Synthesis and formulation of vinyl-containing polyacids for improved light-cured glass-ionomer cements

Vinyl-containing poly(acrylic acid-co-itaconic acid) copolymers were synthesized and used to formulate light-curable cements containing reactive glass fillers (Fuji II LC). The conditions for light curing were studied and optimized. Effects of molecular weight (MW), grafting ratio, comonomer, liquid composition, powder/liquid (P/L) ratio, glass powder and aging were evaluated. The results show that the vinyl-containing glass-ionomer cements (GICs) prepared in this study exhibit higher compressive strength (CS, 225.6 MPa), diametral tensile strength (DTS, 28.4 MPa) and much higher flexural strength (FS, 116.4 MPa), as compared to commercial Fuji II LC GIC (186.6 in CS, 19.1 in DTS and 57.1 in FS). The optimal light-exposure time was found to be around 10 min, and concentrations of CQ and DC were 0.5% (by weight) and 1.0%, respectively. Effects of MW, grafting ratio, P/L ratio and content of polymer in the liquid formulation were significant. The highest strengths were found for the optimal formulations where the MW was 15,000 (weight average), grafting ratio 25 mol%, P/L ratio 2.7 and liquid composition 50:20:30. During aging, the cement showed an increase of strength over the first week and then no change for a month. SEM analysis suggests that more integrated microstructures and smaller glass particles can lead to higher FS and higher polymer content in GICs leads to tough fracture surface and plastic deformation.     

接枝微球PMAA-HEMA/NVP对溶菌酶的吸附行为与吸附机理

采用反相悬浮聚合法制备了甲基丙烯酸羟乙酯(HEMA)与N-乙烯基吡咯烷酮(NVP)的交联共聚微球HEMA/NVP,然后采用"接出"法,实施了甲基丙烯酸(MAA)在交联微球表面的接枝聚合,制得了接枝微球PMAA-HEMA/NVP.以溶菌酶(LYZ)为模型碱性蛋白,深入研究了接枝微球PMAA-HEMA/NVP对碱性蛋白的吸附性能与吸附机理.测定了微球PMAA-HEMA/NVP的zeta电位,考察了PMAA接枝度、介质pH值及离子强度等因素对体系吸附性能的影响.结果表明,在较大的pH范围内,接枝微球PMAA-HEMA/NVP的zeta电位为绝对值较大的负值,即其表面携带有高密度的负电荷.在强静电相互作用的驱动下,接枝微球PMAA-HEMA/NVP对溶菌酶表现出很强的吸附能力.随介质pH值的增高,接枝微球对溶菌酶的吸附容量呈现先增大后减小的变化趋势,在与溶菌酶等电点接近的pH值处(pH=9),具有最大的吸附容量(90mg.g-1);离子强度对接枝微球的吸附能力也有较大的影响,当pH9时,溶菌酶吸附容量随NaCl浓度的增高而减小;当pH9时,吸附容量随NaCl浓度的增高而增大.     

Improved Flexural Strength of N-Vinyl-Pyrrolidone Modified Acrylic Acid Copolymers for Glass-Ionomers

Abstract

The flexural strengths of N-vinylpyrrolidone modified glass-ionomer cements were investigated. The optimal molar ratio of the monomers in copolymers, composed of the three components acrylic acid, itaconic acid and N-vinylpyrrolidone, was determined using a SAS statistical program. The copolymers were prepared using a free-radical polymerization process. The viscosities of aqueous solutions of these polymers were determined. Cements were formed by the reaction of these solutions with glass particles. Flexural strength (FS) was used as the basic screening property to find the optimum molar ratio. Statistical models were applied to predict the optimum molar ratios. All strength values were recorded on the specimens conditioned in distilled water at 37°C for 7 days. The optimal molar ratio for these copolymers was 7:1:3 for poly(acrylic acid-co-itaconic acid-co-N-vinylpyrrolidone), based on flexural strength and viscosity. The effect of molecular weight (MW) on FS was also evaluated. Copolymer with a MW of 10, 800 (M_n) showed 85% higher FS than the Ketac-Molar (KM) system, along with a reasonable working viscosity.     

NEW MATRIX RESINS FOR GLASS POLYALKENOATES OR GLASS-IONOMERS WITH PENDANT AMINO ACID RESIDUES

The monomers N-acryloyl (AGA) and N-methacryloylglutamic acid (MGA) have been prepared and copolymerized with acrylic acid (AA) and itaconic acid (IA) to make polyelectrolytes for evaluation in glass polyalkenoates or glass-ionomers. It was shown that poly(AA-co-IA-co-AGA) and poly(AA-co-IA-co-MGA), having a monomers ratio, respectively, of 7:3:3 could be formulated with glass powders used in Fuji II (GC America), α-Silver (DMG-Hamburg), α-Fil (DMG-Hamburg) and Ketac-Molar (ESPE, Seefeld, Germany) to produce conventional glass-ionomers with improved compressive strength (CS), flexural strength (FS) and fracture toughness (FT), compared to Fuji II, α-Silver, α-Fil and Ketac-Molar controls. Since MGA is much easier to produce in high yields than AGA, it was important to show that MGA could be used as well as AGA to produce new matrix resins for glass-ionomers. Furthermore, we demonstrated that both the 7:3:3 AGA and MGA copolymers could be reacted with 2-isocyanatoethyl methacrylate (IEM) to produce intermediates useful for formulating visible light-curable (VLC) glass-ionomers with improved CS, FS and FT, compared to two com-mercial VLC materials Fuji II^TM LC and Vitremer^TM Tricure. Here again, it was found that MGA could be used as well as AGA to prepare improved materials. We also demonstrated that poly(AA-co-MGA) could be used to formulate glass-ionomers with improved properties. Further, we demonstrated that small amounts of MGA could be used as a reactive diluent in VLC formulations such as Fuji II^TM LC, Vitremer^TM Tricure, and an experimental VLC formulation to improve their mechanical properties, adhesion to tooth structure, and fluoride release.     

Microhardness of N-Vinylpyrrolidone Modified Glass-Ionomer Cements

ABSTRACT

The water soluble N-vinylpyrrolidone (NVP) monomer was used to prepare poly(N-vinylpyrrolidone-co-itaconic acid-co-acrylic acid) glass-ionomer copolymers, using a free-radical polymerization process. NVP modified terpolymer was mixed with glass powders from four commercial glass ionomer systems. Microhardness from the set cement was measured and compared to several commercial glass-ionomer systems. The Knoop hardness number (KHN) values were recorded on polished specimens conditioned for 48 hours and 7 days. One-way analysis of variance and Tukey-Kramer tests were used to determine the significant differences among the materials tested in each group. Among the four commercial cements, Ketac-Molar (KM) showed the highest value and α-Silver (AS) snowed the lowest value in KHN. Fuji II (F2) and α-Fil (AF) showed much the same values in KHN. At the same P/L ratio, NVP modified glass-ionomers showed higher KHN values than the AS, similar to the AF and F2, and lower than the KM. The effect of P/L ratios was evident and highest KHN values for each group were basically presented by the one with a higher P/L ratio. Higher P/W ratio did not improve the KHN for the AS and KM group, but improved the F2 group.     

SYNTHESIS OF POLY(METHYL METHACRYLATE)-SILICA NANO-COMPOSITE

ABSTRACT

Transparent organic/pre-ceramic composite films of poly(methyl methacrylate) [PMMA] and perhydropolysilazane [PHPS] were synthesized by blending poly(methyl methacrylate-co-2-hydroxyethyl methacrylate) [P(MMA-co-HEMA)] random copolymers and PHPS. In the blend films, P(MMA-graft-PHPS) graft copolymers were formed, PMMA and PHPS were microscopically phase-separated in the solid state. Morphology of the microphase separation was investigated by transmission electron microscopy by changing HEMA content of the random copolymers and blend ratio of PHPS to HEMA. To convert PHPS to silica glass, the blend films were calcinated at 100°C. The morphology of the microphase separation of the films was not changed by the calcinations; the calcinated films were transparent. When the molar content of HEMA of P(MMA-co-HEMA) and the molar content of PHPS to HEMA in feed were 14.5% and 150%, respectively, the morphology was well ordered lamellae of PMMA and silica.     

Negative‐working photoresist of methacrylate polymers based on the transesterification of the 2‐hydroxyethyl group in the presence of an acid

This article reports a novel crosslinking functionality of the 2‐hydroxyethyl methacrylate unit (HEMA) in the presence of an acid. The polymeric compositions, consisting of a polymer containing the HEMA unit and a photoacid generator, were insolubilized in an aqueous base developer on exposure to UV light and a successive baking process to provide a negative‐working photoresist. A series of poly(benzyl methacrylate‐co‐methacrylic acid‐co‐2‐hydroxyethyl methacrylate) terpolymers with various contents of HEMA were prepared to elucidate the photopolymeric characteristics. The polymer behavior in films was examined by a comparison of the photosensitivity and IR spectroscopic method. Experiments with a model compound were also carried out. On the basis of the results, we found that the resist was insolubilized by crosslinking through the transesterification of HEMA segments due to acid generated from the photoacid generator and subsequent heating. The advantage of using the 2‐hydroxyethyl group is that in the terpolymer, the HEMA unit is transparent at a short‐wavelength region and is a promising crosslinking unit for ArF lithographic photoresists. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1858–1867, 2002     

PREPARATION AND EVALUATION OF ACRYLIC ACID,ITACONIC ACID,AND N-METHACRYLOYLGLUTAMIC ACID COPOLYMERS FOR USE IN GLASS-IONOMER TYPE DENTAL RESTORATIVES

A series of copolymers containing various molar ratios of acrylic acid, itaconic acid and N-methacryloylglutamic acid were prepared in aqueous solution, using standard free-radical polymerization conditions. Specimens for mechanical property studies were prepared by mixing water solutions of the copolymers (50:50, wt:wt) with a commercial, calcium-fluoroaluminosilicate glass powder, with curing or hardening achieved by salt-bridge formation. The glass powder used in the formulation(s) was the same as that used in Fuji II (GC America) glass-ionomer. The working and setting times of the various formulations were evaluated. The compressive strength was used as the basic screening property to find the optimum molar ratio of the three monomers. The diametral tensile strength, flexural strength and Knoop surface hardness of the cured materials were also determined. All mechanical properties were measured after the specimens were conditioned in distilled water for 7 days at 37°C. Based on the compressive strength (CS), poly (AA-co-IA-co-MGA) with a monomers ratio of 8:1:1, respectively, showed the highest CS (269.9 MPa). The 8:1:1 copolymer with different molecular weights were also prepared to evaluate the effect of MW on the compressive strength. The optimum MW copolymer gave a glass-ionomer having the compressive strength improved by 30%, compared to Fuji II (293.9 MPa vs. 224.9 MPa). The same polymer solution was also mixed with glass powders used in other commercial glass-ionomers, i. e., Ketac-Molar (ESPE, Seefeld, Germany), α-Fil and α-Silver (DMG, Hamburg, Germany) to produce conventional glass-ionomers test specimens. The mechanical properties of these materials were also obtained and compared to the Fuji II, Ketac-Molar, α-Fil and α-Silver controls.     

Novel resin modified glass-ionomer cements with improved flexural strength and ease of handling

Poly(acrylic acid-co-itaconic acid) copolymers containing pendent methacrylates were synthesized and used to formulate redox-initiated in situ cured glass-ionomer cements (GICs) by mixing with reactive glass fillers (Fuji II LC). Various formulations for the redox initiator were studied, and flexural strength (FS) was used as a screening tool for optimization. Effects of molecular weight (MW), grafting ratio, comonomer, polymer content in the liquid composition, powder/liquid (P/L) ratio, and aging on FS were investigated. The results show that the in situ cured GICs demonstrated higher FS (89.6-123.2 MPa), as compared to commercial Fuji II LC GIC (57.1 MPa). The optimal concentrations for redox initiators were found to be 0.15% (by weight) for K₂S₂O₈ and 0.2% for ascorbic acid (or 0.6% for microencapsulated ascorbic acid), respectively. Effects of MW, grafting ratio, P/L ratio and polymer content in the liquid formulation were significant. During aging, the cement showed an increase in strength over 24 h and then no change for time periods up to six months. SEM analysis supports the strength data associated with the formulations. The exotherm and setting time suggest that novel redox-initiated resin-modified GICs hold promise as biocompatible and workable cement for orthopedic applications.     

Removal of Pb2+ and Cd2+ ions from aqueous solutions using guanidine modified hydrogels

In this study, experimental measurements have been made on the batch adsorption of cadmium and lead ions from aqueous solutions using poly(guanidine modified 2‐acrylamido‐2‐methylpropan sulfonic acid/acrylic acid/N‐vinylpyrrolidone/2‐Hydroxyethyl methacrylate), P(AMPSG/AAc/NVP/HEMA) hydrogels. The guanidyl end group bearing AMPSG monomer was synthesized from the reaction of AMPS and guanidine. The hydrogels were prepared by UV‐curing technique. The morphology of the dry H10‐hydrogel sample was examined by SEM. The influence of the uptake conditions, such as pH, functional monomer per cent, contact time, initial feed concentration, and foreign metal ions on the metal ion binding capacity of hydrogel, was also tested. The selectivity of the hydrogel toward the different metal ions tested was Hg(II) > Pb(II) > Au(III) > Cd(II). The adsorption isotherm models were applied to the experimental data, and it was seen that the Langmuir isotherm model was the best fit for the adsorption of Cd(II) and Pb(II) ions on P(AMPSG/AAc/NVP/HEMA) hydrogel. It was found that adsorbed lead and cadmium ions on P(AMPSG/AAc/NVP/HEMA) hydrogel can be effectively desorbed by acid leaching and the regenerated P(AMPSG/AAc/NVP/HEMA) hydrogel can be reused almost five times less without any loss of adsorption capacity. Copyright © 2009 John Wiley & Sons, Ltd.     

Itaconic copolymer modified loess for high-efficiently removing copper ions from wastewater

Using Loess of clay (LC) which is low-cost, highly hydrophilic and small granule materials, biocompatible itaconic acid (IA), 2-hydroxyethyl methacrylate (HEMA) and N-vinyl-2-pyrrolidone (NVP) as functional monomers, a novel biocompatible polymer composite adsorbent (LC/PIHN) was prepared by in-situ copolymerization. It was applied to remove copper ions from wastewater, and the mechanism of adsorption was investigated. It showed that the Cu(II) removal was more than 99.8% at room temperature. The adsorption kinetics and isotherms of LC/PIHN fit the pseudo-second-order model and the Freundlich model, respectively. In summary, LC/PIHN is a kind of biocompatible, low-cost and excellent polymer composite adsorbent for removing heavy metal ions from wastewater.     

Synthesis of amino acid-containing polyacids and their application in self-cured glass-ionomer cement

Six methacrylate or acrylate derivatives of natural amino acids were synthesized and characterized. Based upon these monomers, six terpolymers [poly(acrylic) acid-co-itaconic acid-co-amino acid] were prepared and characterized. The synthesized polymers were used to formulate glass-ionomer cements (GICs) using Fuji II glass filler. The effects of the molecular weight (MW) and powder/liquid (P/L) ratio were evaluated. Scanning electron microscopy (SEM) was used to examine the fracture surfaces of the selected cement specimens. Results show that all the amino acid modified GICs exhibited higher compressive strengths (CS, 193-236 MPa) and much higher flexural strengths (FS, 55-71 MPa) as compared to commercial Fuji II GIC (191 in CS and 16 in FS). Both MW and P/L ratio affected the strength of the formed cement. It was important to find the optimal MW and P/L ratio to obtain the highest FS. In this study, optimized MW (number average) of the polyacids and P/L ratio were around 50,000 and 2.7/1, respectively. The microstructures of the fracture surfaces helped to explain the strength differences among the materials tested in the study. SEM analysis suggests that more integrated microstructures and fewer defects can lead to higher FS.     

Novel hydrogel membrane based on copoly(hydroxyethyl methacrylate/p-vinylbenzyl-poly(ethylene oxide)) for biomedical applications: properties and drug release characteristics

The aim of this study was to synthesize and characterize a novel biocompatible polymeric membrane system and demonstrate its potential use in various biomedical applications. Synthetic hydrogels based on poly(hydroxyethyl methacrylate), poly(HEMA), have been widely studied and used in biomedical fields. A novel copolymer hydrogel was prepared in the membrane form using 2-hydroxyethyl methacrylate monomer (HEMA) and a macromonomer p-vinylbenzyl-poly(ethylene oxide) (V-PEO) via photoinitiated polymerization. A series of poly(HEMA/V-PEO) copolymer membranes with different compositions was prepared. The membranes were characterized using infrared, thermal and SEM analysis. The thermal stabilities of the copolymer membranes were found to be lowered by an increase in the ratio of macromonomer (V-PEO) in the membrane structure. Because of the incorporation of PEO segments, the copolymers exhibited significantly higher hydrophilic surface properties than pure poly(HEMA), as demonstrated by contact angle measurements. Equilibrium swelling studies were conducted to investigate the swelling behavior of the membranes. The equilibrium water uptake was reached in about 4 h. Moreover, the blood protein adsorption and platelet adhesion were significantly reduced on the surface of the PEO containing copolymer membranes compared to control pure poly(HEMA). Drug release experiments were performed in a continuous release system using model drug (vancomycin) loaded copoly(HEMA/V-PEO) membranes. A specific poly(HEMA/V-PEO) membrane formulation possessing the highest PEO content (with a HEMA:V-PEO (mmol:mmol) feed ratio of 112:1 and loaded with 40 mg antibiotic/g polymer) released about 81% of the total loaded drug in 24 h at pH 7.4. This membrane composition provided the best results and can be considered as a potential candidate for a transdermal antibiotic carrier and various biomedical and biotechnological applications.     

Graft copolymerization of 2-hydroxyethyl methacrylate and methyl methacrylate onto hide powder

Graft copolymerization of 2-hydroxyethyl methacrylate(HEMA) and mixtures of HEMA with methyl methacrylate (MMA) onto hide powder was attempted using ceric ammonium nitrate as initiator, with a view to optimize the conditions for graft copolymerization. Percent grafting and grafting efficiency were calculated for various variables such as monomer concentration, initator concentration and mole ratio of HEMA to MMA. R_p, R_g and R_h (rates of polymerization, grafting and homopolymerization respectively) were also evaluated. It was observed that R_p increased linearly with increasing concentration of MMA except at very low concentrations of the monomer. An explanation is given for the effect of variables on extent of grafting and grafting efficiency.     

Influence of hydrophobic monomers on secondary nucleation of hydroxyl‐functionalized latexes

The influence of butyl acrylate (BA) and methyl methacrylate (MMA) on hydroxyl functionalized latexes was investigated. The hydrophobicity of the monomer feed was varied via the BA/MMA ratio. In addition to monitoring the effect of hydrophobic monomer feed on secondary nucleation, the polymerization kinetics and final latex properties were also obtained for comparison. Five different BA to MMA molar ratios were combined with five 2‐hydroxyethyl methacrylate (HEMA) concentrations (0, 10, 20, 30 and 40 mol% in monomer composition). All latexes were synthesized through seeded semibatch emulsion polymerization process. Particle size distributions and average particle sizes of the latexes were determined by dynamic light scattering (DLS) and qualitatively compared with transmission electron microscope (TEM) images. The BA to MMA ratio significantly influences the boundary HEMA concentration at which homogeneous secondary nucleation occurs. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2190–2202     

Preparation of cationic nanoparticles by the particle dissolution method from submicron-sized,styrene-butyl acrylate-dimethylaminoethyl methacrylate terpolymer particles

Cationic nanoparticles were prepared from submicron-sized styrene-butyl acrylate-dimethylaminoethyl methacrylate terpolymer (59.2/20.8/20.0, molar ratio) particles in a polyoxyethylene nonylphenylether nonionic emulsifier aqueous solution at pH 2.0 above 150 °C.     

EFFECT OF 2-HYDROXYETHYL METHACRYLATE ON SEMIBATCH EMULSIFIER-FREE EMULSION COPOLYMERIZATION OF METHYLMETHACRYLATE AND BUTYL ACRYLATE

IINTRODUCTIONSemibatchemulsionpolymerizationisanimportalmethodfortheproductionofpolymersforthecoatingsandadhesivesindustries.Thetraditionallatexproductsaregenerallystabilizedbyemulsifiers.However,theemulsifiersremaininginthelatexproductcanhaveanegativeeffectontheapplicationpropertiessuchasadhesiontosubstratesandfilmformationandwaterresistanceofthecoatingmaterials,becausethesmallandmobileemulsifiermoleculestendtomigratetothesurfacelayerofthepolymericfilm.Withtheemulsifier-freeemulsionpolym…     

Bis(ethyl-3-Oxo-Butanolato-O1,O3) -bis(2-propanolato)titanium (tyzor) DCR) as a reactant and catalyst in the polymerization of 2-isocyanatoethyl methacrylate (IEM)

The reaction of bis(ethyl-3-oxo-butanolato-O¹,O³)-bis(2-propanolato)titanium(Tyzor DC^R and 2-isocyanatoethyl methacrylate (IEM) in refluxing hexane produced a mixture of trimer and polymers of 2-isocyanatoethyl methacrylate which varied considerably from 23 to 92% polymer as the molar ratio of bis(ethyl-3-oxo-butanolato-O¹,O³)-bis(2-propanolato)titanium(Tyzor DC^R) to 2-isocyanatoethyl methacrylate (IEM) varied from 1:4 to 1:32. The IEM 1-nylon polymer which was soluble in cresol and phenol was characterized by FTIR, ¹H-NMR, and ¹³C-NMR. This analysis also showed that the methacrylate carbon–carbon double bond survived our reaction conditions intact. Based on atomic absorption determination of titanium, the molecular weight of the polymer ranged between 3000 and 4000 g/mol. Thermal gravimetric analysis (TGA) showed the polymer to be stable in air to approximately 250°C.     

Preparation of amphiphilic statistical copolymers of 2‐hydroxyethyl methacrylate with 2‐diethylaminoethyl methacrylate,precursors of water‐soluble copolymers

Statistical copolymers of 2‐hydroxyethyl methacrylate (HEMA) and 2‐diethylaminoethyl methacrylate (DEA) were synthesized at 50 °C by free‐radical copolymerization in bulk and in a 3 mol L^?1 N,N′‐dimethylformamide solution with 2,2′‐azobisisobutyronitrile as an initiator. The solvent effect on the apparent monomer reactivity ratios was attributed to the different aggregation states of HEMA monomer in the different solvents. The copolymers obtained were water‐insoluble at a neutral pH but soluble in an acidic medium when the molar fraction of the DEA content was higher than 0.5. The quaternization of DEA residues increased the hydrophilic character of the copolymers, and they became water‐soluble at a neutral pH when the HEMA content was lower than 0.25. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2427–2434, 2002     

Chemo-enzymatic synthesis of comb polymers

The paper describes the synthesis and characterization of comb polymers by a two-step chemo-enzymatic process. In the first step macromonomers bearing unsaturation at the chain end were prepared by lipase catalyzed ring-opening polymerization (ROP) of ε-caprolactone (CL) and 1,5-dioxepane-2-one (DXO). The ROP was carried out in bulk at 60 °C under anhydrous conditions using 2-hydroxyethyl methacrylate (HEMA) as the initiator. The DP of the macromonomers was controlled by regulating the monomer: HEMA molar feed concentration. The macromonomers were then homo- or co-polymerized in the second step with alkyl methacrylate monomers (methyl methacrylate or HEMA) using AIBN initiated free radical polymerization. Characterization of the polymers was done by ¹H NMR, SEC and DSC techniques.