Miniemulsion copolymerization of styrene and butyl acrylate initiated by redox system at lower temperature-preparation and polymerization of miniemulsion

Miniemulsions of styrene and butyl acrylate with sodium dodecyl sulfate (SDS) as the surfactant and hexadecane (HDE) and cetyl alcohol (HDL) as cosurfactants were prepared under high-speed stirring or ultrasonification. Results indicate that the stability of miniemulsions produced with HDE is more stable than that with HDL, when the feeding method, in which the cosurfactant is mixed with monomers, is used. There is an optical ratio (¼) of the surfactant to the cosurfactant for maximum stabilization of the miniemulsions. The miniemulsions prepared by ultrasonification are much more stable than those by high-speed stirring. Also, a stable miniemulsion can be prepared at lower temperature (45°C) when homogenizing way of ultrasonification is used. The emulsions were of a droplet-size range common to miniemulsions and some of them exhibited long-term stabilities (3 months). When these emulsions were initiated, particle formation occurred predominantly by monomer droplet nucleation. The effects of temperature, ultrasonification time, ratio of monomers, and concentrations of surfactant, cosurfactant, and initiator on the polymerization rate, conversion, and particle size were determined. It was found that the miniemulsion copolymerization of styrene and butyl acrylate with a midial amount of a redox initiator ((NH₄)₂S₂O₈/NaH SO₃) at lower temperature (45°C) can be carried out successfully by using a suitable amount of the surfactant SDS (10 mM) and the cosurfactant HDE (40 mM), when a homogenizing way of ultrasonification is applied. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 2029–2039, 1998     

A polyampholyte triblock copolymer synthesized for using as the surfactant of miniemulsion polymerization and production of highly uniform microspheres

Miniemulsions based on styrene/azobisisobutyronitrile (AIBN) in the presence of polyampholyte triblock copolymers as a surfactant and hexadecane (HD) as a cosurfactant were developed. The polyampholyte was prepared by using methyl methacrylate (MMA), methacrylic acid (MAA), and 2‐(dimethylamino) ethyl methacrylate (DMAEMA) as monomers. For the sake of comparison, a miniemulsion polymerization with sodium dodecyl sulfate (SDS) was carried out using the same procedure as the above series. The monomer droplet sizes and their shelf life tests revealed that the polyampholyte could stabilize miniemulsion and lead nucleation mechanisms to droplet nucleation. Miniemulsion polymerization using SDS as the surfactant possess a higher polymerization rate than that of polyampholyte, probably due to the smaller droplet size. Production of uniform microspheres was also carried out in this work. Highly uniform microspheres prepared using polyampholyte as the surfactant in the presence of acetone could be obtained. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2230–2237, 2003     

Batch polymerization of methyl methacrylate in mini/macroemulsions

The kinetics of the isothermal batch macroemulsion and miniemulsion polymerizations of methyl methacrylate (MMA) at 50°C have been studied. Hexadecane was used as the cosurfactant or swelling agent. The nucleation mechanisms were observed to be different between macroemulsions and miniemulsions. The effect of surfactant, cosurfactant, initiator, shear, and hold time on droplet nucleation was studied. The miniemulsion particles were found to contain more radicals on average than the macroemulsion particles using certain recipes. This resulted in higher polymerization rates for the miniemulsions at identical particle numbers. The latex-particle-size distributions were similar even though the mini-emulsion droplets start out with a high polydispersity of around 1.5. Miniemulsion latexes were found to be more stable under shear. Conductance of emulsions during polymerization was found to be a valuable on-line tool for investigating particle nucleation and growth. © 1993 John Wiley & Sons, Inc.     

In-situ polyurethane/polyacrylate microemulsion formation: the effects of acrylic content in wood coating application

In-situ surfactant-free emulsion polymerization was utilized to prepare polyacrylate/polyurethane (PUA) microemulsions in the absence of surfactant and organic solvent. For this purpose, PUA with higher acrylate content was successfully prepared, with the aim to reduce the coating cost. The dynamic light scattering results showed that the particle size of PUA microemulsion displayed a unimodal distribution and the particle size was ranged from 33 to 61 nm. In comparison with PUA prepared with conventional miniemulsion polymerization, the particle size distribution coefficient dropped by one order. Atomic force microscopy, together with thermogravimetric analyzer, demonstrated good compatibility and interaction between PU and acrylic components, and no phase separation was detected even at 58 wt% acrylic content. With the incorporation of acrylic component, the thermal stability and maximum stress were improved. The maximum stress greatly increased from 4.6 to 30.9 MPa, and the maximum stress of in-situ PUA was nearly three times larger than that of PUA prepared by miniemulsion polymerization. The effects of acrylic content on water resistance, pencil hardness, adhesion, and impact strength of wood coating were evaluated. With increasing the acrylic content, the water resistance and pencil hardness increased, though the impact strength of in-situ PUA films was slightly reduced.     

Emulsion and miniemulsion copolymerization of acrylic monomers in the presence of alkyd resin

Emulsion and miniemulsion copolymerizations were carried out with acrylic monomers (methyl methacrylate, butyl acrylate, and acrylic acid) in the presence of an alkyd resin. Poly(methyl methacrylate) was used as a hydrophobe or cosurfactant in the miniemulsion reactions. The results demonstrate that miniemulsion polymerization is the preferred process, probably because of mass transport limitations of the alkyd in the conventional emulsion polymerization reactions. The monomer emulsions prepared for the miniemulsion reactions were much more stable and the polymerizations were free of coagulum. Reaction rates, particle size characteristics, grafting efficiencies, and some film properties were measured. © 1996 John Wiley & Sons, Inc.     

丙烯酸酯PSA环形初粘力影响因素研究

以反应型乳化剂(DNS-86)/阴离子型乳化剂(2A1)为复合乳化剂、甲基丙烯酸(MAA)与甲基丙烯酸羟乙酯(HEMA)为极性单体和正十二硫醇为链转移剂时,采用单体预乳化法和半连续乳液聚合法制备丙烯酸酯PSA(压敏胶)乳液。考察了PSA胶带的基材、干胶厚度、烘干条件、复合乳化剂、极性单体和链转移剂等对环形初粘力的影响。结果表明:当基材为白色BOPP(双向拉伸聚丙烯)薄膜、干胶厚度为50μm、烘干时间为3 min、烘干温度为110~115℃、w(正十二硫醇)=0.09%、同时引入MAA和HEMA极性单体、w(复合乳化剂)=1.5%和m(2A1)∶m(DNS-86)=2∶1时,相应丙烯酸酯PSA乳液的环形初粘力相对最大(14.73 N/25 mm)。     

Preparation of highly conductive reduced graphite oxide/poly(styrene-co-butyl acrylate) composites via miniemulsion polymerization

Polymer/reduced graphite oxide (rGO) composite nanoparticles with a high electrical conductivity were synthesized using the miniemulsion polymerization technique. The rGO was modified with a reactive surfactant, 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS), to facilitate monomer intercalation into the rGO nanogalleries. The AMPS-modified rGO was emulsified in the presence of styrene (St) and butyl acrylate (BA) monomers, and the stable miniemulsion was polymerized to form poly(St-co-BA)/rGO composite latex nanoparticles. The transition in the composite nanoparticles from an electrical insulator to an electrical conductor occurred at an rGO content of 10 wt% (relative to the monolayer content), yielding an electrical conductivity of 0.49 S/cm. The electrical conductivity of the composite nanoparticles reached 2.22 S/cm at 20 wt% rGO, yielding a much better conductivity than other polymer composites prepared using a GO filler. Importantly, the miniemulsion polymerization method for fabricating poly(St-co-BA)/rGO composite nanoparticles is easy, green, low-cost, and scalable, providing a universal route to the rational design and engineering of highly conductive polymer composites.     

Particle nucleation and growth mechanisms in miniemulsion polymerization of styrene

Styrene miniemulsion polymerizations stabilized by sodium lauryl sulfate in combination with a reactive costabilizer, lauryl methacrylate (LMA) or stearyl methacrylate (SMA), were studied. A small amount of extremely hydrophobic dye was incorporated into monomer droplets (10² nm in diameter) to investigate particle nucleation and growth mechanisms. In addition to monomer droplet nucleation, particle nuclei generated in the aqueous phase (homogeneous nucleation) also play an important role in both LMA‐ and SMA‐containing polymerization systems. The way that these two nucleation mechanisms compete with each other is closely related to the water solubility of the costabilizer (LMA > SMA). The fraction of latex particles originating from homogeneous nucleation increases with decreasing hydrophobicity of the costabilizer. Zeta potential data of latex particles and the molecular weight and molecular weight distribution of emulsion polymers provide supporting evidence for the proposed competitive particle nucleation and growth mechanisms. © 2002 Society of Chemical Industry     

Miniemulsion copolymerization of styrene and butyl acrylate initiated by redox system at lower temperature: Reaction kinetics and evolution of particle‐size distribution

The kinetics of the miniemulsion copolymerization of styrene (St) and butyl acrylate (BA) initiated by redox initiators, (NH₄)₂S₂O₈/NaHSO₃, at lower temperature (45°C) was studied. The polymerization rate in miniemulsion copolymerization is lower than that of the corresponding conventional emulsion copolymerization. In regard to the rate of polymerization, the initiator concentration plays a more important role in miniemulsion copolymerization than in conventional emulsion polymerization, while the surfactant concentration has a more important role in conventional emulsion polymerization than in miniemulsion polymerization. These are attributed to their different nucleation mechanisms, which are the same as those found in the miniemulsion polymerization carried out at higher temperatures. While by eliminating nucleation via micelle and ensuring against homogeneous nucleation, miniemulsion polymerization can be carried out by the sole nucleation mechanism—monomer droplet nucleation—at lower temperature. Because of this, the particles become narrower during the polymerization and, finally, monodisperse polymer particles are obtained. The result of the particle numbers indicated that a continuous nucleation will cease at about 60% conversion. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 315–322, 1999     

乳液型CPP-g-MAH复膜胶的研制

以酯溶性CPP-g-MAH(马来酸酐接枝改性氯化聚丙烯)、BA(丙烯酸丁酯)、HEA(丙烯酸羟乙酯)和β-CEA(β-羧乙基丙烯酸酯)为共聚单体,DNS-86[烯丙氧基壬基酚丙醇聚氧乙烯(10)醚硫酸铵]为反应型乳化剂,采用半连续预乳化乳液聚合法制备乳液型CPP-g-MAH复膜胶。研究结果表明:当m(BA)∶m(CPP-g-MAH)=9∶4、聚合温度为82⁸5℃、聚合时间为4 h、w(DNS-86)=3.0%(相对于配方中各物料总质量而言)和w(引发剂)=0.5%(相对于聚合单体总质量而言)时,制得的乳液型复膜胶具有环保、成本低等优势,并且其黏度、初粘力(2.5 cm)和180°剥离强度(5.1 N/cm)俱佳。     

Mass transfer and radical flux effects in dispersed‐phase polymerization of isooctyl acrylate

The kinetics of dispersed phase polymerization of a highly water‐insoluble monomer (isooctyl acrylate) were explored in emulsion, miniemulsion, and microsuspension polymerization. The effects of monomer water solubility and choice of initiator (oil‐ vs. water‐soluble) strongly impact the final product (particle size and molecular weight distribution). For emulsion polymerization, as the surfactant concentration was increased, there was a transition from homogenous to micellar nucleation near the CMC, then a drop in nucleation rate at high surfactant concentration due to insufficient radical flux to support more nucleation. For miniemulsion polymerization, a slow rate of growth of (droplet) nucleation with surfactant concentration was found, followed (at the CMC) by an increase in the rate of nucleation with added surfactant as the mode of nucleation switched to micellar. The conversion‐time kinetics of microsuspensions could be modeled with a bulk polymerization model. IOA is sufficiently insoluble in the aqueous phase that emulsion polymerization may or may not be reaction limited. The presence of a stabilizer such a PAA, the use of an oil‐soluble initiator such as BPO, and the insolubility of IOA in the aqueous phase all push the polymerization locus toward droplet (microsuspension) nucleation and bulk kinetics.© 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5649–5666, 2006     

高固含量苯丙微乳液的制备与性能研究

以苯乙烯(St)、甲基丙烯酸甲酯(MMA)和丙烯酸丁酯(BA)为共聚单体,丙烯酸(AA)为功能单体,反应型乳化剂(DNS-86)、十二烷基硫酸钠(SDS)和壬基酚醚磺基琥珀酸酯钠盐(OS)为复合乳化剂,采用种子乳液聚合法制备了粒径小、耐水性好且固含量为50%的苯丙微乳液。研究结果表明:当w(引发剂)=0.7%、m(MMA+St)∶m(BA)∶m(AA)=5.0∶4.7∶0.3、w(St)=15%~25%、m(DNS-86)∶m(SDS+OS)=3∶2且w(复合乳化剂)=5%时,高固含量苯丙微乳液的综合性能良好。     

Thermal and mechanical properties of poly(lactic acid) modified by poly(ethylene glycol) acrylate through reactive blending

Poly(lactic acid) (PLA) was modified using a simple reactive blending method, where a low molecular weight poly(ethylene glycol) acrylate (PEGA) was blended with PLA in the presence of a radical initiator. To examine the initiation effect on the modification of PLA, various amounts of radical initiator (between 0 and 1.5 %) were added to the PLA/PEG acrylate mixture. The modified PLAs (PLMs) were characterized by gel permeation chromatography, Fourier transform infrared spectroscopy, wide-angle X-ray diffraction, and solvent extraction. The properties of the PLMs were investigated using tensile testing, differential scanning calorimetry, thermogravimetric analysis, scanning electron microscopy, and hydrolytic degradable analysis. The PEGA significantly influenced the molecular structure and properties of the modified PLA. The glass transition temperature of the PLMs was decreased by approximately 15 °C (for PLM15) from 59.3 °C of PLA, whereas their toughness increased considerably compared to PLA. In addition, PEG acrylate facilitates hydrolytic degradation, even after radical polymerization by reactive blending.     

丙烯酸酯微乳液动力学研究

采用一次投料法,以烯丙氧基壬基酚聚氧乙烯(10)醚硫酸铵(DNS-86)和辛基酚聚氧乙烯(10)醚(OP-10)为乳化剂制备了固含量为10%的纯丙微乳液,对其聚合反应动力学进行了研究。结果表明:温度对纯丙微乳液聚合反应的最终转化率没有影响;整个反应过程不存在恒速期;但随温度的升高乳胶粒粒径减小,反应速率增快,乳液的聚合稳定性下降;纯丙微乳液聚合成核方式主要以胶束成核为主。     

超声辐照废聚苯乙烯泡沫／丙烯酸丁酯共聚乳液研究

以十二烷基硫酸钠和壬基酚聚氧乙烯醚为乳化剂,在超声波作用下合成了聚苯乙烯（PSt）与丙烯酸丁酯（BA）的共聚乳液．研究了聚合方法、超声波强度、环境温度、聚合物浓度对单体转化率的影响,透射电镜图表明,乳液粒子有核壳结构,粒径分布呈多分散型,由此可以推测该乳液的成核方式是液滴成核．     

超细分散染料/乳胶粒复合色素分散体的制备

采用可聚合乳化剂(DNS-86),通过细乳液聚合制备了超细分散染料/乳胶粒复合色素分散体,考察了助乳化剂、乳化剂、细乳化时间对复合色素分散体性能的影响。结果表明,十六烷(HD)助乳化作用较十六醇(CA)、十二硫醇(DDM)好;以DNS-86制备超细分散染料/乳胶粒复合色素分散体的稳定性明显优于传统乳化剂;当DNS-86浓度14.4 mmol/L,助乳化剂HD用量占单体质量的7.5%,细乳化时间15 min时,制备的超细分散染料/乳胶粒复合色素分散体的粒径为123 nm,Npf/Nmi值为1.23,聚合反应以液滴成核为主。     

Preparation of fluorinated polyacrylate composite latex with in situ generated nano-silica dispersion and film durability

Nano-silica dispersion was generated in situ through the hydrolysis and condensation of tetraethyl orthosilicate with methyl methacrylate and butyl acrylate in micelles as dispersing media, hydrochloric acid as catalyst and methacryloxypropyl trimethoxysilane as modifier. Then, the nano-silica/fluorinated polyacrylate composite latexes were prepared via emulsion polymerization directly using the in situ generated nano-silica dispersion as seeds. Dodecafluoroheptyl methacrylate (DFHMA) as functional monomer was incorporated into shell layer of the composite particles by semi-continuous starved condition at the second stage. Fourier transform infrared spectroscopy indicated that silica was generated in situ and DFHMA took part in the copolymerization. Transmission electron microscopy showed uniform composite latex particle morphology and obvious core–shell structure. Dynamic light scattering demonstrated that DNS-86 could control the composite latex particle size ranging from 90 to 180 nm. DFHMA had an important effect on the particle size. Zeta potential (ζ) revealed that the composite latex had good stability. The resulted composite films were characterized by angle-resolved X-ray photoelectron spectroscopy, contact angle measurements and thermo-gravimetric analysis. The well-tailored composite latex particle structure of nano-silica core and fluorinated polyacrylate can effectively improve the hydrophobicity of the resultant films. Water contact angle could reach 123.5° when 6 wt% DFHMA was incorporated in the film. Moreover, water contact angles remained 106° after water immersion in the range of the experimental sample films. In addition, the incorporation of fluorinated monomer and nano-silica contributed to the improvement of thermal stability of the composite film.     

Particle Nucleation Loci in Styrene-Butyl Acrylate Miniemulsion Copolymerization

Summary Miniemulsion polymerizations of styrene and butyl acrylate in the presence of sodium dodecyl sulfate (SDS) as the surfactant and stearyl methacrylate (SMA) as reactive cosurfactant were carried out by using water-soluble (potassium persulfate) and oil-soluble (2,2-azobisisobutyronitrile) (AIBN) initiators respectively. Effects of the two initiators on the particle nucleation mechanisms are investigated. By comparison with the mean diameter of monomer droplets and polymer particles, it is shown that both homogeneous nucleation and monomer droplets nucleation coexist in the presence of a water-soluble initiator but homogeneous nucleation becomes less significant with SDS concentration increasing. Meanwhile, using oil-soluble initiator, the possibility of homogeneous nucleation is depressed effectively. As a result, monomer droplets are definitely the main loci of particle nucleation.     

Hyperbranched poly(methyl methacrylate)s prepared by miniemulsion polymerization and their (non)-Newtonian flow behaviors

Miniemulsion polymerization is most suitable for the targeted synthesis of vinyl copolymers than the conventional emulsion polymerization, because in miniemulsion polymerization each monomer nanodroplet is a nanoreactor, and the monomers in each droplet are in situ converted to the corresponding polymers. Soluble and hyperbranched poly(methyl methacrylate)s (PMMA) were prepared with quantitative monomer conversion and without gelation by the miniemulsion copolymerization with di- and tri-acrylate and mediated with 1-dodecyl thiol (DDT). DDT acted both as a gelation prohibitor and as a reactive cosurfactant. The PMMAs with varied “X” or “Ж” shaped branches, depending on the di- and tri-functional acrylate used as the branching agent, are characterized and interpreted in terms of the repeating units per part, parts and branches per macromolecule, average molecular weight, latex particle size and size distribution. Effects of topology changes of the branched PMMAs on the rheological behaviors are observed for the first time: from Newtonian flow for the densely branched PMMAs to the non-Newtonian flow with pronounced shear thickening for the PMMA samples with high-molecular-weight and longer parts.     

聚合条件对丙烯酸酯微乳液粒径及其分布的影响

以烯丙氧基壬基酚聚氧乙烯(10)醚硫酸铵(DNS-86)为阴离子型反应性乳化剂、过硫酸钾(KPS)为引发剂,制备丙烯酸酯微乳液。研究了聚合工艺、乳化剂、引发剂和单体等对微乳液的粒径及其分布的影响。结果表明:随着DNS-86、KPS用量的不断增加,乳胶粒的粒径逐渐减小,但过多加入KPS时会导致乳胶粒的粒径增大;乳胶粒的粒径均呈双峰分布,并且双峰随单体用量增加均向大粒径方向偏移;当w(DNS-86)=11%、w(KPS)=0.5%和m(单体)∶m(水)=6∶14时,采用种子预乳化半连续聚合法,可以制备出粒径小(平均粒径为39 nm)、分布窄(粒径分布指数为0.202)的丙烯酸酯微乳液。