Photopolymerizable multifunctional monomers and their evaluation as reactive Bis‐GMA eluents

Bis‐GMA {2,2‐bis[4‐(2′‐hydroxy‐3′‐methacryloyloxy‐propoxy)‐phenyl]‐propane}, TEGDMA <2‐{2‐[2‐(2‐methylprop‐2‐enoyloxy)ethoxy]ethoxy}ethyl‐2‐methylprop‐2‐enoate>, and methyl methacrylate (MMA) are some of the most commonly used monomers in the field of restorative dentistry. These compounds are characterized by having one or two terminal double bonds. Besides the effort to synthesize new monomers, several problems still affect the clinical behavior of contemporary dental materials. In this work, two monomers with three terminal double bonds, 5A13DA and 5A13DMA, were synthesized. Both monomers were used to completely replace TEGDMA as reactive diluent of photopolymerizable dental resin composites containing Bis‐GMA. The effects of 5A13DA and 5A13DMA on flexural properties, double bond conversion, water sorption, solubility, and polymerization shrinkage were evaluated. In addition, both monomers were evaluated as crosslinking agents for methylmethacrylate, resulting in copolymers with enhanced thermal stability. The results obtained suggest that newly synthesized monomers are potential substitutes for TEGDMA in the formulation of dental composites, providing 50% lower volumetric shrinkage than the composite resin used as control and adequate mechanical properties. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46240.     

Effect of polyhedral oligomeric silsesquioxane on water sorption and surface property of Bis‐GMA/TEGDMa composites

2,2‐Bis[4‐(2‐hydroxy‐3‐methacryloxypropoxy)phenyl]propane (Bis‐GMA), one of the most important light‐curable dimethacrylate resins, is widely used as dental restorative material. However, one problem of Bis‐GMA is the high water sorption due to the hydrophilic hydroxyl (–OH) group, resulting in a short life in actual application. In this study, to overcome the drawback stated above, novel organic–inorganic dimethacrylate monomer containing polyhedral oligomeric silsesquioxanes (POSS), Bis‐GMA‐graft‐POSS, is synthesized via the nucleophilic addition reaction of isocyanate functionalized POSS (IPOSS) and pendent hydroxyl group of Bis‐GMA. Then the as‐synthesized Bis‐GMA‐graft‐POSS, of which hydroxyl group was substituted by hydrophobic POSS, is also introduced into the Bis‐GMA/TEGDMA matrix to prepare a series of methacrylate‐based hybrids for dental materials under visible light with camphorquinone and ethyl‐4N,N‐dimethy‐laminobenzoae (EDMAB) as initiator and coinitiator, respectively. Compared to Bis‐GMA/TEGDMA composites, water sorption of modified composites can be significantly reduced with the addition of Bis‐GMA‐graft‐POSS. Moreover, the Bis‐GMA/TEGDMA/POSS hybrids show hydrophobic surfaces, leading to much higher water contact angles than that of Bis‐GMA/TEGDMA composites. The morphology of hybrids containing POSS was furthermore studied by X‐ray diffraction (XRD) analysis and X‐ray photoelectron spectroscopy (XPS). The results show that POSS disperses in the matrix in noncrystalline form and tend to migrate to the surface of the modified composites that lead to the lower water sorption and higher water contact angles. These results are very useful for design of novel methacrylate monomers and clinical application. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis of two PET waste derived bisacrylic and bisallylic monomers and their potential use as crosslinking agents and dental resin composites

Two novel bifunctional monomers obtained from PET waste glycolisis are reported. Bis(2‐(acryloyloxy)ethyl) terephthalate and bis(2‐(((allyloxy)carbonyl)oxy)ethyl) terephthalate (BACET) monomers were obtained from bis(hydroxyethyl) terephthalate derived from PET waste and acryloyl chloride and allyl chloroformate, respectively. The monomers were characterized by FTIR and ¹H‐NMR spectroscopies. They were evaluated as crossslinking agents for acrylic acid (AA) and methacrylic (MA) acids using thermally initiated polymerization. The obtained copolymers showed higher thermal stability than the acrylic homopolymers. They were also tested for dental formulations as Bis‐GMA substitutes in heat curing resin composites. In spite of its lower reactivity, only BACET was able to substitute Bis‐GMA, due to its high solubility in the TEGDMA comonomer. Resin formulations containing nanosized silica and the mixture Bis‐GMA/TEGDMA or BACET/TEGDMA were prepared in order to compare physical and chemical properties. Water sorption, solubility, and flexural strength were found statistically similar for both formulations. However, flexural modulus was lower and double bond conversion was higher for the BACET resin, which could make it appropriate for its potential use in dental resin composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41487.     

Biobased isosorbide methacrylate monomer as an alternative to bisphenol A glycerolate dimethacrylate for dental restorative applications

In this study, a new biobased isosorbide urethane methacrylic monomer [isosorbide‐derived urethane dimethacrylate (Is‐UDMA)] was evaluated as a replacement for currently used bisphenol A glycerolate dimethacrylate (Bis‐GMA) based dental restorative materials. Dental composites were prepared at different Is‐UDMA and Bis‐GMA concentrations. For these composites, the photocuring kinetics, volumetric shrinkage, viscoelastic properties, water sorption, and solubility were evaluated. The photocuring kinetics, followed by real‐time IR spectroscopy, showed higher double‐bond conversion (DC) values for the formulations containing the Is‐UDMA monomer; the highest DC (82%) was achieved by the formulation prepared with only the Is‐UDMA monomer. The volumetric shrinkage was reduced to 23.7% as compared with the dental resin formulated with Bis‐GMA. The viscoelastic properties of the formulations containing both Is‐UDMA and Bis‐GMA monomers in a 50:50 composition were superior to the rest of the tested formulations, including those prepared with pure polymers. This behavior was explained in terms of a compromise between crosslinking and rigidity (or flexibility) of the resulting polymer network. A preliminary test on microleakage in a dental enamel demonstrated that the new Is‐UDMA monomer is a potential replacement for the Bis‐GMA monomer in dental restorative materials. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44591.     

Composite resins based on novel and highly reactive bisglycidyl methacrylate monomers

Three new bisglycidyl monomers; 1,4‐bis((2‐hydroxy‐3‐methacryloxypropoxy) methyl)benzene (MB‐Phe‐OH), 1,4‐bis(2‐hydroxy‐3‐methacryloxypropoxy)2‐cis‐butene (MB‐Cis‐OH), and 1,7‐bis(2‐hydroxy‐3‐methacryloxypropoxy)heptane (MB‐1,7‐OH); were synthesized and used as Bis‐GMA/TEGDMA (bisphenolglycidyl methacrylate/triethylene glycol dimethacrylate) composite resin additives. Flexural properties and double bond conversion of the dental resins composed of silanizated inorganic filler and organic matrices containing new monomers were evaluated. The composite resins formulated, using the monomers MB‐Cis‐OH and MB‐1,7‐OH, have mechanical properties and double bond conversion comparable with those of Bis‐GMA/TEGDMA composite resin used as control. The composite containing the new monomer MB‐Phe‐OH has better flexural properties (flexural strength 65.01 MPa and flexural modulus 5675.91 MPa) than the control composite resin (flexural strength 52.85 MPa and flexural modulus 4879.72 MPa); this could be attributed to the molecular structure of the monomer and its high double bond conversion level of 74.19%. The new bisglycidyl methacrylate monomer MB‐Phe‐OH could be potentially useful in the development of new organic matrices for dental composite resins with high double bond conversion and enhanced mechanical properties. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40971.     

Synthesis and characterization of binary copolymers of methyl methacrylate with glycidyl methacrylate and 2‐hydroxy ethyl methacrylate as carriers for cellulase

Cellulase was immobilized directly on methyl methacrylate‐glycidyl methacrylate copolymer (MMA‐co‐GMA) and methyl methacrylate‐2‐hydroxy ethyl methacrylate copolymer (MMA‐co‐HEMA) by covalent attachment and crosslinking methods. The properties of the immobilized cellulase were investigated and compared with those of the free one. For the assays carried out through crosslinking method at 25°C and pH 7, the retained activities were found to be 91.92% and 74.63%, respectively, for MMA‐co‐GMA and MMA‐co‐HEMA crosslinked with 0.1% of 1‐cyclohexyl‐3‐(2‐morpholino‐ethyl) carbodiimide metho‐p‐toluenesulfonate (CMCT), respectively. The immobilized cellulase had better stability and higher retained activities with respect to pH, temperature, and storage stability than the free one. In the repeated use experiments, the immobilized cellulase using (MMA‐co‐GMA)‐CMCT (0.1%) and (MMA‐co‐HEMA)‐CMCT (0.1%) did not change after 10 and eight times of repeated use and maintained 67% and 62% from their original activities after 25 times, respectively. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and photopolymerizations of new phosphonated methacrylates from alkyl α‐hydroxymethacrylates and glycidyl methacrylate

Novel aromatic mono‐ and di(phosphonate) or phosphonic acid monomers for use in dental composites were synthesized. Synthesis of monomer 1a involved three steps: (i) reaction of t‐butyl α‐bromomethacrylate (t‐BuBMA) and Bisphenol A, (ii) conversion to diacid chloride derivative using thionyl chloride, (iii) reaction of diacid chloride with diethyl (2‐hydroxyphenyl) phosphonate. Monomer 2a was synthesized from the reaction of 2‐chloromethacryloyl chloride and diethyl (2‐hydroxyphenyl) phosphonate. Synthesis of monomer 3a involved reaction of glycidyl methacrylate (GMA) with diethyl (2‐hydroxyphenyl) phosphonate. Hydrolysis of the phosphonate groups of monomers 1a and 2a with trimethylsilyl bromide (TMSBr) gave monomers 1b and 2b with phosphonic acid functionality, which is intended to improve binding ability of dental composites. The homopolymerization and copolymerization behaviors of the synthesized monomers with (Bis‐GMA) were investigated using photodifferential scanning calorimetry at 40°C with 2,2′‐dimethoxy‐2‐phenyl acetophenone as photoinitiator. The interaction of the monomer 1b with hydroxyapatite (HAP) was investigated using Fourier transform infrared technique. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis of novel antibacterial monomers (UDMQA) and their potential application in dental resin

To prepare antibacterial dental resin, a series of novel urethane dimethacrylates quaternary ammonium methacrylate monomers (UDMQAs) with different substituted alkyl chain length were synthesized, and their structures were confirmed by FTIR and ¹H‐NMR spectra. The obtained UDMQAs were used to replace 2,2‐Bis[4‐(2‐hydroxy‐3‐methacryloyloxypropyl)‐phenyl]propane (Bis‐GMA) totally as base monomers of dental resin and mixed with Tri‐ethyleneglycol dimethacrylate (TEGDMA) at the mass ratio of 50/50. The properties of these prepared resins like antibacterial activity, double bond conversion (DC), polymerization shrinkage, flexural strength (FS), and modulus (FM), water sorption and sol fraction were investigated. The most commonly used dental resin Bis‐GMA/TEGDMA (50wt/50wt) was chosen as a reference. The results showed that UDMQAs could endow dental resin with antibacterial activity. Compared with Bis‐GMA‐based dental resin, UDMQAs‐based resin had the same or higher DC, lower polymerization shrinkage, lower flexural strength and modulus, and higher water sorption and sol fraction. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Properties of 2,2‐Bis[p‐(2′‐hydroxy‐3′‐methacryloxy propoxy)phenyl]propane/Isobornyl (Meth)acrylate copolymers

Isobornyl acrylate (IBOA) and isobornyl methacrylate (IBOMA) were used to replace triethylene glycol dimethacrylate (TEGDMA) as reactive diluents in dental restorative materials. Photopolymerization behaviors of mixtures of IBO(M)A and 2,2‐bis[p‐(2′‐hydroxy‐3′‐methacryloxy propoxy)phenyl]propane (Bis‐GMA) were investigated by Fourier transform infrared spectroscopy. The degree of conversion, volume shrinkage, contact angle, water sorption, water solubility, flexural strength, and modulus values of the Bis‐GMA/IBO(M)A formulations were measured and compared with those of a Bis‐GMA/TEGDMA formulation. The results illustrate that the degree of conversion, volume shrinkage, contact angle, water sorption, flexural strength, and modulus values of the Bis‐GMA/IBO(M)A systems were all lower than those of the Bis‐GMA/TEGDMA system; the water solubility values of the Bis‐GMA/IBO(M)A systems were higher than that of the Bis‐GMA/TEGDMA system. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and characterization of high molecular weight side chain liquid crystalline/photoactive polymers

Various liquid crystalline and photoactive azobenzene monomers were synthesized and attached to copoly(methyl methacrylate‐glycidyl methacrylate) [copoly (MMA‐GMA)] to get high molecular weight side chain liquid crystalline (LC)/photoactive copolymers. Further, spacers are generated in situ and reactive groups are obtained after the modification. All monomers and polymers were thoroughly characterized by FTIR, ¹H and ¹³C NMR, UV‐VIS spectrophotometry, gel permeation chromatography, thermogravimetric analysis, differential scanning calorimetry, and polarized optical microscopy. All side chain LC polymers showed higher thermal stability than that of copoly(MMA‐GMA). Three LC and one azo monomer exhibited characteristic nematic mesophase where as one LC monomer has shown nematic and sanded smectic‐A texture. The rate of trans‐cis isomerization of polymer was lower than that of the monomer and both monomers and polymers showed slow back isomerization. Present approach offers convenient way to synthesize high/desired molecular weight photoactive LC polymers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and Photopolymerizations of New Crosslinkers for Dental Applications

Summary: Five new crosslinkers for use in dental composites were synthesized. Four are based on TBHMA: 1 via reaction of TBBr and Bisphenol A; 2 by hydrolysis of t‐butyl groups of the first monomer to give a diacid derivative; 3 by conversion of the first monomer to an amide derivative using benzyl amine; 4 by conversion of the first monomer to amide derivative using APTES. The AHM‐based monomer 5 was synthesized from the Michael addition of APTES to AHM. The photopolymerization behaviors of the synthesized monomers with Bis‐GMA, TEGDMA and HEMA were investigated using photodifferential scanning calorimetry at 40 °C using DMPA as photoinitiator. The polymerization rates and degrees of conversion for mixtures of any of the monomers 1 – 4 with Bis‐GMA:TEGDMA were found to be similar to Bis‐GMA:TEGDMA, higher than Bis‐GMA:HEMA, and also higher than mixtures with Bis‐GMA:HEMA. The incorporation of TBHMA‐based monomers into the conventional resin mixture (Bis‐GMA and TEGDMA) reduced the polymerization shrinkages. Monomer 5 and its mixtures polymerized much faster and to higher degrees of conversion than the other investigated systems, however, this system exhibited the largest volume shrinkage.

Structures of some of the new crosslinkers synthesized.     

Synthesis,characterization, and cure reaction of methacrylate‐based multifunctional monomers for dental composites

The synthesis of 2,2‐bis[(4‐(2‐hydroxy‐3‐methacryloxyethoxy)phenyl]propane (BHEP) and (1‐methacryloxy‐3‐ethoxymethacryloxy‐2‐hydroxy)propane (MEHP) for use as the monomer phase in dental composites are reported. The monomers were prepared by the reaction of 2‐hydroxyethyl methacrylate (HEMA) with diglycidyl‐ether of bisphenol A (DGEBA) and with glycidyl methacrylate (GMA), respectively. The progress of the reaction was followed by measuring the disappearance of the epoxide group peak using FTIR and the structure of the monomers was characterized by ¹H‐NMR. BHEP and MEHP have lower viscosity because of the presence of long aliphatic spacer on both sides of the aromatic ring in BHEP and the absence of aromatic rings and the presence of only one hydroxyl group in each molecule of MEHP. Thermal curing of the monomers was conducted in a DSC using benzoyl peroxide as an initiator. Photopolymerization of the monomers was also conducted with the visible light using camphorquinone and N,N‐dimethylaminoethyl methacrylate as the photoinitiating system. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Synthesis and photopolymerization of multifunctional methacrylates derived from Bis‐GMA for dental applications

Two multimethacrylates having three methacrylate groups (BPA‐3M) and four methacrylate groups (BPA‐4M) have been prepared by reacting hydroxyl groups of 2,2‐bis[4‐(2′‐hydroxy‐3′‐methacryloyloxypropoxy)phenyl]propane (Bis‐GMA) with methacryloyl chloride. BPA‐3M and BPA‐4M have much lower viscosities than the starting Bis‐GMA, because they have only one or no hydroxyl group. Photopolymerizations of the multifunctional methacrylates were conducted by exposure to visible light using camphorquinone and 2‐(N,N‐dimethylamino)ethyl methacrylate as a photoinitiating system. High conversions >50% resulted from photopolymerization of BPA‐3M, whereas Bis‐GMA showed lower conversions under the same condition, implying better mechanical properties for the composite resins made from BPA‐3M. BPA‐4M showed much lower conversions in the photopolymerization condition. Water sorption of the photocured composite of BPA‐3M containing 50 wt % of inorganic fillers was found to be 0.15%, which is only one‐tenth of the commercial Bis‐GMA composite. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2033–2037, 1999     

Adsorption of IgG on spacer‐arm and L‐arginine ligand attached poly(GMA/MMA/EGDMA) beads

This work presents data on human immunoglobulin G (HIgG) adsorption onto L ‐arginine ligand attached poly(GMA/MMA/EGDMA)‐based affinity beads which were synthesized from methyl methacrylate (MMA) and glycidiyl methacrylate (GMA) in the presence of a crosslinker (i.e., ethylene glycol dimethacrylate; EGDMA) by suspension polymerization. The epoxy groups of the poly(GMA/MMA/EGDMA) beads were converted into amino groups after reaction with ammonia or 1,6‐diaminohexane (i.e., spacer‐arm). With L ‐arginine as a ligand, it was covalently immobilized on the aminated (poly(GMA/MMA/EGDMA)‐ AA) and/or the spacer‐arm attached (poly(GMA/MMA/EGDMA)‐SA) beads, using glutaric dialdehyde as a coupling agent. Both affinity poly(GMA/MMA/EGDMA)‐based beads were used in HIgG adsorption/desorption studies under defined pH, ionic strength, or temperature conditions in a batch reactor, using acid‐treated poly(GMA/MMA/EGDMA) beads as a control system. The poly(GMA/MMA/EGDMA)‐SA affinity beads resulted in an increase in the adsorption capacity to HIgG compared with the aminated counterpart (i.e., poly(GMA/MMA/EGDMA)‐AA). The maximum adsorption capacities of the poly(GMA/MMA/EGDMA)‐AA and poly(GMA/MMA/EGDMA)‐SA affinity beads were found to be 112.36 and 142 mg g^?1, and the affinity constants (K_d), evaluated by the Langmuir model, were 2.48 × 10^?7 and 6.98 × 10^?7M, respectively. Adsorption capacities of the poly(GMA/MMA/EGDMA)‐AA and poly(GMA/MMA/EGDMA)‐SA were decreased with HIgG by increasing the ionic strength adjusted with NaCl. Adsorption kinetic of HIgG onto both affinity adsorbents was analyzed with first‐ and second‐order kinetic equations. The first‐order equation fitted well with the experimental data. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 672–679, 2007     

Effects of water on the long‐term properties of Bis‐GMA and silylated‐(Bis‐GMA) polymers

Bis‐GMA (2,2‐bis‐[4‐(2‐hydroxy‐3‐methacryloxypropoxy)phenyl]propane) is a viscous hygroscopic monomer which is used with triethyleneglycol‐dimethacrylate (TEGDMA) for dental restorations. Bis‐GMA was silylated with dimethyl‐isopropyl‐siloxane and further polymerized in order to increase water resistance and viscosity. The viscosity of the silylated monomer, Sil·Bis‐GMA, was 50 times lower than that of the parent monomer. After 1 month in water, poly(Bis‐GMA/TEGDMA) absorbed 2.6% water and the silylated polymer, poly(Sil·Bis‐GMA), only 0.56%. During this process water extracted residual monomer from each polymer. The behavior of water sorption and desorption as a function of time in poly(Sil·Bis‐GMA) was completely different from that shown by poly(Bis‐GMA/TEGDMA). The difference is discussed in terms of diffusion coefficients. Initially, water advancing contact angles (θ_ADV) were 75° and 95°, respectively. After 1 month in water both polymers showed a reduction of about 20° in θ_ADV. In poly(Bis‐GMA/TEGDMA), the reduction in θ_ADV obey to water absorption and bulk plasticization; it showed a reduction of 15°C in glass transition temperature, T_g. In contrast, the reduction in θ_ADV in poly (Sil·Bis‐GMA) obeyed to water adsorption and reorientation of the molecules at the surface in contact with the water phase; it only showed a change of 2°C in T_g. Contact angle hysteresis provided further evidence about plasticization. According to our results poly(Sil·Bis‐GMA) is more stable in water than poly(Bis‐GMA/TEGDMA). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Network structure/mechanical property relationship in crosslinked dimethacrylates of different chain lengths

In this article, the syntheses of three novel dimethacrylates of different chain lengths as well as the mechanical and thermal properties of their copolymers with methyl methacrylate and styrene were studied. The monomers were prepared by the reaction of glycidyl methacrylate with dicarboxylic acid esters obtained from maleic anhydride and ethylene, 1,4‐butylene and 1,6‐hexylene glycols. The addition reaction of glycidyl methacrylate and the acidic compound was carried out in the presence of basic catalyst, tetraethylammonium bromide. The monomers were UV‐copolymerized with methyl methacrylate and styrene in the presence of a photoinitiator which was 2,2‐dimethoxy‐2‐phenyloacetophenone. The prepared polymers were subjected to different studies concerning evaluation of their flexural properties, thermal stability, dynamic mechanical behavior as well as qualitative estimation of the content of unreacted double bonds. The dependence of glass transition temperatures (T_g) as well as degree of inhomogeneity on the crosslinking density has been examined in different copolymer systems. Evidence that the dependence of the T_g on the crosslinking density is not straightforward is presented. Dynamic mechanical measurements have demonstrated that the heterogeneity of the crosslinked polymers depends strongly on the crosslinking density of the system and the nature of methacrylate monomers used. Depending on the monomer size as well as its functionality, the resultant polymer may have features such as crosslinks or residual unsaturations that influence and define the properties of the materials. It is proved that the new dimethacrylates change their functionality in copolymerization with different monovinyl monomers. Also, the degree of unsaturated bonds conversion was found to be growing with the amount of monovinyl in the copolymer. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis of defined polyhedral oligosilsesquioxane‐containing diblock and triblock methacrylate copolymers by atom transfer radical polymerization

Defined diblock and triblock copolymers composed of methyl methacrylate‐co‐glycidyl methacrylate block and 3‐{3,5,7,9,11,13,15‐hepta(2‐methylpropyl)‐pentacyclo[9.5.1.1^3,9.1^5,15.1^7,13]‐octasiloxan‐1‐yl}propyl methacrylate block(s), i.e., P(MMA‐co‐GMA)‐b‐PiBuPOSSMA and PiBuPOSSMA‐b‐P(MMA‐co‐GMA)‐b‐PiBuPOSSMA, were synthesized by atom transfer radical polymerization (ATRP). First, monofunctional and bifunctional P(MMA‐co‐GMA) copolymers were synthesized by ATRP. Subsequently, these copolymers were successfully used as macroinitiators for ATRP of POSS‐containing methacrylate monomer. The process showed high initiation efficiency of macroinitiators and led to products with low dispersity. The synthesized block copolymers were characterized by size exclusion chromatography, ¹H‐NMR spectroscopy and their glass transition temperatures were determined by differential scanning calorimetry. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation of polymer‐supported polyethylene glycol and phase‐transfer catalytic activity in benzoate synthesis

The crosslinked polymeric microspheres (GMA/MMA) of glycyl methacrylate (GMA) and methyl methacrylate (MMA) were prepared by suspension polymerization. Polyethylene glycol (PEG) was grafted on GMA/MMA microsphers via the ring‐opening reaction of the epoxy groups on the surfaces of GMA/MMA microspheres, forming a polymer‐supported triphase catalyst, PEG‐GMA/MMA. The Phase‐transfer catalytic activity of PEG‐GMA/MMA microspheres was evaluated using the esterification reaction of n‐chlorobutane in organic phase and benzoic acid in water phase as a model system. The effects of various factors on the phase transfer catalysis reaction of liquid–solid–liquid were investigated. The experimental results show that the PEG‐GMA/MMA microspheres are an effective and stable triphase catalyst for the esterification reaction carried out between oil phase and water phase. The polarity of the organic solvent, the ratio of oil phase volume to water phase volume and the density of the grafted PEG on PEG‐GMA/MMA microspheres affect the reaction rate greatly. For this investigated system, the solvent with high polarity is appropriate, an adequate volume ratio of oil phase to water phase is 2:1, and the optimal PEG density on the polymeric microspheres is 15 g/100 g. Triphase catalysts offer many advantages associated with heterogeneous catalysts such as easy separation from the reaction mixture and reusability. The activity of PEG‐GMA/MMA microspheres is not nearly decreased after reusing of 10 recycles. © 2009 American Institute of Chemical Engineers AIChE J, 2010     

Sorption and desorption parameters of water or ethanol in light‐cured dental dimethacrylate resins

Two cycles of sorption/desorption of water or ethanol by light‐cured dental resins of bisphenol A glycol dimethacrylate (Bis‐GMA), bisphenol A ethoxylated dimethacrylate (Bis‐EMA) urethane dimethacrylate (UDMA) triethylene glycol dimethacrylate and decanediol dimethacrylate (D₃MA) were studied. The experimental curves m_t = f(t) taken for the first water sorption by poly‐Bis‐GMA, poly‐Bis‐EMA and poly‐UDMA showed a maximum. A maximum was also observed in the curve obtained for first sorption of ethanol by poly‐Bis‐GMA. In all other cases, the curves for sorption or desorption of water or ethanol showed Fickian behavior. The experimental data obtained for first sorption of water or ethanol were perfectly fitted to a new proposed equation, which predicts water or ethanol sorption with simultaneous extraction of unreacted the monomer. This equation gave us the possibility for the determination of the diffusion coefficient of the extraction of the unreacted Bis‐GMA during the water and ethanol sorption, as well as the diffusion coefficient of the extraction of the unreacted Bis‐EMA and UDMA during the water sorption. The maximum water or ethanol absorbed at equilibrium and the diffusion coefficient are determined from the second sorption/desorption cycle during which the extraction of the monomer is negligible. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and thermal self-crosslinking reaction of copolymers from 2,3-epoxypropyl methacrylate and p-substituted phenyl methacrylates

Copolymers of 2,3-expoxypropyl (glycidyl) methacrylate (GMA) with various phenyl methacrylates such as 4-nitrophenyl methacrylate (NPMA), 4-chlorophenyl methacrylate (CPMA), or phenyl methacrylate (PMA), and other monomers such as methyl methacrylate (MMA), ethyl acrylate (EA), or styrene (ST) were synthesized by radical copolymerization, and then thermal self-crosslinking reactions of the obtained copolymers were carried out using various catalysts such as quarternary ammonium salts, tert-amines, or the crown ether/potassium salt systems at 100–150°C. Although the copolymer of GMA–NPMA–MMA does not produce any gel products without catalyst upon heating at 110°C for 5 h, this copolymer gives gel products in 82% yield using 10 mol% of tetrabutylammonium bromide as a catalyst under the same conditions. The rate of gel production of the copolymer of NPMA is faster than those of copolymers of CPMA and PMA. The rate of the gel production of the copolymer of GMA–NPMA–EA is also faster than those of copolymers of MMA and ST. Furthermore, it was found that the rate of gel production of the copolymer was strongly affected by the kind of catalyst, the catalyst concentration, and the reaction temperature.