Morphologies of polybutylacrylate/poly(styrene‐co‐methyl methacrylate) latex prepared by starved emulsion polymerization Part I. Thermodynamics equilibrium morphology

Heterogeneous latexes were prepared by a semicontinuous seeded emulsion polymerization process under monomer starved conditions at 80 °C using potassium persulfate as the initiator and sodium dodecyl sulfate as the emulsifier. Poly(butyl acrylate) latexes were used as seeds. The second‐stage polymer was poly(styrene‐co‐methyl methacrylate). By varying the amounts of methyl methacrylate (MMA) in the second‐stage copolymer, the polarity of the copolymer phase could be controlled. Phase separation towards the thermodynamic equilibrium morphology was accelerated either by ageing the composite latex at 80 °C or by adding a chain‐transfer agent during polymerization. The morphologies of the latex particles were examined by transmission electron microscopy (TEM). The morphology distributions of latex particles were described by a statistical method. It was found that the latex particles displayed different equilibrium morphologies depending on the composition of the second‐stage copolymers. This series of equilibrium morphologies of [poly(butyl acrylate)/poly(styrene‐co‐methyl methacrylate)] (PBA/P(St‐co‐MMA)) system provides experimental verification for quantitative simulation. Under limiting conditions, the equilibrium morphologies of PBA/P(St‐co‐MMA) were predicted according to the minimum surface free energy change principle. The particle morphology observed by TEM was in good agreement with the predictions of the thermodynamic model. Therefore, the morphology theory for homopolymer/homopolymer composite systems was extended to homopolymer/copolymer systems. © 2002 Society of Chemical Industry     

Interpenetrating polymer networks of castor oil polyester and poly(methyl methacrylate)

The physical and mechanical properties of interpenetrating polymer networks (IPNs) and semi-I IPNs of the castor oil polyester network and poly(methyl methacrylate) were investigated. In the semi-I IPNs, the second component was a copolymer of poly(methyl methacrylate) and polystyrene (PS) or poly(methyl methacrylate) and poly(n-butyl acrylate) (PnBA). The dynamic mechanical properties indicated the semi-I IPNs to be more compatible than the IPNs. The degree of molecular mixing was higher than that for IPNs. The impact strength showed a gradual increase with the increase in the percentage of PS or PnBA in the copolymer. The effect of the copolymerization of the second component on transparency was investigated. The transparency of the semi-I IPNs increased with the increasing composition of PnBA, but reduced with the increasing composition of PS. These results are discussed in light of existing theories.     

Interpenetrating polymer networks of poly(butyl methacrylate) and poly(α‐terpineol‐co‐styrene): Synthesis and characterization

Simultaneous interpenetrating polymer networks (IPNs) based on poly(butyl methacrylate) and poly(α‐terpineol‐co‐styrene) were synthesized with azobisisobutyronitrile (AIBN) as the initiator and divinyl benzene as the crosslinking agent in xylene under an inert nitrogen atmosphere. Fourier transform infrared spectra provided structural evidence for the IPNs, indicating characteristic frequencies of ester groups of butyl methacrylate at 1723 cm^?1 and alcoholic groups of α‐terpineol at 3436 cm^?1. Scanning electron microscopy revealed threadlike network structures. Properties such as percentage swelling and average molecular weight between crosslinks were direct functions of the copolymer and initiator (AIBN) concentrations and inverse functions of the monomer (butyl methacrylate) and crosslinking agent (divinyl benzene) concentrations. Differential scanning calorimetry showed an IPN glass‐transition temperature at 80.2°C. The thermal decompositions of the IPNs were established with the help of thermogravimetric analysis. The value of the activation energy, calculated from thermogravimetric analysis with the Coats and Redfern equation, was 23 kJ/mol. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 343–352, 2006     

Complexation of poly(dimethylsiloxane)/poly(methyl methacrylate‐co‐butyl acrylate‐co‐methacrylic acid) latex with poly(dimethylsiloxane)/poly(vinyl acetate‐co‐butyl acrylate) latex

Two latices—the poly(dimethylsiloxane) (PDMS)/poly(methyl methacrylate‐co‐butyl acrylate‐co‐methacrylic acid) system (PA latex) and the PDMS/poly(vinyl acetate‐co‐butyl acrylate) system (PB latex)—were prepared by seeded emulsion polymerization, and PA/PB complex latices were obtained through the interparticle complexation of the PA latex with the PB latex. In addition, for the further study of the interparticle complexation of the PA latex with the PB latex, copolymer latices [PDMS/methyl methacrylate‐co‐butyl acrylate‐co‐vinyl acetate‐co‐methacrylic acid) (PC)] were prepared according to the monomer recipe of the complex latices and the polymerization process of the component latices. The properties of the obtained polymer latices and complex latices were investigated with surface‐tension, contact‐angle, and viscosity measurements. The mechanical properties of the coatings obtained from the latices were investigated with tensile‐strength measurements. The results showed that, in comparison with the two component latices (PA latex and PB latex) and the corresponding copolymer latices (PC latices), the PA/PB complex latices had lower surface tension, lower viscosities, and better wettability to different substrates. The tensile strengths of the coatings obtained from the complex latices were higher than the tensile strengths of the coatings from the two component latices and copolymer latices. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2522–2527, 2004     

Acrylate/EVA reactive blends and semi‐IPN: Chemical,chemical–physical,and thermo‐optical characterization

In the present work, blends between poly(methyl methacrylate) (PMMA) or its copolymer with butyl methacrylate P(MMA‐co‐BMA) and poly(ethylene‐co‐vinyl acetate) (EVA) rubbers obtained applying the reactive blending principles were deeply investigated to clarify the chemistry of the system. A copolymeric phase, which is created in situ, was isolated and its chemical structure was determined through NMR analysis. The blends were also crosslinked with a flexible dimethacrylate to realize semi‐interpenetrated networks. The blends were characterized for their properties of interest (mechanical and optical behaviors). Particularly, an accurate investigation of the optical properties as a function of the temperature was performed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

n‐Butyl acrylate based latex interpenetrating polymer networks used as processing modifiers and impact modifiers of poly(vinyl chloride)

A latex interpenetrating polymer network (LIPN), consisting of poly(n‐butyl acrylate), poly(n‐butyl acrylate‐co‐ethylhexyl acrylate), and poly(methyl methacrylate‐co‐ethyl acrylate) and labeled PBEM, with 1,4‐butanediol diacrylate as a crosslinking agent was synthesized by three‐stage emulsion polymerization. The initial poly(n‐butyl acrylate) latex was agglomerated by a polymer latex containing an acrylic acid residue and then was encapsulated by poly(n‐butyl acrylate‐co‐ethylhexyl acrylate) and poly(methyl methacrylate‐co‐ethyl acrylate). A polyblend of poly(vinyl chloride) (PVC) and PBEM was prepared through the blending of PVC and PBEM. The morphology and properties of the polyblend were studied. The experimental results showed that the processability and impact resistance of PVC could be enhanced considerably by the blending of 6–10 phr PBEM. This three‐stage LIPN PBEM is a promising modifier for manufacturing rigid PVC. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1168–1173, 2004     

Thermal and sonochemical degradation kinetics of poly(n‐butyl methacrylate‐co‐alkyl acrylates): Variation of chain strength and stability with copolymer composition

The thermal degradation of poly(n‐butyl methacrylate‐co‐alkyl acrylate) was compared with ultrasonic degradation. For this purpose, different compositions of poly (n‐butyl methacrylate‐co‐methyl acrylate) (PBMAMA) and a particular composition of poly(n‐butyl methacrylate‐co‐ethyl acrylate) (PBMAEA) and poly(n‐butyl methacrylate‐co‐butyl acrylate) (PBMABA) were synthesized and characterized. The thermal degradation of polymers shows that the poly(alkyl acrylates) degrade in a single stage by random chain scission and poly(n‐butyl methacrylate) degrades in two stages. The number of stages of thermal degradation of copolymers was same as the majority component of the copolymer. The activation energy corresponding to random chain scission increased and then decreased with an increase of n‐butyl methacrylate fraction in copolymer. The effect of methyl acrylate content, alkyl acrylate substituent, and solvents on the ultrasonic degradation of these copolymers was investigated. A continuous distribution kinetics model was used to determine the degradation rate coefficients. The degradation rate coefficient of PBMAMA varied nonlinearly with n‐butyl methacrylate content. The degradation of poly (n‐butyl methacrylate‐co‐alkyl acrylate) followed the order: PBMAMA < PBMAEA < PBMABA. The variation in the degradation rate constant with composition of the copolymer was discussed in relation to the competing effects of the stretching of the polymer in solution and the electron displacement in the main chain. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Poly(vinyl acetate)/polyacrylate semi‐interpenetrating polymer networks. II. Thermal,mechanical, and morphological characterization

The thermal, dynamic mechanical, and mechanical properties and morphology of two series of semi‐interpenetrating polymer networks (s‐IPNs) based on linear poly(vinyl acetate) (PVAc) and a crosslinked n‐butyl acrylate/1,6‐hexanediol diacrylate copolymer were investigated. The s‐IPN composition was varied with different monoacrylate/diacrylate monomer ratios and PVAc concentrations. The crosslinking density deeply affected the thermal behavior. The results showed that a more densely crosslinked acrylate network promoted phase mixing and a more homogeneous structure. The variation in the linear polymer concentration influenced both the morphology and mechanical properties. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Dynamic mechanical properties of semi‐interpenetrating polymer network‐based on nitrile rubber and poly(methyl methacrylate‐co‐butyl acrylate)

In this article, semi‐interpenetrating polymer network (Semi‐IPNs) based on nitrile rubber (NBR) and poly(methyl methacrylate‐co‐butyl acrylate) (P(MMA‐BA)) were synthesized. The structure and damping properties of the prepared Semi‐IPNs blends were characterized and by fourier transform infrared spectrum (FTIR), dynamic mechanical analysis (DMA), scanning electron microscopy (SEM), thermogravimetric analysis (TGA/DTG), and tensile mechanical properties. The results showed that interpenetrating network based on P(MMA‐BA) and NBR was successfully obtained, which showed the improved thermal stability compared to NBR/P(MMA‐BA)‐based two‐roll mill blends. Furthermore, Semi‐IPNs showed significantly better the dynamic mechanical properties than that of the two‐roll mill system. With the increasing feed ratio of BA and MMA during the preparation of Semi‐IPNs, the loss peak position for P(MMA‐BA) in NBR/PMMA IPNs shifted to a lower temperature from 20°C to ?17°C, and when NBR in Semi‐IPNs was accounted for 40 wt %, the dynamic mechanical thermal analysis showed that much more advanced damping material with wider temperature range (?30°C < T < 80°C) as tan δ > 0.45 can be achieved. Therefore, it was expected as a promising way to obtain the excellent damping materials with good oil‐resisted properties according the Semi‐IPNs system. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40217.     

Synthesis and characterization of crosslinkable latex with interpenetrating network structure based on polystyrene and polyacrylate

Functional poly[styrene‐co‐(2‐ethylhexyl acrylate)‐co‐(1,6‐hexanediol diacrylate)]/poly[(methyl methacrylate)‐co‐(butyl acrylate)‐co‐(methacrylic acid)‐co‐(diacetone acrylamide)] (PS/PA) semi‐interpenetrating polymer networks (semi‐LIPNs) containing ketone carboxyl groups were synthesized by two‐stage emulsion polymerization, and characterized by Fourier transform infrared, transmission electron microscopy, dynamic light scattering and DSC. A unique feature of the PS/PA semi‐LIPNs is their ability to crosslink and form thermosetting full‐IPN polymers through the reaction of ketone carboxyl and hydrazide in the course of film formation at ambient temperatures. Series of latex particles with various levels of crosslinking density in the PS and PA domain and varied composition of PS/PA LIPNs were obtained. The effects of the LIPN PS/PA composition and the level of crosslinking density in the PS and PA domain on film density, swell ratio, mechanical properties and contact angle with water were investigated. Maximum synergy effects obtained at around 50/50 (PS/PA) in terms of mechanical properties, density and contact angle with water indicate that the maximum degree of interpenetration is obtained at this composition. Copyright © 2006 Society of Chemical Industry     

The effects of acrylate monomers and polystyrene addition on the morphology of DOP‐plasticized styrene–acrylate polymer particles prepared by SPG emulsification and suspension polymerization

Fairly uniform copolymer particles of methyl acrylate (MA), butyl acrylate (BA), or butyl methacrylate (BMA) were synthesized via Shirasu porous glass (SPG) membrane and followed by suspension polymerization. After a single‐step SPG emulsification, the emulsion composed mainly of the monomers. Hydrophobic additives of dioctyl phthalate (DOP), polystyrene molecules, and an oil‐soluble initiator, suspended in an aqueous phase containing poly(vinyl alcohol) (PVA) stabilizer and sodium nitrite inhibitor (NaNO₂), were subsequently subjected to suspension polymerization. Two‐phase copolymers with a soft phase and a hard phase were obtained. The composite particles of poly(St‐co‐MA)/PSt were prepared by varying the St/PSt ratios or the DOP amount. The addition of PSt induced a high viscosity at the dispersion phase. The molecular weight slightly increased with increasing St/PSt concentration. The multiple‐phase separation of the St‐rich phase and PMA domains, observed by transmission electron microscopy, was caused by composition drift because the MA reactivity ratio is greater than that of St. The addition of DOP revealed the greater compatibility between the hard‐St and soft‐MA moieties than that without DOP. The phase morphologies of poly(St‐co‐MA), poly(St‐co‐BMA), and their composites with PSt were revealed under the influence of DOP. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1195–1206, 2006     

Effects of poly(methyl methacrylate)‐based low‐profile additives on the properties of cured unsaturated polyester resins. II. Volume shrinkage characteristics and internal pigmentability

The effects of three series of self‐synthesized poly(methyl methacrylate) (PMMA)‐based low‐profile additives (LPAs), including PMMA, poly(methyl methacrylate‐co‐butyl acrylate), and poly(methyl methacrylate‐co‐butyl acrylate‐co‐maleic anhydride) with different chemical structures and MWs on the volume shrinkage characteristics and internal pigmentability for low‐shrink unsaturated polyester (UP) resins during curing were investigated by an integrated approach of static phase characteristics of the ternary styrene (ST)/UP/LPA system, reaction kinetics, cured‐sample morphology, microvoid formation, and property measurements. The relative volume fraction of microvoids generated during the cure was controlled by the stiffness of the UP resin used, the compatibility of the uncured ST/UP/LPA systems, and the glass‐transition temperature of the LPAs used. On the basis of the Takayanagi mechanical model, the LPA mechanism on volume shrinkage control, which accounted for phase separation and microvoid formation, and factors leading to both a good volume shrinkage control and acceptable internal pigmentability for the molded parts are discussed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3388–3397, 2004     

Properties of n‐butyl methacrylate copolymer latex films derived from crosslinked latex particles

Films obtained from copolymer latexes of n‐butyl methacrylate (BMA) with a series of crosslinking monomers [i.e., a macromonomer crosslinker (Mac), ethylene glycol dimethacrylate (EGDMA), and aliphatic urethane acrylate] exhibited differences in their tensile properties and swelling behaviors. For P(BMA‐co‐EGDMA) copolymer, a dependence on the initiator type was obtained. It is postulated that the network microstructures for the various copolymers evolved as the result of the copolymerization reactions between the monomer pairs during the synthesis in the miniemulsion free‐radical copolymerization. These network microstructures are, therefore, hypothesized to influence the mechanical properties of the resultant films. Copolymers prepared with Mac were tough in comparison with copolymers made with EGDMA. The presence of longer linear or lightly crosslinked poly(n‐butyl methacrylate) (PBMA) chains and the looseness of the crosslinked network structures in the PBMA‐co‐Mac copolymers appear to be the factors responsible for the differences. All of the copolymer films disintegrated into swollen individual microgels when they were immersed in tetrahydrofuran. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 42–49, 2003     

Synthesis of an acrylate elastomer with UV stabilization and its application in polyoxymethylene

In this study, an acrylate elastomer with light‐stable functional groups was synthesized by methyl methacrylate (MMA), butyl acrylate (BA), and a polymerizable UV stabilizer 2‐hydroxy‐4‐(3‐methacryloxy‐2‐hydroxylproroxy) benzophenone (BPMA) via emulsion polymerization, and the product was poly[methyl methacrylate‐co‐butyl acrylate‐co‐2‐hydroxy‐4‐(3‐methacryloxy‐2‐hydroxylproroxy) benzophenone] [poly(MMA‐co‐BA‐co‐BPMA)]. The composition and characteristics of poly (MMA‐co‐BA‐co‐BPMA) were determined by using Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance (¹H‐NMR), and ultraviolet–visible absorption spectroscopy (UV–vis). Further, the obtained poly(MMA‐co‐BA‐co‐BPMA) was blended with polyoxymethylene (POM) to modify its photostabilization, as well as the mechanical properties of POM composite were tested before and after UV irradiation. The result showed that poly(MMA‐co‐BA‐co‐BPMA) can be dispersed well in the POM matrix, which could play a role of improving compatibility with and toughening for POM, and its light‐stable functional groups could increase the UV resistance of POM composite. Mechanical properties of modified POM were kept well with higher impact strength and elongation at break than pure POM after UV irradiation. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effects of poly(methyl methacrylate)‐based low‐profile additives on the properties of cured unsaturated polyester resins. I. Miscibility,curing behavior,and glass‐transition temperatures

The effects of three series of self‐synthesized poly(methyl methacrylate) (PMMA)‐based low‐profile additives (LPAs), including PMMA, poly(methyl methacrylate‐co‐butyl acrylate), and poly(methyl methacrylate‐co‐butyl acrylate‐co‐maleic anhydride), with different chemical structures and MWs on the miscibility, cured‐sample morphology, curing kinetics, and glass‐transition temperatures for styrene (ST)/unsaturated polyester (UP) resin/LPA ternary systems were investigated by group contribution methods, scanning electron microscopy, differential scanning calorimetry (DSC), and dynamic mechanical analysis, respectively. Before curing at room temperature, the degree of phase separation for the ST/UP/LPA systems was generally explainable by the calculated polarity difference per unit volume between the UP resin and LPA. During curing at 110°C, the compatibility of the ST/UP/LPA systems, as revealed by cured‐sample morphology, was judged from the relative magnitude of the DSC peak reaction rate and the broadness of the peak. On the basis of Takayanagi's mechanical models, the effects of LPA on the final cure conversion and the glass‐transition temperature in the major continuous phase of ST‐crosslinked polyester for the ST/UP/LPA systems was also examined. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3369–3387, 2004     

Spin Probe Study of IPN-like Systems based on Polyethylene and Polymethacrylates

A system similar to an interpenetrating polymer network (IPN), based on polyethylene/poly(methylmethacrylate-co-dodecyl methacrylate), was studied by the spin probe method with a nitroxide spin probe, 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO). The influence of changes in the composition of the copolymer (methyl methacrylate-co-dodecyl methacrylate) on the molecular mobility and composition of the IPNs is characterized by changes of the empirical spectral parameters T_50G and τ_R. The molecular mobility was shown to diminish with rising content of methyl methacrylate in the copolymer. © of SCI.     

Bulk and emulsion copolymerizations of n-butyl acrylate and poly(methyl methacrylate) macromonomer

Bulk and emulsion copolymerizations of an ω-unsaturated poly(methyl methacrylate) (PMMA) macromonomer with n-butyl acrylate (n-BA) were investigated. The reactivity of PMMA macromonomer in bulk copolymerization with n-BA was found to be lower than that of methyl methacrylate monomer with n-BA. The incorporation of PMMA macromonomer into poly(butyl acrylate) (PBA) latex particles by miniemulsion copolymerization was proved by high performance liquid chromatography-silica adsorption spectroscopy. Dynamic mechanical studies showed that PMMA macromonomer was grafted to the PBA backbone, and the degree of grafting increased as the ratio of PMMA macromonomer to n-BA increased. Microphase separation of the PMMA macromonomer grafts was observed at higher ratio of macromonomer (higher or equal to 10% weight of macromonomer based on total polymer phase). The n-BA/PMMA macromonomer copolymer behaved completely differently from the physical blend of PBA and PMMA macromonomer particles of the same composition. © 1996 John Wiley & Sons, Inc.     

Synthesis and characterization of hydrophilic copolymers of maleimide derivatives with 2‐hydroxyethyl methacrylate: electrochemical and thermal behavior

BACKGROUND: The high‐technology industries have been the driving force in the development of new synthetic polymers that combine thermal stability with specific functional properties. In this study p‐chlorophenylmaleimide, p‐hydroxyphenylmaleimide and p‐nitrophenylmaleimide (R‐PhMI) with 2‐hydroxyethyl methacrylate (HEMA) were synthesized by free radical polymerization to obtain hydrophilic polymers, in order to study the effect of the p‐chloroaryl, p‐hydroxyaryl or p‐nitroaryl group on the copolymer composition, electrochemical behavior and thermal properties. RESULTS: The thermal behavior was correlated with the copolymer composition and functional groups, maleimide derivatives, on the copolymers. Thermal decomposition temperature (TDT) and glass transition temperature (T_g) were influenced by the functional groups of R‐PhMI moiety on the copolymer. The polymers showed an electrochemically irreversible reduction process under the conditions tested. CONCLUSION: Poly[(p‐chloromaleimide)‐co‐(2‐hydroxyethyl methacrylate)] copolymer shows a higher TDT than poly[(p‐hydroxymaleimide)‐co‐(2‐hydroxyethyl methacrylate)] or poly[(p‐nitromaleimide)‐co‐(2‐hydroxyethyl methacrylate)] (NPHE). T_g decreases in going from nitro to hydroxyl to chloro groups. The NPHE copolymer shows a lower stability, losing weight at 200 °C. The NPHE copolymer shows a well‐defined reduction wave which is similar to those of the other copolymers and it also shows an additional quasi‐reversible reduction wave corresponding to the nitrobenzene group. Copyright © 2009 Society of Chemical Industry     

Synthesis and property behavior of dioctyl phthalate plasticized styrene–acrylate particles by Shirasu porous glass emulsification and subsequent suspension copolymerization

Two‐phase model styrene–acrylate copolymers were synthesized with a soft phase consisting of methyl acrylate, butyl acrylate, and butyl methacrylate. Besides the styrenic copolymers, copolymers containing a hard phase of methyl methacylate and methyl acrylate were also synthesized. Comonomer droplets with a narrow size distribution and fair uniformity were prepared using an SPG (Shirasu porous glass) membrane having pore size of 0.90 μm. After the single‐step SPG emulsion, the emulsion droplets were composed mainly of monomers, hydrophobic additives, and an oil‐soluble initiator, suspended in the aqueous phase containing a stabilizer and inhibitor. These were then transferred to a reactor, and subsequent suspension polymerization was carried out. Uniform copolymer particles with a mean diameter ranging from 3 to 7 μm, depending on the recipe, with a narrow particle size distribution and a coefficient of variation of about 10% were achieved. Based on the glass‐transition temperatures, as measured by differential scanning calorimetry, the resulting copolymer particles containing a soft phase of acrylate were better compatibilized with a hard phase of methyl methacrylate than with styrene with dioctyl phthalate (DOP) addition. Glass‐transition temperatures of poly(MMA‐co‐MA) particles were strongly affected by the composition drift in the copolymer caused by their substantial difference in reactivity ratios. Incorporation of DOP in the copolymer particles does not significantly affect the glass‐transition temperature of MMA‐ or MA‐containing copolymer particles, but it does affect the St‐containing copolymer and particle morphology of the copolymers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3037–3050, 2003     

Pervaporation separation of 1,1,2‐trichloroethane–water mixture through crosslinked acrylate copolymer composite membranes

The separation of a chlorinated hydrocarbon from a dilute aqueous solution through a crosslinked acrylate copolymer–porous substrate composite membrane by pervaporation was investigated. Poly(n‐butyl acrylate‐co‐acrylic acid) and poly(n‐butyl acrylate‐co‐2‐hydroxyethyl acrylate) were synthesized and composite membranes were prepared, which were made from the crosslinked polymer and a porous substrate. Pervaporation measurement was carried out for a dilute aqueous solution of 1,1,2‐trichloroethane at 25°C and under a vacuum on the permeate side (below 10 mmHg). The separation factor, overall flux, 1,1,2‐trichloroethane concentration in the membrane, and the degree of swelling decreased with increase in the acrylic acid or 2‐hydroxyethyl acrylate content of the acrylate copolymer. The influence of the crosslinking agent content on the pervaporation performance was small, and the separation factor and the overall flux showed a convex curve. The structure of the crosslinking agent had no effect on the separation. The influence of the pore size of the substrate and the thickness of the polymer layer on the separation of 1,1,2‐trichloroethane was observed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 983–994, 1999