Tetrahydrofurfuryl Methacrylate Research Articles

Isoprene–styrene copolymer elastomer and tetrahydrofurfuryl methacrylate mixtures for soft prosthetic applications

Novel elastomer/methacrylate systems have been developed for potential soft prosthetic applications. Mixtures of varying compositions of an isoprene–styrene copolymer elastomer and tetrahydrofurfuryl methacrylate (SIS/THFMA) formed one-gel systems and were heat cured with a peroxide initiator. The blends were characterised in terms of sorption in deionised water and simulated body fluids (SBF), tensile properties and viscoelastic parameters of storage modulus and tan δ, as well as glass transition temperatures using dynamic mechanical analysis (DMA). DMA data gave two distinct peaks in tan δ, a lower temperature transition due to the isoprene phase in SIS and one at high temperature thought to be a combination of THFMA and the styrene phase in SIS. The tensile data showed a clear phase inversion within the mid range compositions changing from plastic to elastomeric behaviour. The sorption studies in deionised water showed a two stage uptake with an initial Fickian region that was linear to t 1/2 followed by a droplet growth/clustering system. The slope of the linear region was dependent on the composition ratio. The extent of overall uptake was osmotically dependent as all materials equilibrated at a much lower uptake in SBF. The diffusion coefficients were found to be concentration dependent.

NMR imaging of water sorption into poly(hydroxyethyl methacrylate-co-tetrahydrofurfuryl methacrylate).

The diffusion of water into a series of hydroxyethyl methacrylate, HEMA, copolymers with tetrahydrofurfuryl methacrylate, THFMA, has been studied over a range of copolymer compositions using NMR imaging analyses. For polyHEMA the diffusion was found to be consistent with a Fickian model. The mass diffusion coefficient of water in polyHEMA at 37 degrees C was determined from the profiles of the diffusion front to be 1.5 x 10(-11) m(2) s(-1), which is less than the value based upon mass uptake, 2.0 x 10(-11) m(2) s(-1). The profiles of the water diffusion front obtained from the NMR images showed that stress was induced at the interface between the rubbery and glassy regions which led to formation of small cracks in this region of the glassy matrix of polyHEMA and its copolymers with mole fractions of HEMA greater than 0.6. Water was shown to be able to enter these cracks forming water "pools". For copolymers of HEMA and THFMA with mole fractions of HEMA less than 0.6 the absence of cracks was attributed to the ability of the THFMA sequences to undergo stress relaxation by creep.

Water absorption and surface properties of novel poly(ethylmethacrylate) polymer systems for use in bone and cartilage repair

The surface and bulk properties of novel methacrylate polymers prepared by gelling poly(ethyl methacrylate) (PEMA) powder with different ratios of tetrahydrofurfuryl methacrylate (THFMA) and hydroxyethyl methacrylate (HEMA) monomers were investigated. The water adsorption and desorption characteristics of these polymers were measured in water and phosphate buffered saline (PBS). The desorption diffusion coefficients were higher than the adsorption coefficients in both water and PBS. Linear relationships between the equilibrium mass of water taken up and the mass of water desorbed with the concentration of HEMA in the polymer were established. Polymer surfaces were analysed using scanning electron microscopy (SEM) and atomic force microscopy (AFM). Surface features varied with polymer composition; during hydration only selective areas of the surface hydrated indicating a heterogeneous surface. Contact angle data showed no trend between the different polymers indicating that contact angles are not an acceptable method of assessing hydrophobicity/wettability of a material which does not have a homogeneous surface. The effect of these bulk and surface characteristics on biological interactions were examined using bovine chondrocytes and human osteoblast (HOB) cell cultures. Cell attachment decreased when HEMA was present in the copolymer.

Osteoblast cell death on methacrylate polymers involves apoptosis.

The success of an implant depends on the implant-tissue interface. There are many causes of implant failure, one of which is tissue necrosis. The aim of this in vitro study was to determine whether cell death of primary human osteoblasts (implant site specific cells) occurred by apoptosis (a form of programmed cell death) on two methacrylate polymers. Cells were cultured on poly(ethyl methacrylate)/tetrahydrofurfuryl methacrylate and poly(methyl methacrylate in the form of 13-mm discs, in conditioned medium containing leachable monomer and in the presence of various concentrations of monomer itself in the culture medium. It was found that monomer and leached monomer caused apoptosis of human osteoblast cells in this system. Tetrahydrofurfuryl methacrylate monomer was found to be more toxic than currently used monomer methylmethacrylate. Preincubation of polymers in serum containing medium was found to increase the biocompatibility of the polymers. High levels of apoptosis occurred on polymer used directly after polymerization. Apoptosis levels were decreased after polymer was incubated at 60 degrees C overnight or for 3 days. Apoptosis therefore may occur in cells at the implant site in vivo.

An in vitro investigation of the PEMA/THFMA polymer system as a biomaterial for cartilage repair

A polymer system consisting of poly(ethyl methacrylate)/tetrahydrofurfuryl methacrylate (PEMA/THFMA) was investigated as a biomaterial for cartilage repair using chondrocyte culture. The PEMA/THFMA system and Thermanox control were shown to support chondrocytes seeded directly onto the surface for up to 28 days in culture. Differences were seen between the PEMA/THFMA system and Thermanox in DNA content, proliferation and glycosaminoglycon (GAG) synthesis. There was a significantly greater medium : cell GAG ratio for the PEMA/THFMA system compared to Thermanox. A greater number of chondrocytes isolated from the superficial zone of bovine cartilage attached to the PEMA/THFMA system compared to cells isolated from the deep zone, whereas the converse was seen for Thermanox. Matrix constituents including collagen type II were synthesised indicating that the differentiated phenotype was maintained for some of the chondrocytes, although the production of type I collagen indicated that dedifferentiation of some of the chondrocytes had occurred. In conclusion, this study has shown that the PEMA/THFMA system can support chondrocytes in vitro and together with further investigations could lead to the development of the polymer as an ideal candidate for articular cartilage repair.

A study of the copolymerization of hydroxyethyl methacrylate and tetrahydrofurfuryl methacrylate

The free radical copolymerizations of hydroxyethyl methacrylate and tetrahydrofurfuryl methacrylate have been investigated at 50 degrees C. The compositions of polymers prepared at low conversions have been determined using C-13-NMR, and the glass transition temperatures determined by DSC. The copolymerizations were found to be best described by a terminal model with reactivity ratios of r(H) = 1.79 and r(T) = 0.76. The triad fraction sequence distributions have been calculated based on the terminal model and the calculated reactivity ratios. The glass transitions have been fitted to the Gordon-Taylor equation. The best value of the Gordon-Taylor constant was found to be k(H) = 1.42 +/- 0.2, indicating nonideal mixing of the two monomer components in the copolymers. (C) 1999 John Wiley & Sons, Inc.

Bulk polymerization and characterization of isocyanatoacrylate copolymers

The purpose of this investigation was to prepare by bulk polymerization six new isocyanatoacrylate copolymers and to characterize them. The isocyanatoacrylate copolymers, which were prepared by tri-n-butylborane oxide (TBBO)-initiated free-radical polymerization, were formed from 1 : 1 mol mixtures of 2-isocyanatoethyl methacrylate (IEM) with 2-hydroxyethyl methacrylate (HEMA), hydroxypropyl methacrylate (HPMA), 2-hydroxyethyl thiomethacrylate (HETMA), ethylthioethyl methacrylate (ETEMA), 2-(acetoxyacetoxy)ethyl methacrylate (AAEMA), and tetrahydrofurfuryl methacrylate (THFMA). These six copolymers were compared to the homopolymer of IEM, which was polymerized in an identical fashion. The bulk polymers were fractionated into their acetone-soluble and acetone-insoluble components. Physical characterization via photoacoustic infrared (PASIR) spectroscopy showed vast differences in residual isocyanate content. Differential scanning calorimetry (DSC) thermal analysis was carried out on all polymers. Elemental analysis (nitrogen) determined the ratio of IEM to the comonomer and boron analysis showed whether the initiator stayed in the acetone-insoluble fraction or was “extracted” into the acetone-soluble fraction. In conclusion, we found that the composition of the copolymers correlated well with the predicted design. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1577–1583, 1999

3He ion-beam analysis of water uptake and drug delivery

3He ion-beam analysis utilises a micronuclear reaction analysis (of deuterium and carbon) and microparticle induced X-ray emission (in this case silicon and chlorine), to determine an elemental map of the surface of a sample. This study used D2O to model the behaviour of water in poly(tetrahydrofurfuryl methacrylate–polyethyl methacrylate) and chlorhexidine diacetate doped silicone elastomers. The poly(tetrahydrofurfuryl methacrylate–polyethyl methacrylate) systems demonstrated an initial Fickian absorption process (diffusion coefficient 1.1×10−11 m2s−1) which indicated the 2-stage nature of the polymer’s absorption kinetics. The doped silicone samples demonstrated an osmotic mechanism for the controlled release of drugs, with correlation between the D2O and the chlorhexidine diacetate inclusions increasing during the experiment. The technique proved valuable in the analysis of delivery polymers and will undoubtedly have further applications in the development of drug delivery systems.

The water uptake of poly(tetrahydrofurfuryl methacrylate)

Poly(tetrahydrofurfuryl methacrylate) possesses some unique characteristics with respect to its biocompatibility and behaviour in water. The water uptake is high (>70%) and very slow (over 3 yr), but the material remains rigid throughout the process. The mechanism behind the uptake is in two stages; an initial Fickian stage, then as the matrix approaches saturation (about 3 wt%) a second clustering mechanism takes over. The rate of uptake of the second stage of the uptake is controlled by creep (or stress relaxation), and the chemical potential driving the uptake from clustering of the furfuryl rings of the polymer. If clustering or the creep is prevented (by appropriate co-polymerisation) the polymer behaves in an ideal, Fickian manner.

Water sorption behaviour of polymeric systems based on tetrahydrofurfuryl methacrylate.

Earlier research has described the water absorption behaviour, drug release and biological properties of a room temperature polymerizing system based on poly(ethyl methacrylate) (PEM) powder and tetrahydrofurfuryl methacrylate (THFM) monomer. This work has been extended, with respect to water sorption behaviour, by replacing the monomer to various extents with hydroxyethyl methacrylate (HEMA), and poly(ethyl methacrylate) by ethyl methacrylate (EM)-THFM copolymers. Replacing the THFM with HEMA, and gelling with PEM, increased the diffusion coefficient progressively. The replacement of PEM by EM-THFM copolymers, when gelled with THFM monomer, substantially reduced equilibrium water uptake, and increased diffusion coefficients. However, with HEMA monomer, equilibrium uptake was unaffected, but the diffusion coefficient decreased with increasing THFM content of the copolymer. This is due to a complex interaction of THFM cross-linking the copolymer, and the effect of EM on the water uptake. Heat polymerizing the PEM-THFM system reduced equilibrium uptake and the diffusion coefficient, compared with the room temperature polymerizing system; this could reflect molecular weight differences.

Attachment of cultured human bone cells to novel polymers

The initial attachment of human bone-derived cells (HBDC) to several polymer systems has been studied in vitro. A novel polymer system based on poly(ethyl methacrylate) polymer and tetrahydrofurfuryl methacrylate monomer (PEMA/THFMA) was compared with a variant in which THFMA was replaced by 2-hydroxyethyl methacrylate (PEMA/HEMA). Tissue culture polystyrene (TCPS) and polystyrene (PS) were used as reference materials. The ability of the substrates to adsorb the attachment glycoproteins fibronectin (Fn) and vitronectin (Vn) from serum and the subsequent effect on radiolabeled HBDC attachment were examined. Initial cell attachment from the medium containing 10% (v/v) serum was highest on TCPS; on PEMA/THFMA and PEMA/HEMA substrates it was about 25% of this level, and on PS it was only 10% of that on TCPS. Attachment of HBDC to all substrates was dependent on the presence of Vn, which, unlike Fn, was able to adsorb in the face of competition from other serum components. Both Vn and Fn were able to support cell attachment when precoated onto all substrates. In comparison to TCPS, PEMA/THFMA did not show enhanced adsorption of either Fn or Vn from serum, and this was reflected in the level of cell attachment. Interestingly, the potency of preadsorbed Fn for cell attachment was much higher on this substrate than on any other: 45 ng/cm2 Fn when adsorbed to PEMA/THFMA gave a level of cell attachment 1.6-fold higher than the same density of Fn on PS or TCPS. The maximum Fn surface density achieved on HEMA/PEMA was 16 ng/cm2. Cells on PEMA/THFMA showed typical clustering of the α5 β1 Fn receptor, but this was not evident in cells attached to PEMA/HEMA even when precoated with Fn. This study indicates that the initial attachment of HBDC to all substrates was Vn dependent. It also indicates that on PEMA/THFMA the favorable presentation of subsequently adsorbed Fn may assist matrix assembly. © 1999 John Wiley & Sons, Inc. J Biomed Mater Res, 44, 1–11, 1999.

Attachment of cultured human bone cells to novel polymers.

The initial attachment of human bone-derived cells (HBDC) to several polymer systems has been studied in vitro. A novel polymer system based on poly(ethyl methacrylate) polymer and tetrahydrofurfuryl methacrylate monomer (PEMA/THFMA) was compared with a variant in which THFMA was replaced by 2-hydroxyethyl methacrylate (PEMA/HEMA). Tissue culture polystyrene (TCPS) and polystyrene (PS) were used as reference materials. The ability of the substrates to adsorb the attachment glycoproteins fibronectin (Fn) and vitronectin (Vn) from serum and the subsequent effect on radiolabeled HBDC attachment were examined. Initial cell attachment from the medium containing 10% (v/v) serum was highest on TCPS; on PEMA/THFMA and PEMA/HEMA substrates it was about 25% of this level, and on PS it was only 10% of that on TCPS. Attachment of HBDC to all substrates was dependent on the presence of Vn, which, unlike Fn, was able to adsorb in the face of competition from other serum components. Both Vn and Fn were able to support cell attachment when precoated onto all substrates. In comparison to TCPS, PEMA/THFMA did not show enhanced adsorption of either Fn or Vn from serum, and this was reflected in the level of cell attachment. Interestingly, the potency of preadsorbed Fn for cell attachment was much higher on this substrate than on any other: 45 ng/cm2 Fn when adsorbed to PEMA/THFMA gave a level of cell attachment 1.6-fold higher than the same density of Fn on PS or TCPS. The maximum Fn surface density achieved on HEMA/PEMA was 16 ng/cm2. Cells on PEMA/THFMA showed typical clustering of the alpha5 beta1 Fn receptor, but this was not evident in cells attached to PEMA/HEMA even when precoated with Fn. This study indicates that the initial attachment of HBDC to all substrates was Vn dependent. It also indicates that on PEMA/THFMA the favorable presentation of subsequently adsorbed Fn may assist matrix assembly.

Interactions of chondrocytes with methacrylate copolymers.

Copolymers of poly(ethylmethacrylate) (PEMA) and tetrahydrofurfurylmethacrylate (THFMA) have been shown to exhibit potential as a biomaterial for use in cartilage repair. However, the interactions of chondrocytes with the polymer surface is not well understood. A series of novel methacrylate copolymers containing PEMA, THFMA and hydroxyethylmethacrylate (HEMA) were prepared and the ability of these various copolymers to support chondrocytes attachment in vitro has been assessed by the Alamar blue assay for cell number and environmental scanning electron microscopy (ESEM). As the mole fraction of HEMA in PEMA/THFMA/HEMA copolymers increased, chondrocyte attachment to the polymer surface in 24 h decreased. Chondrocytes maintained a rounded morphology and were strongly attached on the THFMA/PEMA polymer surface, but as the mole fraction of HEMA increased the cells present became much smaller with fewer cell to cell interactions. The effect of pre-adsorbing fibronectin on to the polymer surface on cell attachment was assessed both in the presence and absence of serum. Chondrocyte attachment was significantly reduced in serum-free medium. Pre-adsorption of fibronectin on to the copolymer surface substantially increased cell attachment in all cases. In conclusion, chondrocyte attachment and proliferation on these copolymers may be controlled by changes in the polymer surface chemistry and is highly sensitive to the presence of proteins either in the culture media or pre-adsorbed on to the copolymer surface.

Fluoride ion release from two methacrylate polymer systems

The release of fluoride ions from two room-temperature polymerising systems containing sodium and potassium fluoride, respectively, has been studied. The polymer systems comprised poly(ethyl methacrylate) powder (PEM), with tetrahydrofurfuryl methacrylate (THFM), and n-butyl methacrylate (nBM), respectively. The water uptake of these systems was drastically increased by the presence of fluorides, the increase being much higher with the PEM/THFM system. In both cases, uptake was a monotonic function of the molarity of the fluoride added. The uptake process was in general non-Fickian. However, for all systems, the fluoride release process was Fickian, and diffusion coefficients could be calculated. The amount of fluoride released, and the diffusion coefficients obtained, appeared unrelated to the extent of water uptake of the parent polymers.

Monomethacrylate co-monomers for dental resins.

Polymerisation shrinkage is widely recognised as a major drawback of resin based dental restoratives. Bis-GMA is often employed as the principal dimethacrylate monomer. Due to its high viscosity, Bis-GMA is normally mixed with large proportions of low viscosity glycol dimethacrylates. The purpose of this study was to determine whether the polymerisation shrinkage of Bis-GMA-based resins would be lower if alternative monomethacrylate co-monomers were used in place of conventional dimethacrylate co-monomers as viscosity modifiers. Conventional resins used were ethyleneglycol dimethacrylate and triethyleneglycol dimethacrylate; the alternative monofunctional co-monomers were tetrahydrofurfuryl methacrylate, hydroxypropyl methacrylate and isobornyl methacrylate. Model resins containing 54% mol/mol of co-monomer in Bis-GMA and 1% w/w of benzoyl peroxide as initiator were heat-cured at 70 degrees C for 8 h. Polymerisation shrinkage, degree of conversion and concentration of remaining methacrylate groups were calculated from density changes obtained gravimetrically. Other properties evaluated were Young's modulus, water uptake and viscosity of the monomer mixtures. The Bis-GMA-based resins exhibited lower shrinkage when mixed using the monomethacrylates rather than with conventional glycol dimethacrylates. Among the alternative co-monomers, tetrahydrofurfuryl methacrylate conferred the best balance of all measured properties.

A methacrylate-based cement used as a root canal sealer

In this study, a methacrylate-based orthopaedic bone cement was modified for use as a root canal sealer by changing the monomer from n-butyl methacrylate to tetrahydrofurfuryl methacrylate. The sealing and bonding capabilities, solubility and handling properties of the resin were evaluated. Seventy-three extracted mature human teeth with single canals were used. The teeth were randomly divided into two experimental groups each of 30 teeth; three control teeth were set aside for the leakage tests. Ten teeth were reserved for the scanning electron microscope studies. All the experimental teeth were root filled with gutta-percha and the resin sealer. The particle size of the polymer was limited in Group 1 to 75 μm or less and in Group 2 to 45 μm or less. The controls were filled with gutta-percha only. Silver nitrate solution was used as the leakage indicator. In Group 1 the mean linear penetration of the indicator was 1.10 mm ± 1.04; four roots showed no leakage. In Group 2 the mean linear penetration of the indicator was 0.57 mm ± 0.65; 12 roots showed no leakage. The test bodies showed no weight change after 1 and 3 months' storage in saline at 37°C. The scanning electron microscope examination revealed a bond both between the resin and the dentine and between the resin and the gutta-percha. The working time of the new resin composition was normally about 50 min, and handling was found to be easy.

A methacrylate‐based cement used as a root canal sealer

In this study, a methacrylate-based orthopaedic bone cement was modified for use as a root canal sealer by changing the monomer from n-butyl methacrylate to tetrahydrofurfuryl methacrylate. The sealing and bonding capabilities, solubility and handling properties of the resin were evaluated. Seventy-three extracted mature human teeth with single canals were used. The teeth were randomly divided into two experimental groups each of 30 teeth; three control teeth were set aside for the leakage tests. Ten teeth were reserved for the scanning electron microscope studies. All the experimental teeth were root filled with gutta-percha and the resin sealer. The particle size of the polymer was limited in Group 1 to 75 microns or less and in Group 2 to 45 microns or less. The controls were filled with gutta-percha only. Silver nitrate solution was used as the leakage indicator. In Group 1 the mean linear penetration of the indicator was 1.10 mm +/- 1.04; four roots showed no leakage. In Group 2 the mean linear penetration of the indicator was 0.57 mm +/- 0.65; 12 roots showed no leakage. The test bodies showed no weight change after 1 and 3 months' storage in saline at 37 degrees C. The scanning electron microscope examination revealed a bond both between the resin and the dentine and between the resin and the gutta-percha. The working time of the new resin composition was normally about 50 min, and handling was found to be easy.

Emulsifier-free emulsion polymerization of the comonomer system styrene/tetrahydrofurfuryl metacrylate

The emulsifier-free emulsion copolymerization of styrene and tetrahydrofurfuryl methacrylate (TMA) in aqueous phase is described. Monidisperse latex particles with diameters from about 280 to 620 nm are obtained consisting of a hydrophobic polystyrene core and a hydrophilic poly-TMA shell. The influence of a variation of TMA, styrene and initiator (potassium persulfate) concentration in the original emulsion on particle size, molecular weight and composition of the copolymer is described. The concentration of TMA and initiator affects the number of primary particles but not the size of the final particles, whereas the styrene concentration strongly influences the particle diameter, a large size being favored by a high styrene concentration. The molecular weights of the polymers are between 6.2×104 and 7.0×105 g/mole. Size exclusion chromatography of polymer solutions in tetrahydrofuran shows that high molecular weights are especially found in large particles, which are preferentially formed in emulsions with a high concentration of styrene. 1H-NMR spectroscopy of the polymer shows that only about 50% of the initial TMA concentration are polymerized in the particles. Thus the copolymers prepared at increasing styrene concentration and constant initiator concentration of the emulsion show an increasing polystyrene content and are formed in particles of increasing size.

Two-photon resonance enhanced nonlinear optical response in C 60-copolymer charge transfer complex

Ultrafast third-order nonlinearity of C 60-poly tetrahydrofurfuryl methacrylate charge transfer complex was measured using femtosecond optical Kerr gate at both 640 nm and 820 nm wavelength. In the material's two-photon absorption region, extra large third-order nonlinear optical response was observed.

N.m.r. imaging of the diffusion of water into poly(tetrahydrofurfuryl methacrylate- co-hydroxyethyl methacrylate)

Nuclear magnetic resonance (n.m.r.) imaging was used to study the ingress of water into poly(tetrahydrofurfuryl methacrylate- co-hydroxyethyl methacrylate). The study offers strong evidence that the diffusion is Fickian in nature. The diffusion coefficient, D, obtained by fitting the underlying diffusion profile, attainable from the images, according to the equation for Fickian diffusion, is 1.5 × 10 −11 m 2 s −1, which is in good correlation with the value of 2.1 × 10 −11 m 2 s −1, obtained from mass uptake measurements. Additionally, from the T 2-weighted images, superimposed features observed in addition to the underlying Fickian diffusion profiles were shown to have a longer spin-spin relaxation time, T 2. This suggests the presence of two types of water within the polymer matrix; a less mobile phase of absorbed water that is interacting strongly with the polymer matrix and a more mobile phase of absorbed water residing within the cracks observed in the environmental scanning electron micrograph.