Nanostructured latexes made by a sequential multistage emulsion polymerization

A series of linear and lightly crosslinked nanostructured latices was prepared by a sequential multistage semicontinuous emulsion polymerization process alternating styrene (S) and n‐butyl acrylate (BA) monomer feeds five times, that is ten stages, and vice versa, along with several control latices. Transmission electron micrographs of the RuO₄‐stained cross sections of nanostructured and copolymer latex particles and films showed that their particle morphologies were not very different from each other, but the nanostructured latex particles were transformed into a nanocomposite film containing both polystyrene (PS) and poly(n‐butyl acrylate) (PBA) nanodomains interconnected by their diffuse polymer mixtures (i.e. interlayers). The thermal mechanical behaviors of the nanostructured latex films showed broad but single T_gs slightly higher than those of their counterpart copolymer films. These single T_gs indicated that their major component phases were the diffuse interlayers and that they behaved like pseudopolymer alloys. The minimum film formation temperatures of nanostructured latices capped with PBA and PS, respectively, were 15 °C lower than and equal to those of their counterpart copolymer latices, but their T_gs were about 10 °C higher. Consequently, nanostructured latices enabled us to combine good film formation with high strengths for adhesives and coatings applications. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2826–2836, 2006     

Polystyrene(1)/poly(butyl acrylate-methacrylic acid)(2) core-shell emulsion polymers. Part I. Synthesis and colloidal characterization

Polystyrene (PS) (1)/Poly(n-butyl acrylate (BA)-methacrylic acid (MAA)) (2) structured particle latexes were prepared by emulsion polymerization using monodisperse polystyrene latex seed (118 nm) and different BA/MAA ratios. Three main aspects have been investigated: i) the polymerization kinetics; ii) the particle morphology as a function of reaction time; iii) the distribution of MAA units between the water phase and the polymer particles.The amount of MAA in the shell copolymer was found to be the main factor controlling the particle shape and morphology. The shape of the structured particles was, generally, non-spherical, and the shape irregularities increased as a particles was, generally, non-spherical, and the shape irregularities increased as a function of reaction time. At the beginning of the second stage reaction, new small particles were observed, which coalesced onto the PS seed as the polymerization proceeded. The distribution of the MAA groups in the latex particles and the serum was analyzed by alkali/back-acid titration, using ionic exchanged latexes. No MAA groups were detected in the latex serum. Due to the lowTg of the BA-MAA copolymers, alkali conductimetric titrations accounted for all the MAA groups on and within the polymer particles. Therefore, for these systems, this method is not only limited to a thin surface layer, as it is often assumed.     

Studies on the Preparation of Stable and High Solid Content Emulsifier-Free Poly(MMA/BA/HEA) Latex with the Addition of AMPS and Characterization of the Obtained Copolymers

The 2-acrylamido -2-methylpropane sulfonic acid (AMPS) was used as a reactive comonomer for the methyl methacrylate (MMA), n-butyl acrylate (BA) and 2-hydroxyethyl acrylate (HEA) emulsifier-free emulsion copolymerization system to obtain latices of stable and high-solid content (50 wt%).The polymerization and storage process is very stable, and the emulsion could store at room temperature for more than six months with the addition of AMPS. Properties of the latices, such as stability, flow behavior, particles diameter and morphology were studied. In addition, physical properties of the obtained copolymers, such as water resistance, glass transition temperature (T_g) were also investigated. The final size of the latex particles is 200～300 nm in diameter. Compared with the copolymers that were prepared by surfactant emulsion polymerization water resistance is greatly improved.     

Discussion of craze formation and growth in amorphous polymers in terms of the multiplicity of glass transition at low temperatures

A craze, the typical deformation zone in an amorphous polymer, can be divided into a precraze and a proper craze. A better understanding of the two corresponding formation processes is possible in terms of glass transition multiplicity.The precraze is associated with the molecular mobility in the confined flow zone, which is part of the main transition. The proper craze corresponds to the mobility in the flow transition zone (terminal zone for shear). A negative pressure generated by nonuniaxial stress is considered to be important for the maintainance of the molecular mobility in these zones belowT _g . The behavior of the zones at negative pressure and low temperatures Tg is considered using a pressure-temperature diagram. The fibril structure of crazes is discussed by a defect diffusion model for the proper glass transition; it is correlated with the sequential physical aging of the corresponding frozen structural defects. Typical mode lengths of the molecular mobilities in the different zones are compared with typical craze parameters. The structure of the craze material is considered to result from confined flow processes which cannot percolate because in the main transition the flow is confined by entanglements, and in the flow transition zone the flow is stopped by releasing the negative pressure due to crack propagation.     

Effect of the structure of latex particles on adhesion. Part I: Synthesis and characterization of structured latex particles of acrylic copolymers and their peel adhesion behavior

This is a series of articles that deals with fundamental aspects of the effects of the structure of latex particles of acrylic copolymers on their adhesion behavior. Specifically, relationship or analogy between rheological properties and adhesion performance of the acrylic copolymers was demonstrated. The first part of this series concerns the synthesis and characterization of latex particles with desired structures and compositions, and the experimental results of peel adhesion. The second part develops an analogy between the peel adhesion performance of the adhesives and rheological properties of the corresponding copolymers. The third part addresses the generalities and particularities of three major tests for adhesion: peeling, blistering, and spontaneous peeling. Three types of structured latex particles were synthesized by three different emulsion polymerization processes: the first type had a uniform composition over the entire particles with a glass transition temperature (T_g) varying between ?40°C and 0°C, depending upon the compositions of monomers involved in the copolymer; the second type was of core-shell structure. As for the third type, the composition of monomers varied gradually across the particle radii. The glass transition behavior and the dynamic mechanical properties in the solid state of the copolymers confirmed the structures of the corresponding latex particles. On the other hand, the peel adhesion performance of the films of these latex particles varied with the dynamic mechanical properties of the corresponding copolymers. This implies that a correlation could be found between the structure of the latex particles, dynamic mechanical properties in the solid state of the corresponding copolymers, and the peel adhesion performance of the adhesive films. ©1995 John Wiley & Sons, Inc.     

Breadth of glass transition temperature in styrene/acrylic acid block,random, and gradient copolymers: Unusual sequence distribution effects

Block, random, and gradient copolymers of styrene (S) and acrylic acid (AA) are synthesized by conventional or controlled radical polymerization, and their glass transition temperature (T_g) behaviors are compared. The location and breadth of the T_gs are determined using derivatives of differential scanning calorimetry heating curves. Each S/AA random copolymer exhibits one narrow T_g, consistent with a single phase of limited compositional nanoheterogeneity. Block copolymers exhibit two narrow T_gs originating from nanophase separation into ordered domains with nearly pure S or nearly pure AA repeat units. Each gradient copolymer exhibits a T_g response with a ～50–56 °C breadth that extends beyond the upper T_g of the block copolymers. For copolymers of similar composition, the maximum value in the gradient copolymer T_g response is consistent with that of a random copolymer, which has an enhanced T_g relative to poly(acrylic acid) due to more effective hydrogen bonding when AA units are separated along the chain backbone by S units. These results indicate that gradient copolymers with ordered nanostructures can be rationally designed, which exhibit broad glass transitions that extend to higher temperature than the T_gs observed with block copolymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2842–2849, 2007     

Interface stabilization and micelle formation in blends with a block copolymer

The phase separation behavior of ternary blends of two homopolymers, PMMA and PS, and a block copolymer of styrene and methylmethacrylate, P(S-b-MMA), was studied. The homopolymers were of equal chain length and were kept at equal amounts. Two copolymers were used with blocks of equal length, which exceeded or equaled that of the homopolymer chains. Varied was the copolymer contentf. Films were cast from toluene, which is a nonselective solvent. The morphologies of the cast films were compared with the structure of the critical fluctuations in solution, which were calculated in mean field approximation. The axis of blend compositionsf can be divided into parts of dominating macrophase and microphase separation. Above a transition concentrationf _o, all copolymer chains are found in phase interfaces. Belowf _o, part of them form micelles within the homopolymer phases.     

Participation of electrolyte cations in albumin adsorption onto negatively charged polymer latices

The participation of electrolyte cations in the adsorption of bovine serum albumin (BSA) onto polymer latices was investigated. The latices used were hydrophobic polystyrene (PS), and hydrophilic copolymers, i.e., styrene (St)/2-hydroxyethyl methacrylate(HEMA) copolymer [P(St/HEMA)] and styrene/acrylamide (AAm) copolymer [P(St/AAm)]. Three kinds of electrolyte cations (Na⁺, Ca²⁺, Mg²⁺) were used as the chloride. The amount of BSA adsorbed in every cation medium showed a maximum near the isoelectric point (iep, pH about 5) of the protein. The amounts of BSA adsorbed onto copolymer latices (except in the acidic pH region lower than the iep) were considerably smaller than that onto PS latex because of the steric repulsion and the decrease in the hydrophobic interaction between BSA and copolymer latices. In the acidic pH region, there was little difference in the amount of BSA adsorbed in every cation medium. However, in the pH region higher than the iep, the amounts of BSA adsorbed (particularly onto PS latex) in divalent cations (Ca²⁺ and Mg²⁺) media were relatively greater compared with that in a monovalent (Na⁺) one. This result was interpreted on the basis of the differences in such effects of electrolyte cations as dehydration power, suppression of the electrostatic repulsion, and binding affinity to BSA molecule. Ion Chromatographic estimation of the amounts of electrolyte cations captured upon BSA adsorption (in pH > 5) revealed that divalent cations were incorporated into the contact interface between the latex and BSA molecule so as to prevent the accumulation of anion charge and facilitate the protein adsorption.     

Deposition of polymer latices on grafted Nylon 6 fiber

Deposition of polymer latices on a grafted Nylon 6 fiber was studied as a function of pH and the degree of grafting. The latices were polystyrene (PS), styrene/acrylamide copolymer (P(St/AAm)) and styrene/acrylic acid copolymer (P(St/AA)). The deposition of the latices on the grafted fiber decreased in every case with increasing pH and no deposition was observed at alkaline pH. The grafting of fiber with acrylic and methacrylic acid reduced the deposition of P(St/AAm) and P(St/AA) latices but had no influence on the deposition of PS latex. The relation between the deposition rates and the interaction energy at acidic pH indicates that the deposition of PS latex on the grafted fiber mainly depends on the electrostatic interaction. These results suggest that the expansion of water-soluble polyelectrolyte layer on the surface of grafted fiber plays an important role on the deposition.     

Batch emulsion copolymerization of 3‐O‐methacryloyl‐1,2:5,6‐di‐O‐isopropylidene‐α‐D‐glucofuranose and butyl acrylate: Synthesis and properties of the sugar latices

To obtain new polymer latices based on sugar derivative, batch emulsion copolymerizations of 3‐O‐methacryloyl‐1,2:5,6‐di‐O‐isopropylidene‐α‐D ‐glucofuranose (3‐MDG) and n‐butyl acrylate (BA) were carried out at 70 °C, with potassium persulfate as the initiator. 3‐MDG polymerizes faster than BA because of its higher reactivity ratio, r_(3‐MDG) = 1.94 versus r_(BA) = 0.54. The effect of the initial monomer composition on the polymerization rate and the thermal properties of the end copolymers was investigated. The overall rate of polymerization increases by enhancing the sugar content in the initial monomer composition. The glass‐transition temperature is linearly related to the sugar content in the copolymer. The influence of the type of surfactant showed that the particle size increases by changing from ionic to nonionic surfactant. Furthermore, the effect of the added acrylic acid (AA) on the rheological properties suggests that the sugar latices exhibit different non‐Newtonian flows depending on the pH of the latex and on the AA concentration on the particle surface. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 788–803, 2003     

Preparation of composite polyacrylate latex particles with in situ‐formed methylsilsesquioxane cores

Composite polyacrylate latex particles were prepared through a simple method by dissolving organosilicon monomer methyltrimethoxysilane in a monomer mixture of acrylic monomers methyl methacrylate (MMA), n‐butyl acrylate (n‐BA), and acrylic acid (AA). With the addition of water needed for hydrolysis, methyltrimethoxylsilane hydrolyzed under catalysis by AA and further condensed to form polymeric methylsilsesquioxane (MSQ). The monomer mixture containing in situ‐formed MSQ was then subjected to emulsification and emulsion polymerization. Transmission electron microscopy (TEM) images showed that the obtained latex particles had a core–shell structure. Differences between the X‐ray photoelectron spectroscopy (XPS) results of the contents of silicon atoms on surfaces of films formed at temperatures above and below glass transition temperatures (T_gs) of polyacrylate evidenced that the cores were made up of MSQ and the shells were made up of polyacrylate. The static water contact angle measurements indicated that the incorporation of MSQ can result in composite latex with higher hydrophobicity. Copyright © 2009 John Wiley & Sons, Ltd.     

Phase transition of polycarbonate in blends with liquid crystal

Phase transition temperatures of polycarbonate film consisting of micron-sized liquid crystalline droplets were investigated using differential scanning calorimetry (DSC) and thermo-optical analysis (TOA) methods. Both a decrease in (T _g ) and (T _m ) of the polycarbonate with an increase of liquid crystal (LC) content in the sample were observed. The decrease ofT _g is related to the plastifying effect of a low molecular weight LC substance remaining soluble in the polycarbonate matrix. A fraction of the liquid crystal contained in the droplets was estimated on the basis of theT _g decrease.     

Radiation-induced copolymerization of styrene/n-butyl acrylate in the presence of ultra-fine powdered styrene–butadiene rubber

Styrene (St)/n-butyl acrylate (BA) copolymers were prepared by two-stage polymerization: St/BA was pre-polymerized to a viscous state by bulk polymerization with initiation by benzoyl peroxide (BPO) followed by ⁶⁰Co γ-ray radiation curing. The resultant copolymers had higher molecular weight and narrower molecular weight distribution than conventional methods. After incorporation of ultra-fine powdered styrene–butadiene rubber (UFSBR) with a particle size of 100 nm in the monomer, the glass transition temperature (T_g) of St–BA copolymer increased at low rubber content. Both the St–BA copolymer and the St–BA copolymer/UFSBR composites had good transparency at BA content below 40%.     

Characteristic changes of pH during the alkalization of latex dispersions of the ethyl acrylate — methacrylic acid copolymers

The titration curves of latex dispersions of ethyl acrylate — methacrylic acid copolymers have a rather complex shape which indicates a strong dependence of the apparent dissociation constant of carboxylic groups on the degree of neutralization and copolymer composition. These dependences seem to be related to changes in the macroscopic structure (swelling and disintegration) of dispersion particles during alkalization.     

Structure-property relationship of polyurethane ionomer

Polyurethane (PU) ionomers were prepared using various types of polyol (PTAd, PCL, PTMG, and PPG) and isocyanate (MDI, HDI, and IPDI), together with different extender (DMPA) contents, degree of neutralization, and number average molecular weight (M _n) of polyol. Modulus (E), strength (_b), and glass transition temperature (T _g) significantly increased with the increased amount of extender and extender neutralization. Among three of the iocyanate used, PU from MDI gave the highest modulus, strength, andT _g. With regard to theM _n of PTAd (600, 1000, 2000), PU from PTAd 600M _n gave the highest modulus, strength, andT _g, due probably to the highest hard segment content and phase mixing. On the other hand, PU from PTAd 2000M _n gave significantly improved strength over PTAd 1000M _n, and the highest elongation. The results were interpreted in terms of soft-segment crystallization, and soft-hard phase separation, which was concluded from the lowered softT _g.     

Batch and semicontinuous emulsion copolymerization of vinyl acetate–butyl acrylate. II. Morphological and mechanical properties of copolymer latex films

Vinyl acetate/(VAc)-butyl acrylate/(BuA) copolymer latex films of various copolymer compositions were investigated for their morphological properties by electron microscopy techniques, and for their mechanical properties by dynamic mechanical spectroscopy (DMS), differential scanning calorimetry (DSC), and tensile strength measurements. Batch copolymer latex films showed domains of PBuA dispersed in PVAc matrix; the domain sizes were increased with increased BuA content. Semicontinuous latex films were homogeneous in composition. Glass transition temperatures T_g determined from DMS and DSC indicated the presence of two, low and high, transition temperatures for batch latex films. The two temperatures approached the individual homopolymers, with increased PBuA content up to 51 mol %. Semicontinuous latex films showed only one single T_g. Tensile properties of the batch copolymer films showed a higher ultimate tensile strength, higher Young's modulus, and lower percent elongation to break compared to semicontinuous latex films. These differences were found to reflect the effect of mode of monomer addition during the emulsion copolymerization process on the particle morphology, and confirmed earlier data on bulk, colloidal, and surface properties of the same copolymer latexes.     

Preparation and clinical application of immunomagnetic latex

Magnetic poly(methyl methacrylate) (PMMA)/poly(methyl methacrylate‐co‐methacrylic acid) [P(MMA–MAA)] composite polymer latices were synthesized by two‐stage soapless emulsion polymerization in the presence of magnetite (Fe₃O₄) ferrofluids. Different types and concentrations of fatty acids were reacted with the Fe₃O₄ particles, which were prepared by the coprecipitation of Fe(II) and Fe(III) salts to obtain stable Fe₃O₄ ferrofluids. The Fe₃O₄/polymer particles were monodisperse, and the composite polymer particle size was approximately 100 nm. The morphology of the magnetic composite polymer latex particles was a core–shell structure. The core was PMMA encapsulating Fe₃O₄ particles, and the shell was the P(MMA–MAA) copolymer. The carboxylic acid functional groups (COOH) of methacrylic acid (MAA) were mostly distributed on the surface of the composite polymer latex particles. Antibodies (anti‐human immunoglobulin G) were then chemically bound with COOH groups onto the surface of the magnetic core–shell composite latices through the medium of carbodiimide to form the antibody‐coated magnetic latices (magnetic immunolatices). The MAA shell composition of the composite latex could be adjusted to control the number of COOH groups and thus the number of antibody molecules on the magnetic composite latex particles. With a magnetic sorting device, the magnetic immunolatices derived from the magnetic PMMA/P(MMA–MAA) core–shell composite polymer latex performed well in cell‐separation experiments based on the antigen–antibody reaction. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1342–1356, 2005     

Emulsion copolymerization of tribromophenyl maleimide with styrene

Emulsion copolymerization of Tribromophenyl Maleimide (TBPMI) and styrene was conducted by semi-batch and batch processes. The effects of monomer composition and copolymerization method on copolymerization rate, molecular weight and molecular weight distribution, latex particle size and size distribution, glass transition temperature (T_g), thermal stability and mechanical properties were investigated. A kinetic study has shown that the rate of copolymerization in the batch process increased with increasing TBPMI content in the monomer feed. For the semi-batch polymerized samples, molecular weight decreased and molecular weight distribution increased with increasing TBPMI content in the monomer feed. For the batch polymerized samples, molecular weight also decreased but no obvious tendency was observed for the molecular weight distribution when TBPMI content increased. Compared with the batch copolymers, the semi-batch copolymers have a higher molecular weight at the same initial monomer mixture composition. Latex particle size decreased, while particle size distribution slightly increased with increasing TBPMI content in both semi-batch and batch latices. The semi-batch samples exhibit only a single T_g, the value of which increses linearly with increasing TBPMI content. For the batch copolymers, two T_gs were found, reflecting a mixture of styrene-rich and TBPMI-rich copolymer chains. TGA results indicate that the thermal stability of the semi-batch copolymers increased with increasing TBPMI concentration. Young's and flexural moduli increased, while tensile and flexural strengths decreased by increasing the TBPMI content for both the semi-batch and batch specimens. The semi-batch specimens have higher tensile and flexural strenghts than the batch ones.     

Geometrical constraints on microstructural development in block copolymer ultrathin films

The fact that microstructures form in microphase-separated block copolymers, endowing the materials with unique thermo-mechanical properties, is well-established. However, no thermodynamic theories directly address the problem of microstructural development in ultrathin films, which might be useful as adhesives or resists. To predict the microstructural dimensions in such films, a model based on unit-cell geometries and material/volume balances is developed. Predictions of the ratio of the characteristic length of the domain core to domain repeat distance are obtained for poly (styrene-butadiene) diblock (SB) copolymers at 298 K. The finite interphase region is included in the volume balances with the parameterf, the volume fraction of interphase material, obtained from a modified version of the Leary-Henderson-Williams thermodynamic theory and shown here not to be a strong function of composition. An approach, implementingf, for accurately estimating the critical molecular weight of microphase separation in the strong-segregation limit (M _c ), as a function of bulk composition for monodisperse SB copolymers at 298 K, is also presented.     

Thermal properties of poly(methyl methacrylate-co-butyl acrylate-co-acrylic acid) modified with divinyl benzene and vinyltrimethoxysilane

The effect of butyl acrylate (BA), divinyl benzene (DVB) and vinyltrimethoxysilane (TMVS) on the thermal properties of poly(methyl methacrylate-co-butyl acrylate-co-acrylic acid) was investigated. Glass transition temperature (T_g), melting temperature (T_m) and specific heat capacity of the copolymers were investigated using Differential Scanning Calorimetry. Thermal stability of the copolymers which is associated with the degradation temperature (T_d) was studied by Thermogravimetric Analysis. Polyacrylates with T_g ranges between -19°Cand 19°C were obtained. With the incorporation of >7 wt% of DVB, the T_g of the copolymer increases from about ?17°C to ?10°C even though they have not undergone UV irradiation. Gel content results prove that crosslinking has occurred in the copolymers. With increasing amount of TMVS from 0 wt% to 7 wt%, the T_m of the copolymers prepared at acidic pH is about 40-60°C higher than that at the alkaline pH. However, the addition of TMVS gives no significant effect to the T_g and T_d of the copolymer films. The thermal stability of the copolymer has improved with increasing amount of BA and DVB, with DVB being more effective. The highest T_d of 425°C with 8% of DVB has been obtained. Consequently, a polyacrylate copolymer with a T_g of about ?13°C, a T_m of 170 °C and a T_d of about 424°C has been successfully synthesized. Hence, the soft polyacrylate with its relatively high T_m and T_d could serve as a superb material especially to be applied in the areas that require high melting temperature and good thermal stability.