Estimation of morphology of composite polymer emulsion particles by the soap titration method

The occupied area (A_m) of a sodium dodecyl benzene sulfonate molecule adsorbed on particles was measured by the soap titration method. The A_m values are 214, 133, and 53 Ų for poly(methyl acrylate) (I), poly(methyl methacrylate) (II), and polystyrene (III), respectively. For methyl metharylate-styrene copolymer emulsions the additivity was established between the A_m value and copolymer composition. Composite emulsion particles consisting of I/II, I/III, and II/III were prepared by seeded emulsion polymerization. For these emulsions the relationship between polymer composition at the surface layer calculated from the A_m value and that in a particle calculated from the polymerization process was investigated. This relationship is remarkably affected by the order of polymerization, the hydrophilicity of polymer, the flexibility of the seed polymer, and the monomer addition method. The models of the morphology of these composite particles explain the results successfully.     

The morphology of composite polymer particles produced by multistage soapless seeded emulsion polymerization

 Composite polymer particles which contain poly(methyl methacrylate) (PMMA) and polystyrene (PS) components (PMMA/PS composite particle) were synthesized by the method of multistage soapless seeded emulsion polymerization. In this study, the process of multistage soapless seeded emulsion polymerization included two-stage polymerization, three-stage polymerization or four-stage polymerization. The morphologies of the PMMA/PS composite particles were studied. The kinetic factor was the main force to control the morphology of the linear PMMA–PS composite particles which were synthesized by the method of two-stage reaction. Both the kinetic factor and the thermodynamic factor decide the morphology of the linear composite particles which were synthesized by the method of either three-stage or four-stage reaction. However, the thermodynamic factor cannot influence the morphology of the PMMA/PS composite particles with a cross-linked structure which were synthesized by the method of three-stage reaction. The cross-linked composite polymer particles had the morphology of a multilayer structure, which showed that the polymer layers accumulated in their order of production. Received: 9 January 2001 Accepted: 14 June 2001     

Reconstruction of morphology of micron-sized,monodisperse composite polymer particles by the solvent-absorbing/releasing method

Micron-sized, monodisperse polystyrene (PS)/poly(n-butyl methacrylate) (PBMA) (2/1 w/w) composite particles having different morphologies were prepared by the solvent-absorbing/releasing method (SARM). There was an obvious influence of the releasing rate of toluene from the toluene-swollen composite particles on the reconstructed morphology by the SARM. In the case of fast release, the reconstructed morphology was a bicontinuous structure that is similar to that formed by spinodal decomposition. On the other hand, in the case of slow release, a hemispherical structure was formed that consisted of PS and PBMA phases.Part CCLIV of the series Studies on Suspension and Emulsion     

Influence of particle diameter on the morphology of micron-sized, monodispersed composite polymer particles produced by seeded polymerization for the dispersion of highly monomer-swollen polymer particles

 Micron-sized, monodispersed polystyrene (PS)/poly (n-butyl methacrylate) (PBMA) composite particles, in which the PS domain(s) were dispersed in a PBMA continuous phase, were produced by seeded polymerization for dispersions of n-butyl methacrylate (BMA) swollen PS particles in a wide range of PS/BMA ratios in the presence of NaNO₂ as a water-soluble inhibitor. Moreover, in order to change the diameter of the composite particles at same PS/BMA ratio, PS/PBMA (1/150 w/w) composite particles were produced using five kinds of PS particles in a range of diameters from 0.64 to 3.27 μm as seeds. The percentages of the PS/PBMA composite particles having double and triple and over PS domains, which were thermodynamically unstable morphologies, increased with the increase in the diameter of BMA swollen PS particles. There was a clear influence of the size of the swollen particles on the morphology of the PS/PBMA composite particles produced. Received: 30 September 1999/Accepted: 18 April 2000     

Synthesis of temperature-sensitive submicron-size composite polymer particles

Temperature-sensitive composite polymer particles were prepared by seeded emulsion copolymerization of dimethylaminoethyl methacrylate and ethylene glycol dimethacrylate with 0.17 m-sized monodispersed polystyrene seed particles. The adsorption and desorption behaviors of low molecular weight cationic emulsifier as well as albumin were examined to determine the variation of surface properties as a function of temperature below and above 35°C.     

Influence of viscosity within polymerizing particle on the morphology of micron-sized,monodisperse composite polymer particles produced by seeded polymerization for the dispersion of highly monomer-swollen polymer particles

Micron-sized, monodisperse polystyrene (PS)/poly( n-butyl methacrylate) (PBMA) composite particles, in which PS domain(s) were dispersed in a PBMA continuous phase, were produced by seeded polymerization for the dispersion of highly n-butyl methacrylate (BMA)-swollen PS particles (PS/BMA=1/150, w/w) using various concentrations of benzoyl peroxide as initiator in the absence/presence of sodium nitrite (NaNO ₂) as a water-soluble inhibitor. The percentages of the composite particles having double, triple and over PS domains, which were thermodynamically unstable morphologies, increased with a rapid increase of viscosity within the polymerizing particle.     

Preparation and thermodynamic stability of micron-sized, monodisperse composite polymer particles of disc-like shapes by seeded dispersion polymerization

Micron-sized, monodisperse composite polymer particles having "disc-like" and "polyhedral" shapes were prepared by seeded dispersion polymerization of 2-ethylhexylmethacrylate (EHMA) with 2.67-mum-sized polystyrene (PS) seed particles in methanol/water media in the presence of droplets of various saturated hydrocarbons and evaporation of the hydrocarbon after the polymerization. Such nonspherical shapes were based on the volume reduction due to the evaporation. The primary factors influencing the particle shape seemed to be the absorption rate of the hydrocarbon into the resulting PS/poly(EHMA)/hydrocarbon composite particles during the polymerization, which affected the viscosities and the volumes of the PS and poly(EHMA) phases. It was found that the morphological development during the polymerization was retarded at "hamburger-like" morphology, which is a precursor of the disc-like particle, although this morphology is a thermodynamically metastable state.     

Estimation of surface morphology of composite polymer particles prepared by the stepwise heterocoagulation method with ζ-potential measurement

 Core-shell composite polymer particle was prepared by the stepwise heterocoagulation of cationic small polymer particles (SPs) onto an anionic large polymer particle (LP), following heat treatment at temperatures which were higher than glass transition temperature (T _g=18 °C) of SP. At pH 9 ζ-potential of the hetero-coagulated particle (HP) was negative, but it changed to positive by the heat treatment and increased with the treatment time and finally attained to that of SP. The treatment time to attain the ζ-potential of SP became short by elevating the treatment temperature. This indicates that during the heat treatment, SP continued to melt on the surface of LP and finally formed a continuous shell. Received: 3 September 1997 Accepted: 29 October 1997     

Dynamic modeling of the morphology of multiphase waterborne polymer particles

Multiphase waterborne polymer particles provide advantages in more demanding applications, and their performance depends on particle morphology. Currently, no dynamic model for the prediction of the development of the morphology of multiphase latex particles is available. In this work, a model was developed for the prediction of the dynamic development of the morphology of multiphase waterborne systems, such as polymer–polymer and polymer–polymer–inorganic hybrids.     

Influence of the swelling state of seed polymer particles with monomer on the morphology of micron-sized monodispersed composite polymer particles produced by seeded polymerization utilizing the dynamic swelling method

 Micron-sized mono-dispersed polystyrene (PS)/poly(n-butyl methacrylate) (PBMA) composite particles (PS/PBMA=2/1 by weight) having a heterogeneous structure in which many fine PBMA domains dispersed in a PS matrix near the particle surface were produced by seeded polymerization of n-butyl methacrylate (BMA) of which almost all had been absorbed by 1.8 μm-sized monodispersed PS seed particles utilizing the dynamic swelling method. The morphology was varied by changing the PS/BMA ratio and polymerization temperature. It was concluded that the swelling state of 2 μm-sized BMA-swollen PS particles in the seeded polymerization process is one of the important factors to control the morphology of the composite particles. Received: 27 November 1996 Accepted: 21 March 1997     

Effects of surfactants on the morphology of composite polymer particles produced by two‐stage seeded emulsion polymerization

Poly(methyl methacrylate) (PMMA)–polystyrene (PS) composite polymer particles were synthesized in the presence of a surfactant by two‐stage seeded emulsion polymerization. The first stage was the synthesis of PMMA particles by soapless emulsion polymerization; the second stage was the synthesis of the PMMA–PS composite polymer particles with the PMMA particles as seeds. In the second stage of the reaction, three kinds of surfactants—sodium laurate sulfate (SLS), polyoxyethylene (POE) sorbitan monolaurate (Tween 20), and sorbitan monolaurate (Span 20)—were used to synthesize the PMMA–PS composite particles. Both the properties and concentrations of the surfactants influenced the morphology of the composite particles significantly. Core–shell composite particles, with PS as the shell and PMMA as the core, were synthesized in the presence of a low concentration of the hydrophilic surfactant SLS. This result was the same as that in the absence of the surfactant. However, a low concentration of Tween 20 led to composite particles with a core/strawberry‐like shell morphology; the core region was a PS phase, and the strawberry‐like shell was a PS phase dispersed in a PMMA phase. With an increase in the concentration of SLS, the morphology of the composite particles changed from core (PMMA)–shell (PS) to core (PS)–shell (PMMA). Moreover, the effects of a high concentration of Tween 20 or Span 20 on the morphology of the PMMA–PS composite particles were investigated in this study. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2224–2236, 2005     

Practical methods to control morphology of heterogeneous polymer particles

This review focusses on processes in which emulsion polymerizations are carried out in stages so that previously formed particles are either overcoated in subsequent polymerization stages or engulf the second and later stage polymers. These products are often called “core-shell” particles. Basically, the most stable state of the final system is the one with the lowest net interfacial energy. In the case of a two-stage emulsion polymerization there can be three interfacial tensions to consider. Several mutually consistent, effective thermodynamic treatments have been published. At present, they serve primarily to predict when the morphology of multi-stage polymerization products may not be a simple reflection of the synthesis sequences. It is possible, and frequently desirable, however to produce particle structures that appear at first glance to be thermodynamically forbidden. This is achieved either by changing the surface characteristics of a polymer from those of the bulk material or by employing kinetic factors to anchor energetically unprofitable morphologies. This paper summarizes methods of both types that have been reported to control the texture of structured latex particles in order to produce designed morphologies.     

Morphology of micron-sized monodispersed composite polymer particles produced by seeded polymerization for the dispersion of highly monomer-swollen polymer particles

 Monodispersed polystyrene (PS)/poly(n-butyl methacrylate) (PBMA) composite particles having 9.4 μm in diameter were produced by seeded polymerization for the dispersion of highly n-butyl methacrylate (BMA)-swollen PS particles, and their morphologies were examined. The highly BMA-swollen PS particles (about 150 times the weight of the PS seed particles) were prepared by mixing monodispersed 1.8 μm-sized PS seed particles and 0.7 μm sized BMA droplets prepared with an ultrasonic homogenizer in ethanol/water (1/2, w/w) medium at room temperature. After NaNO₂ aqueous solution as inhibitor was added in the dispersion, the seeded polymerization was carried out at 70 °C. In an optical microscopic observation, one or two spherical high contrast regions which consisted mainly of PS were observed inside PS/PBMA composite particles. In the PS domain, there were many fine spherical PBMA domains. Such morphologies were based on the phase separation of PS and PBMA within the homogeneous swollen particles during the seeded polymerization. Received: 04 June 1997 Accepted: 27 August 1997     

Formation of multihollow structures in crosslinked composite polymer particles

Micron-size monodisperse polymer particles having multihollow structures were prepared as follows. First, micron-size monodisperse polystyrene/poly(styrene-divinylbenzene) (PS/P(S-DVB)) composite particles were produced by seeded copolymerization of S and DVB with 2,2-azobisisobutyronitrile as an initiator in the ethanol/water (76/24, weight ratio) medium in the presence of 2.37 m-size monodisperse PS seed particles produced by dispersion polymerization. The molar ratio of S/DVB was changed in the range of 1/110/1. The uncrosslinked polymer within the composite particles was extracted with toluene under reflux. For the highest DVB content (S/DVB=1/1, molar ratio), one large hollow was observed in a part of the composite particles after the extraction. For the middle DVB content (S/DVB=4/1, molar ratio), multihollow structure was observed in all the particles. For the lowest DVB content (S/DVB=10/1, molar ratio), fine multihollow structure was observed in all the particles.Part CXLIII of the series Studies on Suspension and Emulsion     

Enzymatic activity of trypsin adsorbed on temperature-sensitive composite polymer particles

Two kinds of temperature-sensitive composite polymer particles were prepared by seeded emulsion copolymerizations of (dimethylamino)ethyl methacrylate and ethylene glycol dimethacrylate with 0.14 μm-sized polystyrene and 0.26 μm-sized poly(methylmethacrylate) seed particles. To evaluate the usefulness as a carrier for biomolecules, the enzymatic activities of trypsin adsorbed on these two composite polymer particles were measured at temperatures above and below each lower critical solution temperature (LCST). In both cases, adsorbed trypsin retained its enzymatic activity during repeated adsorption/desorption measurements. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 883–888, 1998     

A thermodynamic analysis on the coincidence of extrema conditions in the sorption equilibrium for ternary polymer systems

Flory-Huggins theory of polymer solutions has been used to express the condition of extrema values in the total sorption, as well as the inversion point in the preferential adsorption parameters for termary polymer systems. Two approaches have been followed, the first considers the binary and ternary interaction parameters independent of polymer concentration and solvent composition. In the second one, this dependence has been introduced. Our attention is focused on the volume fraction of solvent mixture dependence of the above parameters, in order to confirm or not the coincidence between the extrema values and the inversion point. Several cosolvent and cononsolvent ternary polymer systems, have been used to test the validity of the equations obtained. Also, it has been verified, from an experimental point of view, that in cosolvent ternary polymer systems there is coincidence in both compositions while in cononsolvent ternary polymer systems, such coincidence does not appear.     

Colloid thermodynamic effect as the universal driving force for fabricating various functional composite particles

The design and fabrication of functional nanocomposites is an active area of research because composite particles have significantly improved physical and chemical properties over those of their single-component counterparts. Traditionally, chemical pretreatments of the components were used to enhance their physicochemical or chemical interactions. Here, we propose a novel approach to taking advantage of the beauty of thermodynamics. A series of functional materials, including graphene nanosheets, carbon nanotubes, noble metals, magnetic materials, conducting polymers, attapulgite, and etc. were incorporated with polystyrene particles by a thermodynamic driving force. This unique approach is facile and versatile and shows the considerable significance of developments in both scientific methodology and particle engineering.     

Effect of shell thickness on the temperature-sensitive property of core-shell composite polymer particles

Core-shell composite polymer particles having temperature-sensitive shell were prepared by seeded emulsion copolymerization of dimethylaminoethyl methacrylate and ethylene glycol dimethacrylate (EGDM) with 0.14 μ-sized polystyrene seed particles according to our previous article. In this article, the effects of crosslinking density and thickness of the shell on the temperature-sensitive property were studied. Two series of composite particles, one with various EGDM contents in the shell and the other with various shell contents, were prepared for this study. The composite particles at the EGDM content of 3 wt % with the shell content of 47 wt %, showed the maximum swelling and deswelling phenomena at temperatures, respectively, below and above the lower critical solution temperature. The adsorption and desorption behaviors of low molecular weight cationic emulsifier and bio-molecules were dependent on the shell content. In almost all cases, the adsorption/desorption behavior reached to the maximum variations at the shell content of 17 wt %. © 1996 John Wiley & Sons, Inc.