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1.
A series of novel homo‐ and copolyimides containing pyridine units were prepared from the heteroaromatic diamines, 2,5‐bis (4‐aminophenyl) pyridine and 2‐(4‐aminophenyl)‐5‐aminopyridine, with pyromelltic dianhydride (PMDA), and 3,3′, 4,4′‐biphenyl tertracarboxylic dianhydride (BPDA) via a conventional two‐step thermal imidizaton method. The poly(amic acid) precursors have inherent viscosities of 1.60–9.64 dL/g (c = 0.5 g/dL in DMAC, 30°C) and all of them can be cast and thermally converted into flexible and tough polyimide films. All of the polyimides show excellent thermal stability and mechanical properties. The polyimides have 10% weight loss temperature in the range of 548–598°C in air. The glass transition temperatures of the PMDA‐based samples are in the range of 395–438°C, while the BPDA‐based polyimides show two glass transition temperatures (Tg1 and Tg2), ranging from 268 to 353°C and from 395 to 418°C, respectively. The flexible films possess tensile modulus in the range of 3.42–6.39 GPa, strength in the range of 112–363 MPa and an elongation at break in the range of 1.2–69%. The strong reflection peaks in the wide‐angle X‐ray diffraction patterns indicate that the polyimides have a high packing density and crystallinity. The polymer films are insoluble in common organic solvents exhibiting high chemical resistance. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1844–1851, 2006  相似文献   

2.
A series of new polyimides was prepared by reacting 2,6‐diaminopyridine with various aromatic dianhydrides in DMF in 1 : 1 mole ratio. All the resulting polyimides were readily soluble in organic solvents such as dimethylformamide, N,N‐dimethylacetamide, pyridine, m‐cresol, THF, etc. They also show good film‐forming ability. The polyimides exhibit good thermal stability and mechanical properties. The polymers have high Tg in the range of 252–296°C. The inherent viscosities of the polymers vary from 0.81 to 1.28 dL/g. A new class of bismaleimide and polyaspartimide as also synthesized. All the resulting polymer structures were characterized by FTIR and elemental analysis. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1846–1853, 2004  相似文献   

3.
Two series of isomers containing pyridine and sulfur unit aromatic diamine monomers, 4,4′‐bis(5‐amino‐2‐pyridinylsulfanyl)diphenyl sulfide ( 2a ), 4,4′‐bis(6‐amino‐3‐pyridinylsulfanyl)diphenyl sulfide ( 2b ) and 4,4′‐bis(5‐amino‐6‐methyl‐2‐pyridinylsulfanyl)diphenyl sulfide ( 2c ), 4,4′‐bis(5‐amino‐4‐methyl‐2‐pyridinylsulfanyl)diphenyl sulfide ( 2d ), were designed and synthesized. Aimed at clarifying the structure–property relationships of pyridine‐ and sulfur‐containing high refractive polymers, 2a was polymerized with various dianhydrides to prepare polyimides PI ‐1?PI ‐7 and 2b , 2c , 2d were reacted with 4,4′‐[p ‐thiobis(phenylenesulfanyl)]diphthalic anhydride to prepare polyimides PI ‐8?PI ‐10. The polyimides showed excellent optical properties with average refractive indices ranging from 1.7006 to 1.7620 and birefringence as low as 0.0056. Meanwhile, comparative studies on their properties including solubility, thermal and mechanical, and optical transparency properties were performed. Some property differences of the isomers caused by the sequence changes were found. © 2017 Society of Chemical Industry  相似文献   

4.
Polypyrrole (PPy) and Polypyrrole‐ZnO (PPy‐ZnO) nanocomposites were electrodeposited on mild steel and its corrosion protection ability was studied by Tafel and Impedance techniques in 3.5% NaCl solution. Pure Polypyrrole film was not found to protect the mild steel perfectly but the coating with nano‐sized ZnO (PPy‐ZnO) has dramatically increased the corrosion resistance of mild steel. Electrochemical Impedance Spectroscopy (EIS) measurements indicated that the coating resistance (Rcoat) and corrosion resistance (Rcorr) values for the PPy‐ZnO nanocomposite coating was much higher than that of pure PPy coated electrode. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

5.
A novel aromatic diamine, 3,3′‐diisopropyl‐4,4′‐diaminophenyl‐4″‐methyltoluene with a 4‐methylphenyl pendant group and isopropyl side groups, was designed and synthesized in this study. Then it was polymerized with various aromatic dianhydrides including pyromellitic dianhydride, 3,3′,4,4′‐biphenyltetracarboxylic dianhydride, 4,4′‐oxydiphthalic anhydride, 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride and 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride via a one‐pot high temperature polycondensation procedure to produce a series of aromatic polyimides. These polyimides exhibited excellent solubility even in common organic solvents, such as chloroform and tetrahydrofuran. The flexible and tough films can be conveniently obtained by solution casting. The films were nearly colorless and exhibited high optical transparency, with the UV cutoff wavelength in the range 302–365 nm and the wavelength of 80% transparency in the range 385–461 nm. Moreover, they showed low dielectric constants (2.73–3.23 at 1 MHz) and low moisture absorption (0.13%–0.46%). Furthermore, they also possessed good thermal and thermo‐oxidative stability with 10% weight loss temperatures (T10%) in the range 489–507 °C in a nitrogen atmosphere. The glass transition temperatures of all polyimides are in the range 262–308 °C. Copyright © 2012 Society of Chemical Industry  相似文献   

6.
Man He  Jia Dai  Yiping Cui 《Polymer》2009,50(16):3924-2572
The novel fluorinated polyimides with side-chain nonlinear optical (NLO) chromophores were synthesized from hydroxyl polyimides, followed by the Mitsunobu reaction with NLO chromophores. Molecular structural characterization for the resulting polymers was achieved by 1H NMR, FT-IR, UV-Vis spectra, elemental analysis and gel permeation chromatography (GPC). The polymers exhibit excellent solubility in common organic solvents, good film-forming properties, high glass transition temperature (Tg) in the range from 193 to 200 °C and thermal stability up to 290 °C. The polyimides P1 and P2 containing hetarylazo chromophores with large hyperpolarizability possess a high electro-optic (EO) coefficient (r33), which is larger than that of the polyimide P3 attached DR1. Excellent temporal stability and low optical losses in the range of 1.9-2.1 dB/cm at 1.55 μm were observed for these polymers. Such new NLO fluorinated polyimides are distinguished by an excellent combination of NLO activity, temporal stability, and optical loss.  相似文献   

7.
Thermally stable second-order nonlinear optical (NLO) polyimides were synthesized using a standard condensation polymerization technique. The polyimides were prepared from 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) and pyromellitic dianhydride (PMDA) with two aromatic azo- and diazo-diamine derivatives as the NLO chromophores. The resulting polyimides were characterized by FTIR, 1H-NMR, UV-vis spectroscopies, differential scanning calorimetry, thermogravimetric analysis, and gel permeation chromatography. The weight-average molecular weights of polyimides determined by gel permeation chromatography (GPC) were in the range of 32,100 to 39,300 (Mw/Mn = 1.58–1.74). All the polyimides exhibited an excellent solubility in many of the aprotic polar organic solvents, manifesting that these polyimides offer good processability. The glass transition temperature for the resulting polyimides was in the range of 152 to 194°C and most of them showed high thermal stability. Particularly, the polyimides containing diazo group and PMDA backbone showed an enhanced thermal stability and glass transition temperature. The second harmonic generation (SHG) coefficients (d33) of the poled polyimide films range from 43.71 to 80.49 pm/V at 532 nm. Further, it is noticed that there was no SHG decay below 180°C because of the partial main-chain character of the polyimide structure, which is acceptable for nonlinear optical device applications. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

8.
薛超  肖国民  高李璟  张进  魏瑞平 《精细化工》2023,40(7):1464-1469+1531
对苯二酚依次与2-氯-5-硝基三氟甲苯和2-氯-5-硝基吡啶进行亲核取代反应,还原后制备了一种含吡啶杂环的氟化二胺单体6-{4-[4-氨基-2-(三氟甲基)苯氧基]苯氧基}吡啶-3-胺,并采用两步法将其与二酐聚合,得到4种芳香族聚酰亚胺(PI)。对所得PI的溶解性、耐热稳定性、光学性能、力学性能进行了测试。结果表明,基于4,4’-氧双邻苯二甲酸酐和六氟二酐的PI在常见有机溶剂中均具有良好的溶解性。N2氛围下,这些PI的5%和10%热失重温度分别在548.8~594.2和566.3~609.7℃之间,玻璃化转变温度在226~290℃之间,具有良好的耐热稳定性。这些PI薄膜有较好的光学透明度和力学性能,截止波长在382~438 nm范围内,500 nm处的透过率在52%~78%范围内,拉伸强度为98.3~110.5 MPa,杨氏模量为1.86~2.14 GPa,断裂伸长率为9%~23%。  相似文献   

9.
To tune the photophysical properties of polyimides (PIs), a diamine containing naphthalene and triphenylamine units, N1‐(4‐aminophenyl)‐N1‐[(4‐naphthalene‐2‐yloxy)phenyl]benzene‐1,4‐diamine (DA), was synthesized. A series of fluorescent electroactive new PIs from synthesized DA were prepared with conventional thermal imidization with dianhydride. The selected dianhydride were used to study and compare the effects of rigid planar phenyl, flexible phenoxy, and nonplanar flexible hexafluoroisopropyidene and carbonyl groups in the main polymer backbone on the optoelectronic properties and processability of materials. The structures of the synthesized diamine and its PIs were evaluated by spectral and CHNS elemental analysis. The optoelectronic and thermal properties of PIs revealed intense blue‐light emission (428–477 nm), a low oxidation potential (0.3–1.3 V), and a lower highest occupied molecular orbital–lowest unoccupied molecular orbital gap (2.92–3.21 eV). The observed behavior and properties of our synthesized PIs suggest their potential as future hole‐transport materials in optoelectronic applications. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44526.  相似文献   

10.
A novel diamine monomer having pendant 4‐(quinolin‐8‐yloxy) aniline group was successfully synthesized via aromatic substitution reaction of 8‐quinolinol with p‐fluoronitrobenzene followed by Pd/C catalyzed hydrazine reduction, amidation reaction between 4‐(quinolin‐8‐yloxy) aniline and 3,5‐dinitrobenzoylcholoride followed by Pd/C catalyzed hydrazine reduction. The diamine monomer was fully characterized by using FTIR, 1H‐NMR, 13C‐NMR, and elemental analysis. The diamine monomer was polymerized with various aromatic and aliphatic dicarboxylic acids to obtain the corresponding polyamides. The polyamides had inherent viscosity in the range of 0.30–0.41 dL/g and exhibited excellent solubility in the polar aprotic solvents such as DMAc, NMP, N,N‐dimethylformamide, Pyridine, and DMSO. The glass transition temperatures (Tg) of the polymers are high (up to 313°C) and the decomposition temperatures (Ti) range between 200 and 370°C, depending on the diacids residue in the polymers backbone. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

11.
A series of polyimides were synthesized from new diamine, Bis [4,4′‐amino‐5,5′ trifluoromethyl phenoxy‐(hexafluoro isopropylidine) phenoxy phenyl] benzonitrile [BATFB] and various aromatic tetracarboxylic anhydrides by thermal and chemical imidization routes. The BATFB was synthesized in two steps by nucleophilic displacement reaction of 2,6‐dichloro benzonitrile, 4,4′‐(hexafluoro isopropylidine) diphenol and 2‐amino‐5‐fluoro benzotrifluoride in the presence of anhydrous potassium carbonate in N,N′‐dimethyl acetamide (DMAc) and the structure was confirmed by FTIR spectroscopy and CHNSO analyzer. The polymers were characterized by FTIR spectroscopy and thermal analysis were performed by differential scanning calorimetry and thermogravimetric analysis methods. The prepared polyimides had glass transition temperatures between 230 and 290°C and their 10% weight loss were recorded in the range 550–590°C in N2 atmosphere. Majority of polymers are found to be soluble in most of the organic solvents such as DMSO, DMF, DMAc, m‐cresol, and THF even at room temperature and few becomes soluble on heating. The prepared polyimides showed water uptake values 0.34–0.54 wt % at room temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3455–3461, 2006  相似文献   

12.
A series of highly soluble aromatic polyimides with excellent thermal properties were fabricated by traditional two‐step polycondensation reaction of dianhydride monomer 4,4′‐(4,4′‐isopropylidenediphenoxy)bis(phthalic anhydride) or 4,4‐(hexafluoroisopropylidene)diphthalic anhydride with diamine monomer 1,3‐bis(4‐aminophenoxy)benzene or 1,3‐bis(3‐aminopropyl) tetramethyldisiloxane in N,N‐dimethylacetylamide solvent. Results revealed that copolyimide of PI‐4 containing trifluoromethyl and tetramethyldisiloxane possessed excellent solubility and remarkable thermal properties. PI‐4 could dissolve well in common low boiling point solvents such as THF of up to 80 mg/mL and acetone of 40 mg/mL. Moreover, the 10% weight loss temperature of the PI‐4 was 539°C and the Tg value of the PI‐4 was 311°C. PI‐4 might be easily cast into flexible and tough films applied in optoelectronic devices. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41713.  相似文献   

13.
Two diazo‐coupling novolac derivative resins (carbonyl phenyl azo novolac resin and carbonyl phenol–biphenylene azo novolac resin) were used as flame retardants. The cured resins exhibited elevated glass‐transition temperatures from 115°C (blank) to 195 and 167°C, respectively. The char yield at 800°C was increased, which elaborated the effectiveness of flame retardancy with evaluated limiting oxygen indices around 36 to 40. This was mainly attributed to the increased crosslink densities and highly aromatic contents in the modified phenol novolac derivative resins, which exhibited higher thermal degradation energies. Furthermore, the more effective flame retardancy was expected because of the loss of nitrogen during combustion. Through the evaluation of the cooperative flame retardancy in the organic/inorganic hybrid with char yield and increasing limiting oxygen index percentage, the effects of the filler showed cooperative flame retardancy only with the appropriate addition and with a difference in the crosslinking densities. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

14.
A new indane containing unsymmetrical diamine monomer ( 3 ) was synthesized. This diamine monomer leads to a number of novel semifluorinated poly (ether imide)s when reacted with different commercially available dianhydrides like benzene‐1,2,4,5‐tetracarboxylic dianhydride (PMDA), benzophenone‐3,3′, 4,4′‐tetracarboxylic dianhydride (BTDA), 4,4′‐(hexafluoro‐isopropylidene)diphthalic anhydride (6FDA), 4,4′‐oxydiphthalic anhydride (ODPA), and 4,4′‐(4,4′‐Isopropylidenediphenoxy)bis(phthalic anhydride) (BPADA) by thermal imidization route. All the poly(ether imide)s showed excellent solubility in several organic solvents such as N‐methylpyrrolidone (NMP), N,N‐dimethylformamide (DMF), N,N‐dimethylacetamide (DMAc), tetrahydrofuran (THF), chloroform (CHCl3) and dichloromethane (DCM) at room temperature. These light yellow poly (ether imide)s showed very low water absorption (0.19–0.30%) and very good optical transparency. Wide angle X‐ray diffraction measurements revealed that these polymers were amorphous in nature. The polymers exhibited high thermal stability up to 526°C in nitrogen with 5% weight loss, and high glass transition temperature up to 265°C. The polymers exhibited high tensile strength up to 85 MPa, modulus up to 2.5 GPa and elongation at break up to 38%, depending on the exact polymer structure. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

15.
Jianda Xie  Zhuangqi Cao  Wenquan Zhang 《Polymer》2007,48(20):5988-5993
Two hyperbranched polymers with methyl ester (P1) and epoxy (P2) terminal groups containing pendant azobenzene chromophores were prepared through an “A2 + B3” approach used for second-order nonlinear optical materials. Their chemical structures were characterized by NMR and GPC analyses. The polymers have good solubility in common organic solvents and film-forming ability. The pure films were fabricated successively without doping into other matrices. The poled films exhibit high second-harmonic generation coefficients (>50 pm/V) due to the three-dimensional spatial isolation effect resulting from their highly branched structures. The optical nonlinearity of the poled P2 film is thermally more stable than that of P1 due to the cross-linking of epoxy groups with carboxylic acid groups in the former during poling. The onset decay temperature of SHG intensity of P2 was determined to be at around 155 °C, which was 20 °C higher than that of P1.  相似文献   

16.
A new diamine monomer, 3,3′‐diisopropyl‐4,4′‐diaminophenyl‐4″‐phenyltouene, was designed, synthesized, and then polymerized with five commercial dianhydrides to obtain a series of novel polyimides via a one‐step method. The obtained polymers showed excellent solubility in most common solvents, even in low‐boiling solvents, such as chloroform, dichloromethane, and tetrahydrofuran. They exhibited a high thermal stability with the glass‐transition temperature in the range 262–318°C and 10% weight loss temperatures in the range 464–488°C under a nitrogen atmospheres. Meanwhile, these polymer films also displayed a high optical transparency with a cutoff wavelength in the range 305–365 nm; prominent mechanical properties with a tensile strength of 65.6–94.9 MPa, a Young's modulus of 1.6–2.8 GPa, and an elongation at break of 9.3–13.7%; a low dielectric constant in the range of 2.91–3.18 at 1 MHz; and an outstanding hydrophobicity with a contact angle above 90.6°. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43266.  相似文献   

17.
A new kind of pyridine‐containing aromatic diamine monomer, 4‐phenyl‐2,6‐bis[4‐(4‐aminophenoxy)phenyl]‐pyridine (PAPP), was successfully synthesized by a modified chichibabin reaction of benzaldehyde and a substituted acetophenone, 4‐(4‐nitrophenoxy)‐acetophenone (NPAP), followed by a reduction of the resulting dinitro compound 4‐phenyl‐2,6‐bis[4‐(4‐nitrophenoxy)phenyl]‐pyridine (PNPP) with Pd/C and hydrazine monohydrate. The aromatic diamine was employed to synthesize a series of new pyridine‐containing polyimides by polycondensation with various aromatic dianhydrides in N‐methy‐2‐pyrrolidone (NMP) via the conventional two‐step method, i.e., ring‐opening polycondensation forming the poly (amic acid)s and further thermal or chemical imidization forming polyimides. The inherent viscosities of the resulting polyimides were in the range of 0.79–1.13 dL/g, and most of them were soluble in common organic solvents such as N,N‐dimethylacetamide (DMAc), NMP, and tetrahydrofuran (THF), etc. Meanwhile, strong and flexible polyimide films were obtained, which had good thermal stability, with the glass transition temperatures (Tg) of 268–338°C and the temperature at 5% weight loss of 521–548°C in air atmosphere, as well as outstanding mechanical properties with tensile strengths of 89.2–112.1 MPa and elongations at break of 9.5–15.4%. The polyimides also were found to possess low dielectric constants ranging from 2.53 to 3.11. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 212–219, 2007  相似文献   

18.
Four cyclolinear poly(aryloxycyclotriphosphazenes) derived from poly[4,4′‐(isopropoylidene)diphenoxytetrachlorocyclotriphosphazene] and poly[4,4′‐(hexafluoroisopropylidene)diphenoxytetrachlorocyclotriphosphazene] were synthesized from the reaction of hexachlorocyclotriphosphazene (HCP) with 4,4′‐(isopropylidene)diphenol (bisphenol A) or 4,4′‐(hexafluoroisopropylidene)diphenol (bisphenol AF) in molar ratio 1 : 1 via a one‐step condensation polymerization. Subsequent reaction of the resulted chlorine‐bound polymers with adequate amount of the sodium salts of 4‐methoxycarbonylphenoxide or 4‐propoxycarbonylphenoxide yielded the corresponding chlorine‐free polymers, [poly(tetra‐4‐methoxycarbonylphenoxy)‐4,4′‐(isopropoylidene)diphenoxy cyclotriphosphazene] (MBACP), [poly(tetra‐4‐propoxycarbonylphenoxy)‐4,4′‐(isopropoylidene)diphenoxycyclotriphosphazene] (PBACP), [poly(tetra‐4‐methoxycarbonylphenoxy)‐4,4′‐(hexafluoroisopropylidene)diphenoxycyclotriphosphazene] (MBAFCP), [poly(tetra‐4‐propoxycarbonylphenoxy)‐4,4′‐(hexafluoroisopropylidene)diphenoxycyclotriphosphazene] (PBAFCP), respectively. The chemical structures were characterized by Fourier transformer infrared, 1H, and 13C‐NMR. Thermal properties of polymers were investigated using DSC and TGA analysis. The obtained polymers were thermoplastic, having moderate Tg values in the range of 26–78°C and good thermal stability up to 350°C in N2 and O2 gases. The thermal decomposition of the isopropylidene‐containing polymers is a one‐step process, while that of hexafluoroisopropylidene‐containing polymers is a two‐step process. However, presence of the latter group in the polymers backbone showed negligible effects on the thermo‐oxidative stability. The adhesive strength was measured by lap‐shear strength test on glass–glass bonded joint and found to be in the range of 1.78–2.62 MPa, this property may be attributed to the physical interactions between glass–glass interfaces and the polar‐pendant units present at the polymers backbone. The products showed high optical transparency when they applied between two glass surfaces, the adhesive layers were colorless, with the UV cut‐off wavelength of 300–302 nm, and the maximum transparency of about 90% was observed within the wavelengths range of 400–700 nm. Because of their properties, the cyclolinear poly(aryloxycyclotriphosphazenes) synthesized in this study are recommended as potential candidates for high thermally stable, transparent adhesives required in industrial applications. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.  相似文献   

19.
The goal of this article was to synthesize a series of flexible polyimides containing ether linkage in main chain and clarified the effect of this ether linkage on some physical properties such as optical and thermal decomposition. Also, different functional group effects such as carbonyl (? C?O), hexa‐fluoro‐isopropylidene [? C(CF3)2? ] and phenyl (? C6H5) on these physical properties were evaluated. The structural characterization of poly(ether imide)s was performed using Fourier transform infrared, 1H‐nuclear magnetic resonance (NMR), and 13C‐NMR techniques. Optical band gap of polyimides was calculated in the range from 2.57 to 2.81 eV. Thermal characterization of poly(ether imide)s was carried out using thermogravimetry–differential thermal analysis and differential scanning calorimetry. Thermal stability of poly(ether imide)s was evaluated by initial decomposition temperature (Ton) and char. Ton value of polymers was determined in the range from 100 to 195 °C. In addition, glass transition temperatures of poly(ether imide)s were found between 144 and 148 °C. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46573.  相似文献   

20.
The synthesis, mesomorphic character, and effect of spacers in ferrocene‐containing main‐chain liquid‐crystalline polymers are reported in this article. Two different monomers containing ferrocene and phenyl/biphenyl phosphate groups possessing even numbers of spacers from 2 to 10 were prepared and polymerized by polycondensation at room temperature. All the polymers gave birefringent melt except one. The identification of the mesophase was transparent with an increase in spacers. The effect of substitution in the side chain with regard to bulkiness and spacers were studied with thermogravimetric analysis and differential scanning calorimetry. The results reveal that the thermal stability of the polymers increased with the increasing bulkiness of the side chain and decreased with increasing spacer length. The incorporation of the phosphorous moiety also had a considerable effect on the glass‐transition temperature. Char yield of the polymer decreased with increasing methylene chain length, and it did not vary much with the size of the pendent groups. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 831–841, 2002  相似文献   

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