改性丙烯酸乳液合成及性能研究

通过核壳乳液聚合法合成了烷基丙烯酸酯磷酸酯改性的丙烯酸乳液,讨论了聚合温度、乳化剂、磷酸酯的加入方式和用量、pH值等因素对乳液合成以及涂膜性能的影响。结果表明:聚合温度控制在75～80℃之间较为合适,使用了烷基丙烯酸酯磷酸酯进行改性的乳液,单体转化率和固含量提高,凝胶率以及涂膜吸水率明显下降,乳液的稳定性得到提升。当聚合温度为78℃,磷酸酯占单体总质量0.5%(wt)、反应体系pH值在5左右以及采用延后滴加磷酸酯单体的方式时,能够提高乳液耐水等性能以及涂膜的交联度,合成性能优异的磷酸酯改性丙烯酸乳液。     

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.     

功能单体α-烯烃磺酸钠用于无皂乳液共聚合

用工业原料α-烯烃磺酸钠(AOS)作为功能单体与甲基丙烯酸甲酯(MMA)和丙烯酸丁酯(BA)进行了乳液共聚合,通过测定AOS与MAA的竞聚率,确定了适宜的聚合方式为连续加料法.使用5%AOS制备了高固含量(>60%)的胶乳,并与用十二烷基硫酸钠(SDS)作乳化剂时该体系的乳液共聚合进行了比较.AOS是影响乳液稳定性和胶粒大小的主要因素,当AOS含量为单体总质量的1%时可以得到固含量大于40%粒径小于100 nm的乳液;当AOS含量为5%时可以得到固含量大于60%的乳液.两种情况下胶粒粒径分散性均较窄,明显优于同样条件下用SDS制备的胶乳.使用1%AOS制得的胶乳静置1年后粒径及其分布基本保持不变.     

沉淀聚合法制备单分散聚(4-乙烯基吡啶-co-二乙烯基苯/三羟甲基丙烷三甲基丙烯酸酯)聚合物微球

以4-乙烯基吡啶(4-VP)为功能单体、二乙烯基苯(DVB)和三羟甲基丙烷三甲基丙烯酸酯(TRIM)为混合交联剂,偶氮二异丁腈(AIBN)为引发剂,乙腈为反应介质,采用沉淀聚合法制备单分散聚合物微球.考察了共聚单体、溶剂、引发剂等聚合条件对聚合物微球粒径、分散性以及产率的影响.并用扫描电镜(SEM)、激光粒度分析仪、热重分析仪和红外光谱对微球进行了表征.结果表明,聚合物微球的表面形貌和产率可通过改变溶剂体积、单体/交联剂摩尔比和引发剂浓度等因素进行控制.降低乙腈溶液体积、增加DVB摩尔比例及交联剂摩尔比、可增加聚合物粒径及粒度分布均匀性,而聚合物产率随溶剂体积和DVB摩尔比增大而减小,随交联剂摩尔比和引发剂浓度的增加而增加.在最优条件下,即DVB和TRIM两者摩尔比4∶1,单体/交联剂摩尔比1∶5,乙腈用量为5.6 m L(单体和交联剂占介质体积的7%),引发剂浓度为2 wt%~6 wt%(占总反应单体的量)时,可获得形貌规则、产率较高的单分散poly(4-VP-co-DVB/TRIM)微球,微球平均粒径约4.02μm,粒径分布指数(U)为1.013.此外,热重分析结果显示,聚合微球于350℃时开始分解,600℃时失重率达84.9%.     

紫外光-热双固化聚苯胺防腐涂料

以酸性磷酸酯为掺杂剂对本征态聚苯胺(EB)进行掺杂,制备了可在聚氨酯和聚氨酯丙烯酸酯中进行纳米分散的导电聚苯胺(ES),其粒径分布在80~750 nm之间可控。 在此基础上,制备了不含重金属的紫外光-热双固化聚苯胺防腐涂料。 该防腐涂料先后经过3~5 s紫外光固化和80 ℃下1~3 min的热固化,即可完成紫外光-热双固化过程。 由于ES与聚氨酯或聚氨酯丙烯酸酯之间是不相容体系,因此随着ES质量分数的增大,会导致ES的团聚,分散粒径增大。 当ES质量分数从1.0%增大到5.0%时,ES的粒径从80~119 nm增加到500~750 nm。 ES的分散粒径增大会导致防腐涂层的致密性变差,降低防腐效果。 与普通紫外光固化聚苯胺防腐涂层相比,当ES为1.0%时,紫外光-热双固化防腐涂层在质量分数为3.5%的NaCl水溶液中浸泡2160 h后,其0.1 Hz下的绝对阻抗值(|Z|_{0.1 Hz})仍高于1.0×10⁸ Ω·cm²,优于普通紫外光固化聚苯胺防腐涂层的|Z|_{0.1 Hz}(1.0×10⁷ Ω·cm²),表明紫外光-热双固化涂层的防腐效果有了显著改善。 经过500 h划叉中性盐雾试验后,普通紫外光固化防腐涂层的板面出现了锈蚀宽度小于1 mm的锈蚀,而紫外光-热双固化防腐涂层经过500 h划叉中性盐雾试验,板面没有出现生锈、起泡的现象,表明紫外光-热双固化路线对提高涂层的防腐性能具有较大的价值。     

醇溶性聚丙烯酸酯乳液的合成及性能研究

以丙烯酸乙酯(EA)、甲基丙烯酸甲酯(MMA)和甲基丙烯酸(MAA)为主单体,采用过硫酸盐作引发剂,经预乳化乳液聚合工艺合成了聚丙烯酸酯乳液.讨论了乳化剂种类、单体种类以及功能性单体、引发剂加入工艺对乳液聚合过程及乳液产品性能的影响.结果表明:单体组成为m(MMA)∶m(EA)∶m(MAA)=45∶40∶15所得乳液聚合物能满足使用性能要求;种子引发剂加入质量控制在单体总质量的0.3%,而总的引发剂用量占单体总质量的0.8%较适宜.用差热分析仪和凝胶渗透色谱仪对乳液聚合物进行了表征.     

小粒径无皂阳离子PMMA胶乳粒子的制备与表征

采用溶剂热法,以AIBA为引发剂制得小粒径无皂阳离子PMMA胶乳纳米粒子。讨论了单体用量、引发剂用量和反应温度对胶乳粒径及乳液的粒径分布的影响;用^1H—NMR、TEM、FTIR、GPC、DTA等对聚合物进行了表征。结果表明：采用溶剂热法制得的无皂阳离子胶乳粒子粒径约为35nm,分散均匀;随着温度的升高,粒径逐渐减小;间同、无规、全同立构的相对含量分别为：55．3％、37．8％、6．9％;乳液的抗电解质稳定性好。     

微波辐照下无皂阳离子聚(St-MMA)高分子纳米粒子的制备和表征

讨论了微波辐照下 ,以丙酮 水为分散介质 ,利用阳离子型自由基引发剂偶氮二异丁基脒盐酸盐(AIBA)引发苯乙烯 (St)和甲基丙烯酸甲酯 (MMA)共聚 ,合成出表面带正电荷的P(St MMA)共聚物纳米粒子 ,考察了丙酮用量、单体和引发剂浓度对纳米粒子粒径、粒径分布和乳液稳定性的影响 .结果表明 ,丙酮 水的体积比由 0增加到 1 2 6∶1时 ,粒子的平均水化半径从 12 2 2 1nm降低到 2 4 6 8nm ,粒径分布变宽 ,乳液抗电解质稳定性逐渐增强 ;增加引发剂和共聚单体MMA的浓度 ,粒子的水化半径逐渐减小 ,粒径分散系数增大 .     

大分子不饱和单体法合成具有核壳结构的丙烯酸酯/聚氨酯乳液及表征

采用丙烯酸酯（AC）对水性聚氨酯（WPU）进行改性,合成了接枝型丙烯酸酯/聚氨酯(PUA)复合乳液。 随着共聚物中丙烯酸酯质量分数的增加,乳液外观由透明变为不透明,乳液粒径随之增大、分布变宽。 TEM显示,PUA乳胶粒子呈现清晰的核壳结构,且形态规整,粒径分布在60~120 nm之间。 FTIR测试表明,随着丙烯酸酯质量分数的增加,聚氨酯(PU)硬段氢键化作用先增强后减弱,硬段的有序度逐渐降低。 DSC分析表明,当AC的质量分数低于75%时,PU、聚丙烯酸酯(PA)两组分相容性较好,只出现一个玻璃化转变温度,并且随着PA质量分数的增加逐渐升高。 PA质量分数的增加,使胶膜的最大热失重速率从363 ℃提高至412 ℃,吸水率从11.3%降低至5.7%,弹性模量从16.4 MPa提高至47.6 MPa,拉伸强度从9.0 MPa提高至23.7 MPa,断裂伸长率从365%提高至408%,同时乳液的粘度下降,干燥时间变短,胶膜的附着力变好。     

转相乳化制备高分子蜡乳液及其在水性涂料中的应用

本文采用转相乳化法以脂肪醇聚氧乙烯醚(MOA-15)、丙二醇嵌段聚醚(L31)、月桂酸聚氧乙烯酯(LAE-4)为复合乳化剂对高分子蜡进行乳化,通过正交实验法得出了乳化高分子蜡的较佳工艺条件为:复合乳化剂的HLB值9,乳化剂用量8%,乳化温度80℃。通过动态激光光散射分析仪测试了蜡乳液的粒径分布,蜡乳液粒径为317.6nm。通过动态流变研究了高分子蜡乳液的模量与动态频率的关系,测试结果表明,蜡乳液体系具有较佳的黏弹性。将蜡乳液与水性树脂复配,研究了不同蜡乳液含量对水性涂料涂膜性能的影响。随着蜡乳液含量从0增加至4%时,涂膜的磨耗量从29.2mg降至13.9mg,吸水率从34.1%降至20.5%,涂膜光泽度不断增加。     

The Effect of Nano-SiO2 Colloid on Soap-free Emulsion Polymerization of Methyl Methacrylate and Hydroxyethyl Methacrylate

Soap-free emulsion polymerization of methyl methacrylate (MMA) and hydroxyethyl methacrylate (HEMA) was carried out in the presence of colloidal nano-SiO₂ particles. The effect of nano-SiO₂ level on the monomer conversion, polymerization rate (Rp), and emulsion stability was investigated. The viscosity, particle size distribution of the emulsions, surface tension, and ionic conductivity of these systems were determined. Upon the introduction of the nano-SiO₂ particles into this system, the Rp and monomer conversion increased and the average particle size of the P(MMA-HEMA) emulsion decreased in comparison to emulsions formed in the absence of nano-SiO₂. However, the particle size distribution became broader to some degree. Scanning electron microscope observations demonstrated that the shape of these latex particles were uniformly spherical. The surface tension and ionic conductivity of the system increased significantly after polymerization, but the presence of nano-SiO₂ resulted in an increase in surface tension and a decrease in ionic conductivity in comparison to the particle–free system.     

The effect of MWCNTs on molar mass in in situ polymerization of styrene and methyl methacrylate

Two different in situ-polymerization techniques were studied, emulsion polymerization and combined emulsion/suspension polymerization, with styrene and methyl methacrylate in the presence of different multiwalled carbon nanotubes (MWCNTs). Molar masses and molar mass distributions were determined by size exclusion chromatography, and particle size of the emulsions by dynamic light scattering and rotation rheometry. The compatibility of the MWCNTs and monomer affected polymerization and therefore the molar masses. The MWCNTs stabilized the emulsions, and molar mass distributions narrowed with higher amounts of MWCNTs. In emulsion polymerization of styrene, MWCNTs increased the molar mass. The increase of molar mass was based on the compatible molecular structures of MWCNTs and styrene, so that individual nanotubes were covered by monomer clouds when initiator arrived. In combined emulsion/suspension polymerization of styrene, MWCNTs reacted with the initiator and there was less initiator to polymerize the monomer. There is probably a critical surface area of MWCNTs, for which more initiator is consumed in the reaction with MWCNTs than in polymerization of the monomer. In emulsion polymerization of MMA, monomer clouds around MWCNTs do not form due to incompatible molecular structures, and nanotubes do not enhance polymerization of MMA. In combined polymerization, the initiator is reacting with the nanotubes and the tube is acting as a carrier for initiator, and molar masses are higher.     

Study on soap‐free P(MMA‐EA‐AA or MAA) latex particles with narrow size distribution

Soap‐free poly(methyl methacrylate‐ethyl acrylate‐acrylic acid or methacrylic acid) [P(MMA‐EA‐AA or MAA)] particles with narrow size distribution were synthesized by seeded emulsion polymerization of methyl methacrylate (MMA), ethyl acrylate (EA) and acrylic acid (AA) or methacrylic acid (MAA), and the influences of the mass ratio of core/shell monomers used in the two stages of polymerization ([C/S]_w) and initiator amount on polymerization, particle size and its distribution were investigated by using different monomer addition modes. Results showed that when the batch swelling method was used, the monomer conversion was more than 96.0% and particle size distribution was narrow, and the particle size increased first and then remained almost unchanged at around 600 nm with the [C/S]_w decreased. When the drop‐wise addition method was used, the monomer conversion decreased slightly with [C/S]_w decreased, and large particles more than 750 nm in diameter can be obtained; with the initiator amount increased, the particle size decreased and the monomer conversion had a trend to increase; the particle size distribution was broader and the number of new particles was more in the AA system than in the MAA system; but the AA system was more stable than the MAA system at both low and high initiator amount. Copyright © 2006 John Wiley & Sons, Ltd.     

Morphological and spectroscopic analyses of poly(alkyl methacrylate)/poly(thiophene) composite nanoparticles prepared by dual initiation system

Poly(alkyl methacrylate)/poly(thiophene) (PAMA/PTh) core/shell nanoparticles were synthesized using a one-pot dual initiation system. A ferric chloride/hydrogen peroxide mixture and sodium vinyl sulfonate were used as an initiator couple and a reactive surfactant, respectively. In the dual initiation, process variables such as the concentration of reactive surfactant, monomer ratio, and monomer type were adjusted to control the particle size of PAMA/PTh core/shell nanoparticles from 192 to 1,172 nm. The inner structure of the core/shell nanoparticles was confirmed in their morphological transition from spherical particles to a crumpled sheath using a solvent extraction method and field-emission scanning electron microscopy. From the spectroscopic data, it was found that the UV-adsorption and fluorescent emission intensity of PAMA/PTh latexes increased with a decrease in the average particle size. The quantum efficiency of all the samples was approximately 12 % and was unaffected by the particle size.     

无乳化剂乳液聚合法合成单分散大粒径高分子微球的研究

无乳化剂乳液聚合法合成单分散大粒径高分子微球的研究朱世雄杜金环金熹高陈柳生（中国科学院化学研究所北京１０００８０）关键词无乳化剂乳液聚合，单分散，均相成核，低聚物胶束微米级大粒径单分散高分子微球在标准计量、情报信息、分析化学等许多领域都有广泛的...     

离子型共聚单体参与下的全氟丙烯酸酯无皂乳液共聚

离子型共聚单体参与下的全氟丙烯酸酯无皂乳液共聚;全氟烷基丙烯酸酯;无皂乳液;离子型共聚单体     

高固含量低粘度P(MMA/BA/AA)乳液的制备及性能研究

先利用半连续种子乳液聚合法制备固含量为50%,粒径480nm的单分散甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)与丙烯酸(AA)的共聚物种子乳液;然后以上述种子乳液为介质,十二烷基硫酸钠为乳化剂,碳酸氢钠为缓冲剂,过硫酸铵为引发剂制备固含量72%,乳胶粒具有二元分布特征的高固含量、低粘度稳定乳液:其中大乳胶粒径500～600nm,小乳胶粒径约80nm.所得乳液中乳化剂总含量为聚合物质量的2.1%;粘度在剪切速率为21s-1时为400mPa·s.另外,相对于常规乳液,所制备高固含量乳液胶膜具有更好的光泽度.     

相互缠结的聚甲基丙烯酸甲酯/磺化聚苯乙烯复合水基微乳液Ⅰ:制备及影响因素

将聚苯乙烯制成磺化聚苯乙烯离聚体 (SPS) ,利用相反转技术 ,将磺化聚苯乙烯离聚体加水制成具有纳米级的稳定的水基微乳液。利用SPS纳米微粒核内部作为反应场所 ,用引发剂引发亲油性单体甲基丙烯酸甲酯聚合 ,制备具有相互缠结结构的PMMA/SPS复合水基微乳液。研究了引发剂的用量、MMA的用量、溶剂极性对聚合反应及复合水基微乳液的影响     

高浓度窄分布无皂高分子纳米粒子胶乳的制备

在微波辐照和丙酮存在下,进行了苯乙烯(ST)和甲基丙烯酸甲酯(MMA)的无皂乳液聚合.当丙酮的含量在50％以下时,可以得到稳定的窄分布的纳米粒子胶乳.丙酮的含量由0增加到50％,粒子的平均水化半径由278nm降低到35.4nm.在一定的浓度范围内,固定引发剂过硫酸钾（KPS）的用量,则粒子的平均水化半径与单体的浓度成正比;当单体浓度一定时,随着引发剂浓度的增加,粒子平均水化半径从25nm减少到22nm然后又增大.考虑到引发剂既是粒子表面电荷的来源,又增加了体系的离子强度,在粒子形成过程中,起着稳定和絮凝的双重作用,我们得到了一个简单的公式用以描述粒子的平均水化半径<R     

MMA-EA-AA无皂乳液聚合中粒径及粒径分布的控制

系统研究了MMA EA AA三元无皂乳液聚合体系中各种因素对乳胶粒大小及分布的影响 ,制得了单分散、粒径在 30 0～ 6 0 0nm可控聚合物乳胶粒 .结果表明 ,在过硫酸铵用量一定的条件下 ,聚合初期加入大量引发剂可同时提高单体转化率和乳胶粒的单分散性 ;随着引发剂和AA用量的增加以及聚合温度的升高 ,胶粒粒径逐渐减小 ,转化率逐渐升高 ;随着NH4 HCO3用量的增加 ,粒径逐渐增大 ,当NH4 HCO3用量达到 0 5g以后 ,转化率逐渐降低 ;搅拌速率为 30 0r min左右时 ,单体转化率最高 ,所得乳胶粒粒径最均一 .