Effects of the functionalizing agent,itaconic acid,on the mechanical properties of microemulsion‐made core/shell polymers

The effect of itaconic acid (IA) as functionalizing agent on the static mechanical properties (Young's modulus, tensile stress, ultimate properties, and hardness) of core/shell polymers made of styrene and butyl acrylate by a two‐stage microemulsion polymerization process is reported. High‐polymer content (>35 wt%) was obtained in the first stage (seed) by adding more monomer semicontinuously to the parent microemulsion‐latex; however, the characteristics of microemulsion‐made latexes were preserved, that is, nanometer particles (<50 nm) and high molar masses (>2 × 10⁶ g/mol). The IA content in the shell was varied from 0 to 20 wt% with respect to that of the polymer in the shell, either polystyrene or poly(butyl acrylate) (PBA). High conversions in both stages (>84 %), final core‐shell latex with relatively high‐polymer content (ca. 20 wt%), and particle with diameters smaller than 78 nm were obtained. The fact that particle size grew from the first (ca. 50 nm) to the second stages (ca. 75 nm) and that the polymers showed two glass transitions suggests that a core shell structure was obtained. The presence of the functionalizing agent (IA) modified the mechanical properties, especially when PBA was in the shell. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers.     

Preparation of core-shell emulsion polymer and optimization of shell composition with respect to opacity of paint film

A series of core-shell latexes comprising a poly(n-butyl acrylate-co-methyl methacrylate-co-methacrylic acid) (PBA/MMA/MAA) core and a poly(styrene-co-acrylonitrile) (PS/AN), poly(butyl acrylate-co-methyl methacrylate) (PBA/MMA) shell were prepared at different shell composition ratios. These core-shell binders were used for preparation of decorative coatings. The latexes were synthesized by a semi-continuous sequential emulsion polymerization and characterized by using transmission electron microscopy (TEM), particle size analyser, viscometry and opacity of paint film. The core-shell emulsion with styrene/acrylonitrile ratio 60/40 as shell composition shows the best optical properties.     

Effects of compatibilizing agents in poly(n-butyl acrylate)/poly(methyl methacrylate) composite latexes

Graft copolymers with poly(n-butyl acrylate) (PBA) backbones and poly(methyl methacrylate) (PMMA) macromonomer side chains are used as compatibilizing agents for PBA/PMMA composite latexes. The composite latexes are prepared by seeded emulsion polymerization of methyl methacrylate (MMA) in the presence of PBA particles. Graft copolymers were already incorporated into the PBA particles prior to using these particles as seed via miniemulsion (co)polymerization of n-butyl acrylate (BA) in the presence of the macromonomers. Comparison between size averages of composite and seed particles indicates no secondary nucleation of MMA during seeded emulsion polymerization. Transmission electron microscopy (TEM) observations of composite particles show the dependence of particle morphologies with the amount of macromonomer (i.e., mole ratio of macromonomer to BA and molecular weight of macromonomer) in seed latex. The more uniform coverage with the higher amount of macromonomer suggests that graft copolymers decrease the interfacial tension between core and shell layers in the composite particles. Dynamic mechanical analysis of composite latex films indicates the existence of an interphase region between PBA and PMMA. The dynamic mechanical properties of these films are related to the morphology of the composite particles, the arrangement of phases in the films, and the volume of the interphase polymer. © 1997 John Wiley & Sons, Inc.     

The effect of synthesis methods on the mechanical properties of self‐crosslinkable poly(n‐butyl methacrylate‐co‐N‐methylolacrylamide) films

The effects of particle size and parent polymer characteristics on the mechanical properties, gel fraction, and swelling index of self‐crosslinkable poly(n‐butyl methacrylate‐co‐N‐methylolacrylamide) films made by two‐stage emulsion or microemulsion polymerization in the presence of variable amounts of the chain transfer agent, n‐butyl mercaptan, are reported here. In films prepared with latexes made by microemulsion polymerization, the crosslinking degree increased greatly on curing; by contrast, in those made by emulsion polymerization, the crosslinking degree practically did not increase after curing. Stress–strain tests of uncured and cured films indicate that microemulsion‐made films are tougher than the emulsion‐made films. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

硅溶胶／聚丙烯酸酯乳液型压敏胶的制备与性能

采用半连续加料乳液聚合方法制备了硅溶胶／聚丙烯酸酯核／壳结构聚合物,采用动态光散射方法跟踪了复合乳胶粒的粒径随反应进程的变化,其理论粒径与实测值基本一致,说明该聚合过程没有明显的二次成核过程。考查了壳层硬单体-甲基丙烯酸甲酯（MMA）含量对乳液聚合的影响,通过动态热机械分析仪（DMA）对聚合物的黏弹性能进行了表征,对制成的胶粘剂进行了压敏特性的测定,并与复合粒子的分子结构进行了关联。研究表明,随着MMA含量的增加,压敏胶的初粘性略有下降,而持粘性显著提高,剥离强度呈先升后降的趋势。     

粒径可控的聚丙烯酸丁酯/聚甲基丙烯酸甲酯核壳乳液的制备及表征

采用种子乳液聚合法制备了聚丙烯酸丁酯(PBA)乳液,然后通过第二单体甲基丙烯酸甲酯的预溶胀法聚合制备了PBA/聚甲基丙烯酸甲酯(PMMA)乳液,用激光散射粒度仪和透射电子显微镜对乳液粒径和结构进行了表征.结果表明,当乳化剂十二烷基硫酸钠质量分数为丙烯酸丁酯的1.5%时,可制备粒径为53.6 nm且分布窄的PBA种子乳液;通过调整补加乳化剂、单体与种子乳液的用量,可制得粒径为53.6～443.8 nm的一系列单分散PBA乳液;PBA/PMMA乳液具有完善的核壳结构,且在核壳两相间存在着一个过渡层.     

Effect of amount of emulsifier added in the second stage on morphology of composite latex particles

In this article, PBA/P(MMA–crosslinking agent)-composite particle latexes were prepared by semicontinuous seeded emulsion polymerization. To determine the seed emulsion's saturating capacity of an emulsifier, a mathematical model was built to simulate the changes of the seed PBA emulsion's surface tension with the amount of emulsifier added dropwise. The effects of the emulsifier amount added in the second stage and the addition method on the morphology of the composite particles were studied. The results were shown as follows: If the amount of emulsifier added in one batch to the seed emulsion in the second stage was less than or equal to the saturating capacity of emulsifier of the seed emulsion (Cs), the morphology of the particles was “core–shell”; otherwise, a few particles were of a core–shell structure. However, if shell materials were preemulsified and added dropwise at an appropriate rate, the latex particles were still of a core–shell structure, even when the amount of emulsifier added to the seed emulsion was greater than the Cs. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 969–975, 1998     

Grafting behavior of n-butyl acrylate onto poly(butadiene-co-styrene) latexes

The radical-induced grafting of n-butyl acrylate (BA) onto poly(butadiene-co-styrene) [(P(Bd-S)] latexes during seeded emulsion polymerization was studied. This P(Bd-S)/PBA rubber/rubber core/shell latex system exhibited unique grafting behavior as compared to other extensively studied rubber/glass core/shell latex systems, such as poly(butadiene-co-styrene)/poly(methyl methacrylate) [P(Bd-S)/PMMA], poly(butadiene-co-styrene)/polystyrene [P(Bd-S)/PS] and poly(butadiene-co-styrene)/poly(acrylonitrile)[P(Bd-S)/PAN]. These composite latexes were characterized by the formation of a highly grafted/crosslinked P(Bd-S)/PBA interphase zone generated during the seeded emulsion polymerization process. Although both of the individual core and shell polymers studied were “soft” themselves, the resulting P(Bd-S)/PBA composite latex particles were found to be rather “hard.” The formation of the interphase zone was studied by using techniques such as solvent extraction, differential scanning calorimetry (DSC), and transmission electron microscopy (TEM). © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:511–523, 1997     

The surface modification of nanosilica,preparation of nanosilica/acrylic core‐shell composite latex,and its application in toughening PVC matrix

The properties and morphology of nanosilica modified with silane coupling agent, methacryloxypropyltrimethoxysilane (MPS), were characterized by fourier transform infrared, zeta potentials, thermogravimetric analysis, and transmission electron microscopy. The results showed that the grafting ratio of MPS on the surface of nanosilica increased with the MPS content. MPS‐silica/PBA/PMMA core‐shell latexes (MPS‐Si/ACR) were prepared by seeded emulsion polymerization. Then they were used to mix with PVC resin. The outer layer (PMMA) enhanced the dispersibility of MPS‐Si/ACR in the PVC matrix by increasing the interfacial interaction of these composite particles with PVC. The notched impact strengths of the blends were influenced by the weight ratio of MPS to silica, the concentration of emulsifier (SDS), and the MPS‐Si/ACR content. The relationships between the mechanical properties and the core‐shell composite structures were elaborated. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Preparation and characterization of nano‐CaCO3 encapsulated with polyacrylic and its application in PVC toughness

The properties and morphology of nano‐calcium carbonate (nano‐CaCO₃) modified with the titanate coupling agent isopropyl trioleoyl titanate (IPTT) were characterized by Fourier transform infrared, thermogravimetric analyses, surface tension, and transmission electron microscopy. The results showed that the grafting ratio of IPTT on the surface of nano‐CaCO₃ (IPTT‐Ca) increased with IPTT content. IPTT‐Ca/PBA/PMMA (IPTT‐Ca/ACR, PBA/PMMA core‐shell polymer, referred to ACR) latexes were prepared by seeded emulsion polymerization. They were then used to mix with PVC resin. The outer layer (PMMA) enhanced the dispensability of IPTT‐Ca/ACR in the PVC matrix by increasing the interfacial interaction of these composite particles with PVC. The notched impact strengths of the blends were influenced by the weight ratio of IPTT‐Ca to BA/MMA monomers, the weight ratio of BA/MMA. The relationships between the mechanical properties and the core‐shell composite structures were elaborated. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Fabrication and characterization of polysiloxane/polyacrylate composite latexes with balanced water vapor permeability and mechanical properties: effect of silane coupling agent

In order to improve the water vapor permeability and mechanical properties of latex films, polysiloxane/polyacrylate (PSi/PA) composite latexes were fabricated via seeded emulsion polymerization of methyl methacrylate and butyl acrylate onto PSi latex particles, and the effects of the silane coupling agent 3-methacryloyloxypropyl trimethoxysilane (MATS) on the morphologies of the latex particles and films, as well as the microphase separation degree, the water vapor permeability and the mechanical properties of the latex films were investigated. Results indicated that MATS was essential for obtaining the PSi/PA composite latex particles with PSi as core and PA as shell and made a great contribution to restrict the phase separation. The PSi/PA core/shell latex films showed similar tensile strength and elongation with pure PA film, while exhibiting promising water vapor permeability. It was found that the influences of MATS content on the water vapor permeability and mechanical properties were opposite, and on the premise of the requirements for mechanical properties, lower MATS content could provide the PSi/PA core/shell latex films with better water vapor permeability.     

Synthesis and characterization of poly(butyl acrylate)/silica and poly(butyl acrylate)/silica/poly(methyl methacrylate) composite particles

Poly(butyl acrylate)/poly(methyl methacrylate) (PBA/PMMA) core–shell particles embedded with nanometer‐sized silica particles were prepared by emulsion polymerization of butyl acrylate (BA) in the presence of silica particles preabsorbed with 2,2′‐azobis(2‐amidinopropane)dihydrochloride (AIBA) initiator and subsequent MMA emulsion polymerization in the presence of PBA/silica composite particles. The morphologies of the resulting PBA/silica and PBA/silica/PMMA composite particles were characterized, which showed that AIBA could be absorbed effectively onto silica particles when the pH of the dispersion medium was greater than the isoelectric potential point of silica. The critical amount of AIBA added to have stable dispersion of silica particles increased as the pH of the dispersion medium increased. PBA/silica composite particles prepared by in situ emulsion polymerization using silica preabsorbed with AIBA showed higher silica absorption efficiency than did the PBA/silica composite particles prepared by direct mixing of PBA latex and silica dispersion or by emulsion polymerization in which AIBA was added after the mixing of BA and silica. The PBA/silica composite particles exhibited a raspberrylike morphology, with silica particles “adhered” to the surfaces of the PBA particles, whereas the PBA/silica/PMMA composite latex particles exhibited a sandwich morphology, with silica particles mainly at the interface between the PBA core and the PMMA shell. Subsequently, the PBA/silica/PMMA composite latex obtained had a narrow particle size distribution and good dispersion stability. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3425–3432, 2006     

Synthesis and characterization of core/shell ionomeric latexes. I. Latex and film properties

This research work involved studies on the synthesis and characterization of core/shell ionomeric latexes in order to understand the process of ionic aggregate formation. The core/shell structure of the ionomeric latexes prepared in this study confines the ionic domains to the copolymeric matrix within the shell polymer, and in addition, benefits from the ionomeric properties and core/shell structure simultaneously. Core/shell ionomeric latexes with polystyrene cores and styrene/n-butyl acrylate/methacrylic acid terpolymer shells were synthesized by a semicontinuous seeded emulsion copolymerization process. The distribution of the methacrylic acid in the core/shell latexes was determined using conductometric titration techniques. The results of the conductometric titration analysis indicate that the principal locus of the carboxyl groups in the core/shell latexes is at the particle surface, but specific information about the differences in the distribution of methacrylic acid inside the latex particles could not be obtained. Mechanical characterization of the core/shell ionomeric latex films was carried out to understand the structure-property relationships using Dynamic Mechanical Analysis (DMA) and tensile testing. It was discovered that the core/shell latexes exhibited significantly different properties, owing to the differences in the overall carboxyl content and surface loading. Extensive studies were carried out to study the effect of water plasticization on the mechanical behavior of the core/shell ionomeric latex films; water adsorption causes the solvation of ionic aggregates. A preliminary investigation of the effect of the type of counterion used for the neutralization of carboxyl groups on the properties of core/shell ionomeric latex films was also carried out. © 1995 John Wiley & Sons, Inc.     

中空聚合物微球的制备——酸含量的影响

采用预乳化滴加工艺结合多段乳液聚合方法先制备聚(甲基丙烯酸甲酯-丙烯酸丁酯-甲基丙烯酸)/聚(苯乙烯-甲基丙烯酸)核壳乳液,随后以碱/酸溶胀处理得到了单分散性优异且中空度为30%的中空聚合物微球.以动态光散射(DLS)、透射电子显微镜(TEM)和场发式扫描电子显微镜(FESEM)等对各阶段乳液聚合的胶粒大小和分布以及形态结构进行了表征.实验考察了种子酸含量对种子和核壳乳胶的特性以及中空聚合物微球形态的影响规律.结果表明,种子制备时的酸用量以30%～35%为宜,核壳胶粒中约85%的酸单元存在于核聚合物内部.另外,探讨了核壳胶粒在碱/酸溶胀处理过程中的中空形成机理.     

Particle size and shell composition as effective parameters on MFFT for acrylic core–shell particles prepared via seeded emulsion polymerization

In this study, acrylic-based copolymer particles were prepared with core–shell morphology and the effect of T_g of the shell, particle size and their bimodal size distribution on minimum film formation temperature (MFFT) were investigated. The main goal was to optimize conditions to obtain latexes with low MFFT and appropriate mechanical properties. These will develop the applicability of such water-borne binders as paints and coatings at ambient conditions. A series of latexes with core–shell morphology with variable T_g of the shell from −56 to 30 °C were prepared and the MFFT, hardness and thermal behavior of the obtained films were studied. Then a series of latexes with particle sizes ranging from 46 to 960 nm were prepared and the effect of particle size on MFFT was studied too. By inducing the formation of secondary nucleation during emulsion polymerization, latexes with bimodal size distribution were obtained and the effect of presence of such particles on film formation was investigated. Results indicate that latexes with appropriate composition and bimodal particle size distribution lead to optimized performance in both mechanical and film formation properties as a proper choice for water-borne coatings.     

松香改性丙烯酸酯乳液的合成及其在PVC地板胶的应用

采用半连续种子乳液聚合的方法制备了一种具有核壳结构的松香树脂改性PVC地板胶用丙烯酸酯聚合物乳液,讨论了松香树脂质量分数、松香树脂加入方式、核壳质量比等因素对聚合物乳液性能的影响。结果表明,当松香树脂质量分数为2%,核壳单体的质量比为1∶2时,乳液的初黏性(#33)达到1.3 cm,粘接强度达到0.32 MPa。     

Effect of ethyleneglycol dimethacrylate crosslinker on the performance of core‐double shell structure poly(vinyl acetate‐butyl acrylate) emulsion

Core‐double shell structure poly(vinyl acetate‐butyl acrylate) emulsion was prepared by semicontinuous emulsion polymerization, and the effects of ethyleneglycol dimethacrylate crosslinker (EGDMA) on the emulsion particle structure and film performance were studied systematically. The emulsion particles' structure was characterized by transmission electron microscopy and Fourier transform infrared spectroscopy, and the particle size and distribution were characterized by Zeta potential—particle analyzer, as well as analysis of the film mechanical properties, water resistance, thermal properties, and so on. The results show that, when 0.1 and 0.5% EGDMA were added to the inner‐shell and outer‐shell reaction stage under the core‐double shell P(VAc‐BA) emulsion preparation process, respectively, it led to a more clear core‐double shell structure and a larger particle size (about 500–800 nm) of emulsion particles, and the comprehensive performance of the P(VAc‐BA) emulsion showed better. This work provided some insight into modifying the surface properties of the emulsion particles, which may expand the application field of the emulsion. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41899.     

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。     

自交联封闭性乳液的合成与性能

以双丙酮丙烯酰胺（DAAM）、甲基丙烯酸甲酯（MMA）、丙烯酸丁酯（BA）和甲基丙烯酸（MAA）为共聚单体,采用半连续种子乳液聚合工艺合成自交联封闭性聚丙烯酸酯乳液（PAE）,考察了DAAM和复合乳化剂对乳液聚合稳定性以及涂膜性能的影响。研究发现：随着DAAM含量的增加,乳液聚合稳定性下降,粒径增大,涂膜的耐介质性能和交联度提高,合适的DAAM加入量为总单体质量的3.0%,DAAM和己二酰肼(ADH)的最佳摩尔比为2∶1。采用SDBS+OP-10+OP-40为复合乳化剂体系,选用乳化剂的含量为2.35%,阴/非离子乳化剂质量比为1∶1.25;复合乳化剂在种子、核、壳比例为1.5∶1∶2,制备的乳液具有较好的聚合稳定性（乳液凝胶率低和单体转化率高）,乳液耐电解质（钙离子）稳定性好,涂膜具有优异的封闭性。傅里叶红外光谱（FTIR）表明在涂膜形成过程中DAAM的酮羰基与ADH的酰肼基反应生成腙（C=N）,TEM分析显示乳液的乳胶粒子呈核壳结构,TGA分析发现DAAM改性的PAE降低了涂膜的热稳定性。     

Investigation of the effect of molar mass on coating properties of self-crosslinking latexes based on acrylic microgels

The effect of reducing the molar mass of the shell layer of core–shell latex particles on film-forming and final coating properties of self-crosslinking latexes was investigated. Latex particles were prepared by the semi-continuous non-seeded emulsion polymerization of methyl methacrylate, butyl acrylate and methacrylic acid as main monomers. The particle core was slightly cross-linked (using a constant amount of allyl methacrylate as a comonomer) to prevent the copolymers forming the core phase from migration into the shell phase. For interfacial cross-linking, diacetone acrylamide was copolymerized into the shell layer of latex particles to provide sites for subsequent reaction with adipic acid dihydrazide. The molar mass of copolymers forming the shell layer was systematically varied by isooctyl 3-mercaptopropionate chain transfer agent included in the synthesis of each of the shell layers and the molar mass distribution was determined using size exclusion chromatography coupled with a multi-angle light scattering detection. Fundamental properties of latexes and cast films were systematically compared. These properties included minimum film-forming temperature, pendulum hardness, adhesion, impact resistance, stress–strain properties as well as the characterization of water absorption. The results confirmed theoretical predictions and described empirically the effects of reducing the molar mass of the shell layer copolymer on final properties of coating films.