A systematic approach to the study of multicomponent polymerization kinetics: butyl acrylate/methyl methacrylate/vinyl acetate. III. Emulsion homopolymerization and copolymerization in a pilot plant reactor

A systematic study of the terpolymerization of butyl acrylate/methyl methacrylate/vinyl acetate (BA/MMA/VAc) is being conducted. In this third stage of the study,

1 Parts 1 and 2: Dubé, M. A. & Penlidis, A., Polymer, 36 (1995) 587. Dubé, M. A. & Penlidis, A., Macromol. Chem. Phys., 196 (1995) 1101.

emulsion homopolymerizations and copolymerizations of the monomers comprising the BA/MMA/VAc system were performed in a 5 litre stainless steel pilot plant reactor, mainly for troubleshooting purposes and as a precursor to the detailed terpolymerization experiments to follow. First, a search for a stable emulsion recipe was conducted. At the same time, experimental procedures were established for the 5 litre pilot plant reactor along with product characterization techniques. Finally, selective emulsion homopolymerizations and copolymerizations were run for each of the three monomers and each combination of the three monomers, respectively. The polymers produced were characterized for conversion, composition, molecular weight and particle size. Although the emphasis of the experiments was to establish recipes, techniques, and procedures for emulsions terpolymerization, several useful observations were made regarding the kinetics even from these troubleshooting experiments.     

VAc/BA核壳乳液聚合乳胶粒形态模拟

以醋酸乙烯酯和丙烯酸丁酯两种单体两阶段种子聚合制备核壳乳胶粒为例,研究了用簇迁移动力学模拟方法,进行对指定实验条件下核壳形态的预测。结果与实验相符合。讨论了用简化的簇迁移动力学模型方法进行核壳形分子设计的进行步骤。     

Semicontinuous heterophase copolymerization of vinyl acetate and butyl acrylate

Vinyl acetate (VAc) and butyl acrylate (BuA) were copolymerized in heterophase by a semicontinuous process (unseeded) and compared with the seeded semicontinuous microemulsion polymerization of the same monomers. A mixture of sodium dodecyl sulfate (SDS) and poly(ethylene oxide) dodecyl ether (Brij‐35®) were used as surfactants. The effects of monomer addition rate (R_a) and surfactants concentrations (4 or 1 wt % with respect to the initial mixture of reaction) on polymer and latex properties were studied. High copolymer content latexes (24–36 wt %) with average particle diameters (D_p) from 38 to 55 nm and relatively narrow particle size distributions, high polymerization rates, weight ratios of polymer to surfactant (P/S) from 13.3 to 32.8 were obtained. The number‐average molecular weights (M_n) were between 96,000 and 188,000 g/mol. Homogeneous copolymer compositions were obtained throughout the reaction for both, seeded and unseeded processes, which is not possible by the usual batch microemulsion process. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Free radical copolymerization behavior of vinyl acetate with butyl acrylate in the presence of GeCl4 and BCl3

No alternating copolymers of vinyl acetate (VAc) and butyl acrylate (BA) were obtained by free radical copolymerization in the presence of GeCl₄ and BCl₃ (compared with the acrylic acid–vinyl acetate copolymerization system). By ultraviolet spectral analysis, it was concluded that both BCl₃ and GeCl₄ can form complexes with butyl acrylate. The BA–BCl₃ complex constants were determined by ¹H NMR; K_B=33·2 (25°C). The reason for the gel formation in the BA–Vac–BCl₃ copolymerization system was discussed. When vinyl acetate reacted with BCl₃, cationic polymerization probably occurred. A white gel product probably resulted from the polymerization of the BA–BCl₃ complex. © 1998 SCI.     

Effect of initiators and ethoxylation degree of non‐ionic emulsifiers on vinyl acetate and butyl acrylate emulsion copolymerization in the loop reactor

Vinyl acetate and butyl acrylate copolymers were synthesized in the presence of ammonium persulfate and potassium persulfate initiators, mixture of non‐ionic and anionic emulsifiers, and polyvinyl alcohol as protective colloid in a loop reactor. The monomer ratio was chosen 85:15. The series of non‐ionic emulsifiers, which have 10–40 moles ethoxylated nonyl phenol, were combined with Nansa 66 (sodium dodecyl benzene sulfonate). The effects of the initiators on the physicochemical properties of copolymers were investigated by measuring conversion, viscosity, molecular weight, molecular weight distribution, and surface tension, respectively by using gravimetric method, Brookfield viscometer, gel permeation chromatograpy (GPC), and ring method. The effects of ethoxylation degrees of the non‐ionic emulsifiers to the same properties of copolymers were also investigated. It was determined that the copolymer viscosities showed different tendency for two initiators. They were increased by the increasing ethoxylation degree of the non‐ionic emulsifier for ammonium persulfate. In contrast, latex viscosity was decreased by increasing the ethoxylation degree in presence of potassium persulfate. Similar changes were also found in number average molecular weights of copolymers. On the other hand, weight average molecular weights of copolymers increased by increasing the ethoxylation degree of the non‐ionic emulsifier for both initiators. In the case of potassium persulfate, the surface tension values of copolymers increased by increasing the ethoxylation degree, but generally increasing the ethoxylation degree did not affect the surface tension of copolymer very seriously for two initiators. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 537–543, 2003     

醋酸乙烯酯与丙烯酸-2-羟基乙酯乳液共聚

研究了醋酸乙烯酯与丙烯酸-2-羟基乙酯共聚的合成路线，通过乳液聚合所制得的共聚产物可有效地改善聚醋酸乙烯酯的耐水性能与粘接性能；对影响共聚反应的各种因素进行了分析，并通过红外谱图和差热扫描量热分析法确定了共聚产物的生成。     

三元共聚醋丙乳液的研制

制备有机硅-丙烯酸丁酯-醋酸乙烯酯三元共聚乳液。研究了有机硅、丙烯酸丁酯、醋酸乙烯酯、乳化剂含量、乳化剂配比、引发剂含量、保护胶体对乳液聚合和性能的影响,并确定了它们的最适宜条件。结果表明该共聚乳液具有良好的耐水、耐侯、耐酸碱、耐污染和稳定性能。该三元共聚醋丙乳液能良好应用于制备普及型内墙建筑涂料。     

Emulsion copolymerization of vinyl acetate and 2‐ethyl hexyl acrylate using nonionic emulsifiers in loop reactor

Batch emulsion copolymerization of vinyl acetate and 2‐ethyl hexyl acrylate (VAc/2EHA = 90 : 10) was initiated by the thermal initiators ammonium persulfate and potassium persulfate at 70°C in the presence of nonylphenol ethoxylates with varying chain lengths and poly(vinyl alcohol). VAc–2EHA copolymer latexes were synthesized as two different series in a loop reactor. The first series was initiated by ammonium persulfate, and the second series was initiated by potassium persulfate. The influence of the counterions or initiators and chain lengths of a nonionic emulsifier on the properties of VAc–2EHA copolymer latexes were determined by measuring the viscosities, weight‐average molecular weights, number‐average molecular weights, molecular weight distribution, and surface tension of latexes to air. The results for the copolymer latexes indicated that some of their physicochemical properties increased with increasing chain length of the nonionic emulsifier, but some of them followed a different trend for the two initiators. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1380–1384, 2005     

VAc／BA／AA乳液共聚反应动力学研究

用丙烯酸丁酯（BA）和丙烯酸（AA）对醋酸乙烯酯（VAc）进行共聚改性,制备了稳定的VAc／BA／AA共聚乳液。研究了该聚合体系的动力学特征,讨论了乳化剂浓度（CE）、引发剂浓度（C1）和反应温度（T）对聚合速率和单体转化率的影响。实验结果表明,乳液聚合速率随着CE、C1和T的增加而增大;单体转化率随着CE和C1的增加而增大,在75℃时转化率有最大值;得到该共聚乳液体系的表观活化能Ea=64．4kJ·mol^-1;聚合反应速率Rp^∝CE^0.45C1^0．76该式与经典的乳液聚合动力学模型有较大偏差。     

乙烯基三乙氧基硅烷/丙烯酸酯共聚乳液的研究

以聚丙烯酸丁酯为种子乳液，将乙烯基三乙氧基硅烷（VTES）与丙烯酸酯进行乳液共聚，制成了聚合稳定性良好，性能稳定的有机硅／丙烯酸酯共聚乳液，详细讨论了VTES用量对聚合过程稳定性和乳液粒径大小及分布的影响，采用动态光散射法跟踪了聚合过程的粒径大小及分布，采用TEM表征了粒子形态；同时研究了乳液的粘度及乳胶膜的耐水性能，结果表明：乳胶粒的平均粒径随聚合时间的延长逐渐增大，乳胶粒呈球形，具有核壳结构，随着VTES用量的增加，乳液聚合的稳定性变差，乳胶粒的平均粒均增大，乳液的粘度增加，乳胶膜的吸水率减小。     

VAc/BA/NaAA共聚物乳液的合成及性能研究

采用半连续种子乳液聚合法制备了固含量较高（40%）、稳定性较好（常温贮存期6个月以上）的VAc/BA/NaAA共聚物乳液。通过DLS、GPC、接触角测试仪等对乳液粒径、聚合物相对分子质量、接触角进行测试和表征,并测试了乳液保水率、乳胶膜吸水率、拉伸强度等性能。研究结果表明：适量功能性单体的引入,对乳液稳定性、保水性有明显改善;同时乳胶膜的亲水性和力学强度也有所提高。     

VAc/BA/AA共聚乳液胶粘剂的制备与性能研究

以醋酸乙烯酯(VAc)为原料、丙烯酸(AA)和丙烯酸丁酯(BA)为改性单体、过硫酸铵(APS)为引发剂、辛基酚聚氧乙烯醚(OP-10)和烷基酚聚氧乙烯醚琥珀酸酯磺酸钠(MS-1)为新型乳化剂体系,采用半连续种子乳液聚合法制备了VAc/BA/AA共聚乳液胶粘剂。研究了引发剂用量、乳化剂配比及用量、单体及种子单体用量对乳液性能的影响,并采用FT-IR对其结构进行表征。研究结果表明,当m(VAc)∶m(BA)∶m(AA)∶m(APS)∶m(OP-10)∶m(MS-1)=83∶14∶3∶0.4∶1.25∶0.25、w(种子单体)=17%(相对于总单体而言)时,乳液的综合性能最佳。     

高固含量无皂丙醋乳液的制备

以P（VAc／AANa）两亲聚合物为乳化剂，对无皂聚丙烯酸丁酯／乙酸乙烯酯乳液的合成进行了研究，并对其性能进行了初步测试。得到的较佳合成工艺条件为：醋酸乙烯酯和丙烯酸丁酯的单体配比为70：30，引发剂为单体用量的0．5％，乳化剂为单体总质量的3％，反应温度为70℃，反应时间为3．5h，再保温1h。制得的无皂丙醋乳液各方面性能良好。     

醋酸乙烯酯与丙烯酸酯共聚乳胶涂料的研制

以醋酸乙烯酯和丙烯酸酯单体为原料,制备了醋丙共聚乳液及乳胶漆,并对某些性能做了测试。讨论了单体的配比等因素对乳液聚合反应及涂膜性能的影响,确定了适宜的反应条件及较佳的配方。     

淀粉接枝丙烯酸异辛酯-醋酸乙烯共聚反应的研究

采用乳液聚合的方法,以硝酸铈铵为引发剂,十二烷基硫酸钠为乳化剂,重点考察了淀粉与醋酸乙烯／丙烯酸异辛酯的接枝共聚反应中引发剂浓度、单体浓度、反应温度、反应时间等条件对接枝率、接枝效率以及接枝反应速率的影响,得到了较为理想的产物。结果表明,接枝率最高可达248.9％,接枝效率可达72.1％,单体转化率可达94.3％。     

醋酸乙烯酯/马来酸/丙烯酸丁酯无皂共聚乳液研究

采用无皂乳液聚合方法合成聚醋酸乙烯酯/马来酸/丙烯酸丁酯乳液。以透射电镜观察乳胶粒的表面形态并测量粒径,对乳胶粒的增长机理进行了分析。以转化率、吸水性、拉伸强度和乳液的稳定性为主要指标考查了共聚单体用量、pH等因素对乳液性能的影响。结果表明,马来酸占总单体量的3%,丙烯酸丁酯占8%,pH为6时共聚乳液具有良好的性能。     

苯乙烯/丙烯酸丁酯交联体系乳液聚合动力学研究

以十二烷基苯磺酸钠(SDBS)为乳化剂,过硫酸钾(KPS)引发苯乙烯/丙烯酸丁酯(St/BA)乳液共聚,加入二甲基丙烯酸乙二醇酯(EGDMA)、聚丁二烯生胶(PB)作为交联剂,研究了聚合温度、引发剂浓度、乳化剂浓度、单体配比对聚合速率的影响。实验结果表明,共聚体系的表观活化能为70.67kJ/mol,聚合初始速率与引发剂浓度的0.43次方、乳化剂浓度的0.56次方和单体BA的0.49次方成正比。     

乙酸乙烯酯—丙烯酸丁酯乳液聚合共聚物组成

测定了乙酸乙烯酯/丙烯酸丁酯（VAc/BA）为70/30（质量比）、过硫酸钾为引发剂、十二烷基硫酸钠为乳化剂、碳酸氢钠为pH值调节剂的聚合反应体系在60℃反应温度下的竞聚率,r_（HA）=4.77±0.3,r_（VAc）=0.105±0.005。研究了反应温度、引发剂浓度、单体配比对共聚物组成的影响,分析了共聚物组成随转化率的变化规律。     

丙烯酸乙酯与含环氧基烯类单体的乳液共聚合及共聚物表征

以乳液共聚合法合成了丙烯酸乙酯／含环氧基烯类单体共聚物,研究了含环氧基单体的种类,聚合工艺对单体转化率,共聚物相对分子质量和凝胶含量的影响,结果表明,以甲基丙烯酸缩水甘油酯作硫化点单体,单体的转化率和共聚物的相对分子质量较高;采用连滴加单体、“饥饿”态下聚合,有利于甲基丙烯酸缩水甘油酯在共聚物链上均匀分布;硫醇全部加入预聚单体中,共聚物的相对分子质量高;用ＩＲ＾１Ｈ－ＮＭＲ表征了共聚物结构和环氧基     

有机硅氧烷改性醋酸乙烯酯-丙烯酸酯乳液的合成与性能

采用种子乳液聚合,引入乙烯基三甲氧基硅烷(A-171),以十二烷基苯磺酸钠(DSB)和壬基酚聚氧乙烯(20)醚(OP-10)作复合乳化剂,以过硫酸钾(KPS)为引发剂,在反应温度为78±2℃条件下,合成了A-171改性醋酸乙烯酯(VAc)-丙烯酸酯共聚乳液。实验采用单体滴加工艺,考察了配方中丙烯酸丁酯(BA)、甲基丙烯酸(MAA)和A-171用量对共聚物性能和乳液聚合过程的影响,并用红外光谱仪(FTIR)、粒度仪和差示量热扫描仪(DSC)对共聚物的结构及性能进行了表征。结果表明,引入w(BA)=10%~15%(相对于配方中单体总质量,下同)、w(MAA)=4%、w(A-171)=1%到VAc-丙烯酸酯共聚物乳液中,共聚物乳液涂膜的吸水率<5.0%,耐寒性通过10个循环,60℃加速贮存稳定性>100 d。