Synthesis and characterization of curable methacrylate-based monomers (original) (raw)
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Journal of the Chemical Society of Pakistan, 2011
Homopolymerization of 4-methoxybenzyl methacrylate (MBMA) and copolymerization with isobornyl methacrylate (IBMA) by the atom transfer radical polymerization method (ATRP) were performed at 90 °C. The homopolymer [poly(MBMA)] and copolymer [poly(MBMA-co-IBMA)] were characterized by Fourier transform infrared (FTIR), 1 H and 13 C NMR and gel permeation chromatography (GPC) techniques.. The compositions of the copolymers were calculated from 1 H NMR spectra. For the atom transfer radical copolymerization system, their monomer reactivity ratios were obtained by using the Kelen-Tüdos and Fineman-Ross equation, as r1: 0.88, r2: 0.63 (r1 is the monomer reactivity ratio of IBMA) and r1: 0,90, r2 :0,65.The initial decomposition temperatures of the resultant copolymers decreased with an increasing mol fraction of IBMA, which indicates that the heat resistance of the copolymer has been improved by decreasing the MBMA units.
Journal of Applied Polymer Science, 2007
The synthesis of 2,2-bis[(4-(2-hydroxy-3-methacryloxyethoxy)phenyl]propane (BHEP) and (1-methacryloxy-3ethoxymethacryloxy-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 1 H-NMR. BHEP and MEHP have lower viscosity because of the presence of long ali-phatic 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,Ndimethylaminoethyl methacrylate as the photoinitiating system.
The Journal of Physical Chemistry C
MATERIALS AND METHODS Synthesis of 2-isopropoxyethyl methacrylate (IEMA), and 2-tertbutoxyethyl methacrylate (TEMA) IEMA. To a solution of 2-isopropoxy ethanol (37.2 g, 0.36 mol) in pyridine (102 mL) and dichloromethane (68 mL), methacryloyl chloride (41.9 g, 0.40 mol) and dichloromethane (21 mL) were added. The reaction was carried out below 5 o C in an ice bath, and once all the reagents are added, the mixture was continuously stirred at room temperature overnight. The reaction mixture was washed with 5% sodium bicarbonate solution (1.05 L) and deionized water (0.45 L). The mixture was dried with calcium sulfate and filtered after washing. 1% (w/v) monomethyl hydroquinone (MEHQ) was added to the solution before purification. The Vigreux distillation of the product produced a clear liquid (86 mL, 82.6 g, 62% yield, and 97% purity). 1 H NMR δ 1.17
The synthesis and polymerization of methacrylate macromonomers
1998
Macromonomers of a range of functional methacrylate monomers are prepared using a catalytic chain transfer agent. The lower molecular weight oligomers, e.g. dimer, trimer, are isolated by reduced pressure distillation and characterised by IR and *H and 13C NMR spectroscopy. It has previously been established in the published literature that methacrylate macromonomers can undergo three different types of reaction when added to radical polymerizations. They can copolymerize or undergo an addition- fragmentation reaction ((5-scission) or they can undergo a depropagation mechanism along the backbone to yield the starting materials. This (5-scission mechanism is utilised to prepare a range of telechelic methacrylate polymers using functional dimers, some of which have been shown to undergo further reactions. The chain transfer constants of MMA dimer, MMA trimer and BMA trimer in bulk polymerizations of MMA and BMA are determined using an integrated form of the Mayo equation. The trends s...
Reactive & Functional Polymers, 2008
The acrylamide monomer, N-(4-bromophenyl)-2-methacrylamide (BrPMAAm) has been synthesized by reacting 4-bromoaniline with methacryloyl chloride in the presence of triethylamine(NR 3) at 0-5°C. Copolymers of N-(4-bromophenyl)-2-methacrylamide (BrPMAAm), with glycidyl methacrylate (GMA) were synthesized in 1,4-dioxane solution at 70 ± 1°C using 2,2 0-azobisisobutyronitrile (AIBN) as an initiator with different monomer-to-monomer ratios in the feed. The copolymers were characterized by FTIR, 1 Hand 13 C NMR spectroscopy. The copolymer composition was evaluated by nitrogen content (N for BrPMAAm-units) in polymers led to the determination of reactivity ratios. The monomer reactivity ratios for BrPMAAm (M 1)-GMA (M 2) pair were determined by the application of conventional linearization methods such as Fineman-Ross (r 1 = 0.2893; r 2 = 0.7114), Kelen-Tü dö s (r 1 = 0.3361; r 2 = 0.8645) and extended Kelen-Tü dö s (r 1 = 0.3096; r 2 = 0.8577) as well as by a non-linear error variables model (EVM) method using a computer program, RREVM (r 1 = 0.3453; r 2 = 0.8606). The mean sequence lengths determination indicated that the copolymer was statistically in nature. The polydispersity indices of the polymers determined using gel permeation chromatography suggest a strong tendency for chain termination by disproportionation. Thermal decomposition of the polymers occurred in three stages in the temperature range of 100-500°C and the glass transition temperature (T g) range of 94-165°C.
Development of reactive methacrylates based on glycidyl methacrylate
Journal of Polymer …, 2010
Six methacrylate monomers have been synthesized for use as reactive diluents in dental composites and evaluated to investigate the relationship between molecular structure and monomer reactivity. Four were synthesized by reactions of glycidyl methacrylate (GMA) with various acids, 2-(2-methoxyethoxy)acetic acid (1), 2-(2-(2-methoxyethoxy)ethoxy)acetic acid (2), cyanoacetic acid , and benzoic acid (4); others were synthesized by reactions of GMA with diethyl hydrogen phosphate (5) or methanol . Monomers 1 and 2 are novel, 3 seems to be novel, 4 and 6 were synthesized via a novel method, and the synthesis of 5 was described in the literature. The monomers showed high crosslinking tendencies during thermal bulk polymerizations. The photo-, homo-, and copolymerization behavior of the monomers with 2,2-bis[4-(2-hydroxy-3-methacryloyloxy)phenyl]propane (Bis-GMA) were investigated. The maximum rate of polymerizations of monomers 2-6 was found to be greater than triethyleneglycol dimethacrylate, Bis-GMA, 2-hydroxyethyl methacrylate, and glycerol dimethacrylate. For the more reactive monomers , the oxygen sensitivity of polymerization was found to be low due to a hydrogen abstraction/chain transfer reaction. The computationally calculated dipole moment and lowest unoccupied molecular orbital energies indicated that there seems to be a correlation between these quantities and reactivity for ester linked monomers (1-5), which was also supported by 13 C NMR data.
Reactive and Functional Polymers, 2003
The synthesis of a number of new methacrylate esters containing aryl-oxycarbonyl group are described. The monomers produced from the reaction of corresponding aryl-oxycarbonyl methylchlorides with sodium methacrylate, were polymerized 1 1 3 in 1,4-dioxane with AIBN as an initiator at 60 8C. The monomers and their polymers were characterized by IR, H and C NMR spectroscopy. The glass transition temperature and thermal decomposition temperature of the polymers were investigated by DSC-50 and TGA-50 thermobalance, respectively. The activation energies of these polymers of thermal ] ] decomposition were evaluated by using the MHRK method. The molecular weights (M and M ) of the polymers were w n determined by the GPC technique. The photochemical properties of the polymers were also examined.
Novel macroporous functionalized copolymers with different cross-linker concentrations and porosity parameters were synthesized by reaction of the pendant epoxy groups of poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) (poly(GMA-co-EGDMA)) with hexamethylene diamine, 1,3-bis(3-aminopropyl)tetramethyldisiloxane, and α,ω-diaminopropyl poly(dimethylsiloxane). The copolymers were prepared in forms of spherical beads and characterized by Fourier transform infrared (FTIR), 13 C and 29 Si solid-state NMR, mercury porosimetry, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). Copolymers prepared with the higher cross-linker concentrations have better thermal stability, higher glass transition temperatures, higher specific surface areas, and smaller pore diameters that correspond to half of the pore volumes. Our results show that functionalization significantly changed porosity parameters, mechanism of thermal degradation, and increased thermal stability in comparison with the initial copolymers. These macroporous copolymers could potentially have many applications, i.e. for sorption of heavy and precious metals or as material for gas chromatography columns.
Journal of Macromolecular Science, Part A
A new methacrylate monomer 2-(4-nitrophenyl)-2-oxoethyl-2-methacrylate (NFM) was synthesized and its radical copolymerization with glycidyl methacrylate (GMA) was studied in 1,4-dioxane solution at 65 C using 2,2 0-azobisisobutyronitrile as an initiator. The synthesized monomer and copolymers were characterized by FTIR, 1 H and 13 C-NMR spectroscopy. The analysis of reactivity ratios revealed that NFM is less reactive than GMA, and copolymers formed are statistically in nature. Thermogravimetric analysis of the polymers reveals that the thermal stability of the copolymers increases with an increasing in the mole fraction of NFM in the copolymers. Glass transition temperatures of the copolymers decreased with an increasing of NFM molar fraction in copolymers. In addition, according to the results obtained from the contact angle and zeta potential measurements the hydrophobic character of the polymer decreases (it means surface free energy increases) and its zeta potential becomes more negative with increase of NFM ratio in the copolymer. Polymers with carbonyl functional groups have been particularly interesting because of their use as photoresists.
Journal of Macromolecular Science, Part A, 2007
The acrylamide monomer, N-(4-bromophenyl)-2-methacrylamide (BrPMAAm) has been synthesized by reacting 4-bromoaniline with methacryloyl chloride in the presence of triethylamine(NR 3) at 0-5°C. Copolymers of N-(4-bromophenyl)-2-methacrylamide (BrPMAAm), with glycidyl methacrylate (GMA) were synthesized in 1,4-dioxane solution at 70 ± 1°C using 2,2 0-azobisisobutyronitrile (AIBN) as an initiator with different monomer-to-monomer ratios in the feed. The copolymers were characterized by FTIR, 1 Hand 13 C NMR spectroscopy. The copolymer composition was evaluated by nitrogen content (N for BrPMAAm-units) in polymers led to the determination of reactivity ratios. The monomer reactivity ratios for BrPMAAm (M 1)-GMA (M 2) pair were determined by the application of conventional linearization methods such as Fineman-Ross (r 1 = 0.2893; r 2 = 0.7114), Kelen-Tü dö s (r 1 = 0.3361; r 2 = 0.8645) and extended Kelen-Tü dö s (r 1 = 0.3096; r 2 = 0.8577) as well as by a non-linear error variables model (EVM) method using a computer program, RREVM (r 1 = 0.3453; r 2 = 0.8606). The mean sequence lengths determination indicated that the copolymer was statistically in nature. The polydispersity indices of the polymers determined using gel permeation chromatography suggest a strong tendency for chain termination by disproportionation. Thermal decomposition of the polymers occurred in three stages in the temperature range of 100-500°C and the glass transition temperature (T g) range of 94-165°C.