Syntheses of acrylate core/shell imbiber beads by seeded suspension copolymerization and one‐stage copolymerization for solvent absorption–desorption

Seeded suspension copolymerization or a one‐stage copolymerization was used to synthesize acrylate core/shell imbiber beads. A two‐stage polymerization technique was used for seeded suspension polymerization. The seed particles for poly(methyl acrylate) or poly(2‐ethylhexyl acrylate) were synthesized first in a mixed solvent of toluene/isooctane containing the ethylene glycol dimethacrylate (EGDMA) crosslinking agent. These beads were swollen in styrene‐EGDMA‐BPO (benzoyl peroxide) and then polymerized in the aqueous phase to produce the polystyrene (PS) shell. The one‐stage copolymerization was carried out in toluene/isooctane containing methyl methacrylate (MMA), styrene (St), EGDMA, and BPO at 75°C for 10 h to give a core/shell copolymer of St‐MMA morphology. The appearance of core/shell imbiber beads prepared from these two techniques varied from monomer to monomer. This article describes the preparation, characterization, and application of the core/shell beads for organic solvent absorption/desorption. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 670–682, 2002     

Oil absorbents based on styrene–butadiene rubber

Four oil absorbents based on styrene–butadiene (SBR)—pure SBR (PS), 4‐tert‐butylstyrene–SBR (PBS), EPDM–SBR network (PES), and 4‐tert‐butylstyrene‐EPDM‐SBR (PBES)—were produced from crosslinking polymerization of uncured styrene–butadiene rubber (SBR), 4‐tert‐butylstyrene (tBS), and ethylene–propylene–diene terpolymer (EPDM). The reaction took place in toluene using benzoyl peroxide (BPO) as an initiator. Uncured SBR was used as both a prepolymer and a crosslink agent in this work, and the crosslinked polymer was identified by IR spectroscopy. The oil absorbency of the crosslinked polymer was evaluated with ASTM method F726‐81. The order of maximum oil absorbency was PBES > PBS > PES > PS. The maximum values of oil absorbency of PBES and PBS were 74.0 and 69.5 g/g, respectively. Gel fractions and swelling kinetic constants, however, had opposite sequences. The swelling kinetic constant of PS evaluated by an experimental equation was 49.97 × 10^?2 h^?1. The gel strength parameter, S, the relaxation exponent, n, and the fractal dimension, d_f, of the crosslinked polymer at the pseudo‐critical gel state were determined from oscillatory shear measurements by a dynamic rheometer. The morphologies and light resistance properties of the crosslinked polymers were observed, respectively, with a scanning electron microscope (SEM) and a color difference meter.     

Studies of crosslinked styrene–alkyl acrylate copolymers for oil absorbency application. I. Synthesis and characterization

The prepolymers for a novel oil absorbent were synthesized by copolymerizing styrene with 2‐ethylhexyl acrylate (EHA), lauryl acrylate (LA), lauryl methacrylate (LMA), and stearyl acrylate (SA). Suspension polymerization was carried out using benzoyl peroxide (BPO) as an initiator with a varying monomer feed ratio, and the copolymers were characterized by FTIR, ¹H‐NMR, DSC, and a solubility test. The copolymers were random copolymers with a single phase, and their compositions were similar to those in the monomer feed. The T_g of the copolymer could be controlled by varying the styrene/acrylate ratio. Acrylates introduced the crosslinking to linear polymers as a side reaction. Crosslinked copolymers were synthesized by adding divinylbenzene (DVB) as a crosslinking agent. At a low degree of crosslinking (0.5 wt % DVB), the T_g of the crosslinked copolymers was lower than or similar to that of the uncrosslinked ones. At a high degree of crosslinking, the T_g increased with increasing crosslinking density. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 903–913, 2000     

Polymerization of acrylated epoxidized soybean oil with phenol furfural resins via repeated forward and retro diels–alder reactions

In this work, the Diels–Alder reaction between the acrylate groups of acrylated epoxidized soybean oil and the furan rings of p‐tertiary butyl phenol furfural resin (TBPF) is described. The reaction was carried out at 110°C in presence of FeCl₃ catalyst, and tough polymers were obtained in 1 h. Surprisingly, samples that were heated and cooled 5, 10, and 20 times to 140°C and room temperature had better mechanical properties than samples that were kept at 140°C for the same total duration. This unexpected behavior is attributed to a series of forward and retro Diels–Alder reactions between the functional groups. To prove this hypothesis, a model reaction between TBPF and n‐butyl acrylate was studied. At 100°C, ¹H‐nuclear magnetic resonance signals of the furan ring protons disappeared, only to reappear at 140°C. Thermogravimetric analysis of the adduct showed a weight loss at 140–150°C, which was in quantitative agreement with the amount of butyl acrylate. Infrared analysis showed that furan rings were not completely consumed by extended heating at 110°C. After five heating and cooling cycles of much shorter duration at 140°C, the furan absorption in the infrared disappeared. The storage modulus of acrylated epoxidized soybean oil‐TBPF samples after 20 heating cycles was 1.15 GPa. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Characterization and determination of swelling and diffusion characteristics of poly(n‐vinyl‐2‐pyrrolidone) hydrogels in water

Hydrogels in the form of rods with varying crosslink densities and three‐dimensional network structures were prepared from Poly(N‐vinyl‐2‐pyrrolidone) (PVP)/water and PVP/water/persulfate systems by irradiation with γ rays at ambient temperature. Average molecular weights between crosslinks, percent swelling, swelling equilibrium values, diffusion/swelling characteristics (i.e., the structure of network constant, the type of diffusion, the initial swelling rate, swelling rate constant), and equilibrium water content were evaluated for both hydrogel systems. Water diffusion to the hydrogel is a non‐Fickian type diffusion and diffusion coefficients vary from 6.56 × 10⁻⁷ to 2.51 × 10⁻⁷cm²min⁻¹ for PVP and 6.09 × 10⁻⁷ to 2.14 × 10⁻⁷ cm²min⁻¹ for PVP/persulfate hydrogel systems. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 994–1000, 2000     

Synthesis of high rubber styrene–EPDM–acrylonitrile graft copolymer and its toughening effect on SAN

High rubber styrene–EPDM–acrylonitrile (AES) was prepared by the graft copolymerization of styrene (St) and acrylonitrile (AN) onto ethylene–propylene–diene terpolymer (EPDM) in n‐heptane/toluene cosolvent using benzoyl peroxide as an initiator. The effects of reaction conditions, such as reaction temperature, initiator concentration, EPDM content, the solvent component, and reaction time, on the graft copolymerization are discussed. In addition, according to the research on mechanical properties of the SAN/AES blend, a remarkable toughening effect of AES on SAN resin was found. By means of scanning electron microscopy, the toughening mechanism is proposed to be crazing initiation from rubber particles and shear deformation of SAN matrix. Uniform dispersion of rubber particles, as shown by transmission electron microscopy, is attributed to the good compatibility of SAN and AES. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 416–423, 2004     

Effect of acrylic acid neutralization on ‘livingness’ of poly[styrene‐ran‐(acrylic acid)] macro‐initiators for nitroxide‐mediated polymerization of styrene

BACKGROUND: The effect of acrylic acid neutralization on the degradation of alkoxyamine initiators for nitroxide‐mediated polymerization (NMP) was studied using styrene/acrylic acid and styrene/sodium acrylate random copolymers (20 mol% initial acrylate feed concentration) as macro‐initiators. The random copolymers were re‐initiated with fresh styrene in 1,4‐dioxane at 110 °C at SG1 mediator/BlocBuilder^® unimolecular initiator ratios of 5 and 10 mol%. RESULTS: The value of k_pK (k_p = propagation rate constant, K = equilibrium constant) was not significantly different for styrene/acrylic acid and styrene/sodium acrylate compositions at 110 °C (k_pK = 2.4 × 10^?6–4.6 × 10^?6 s^?1) and agreed closely with that for styrene homopolymerization at the same conditions (k_pK = 2.7 × 10^?6–3.0 × 10^?6 s^?1). All random copolymers had monomodal, narrow molecular weight distributions (polydispersity index M?_w/M?_n = 1.10–1.22) with similar number‐average molecular weights M?_n = 19.3–22.1 kg mol^?1. Re‐initiation of styrene/acrylic acid random copolymers with styrene resulted in block copolymers with broader molecular weight distributions (M?_w/M?_n = 1.37–2.04) compared to chains re‐initiated by styrene/sodium acrylate random copolymers (M?_w/M?_n = 1.33). CONCLUSIONS: Acrylic acid degradation of the alkoxyamines was prevented by neutralization of acrylic acid and allowed more SG1‐terminated chains to re‐initiate the polymerization of a second styrenic block by NMP. Copyright © 2008 Society of Chemical Industry     

Effects of molecular weight and arm number on properties of star‐shape styrene–butadiene–styrene triblock copolymer

A star‐shape styrene–butadiene–styrene triblock copolymer SBS (802) was synthesized and fractionated into four fractions coded as 802‐F1 (four arms), 802‐F2 (two arms), 802‐F3 (one arm), and 802‐F4 by repeating fractional precipitation. Their weight‐average molecular weight (M_w) was measured by size‐exclusion chromatography combined with laser light scattering to be 16.0 × 10⁴, 8.2 × 10⁴, 4.3 × 10⁴, and 1.19 × 10⁴, respectively. The samples were, respectively, compression‐molded and solution‐cast to obtain the sheets coded as 802C, 802‐F1C, 802‐F2C, and 802S, 802‐F1S, 802‐F2S. The structures and mechanical properties of the sheets were characterized by ¹H‐NMR, scanning electron microscope, wide‐angle X‐ray diffractometer, tensile testing, and dynamic mechanical thermal analysis. The results indicated that the compression‐molded 802‐F1C exhibited the higher tensile strength (σ_b, 28.4 MPa) and elongation at break (ε_b, 1610%), and its optical transmittance is much higher than those of 802C and 802‐F2C. This work revealed that the star‐shape SBS with four arms could be helpful in the enhancement of the properties as a result of good miscibility of the compression‐molded SBS sheets. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 832–840, 2005     

Polystyrene nanocomposite materials by in situ polymerization into montmorillonite–vinyl monomer interlayers

A different series of new polystyrene–clay nanocomposites have been prepared by grafting polymerization of styrene with vinyl‐montmorillonite (MMT) clay. The synthesis was achieved through two steps. The first step is the modification of clay with the vinyl monomers, such as N,N‐dimethyl‐n‐octadecyl‐4‐vinylbenzyl‐ammonium chloride, n‐octadecyl‐4‐vinylbenzyl‐ammonium chloride, triphenyl‐4‐vinylbenzyl‐phosphonium chloride, and tri‐n‐butyl‐4‐vinylbenzyl‐phosphonium chloride. The second step is the polymerization of styrene with different ratios of vinyl‐MMT clay. The materials produced were characterized by different physical and chemical methods: (1) IR spectra, confirming the intercalation of the vinyl‐cation within the clay interlayers; (2) thermogravimetric analysis (TGA), showing higher thermal stability for PS–nanocomposites than polystyrene (PS) and higher thermal stability of nanocomposites with of phosphonium moieties than nanocomposites with ammonium moieties; (3) swelling measurements in different organic solvents, showing that the swelling degree in hydrophobic solvents increases as the clay ratio decreases; (4) X‐ray diffraction (XRD), illustrating that the nanocomposites were exfoliated at up to a 25 wt % of organoclay content; and (5) scanning electron microscopy (SEM), showing a complete dispersion of PS into clay galleries. Also, transmission electron microscopy (TEM) showed nanosize spherical particles of ～ 150–400 nm appearing in the images. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3739–3750, 2007     

Characterization of sulfonated poly(styrene–divinylbenzene) and poly(divinylbenzene) and its application as catalysts in esterification reaction

Polymeric supports based on divinylbenzene (DVB) were prepared by aqueous suspension polymerization in presence or absence of styrene (S), using toluene and n‐heptane as diluents of the monomers. Poly(S–DVB) and poly(DVB) were sulfonated with sulfuric acid in presence of 1,2‐dichloroethane. The influence of the morphological structure of the supports and as a consequence of the catalyst on the esterification reaction of acetic acid with n‐butanol was evaluated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3616–3627, 2006     

Photocrosslinking of functionalized rubbers. X. Butadiene–acrylonitrile copolymers

The photocrosslinking of polyacrylonitrile‐block‐polybutadiene‐block‐polyacrylonitrile (ABA) was shown to proceed within seconds at ambient temperature upon UV exposure in the presence of an acylphosphine oxide photoinitiator. The curing process was followed by infrared spectroscopy, insolubilization, and hardness measurements. Complete insolubilization could not be achieved with the neat ABA rubber because of the poor reactivity of the 2‐butene double bond and the low vinyl content of the polybutadiene chain. The addition of multifunctional acrylate monomers (20 wt %) causes a substantial increase of both the reaction rate and the crosslink density of the polymer, which becomes completely insoluble in toluene in less than 1 s upon UV irradiation. An even greater effect was observed by using small amounts (1 wt %) of a trifunctional thiol crosslinker. Both the thiol and the photoinitiator concentrations were shown to affect the kinetics of the thiol–ene polymerization and the polymer network crosslink density. A direct relationship was found to exist between the swelling degree of the UV‐cured rubber and the interchain molecular weight of the network. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2204–2216, 2001     

Postcrosslinking of macroporous styrene–divinylbenzene copolymers via pendant vinyl groups: Effect of the starting copolymers on the pore structure of the postcrosslinked products

In the presence of anhydrous ferric chloride as a Friedel–Crafts catalyst, the postcrosslinking reaction of macroporous styrene–divinylbenzene (St–DVB) copolymers synthesized under different conditions was carried out with 1,2‐dichloroethane as a solvent. Without an externally added crosslinking agent, the specific surface area and pore volume, for copolymers with different DVB isomers or different DVB contents after reaction, in most cases increased significantly, and the increase was found to be heavily dependent upon the amount of the pendant vinyl groups in the starting copolymers. These results further confirm the role of the pendant vinyl groups in creating new crosslinking bonds in addition to those created by a free‐radical crosslinking reaction in the starting copolymers, and an alkylation reaction of the vinyl groups with neighboring aromatic rings is believed to dominate the course of the postcrosslinking at a relatively high level of the vinyl group contents. The synthesis conditions, including the n‐heptane content in a mixed diluent and the amount of the diluent, under which the starting copolymers were synthesized, play an important role in the increase of the surface area and pore volume of the copolymers after postcrosslinking. The effect of these conditions is attributed mainly to the swelling ability of the starting copolymers thus obtained in the solvent used for reaction. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1668–1677, 2002     

Styrene-Divinylbenzene Copolymers: Influence of the Diluents on Absorption and Desorption Properties

Styrene-divinylbenzene copolymers with porous structures were prepared by seeded suspension polymerization using toluene and heptane as diluents. The influence of each diluent on the formation of porous structure and the swelling ratio was investigated. The styrene-DVB beads are capable of absorption and desorption of organic solvents having solubility parameters in the range of 17.6–19.6 (MPa)1/2. Styrenic imbiber beads were swelled in toluene and the kinetics of absorption was studied. The imbiber bead could absorb toluene completely within 90 min and yielded a maximum swelling ratio of 12.7. The diffusion coefficient values of these beads were in the range of 1.55 × 10–5 to 3.68 × 10–5 cm2 · s–1.     

Vinyl triazole carrying metal‐chelated beads for the reversible immobilization of glucoamylase

Poly(ethylene glycol dimethacrylate–1‐vinyl‐1,2,4‐triazole) [poly(EGDMA–VTAZ)] beads with an average diameter of 100–200 μm were obtained by the copolymerization of ethylene glycol dimethacrylate (EGDMA) with 1‐vinyl‐1,2,4‐triazole (VTAZ). The copolymer hydrogel bead composition was determined by elemental analysis and was found to contain 5 EGDMA monomer units for each VTAZ monomer unit. The poly(EGDMA–VTAZ) beads were characterized by swelling studies and scanning electron microscopy (SEM). The specific surface area of the poly(EGDMA–VTAZ) beads was found 65.8 m²/g. Cu²⁺ ions were chelated on the poly(EGDMA–VTAZ) beads. The Cu²⁺ loading was 82.6 μmol/g of support. Cu²⁺‐chelated poly(EGDMA–VTAZ) beads with a swelling ratio of 84% were used in the immobilization of Aspergillus niger glucoamylase in a batch system. The maximum glucoamylase adsorption capacity of the poly(EGDMA–VTAZ)–Cu²⁺ beads was 104 mg/g at pH 6.5. The adsorption isotherm of the poly(EGDMA–VTAZ)–Cu²⁺ beads fitted well with the Langmuir model. Adsorption kinetics data were tested with pseudo‐first‐ and second‐order models. The kinetic studies showed that the adsorption followed a pseudo‐second‐order reaction model. The Michaelis constant value for the immobilized glucoamylase (1.15 mg/mL) was higher than that for free glucoamylase (1.00 mg/mL). The maximum initial rate of the reaction values were 42.9 U/mg for the free enzyme and 33.3 U/mg for the immobilized enzyme. The optimum temperature for the immobilized preparation of poly(EGDMA–VTAZ)–Cu²⁺–glucoamylase was 65°C; this was 5°C higher than that of the free enzyme at 60°C. The glucoamylase adsorption capacity and adsorbed enzyme activity slightly decreased after 10 batch successive reactions; this demonstrated the usefulness of the enzyme‐loaded beads in biocatalytic applications. The storage stability was found to increase with immobilization. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Superabsorbent polymeric materials VIII: Swelling behavior of crosslinked poly[sodium acrylate‐co‐trimethyl methacryloyloxyethyl ammonium iodide] in aqueous salt solutions

A series of xerogels based on sodium acrylate (SA), cationic comonomer, trimethyl methacryloyloxyethyl ammonium iodide (TMMAI), and N,N‐methylene‐bis‐acrylamide (NMBA) were prepared by inverse suspension polymerization. The water absorbency and the swelling behavior for these high absorbent polymers in deionized water and various saline solutions were investigated. Results indicated that the water absorbency for the present copolymer gel increased when a small amount of TMMAI monomer was introduced into the SA gel, then decreased with increase in TMMAI content. The water absorbency was 583 g H₂O/g for a gel sample in deionized water containing 2.5 × 10⁻³ molar fraction TMMAI. But a contrary result was observed for initial absorption rate, that is, the initial absorption rates increased with an increase of TMMAI in deionized water and 0.9 wt % NaCl solution. The absorbency in the chloride salt solution decreased with an increase in the ionic strength of the salt solution. Finally, the adsorption of copper ion by these gels was also investigated. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1665–1674, 2001     

Study of Carbon Deposition Behavior on Cu–Co/CeO2–YSZ Anodes for Direct Butane Solid Oxide Fuel Cells

Electro‐catalytic activity of Cu–Co/CeO₂–YSZ anodes towards oxidation of H₂ and n‐C₄H₁₀ fuels and carbon depositions are investigated using different Cu–Co loadings. Cu–Co/CeO₂–YSZ anode based SOFCs with YSZ as electrolyte and LSM/YSZ as cathode were prepared by tape casting and wet impregnation methods and performance was analyzed using I–V characteristics and impedance spectroscopy. The Cu–Co/CeO₂–YSZ anodes with Cu–Co loading of 10, 15, and 25 wt.% produced power density of 60, 197, and 400 mW cm^–2 in H₂ and 190, 225, and 275 mW cm^–2 in n‐C₄H₁₀ at 800 °C. The power density is increased with the increase in Cu–Co loading in Cu–Co/CeO₂–YSZ anodes. The electrochemical impedance spectra shows less ohmic and polarization resistance for 25 wt.% Cu–Co loading in comparison to 10 and 15 wt.% Cu–Co. Scanning electron microscopy and high resolution transmission electron microscopy shows that the carbon fibers formed are hollow in nature with 70 nm size, whereas, thermal gravimetric analysis and X‐ray diffraction points out that they are amorphous in nature. The performance degradation of Cu–Co/CeO₂–YSZ anodes in n‐C₄H₁₀ in 16 h is attributed to increasing amount of carbon deposition with time, which is contrary to our earlier observation in Cu‐Fe/CeO₂–YSZ anode.     

Novel method for preparation of quaternary ammonium ionomer from epoxidized styrene–butadiene–styrene triblock copolymer and its use as compatibilizer for blending of styrene–butadiene–styrene and chlorosulfonated polyethylene

A novel method for the preparation of a quaternary ammonium ionomer of styrene–butadiene–styrene triblock copolymer (SBS) was developed by a ring‐opening reaction of epoxidized SBS with triethylamine hydrochloride in the presence of a phase transfer catalyst. The optimum conditions were studied. The ionomer was characterized by quantitative analysis, IR spectroscopy, and ¹H‐NMR spectroscopy. Its water absorbency, oil absorbency, dilute solution viscosity, and use as a compatibilizer for the blending of SBS and chlorosulfonated polyethylene (CSPE) were investigated. The results showed that, under optimum conditions, the epoxy groups can be completely converted to the quaternary ammonium groups. The IR spectrum did not exhibit the absorption peak for quaternary ammonium groups, whereas the ¹H‐NMR spectrum and titration method demonstrated it. With increasing ionic group content, the water absorbency of the ionomer increased whereas its oil absorbency decreased. These indicated the amphiphilic character of the SBS ionomer. The dilute solution viscosity of the ionomer in toluene/methanol (9/1) solvent increased with increasing quaternary ammonium group content. The ionomer was used as a compatibilizer for the blends of SBS and CSPE. The addition of a small amount of the ionomer to the blend enhanced the mechanical properties of the blends: 2 wt % ionomer based on the blend increased the tensile strength and ultimate elongation of the blend nearly 2 times. The blends of equal parts SBS and CSPE behaved as oil‐resistant thermoplastic elastomers. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1975–1980, 2006     

Stability of electrical properties of carbon black‐filled rubbers

Conducting composites were prepared by melt mixing of ethylene–propylene–diene terpolymer (EPDM) or styrene‐butadiene rubber (SBR) and 35 wt % of carbon black (CB). Stability of electrical properties of rubber/CB composites during cyclic thermal treatment was examined and electrical conductivity was measured in situ. Significant increase of the conductivity was observed already after the first heating–cooling cycle to 85°C for both composites. The increase of conductivity of EPDM/35% CB and SBR/35% CB composites continued when cyclic heating‐cooling was extended to 105°C and 125°C. This effect can be explained by reorganization of conducting paths during the thermal treatment to the more conducting network. EPDM/35% CB and SBR/35% CB composites exhibited very good stability of electrical conductivity during storage at ambient conditions. The electrical conductivity of fresh prepared EPDM/35% CB composite was 1.7 × 10⁻² S cm⁻¹, and slightly lower conductivity value 1.1 × 10⁻² S cm⁻¹ was measured for SBR/35% CB. The values did not significantly change after three years storage. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Michaelis–Menten kinetics for enzymatic depolymerization of a linear polyester synthesized from Z‐protected glutamic acid

A biodegradable polyester resin was polymerized from N‐benzyloxycarbonyl‐L ‐glutamic acid and ethylene glycol. Rhizopus delemar lipase was used as a biocatalyst for the rupture of ester bonds during the hydrolysis studies. Depolymerization was observed to follow a Michaelis–Menten mechanism, with the maximum rate of monomer formation dP/dt_max = 1.12 × 10⁻⁸ mol/s and the rate constant K_m × 2.03 × 10⁻⁴ mol. Subject to initial conditions described by the most probable distribution and Michaelis–Menten–type depolymerization rate expressions, population density distribution dynamics of the polymeric molecules that formed the resin were explicitly described using a deterministic approach. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 514–520, 2001     

Pore memory of macroporous styrene–divinylbenzene copolymers

The variation of the pore structure of styrene–divinylbenzene (S–DVB) copolymer beads with the drying conditions was investigated. Macroporous S–DVB copolymer beads with various DVB contents were prepared in the presence of toluene‐cyclohexanol mixtures as a diluent. It was found that the pores of 10¹‐nm radius, corresponding to the interstices between the microspheres, collapse upon drying of the copolymers from toluene. The collapsed pores reexpand if the copolymers were dried from methanol. The collapse–reexpansion process of the pores was found to be reversible, indicating that the actual pore structure formed during the crosslinking copolymerization is memorized by the copolymer network. The magnitude of the pore structure variation increased on worsening the polymer–diluent interactions during the gel formation process due to the simultaneous increase in crosslink density distribution. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1055–1062, 1999