氯乙烯微悬浮聚合成粒机制探讨

以不同均化方式得到微悬浮分散液,再经微悬浮聚合制备了PVC糊树脂。首先以三氯乙烯为氯乙烯单体的模拟液,研究了十二烷基硫酸钠乳化剂/十六、十八混合醇助稳定剂复合胶束和单体亚微液滴的形成过程,发现复合胶束的形成过程和三氯乙烯溶胀进入复合胶束形成亚微液滴的过程均受扩散动力学控制,延长溶胀时间及施加高速剪切分散可以强化溶胀过程,复合胶束对单体具有"超级溶胀"能力。然后采用搅拌溶胀和高速剪切微悬浮聚合得到PVC乳胶粒子,发现两者形貌相同,而前者粒径略大、分布略宽;延长搅拌溶胀时间,可使粒度分布更接近高速剪切均化微悬浮聚合得到的PVC乳胶粒子的粒度分布。     

苯乙烯-甲基丙烯酸甲酯悬浮-乳液耦合聚合动力学

采用苯乙烯(St)悬浮聚合过程滴加甲基丙烯酸甲酯(MMA)乳液聚合组分,进行悬浮-乳液耦合聚合(SECP), 制备大粒径聚苯乙烯-聚甲基丙烯酸甲酯(PS-PMMA)复合粒子.采用¹H NMR分析方法,讨论了SECP动力学特征.St的SECP聚合速率和转化率与悬浮聚合一致;MMA聚合速率决定于乳胶粒子聚合速度和凝并在悬浮粒子表面的速度,聚合速率比常规乳液聚合速率低.由于凝并在悬浮粒子表面的PMMA乳胶粒子不再有乳液聚合特征,MMA在SECP中转化率低于同条件常规乳液聚合.分别得到乳化剂和引发剂浓度与SECP和普通乳液聚合恒速段聚合速率的关系.     

新型无毒引发剂在卫生级聚氯乙烯糊树脂生产中的应用研究

针对卫生级糊树脂的开发要求,采用新型无毒过氧化物引发剂(Luperox 701)替代现有的偶氮引发剂(ABVN)进行糊树脂生产的工业试验。试验表明各替代条件下的聚合过程都较平稳,胶乳性能和产品糊树脂性能均达到企业质量标准,其生产过程和产品性能与原工艺相近。由于Luperox 701的活性较ABVN略低,需进一步优化配方,缩短聚合时间,以提高装置生产能力。     

国内专利精选

正一种低黏度聚氯乙烯糊树脂的制备方法:CN112457437A//孟永华(江苏康宁化学有限公司),公开日期:2021-03-09公开了一种低黏度聚氯乙烯糊树脂的制备方法,包括以下步骤:(1)将微悬浮法聚合釜抽真空;(2)将去离子水、氯乙烯、引发剂、乳化剂在微悬浮法分散罐中分散均匀后通过泵打入微悬浮法聚合釜中;(3)在微悬浮法聚合釜中进行聚合反应,反应结束后得到乳胶,其通过雾化干燥得到聚氯乙烯糊树脂成品。该发明采用复合乳化剂,结合了不同乳化剂的特点,制得的产品糊黏度更低,适应低黏度加工的需求。     

混合法PVC糊树脂聚合反应机制研究

介绍了混合法PVC糊树脂的聚合工艺特点和配方设计理论基础,详述了混合法聚合工艺中VCM乳液聚合和微悬浮聚合的机制。     

乳化剂及助剂对乳液聚合及糊树脂性能的影响

一、序言 近来PVC糊树脂的用途日益扩大,产量不断增加。而制备糊树脂的方法也在不断革新,现在有VC乳液种子聚合方法、微悬浮聚合方法和种子微悬浮聚合方法等。由于PVC糊树脂加工方法简单,设备少,投资少,国内外都出现增产糊树脂的倾向。同时也在深入研究改善糊性能,不断增加糊树脂的品种和产量,以满足不断发展的各行各业的需要。     

原位乳液聚合制备丙烯腈聚合物/纳米氧化硅复合粒子

利用2,2'-偶氮(2-脒基丙烷)二氯化氢(AIBA)引发剂与纳米氧化硅粒子的静电作用而使AIBA吸附在纳米氧化硅表面,进而引发丙烯腈-甲基丙烯酸甲酯(AN-MMA)原位乳液聚合.考察了AIBA浓度和反应温度对AN-MMA原位乳液聚合动力学的影响以及氧化硅含量对AN-MMA共聚物/纳米氧化硅复合乳胶粒径分布和形态的影响.结果表明:聚合速率随AIBA浓度和聚合温度的升高而增大; AIBA浓度相同时,原位乳液聚合速率小于普通乳液聚合;AN-MMA共聚物/纳米氧化硅复合粒子粒径随纳米氧化硅含量增加而增大;原位乳液聚合得到的复合胶粒表面粗糙,当纳米氧化硅质量分数为10%时,纳米氧化硅与聚合物乳胶粒子复合良好;当纳米氧化硅质量分数为20%和30%时,有部分纳米氧化硅粒子与乳胶粒子分离而分散在连续相中.     

两种制备疏松PVC树脂的新型聚合方法

介绍了制备疏松PVC树脂的两种新聚合方法——以正丁烷为反应介质分散聚合和悬浮态乳液聚合，并对树脂颗粒的特性进行了简述。结果表明：以正丁烷为反应介质的非均相VC分散聚合所得树脂的粒径和颗粒形态与聚合体系VC／But比例和转化率等有关，由于存在向But的链转移，PVC分子质量小于相同聚合温度下生产的悬浮PVC树脂。悬浮态乳液聚合所得树脂粒径分布和颗粒形态与水油比、转化率和添加剂品种有关。     

不同聚合工艺下的聚氯乙烯糊树脂研究

采用凝胶渗透色谱仪、扫描电子显微镜、热重分析仪和差示扫描量热仪对不同聚合工艺下的聚氯乙烯(PVC)糊树脂进行测定,并对160℃下树脂颜色的变化进行了探究。结果表明:相同聚合工艺下的糊树脂具有类似的颗粒形态,但在热作用下树脂的颜色变化不一;而不同聚合工艺下的糊树脂颗粒形态具有明显的差异,且乳液聚合法生产的糊树脂热降解后的聚结紧密程度明显高于微悬浮聚合法;同时具有相同相对分子质量及其分布条件下的乳液聚合法得到的糊树脂的动态热学性能较微悬浮聚合的糊树脂较好,但是其静态条件下的热着色性较后者差,这对后期的使用具有一定的借鉴意义。     

基于30m~3聚合釜的纳米CaCO_3原位聚合PVC树脂颗粒特性预测与优化

通过微乳化分散技术使CaCO3实现良好分散,通过氯乙烯原位悬浮聚合制得了纳米CaCO3微乳化法原位聚合PVC树脂(简称纳米PVC树脂)。为解决纳米PVC树脂的颗粒形态控制难题,提出了基于组合神经网络的软测量方法,建立了纳米PVC树脂颗粒特性的软测量预测模型,应用效果表明该软测量模型能较准确地预测纳米PVC树脂的平均粒径。利用该软测量预测模型在30 m3聚合釜上实现了纳米PVC树脂颗粒特性优化,制得具有较理想颗粒特性的纳米PVC树脂。     

有机硅/丙烯酸酯乳液的粒径与分散行为研究

采用半连续乳液聚合法合成了以丙烯酸丁酯和甲基丙烯酸甲酯为成核单体,丙烯酸丁酯(MAA)、甲基丙烯酸甲酯(BA)、丙烯酸(AA)和γ―甲基丙烯酰氧基丙基三甲氧基硅烷为成壳单体的核壳结构乳液。采用马尔文纳米粒度仪等研究了乳液的粒径及其分布与引发剂和乳化剂用量之间的关系,粒径对乳液稳定性的影响以及乳液粒径与温度的关系,通过透射电镜对乳液微粒形态进行了分析。结果表明,乳液的粒径随着引发剂和乳化剂用量的增加而减小,乳液粒径在30～60℃时较为稳定,当引发剂过硫酸铵质量分数为0.55%,乳化剂十二烷基苯磺酸钠质量分数为2%时,制得的乳液粒径在120 nm左右,具有明显的核壳结构和较好的稳定性。     

PMMA/PAN核-壳粒子制备工艺研究

加入适量的引发剂,通过无皂乳液聚合,以聚甲基丙烯酸甲酯( PMMA)核体为种子乳液,制备了PMMA/PAN核-壳乳液.实验中分别对引发剂量、丙稀腈( AN)滴加量对PMMA/PAN壳层厚度及其粒径和粒径分布的影响进行了较详细的研究,确定了种子乳液聚合法制备PMMA/PAN核-壳结构聚合物粒子的实验方法及条件.通过激光粒度仪、扫描电镜和透射电镜对核-壳粒子的形态结构进行了表征,证明了PMMA/PAN复合粒子的核-壳结构.     

ACR—g—VC共聚物的合成与性能研究

由两步乳液聚合合成了核－壳结构型ACR胶乳,并进一步通过ACR胶乳存在下的VC悬浮聚合合成ACR－g-VC共聚物,对接枝共聚物的结构和性能进行表征。结果表明：ACR胶乳的存在影响VC悬乳聚合的稳定性,增加分散剂用量能得到颗粒特性较好的共聚树脂;ACR－g-VC共聚物的溶胶聚合度略低于相同聚合温度的均聚PVC,凝胶含量随共聚组成中ACR含量的增加而增加;ACR－g-VC共聚物的塑化时间小于聚合度接近的均聚PVC,而加工转矩大于均聚ACR－g-VC共聚物的冲击强度随ACR含量的增加而增大,且大于ACR含量相当的PVC／ACR共混物。     

Influence of emulsifiers on particle size and particle size distribution of PVC latex synthesized by miniemulsion polymerization

We synthesized poly(vinyl chloride) (PVC) latexes via miniemulsion polymerization using a mixture of cetyl alcohol (CA) and sodium lauryl sulfate (SLS). A vinyl chloride miniemulsion is easily prepared by conventional mechanical stirring. Experimental design methods were applied to investigate the effects of composition and polymerization conditions on average particle size (APS) and particle size distribution (PSD) of the latexes produced. The APS of the latexes produced ranged from 0.4–0.7 μm. When the APS of the latex produced was above 0.7 μm, the resulting latex was highly unstable. The emulsifier ratio (CA/SLS) was the most prominent factor influencing APS and PSD.     

氧化还原引发体系对多层核壳结构ACR乳液聚合的影响

采用多步乳液聚合方法合成多层核壳结构的ACR树脂。用过硫酸钾/亚硫酸氢钠体系作为氧化/还原引发体系,研究了氧化剂和还原剂用量的不同及氧化还原引发体系的加入方式对ACR的转化率、乳胶粒的粒径和PVC/ACR共混物加工流变性能的影响。实验结果表明:氧化剂和还原剂用量增加后,乳液聚合各个阶段的转化率提高,乳胶粒的粒径变大,明显改善了共混物的加工性能。过量的还原剂起阻聚和缓聚作用,采用分阶段加入氧化还原引发剂有利于提高转化率。     

Experimental investigation of vinyl chloride drop behavior during suspension polymerization

The effects of some polymerization conditions on poly(vinyl chloride) (PVC) particles produced by the suspension polymerization process were studied on a laboratory scale. The different stages of vinyl chloride suspension polymerization were investigated experimentally by using an on-line sample withdrawal technique during reaction. It was found that the method of addition of initiator has a great effect on the PVC particle uniformity as well as the size distribution. Furthermore, when the initiator was predispersed in the continuous phase, some latex particles were formed. The effect of the type of stabilizer was also studied with two different types of PVA [partially hydrolyzed poly(vinyl acetate)]. It was found that by changing the stabilizer, the particle size, the porosity, and the morphology could change. When H80 (PVA with a degree of hydrolysis of 80% and a molecular weight of 259,000) stabilizer was used, the rigidity of the PVC particles was weak. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 127–134, 1997     

Particle size and morphology of poly[styrene‐co‐(butyl acrylate)]/nano‐silica composite latex

Nanocomposite latex with nano‐silica of varying particle sizes was prepared via in situ polymerization and investigated by submicron particle size analysis, transmission electron microscopy (TEM), scanning electron microscopy (SEM), Fourier‐transform infrared spectrometry (FTIR) and Raman spectrometry. It was found that nanocomposite latex exhibited a core–shell structure with nano‐silica particles enwrapped, resulting in an increase in the latex particle size. The smaller the nano‐silica particles, the more were embedded in each latex particle. The increase in the particle size of latex depended not only on the particle size of nano‐silica, but also on the number of nano‐silica particles in each latex particle. Copyright © 2004 Society of Chemical Industry     

甲基丙烯酸甲酯-丙烯酸乙酯乳液共聚动力学研究

为了合成适于药物包衣用的甲基丙烯酸甲酯-丙烯酸乙酯(MMA-EA)共聚物胶乳,对以非离子型乳化剂OP-10为乳化剂、过硫酸钾为引发剂的MMA-EA乳液共聚动力学进行了研究。发现初期共聚速率随着乳化剂浓度、引发剂浓度和聚合温度的增加而增大,这是由于共聚物乳胶粒子平均粒径随着乳化剂、引发剂浓度和聚合温度的增加而减小,乳胶粒子数目增加所致。通过调节乳化剂、引发剂以及反应温度可以达到合适的聚合反应速率,最终合成出转化率大于95%的MMA-EA共聚乳液。     

Preparation and characterization of composite resin by vinyl chloride grafted onto poly(BA-EHA)/poly(MMA-St)

Crosslinked poly(butyl acrylate-co-2-ethylhexyl acrylate)/poly(methyl methacrylate-co-styrene) (ACR I) latex was synthesized by multi-stage emulsion polymerization. A series of grafting vinyl chloride (VC) composite latices were prepared by emulsion copolymerization in the presence of core-shell ACR I latex. The effects of ACR I amount and its core/shell ratio on particle diameters of the composite latices and mechanical properties of the prepared materials were investigated. The grafting efficiency (GE) of VC grafted onto ACR I increases with an increasing ACR I content. Transmission electron microscope (TEM) study indicates that ACR I latex particles have a regular core-shell structure obviously. However, when styrene content in the shell of ACR I is more than 70 percent of the shell by weight, ACR I latex particles have an irregular core-shell morphology like sandwich. The composite latex particles synthesized by core-shell ACR I latex grafting VC have a clear three-layered core-shell structure. Dynamic mechanical analysis (DMA) study reveals that the compatibility between ACR I and PVC is well improved. With increasing ACR I content, the loss peak in low temperature range for every composite sample becomes stronger and stronger and gradually shifts to a higher temperature. Scanning electron microscope (SEM) graphs showed that the fractured surface of the composite sample exhibited better toughness of the material. TEM graphs showed that ACR I was uniformly dispersed in the PVC matrix.