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1.
In this article, three copolymers used as denture base resins were prepared via suspension copolymerization using butyl acrylate (BA), butyl methacrylate (BMA), or methyl acrylate (MA) with methyl methacrylate (MMA), respectively. The homopolymers and copolymers were characterized by 13C nuclear magnetic resonance (13C NMR). The influence of the three comonomers on the mechanical property was investigated in details and the fracture surfaces of copolymer specimens were examined using scanning electron microscopy (SEM). Meanwhile, the Tg values of three copolymers were examined by differential scanning calorimetry (DSC). The results indicate that, poly(methyl methacrylate) (PMMA) copolymers with BA, BMA, or MA have been successfully prepared via suspension copolymerization. The presence of BA, BMA, or MA could improve the mechanical property especially the impact strength, the toughness of the materials was remarkably improved. The toughening effect of BMA monomer is most significant. When the content of BA is 2 wt %, the flexural strength improves by 51% and the impact strength improves by 81.3%. The Tg values of three copolymers all decrease. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

2.
A new polymerizable monomer, [4‐(9‐ethyl)carbazolyl]methyl methacrylate ( 2 ), was synthesized by reacting of methacrylic acid and 4‐hydroxymethyl‐9‐ethyl carbazole ( 1 ) by esterification procedure in the presence of N,N′‐dicyclohexylcarbodiimide. The resulting monomer was then polymerized free‐radically to form the poly(methyl methacrylate) containing 4‐(9‐ethyl)carbazolyl pend ent groups. Also, copolymerization of monomer 2 with various acrylic monomers such as methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, and n‐butyl acrylate by azobisisobutyronitrile as a free radical polymerization initiator gave the related copolymers in high yields. The structure of all the resulted compounds was characterized and confirmed by FTIR and 1H NMR spectroscopic techniques. The average molecular weight of the obtained polymers was determined by gel permeation chromatography using tetrahydrofurane as the solvent. The thermal gravimetric analysis and differential scanning calorimeter instruments were used for studying of thermal properties of polymers. It was found that, with the incorporation of bulky 4‐(9‐ethyl)carbazolyl substitutes in side chains of methyl methacrylate polymers, thermal stability and glass transition temperature of polymers are increased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4989–4995, 2006  相似文献   

3.
Suspension Copolymerization of glycidyl methacrylate (GMA), phenyl methacrylate (PhMA), 2,4,6-tribromophenyl acrylate (TBPA), and 4-acetylphenyl acrylate (APA) with divinyl benzene (DVB) was carried out at 80 ± 1°C in aqueous medium, as basic supports for possible applications in polymer-supported chemistry. The resulting copolymer heads were characterized with various techniques. The identification of monomers in the copolymer was attempted using FTIR and 13C-CP/MAS-NMR spectroscopic techniques. The optical and scanning electron microscopic methods were used to study the shape, size, and surface morphology of the beaded copolymers. The particle-size distribution was measured, and the average particle size of the particulate copolymers were carried out using a Malvern particle-size analyzer. The decomposition temperatures and energy of activation involved in the thermal degradation were studied with thermogravimetry. The solvent imbibition of the polymer supports in various solvents was carried out with a centrifuge method.  相似文献   

4.
Acrylate‐functionalized copolymers were synthesized by the modification of poly(butyl acrylate‐co‐glycidyl methacrylate) (BA/GMA) and poly(butyl acrylate‐co‐methyl methacrylate‐co‐glycidyl methacrylate). 13C‐NMR analyses showed that no glycidyl methacrylate block longer than three monomer units was formed in the BA/GMA copolymer if the glycidyl methacrylate concentration was kept below 20 mol %. We chemically modified the copolymers by reacting the epoxy group with acrylic acid to yield polymers with various glass‐transition temperatures and functionalities. We studied the crosslinking reactions of these copolymers by differential scanning calorimetry to point out the effect of chain functionality on double‐bond reactivity. Films formed from acrylic acrylate copolymer precursors were finally cured under ultraviolet radiation. Network heterogeneities such as pendant chains and highly crosslinked microgel‐like regions greatly influenced the network structure and, therefore, its viscoelastic properties. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 753–763, 2002  相似文献   

5.
Summary It has been previously shown that copolymer of 2-ethylhexyl acrylate with an 4-acryloyloxy benzophenone can be used as PSA. This paper presents synthesis and application of solvent-based polymer system for the preparation of acrylic pressure-sensitive adhesives (PSA). 2-Ethylhexyl acrylate benzophenone copolymers, having molecular mass in the range of 120 000 to 380 000 Dalton were prepared by free-radical solution polymerization. These copolymers were tacky but possessed insufficient cohesive strength after UV-crosslinking to be useful as PSAs. These copolymers resulted in materials having a balance of cohesive and adhesive characteristics required of a good PSA. Some of the parameters affecting the pressure-sensitive adhesive properties of the copolymer are: amount of the 4-acryloyloxy, molecular mass of the polymeric components, UV-reactivity and such properties like tack, peel adhesion and cohesion.  相似文献   

6.
A new silane-containing acrylic macromonomer, maleimidedoethoxybutoxydimethylsiloxy butyl acrylate (MEBDMSBA), based on maleic anhydride (MA), ethanolamine (EA), 1,4-butanediol (BDO), dichlorodimethylsilane (DCDMS), and acrylic acid (AA) has been synthesized for formulation of waterborne polyurethane (WPU). Also a series of new silane-containing WPU, methyl methacrylate (MMA), MEBDMSBA, and montmorillonite (MMT) with organically modified montmorillonite (OMMT) content (1.25 wt%) hybrid nanocomposites have been successfully prepared by the emulsion polymerization in the presence of a WPU dispersion, using ammonium peroxodisulfate (APS) as an initiator. The WPU dispersion has been synthesized by a polyaddition reaction of isophorone diisocyanate (IPDI) on polypropylene glycol (PPG-1000) and dimethylol propionic acid (DMPA) as chain extender. The monomer was characterized by Fourier transformer infrared spectroscopy (FTIR), elemental analysis, proton (1H NMR), and carbon (13C NMR) nuclear magnetic resonance spectroscopes, respectively. The nanocomposite emulsions were also characterized using Fourier transform infrared spectroscopy (FTIR) and laser light scattering. Thermal properties of the copolymers were studied using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The OMMT was characterized by FTIR and X-ray diffraction (XRD). The morphology of copolymers was investigated by scanning electron microscopy (SEM) and transition electron microscopy (TEM), and then the effects of silane concentrations on the water absorption ratio were examined. Results showed that OMMT could improve the properties of emulsion; in other words, the properties of nanocomposite emulsion were better when compared with those of the silane–acrylate emulsion.  相似文献   

7.
Summary Glycidyl methacrylate (GMA) random copolymers with methyl acrylate (MA), ethyl acrylate (EA), n-butyl acrylate (BA), methyl methacrylate (MMA), ethyl methacrylate (EMA) and n-butyl methacrylate (BMA) were synthesized by solution free radical polymerizations, at 70±1 °C using α,α’-azobis(isobutyronitrile) as an initiator to give the copolymers I – VI in good yields. The copolymer compositions were obtained using related 1H NMR spectra and the polydispersity indices of the copolymers determined using gel permeation chromatography (GPC). Tris(trimethylsilyl)methyl (Tsi=trisyl) groups were then covalently attached to the obtained copolymers as side chains by ring opening reaction between excess of TsiLi and expoxide groups of GMA units to give the copolymers ITsi – VITsi in good yields. In the coupling reaction, the TsiLi reacted selectively with the epoxy groups of the backbone polymer rather than with the carbonyl groups of the backbone. This method of preparing functionalized silanes is limited by the readiness with which TsiLi abstracts a proton, if one is available, rather than attacks at carbon. In addition in the reaction with epoxides, the product alkoxide can transfer a silyl group from carbon to oxygen or ring opening polymerization. However these were shown not to occur at the conditions of interest here. The epoxy group possesses a higher reactivity for the TsiLi than the ester and chloromethyl groups. The ring opening reaction between the epoxy group and the TsiLi is simple and fast. All the resulted polymers were characterized by FT-IR and 1H NMR spectroscopic techniques. The glass transition temperature (Tg) of all copolymers was determined by differential scanning calorimetry (DSC) apparatus. All the polymers containing trisyl groups showed a high glass transition temperature in comparison with unmodified copolymers (I – VI). Attaching the tris(trimethylsilyl)methyl group to macromolecular chain should lead to important modifications of polymer properties such as gas permeability and perm selectivity parameters.  相似文献   

8.
Bis(1H, 1H, 2H, 2H‐perfluoro‐octyl)methylenesuccinate (FOM)/ethyl acrylate (EA)/methyl methacrylate (MMA) copolymer (FOME) latexes, FOM/butyl acrylate (BA)/MMA copolymer (FOMB) latexes, and FOM/octyl acrylate (OA)/MMA copolymer (FOMO) latexes were synthesized by continuous emulsion polymerization. Solution polymerization was also carried out to prepare FOMB. The influences of fluorine content and curing conditions on the surface properties of polymer films were discussed. The water and oil repellency of cotton fabrics treated with the FOM copolymers was better than that of conventional poly(fluoroalkyl acrylate)s containing the same fluorinated chain. The polymer films or the treated fabrics were characterized by Fourier transform infrared, scanning electron microscope, atomic force microscopy, thermogravimetric analysis, x‐ray photoelectron spectrometry, and wide angle x‐ray diffraction. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci, 2013  相似文献   

9.
Methyl methacrylate (MMA) has been copolymerized with n-butyl acrylate (n-BA), ethyl acrylate (EA), and 2-ethylhexyl acrylate (2-EHA) in solution at 70°C using benzoyl peroxide as free radical initiator. The copolymer composition was estimated by the 1H-NMR spectroscopic technique. The copolymers were further characterized by IR, XRD, TGA, DTA, DSC, GPC, and solubility. The adhesive characteristics of the copolymers to cellulosic substrate are also reported. © 1995 John Wiley & Sons, Inc.  相似文献   

10.
A series of chains of triblock amphiphilic copolymers were synthesized by atom transfer radical polymerization (ATRP) techniques and post modified to polymeric dispersant for waterborne paint. Poly(butyl acrylate (BA))-b-poly(hydroxy ethyl methacrylate (HEMA))-b-poly(methyl methacrylate (MMA)) triblock copolymers having predetermined molecular weights were synthesized by ATRP using CuBr, 2-bromoisobutyrate, and pentamethyldiethylenetriamine as a catalytic system in dioxane at 80 °C. The copolymers were further reacted with cyclic chlorophosphate and triethyl amine to form dispersible modified poly(BA-HEMA-MMA). The synthesized copolymers were structurally evaluated by Fourier transform infrared, 1H NMR, 31P NMR, gel permeation chromatography (GPC), energy dispersive X-ray spectroscopy, and their hydroxyl equivalent, respectively. The surface activity of modified copolymers as dispersing additives was investigated by the surface tension analysis and wetting ability test. The ability of additives to function as wetting and dispersing agents was evaluated by analyzing their mechanical, optical, chemical, and rheological properties of water-based paints at different pigment volume concentrations. The effects of the chain length of copolymers on dispersibility and optical properties were studied. The optical properties of paints suggested that the dispersibility of modified poly (BA)-b-poly (HEMA)-b-poly (MMA) (MPBHM) increased with an increase in the molecular weight of the copolymer.  相似文献   

11.
Narrow‐distribution, well‐defined comb‐like amphiphilic copolymers are reported in this work. The copolymers are composed of poly(methyl methacrylate‐co‐2‐hydroxyethyl methacrylate) (P(MMA‐co‐HEMA)) as the backbones and poly(2‐(dimethylamino)ethyl methacrylate) (PDMAEMA) as the grafted chains, with the copolymer backbones being synthesized via atom‐transfer radical polymerization (ATRP) and the grafted chains by oxyanionic polymerization. The copolymers were characterized by gel permeation chromatography (GPC), Fourier‐transform infrared (FT‐IR) spectroscopy and 1H NMR spectroscopy. The aggregation behavior in aqueous solutions of the comb‐like amphiphilic copolymers was also investigated. 1H NMR spectroscopic and surface tension measurements all indicated that the copolymers could form micelles in aqueous solutions and they possessed high surface activity. The results of dynamic light scattering (DLS) and scanning electron microscopy (SEM) investigations showed that the hydrodynamic diameters of the comb‐like amphiphilic copolymer aggregates increased with dilution. Because of the protonizable properties of the graft chains, the surface activity properties and micellar state can be easily modulated by variations in pH. Copyright © 2004 Society of Chemical Industry  相似文献   

12.
4-Chlorophenyl acrylate (CPA) was prepared by reacting 4-chlorophenol and acryloyl chloride in the presence of triethylamine in ethyl acetate solution. Poly(4-chlorophenyl acrylate) and copoly(4-chlorophenyl acrylate–methyl acrylate) were synthesized by the free radical polymerization in ethyl acetate at 70°C. All the polymers were characterized by infrared (IR) and nuclear magnetic resonance (NMR) spectroscopic techniques. The composition of the copolymers was determined by the 1H-NMR spectroscopic technique, that is, by integrating the aromatic peaks corresponding to the 4-chlorophenyl acrylate unit against the carbomethoxy group in the methyl acrylate unit. The reactivity ratios were calculated by Fineman–Ross, Kelen–Tudos (K–T), and the extended Kelen–Tudos methods. The values of r1 and r2 obtained by these methods were in close agreement with each other; that is, r1(CPA) = 0.64 and r2(MA) = 0.13 by the K–T method. The number-average molecular weight (M̄n = 1.55 × 103), the weight-average molecular weight (M̄w = 8.39 × 103), and the polydispersity index (M̄w/M̄n = 5.42) of poly(CPA) were determined by gel permeation chromatography (GPC). Thermal properties of the polymers were studied in a nitrogen atmosphere using thermogravimetric analysis (TGA). As the CPA increases in the copolymer, thermal stability of the copolymer increases (e.g., 90% weight loss occurs at 480°C for 20 mol % CPA, whereas the same weight loss occurs at 571°C for 80 mol % CPA). Acrylic binders, based on the CPA–MA–BA terpolymer, of different glass transition temperatures were prepared for applications in leather industry as top coat and base coat materials. These acrylic emulsions were cast into thin films, and their characteristics were tested for physical properties. These acrylic emulsions were applied as a base coat on leather, and the compositions having Tg values of 1.08 and 9.25°C were found to have excellent properties as base coats for leather when compared with commercial samples. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1153–1160, 1999  相似文献   

13.
In the addition of stabilizing agents to plastic materials, problems such as incompatibility, migration, volatility, and/or solvent extraction of the additive frequently arise. With a view toward overcoming such problems in the use of ultraviolet absorbing stabilizers, acrylate and methacrylate derivatives containing the 2-hydroxy-4-alkoxybenzophenone moiety have been synthesized. The ultraviolet absorbing monomers were synthesized by reaction of 2, 4-dihydroxybenzophenone with glycidyl acrylate and glycidyl methacrylate. They were homopolymerized and blended with poly(vinyl chloride), poly(vinylidene chloride), polystyrene, and poly(methyl methacrylate). They were also copolymerized with the corresponding monomers. The polymer blends and copolymers were investigated for ultraviolet stability versus corresponding controls. Effective ultraviolet stabilization was observed. Differences in the stability of some blends as compared to corresponding copolymers is thought to be due to incompatibility.  相似文献   

14.
Well-defined statistical, gradient and block copolymers consisting of isobornyl acrylate (IBA) and n-butyl acrylate (nBA) were synthesized via atom transfer radical polymerization (ATRP). To investigate structure-property correlation, copolymers were prepared with systematically varied molecular weights and compositions. Thermomechanical properties of synthesized materials were analyzed via differential scanning calorimetry (DSC), dynamic mechanical analyses (DMA) and small-angle X-ray scattering (SAXS). Glass transition temperature (Tg) of the resulting statistical poly(isobornyl acrylate-co-n-butyl acrylate) (P(IBA-co-nBA)) copolymers was tuned by changing the monomer feed. This way, it was possible to generate materials which can mimic thermal behavior of several homopolymers, such as poly(t-butyl acrylate) (PtBA), poly(methyl acrylate) (PMA), poly(ethyl acrylate) (PEA) and poly(n-propyl acrylate) (PPA). Although statistical copolymers had the same thermal properties as their homopolymer equivalents, DMA measurements revealed that they are much softer materials. While statistical copolymers showed a single Tg, block copolymers showed two Tgs and DSC thermogram for the gradient copolymer indicated a single, but very broad, glass transition. The mechanical properties of block and gradient copolymers were compared to the statistical copolymers with the same IBA/nBA composition.  相似文献   

15.
Vinyl polymers containing pendant acetal groups were synthesized using (2,2-dimethyl-l,3-dioxolan-4-yl)methyl acrylate (DMA) and (2,2-dimethyl-l,3-dioxo-lan-4-yl)methyl methacrylate (DMM), and were evaluated as negative electron beam (EB) resists. It was found that the EB sensitivity of polymers containing acetal groups in the side chain was higher than that of polymers containing acetal groups in the main chain. A high sensitivity of 3.6 × 10?8 C/cm2 was observed. Copolymers of DMA or DMM with styrene were also synthesized in order to improve the durability for dry etching process. It was found that the copolymers had an excellent dry etching durability and were adaptable to EB lithography.  相似文献   

16.
Acrylate-based fluorinated copolymers for high-solids coatings   总被引:1,自引:0,他引:1  
A series of low, medium, and high molecular weight copolymers containing methyl methacrylate, n-butyl acrylate, 2-hydroxyethyl methacrylate, and 2,2,2-trifluoroethyl methacrylate were synthesized by solution polymerization under monomer-starved conditions. The acrylate-based copolymers were characterized by FTIR; 1H, 13C, and 19F NMR, and MALDI-TOF mass spectrometry. The molecular weights and the glass transition temperatures of the copolymers were determined using Gel Permeation Chromatography (GPC) and Differential Scanning Calorimetry (DSC). The copolymers were crosslinked with a methylated melamine formaldehyde resin in order to obtain thermosetting acrylics. Surface, optical, barrier, mechanical, and viscoelastic properties of the acrylic coatings were investigated. An enrichment of fluorinated units at the acrylic surface was directly verified measuring dynamic contact angles. Lower wettability, higher oxygen permeability, and lower refractive index were observed for higher concentrations of fluorinated monomer in the copolymer composition. High number-average hydroxyl functionality of high molecular weight copolymers increased the crosslink density of the acrylic films, resulting in improved tensile strength and tensile modulus.  相似文献   

17.
Polymeric epoxides were converted to corresponding five-membered cyclic carbonates in an effective manner. Poly(glycidyl methacrylate) (PGMA) was converted to a poly(2-oxo-1,3-dioxolane-4-yl) methyl methacrylate (PDOMMA) by the polymer reaction with carbon dioxide using tetraoctylammonium chloride (TOAC) as a catalyst. The miscibility of blends of PGMA or PDOMMA with copolymers of MMA and ethyl acrylate (MMA-EA) of two different EA compositions (2 and 5 wt %) was investigated by differential scanning calorimetry (DSC). The films of PGMA or PDOMMA and MMA-EA (2 and 5 wt %) blends were cast from N,N-dimethylformamide solution. An optical clarity test and DSC analysis showed that PDOMMA blends were miscible over the entire composition range, but PGMA was immiscible with the MMA-EA copolymers. It was also found that the miscibility of PDOMMA with 2 wt % MMA-EA copolymer was better than that of DOMMA with 5 wt % MMA-EA copolymer. The different miscibility behaviors were investigated in terms of Fourier transform IR spectra and interaction parameters based on the binary interaction model. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2161–2169, 2001  相似文献   

18.
pH‐Responsive amphiphilic branched copolymers were prepared from poly(ethylene glycol) methyl ether methacrylate (PEGMA), 2‐(diethylamino)ethyl methacrylate (DEAEMA), 2‐(tert‐butylamino)ethyl methacrylate (tBAEMA), and ethylene glycol dimethacrylate (EGDMA) utilizing a thiol‐modified free radical polymerization. The molecular structures of copolymers were confirmed by proton nuclear magnetic resonance spectroscopy (1H NMR) and triple‐detection gel permeation chromatography (tri‐GPC). The aqueous solution behaviors of the obtained copolymers were investigated by dynamic light scattering (DLS). The DLS data showed that about 16 nm polymer particles comprising of hydrophobic poly(tert‐butylamino)ethyl methacrylate (PtBAEMA) and poly(diethylaminoethyl methacrylate (PDEAEMA) core, hydrophilic PEGMA corona were formed above pH 8. With the decrease of pH from 8 to 6, a dramatic increase in the hydrodynamic radius of polymer particles from 16 nm to 130 nm was observed resulting from the protonation of the PDEAEMA segment. Moreover, in vitro drug release behaviors of the resulting polymer assemblies at different pH values were also investigated to evaluate their potential as sustained release drug carriers. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42183.  相似文献   

19.
The synthesis of novel copolymers consisting of a side‐group liquid‐crystalline backbone and poly (methyl methacrylate) grafts were realized by the use of atom transfer radical polymerization (ATRP). In the first stage, the bromine‐functional copolymers 6‐(4‐cyanobiphenyl‐4′‐oxy)hexyl acrylate and (2,5‐dioxo‐2,5‐dihydro‐1H‐pyrrole‐1‐yl)methyl 2‐bromopropanoate were synthesized by free‐radical polymerization. These copolymers were used as initiators in the ATRP of methyl methacrylate to yield graft copolymers. Both the macroinitiator and graft copolymers were characterized by 1H‐NMR, gel permeation chromatography, differential scanning calorimetry, and thermogravimetric analysis. The ATRP graft copolymerization was supported by an increase in the molecular weight of the graft copolymers compared to that of the macroinitiator and also by their monomodal molecular weight distribution. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

20.
Abstract

A new monomer was prepared in the reaction of bis(4-chloromethylphenyl)sulphide with potassium salt of methacrylic acid. The monomer was characterized by elementary analysis, IR, 1 >H-NMR and 13C-NMR analyses. After determination of the structure, studies on its solubility with common as well as vinyl solvents such as styrene, methyl methacrylate, butyl acrylate, acrylonitrile, and divinylbenzene were carried out. Besides, a hardening system for styrene solutions of bis(4-methacryloylmethylphenyl)sulphide (BMMPhS) was chosen. Combinations of the following components: benzoyl peroxide, methyl ethyl ketone peroxide, N,N-dimethylaniline, and cobalt naphthenate were used for hardening. Polymerization of the following styrene solutions of BMMPhS: 50,40,30, 20 and 10% was performed. The obtained copolymers were tested for mechanical properties like: Young's modulus, tensile strength, elongation at break, hardness of Shore's and Brinnell's methods. For the chosen copolymers, thermal properties were determined.  相似文献   

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