was found to be around 2.5 wt%,or 0.16 mol%.All thickener latexes modified with BEM have better shearing resistance than the BEM-free thickener.     

Effects of nonionic surfactant and associative thickener on the rheology of polyacrylamide in aqueous glycerol solutions

The effect of a low molecular weight nonionic surfactant and an acrylic associative thickener on the rheology of polyacrylamide in aqueous glycerol solutions under steady shear was experimentally investigated. The nonionic surfactant (Tween20), associative thickener (Acrysol TT935) and polyacrylamide (Separan AP30) underwent complex molecular interactions in solution as reflected by rheological measurements. The surfactant also interacted with the glycerol solvent. The addition of surfactant in aqueous glycerol solutions reduced the surface tension, as well as the solution viscosity, at low surfactant concentration. The solution viscosity went through a minimum at certain surfactant concentration, depending on the composition of glycerol/water mixture, before increasing again. Similar behavior was found when the surfactant was added to the polyacrylamide solution, except there was an initial increase in the viscosity before the reduction. The associative thickener, Acrysol TT935 (an anionic acrylic emulsion copolymer) exhibited a strong affinity with polyacrylamide in solution, as indicated by a sharp increase in the solution viscosity. The dilute polyacrylamide solution became highly elastic in the presence of either the nonionic surfactant on the associative thickener. A threestage model was proposed to describe the surfactant/thickener/polymer interactions.     

高剪切乳化法制备的丙烯酸聚酯类纳米聚合物乳液

反应温度;增稠剂;正交试验;高剪切乳化法制备的丙烯酸聚酯类纳米聚合物乳液     

Surfactant and Electrolyte Effects on Latex Depletion Flocculation by Thickeners

Summary: Polymer thickeners can induce good dispersion, bridging, or depletion flocculation of latexes depending on the polymer structure and concentration. Unlike non-associative polymers, associative polymers have the ability to create a good latex dispersion. However, when the associative interactions are destroyed, depletion flocculation of the latex can result. This happens when an excess of ionic surfactant is added to the system. In addition, the surfactant may associate with the thickener backbone, thus modifying the molecular volume of the polymer thickener. This paper explores the effect of anionic surfactant and electrolyte on the molecular volume of both associative and non-associative thickeners. Both HEUR and HASE structures are included. For HEUR thickeners, formation of a pseudo-polyelectrolyte through the association of anionic surfactant with the polyethylene oxide backbone is confirmed. Further, the ability of the thickener to depletion flocculate latexes as a function of surfactant and electrolyte is explored. Experimental critical flocculation concentrations (CFC) are compared to values expected based on molecular volume and potential energy calculations. A good correlation is found between molecular volume and CFC for a wide range of thickener compositions.     

纳米粘土对硅丙乳液的改性

采用原位乳液聚合方法,以纳米粘土改性硅丙乳液,并对所得复合乳液及其涂膜性能进行了研究,结果表明:复合乳液的储能模量、损耗因子和复合粘度较纯硅丙乳液均有明显提高,且其涂膜的耐热性能增强并具有优良的综合性能。     

增稠剂的反相乳液聚合及增稠性能研究

通过反相浮液聚合的方法合成一种印花增稠剂，并对它的应用性能进行了较为全面的测试，结果表明，合成的增稠剂有比较强的增稠性能，而且耐电解质性能明显优于同类产品KG－202。并用电子显微镜观察了在不同pH值时乳胶粒子的结构。     

The adsorption of hydrophobically modified carboxymethylcellulose on a hydrophobic solid: effects of pH and ionic strength

Carboxymethylcellulose with 1.2% dodecyl groups (per glucose unit) was prepared by amidation with dodecylamine. This polymer behaves as a hydrophobically modified polyelectrolyte with the following thickening properties which are determined from viscosity data. It adsorbs from aqueous solution on spin-coated polystyrene films to various extents, depending on pH and ionic strength. The adsorbed amount has a surprising minimum at around pH 6 which coincides with a maximum in viscosity of a dilute solution, and with a very pronounced maximum in the hydrodynamic radius as determined from dynamic light scattering. To our knowledge, such behavior has not been reported before. It suggests that at low pH the polymer is present in the form of small aggregates which upon increasing the pH first swell and then break up into single molecules. Received: 19 June 1997 Accepted: 5 January 1998     

大米淀粉膜的制备及其性能

大米淀粉颗粒粒径较小且均匀,在水中有较好的分散性,具有良好的成膜性并且可以在自然中降解,在食品包装、医用敷料及化妆品行业中有着广泛的应用。以大米淀粉为原料,NaOH为糊化剂,甘油为增塑剂,柠檬酸为交联剂和pH调节剂,采用流延法制备了淀粉膜。通过对淀粉颗粒的形貌观察及糊化温度、淀粉溶液的表观粘度及pH值测定、淀粉膜的力学性能、透光率及承载甘草酸二钾释放性能等的测定,研究了大米淀粉的糊化条件,柠檬酸、淀粉和甘油质量分数对淀粉膜性质的影响以及承载物质的释放情况。结果表明,大米淀粉呈光滑的多边形颗粒,直径为5~8 μm,在偏光显微镜下呈现马耳他十字结构,糊化温度范围为82.5~100.8 ℃。柠檬酸在淀粉成膜过程中会与淀粉分子相互作用,同时能够调节溶液的pH值以适应人体皮肤。淀粉质量分数越高,淀粉膜断裂伸长率越低,拉伸强度越高;甘油质量分数越高,淀粉膜断裂伸长率越高,拉伸强度越低。在甘油质量分数为3.0%时淀粉膜透光率最佳,结晶度最低。制备的淀粉膜能够承载且能高效释放抗炎物质甘草酸二钾,在护肤领域具有广泛的应用前景。