Preparation of monodispersed hollow polymer particles by seeded emulsion polymerization under low emulsifier conditions

In a low emulsifier system, the MMA‐BA‐MAA copolymer emulsions were prepared as seed latices and the seeded emulsion polymerization of MMA‐MAA‐DVB was consequently carried out to prepare carboxylated core particles. The hydrophobic shell was then synthesized onto the core using styrene, acrylonitrile, and divinylbenzene as comonomers. The hollow latex particles were obtained by alkalization treatment of the core‐shell latex particles. The effects of the feeding rate of monomer mixture, contents of emulsifier SDBS and crosslinking agent DVB, and ratio of the monomers during the core stage and shell stage on the morphology and volume expansion of the latex particles were investigated. The results show that the monodispersed hollow latex particles with large size can be obtained when the feeding rate is 0.1 g/min, SDBS content is 0.15 and 0.2 wt % during the core stage and shell stage, respectively, DVB contents are 1% during the preparation of shell copolymers, and the monomer ratio of the core particle to shell layer is 1 : 8. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1505–1510, 2005     

Attapulgite@polymer particles with double‐layer polymer shell via soapless seeded emulsion polymerization

Attapulgite needle encapsulated with double‐layer polymer shell (ATP@DP) were prepared by the soapless seeded emulsion polymerization of the second monomer styrene in the dispersion of the attapulgite needle encapsulated with poly(methyl methacrylate) (ATP@PMMA), which was also conducted by the soapless seeded emulsion polymerization of the first monomer methyl methacrylate with the cetyltrimethylammonium bromide (CTAB) modified attapulgite needle (org‐ATP) as seeds. The different morphologies of ATP, ATP@PMMA particles, and ATP@DP particles were characterized by transmission electron microscopy, and the encapsulation mechanism was also discussed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation of small-sized carboxylated latexes by emulsion polymerization using alkali-soluble random copolymer

Alkali-soluble random copolymer (ASR), poly(styrene/α-methylstyrene/acrylic acid) [M_n: 4,300; acid number: 190], was used as a polymeric emulsifier in the emulsion polymerization of styrene and methyl methacrylate, respectively. ASR containing a large number of carboxyl groups could form aggregates like micelles, and the solubilization ability of the aggregates was dependent on the neutralization degree of ASR. The polystyrene latexes prepared using ASR showed the small particle size (ca. 40 nm) and monodispersed particle size distribution. On the other hand, the particle size distribution of poly(methyl methacrylate) latexes became broader as the neutralization of ASR increased. This could be explained by the effects of water solubility of the monomer and the neutralization degree of ASR on particle formation. Thin layer chromatography/flame ionization detector analysis confirmed that the grafting reaction of polystyrene to ASR occurred during emulsion polymerization. The ζ potentials of final latexes showed high values due to ASR that was adsorbed and grafted on the surface of the latex particle. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 543–550, 1998     

Preparation and structure control of hollow polymer particles: Influence of seeded emulsion polymerization and alkalization treatment process

Hollow polymer latex particles containing a hydrophilic core were prepared by seeded emulsion polymerization with MAA/BA/MMA/St as comonomers, followed by stepwise alkalization treatment with ammonia. The size and morphology of composite latex particles was determined by TEM. The effects of the seeded emulsion polymerization conditions and alkalization treatment on the size and hollow structure of latex were investigated. The results showed that the optimum content of crosslinking agent in the shell polymers was about 0.5–1.0 wt %, emulsifier was about 0.8–1.1 wt %, and the core/shell weight ratio was 1/7. To obtain uniform hollow latex particles with large size, the starved feeding technique should be adopted in seeded emulsion polymerization, and the neutralization temperature should equal to the T_g of the shell polymer. Then, the obtained polymer particles under this condition had an excellent hollow structure. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation of PBAS core-shell structured polymer by seeded emulsion polymerization and investigation in AS resin toughness

The preparation of poly(n-butyl acrylate)/poly(acrylonitrile-co-styrene), i.e., poly(BA)/poly(AN-co-St) (PBAS) core-shell structured modifier with controlled particle size was reported, and the mechanical properties of AS/PBAS blends were investigated. The modifier was prepared at a solid content of 50 wt % by a two-stage sequential emulsion polymerization. Dynamic light scattering (DLS) was used to monitor the particle diameters and showed that the particles grew without significant secondary nucleation occurring. The morphology was confirmed by means of transmission electron microscopy (TEM). According to the research on mechanical properties of the AS/PBAS blends, a remarkable toughening effect of PBAS on AS resin was found. By means of scanning electron microscopy (SEM) observation, the toughening mechanism was proposed to be crazing caused by rubber particles and shear yielding of AS matrix. Uniform dispersion of rubber particles in AS matrix was attributed to the good compatibility between AS and PBAS modifier. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Internal stress of epoxy resin modified with acrylic core-shell particles containing functional groups prepared by seeded emulsion polymerization

In order to reduce the internal stress in a cured epoxy resin, submicrometer-sized poly(butyl acrylate) (PBA)/poly(methyl methacrylate) (PMMA) core-shell particles having cross-links were dispersed in the resin prior to curing. For the introduction of cross-links, monoethylene glycol dimethacrylate or glycidyl methacrylate monomer was copolymerized. Cross-links in the PBA core reduced the shrinkage of the cured epoxy resin, and cross-links at the PMMA shell produced a strong interaction with the epoxy matrix. The internal stress was reduced effectively by the introduction of cross-links.     

Preparation of sub-micron colored particles by controlled emulsion polymerization

Colored particles of poly(methyl methacrylate-co-ethylene glycol dimethacrylate) containing three different kinds of dye including Sudan black, Sudan red 7B and Oil blue N were made by emulsion polymerization. In an effort to find a way to prepare particles with size less than 100 nm with the maximized dye content, methanol is added either to the initial reaction media or during the polymerization. It was found that adding methanol is very efficient way to improve the dye incorporation efficiency while maintaining particle sizes less than 100 nm. By properly choosing methanol addition strategy, the dye content inside of particle could be increased up to four or five times and it was found that the optimum strategy of methanol addition is clearly depending on the nature of dye.     

Preparation of polymer solutions which are free of suspended mechanical particles

Conclusions -- A method of preparing low-concentration polymer solutions which are free of suspended particles in measurements of the molecular characteristics by the light-scattering method has been described.-- The system presented permits one to prepare such solutions directly in the measuring cuvette with monitoring of the concentration and size of residual particles simultaneously with the clean-up.-- Kinetic dependences of concentration and of mean residual particle size on duration of clean-up have been obtained.Translated from Khimicheskie Volokna, No. 5, pp. 3–5, September–October, 1990.     

Liquid exclusion chromatography. A technique for monitoring the growth of polymer particles in emulsion polymerization

An experimental investigation of the growth of polymer particles in the emulsion polymerization of styrene and of vinyl acetate is reported. The growth of polymer particles in the size range of 200–6500 Å was monitored by liquid exclusion chromatography (LEC). This relatively new analytical technique permits very rapid analysis for particles as small as 200 Å and should prove extremely useful as an online monitor of polymer particle size for the control of latex reactors.     

Preparation of multi-responsive amphiphilic particles by one-step soapless emulsion polymerization

A novel multi-responsive amphiphilic copolymer (mRAP) particles with tunable emulsifiability was successfully prepared via one-step soapless emulsion polymerization using common monomers, such as methyl methacrylate, methacrylic acid (MAA), butyl acrylate (BA) and N,N-diethylacrylamide (DEAA). The obtained monodisperse spherical mRAP particles were characterized by dynamic light scattering, Fourier transform infrared spectroscopy, scanning electron microscope and transmission electron microscope, which provided the information of particle size, components and anisotropic structure. Its multiple responsivities were investigated under the condition of diversified pH values, salinity and temperature. The results showed that the mRAP particles exhibited good dispersivity based on uniform particle size, as well as tunable emulsifiability and anticipated multiple responsiveness. Furthermore, the tunable emulsifiability of oil–water mixtures could be easily achieved by adjusting the mass ratios of MAA to DEAA. Meanwhile, the obtained multi-responsive polymers relying on simple and effective copolymerization can be used in fundamental research and industrial production.     

Internal stress of epoxy resin modified with acrylic core-shell particles prepared by seeded emulsion polymerization

In order to reduce the internal stress in a cured epoxy resin, the submicron polymer particles were dispersed therein prior to curing. For this purpose, four kinds of poly(butyl acrylate), poly(methyl methacrylate) core-shell particles were prepared by seeded emulsion polymerization for methyl methacrylate with poly(butyl acrylate) seed particles having different particle diameter, and subsequently were powdered by drying at room temperature. It was observed by SEM that poly(butyl acrylate) particles as core were dispersed in the cured epoxy matrix. Poly(methyl methacrylate) as shell seems to dissolve in the matrix. The internal stress of cured epoxy resin decreased with the modification of the particles and the tendency was enhanced with a decreasing in the particle diameter.     

Preparation and characterization of titanium dioxide core/polymer shell hybrid composite particles prepared by emulsion polymerization

Titanium dioxide inorganic core and polymer shell composite poly(methyl methacrylate‐co‐butylacrylate‐co‐methacrylic acid) [P(MMA‐co‐BA)‐MAA] particles were prepared by emulsion copolymerization. Fourier transform IR (FTIR) spectroscopy was used to measure the content of MAA composite particles. Dynamic light scattering (DLS) characterized the composite particle size and size distribution. The field emission SEM (FE‐SEM) results of the composite particles showed regular spherical shape and no bare TiO₂ was detected on the whole surface of the samples. The composite particles were produced, showing good spectral reflectance compared with bare TiO₂. TGA results indicated the encapsulation efficiency and estimated density of composite particles. Encapsulation efficiency was up to 78.9% and the density ranged from 1.76 to 1.94 g/cm³. Estimated density of the composite particles is suitable to 1.73 g/cm³, due to density matching with suspending media. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2970–2975, 2004     

Formation mechanism of silicone rubber particles with core–shell structure by seeded emulsion polymerization

Silicone rubber particles with core–shell structure were prepared by polymerization of vinyl monomers in the presence of crosslinked and linear poly(dimethyl siloxane-methyl vinyl siloxane) latex. The monomers were added with either continuous or swelled-continuous addition mode. The core–shell morphology of silicone rubber/polystyrene [PST] and silicone rubber/poly(methyl methacrylate-divinyl benzene) [P(MMA-DVB)] composite particles were obtained. The effects of monomer addition mode, the compatibilities of the monomers or their homopolymer with silicone rubber, and the reactivity of polysiloxane with vinyl monomers on the formation of the core–shell structure were discussed. © 1996 John Wiley & Sons, Inc.     

乳液法制备聚合物纳米粒子的研究进展

综述了乳液法制备聚合物纳米粒子的研究进展,详细介绍了采用新型乳化剂,即高分子表面活性剂与反应性表面活性剂,和以超声波辐照技术为主的新技术制备聚合物纳米粒子方面的研究成果。     

Particle coagulation at semicontinuous emulsion polymerization. II. Characterization of surface groups

Semicontinuous emulsion polymerization of acrylic monomers with a monomer emulsion feed has been investigated. The amount of coagulum appearing during the polymerization under conditions of insufficient covering of particle surface by emulsifier was studied from the point of view of particle surface charge. Increasing the surface group concentration via copolymerization of butyl acrylate with acrylic acid or sulfoethyl methacrylate caused increased colloid stability of the system and a rapid decrease in coagulum formation. It was established that during the polymerization acid hydrolysis of ester groups took place, which caused an increase in the carboxyl groups concentration at the particle surface. These carboxyl groups contribute to the colloid stability of the polymerizing system.     

Preparation and characterization of polyacrylate/polymerized rosin composite emulsions by seeded semicontinuous emulsion polymerization

Polyacrylate/polymerized rosin composite emulsions were prepared by seeded semicontinuous emulsion polymerization of acrylate monomers in which polymerized rosin was dissolved. The effects of polymerized rosin content on the polymerization stability, monomer conversion, polymer structure, and adhesive properties were studied. Polyacrylate/polymerized rosin composites were characterized by gel permeation chromatograph (GPC), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and thermogracvimetry (TG). The results showed that with an increase of polymerized rosin content from 0 to 6 wt %, gel fraction and sol molecular weight decreased obviously but monomer conversion was basically unchanged. In contrast, with a further increase of polymerized rosin content, the decreasing rates of gel fraction, and sol molecular weight were slowed down. Meanwhile, monomer conversion decreased remarkably. Moreover, interface failure changed into cohesive failure after the addition of polymerized rosin, and the peel adhesion and shear resistance of composite latex films declined with the increase of polymerized rosin content. Thermal analysis showed that polymerized rosin and polyacrylate were compatible and the composite latex films had good thermal stability. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Study of the preparation of silicone rubber particles with core–shell structure by seeded emulsion polymerization

Silicone rubber particles with core–shell structure were prepared by polymerization of vinyl monomers in the presence of linear or cross-linked poly(dimethyl siloxane–methyl vinyl siloxane) latexes. The monomers were added in either continuous or swelled-continuous modes. Core–shell particles with poly(butyl methacrylate), or poly(methyl methacrylate), as the shell were obtained by using either addition mode. The core–shell structure was not observed for polysiloxane–polystyrene particles. The influence of monomer addition mode, the compatibilities of the monomers and their homopolymers with silicone rubber, and the reactivity ratios of the vinyl monomers with the vinyl group of linear polysiloxane particles, on the formation of the core-shell structure is discussed.     

Preparation of monodispersed polymer-modified silica particles by radical polymerization using silica colloid and introduction of functional groups on the composite surface

Summary Radical polymerizations of vinyl monomers using a initiator of 2,2-azobis(2-amidinopropane) dihydrochloride on monodispersed silica colloid led to formation of spherical polymer/SiO₂ composites, retained particle size. Addition of hydroxypropyl cellulose to the reaction system resulted in yielding excellent dispersible composites into ethanol by short period ultrasonic irradiation. The polymerization of styrene in the presence of mercapto-amine or carboxylic acid derivatives could successfully introduce amino or carboxyl group on the Poly(styrene)/SiO₂ composite.     

Enhancing formation and retention of hollow structural integrity through intermediate and outermost layer design in seeded emulsion polymerization of hollow latex particles

The synthesis of hollow latex particles through seeded emulsion polymerization involves a series of intricate steps, including the formation of distinct polymer layers with specific properties. Despite extensive research, preserving the desired hollow structure remains challenging due to the unclear role of the encapsulating polymer layers. This study systematically adjusts the glass transition temperature (T_g) of the intermediate layer by varying the butyl acrylate (BA) ratio in the monomer feed mixture. By controlling the reaction temperature during alkali swelling, we explore the critical influence of T_g on hollow latex particle formation from carboxylated core latex particles. To ensure long-term hollow structure retention after drying, a rigid outer layer is polymerized onto the intermediate layer. Surprisingly, higher divinylbenzene (DVB) mass ratios (5.0 and 10.0 wt%) do not result in a highly crosslinked hollow shell due to DVB self-nucleation. This paper emphasizes the importance of precise design parameters for both intermediate and outermost layers in achieving and maintaining hollow latex particle structures. Understanding each layer's role and optimizing their compositions contribute to advancing hollow latex particle synthesis through seeded emulsion polymerization.