Temperature effect on the swelling of PAAm‐κ‐carrageenan composites

The steady‐state fluorescence (SSF) technique was used for studying swelling of disc‐shaped polyacrylamide (PAAm)‐κ‐carrageenan (κC) composites which were prepared by free‐radical crosslinking copolymerization at 80°C. Pyranine was introduced as a fluorescence probe during polymerization. Swelling experiments were performed in water at various temperatures by real‐time monitoring of the pyranine (Py) fluorescence intensity, I which decreased as swelling proceeded. Stern–Volmer equation is modified for low quenching efficiencies to interpret the behavior of Py intensity during the swelling of PAAm‐κC composites. The Li‐Tanaka equation was used to determine the swelling time constants, τ₁, and cooperative diffusion coefficients, D₀, from fluorescence intensity, weight, and volume variations of the composites at various temperatures. It was observed that τ₁ first decreased up to 40°C and then increased; naturally, D₀ increased up to 40°C and then decrease for all κC content gels. Swelling activation energies, ΔE, were measured for the swelling composites, which are found to be exothermic and endothermic in between 30–40 and 40–60°C, respectively. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Computed Thermodynamic and Explosive Properties of 1‐Azido‐2‐nitro‐2‐azapropane (ANAP)

Some thermodynamic and explosive properties of the recently reported 1‐azido‐2‐nitro‐2‐azapropane (ANAP) have been determined in a combined computational ab initio (MP2/aug‐cc‐pVDZ) and EXPLO5 (Becker–Kistiakowsky–Wilson's equation of state, BKW EOS) study. The enthalpy of formation of ANAP in the liquid phase was calculated to be Δ_fH°, ANAP(l)=+297.1 kJ mol⁻¹. The heat of detonation (Q_v), the detonation pressure (P), and the detonation velocity of ANAP were calculated to be Q_v=−6088 kJ kg⁻¹, P=23.8 GPa, D=8033 m s⁻¹. A mixture of ANAP and tetranitromethane (TNM) was investigated in an attempt to tailor the impact sensitivity of ANAP, but results obtained indicate that the mixture is almost as sensitive as pure ANAP. On the other hand, ANAP and TNM were found to be chemically compatible (¹H, ¹³C, ¹⁴N NMR; DSC) and a 1 : 1 mixture (by weight) of both components was calculated to have superior explosive properties than either of the individual components: Q_v=−6848 kJ kg⁻¹, P=27.0 GPa, D=8284 m s⁻¹.     

Three‐dimensional color prediction modeling of single‐ and double‐layered woven fabrics

In this research, the three‐dimensional structural and colorimetric modeling of three‐dimensional woven fabrics was conducted for accurate color predictions. One‐hundred forty single‐ and double‐layered woven samples in a wide range of colors were produced. With the consideration of their three‐dimensional structural parameters, three‐dimensional color prediction models, K/S‐, R‐, and L*a*b*‐based models, were developed through the optimization of previous two‐dimensional models which have been reported to be the three most accurate models for single‐layered woven structures. The accuracy of the new three‐dimensional models was evaluated by calculating the color differences ΔL*, ΔC*, Δh°, and ΔE_CMC(2:1) between the measured and the predicted colors of the samples, and then the error values were compared to those of the two‐dimensional models. As a result, there has been an overall improvement in color predictions of all models with a decrease in ΔE_CMC(2:1) from 10.30 to 5.25 units on average after the three‐dimensional modeling.     

Physical properties of hydrogels of poly(2‐hydroxyethyl methacrylate) and copolymers with mono‐methyl itaconate synthesized by bulk and solution polymerization

The physical properties found during the swelling process of poly(2‐hydroxyethyl methacrylate) (PHEMA) and of copolymers of HEMA with mono‐n‐methyl itaconate, synthesized by solution and bulk polymerization, are reported. The swelling kinetics were followed at four different temperatures (295, 300, 305 and 310 K). Experimental data follow second‐order swelling kinetics, from where the kinetic rate constant k_∞ and the swelling capacity at equilibrium W_∞ were calculated as a function of temperature. The kinetic rate constant obeys Arrhenius behaviour. The following network parameters were determined for the hydrogels: Young's moduli E, effective crosslinking density v_e, molar mass per crosslink M_C, volume fraction ϕ₂ and polymer‐liquid interaction parameter χ. © 2000 Society of Chemical Industry     

Colon‐specific oral delivery of vitamin B2 from poly(acrylamide‐co‐maleic acid) hydrogels: An in vitro study

Hydrogels, composed of poly(acrylamide‐co‐maleic acid) were synthesized and the release of vitamin B₂ from these gels was studied as a function of the pH of the external media, the initial amount of the drug loaded, and the crosslinking ratio in the polymer matrix. The gels containing 3.8 mg of the drug per gram gel exhibit almost zero‐order release behavior in the external media of pH 7.4 over the time interval of more than their half‐life period (t_1/2). The amount of the drug loaded into the hydrogel also affected the dynamic release of the encapsulated drug. As expected, the gels showed a complete swelling‐dependent mechanism, which was further supported by the similar morphology of the swelling and release profiles of the drug‐loaded sample. The hydrophilic nature of the drug riboflavin does not contribute toward the zero‐order release dynamics of the hydrogel system. On the other hand, the swelling osmotic pressure developed between the gels and the external phase, due to loading of the drug by equilibration of the gels in the alkaline drug solution, plays an effective role in governing the swelling and release profiles. Finally, the minimum release of the drug in the swelling media of pH 2.0 and the maximum release with zero‐order kinetics in the medium of pH 7.4 suggest that the proposed drug‐delivery devices have a significant potential to be used as an oral drug‐delivery system for colon‐specific delivery along the gastrointestinal (GI) tract. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1133–1145, 2002; DOI 10.1002/app.10402     

Thermoreversible hydrogels. VII. Synthesis and swelling behavior of poly(N‐isopropylacrylamide‐co‐3‐methyl‐1‐vinylimidazolium iodide) hydrogels

A series of N‐isopropylacrylamide/3‐methyl‐1‐vinylimidazolium iodide (NIPAAm/MVI) copolymer gels were prepared from the various molar ratios of NIPAAm, cationic monomer MVI, and N,N′‐methylene bisacrylamide (NMBA) in this study. The influence of the amount of MVI in the copolymer gels on the swelling behaviors was investigated in various aqueous saline solutions. Results showed that the swelling ratios (SRs) of copolymer gels were significantly greater than those of NIPAAm homopolymer gels, and the higher the MVI content, the higher the volume phase transition temperature. The SRs for the NIPAAm/MVI copolymer gels decreased with an increase of the salt concentration. In various saline solutions, results showed that the effect of divalent ions on the SR was greater than that of monovalent ions for these hydrogels. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3242–3253, 1999     

pH‐thermoreversible hydrogels. I. Synthesis and swelling behaviors of the (N‐isopropylacrylamide‐co‐acrylamide‐co‐2‐hydroxyethyl methacrylate) copolymeric hydrogels

A series of pH‐thermoreversible hydrogels that exhibited volume phase transition was synthesized by various molar ratios of N‐isopropylacrylamide (NIPAAm), acrylamide (AAm), and 2‐hydroxyethyl methacrylate (HEMA). The influence of environmental conditions such as temperature and pH value on the swelling behavior of these copolymeric gels was investigated. Results showed that the hydrogels exhibited different equilibrium swelling ratios in different pH solutions. Amide groups could be hydrolyzed to form negatively charged carboxylate ion groups in their hydrophilic polymeric network in response to an external pH variation. The pH sensitivities of these gels also depended on the AAm content in the copolymeric gels; thus the greater the AAm content, the higher the pH sensitivity. These hydrogels, based on a temperature‐sensitive hydrogel, demonstrated a significant change of equilibrium swelling in aqueous media between a highly solvated, swollen gel state and a dehydrated network response to small variations of temperature. pH‐thermoreversible hydrogels were used for a study of the release of a model drug, caffeine, with changes in temperature. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 221–231, 1999     

Effect of comonomer type and concentration on the equilibrium swelling and volume phase transition temperature of N‐isopropylacrylamide‐based hydrogels

The effect of incorporating a hydrophilic monomer into poly(N‐isopropylacrylamide) (polyNIPA) hydrogels on the equilibrium swelling and the volume phase transition temperature is reported here. A nonionizable monomer (acrylamide) and three ionizable monomers (itaconic acid, 2‐ethoxyethyl monoitaconate, and 2,2‐(2‐ethoxyethyl) monoitaconate) were studied. Hydrogels with larger swelling capacity than that of the polyNIPA hydrogel were obtained. With the exception of the hydrogel containing 2,2‐(2‐ethoxyethyl) monoitaconate, which did not exhibit the de‐swelling phenomena, the rest showed a volume phase transition. The hydrogels containing 85 wt % acrylamide and 15 wt % comonomer presented the higher shrinking ratio. For some compositions, the T_c of the polyNIPA hydrogel was within the desired temperature range (38–41°C) for controlled‐drug delivery in the human body. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Swelling characteristics of thermo‐ sensitive poly[(2‐diethylaminoethyl methacrylate)‐co‐(N,N‐dimethylacrylamide)] porous hydrogels

Temperature‐sensitive poly[(2‐diethylaminoethyl methacrylate)‐co‐(N,N‐dimethylacrylamide)] [P(DEAEMA‐co‐DMAAm)] hydrogels with five different DMAAm contents were synthesized with and without the addition of sodium carbonate as porosity generator. The synthesized hydrogels were characterized with dry gel density measurements, scanning electron microscopy observation and the determination of swelling ratio. The influence of the pore‐forming agent and content of DMAAm on swelling ratio and network parameters such as polymer–solvent interaction parameter (χ), average molecular mass between crosslinks (M?_c) and mesh size (ζ) of the cryogels are reported and discussed. The swelling and deswelling rates of the porous hydrogels are much faster than for the same type of hydrogels prepared via conventional methods. At a temperature below the volume phase transition temperature, the macroporous hydrogels also absorbed larger amounts water compared to that of conventional hydrogels and showed obviously higher equilibrated swelling ratios in aqueous medium. In particular, the unique macroporous structure provided numerous water channels for water diffusion in or out of the matrix and, therefore, an improved response rate to the external temperature changes during the deswelling and swelling processes. These properties are attributed to the macroporous and regularly arranged network of the porous hydrogels. Scanning electron micrographs reveal that the macroporous network structure of the hydrogels can be adjusted by applying porosity generation methods during the polymerization reaction. Copyright © 2007 Society of Chemical Industry     

Release of vitamin B12 from poly(N‐vinyl‐2‐pyrrolidone)‐crosslinked polyacrylamide hydrogels: A kinetic study

Hydrogels, composed of poly(N‐vinyl‐2‐pyrrolidone) and crosslinked polyacrylamide, were synthesized and the release of vitamin B₁₂ from these hydrogels was studied as a function of the degree of crosslinking and pH of the external swelling media. The three drug‐loaded hydrogel samples synthesized with different crosslinking ratios of 0.3, 0.7, and 1.2 (in mol %) follow different drug‐release mechanisms, that is, chain relaxation with zero‐order, non‐Fickian and Fickian, or diffusion‐controlled mechanisms. To establish a correlation between their swelling behavior and drug‐release mechanism, the former was studied by the weight‐gain method and, at the same time, the concentration of the drug released was studied colorimetrically. Various swelling parameters such as the swelling exponent n, gel‐characteristic constant k, penetration velocity v, and diffusion coefficient D were evaluated to reflect the quantitative aspect of the swelling behavior of these hydrogels. Finally, the drug‐release behavior of the hydrogels was explained by proposing the swelling‐dependent mechanism. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1706–1714, 2000     

Rapid pH‐dependent phase transition and elasticity of stimuli‐responsive cationic poly(N,N‐dimethylaminoethyl methacrylate) hydrogels prepared with a dimethacrylate crosslinker

Stimuli‐responsive hydrogels prepared from poly(N,N‐dimethylaminoethyl methacrylate) (PDMAEMA) and its copolymers have attracted much interest to serve in biomedical and pharmaceutical applications. To investigate pH‐dependent swelling and elasticity, a series of cationic hydrogels based on N,N‐dimethylaminoethyl methacrylate were prepared by free radical crosslinking copolymerization at 60 °C in the presence of tetraethylene glycol dimethacrylate as the crosslinker. The equilibrium swelling and the mechanical properties of the PDMAEMA hydrogels were investigated as a function of the gel preparation concentration. To explain the effect of pH on the equilibrium swelling of the hydrogels, pH‐dependent swelling studies were carried out in solutions of pH ranging from 2.1 to 10.7. It was found that the PDMAEMA hydrogels exhibit a rapid pH‐dependent phase transition in aqueous solutions; that is, the gels first remain in the swollen state at acidic pH then collapse in a very narrow range of pH. The results showed that the volume of PDMAEMA hydrogels in acidic conditions is about 10‐ to 40‐fold larger than that in the basic pH region. By using the Flory–Rehner theory, the characteristic network parameters of the PDMAEMA hydrogels were calculated and good agreement obtained between the swelling equilibria of hydrogels and their mechanical properties over the whole range of gel preparation concentration. © 2012 Society of Chemical Industry     

Phase behavior of N‐isopropylacrylamide/acrylic acid copolymer hydrogels prepared with ultrasound

N‐Isopropylacrylamide/acrylic acid copolymer hydrogels were synthesized with ultrasound. The thermoresponsive phase behaviors of gels synthesized with ultrasound (US gels) were investigated and compared with those of gels synthesized in the absence of ultrasound (FR gels). The US gels showed thermoresponsive swelling behavior with a large hysteresis over a wide range of temperatures around its phase‐transition temperature. The hysteresis became larger with an increasing copolymerized acrylic acid content. The US gels were also characterized from the viewpoint of chemical, hydration, and macroscopic physical structures. Little difference was observed in the chemical and hydration structures of the FR gels and US gels. The macroscopic physical structure of the US gels was, however, distinct from that of the FR gels. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2449–2452, 2003     

Carbon black‐filled poly(ethylene‐co‐alkyl acrylate) composites: Calorimetric studies

The calorimetric characteristics of carbon black (CB)/poly(ethylene‐co‐alkyl acrylate) composites depend on both the CB and acrylate contents. An increase of the acrylate content in the pure copolymers tends to decrease all the crystalline characteristics: T_c,n, the nonisothermal crystallization temperature; T_m, the melting temperature, and ΔH_m, the melting enthalpy. CB modifies the crystallization kinetics of poly(ethylene‐co‐ethyl acrylate) (EEA) alone and in blends with poly(ethylene‐co‐24% w/w methyl acrylate) (24EMA) and poly(ethylene‐co‐35% w/w methyl acrylate) (35EMA). In the presence of CB, T_c,n, the nonisothermal crystallization temperature of EEA, increases and t_1/2, the half‐crystallization time, decreases for a given isothermal crystallization temperature, T_c,i. The thermograms obtained during the melting of EEA after isothermal crystallization show multiple endotherms, suggesting that crystalline‐phase segregation has occurred. The existence of different crystalline species can be explained by the presence of fractions of different acrylate content in the copolymers as shown by SEC. Therefore, CB does not seem to have much effect on the subsequent melting temperature of EEA, T_m,s. CB also induces a lower melting enthalpy, Δ H_m, in the blends. This decrease of ΔH_m appears to be constant whatever the compound, but when reported to the melting enthalpy of the polymer without CB, δΔH_m/ΔH_m increases with the acrylate content. A slight increase of the amorphous phase stiffness after CB introduction is noticed: The T_g of EEA/24EMA and EEA/35EMA blends increases by several degrees. Therefore, plotting ΔH_m versus ΔC_p shows that for the same ΔH_m the ΔC_p is lower in CB‐filled samples, suggesting there is some kind of rigid amorphous phase not contributing to the glass transition. We propose to explain the CB activity during the crystallization process by the existence of molecular interactions between CB and acrylate groups rather than by a pure nucleating effect. Thus, the increase of T_c,n and the decrease of ΔH_m could be explained by the fact that CB separates acrylate‐rich chains from the crystallization medium, accelerating the crystallization of the acrylate‐poor chains. During such a crystallization process, CB may be preferentially localized in the more polar amorphous phase and scattered between the two crystalline phases of EEA and EXA. These blends of poly(ethylene‐co‐alkyl acrylate) copolymers with CB provide interesting materials with adjustable properties depending on the acrylate and CB contents and on the thermomechanical treatments. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 779–793, 2001     

Improved swelling–deswelling behavior of poly(N‐isopropyl acrylamide) gels with poly(N,N′‐dimethyl aminoethyl methacrylate) grafts

Thermoresponsive and pH‐responsive gels were synthesized from N‐isopropyl acrylamide (NIPA) and N,N′‐dimethyl aminoethyl methacrylate (DMAEMA) monomers. Gelation reactions were carried out with both conventional free‐radical polymerization (CFRP) and controlled free‐radical polymerization [reversible addition fragmentation transfer (RAFT)] techniques. The CFRP gels were prepared by polymerizing mixtures of NIPA and DMAEMA in 1,4‐dioxane in presence of N,N'‐methylene bisacrylamide (BIS) as cross‐linker. The RAFT gels were prepared by a the polymerization of NIPA via a similar process in the presence of different amounts of poly(N,N′‐dimethyl aminoethyl methacrylate) macro chain‐transfer agent and the crosslinker. These gels were characterized by scanning electron microscopy (SEM) and differential scanning calorimetry. SEM analysis revealed a macroporous network structure for the RAFT gels, whereas their volume phase‐transition temperatures (VPTTs) were found to be in the range 32–34°C, close to that of poly(N‐isopropyl acrylamide) gels. However, the CFRP copolymer gels exhibited a higher VPTT; this increased with increasing DMAEMA content. The RAFT gels exhibited higher swelling capabilities than the corresponding CFRP gels and also showed faster shrinking–reswelling behavior in response to changes in temperature. All of the gels showed interesting pH‐responsive behavior as well. The unique structural attributes exhibited by the RAFT gels can potentially open up opportunities for developing new materials for various applications, for example, as adsorbents or carrier of drugs or biomolecules. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42749.     

Preparation and swelling properties of solution crosslinked poly(cis‐1,4‐butadiene) gels

Poly(cis‐1,4‐butadiene) (PCB) gels were prepared by the crosslinking polymerization of 4‐tert‐butylstyrene (tBS) and divinylbenzene (DVB) onto unvulcanized butadiene rubber with a solution polymerization technique with benzoyl peroxide (BPO) as an initiator. The effects of the reaction conditions, such as the amount of the solvent, the amount of DVB and tBS, and the initiator (BPO), on the equilibrium swelling ratio (Q_e) were also investigated. The highest oil absorbencies of crosslinked gels in xylene and cyclohexane were 51.35 and 32.98 g/g, respectively. A swelling kinetic equation was proposed for this system: Q_t = Q_e ? {Kt + [1/(Q_e ? Q₀)]}^?1, where Q_t is the swelling ratio at time t, Q₀ is the initial swelling ratio, and K is the swelling kinetic constant. This equation fit the experimental results quite well. The diffusion of organic solvents in PCB gels was Fickian. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2241–2245, 2003     

Volume phase transition in poly(N‐isopropylacrylamide) gels in seawater at high pressures

The swelling behavior of poly(N‐isopropylacrylamide) (PNIPA) gels in seawater at high pressures up to ～40 MPa is examined in terms of human activity at deep sea. The neutral gel in seawater undergoes a continuous volume transition at 26°C at atmospheric pressure. Addition of the ionic group (sodium acrylate) does not have much effect on the swelling properties of the gels in seawater except that the transition temperature is somewhat increased. At high constant pressures up to ～40 MPa, the gels undergo a continuous volume transition at 26–28°C as the temperature varies. Normally, the gel takes a swollen state at deep sea. The ratio of the volume change associated with the transition is more than 10, which is 3 times larger than that obtained by changing the pressure at a constant temperature. The results suggest a possibility that the phase transition of PNIPA gels is utilized for producing mechanochemical energy at deep sea. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1069–1072, 2005     

Time‐resolved small‐angle X‐ray scattering study of void fraction evolution in high‐density polyethylene during stress unloading and strain recovery

By means of time‐resolved small‐angle X‐ray scattering, we developed an analysis methodology to assess the void volume fraction ?_v in high‐density polyethylene (HDPE) during tensile testing. The specimens were first drawn up to different imposed strains, and subsequently were subjected to stress unloading and strain recovery stages. During the loading stage, ?_v progressively increased with the strain level, starting from a well‐defined onset strain prior to the yield point. In particular, ?_v reached a maximum of 8.75 vol% for a strain of 12.5% in the case of a HDPE grade with a molecular weight of 105 000 g mol^?1. Stress unloading and strain recovery caused a decrease in ?_v attained at the end of the loading stage. For a HDPE grade with a molecular weight of 55 000 g mol^?1, ?_v was more important during the loading stage and the decrease in ?_v was less marked during the stress unloading stage when compared to the HDPE with molecular weight of 105 000 g mol^?1. The residual and reversible components of void volume fraction were revealed. © 2015 Society of Chemical Industry     

Adsorption of ammonium and nitrate ions by poly(N‐isopropylacrylamide) gel and poly(N‐isopropylacrylamide‐co‐chlorophyllin) gel in different states

The adsorption of ammonium and nitrate by temperature‐stimulus‐responsive poly(N‐isopropylacrylamide) (NIPA) gel and poly(N‐isopropylacrylamide‐co‐chlorophyllin) (NIPA‐CH) gel in different states was investigated. Both the NIPA gel and NIPA‐CH gel could adsorb ammonium and nitrate in a swollen state (swollen gel) and a swelling state (swelling gel), and they adsorbed ammonium more than nitrate. When the gels were shrinking (shrinking gel), they could adsorb a little ammonium from solution, but when the gels were in a shrunken state (shrunken gel), they hardly adsorbed ammonium. The adsorption of both ammonium and nitrate increased for the swelling NIPA gel in comparison with the swollen gel. The NIPA‐CH gel was the opposite in this respect. The difference in the amounts of adsorption of ammonium and nitrate by the swollen and swelling NIPA‐CH gels was more significant than that of the NIPA gels. It was suggested that ions such as ammonium and nitrate could not diffuse into the gels freely. The adsorption of ammonium and nitrate was affected not only by the phase transitions of the gels but also by the electrical charges. The experimental results for the adsorption of ammonium and nitrate during the volume changes of the gels imply that if the gels are applied to the immobilization of microorganisms, they may improve mass transfer between the immobilization matrix and bulk liquid under cyclic temperature changes and promote reactions of the immobilized microorganisms, especially the nitrification of nitrifying bacteria immobilized by the NIPA‐CH gel. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2367–2372, 2005     

Temperature‐responsive properties of poly(acrylic acid‐co‐acrylamide)‐graft‐oligo(ethylene glycol) hydrogels

A series of temperature‐ and pH‐responsive hydrogels were prepared from acrylic acid (AAc), acrylamide (AAm), oligo(ethylene glycol)monoacrylate (OEGMA), and oligo(ethylene glycol)diacrylate by varying the AAc:AAm molar ratio and the OEGMA content. Phase‐transition temperatures and swelling ratios of the obtained poly(AAc‐co‐AAm)‐graft‐OEG gels were measured as a function of temperature and pH. At pH < 5, the obvious transition temperatures ranging from 5 to 35°C were obtained as the AAc : AAm molar ratio was varied. The highest transition temperature was obtained at the AAc : AAm ratios of 5 : 5 and 6 : 4, and the sharp transition curves were observed at the AAc : AAm ratios from 5 : 5 to 8 : 2. The transition temperature further increased with increasing OEGMA content. It was suggested that OEG graft chains with a large mobility played an important role for the formation of hydrogen bonding in the hydrogels. The gels prepared here showed obvious reproducibility of the phase transition in response to temperature changes, which suggests the feasibility of their practical applications. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 798–805, 2001     

Preparation and properties of silicone‐containing poly(methyl methacrylate) gels

Poly(methyl methacrylate) (PMMA) gels with varying amounts of silicone and solvent and constant amounts of crosslinker were prepared by solution free radical crosslinking copolymerization of methyl methacrylate (MMA), ethylene glycol dimethacrylate (EGDM), tetraethoxysilane (TEOS) and vinyltriethoxysilane (VTES) comonomer systems. They were then studied in benzene at a total monomer concentration of 3.5 mol L^?1 and 70 °C. The conversion of monomer, volume swelling ratio, weight fraction and gel point were measured as a function of the reaction time, silicone concentration and benzene content up to the onset of macrogelation. Structural characteristics of the gels were examined by using equilibrium swelling in benzene, gel fraction and Fourier‐transform infrared (FTIR) analysis. The morphology of the copolymers was also investigated by SEM. Based on the obtained results, it was concluded that the FTIR data did not have the capacity to show the presence of the VTES or TEOS moiety in these kinds of copolymers. On the other hand, the variation of weight fraction of gel, W_g, and its equilibrium volume swelling ratio in benzene, q_v, exhibited the same behaviour as that of MMA/EGDM copolymers. Also, the dilution of the monomer mixture resulted in an increase in the gel point and swelling degree and a decrease in the percent of conversion and gel fraction. Finally, TEOS is not an ideal silicone compound for reaction in the MMA/EGDM copolymerization system, whereas VTES is a suitable silicone comonomer for this system and it has been proved useful. Copyright © 2005 Society of Chemical Industry