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1.
Poly[2‐methoxy‐5‐(2′‐ethyl‐hexyloxy)‐para‐phenylene vinylene] (MEH‐PPV)/silica nanoparticle hybrid films were prepared and characterised. Three kinds of materials were compared: parent MEH‐PPV, MEH‐PPV/silica (hybrid A films), and MEH‐PPV/coupling agent MSMA/silica (hybrid B films), in which MSMA is 3‐(trimethoxysilyl) propyl methacrylate. It was found that the hybrid B films could significantly prevent macrophase separation, as evidenced by scanning electron and fluorescence microscopy. Furthermore, the thermal characteristics of the hybrid films were largely improved in comparison with the parent MEH‐PPV. The UV‐visible absorption spectra suggested that the incorporation of MSMA‐modified silica into MEH‐PPV could confine the polymer chain between nanoparticles and thus increase the conjugation length. The photoluminescence (PL) studies also indicated enhancement of the PL intensity and quantum efficiency by incorporating just 2 wt% of MSMA‐modified silica into MEH‐PPV. However, hybrid A films did not show such enhancement of optoelectronic properties as the hybrid B films. The present study suggests the importance of the interface between the luminescent organic polymers and the inorganic silica on morphology and optoelectronic properties. Copyright © 2004 Society of Chemical Industry  相似文献   

2.
Two novel phenyl‐substituted poly(p‐phenylene vinylene) derivatives, poly{2‐[3′,4′‐(2″‐ethylhexyloxy)(3″,7″‐dimethyloctyloxy)benzene]‐1,4‐phenylenevinylene} (EDP‐PPV) and poly{2‐[3′,4′‐(2″‐ethylhexyloxy)(3″,7″‐dimethyloctyloxy)benzene]‐5‐methoxy‐1,4‐phenylenevinylene} (EDMP‐PPV), and their copolymer, poly{2‐[3′,4′‐(2″‐ethylhexyloxy)(3″,7″‐dimethyloctyloxy)benzene]‐1,4‐phenylene‐vinylene‐co‐2‐[3′,4′‐(2″‐ethylhexyloxy)(3″,7″‐dimethyloctyloxy)benzene]‐5‐methoxy‐1,4‐phenylenevinylene} (EDP‐co‐EDMP‐PPV; 4:1, 1:1, and 1:4), were successfully synthesized according to the Gilch route. The structures and properties of the monomers and the resulting conjugated polymers were characterized with 1H‐NMR, 13C‐NMR, elemental analysis, gel permeation chromatography, thermogravimetric analysis, ultraviolet–visible absorption spectroscopy, and photoluminescence and electroluminescence (EL) spectroscopy. The EL polymers possessed excellent solubility in common solvents and good thermal stability with a 5% weight loss temperature of more than 380°C. The weight‐average molecular weights and polydispersity indices of EDP‐PPV, EDMP‐PPV, and EDP‐co‐EDMP‐PPV were 1.40–2.58 × 105, and 1.19–1.52, respectively. Double‐layer light‐emitting diodes with the configuration of indium tin oxide/polymer/tris(8‐hydroxyquinoline)aluminum/Al devices were fabricated, and EDP‐co‐EDMP‐PPV (1:1) showed the highest EL performance and exhibited a maximum luminance of 1050 cd/m2 at 19.5 V. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1259–1266, 2005  相似文献   

3.
Fluorescent microspheres have great potential for use as probes in biological diagnostics. In this context, poly[2‐methoxy‐5‐(2′‐ethylhexyloxy)‐p‐phenylenevinylene] (MEH‐PPV), a conjugated polymer which has high quantum yield, controllable emitting wavelength and facile processing in manufacture, was used as a fluorescent material for the preparation of polystyrene (PS)/MEH‐PPV fluorescent microspheres via miniemulsion polymerization. We demonstrate that the emitting wavelength of the PS/MEH‐PPV fluorescent microspheres can be regulated by changing the amount of azobisisobutyronitrile initiator in the polymerization process. Using acrylic acid comonomer, poly[styrene‐co‐(acrylic acid)]/MEH‐PPV fluorescent microspheres with functional carboxyl groups were also prepared. All the microspheres were characterized using transmission electron microscopy, scanning electron microscopy, fluorescence microscopy and fluorescence spectrophotometry. The functional carboxyl groups were characterized using Fourier transform infrared spectroscopy. This work provides a novel platform for the preparation of conjugated polymer fluorescent microspheres for biological applications. © 2012 Society of Chemical Industry  相似文献   

4.
A new soluble fluorescent polymer, poly[2‐decyloxy‐5‐(2′‐(6′‐dodecyl‐oxy)naphthyl)‐1,4‐phenylenevinylene] (DDN‐PPV), with no tolane‐bisbenzyl (TBB) structure defects is prepared by the dehydrohalogenation of 1,4‐bis(bromomethyl)‐2‐decyloxy‐5‐(2′‐(6′‐dodecyloxy)naphthyl)benzene (as monomer) in this study. The aforementioned monomer is synthesized via such chemical reactions as alkylation, bromination, and Suzuki coupling reactions. The structure and properties of the DDN‐PPV are examined by 1H NMR, FTIR, UV/vis, TGA, photoluminescence (PL), and electroluminescence (EL) analyses. The two asymmetric decyloxy and 6′‐dodecyloxynaphthyl substituents on the phenylene ring make the DDN‐PPV soluble in organic solvents and eliminate the TBB structure defects. With the DDN‐PPV acting as a light‐emitting polymer, a device is fabricated with a sequential lamination of ITO/PEDOT/DDN‐PPV/Ca/Ag. The EL spectrum of the device shows a maximum emission at 538 nm. The turn on voltage of the device is about 16.6 V. Its maximum brightness is 14 cd/m2 at a voltage of 18.2 V. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2734–2741, 2007  相似文献   

5.
A series of novel copolymers based on a poly(p‐phenylenevinylene) (PPV) derivative with different content of narrow band‐gap unit 2,1,3‐benzoselenadiazolevinylene (BSeV) was prepared via Stille coupling reaction. The copolymers emit light from deep red to near‐infrared (NIR) depending on BSeV content in the copolymers. The electroluminescence (EL) emission peaked at 752 nm for the copolymer with the content of 30 mol % BSeV is among the longest reported so far for the PPV polymers. The best device performance is observed for the copolymer with 1 mol % BSeV content with external quantum efficiency (QEext) of 0.26% and CIE coordinate 0.65, 0.34 (x,y). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4321–4327, 2006  相似文献   

6.
Two novel poly(1,4‐phenylenevinylene) (PPV) derivatives containing liquid crystalline oxadiazole side chains were prepared by a dehydrochlorination process. The homopolymer poly(2‐methoxy‐5‐((2‐methoxy‐phenyl)‐5‐hexyloxy‐phenyloxy‐1,3,4‐oxadiazole)‐1,4‐phenylenevinylene) (HO–PE6) is insoluble in common solvents, whereas the copolymer poly(2‐methoxy‐5‐((2‐methoxy‐phenyl)‐5‐hexyloxy‐phenyloxy‐1,3,4‐oxadiazole))‐(2‐methoxy‐5‐(2′‐ethylhexyloxy))‐1,4‐phenylenevinylene) (CO–PE6) is soluble in common solvents such as chloroform, THF, and p‐xylene. The molecular structure of CO–PE6 was confirmed by FTIR, 1H‐NMR, UV–vis spectroscopy, and polarized light microscopy. CO–PE6 showed a maximum emission at 556 nm in chloroform and at 564 nm in solid film, when excited at 450 nm. The maximum electroluminescence emission of the device indium–tin oxide (ITO)CO–PE6/Al is at 555 nm. The turn‐on voltage of LEDs based on CO–PE6 and MEH–PPV is 6.5 and 8.5 V, respectively. The electron mobility of CO–PE6 is higher than that of MEH–PPV based on the results of current–voltage and electrochemical behavior of both MEH–PPV and CO–PE6. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 396–403, 2004  相似文献   

7.
New donor–acceptor conjugated copolymers called poly}2,7‐(9,9′‐dihexylfluorene)‐co‐5,10‐[pyrazino(2,3‐g)quinoxaline]{s or PFPQs [where F represents the 2,7‐(9,9′‐dihexylfluorene) moiety and PQ represents the 5,10‐(pyrazino[2,3‐g]quinoxaline) moiety], synthesized by the palladium‐catalyzed Suzuki coupling reaction, are reported. The PQ contents in the PFPQ copolymers were 0.3, 1, 5, and 50 mol %, and the resulting copolymers were named PFPQ0.3, PFPQ01, PFPQ05, and PFPQ50, respectively. Absorption spectra showed a progressive redshift as the PQ acceptor content increased. The relatively small optical band gap of 2.08 eV for PFPQ50 suggested strong intramolecular charge transfer (ICT) between the F and PQ moieties. The photoluminescence emission peaks of the PFPQ copolymer films also exhibited a large redshift with enhanced PQ contents, ranging from 551 nm for PFPQ0.3 to 592 nm for PFPQ50. However, the PFPQ copolymer based electroluminescence (EL) devices showed poor device performances probably due to the strong confinement of the electrons in the PQ moiety or significant ICT. This problem was resolved with a binary blend of poly[2,7‐(9,9‐dihexylfluorene)] (PF) and PFPQ with a volume ratio of 95/5 (BPQ05). Multiple emission peaks were observed at 421, 444, 480, 516, and 567 nm in the BPQ05‐based EL devices because the low PQ content led to incomplete energy transfer. The Commission Internationale de L'Eclairage 1931 coordinates of the BPQ05‐based EL device were (0.31, 0.32), which were very close to the standard white emission of (0.33, 0.33). Furthermore, the maximum luminescence intensity and luminescence yield were 524 cd/m2 and 0.33 cd/A, respectively. This study suggested that a pure white light emission was achieved with the PFPQ copolymers or PF/PFPQ blends through the control of the energy transfer between F and PQ. Such PFPQ copolymers or PF/PFPQ blends would be interesting for electronic and optoelectronic devices. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

8.
An efficient and convenient method was developed for the one‐pot construction of the complex polycyclic heterocycles pyrrolo[1,2‐a:2′,1′‐c]‐/pyrido[2,1‐c]pyrrolo[1,2‐a]quinoxalinones from two simple starting materials via a gold(I)‐catalyzed domino reaction. This strategy presents an atom economical and environmentally friendly transformation, in which two new C N bonds and one new C C bond are formed in a one‐pot reaction process.  相似文献   

9.
Poly(N‐[4‐(N′‐phenyl amino carbonyl)phenyl]maleimide), poly(PhPM), has been investigated for the inhibition of the thermal degradation of rigid poly(vinyl chloride) (PVC) in air, at 180°C. Its stabilizing efficiency was evaluated by measuring the length of the induction period, the period during which no detectable amounts of hydrogen chloride gas could be observed, and also from the rate of dehydrochlorination as measured by continuous potentiometric determination, and the extent of discoloration of the degraded polymer. The results have proved the greater stabilizing efficiency of poly(PhPM) relative to that of the DBLC commercial stabilizer. This is well demonstrated by the longer induction period values and by the lower rates both of dehydrochlorination and discoloration of the polymer during degradation relative to those of the DBLC reference stabilizer. The greater stabilizing efficiency of the poly(PhPM) is most probably attributed not only to its possession of various centers of reactivity that can act as traps for radical species resulting during the degradation process, and replacement of labile chlorine atoms on PVC chains by relatively more thermally stable poly(PhPM) moieties, but also due to the ability of its fragmentation products to react with the evolved hydrogen chloride gas. A radical mechanism is suggested to account for the stabilizing action of this polymeric stabilizer. A synergistic effect is achieved when the poly(PhPM) was blended in various weight ratios with DBLC. This synergism attains its maximum when poly(PhPM) and DBLC are taken at 3 : 1 weight ratio. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

10.
Copolymers of poly[2‐(dimethylamino)ethyl methacrylate]–poly(butylene succinate)–poly[2‐(dimethylamino)ethyl methacrylate] (PDMAEMA–PBS–PDMAEMA, PDBD) were synthesized through a chain‐extension reaction. The thermal properties characterized using differential scanning calorimetry showed that the introduction of PDMAEMA chains slightly decreased the melting temperature of PBS. The water contact angle of PDBD copolymer films with media of various pH decreased with a decrease of pH. This should be ascribed to the conformational transition of PDMAEMA blocks from a compact coil to an expanding shape in accordance with the variation of the pH of the surroundings. The results of dynamic light scattering and scanning electron microscopy revealed that PDBD copolymers could form spherical micelles with small particle size and narrow particle size distribution. Furthermore, drug loading (loading content, ca 10%; encapsulation efficiency, ca 60%) and release experiments were conducted using doxorubicin as a hydrophobic model drug. The results of release experiments of copolymer nanomicelles showed that these micelles had pH‐responsive properties. © 2018 Society of Chemical Industry  相似文献   

11.
A novel bis(ether amine) monomer, 5,5′‐bis[4‐(4‐amino‐2‐trifluoromethylphenoxy)phenyl]‐4,7‐methanohexahydroindan ( 2 ), was synthesized through the nucleophilic aromatic substitution reaction of 5,5′‐bis‐(4‐hydroxyphenyl)‐4,7‐methanohexahydroindan with 2‐chloro‐5‐nitrobenzotrifluoride to yield the intermediate dinitro compound, followed by catalytic reduction with hydrazine and Pd/C. A series of polyimides were synthesized from 2 and various aromatic dianhydrides using a standard two‐stage process with chemical or thermal imidization of poly(amic acid). All of these polymer films were soluble in amide‐type solvents above 10% w/v, had tensile strengths of 97–117 MPa, and the 10% weight loss temperature was above 464 °C with their residues exceeding 46% at 800 °C in nitrogen. Compared with the non‐fluorinated polyimides, the fluorinated series were observed to have lower dielectric constants (2.92–3.28 at 1 MHz) and lower moisture absorptions (0.15–0.43 wt%) as well as lower color intensity and better solubility. Copyright © 2006 Society of Chemical Industry  相似文献   

12.
N,N′‐(Pyromellitoyl)‐bis‐(L ‐leucine) diacid was reacted with ethyl chloroformate in the presence of triethylamine followed by reaction with activated sodium azide and gave N,N′‐(pyromellitoyl)‐bis‐(L ‐leucine) diacylazide in high yield. This diacylazide was heated in dry benzene and gave the unstable N,N′‐(pyromellitoyl)‐bis‐(L ‐leucine) diisocyanate ( 5 ) in quantitative yield. Thus, diisocyanate 5 was generated in situ and polycondensation reaction of this monomer with several aromatic diols, such as 4,4′‐dihydroxybiphenyl, 1,4‐hydroquinone, bisphenol A, phenolphthalein and 1,4‐dihydroxyanthraquinone, was performed in dry toluene under refluxing in the presence of 1,4‐diazabicyclo[2.2.2]octane (triethylenediamine) as a catalyst. The polymerization reactions proceeded within 48 h, producing a series of optically active poly(imide–urethane)s with good yield and moderate inherent viscosity in the range 0.18–0.28 dl g?1. All of the above polymers were fully characterized by infrared spectra, elemental analyses and specific rotation. Some structural characterization and physical properties of these optically active poly(imide–urethane)s are reported Copyright © 2003 Society of Chemical Industry  相似文献   

13.
In this research, new donor–acceptor (D‐A) photovoltaic polymers were synthesized from dithieno[3,2‐b:2′,3′‐d]pyrrole electron donor derivatives, including N‐benzoyldithieno[3,2‐b:2′,3′‐d]pyrrole and N‐(4‐hexylbenzoyl)dithieno[3,2‐b:2′,3′‐d]pyrrole, in combination with the electron deficient unit 2,5‐bis(2‐ethylhexyl)‐3,6‐di(thiophen‐2‐yl)‐2,5‐dihydropyrrolo[3,4‐c]pyrrole‐1,4‐dione via direct (hetero)arylation polymerization. The D‐A conjugated polymers obtained were characterized via 1H NMR, gel permeation chromatography, Fourier transform infrared spectroscopy, DSC, XRD, photoluminescence and UV–visible methods. In addition, these D‐A polymers were used as activated layers in bilayer and bulk heterojunction structures for the fabrication of organic photovoltaic cells. © 2019 Society of Chemical Industry  相似文献   

14.
An integrated fermentation and membrane‐based recovery (pervaporation) process has certain economical advantages in continuous conversion of biomass into alcohols. This article presents new pervaporation data obtained for poly[1‐(trimethylsilyl)‐1‐propyne] (PTMSP) samples synthesized in various conditions. Three different catalytic systems, TaCl5/n‐BuLi, TaCl5/Al(i‐Bu)3, and NbCl5 were used for synthesis of the polymers. It was found that the catalytic system has a significant influence over the properties of membranes made from PTMSP. Although a combination of a high permeation rate and a high ethanol–water separation factor (not less than 15) was provided by all PTMSP samples, the PTMSP samples synthesized with TaCl5/n‐BuLi showed significant deterioration of membrane properties when acetic acid was present in the feed. In contrast, the PTMSP samples synthesized with TaCl5/Al(i‐Bu)3 or NbCl5 showed stable performance in the presence of acetic acid. When using a multicomponent mixture of organics and water, the copermeation of different organic components results in lower separation factor for both ethanol and butanol. These data are consistent with nanoporous morphology of PTMSP. It was demonstrated that pervaporative removal of ethanol improved the overall performance of the fermentation process. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2271–2277, 2004  相似文献   

15.
A new diamine 5,5′‐bis[4‐(4‐aminophenoxy)phenyl]‐hexahydro‐4,7‐methanoindan ( 3 ) was prepared through the nucleophilic displacement of 5,5′‐bis(4‐hydroxylphenyl)‐hexahydro‐4,7‐methanoindan ( 1 ) with p‐halonitrobenzene in the presence of K2CO3 in N,N‐dimethylformamide (DMF), followed by catalytic reduction with hydrazine and Pd/C in ethanol. A series of new polyamides were synthesized by the direct polycondensation of diamine 3 with various aromatic dicarboxylic acids. The polymers were obtained in quantitative yields with inherent viscosities of 0.76–1.02 dl g−1. All the polymers were soluble in aprotic dipolar solvents such as N,N‐dimethylacetamide (DMAc) and N‐methyl‐2‐pyrrolidone (NMP), and could be solution cast into transparent, flexible and tough films. The glass transition temperatures of the polyamides were in the range 245–282 °C; their 10% weight loss temperatures were above 468 °C in nitrogen and above 465 °C in air. © 2000 Society of Chemical Industry  相似文献   

16.
Imide units are incorporated into thermoplastic and solvent‐based polyurethane (PU) chains to improve the thermal stability of PU. However, these poly(urethane‐imide) (PUI) materials have poor processablity and suffer from solvent emission. To prepare easily processable and environmentally friendly PUI products, some waterborne PUIs are synthesized using a prepolymer process. A series of PUI dispersions with 25 wt % solid content, viscosities of 7.5–11.5 cps, and particle sizes of 63–207 nm was prepared. The composition–property relationship of PUIs, including the solubility behavior of PUI cast films, and their thermal and mechanical properties were established. The solvent resistance and tensile strength of PUI film increased with the number of imide groups. All PUIs exhibited improved thermal stability but not char yield as the temperature increased. The inclusion of a little imide increased the decomposition temperature of PUI while maintaining the elasticity of the polymer, revealing successful translation of PUI into the water‐based form. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

17.
4‐[4′‐(2‐Hydroxy‐1‐naphthylazo)phenyl]‐1,2,4‐triazolidine‐3,5‐dione ( HNAPTD ) ( 1 ) has been reacted with excess amount of n‐propylisocyanate in DMF (N,N‐dimethylformamide) solution at room temperature. The reaction proceeded with high yield, and involved reaction of both N? H of the urazole group. The resulting bis‐urea derivative 2 was characterized by IR, 1H‐NMR, elemental analysis, UV‐Vis spectra, and it was finally used as a model compound for the polymerization reaction. Solution polycondensation reactions of monomer 1 with Hexamethylene diisocyanate ( HMDI ) and isophorone diisocyanate ( IPDI ) were performed in DMF in the presence of pyridine as a catalyst and lead to the formation of novel aliphatic azo‐containing polyurea dyes, which are soluble in polar solvents. The polymerization reaction with tolylene‐2,4‐diisocyanate ( TDI ) gave novel aromatic polyurea dye, which is insoluble in most organic solvents. These novel polyureas have inherent viscosities in a range of 0.15–0.22 g dL?1 in DMF at 25°C. Some structural characterization and physical properties of these novel polymers are reported. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3177–3183, 2001  相似文献   

18.
Poly[2‐(methacryloyloxy)ethyl phosphorylcholine](PMPC) with one pendant tocopheryl moiety at the polymer terminus (PMPC‐Toco) was prepared by the radical polymerization of 2‐(methacryloyloxy)ethyl phosphorylcholine (MPC) initiated with 4,4′‐azobis[(3‐tocopheryl)‐4‐cyanopentanoate] in the presence of 2‐mercaptoethanol as a chain transfer reagent. The self‐organization of PMPC‐Toco was analyzed with fluorescence and 1H‐NMR measurements. The critical micelle concentrations of PMPC‐Toco with [η] = 0.25, 0.13, 0.10, and 0.05 dL g?1 were found to be 200, 100, 100, and 90 mg L?1, respectively. The blood compatibility of PMPC‐Toco was evaluated from the Michaelis constant (Km) for the enzymatic reaction of thrombin and a synthetic substrate, S‐2238, in the presence of PMPC‐Toco. The Km values were 0.21, 0.23, 0.36, and 0.21 for PMPC‐Toco‐1, 2, 3, and PMPC ([η] = 0.56 dL g?1), respectively. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

19.
Poly(2‐ethyl‐2‐oxazoline) and acrylic acid were copolymerized in different compositions using γ‐rays‐induced polymerization and cross‐linking to obtain a series of pH‐sensitive hydrogels. The preparation parameters that may affect the copolymerization process such as the feed solution composition and irradiation dose were optimized. Swelling characteristics of the obtained polymeric hydrogels were evaluated. The results show the significant effects of the hydrogel composition, soaking time, and pH on the swelling equilibrium. The diffusion parameters obtained at pH 1 and 7 show the possibility of using the prepared hydrogels in the field of colon‐specific drug delivery systems. Ibuprofen as a model drug was loaded into (poly(2‐ethyl‐2‐oxazoline)/acrylic acid) copolymer hydrogel to investigate their drug release behavior at different pH values. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

20.
A series of new cardo poly(ether imide)s bearing flexible ether and bulky xanthene pendant groups was prepared from 9,9‐bis[4‐(4‐aminophenoxy)phenyl]xanthene with six commercially available aromatic tetracarboxylic dianhydrides in N,N‐dimethylacetamide (DMAc) via the poly(amic acid) precursors and subsequent thermal or chemical imidization. The intermediate poly(amic acid)s had inherent viscosities between 0.83 and 1.28 dL/g, could be cast from DMAc solutions and thermally converted into transparent, flexible, and tough poly(ether imide) films which were further characterized by X‐ray and mechanical analysis. All of the poly(ether imide)s were amorphous and their films exhibited tensile strengths of 89–108 MPa, elongations at break of 7–9%, and initial moduli of 2.12–2.65 GPa. Three poly(ether imide)s derived from 4,4′‐oxydiphthalic anhydride, 4,4′‐sulfonyldiphthalic anhydride, and 2,2‐bis(3,4‐dicarboxyphenyl))hexafluoropropane anhydride, respectively, exhibited excellent solubility in various solvents such as DMAc, N,N‐dimethylformamide, N‐methyl‐2‐pyrrolidinone, pyridine, and even in tetrahydrofuran at room temperature. The resulting poly(ether imide)s with glass transition temperatures between 286 and 335°C had initial decomposition temperatures above 500°C, 10% weight loss temperatures ranging from 551 to 575°C in nitrogen and 547 to 570°C in air, and char yields of 53–64% at 800°C in nitrogen. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

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