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     

Effects of cyclization and pendant vinyl group reactivity on the swelling behavior of polyacrylamide gels

A series of polyacrylamide (PAAm) gels were prepared by free-radical crosslinking copolymerization of acrylamide and N,N′-methylenebis(acrylamide) (BAAm) in water at various crosslinker (BAAm) and chain transfer agent (isopropyl alcohol, IPA) concentrations. It was shown that only 5% of the crosslinker used in the feed forms effective crosslinks in the final hydrogels. At BAAm contents as high as 3 mole%, the equilibrium swelling ratio of the gels in water is independent of the crosslinker content in the feed. This is due to the prevailing multiple crosslinking reactions during the gel formation process. At a fixed crosslinker content, the onset of gelation is shifted towards higher conversions and reaction times as the amount of IPA increases. Addition of IPA in the monomer mixture also increases the equilibrium swelling ratio of PAAm gels. It was shown that the gel crosslinking density increases on rising IPA concentration in the feed due to the increasing rate of intermolecular crosslinking reactions. Received: 30 May 1997/Accepted: 26 June 1997     

Monomer consumption rates during gelation at various temperatures: A fast transient fluorescence study

The gelation during free-radical crosslinking copolymerization (FCC) of methyl methacrylate (MMA) and ethylene glycol dimethacrylate (EGDM) was studied by using fast transient fluorescence (FTRF) technique. Pyrene (Py) was used as a probe for the FTRF experiments. Fluorescence lifetimes of Py from its decay traces were measured and used to monitor the gelation process at various temperatures. MMA consumption rates were measured during gelation process by using the Stern–Volmer model. Gelation activation energy ΔE_G was measured and found to be 15.6 kcal mol⁻¹. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3161–3168, 2001     

In situ fluorescence study of slow release and swelling processes in gels formed by solution free radical copolymerization

A novel method based on steady state fluorescence (SSF) measurements is introduced for studying slow release and swelling processes in gels formed by free radical crosslinking copolymerization (FCC) of methyl methacrylate (MMA) and ethylene glycol dimethacrylate (EGDM) in toluene. Gels were prepared at 75°C with various toluene contents with pyrene (P_y) as a fluorescence probe. After drying these gels, slow release and swelling experiments were performed in toluene at 50°C by real-time monitoring of the pyrene fluorescence intensity. Li-Tanaka and Fickian type equations were used to obtain swelling and slow release parameters. It was observed that slow release takes place after the gel is swollen. Cooperative and desorption (slow release) diffusion coefficients (D_c and D) were measured and found to be 10^-6cm²s^-1 in both cases. ©1997 SCI     

Determination of reaction activation energy during gelation in free radical crosslinking copolymerization using the steady-state fluorescence method

The steady-state fluorescence technique was used to study the sol-gel transition in free radical crosslinking copolymerization of methyl methacrylate and ethylene glycol dimethacrylate (EGDM). Pyrene methyl pivalate was used as a fluorescence probe for the in situ polymerization experiments. The times required for the onset of gelation t_c and the critical exponent β were recorded for various EGDM contents and at different polymerization temperatures. A simple kinetic model was used to interpret the experimental gel point data. The results show that the fluorescence technique can be used to measure the critical exponent β, the gel point t_c, and the activation energy during sol-gel phase transition processes. © 1996 John Wiley & Sons, Inc.     

Molecular weight effect on swelling of polymer gels in homopolymer solutions: a fluorescence study

A novel technique based on in situ steady state fluorescence measurements is introduced for studying swelling processes of gels formed by free radical crosslinking copolymerization of methyl methacrylate (MMA) and ethylene glycol dimethacrylate (EGDM) in homopolymer solutions. Gels were prepared at 55±2 °C for various EGDM contents. After drying these gels, swelling experiments were performed in chloroform solution of anthracene labeled poly(methyl methacrylate) (An-PMMA) in various molecular weights at room temperature by real time monitoring of anthracene fluorescence intensity. Anthracene labeled PMMA chains having various molecular weights were prepared by atom transfer radical polymerization at 90 °C. During the swelling experiments, it was observed that anthracene emission intensities increased due to trapping of An-PMMA chains into the gel as the swelling time is increased. The trapping of An-PMMA chains in swollen gel, increase by obeying parabolic law in time. Penetration time constant, τ of PMMA chains were measured and found to be increased as the crosslinker density of gel is increased. It is observed that τ values are much higher for high molecular weight An-PMMA chains than low molecular weight chains in all gel samples.     

Suppression of inhomogeneities in hydrogels formed by free-radical crosslinking copolymerization

Network microstructures of poly(acrylamide) (PAAm) and poly(N,N-dimethylacrylamide) (PDMA) hydrogels were compared by static light scattering and elasticity measurements. The hydrogels were prepared by free-radical crosslinking copolymerization of the monomers acrylamide (AAm) or N,N-dimethylacrylamide (DMA) with N,N′-methylenebis(acrylamide) as a crosslinker. During the formation of PAAm gels, the reaction time dependence of the scattered light intensity exhibits a maximum at a critical reaction time, while in case of PDMA gels, both a maximum and a minimum were observed, corresponding to the chain overlap threshold and the gel point, respectively. This difference in the time-course between the two gelling systems is due to the late onset of gelation in the DMA system with respect to the critical overlap concentration. Compared to the AAm system, no significant scattered light intensity rise was observed during the crosslinking polymerization of DMA. It was shown that, regardless of the crosslinker ratio and of the initial monomer concentration, PDMA gel is much more homogeneous than the corresponding PAAm gel due to the shift of the gelation threshold to the semidilute regime of the reaction system. The results suggest that the spatial gel inhomogeneity can be controlled by varying the gel point with respect to the critical overlap concentration during the preparation of gels by free-radical mechanism.     

Effect of molar size and solubility parameter of solvent molecules on swelling of a gel: a fluorescence study

Gels were swollen in various solvents with different molar volume V and solubility parameter δ. In situ steady state fluorescence (SSF) measurements were performed for swelling experiments in gels formed by free radical crosslinking copolymerization (FCC) of methyl methacrylate (MMA) and ethylene glycol dimethacrylate (EGDM). Gels were prepared at 75 °C with pyrene (Py) as a fluorescence probe. After drying these gels, swelling and slow release experiments were performed in various solvents with different V and δ at room temperature by time monitoring of the Py fluorescence intensity. The Li–Tanaka equation was used to produce time constant τ₁ values. Cooperative diffusion coefficients (D_c) were measured and found to be strongly correlated to the molar volume of the solvents used. Solvent uptake and degree of swelling were found to be dependent on the solubility parameter of the solvent. © 2000 Society of Chemical Industry     

Structure and protein separation efficiency of poly(N-isopropylacrylamide) gels: Effect of synthesis conditions

Crosslinked poly(N-isopropylacrylamide) (PNIPA) gels with different crosslink densities in the form of rods and beads were prepared by free-radical crosslinking copolymerization. Solution and inverse suspension polymerization techniques were used for the gel synthesis. The gels were utilized to concentrate dilute aqueous solutions of penicillin G acylase (PGA), bovine serum albumin (BSA), and 6-aminopenicillanic acid (6-APA). The discontinuous volume transition at 34°C observed in the gel swelling was used as the basis of concentrating dilute aqueous protein solutions. PNIPA gels formed below 18°C were homogeneous, whereas those formed at higher temperatures exhibited heterogeneous structures. The water absorption capacity of PNIPA gels in the form of beads was much higher, and their rate of swelling was much faster than the rod-shaped PNIPA gels. It was also found that the polymerization techniques used significantly affect the properties of PNIPA gels. The separation efficiency decreased when the protein molecules PGA or BSA in the external solution were replaced with small-molecular-weight compounds, such as 6-APA. The protein separation efficiency by the gel beads increased to 100% after coating the bead surfaces with BSA. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 805–814, 1998     

Effect of spatial gel inhomogeneity on the elastic modulus of strong polyelectrolyte hydrogels

Summary The effect of spatial inhomogeneity on the elastic modulus of ionic poly(acrylamide) (PAAm) hydrogels has been investigated with the static light scattering measurements. The gels were prepared by free-radical crosslinking copolymerization of acrylamide and 2-acrylamido-2-methylpropane sulfonic acid sodium salt (AMPS) monomers and N,N’-methylenebis(acrylamide) crosslinker. The crosslinker concentration of the hydrogels was fixed in our experiments while the mole fraction of AMPS in the comonomer feed (x_i) was varied over a wide range. Elasticity measurements show that the modulus of elasticity of gels increases with increasing x_i from 0 to 0.2. The excess scattering of gels, that is, the degree of spatial gel inhomogeneity rapidly decreases with increasing x_i and approaches to zero at x_i=0.05. Debye-Bueche analysis of the light scattering data indicates frozen concentration fluctuations in gel; the size of the static structures increases while the extent of concentration fluctuations reduces with increasing x_i. It was shown that the macroscopic elastic properties of PAAm gels are mainly controlled by the microscopic gel structure determined by the scattering measurements.     

The effect of preparation temperature on the swelling behavior of poly (N-isopropylacrylamide) gels

Summary The role of the preparation temperature of poly(N-isopropylacrylamide) (PNIPA) gels on their swelling behavior in water and in aqueous solutions of sodium dodecylbenzenesulfonate was investigated. PNIPA gels were prepared by free-radical crosslinking copolymerization of N-isopropylacrylamide and N,N'-methylene(bis) acrylamide in water at fixed monomer and crosslinker concentrations. The equilibrium swelling ratio of the gels increases first slightly up to about 20°C then rapidly with increasing gel preparation temperature. Magnitude of the collapse transition in water at 34°C becomes larger as the gel preparation temperature increases. Calculations indicate a decrease in the effective crosslink density of PNIPA gels with increasing preparation temperature. The gels prepared at temperatures higher then 20°C were heterogeneous consisting of highly crosslinked regions interconnected by the PNIPA chains. Received: 3 May 2000/Revised version: 3 July 2000/Accepted: 17 July 2000     

Size distribution of polymers during the photoinitiated free-radical copolymerization of methyl methacrylate and ethylene glycol dimethacrylate

Summary Photoinitiated methyl methacrylate-ethylene glycol dimethacrylate (MMA/EGDM) copolymerization has been investigated in toluene at a monomer concentration of 35 w/v %. Diphenyl-2,4,6-trimethylbenzoylphosphine oxide (DPTPO) was used as a photoinitiator at 0.3 wt% concentration. Monomer conversions and the size distribution of the polymer molecules were measured as a function of the reaction time up to the onset of macrogelation. Compared to the photoinitiators benzoin or benzoin derivatives, gelation process proceeds at much higher rates in the presence of DPTPO. The size distribution curves obtained by size-exclusion chromatography (SEC) change from monomodal to bimodal distributions as the polymerization proceeds. Strongly bimodal SEC curves were obtained in the close vicinity of the gel point. This finding confirms the coagulation type gelation mechanism of compact primary particles. It also indicates that the present gelation theories cannot describe the structure dependent kinetics of free-radical crosslinking copolymerization.     

In situ fast transient fluorescence technique (FTRF) to study swelling of gels made of various crosslinker contents

The fast transient fluorescence technique (FTRF), which uses the strobe master system (SMS), was employed to study the swelling of disc‐shaped PMMA [poly(methyl methacrylate] gels. Seven gels were prepared by free radical copolymerization (FCC) of methyl methacrylate (MMA) with various ethylene glycol dimethacrylate (EGDM) contents. Pyrene (P_y) was introduced as a fluorescence probe during polymerization. After drying these gels, swelling experiments were performed in chloroform at room temperature. P_y lifetimes were measured from fluorescence decay traces during the in situ swelling experiments. An equation was derived for low quenching efficiencies to interpret the behavior of lifetimes in the gel during swelling. It was observed that P_y lifetimes in the gel decreased as swelling proceeded. The Li–Tanaka equation was used to determine the cooperative diffusion coefficients, D_c, which were found to decrease as the crosslinker content was increased. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 464–472, 2003     

Formation and structure of poly(methyl methacrylate) gels containing triphenyl vinyl silane

A series of Poly(methyl methacrylate) gels (PMMA) were prepared for making optical lenses by solution free radical crosslinking copolymerization of 2,2,2,‐trifluoroethyl methacrylate (TFEMA), methyl methacrylate (MMA), ethylene glycol dimethacrylate (EGDM), and triphenyl vinyl silane (TPVS) comonomer systems. They were then studied in toluene at a total monomer concentration of 5 molL^?1 and 70°C. The conversion of monomer, volume swelling ratio, weight fraction, and gel point were measured as a function of the TPVS concentration, temperature, and chain transfer agents up to the onset of macrogelation. Structural characteristics of the gels were examined by using equilibrium swelling in toluene, gel fraction, and Fourier‐transform infrared (FTIR) analysis. The morphology of the copolymers was also investigated by Scanning electron microscopy (SEM). The dilution of the monomer mixture resulted in an increase in the gel point and swelling degree and a decrease in the percentage of conversion and gel fraction. Finally, TPVS is a compatible vinyl type silicone comonomer for this system. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Crosslinked methyl methacrylate/ethylene glycol dimethacrylate polymer compounds with a macroazoinitiator

A silane‐containing diamine, bis(p‐aminophenoxy) diphenylsilane (BADPS), was prepared by the condensation of p‐aminophenol with dichlorodiphenyl silane in the presence of triethylamine. Then, BADPS was condensed with 4,4‐azobis(4‐cyanopentanoyl chloride) to prepare macroazoinitiators containing silane units (Si–MAIs). A series of poly(methyl methacrylate) gels containing silane were derived by the solution free‐radical crosslinking copolymerization of methyl methacrylate and ethylene glycol dimethacrylate monomers initiated by these macroazoinitiators at a total monomer concentration of 6 mol/L and 80°C. Si–MAIs were characterized with ¹H‐NMR and ¹³C‐NMR spectroscopy, and the structural characteristics of the gels were also examined. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Designing crosslinked hyaluronic acid hydrogels with tunable mechanical properties for biomedical applications

This study develops a simple copolymerization/crosslinking technique to control the swelling and mechanical properties of hyaluronic acid‐based hydrogels. Because of the widespread acceptance of poly(ethylene glycol) in biomedical applications, functionalized oligomers of ethylene glycol (EG) were used as comonomers to crosslink methacrylated hyaluronic acid (MHA). The swelling degree, shear and elastic moduli, and fracture properties (stress and strain) of the gels were investigated as a function of the crosslinking oligomer length and reactive group(s). It was hypothesized that acrylated oligomers would increase the crosslink density of the gels through formation of kinetic chains by reducing the steric hindrances that otherwise may limit efficient crosslinking of hyaluronic acid into gels. Specifically, after crosslinking 13 wt % MHA (47% degree of methacrylation) with 0.06 mol % of (EG)_n‐diacrylate, the swelling ratio of the MHA gel decreased from 27 to 15 g/g and the shear modulus increased from 140 to 270 kPa as n increased from 1 to 13 units. The length and functionality (i.e., acrylate vs. methacrylate) of the oligomer controlled the crosslink density of the gels. The significant changes in the gel properties obtained with the addition of low levels of the PEG comonomer show that this method allows precise tuning of the physical properties of hyaluronic acid (HA) gels to achieve desired target values for biomedical applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42009.     

Two-stage swelling of acrylamide gels: A photon transmission study

Acrylamide gels were prepared from acrylamide (AAm) with various N,N′-methylenebis(acrylamide) (Bis) contents by free-radical crosslinking copolymerization (FCC) in water and dried before used for swelling experiments. Photon transmission measurements were performed using a UV-visible (UVV) spectrometer during the swelling of polyacrylamide gels. Transmitted light intensity I_tr increased linearly at very early times when acrylamide gels were immersed in water, then decreased continuously as swelling time increased. The behavior of I_tr was modeled assuming two-stage swelling mechanisms for the swelling acrylamide gels. The increase in I_tr at early times was quantified using a linear diffusion model and a linear relaxation constant k₀ was measured. The decrease in I_tr was modeled using the Li–Tanaka equation, from which time constants τ₁ and cooperative diffusion coefficients D₀ were determined for acrylamide gels with varying Bis content. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 894–906, 2001     

Poly(methyl methacrylate)/poly(ethylene glycol)/poly(ethylene glycol dimethacrylate) micelles: Preparation,characterization, and application as doxorubicin carriers

A crosslinked amphiphilic copolymer [poly(ethylene glycol) (PEG)–poly(methyl methacrylate) (PMMA)–ethylene glycol dimethacrylate (EGDM)] composed of PMMA, PEG, and crosslinking units (EGDM) was synthesized by atom transfer radical polymerization to develop micelles as carriers for hydrophobic drugs. By adjusting the molar ratio of methyl methacrylate and EGDM, three block copolymer samples (P0, P1, and P2) were prepared. The measurement of gel permeation chromatography and ¹H‐NMR indicated the formation of crosslinked structures for P1 and P2. Fluorescence spectroscopy measurement indicated that PEG–PMMA–EGDM could self‐assemble to form micelles, and the critical micelle concentration values of the crosslinked polymer were lower than those of linear ones. The prepared PEG–PMMA–EGDM micelles were used to load doxorubicin (DOX). The drug‐loading efficiencies of P1 and P2 were higher than that of P0 because the crosslinking units enhanced the micelles' stability. With increasing drug‐loading contents, DOX release from the micelles in vitro was decreased, and in the crosslinked formulations, the release rate was also slower. An in vitro release study indicated that DOX release from the micelles for the linear samples was faster than that for crosslinked micelles. The drug feeding amount increased and resulted in an increase in the drug‐loading content, and the loading efficiency decreased. These PEG–PMMA–EGDM micelles did not show toxicity in vitro and could reduce the cytotoxicity of DOX in the micelles; this suggested that they are good candidates as stable drug carriers. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39623.     

Fluorescence quenching method for measuring monomer consumption rates during free‐radical crosslinking copolymerization

The steady‐state fluorescence (SSF) technique was used to study the polymerization rate in free‐radical crosslinking copolymerization (FCC) of methyl methacrylate (MMA) and ethylene glycol dimethacrylate (EGDM). Pyrene (Py) was used as a fluorescent probe for the in situ polymerization experiments. The increase in Py intensity was monitored during FCC. The Stern–Volmer kinetic was employed to determine the MMA consumption rate during gelation process for various EGDM contents and at different temperatures. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1907–1913, 2001     

Fast transient fluorescence technique for studying swelling of gels made at various crosslinker contents and exposed to organic vapour

Fast transient fluorescence technique (FTRF) was employed for studying swelling of disc‐shaped poly(methyl methacrylate) (PMMA) gels, which were prepared by free radical copolymerization of methyl methacrylate (MMA) using various ethylene glycol dimethacrylate (EGDM) contents at 60 °C. Pyrene (P) was introduced as a fluorescence probe during polymerization. Swelling experiments were performed by using P‐doped PMMA gels under chloroform vapor. Decay curves of P were measured during in situ swelling experiments. Exponential fits were performed to measure pyrene lifetimes, τ, inside the PMMA gels. It was observed that τ values decreased as swelling proceeded. An equation is derived for low quenching efficiencies to interpret the behaviour of P lifetimes during swelling. The Li–Tanaka equation was used to determine the cooperative diffusion coefficients, D_c, for the gels made at various crosslinker contents. It is observed that D_c values decrease as the crosslinker content is increased. © 2002 Society of Chemical Industry