Preparation of Impact and Weather Resistant Copolymer

Synthesis method of the resin is that crosslinked polybutyl acrylate latex is used as base latex. Styrene (St) and acrylonitrile (AN) are grafted onto polybutyl acrylate latex particle and turn into core-shell copolymer. The resin is a good resin's impact modifier. There are study of influence regularity about additive emulsifier, initiator, monomer concentration, the ratio of St to AN, chain transfer to graft polymerization. A kind of core-shell resin used as impact modifier is obtained. (A) Preparation of Crosslinked Butyl Acrylate Rubber Latex     

Kinetic and particle size studies of emulsion polymerization of methyl methacrylate and styrene with using polyamidoamine dendrimer as seed

The emulsion polymerization of methyl methacrylate (MMA) and styrene (St) were investigated with using polyamidoamine (PAMAM) dendrimer as seed, potassium persulfate as initiator and sodium dodecyl sulfate as emulsifier. The effects of 4.0GPAMAM dendrimer concentration, initiator concentration, emulsifier concentration, monomer concentration, and polymerization temperature on the monomer conversion and polymerization rate were investigated. At the same time, the influence of the generation of PAMAM dendrimer on latex particle size was studied also. The results showed that the monomer conversion and polymerization rate increased with increasing initiator concentration, emulsifier concentration, monomer concentration, and polymerization temperature. But polymerization rate increased firstly with an increase in the 4.0GPAMAM dendrimer from 0.03 g to 0.09 g and then decreased with further increase to 0.12 g. When the concentration of 4.0GPAMAM dendrimer less than 1.449 × 10^?4 mol/L, the kinetic equation can be expressed by Rp∝[4.0GPAMAM]^0.772[SDS]^0.562[KPS]^0.589[M]^0.697, and the activation energy (Ea) of emulsion polymerization is 62.56kJ/mol. In additional, the copolymer latex particle size decreased and possessed monodispersity with increasing the generation of PAMAM dendrimer. According to FT-IR spectrum analysis, PAMAM dendrimer is successfully incorporated into the poly(PAMAM-St–MMA) latex particles.     

Morphology and grafting reactions in core/shell latexes

The particle morphology and percent grafting were investigated as a function of the crosslink density of the seed latex in two systems of core/shell latexes of polybutadiene/polymethyl methacrylate (PB/PMMA) and styrene–butadiene rubber/polymethyl methacrylate (SBR/PMMA) prepared by seeded emulsion polymerization at 50°C. The thin layer chromatography/flame ionization detection (TLC/FID) technique was used to characterize the grafting efficiency of the core/shell latexes. The percent grafting of the shell polymer was found to decrease with increasing the crosslink density of the core material. The particle morphology and precent grafting were also investigated as a function of composition and structure of the core material in four core/shell latex systems: polybutadiene/styrene–acrylonitrile copolymer (PB/SAN), (styrene-butadiene) random copolymer/styrene acrylonitrile copolymer (S:B/SAN), polystyrene : polybutadiene/styrene-acrylonitrile copolymer (PS:PB/SAN) and Kraton/styrene-acrylonitrile copolymer (Kraton/SAN), which were prepared by direct emulsification for the seed followed by emulsion polymerization at 70°C for the shell polymer. Grafting and crosslinking of the core material were found to be competitive reactions depending on the microstructure of the seed latex.     

聚硅氧烷/丙烯酸酯核/壳复合胶乳的粒径分布与成核机理

通过种子乳液法合成出具有高有机硅含量核 壳结构的聚硅氧烷 丙烯酸酯复合粒子 .研究了聚合方法、乳化剂浓度、引发剂浓度、单体滴加速度等工艺条件对复合乳液粒径尺寸、分布与形态的影响 ,并对复合乳液的成核机理进行了探讨 .研究表明 ,乳化剂浓度对乳液粒子的粒径分布和形态、结构有显著影响 ,引发剂浓度增加将使粒子粒径减小 ;相对一次投料法 ,种子乳液法生成的粒子分布窄 ,具有明显核壳结构 ,通过壳层单体滴加速度可以控制粒子的粒径尺寸和分布 ;而壳层丙烯酸酯聚合物主要是在聚硅氧烷种子表面的“过渡层”聚合、富集而成 .     

悬浮-乳液复合聚合聚苯乙烯-聚甲基丙烯酸甲酯复合粒子的颗粒特性和成粒机理

采用在苯乙烯 (St)悬浮聚合过程中滴加甲基丙烯酸甲酯 (MMA)乳液聚合组分的悬浮 乳液复合聚合方法 ,制备大粒径聚苯乙烯 聚甲基丙烯酸甲酯 (PS PMMA)复合粒子 .研究聚合物粒径分布和颗粒形态的变化发现 ,在St悬浮反应中期滴加MMA乳液聚合组分后 ,聚合体系逐渐由悬浮粒子与乳胶粒子并存向形成单峰分布复合粒子转变 ,最终形成核 壳结构完整的大粒径PS PMMA复合粒子 ;在St悬浮反应初期滴加MMA乳液聚合组分 ,St与MMA一起分散成更小液滴 ,反应后期凝并成非核 壳结构复合粒子 ;在St悬浮反应后期滴加MMA乳液聚合组分 ,PMMA乳胶粒子与PS悬浮粒子基本独立存在 .根据以上结果 ,提出了St MMA悬浮 乳液复合聚合的成粒机理 .     

超浓乳液聚合制备PU/PS的SIPN粉状树脂研究

将聚氨酯予聚体 (PU ) 苯乙烯 (St)的复合体系 ,用超浓乳液聚合方法制备了半互穿聚合物网络(SIPN)复合聚合物 ,得到了用聚氨酯予聚体改性的聚苯乙烯 (PU/PS)SIPN粉状树脂 .研究了分散相的比例(α)和聚合温度对聚合稳定性及聚合转化率 -时间的关系 ;测定了聚合物胶乳粒子的大小、形态 ,玻璃化温度 ,动态力学性能等 .结果表明 ,超浓乳液聚合较之本体聚合具有较高的聚合速率 ,容易控制所制备的胶乳粒径 ,能够制得PU/PS复合聚合物的SIPN粉状树脂 .该粉状树脂便于加工 ,具有良好的强韧性 ,有利于扩大应用     

Polystyrene (1)/poly(butyl acrylate/amide type functional monomer) (2) two-stage emulsion polymers. Synthesis and thermomechanical properties of latex films

Polystyrene (PS) (1)/Poly (n-butyl acrylate (BA)/amide type functional monomer) (2) structured latex particles were prepared through emulsion polymerization varying the hydrophilicity of the functional monomer employed. The second-stage polymerization kinetics, the size and morphology of latex particles, and the location of the functional groups in the final latexes were studied, in order to relate them to the thermomechanical properties of films cast from these latexes. It has been shown that, as expected, increasing the hydrophobicity leads to a better homogeneity in the copolymer formed during the second-stage polymerization, while the more hydrophilic functional monomer partly homopolymerizes in a separate phase. However, the functionalization by all the monomers used in this work, prevents the PS seed particles to form a continuous skeleton (percolated network). Further heat treatments at 140°C do not lead to the formation of a continuous PS phase as for pure BA/pure PS two-stage particles. In addition, some thermally induced crosslinking effects are discussed in relation with the functional monomer location within the particles. © 1995 John Wiley & Sons, Inc.     

Morphology and grafting in polybutylacrylate-polystyrene core-shell emulsion polymerization

The morphology of polybutylacrylate–polystyrene (PBA–PS) core-shell latex particles prepared by seeded emulsion polymerization was investigated as a function of the addition method of styrene (St). The thin layer chromatography/flame ionization detector (TLC–FID) technique was used to characterize the morphology of the core-shell latexes. It was found that grafting PS to the PBA core occurs during seeded emulsion polymerization. The percentage of grafting depended on the method of addition of St, being greatest for the batch reaction, less for the preswollen batch reaction, and least for the semibatch reaction. Upon aging the PBA core-polymer migrated out of the latex particles with a low degree of grafting to form dumbellshaped particles, whereas the PBA–PS core-shell particles with a high degree of grafting remained spherical because of the emulsifying ability of graft copolymer.     

The inverse emulsion polymerization of acrylamide using polystyrene-graft-polyoxyethylene as the stabilizer

Inverse emulsion polymerization of aqueous solution of acrylamide (AM) in toluene is carried out using polystyrene-graft-polyoxyethylene (PSt-g-PEO) as an emulsifier. The kinetics of polymerization, morphology of the particle, and particle size of the inverse emulsion have been investigated. The rates of polymerization are found to be proportional to the initiator concentration, the monomer concentration, and the emulsifier concentration. The morphology of the particle shows a spherical structure. The effects of amphipathic graft copolymer structure on the average molecular weight of polyacrylamide are studied. The mechanism of the inverse emulsion polymerization using amphipathic graft copolymer as emulsifier is proposed. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2719–2725, 1999     

复合微乳液聚合制备P(MMA-UA)纳米乳胶粒子的研究

将聚氨酯预聚体可聚合乳化剂 (APUA)和甲基丙烯酸甲酯 (MMA)的复合微乳液体系 ,分别用水溶性过硫酸钾 (K2 S2 O8)和油溶性偶氮二异丁腈 (AIBN)作引发剂 ,进行微乳液聚合研究 ,制备了P(MMA UA)复合纳米乳胶粒子 .研究了APUA用量、聚合温度对聚合动力学的影响 ;用透射电子显微镜 (TEM)观察了不同乳化剂浓度及引发剂体系对胶粒形态、大小及分布的影响 .结果表明 ,用可聚合乳化剂APUA可制得稳定性很好的P(MMA UA)纳米级核 壳型乳胶粒子 ,乳胶粒径在 5 0nm左右 .随着乳化剂用量增加 ,粒子变小 ;不同类型的引发剂对胶乳的性质有较大影响 ,以APUA为乳化剂 ,K2 S2 O8为引发剂 ,在聚合反应过程中或在聚合反应后的放置中 ,会出现P(MMA UA)的纳米水凝胶 (Nanogel)现象 .     

Study on controlling particle growth in seeded emulsion polymerization with regulated coagulation based on the electrostatic interactions

30wt% solid content, anionic seed copolymer latex P(methyl acrylate-co-methyl methacrylate) was prepared by conventional emulsion polymerization, and then the seeded emulsion polymerization was carried out accompanied with the electrostatic coagulation during the reaction in the presence of counter-ion species, such as cationic monomer and initiator. In this article, effects of cationic monomer (dimethyl aminoethyl methacrylate, DM) content, secondary monomer to seed polymer weight ratio, M/P and amount of emulsifier (polyoxyethylene nonylphenylether with 23 units of ethylene oxide, PEO23) were investigated on the effective particle growth and the stability of final latex. With 10wt% DM in monomer, M/P ratio at 2.0 were recommended. An optimal policy for handling the emulsifier content without the nucleation of secondary particles while achieving the controlled coagulative growth was proposed from the observations of polymer yield and particle size during the polymerization.     

Contribution of steric and electrostatic repulsion forces to the stability of styrene latices copolymerized with acrylic acid

Acrylic acid (AA) is used in many emulsion polymerization formulations to improve the colloidal stability of the latex product. The improved stability originates from electrostatic repulsion complemented with steric repulsion. The strength of the electrostatic and steric repulsion forces in a styrene (S)/AA copolymer latex was investigated at different pH values, electrolyte concentrations, and temperatures. A comparison was made with an S homopolymer latex. Transmission electron microscopic pictures, combined with visual inspections, provided understanding of the mechanisms leading to coagulation in polystyrene (PS)/AA copolymer latices. Colloidal stability of the unswollen sodium dodecyl sulfate stabilized PS latex is based on electrostatic repulsion. Destabilization by sodium chloride resulted in aggregation. The acidic PS/AA latex remained stable against aggregation at high electrolyte concentrations because of steric repulsion. The acidic PS/AA latex showed a strong tendency to flocculate at increasing electrolyte concentrations. Flocculation was not observed for high‐pH PS/AA latices at high electrolyte concentrations. Steric repulsion of the acid PS/AA latex was lost at temperatures higher than the critical coagulation temperature (35 °C), and flocculation was followed by aggregation and coalescence. The high‐pH PS/AA latex was stable even at high electrolyte concentrations and temperatures up to 80 °C because of strong electrosteric stabilization. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2985–2995, 2003     

Organic solvent‐free catalytic hydrogenation of diene‐based polymer nanoparticles in latex form: Part I. Preparation of nano‐substrate

Poly(butadiene‐co‐acrylonitrile) (NBR) nanoparticles were synthesized in a semibatch emulsion polymerization system using Gemini surfactant trimethylene‐1,3‐bis (dodecyldimethylammonium bromide), referred to as Gemini‐type surfactant (GS) 12‐3‐12, as the emulsifier. In this polymerization system, an enhanced decomposition rate of initiator ammonium persulfate was achieved even under the low temperature of 50 °C which is attributed to the acidic initiation environment provided using GS 12‐3‐12. The microstructure and copolymer composition of the polymer nanoparticles were characterized by Fourier‐transformed infrared and ¹H nuclear magnetic resonance spectroscopy. The effects of the surfactant concentration on the particle size, zeta potential, polymerization conversion, copolymer composition, molecular weight, and glass transition temperature (T_g) were investigated. It was found that the particle diameter can be controlled by the surfactant concentration and monomer/water ratio and particle sizes below 20 nm can be reached. The obtained latex particles exhibit a spherical morphology. A kinetic study of the copolymerization reaction was carried out, which indicated that an azeotropic composition was produced. The synthesized fine NBR nanoparticles can be employed as the nano substrate for a subsequent hydrogenation process so as to overcome the challenge involved in the field of latex hydrogenation of polymers, which can be found in a related report: Organic Solvent‐Free Catalytic Hydrogenation of Diene‐based Polymer Nanoparticles in Latex Form: Part II. Kinetic Analysis and Mechanistic Study. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis and Characterization of β‐CD‐Coated Polystyrene Microspheres by γ‐Ray Radiation Emulsion Polymerization

Polystyrene (PS) microspheres coated with β‐cyclodextrin (β‐CD) were fabricated via γ‐ray‐induced emulsion polymerization in a ternary system of styrene/β‐CD/water (St/β‐CD/water). The solid inclusion complex of St and β‐CD particles formed at the St droplets–water interface can stabilize the emulsion as the surfactant. TEM and XPS results showed that β‐CD remains on the surface of PS particles. The average size of the PS particles increases from 186 to 294 nm as the weight ratio of β‐CD to St rises from 5% to 12.5%. The water contact angle (CA) of PS latex film is lower than 90°, and reduces with the β‐CD content even to 36°. Thus, this work provides a new and one‐pot strategy to surface hydrophilic modification on hydrophobic polymer particles with cyclodextrins through radiation emulsion polymerization.     

Preparation,morphology, and thermoresponsive properties of poly(N‐isopropylacrylamide)‐based copolymer microgels

In this research, thermoresponsive copolymer latex particles with an average diameter of about 200–500 nm were prepared via surfactant‐free emulsion polymerization. The thermoresponsive properties of these particles were designed by the addition of hydrophilic monomers [acrylic acid (AA) and sodium acrylate (SA)] to copolymerize with N‐isopropylacrylamide (NIPAAm). The effects of the comonomers and composition on the synthesis mechanism, kinetics, particle size, morphology, and thermoresponsive properties of the copolymer latex were also studied to determine the relationships between the synthesis conditions, the particle morphology, and the thermoresponsive properties. The results showed that the addition of hydrophilic AA or SA affected the mechanism and kinetics of polymerization. The lower critical solution temperature (LCST) of the latex copolymerized with AA rose to a higher temperature. However, because the strong hydrophilic and ionic properties of SA caused a core–shell structure, where NIPAAm was in the inner core and SA was in the outer shell, the LCST of the latex copolymerized with SA was still the same as that of pure poly(N‐isopropylacrylamide) latex. It was concluded that these submicrometer copolymer latex particles with different thermoresponsive properties could be applied in many fields. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 356–370, 2006     

超声无皂乳液聚合制备BA/St/AM三元共聚物乳胶粒及其聚合机理研究

将超声技术引入到无皂乳液聚合方法中,在不加入任何引发剂和乳化剂的情况下,制备了丙烯酸丁酯(BA)/苯乙烯(St)/丙烯酰胺(AM)三元共聚纳米乳胶粒.研究了不同超声时间对单体转化率、乳胶粒粒径以及乳液粘度的影响.同时还探讨了超声无皂乳液聚合机理,认为AM在聚合过程中起到了引发和稳定的作用.TEM照片表明,乳胶粒直径大约在80nm左右,FTIR及DSC分析表明产物为三元共聚物,而不是共混物.     

核壳结构聚丙烯酸酯抗冲改性剂的合成及粒径控制

采用预乳化多步种子乳液聚合法合成聚丙烯酸酯类聚合物(ACR)胶乳,实验得出种子乳液用量与聚丙烯酸丁酯粒径之间的关系,实现对胶乳粒子粒径的控制;对反应中影响粒子粒径的因素做了分析,以此确定最佳反应条件为:温度为65℃;乳化剂:十二烷基硫酸钠和聚氧乙烯基醚硫酸钠摩尔比为4/3,乳化剂用量为0.9％,单体固含量30％～37％...     

On the emulsion polymerization of styrene in the presence of a nonionic emulsifier

The batch emulsion polymerization kinetics of styrene (St) initiated by a water-soluble peroxodisulfate in the presence of a nonionic emulsifier was investigated. The polymerization rate versus the conversion curves showed two nonstationary rate intervals, two rate maxima, and Smith–Ewart Interval 2 (nondistinct). The rate of polymerization and number of nucleated polymer particles were proportional to the 1.4th and 2.4th powers, respectively, of the emulsifier concentration. Deviation from the micellar nucleation model was attributed to the low water solubility of the emulsifier, the low level of the micellar emulsifier, and the mixed modes of particle nucleation. In emulsion polymerizations with a low emulsifier concentration, the number of radicals per particle and particle size increased with increasing conversion, and the increase was more pronounced at a low conversion. By contrast, in emulsion polymerizations with a high emulsifier concentration, the number of radicals per particle decreased with increasing conversion. This is discussed in terms of the mixed models of particle nucleation, the gel effect, and the pseudobulk kinetics. The formation of monodisperse latex particles was attributed to coagulative nucleation and droplet nucleation for the polymerizations with low and high emulsifier concentrations, respectively. The effects of the continuous release of the emulsifier from nonmicellar aggregates and monomer droplets, the close-packing structure of the droplet surface, and the hydrophobic nature of the emulsifier on the emulsion polymerization of St are discussed. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4422–4431, 1999     

粒径可控阳离子型聚苯乙烯纳米粒子的制备及表征

在采用阳离子型双子（gemini）表面活性剂作为乳化剂,不使用任何助乳化剂的条件下,通过改进微乳液聚合工艺制备了窄分布粒径可控的阳离子型聚苯乙烯（PS）纳米乳液。 改进微乳液聚合的主要特点是：大部分苯乙烯以预乳液的形式恒速滴入引发聚合的微乳液中,使用具有高乳化性能的gemini表面活性剂作为乳化剂能明显降低乳胶粒粒径。 实验结果表明,少量阳离子单体三甲基烯丙基氯化铵作为共聚单体能够明显减小Z均粒径、降低粒度分布,乳化剂用量、引发剂用量和反应温度均能影响制备乳胶粒的粒径及其粒度分布。 乳化剂和引发剂用量分别为苯乙烯质量的5%~10%和1.0%~1.5%、反应温度为70~75 ℃时,能够制备粒径小分布窄的阳离子型聚苯乙烯纳米粒子。 Z均粒径与苯乙烯质量之间的线性关系表明,Z均粒径可以通过苯乙烯用量来控制。 不同聚合工艺下制备的聚合物粒度分布曲线表明,改进微乳液聚合工艺（半连续预乳化工艺）在制备窄分布的聚合物纳米粒子方面具有很强的优越性。     

Effect of glyoxylic oxime ether on radical polymerization of styrene

Methyl benzyloxyiminoacetate (MBOIA), a glyoxylic oxime ether, revealed different behaviors depending on the kinds of monomers used in the radical polymerization. MBOIA served as a retarder for styrene (St) and an inhibitor for vinyl acetate, whereas it showed little effect on the polymerization of methyl methacrylate. The retardation effect of MBOIA on the polymerization of St with dimethyl 2,2′‐azobisisobutyrate (MAIB) was examined in detail in benzene. The rate constant (k_x) of the reaction of MBOIA with polystyrene (PS) radical was 92 L/mol s at 50 °C, 112 L/mol s at 60 °C, and 143 L/mol s at 70 °C, indicating that the reactivity of MBOIA toward PS radical is less than that of St by a factor of about 3. The Arrhenius plot of k_x gave an activation energy of 20.3 kJ/mol. A nitrogen‐centered radical of a stationary state was observed by electron spin resonance (ESR) in the polymerization of St with MAIB at 60 °C in benzene in the presence of MBOIA, which is assignable to the radical (MBOIA ·) formed by addition of PS radical to MBOIA. The stationary MBOIA · concentration increased with increasing MBOIA concentration and then tended to be saturated at high concentrations. The rate constant of termination between MBOIA · radicals was 1.87 × l0⁵ L/mol s at 60 °C with ESR. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2772–2781, 2002