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1.
The synthesis of a new monomer, 2,3‐(2‐hydroxy‐3‐methacryloyloxypropoxy)naphthalene, and its copolymerization with divinylbenzene is presented. This monomer was obtained from naphthalene‐2,3‐diol in a two‐step synthesis. Copolymers in the form of porous microspheres were prepared by a suspension‐emulsion polymerization method. As pore‐forming diluents, toluene, 1‐decanol, benzyl alcohol, and their mixtures were used. In studies of their porous structure, two methods were used: the adsorption of nitrogen at low temperatures, which provided information about the porous structure of the material in a dry state, and inverse exclusion chromatography, which provided information about the porous structure of the polymer swollen by a good solvent. The obtained results suggest that the porous structures for the dry and swollen polymers were different. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1886–1895, 2006  相似文献   

2.
An inverse suspension polymerization method for the preparation of thermoresponsive hydrogel microspheres based on N‐isopropylacrylamide was described in this article. The polymerization reaction was carried out at 200 rpm stirring rate and the microspheres obtained were in the size range of 71–500 μm in the swollen states. The particles were sieved by using ASTM sieves. The selected fraction (180–250 μm) of poly(N‐isopropylacrylamide) (PNIPAAm) microspheres was used for radiation‐induced modification with itaconic acid (IA) to obtain PNIPAAm/poly(itaconic acid) graft copolymer. Viagra and lidocaine were used as model drugs for the investigation of controlled‐release behavior of the microspheres. Incorporation of IA graft chains onto microspheres enhanced significantly the uptake of both drugs and further controlled release at specific pH values. The release studies showed that some of the basic parameters affecting the drug‐loading and ‐release behavior of the microspheres were pH, temperature, particle size, and chemical nature of drug. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1115–1124, 2005  相似文献   

3.
Radical suspension copolymerization of 1‐vinyl‐2‐pyrrolidone (VP) with three different cross‐linkers: divinylbenzene (DVB), trimethylolpropane trimethacrylate (TRIM), and di(methacryloxymethyl) naphthalene (DMN) was used to prepare macroporous microspheres. During the copolymerization, the mixture of toluene and n‐dodecane as a pore‐forming diluent was used. All samples were characterized in terms of particle size and distribution, nitrogen content, specific surface area total pore volume, and pore size distribution. It was found that specific surface area of the obtained beads is strongly dependent on the diluent system and the type of cross‐linker and achieves value from 27 to 845 m2/g. To determine the influence of chemical structure of cross‐linkers on the selectivity and polarity of the copolymers, inverse gas chromatography was applied. In addition, VP–DVB and VP–DMN copolymers were modified by sulfonation into cation‐exchangers with cation exchange capacity equal 1.98 and 2.31 mmol/g, respectively. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

4.
The dispersion polymerization of methyl methacrylate (MMA) with fluorescent monomer tris[2‐((8‐hydroxyquinolin‐5‐yl)methoxy)ethyl methacrylate]aluminium (Al‐HQHEMA) was investigated to obtain fluorescent microspheres under varying conditions (such as composition of dispersion medium, and content of stabilizer polyvinylpyrrolidone (PVP) and Al‐HQHEMA) in methanol–water at 70 °C with 2,2′‐azoisobutyronitrile as the initiator. Fluorescent microspheres with particle size of 2.039 µm and uniformity of 0.171 were obtained under the following conditions: methanol–water, 7:3 (v/v); PVP, 15 wt% of MMA; Al‐HQHEMA solution, 1.5 mL. Maleic monoester of monomethoxyl poly(ethylene glycol) (Mal‐MPEG) was used as a comonomer to simultaneously incorporate carboxyl groups and PEG chains. With Mal‐MPEG, no aggregation was observed in the measurements of particle size and size distribution for the obtained microspheres after cleaning off PVP, indicating that self‐stabilized fluorescent microspheres were obtained. While without Mal‐MPEG, obvious aggregation was observed. The determination of surface carboxyl content using aqueous acid–base titration showed that most of the carboxyl groups of Mal‐MPEG were located on the surface of the microspheres. © 2015 Society of Chemical Industry  相似文献   

5.
Poly(2‐hydroxyethylmethacrylate) (PHEMA)‐based microspheres (150–200 µm in diameter) were produced by a modified suspension polymerization of different type of comonomers—namely, acrylic acid, dimethylaminoethyl‐methacrylate, and methylmethacrylate. These microspheres were activated with cyanogen bromide (CNBr) at pH 11.5, and heparin molecules were then immobilized through covalent bonds. The amount of immobilized heparin was controlled by changing the initial concentration of CNBr and heparin. The increase in the initial concentrations of both CNBr and heparin caused an increase in the amount of heparin immobilized onto microspheres for all polymer surfaces. The maximum heparin immobilization was observed on the PHEMA homopolymer microspheres (180 mg/g). The plain and heparin‐immobilized microspheres were contacted with blood in in vitro systems and in ex vivo animal experiments. Loss of the blood cells and clotting times were followed. Anticoagulant effect of the immobilized heparin was clearly observed with blood coagulation experiments. Loss of cells in the blood contacting with heparin‐immobilized microspheres was significantly lower than those observed with the plain microspheres. Bovine serum albumin adsorption onto the microspheres containing heparin on their surfaces was also studied. High albumin adsorption values (up to 127 mg/g) were observed in which the heparin‐immobilized PHEMA microspheres were used. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 655–662, 1999  相似文献   

6.
Crosslinked poly(vinyl alcohol) (CPVA) microspheres were first prepared via the suspension polymerization of vinyl acetate and the alcoholysis of poly(vinyl acetate). Afterwards, a two‐step method involving graft polymerization and Hofmann degradation was used to prepare functional poly(vinyl amine)‐grafted crosslinked poly(vinyl alcohol) (PVAm–CPVA) microspheres, onto which poly(vinyl amine) (PVAm) macromolecules were grafted. The graft polymerization of acrylamide (AM) on CPVA microspheres was performed with cerium salt as the initiator in an acidic aqueous medium, resulting in polyacrylamide (PAM)‐grafted CPVA microspheres. Subsequently, the grafted PAM was transformed into PVAm via the Hofmann degradation reaction, and PVAm–CPVA microspheres were prepared. The effects of the main factors on the graft polymerization and Hofmann degradation were examined, and the reaction mechanisms were researched in depth. The experimental results showed that for the graft polymerization of AM on CPVA microspheres initiated by cerium salt, the acid concentration and the amount of cerium salt affected the grafting degree of PAM greatly. For the Hofmann degradation reaction of the grafted PAM, the amination degree of PVAm–CPVA microspheres was obviously affected by the amount of sodium hypochlorite in the presence of sodium hydroxide. The preliminary adsorption tests showed that PVAm–CPVA microspheres were multifunctional and had strong adsorption ability for Fe(III) ions by chelation action and for chromate ions (CrO) by strong electrostatic interactions. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

7.
Syndiotactic poly(vinyl alcohol) (PVA)/poly(vinyl pivalate/vinyl acetate) [P(VPi/VAc)] microspheres, with a skin–core structure, were prepared through the heterogeneous saponification of copolymers of vinyl pivalate (VPi) and vinyl acetate (VAc). For the preparation of P(VPi/VAc) microspheres with various particle sizes and a uniform particle size distribution (which are promising precursors of syndiotactic PVA embolic materials to be introduced through catheters for the management of gastrointestinal bleeders, arteriovenous malformations, hemangiomas, and traumatic rupture of blood vessels), VPi and VAc were suspension‐copolymerized at 30°C with a room‐temperature initiator, 2,2′‐azobis(2,4‐dimethylvaleronitrile). The effects of the polymerization conditions were investigated in terms of the size and size distribution of the suspension particles. P(VPi/VAc) microspheres, with various syndiotactic dyad (s‐dyad) contents, were produced through the control of the monomer feed ratio. In addition, monodisperse P(VPi/VAc) particles of various particle diameters were obtained by the separation and sieving of the polymerization product. Monodisperse P(VPi/VAc) microspheres of various particle sizes were partially saponified in the heterogeneous system, and the effects of the particle size and particle size distribution on the saponification rate were investigated in terms of the tacticity and the saponification time and temperature. Novel skin–core PVA/P(VPi/VAc) microspheres of various s‐dyad contents and degrees of saponification were successfully produced through the control of the various polymerization and saponification parameters. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1539–1548, 2005  相似文献   

8.
A novel and effective protocol for the preparation of superparamagnetic immunomicrospheres has been developed. First, micro‐size magnetic poly (methacrylate‐divinylbenzene) (PMA‐DVB) spheres were prepared by a modified suspension polymerization method. The oleic acid coated magnetite (Fe3O4) nanoparticles made by coprecipitation were mixed with monomers of MA, DVB, and initiator benzoyl peroxide (BPO) to form oil in water emulsion droplets with the presence of poly (vinyl alcohol) (PVA‐1788) as a stabilizer. The polymerization reaction was carried out in a 2‐L beaker equipped with four vertical stainless steel baffleplates by increasing the temperature of the mixture at a controlled rate. The resulting magnetic microspheres are micro‐sized (less than 8μm in diameter) and 80 percent of them are in the size ranging from 1 to 5 μm. Then, they were highly functionalized via ammonolysis reaction with ethylenediamine, and the surface amino‐modified magnetic microspheres were obtained. The morphology and properties of these magnetic microspheres were examined by SEM, TEM, VSM, and FT‐IR. Affinity ligand protein A (ProtA) was covalently immobilized to the amino‐modified magnetic microspheres by the glutaraldehyde method. These ProtA‐immobilized magnetic immunomicrospheres were effective for affinity bioseparation processes, as was demonstrated by the efficient immunoaffinity purification of antibodies IgG2a (22mg per gram of microspheres) from mouse ascites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2205–2211, 2004  相似文献   

9.
Polylactide (PLA) and a block copolymer, poly‐DL ‐lactide–poly(ethylene glycol) (PELA) were synthesized by bulk ring‐opening polymerization initiated by stannous chloride. A linear DNA molecule, λDNA, was used as the model DNA. PLA, PELA, λDNA‐loaded PLA and PELA microspheres were prepared by the solvent‐extraction method based on the formation of multiple w1/o/w2 emulsion. The particle‐size distribution, surface morphology, and DNA loading characterized the microspheres. The mean diameter of λDNA‐loaded PELA microspheres was proved to be 3.5 μm. The integrity of the λDNA molecules, after preparing the microspheres, was determined by agarose gel electrophoresis. The result suggested that most of the λDNA molecules could retain their integrity after being encapsulated by PELA. The PELA microspheres could also prevent λDNA from being degraded by DNase. The in vitro degradation and release of PLA, PELA, and λDNA‐loaded PELA microspheres were carried out in a pH 7.4 buffer solution at 37°C. Quantitatively, evaluating the molecular weight reduction, the mass loss, the particle‐size changes, and the particle‐size distribution changes also monitored the degree of degradation. The release profile was assessed by measurement of the amount of λDNA present in the release medium at determined intervals. The degradation profiles of the PELA microspheres were quite different from those of the PLA microspheres. The introduction of the hydrophilic poly(ethylene glycol) domain in PLA and the presence of λDNA within the microspheres exhibit the apparent influence on the degradation and release profiles. A biphasic release profile was proved, that is, an initial burst release during the first days, then a gradual release. It was demonstrated that the PELA microspheres could be used potentially as a controlled release‐delivery system for λDNA. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2557–2566, 2002  相似文献   

10.
Magnetic poly(styrene butyl acrylate methacrylic acid) [P(St–BA–MAA)] microspheres were prepared by emulsifier‐free emulsion polymerization in the presence of a polar solvent and a ferrofluid prepared by a coprecipitation method. The effects of some polymerization parameters, such as the medium polarity, reaction temperature, initiator content, and surfactant content in the ferrofluid, on the particle diameter and particle size distribution of magnetic P(St–BA–MAA) microspheres were examined in detail. The results showed that the electrostatic repulsion in the polymerization system significantly affected the monodispersity of the resulting magnetic polymer microspheres. The proper electrostatic repulsion, achieved through changes in the medium polarity and amount of surfactant in the polymerization system, improved the monodispersity, but a higher or lower repulsion led to a decrease in the monodispersity. Although the existence of surfactant and magnetite particles reduced the monodispersity more or less, the polymerization behavior of an emulsifier‐free emulsion polymerization in the presence of the ferrofluid was analogous to that of a conventional emulsifier‐free emulsion polymerization. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1733–1738, 2003  相似文献   

11.
Fairly uniform microspheres of poly(styrene‐co‐methyl methacrylate) were prepared by employing a microporous glass membrane [Shirasu porous glass (SPG)]. The single‐step SPG emulsification, the emulsion composed mainly of monomers, hydrophobic additives, and an oil‐soluble initiator, suspended in the aqueous phase containing a stabilizer and inhibitor, was then transferred to a reactor, and subsequent suspension polymerization followed. The droplets obtained were polymerized at 75°C under a nitrogen atmosphere for 24 h. The uniform poly(styrene‐co‐methyl methacrylate) microspheres with diameters ranging from 7 to 14 μm and a narrow particle‐size distribution with a coefficient of variation close to 10% were prepared by using SPG membrane with a pore size of 1.42 μm. The effects of the crosslinking agent and hydrophobic additives on the particle size, particle‐size distribution, and morphologies were investigated. It was found that the particle size decreased with a narrower size distribution when the additives were changed from long‐chain alkanes to long‐chain alcohols and long‐chain esters, respectively. Various microspheres with different morphologies were obtained, depending on the composition of the oil phase. The spherical poly(styrene‐co‐methyl methacrylate) particles without phase separation were obtained when using an adequate amount of the crosslinking agent and methyl palmitate as an additive. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1013–1028, 2000  相似文献   

12.
Uniform poly(glycidyl methacrylate‐divinyl‐benzene) (P(GMA‐DVB)) and poly(glycidyl methacrylate‐ethylene dimethacrylate) (P(GMA‐EGDMA)) porous microspheres with several 10 μm were successfully prepared by membrane emulsification–polymerization technology. Conventional suspension polymerization method was first investigated by examining the effects of recipe components on the morphologies of P(GMA‐DVB), including stabilizer, diluent, and crosslinker to select a optimum recipe. The membrane emulsification–polymerization process was developed to prepare uniform PGMA porous microspheres as the following: the oil phase composed of monomer, diluent and initiator was pressed through membrane pores into the aqueous phase to form uniform droplets, and subsequent suspension polymerization was carried out. GMA and 4‐methyl‐2‐pentanol in the selected recipe were relatively hydrophilic, and therefore oil phase could wet the hydrophilic glass membrane and bring about polydispersed droplets. However, when isooctane was added as a component of diluents, the uniform droplets could be prepared by membrane emulsification method. In the membrane emulsification–polymerization, the coagulation between microspheres obviously decreased while yield of microspheres slightly increased. To extend the application of PGMA, as a trail, uniform P(GMA‐EGDMA) porous microspheres were also successfully prepared by membrane emulsification–polymerization with a isooctane contained diluent, even though EGDMA was more hydrophilic than DVB. Therefore, recipe was found the important factor to prepare uniform PGMA porous microspheres using membrane emulsification–polymerization method. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5018–5027, 2006  相似文献   

13.
The synthesis of new porous copolymers for chromatography purposes is presented. They are formed during the suspension and emulsion polymerization of methacrylate derivatives of bisphenol‐S with divinylbenzene in the presence of the pore‐forming diluent. One type of the obtained copolymers contains sulfonyl functional groups in its skeleton and the second sulfonyl and more polar hydroxyl groups. Chemical and porous structures of the obtained polymeric packings were studied. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 142–148, 2000  相似文献   

14.
To prepare high molecular weight (HMW) poly(vinyl acetate) (PVAc) with high yield and high linearity as a precursor of HMW poly(vinyl alcohol) (PVA), vinyl acetate (VAc) was emulsion polymerized using, azo initiator, 2,2′‐azobis(2‐amidinopropane) dihydrochloride (AAPH). This was compared with the polymerization using potassium peroxodisulfate (KPS) as an initiator at various polymerization conditions. PVA, having a maximum number average degree of polymerization (Pn) of 3500 was obtained by the saponification of PVAc with Pn of 13,000–14,000, degree of branching (DB) for the acetyl group of about 3.4–3.5, and a maximum conversion of VAc into PVAc of 95%, which was polymerized by AAPH. These numerical values were superior compared with 14,500–15,000 of Pn of PVAc, obtained by KPS, and 3100 of maximum Pn of resulting PVA, DB of about 3.7–3.8, and maximum conversion of 90%. From the foregoing experimental results, we found that AAPH was a more efficient initiator than KPS in increasing both conversion of PVAc and molecular weight of PVA. In addition, PVAc microspheres, obtained by these emulsion polymerizations, can be converted to PVA / PVAc shell / core microspheres through a series of surface‐saponifications, maintaining their spherical morphology. Various surface morphologies, such as flat or wrinkled and swellable or nonswellable ones formed by the various molecular parameters and saponification conditions, were examined. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2356–2362, 2004  相似文献   

15.
This article describes the synthesis and surface modification of epoxy‐ and hydroxy‐functional polymeric microspheres. The functionalized microspheres were synthesized using aqueous and nonaqueous cationic suspension photopolymerizations using multifunctional silicon‐containing epoxy monomers with iodonium salt photoinitiators. Although generally solid microspheres were obtained using these techniques, macroporous spheres could be obtained though the use of porogens. Various rapid and facile acid‐ and base‐catalyzed ring‐opening addition reactions were performed on the epoxy‐functional microspheres. These reactions include the additions of mercaptans, acid chlorides, isocyanates, amines, sodium azide, water, and alcohols. Similar functionalization reactions were performed on the hydroxy‐functional microspheres. The particle size and size distribution were determined using scanning electron microscopy. Fourier transform infrared spectroscopy was used to monitor the functionalization reactions. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1574–1585, 2005  相似文献   

16.
Fe3O4/poly(styrene‐co‐maleic anhydride) core–shell composite microspheres, suitable for binding enzymes, were prepared using magnetite particles as seeds by copolymerization of styrene and maleic anhydride. The magnetite particles were encapsulated by polyethylene glycol, which improved the affinity between the magnetite particles and the monomers, thus showing that the size of the microspheres, the amount of the surface anhydrides, and the magnetite content in the composite are highly dependent on magnetite particles, comonomer ratio, and dispersion medium used in the polymerization. The composite microspheres, having 0.08–0.8 μm diameter and containing 100–800 μg magnetite/g microspheres and 0–18 mmol surface‐anhydride groups/g microsphere, were obtained. Free α‐amylase was immobilized on the microspheres containing reactive surface‐anhydride groups by covalent binding. The effects of immobilization on the properties of the immobilized α‐amylase [magnetic immobilized enzyme (MIE)] were studied. The activity of MIE and protein binding capacity reached 113,800 U and 544.3 mg/g dry microspheres, respectively. The activity recovery was 47.2%. The MIE had higher optimum temperature and pH compared with those of free α‐amylase and showed excellent thermal, storage, pH, and operational stability. Furthermore, it can be easily separated in a magnetic field and reused repeatedly. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 328–335, 2005  相似文献   

17.
Molecular‐imprinted poly(methacrylic acid) was synthesized with a template of retinoic acid to separate retinoid derivatives. The suspension polymerization technique was used to prepare round microparticles for high‐performance liquid chromatography (HPLC) packing column materials. The effects of the types and amounts of the dispersing agents and surfactants on the structure and size of the prepared molecular‐imprinted‐polymer particles were investigated. The separation of retinoic acid from its derivatives was more efficient when the perfluorocarbon dispersing agent was used instead of water, as the latter reduced the binding force between the objective molecules and monomers. HPLC separation features were also affected by the size and distribution of particles loaded in the column. A higher retention volume was obtained for smaller particles with a broader size distribution. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 200–212, 2005  相似文献   

18.
A series of micron‐grade polyacrylamide microspheres were prepared by inverse suspension polymerization of acrylamide (AM) and N,N′‐methylene bisacrylamide (MBA) in oil phase, with Span80 and Tween80 as dispersion stabilizers, and ammonium persulfate (APS) as an initiator. The conversion rate and coagulum rate were introduced to optimize the inverse suspension polymerization conditions of micron‐grade polyacrylamide microspheres. The swelling property of polyacrylamide microspheres in aqueous solution and the rheology of polyacrylamide microspheres suspension were characterized. The matching factor was introduced to characterize the matching relationship between the particle size of polyacrylamide microspheres and pore‐throat size of reservoirs. The optimized synthesis results show that the conversion rate is high, and the coagulum rate is low when the mass ratio of Span80 to Tween80 is 3 : 1. The particle size of the polyacrylamide microspheres is controlled by varying the concentration of dispersion stabilizer. The polyacrylamide microspheres show an obvious swelling property, which depends on the concentration of NaCl and temperature. The polyacrylamide microspheres suspension shows different rheological properties at different temperature and shear rate. When the temperature is low, it behaves as pseudoplastic fluid, dilatant fluid and quasi‐newtonian fluid in turn with the increase of shear rate. When the temperature is high, it behaves as dilatant fluid and quasi‐newtonian fluid in turn with the increase of shear rate. The micron‐grade polyacrylamide microspheres prefer to plug sand pack with optimal matching factor. When the matching factor is 1.35–1.55, the polyacrylamide microspheres can be transported into the deep area of sand pack, and the ultimate plugging rate is more than 85%, which indicates that the matching factor is an effective parameter to evaluate the matching relationship between polyacrylamide microspheres and reservoirs. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1124‐1130, 2013  相似文献   

19.
In this study, the monodisperse–macroporous particles produced by a relatively new polymerization protocol, the so‐called, “modified seeded polymerization,” were used as column‐packing material in the reversed phase chromatography (RPC) of proteins. The particles were synthesized in the form of styrene‐divinylbenzene copolymer approximately 7.5 μm in size. In the first stage of the synthesis, the monodisperse polystyrene particles 4.4 μm in size were obtained by dispersion polymerization and used as the “seed latex.” The seed particles were swollen by a low‐molecular‐weight organic agent and then by a monomer mixture. The monodisperse–macroporous particles were obtained by the polymerization of monomer mixture in the seed particles. In the proposed polymerization protocol, the number of successive swelling stages was reduced with respect to the present techniques by the use of sufficiently large particles with an appropriate average molecular weight as the seed latex. A series of particles with different porosity properties was obtained by varying the monomer/seed latex ratio. The separation behavior of HPLC columns including the produced particles as packing material was investigated in the RPC mode using a protein mixture including albumin, lysozyme, cytochrome c, and ribonuclease A. The chromatograms were obtained with different flow rates under an acetonitrile–water gradient. The theoretical plate number increased and chromatograms with higher resolutions were obtained with the particles produced by using a lower monomer/seed latex ratio. The separation ability of the column could be protected over a wide range of flow rates (i.e., 0.5–3 mL/min) with most of the materials tested. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 607–618, 2004  相似文献   

20.
Synthesis and physicochemical properties of the new glycidyl methacrylate, styrene, and bis[4(2‐hydroxy‐3‐methacryloyloxypropoxy)phenyl]sulfide terpolymers of different crosslinking degrees are presented. The terpolymers were obtained in the form of regular microspheres by suspension polymerization. The epoxy group content, thermal properties (DSC, thermogravimetric analysis), and swelling characteristic of the functional microspheres were examined. In addition, a selected terpolymer was modified in the epoxide ring opening reaction with diethylenetriamine. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

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