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1.
Free‐radical melt‐grafting of the dual‐monomer systems glycidyl methacrylate–styrene (GMA‐St) and hydroxyethyl methacrylate–styrene (HEMA‐St) onto polypropylene (PP) has been studied using a single‐screw extruder. For single monomer grafting systems, degradation of PP was unavoidable and deterioration of the mechanical properties of the grafted PP subsequently occurred because of β‐scission of PP chains during the free‐radical melt‐grafting process. However, for the dual‐monomer systems, it is shown that the addition of styrene as a comonomer can significantly enhance the GMA or HEMA grafting levels on PP and reduce the extent of β‐scission of PP backbone. It has been found that the grafting degree of dual‐monomer melt‐grafted PP, such as PP‐g‐(GMA‐co‐St) or PP‐g‐(HEMA‐co‐St), is about quadruple that of single‐monomer grafted PP for the same monomer and dicumyl peroxide concentrations. Moreover, the melt flow rate of the dual‐monomer grafted PP is smaller than that of the unmodified PP. Hence, PP not only was endowed with higher polarity, but also kept its good mechanical properties. © 2000 Society of Chemical Industry  相似文献   

2.
The melt grafting of glycidyl methacrylate (GMA) onto powdered isotactic polypropylene (PP) in a Haake Rheocord RC90 mixer was studied. Grafting degrees were determined by nonaqueous back titration of trichloroacetic acid with sodium hydroxide. The extent of degradation and crosslinking of PP during grafting was indicated by the melt-flow rates (MFR) of the grafted samples. The influences of GMA concentration, initiator type and concentration on grafting degree, reaction efficiency, and degradation were evaluated. A novel method was developed to obtain a high grafting degree with little degradation of PP using acrylamide (AM) as the initiating agent. The grafting process occurred before or during the melting of PP (i.e., solid-state grafting), at which temperature crosslinking is preferred over chain scission. Primary free radicals generated from the rapid decomposition of AM have a higher tendency to attack GMA molecules than PP chains. At the same estimated amount of primary radicals, both grafting degree and grafting efficiency increase with decreasing decomposition temperature of the initiator (for the same decomposition half-life) in the order of AM > benzoyl peroxide (BPO) > 2,5-di(t-butylperoxy)-2,5-dimethyl-3-hexyne (LPO). FunctionalizedPP with the desired grafting degree and little degradation of PP could be obtained by the use of mixed initiators. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1957–1963, 1998  相似文献   

3.
The rheology and morphology of polypropylene (PP) modified by grafting and blending with vinyl monomers were studied in this work. The PP powder was impregnated by mixture of methyl methacrylate (MMA)/n‐buthylacrylate (n‐BA) and copolymerized with azobisisobutyronitrile (AIBN) initiator. The simultaneous grafting and blending of PP with MMA‐co‐n‐BA copolymers were performed in a corotating, 40 L/D, twin‐screw extruder in the presence of dicumyl peroxide. The Fourier transform infrared spectroscopy (FTIR) and Scanning Electron Microscopy (SEM) were used to verify the grafting level and dispersion state of MMA/n‐BA copolymer on PP matrix, respectively, and their rheological properties were studied. It is observed that MMA/n‐BA copolymer is finely dispersed in the PP matrix. In this way, PP can be grafted, blended, and simultaneously compatibilized with polar copolymers, as is seen in SEM images. The results showed that by increasing acrylate monomers grafting on to PP increased. The same trend was observed for AIBN initiator. The gel content of samples with 25% monomers showed an increased from 0.7% to 3.5% by increasing AIBN from 0.2% to 0.4%. The grafting reaction took place with chain scission of PP molecules and also cross‐linking reactions. The optimum grafting of 7.3% with lowest chain scission and cross‐linking were obtained for samples containing 15 wt% monomer and 0.3% AIBN initiator. J. VINYL ADDIT. TECHNOL., 21:290–298, 2015. © 2014 Society of Plastics Engineers  相似文献   

4.
Itaconic acid (IA) was grafted onto polypropylene/low‐density polyethylene (PP/LDPE) blends. The ratio of polymeric components was varied from 100 : 0 to 0 : 100. The effect of the variation in the ratios of the components on grafting efficiency and concomitant side processes was studied. Grafting of IA (1 wt %) was initiated by 2,5‐dimethyl‐2,5‐di(tert‐butyl peroxy)‐hexane (0.3 wt %) and was carried out in an extruder reactor equipped with a dynamic mixer. An increase in the PP content of the blend led to a lower yield of the grafted product. With low concentrations of LDPE in the blend (up to 25 wt %), grafting efficiency was observed to increase, and this increase was greater in comparison with the additive rule. Between 25 and 99 wt % of LDPE in the blend, grafting efficiency rose monotonically with LDPE concentration. At or below an LDPE content of 25 wt %, the melt flow index (MFI) of [PP/LDPE]‐g‐IA would increase unlike with PP‐g‐IA systems. But a small quantity of PP (below 25 wt %) in the [PP/LDPE]‐g‐IA blends would result in a decreased MFI unlike with LDPE‐g‐IA. The dependence of swell index and melt strength on the ratio of polymeric components in [PP/LDPE]‐g‐IA blends also was investigated. ©2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5095–5104, 2006  相似文献   

5.
Layered membranes were prepared by sequential grafting—by means of redox initiators—of water‐soluble monomers, with oppositely charged ionic groups, onto ultrafiltration (UF) polyacrylonitrile (PAN) membranes at room temperature. Grafting of a single layer of 2‐hydroxyethylmethacrylate (HEMA) onto a PAN membrane gave a highly grafted membrane with a relatively high water flux. Bilayered membranes with various properties containing poly‐2‐(dimethylamino)ethyl methacrylate (p‐2DMAEMA) as the bottom layer and polymethacrylic acid or polystyrenesulfonic acid (p‐SSA) as the upper layer were prepared and compared—by means of infrared spectroscopy and electron microscopy—with single‐layered membranes of grafted polyhydroxyethylmethacrylate. Layered membranes exhibited a significant decline in water flux in comparison with the initial UF membranes. The flux could, however, be manipulated by controlling the concentration of monomers, the time of grafting, and the number of layers. When four layers of p‐2DMAEMA and p‐SSA were sequentially grafted onto a PAN membrane, pure water fluxes were stable over a wide range of pH values and did not change over long storage times. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 509–520, 2005  相似文献   

6.
The influence of 1‐decene as the second monomer on the melt‐grafting behavior of maleic anhydride (MAH) onto polypropylene (PP) was studied with differential scanning calorimetry and Fourier transform infrared spectroscopy. We found that the value of the grafting degree increased from 0.68% for pure MAH‐g‐PP to 1.43% for the system with a 1‐decene/MAH molar ratio of 0.3, whereas the maximum value with styrene (St) as the second monomer was 0.98% under an St/MAH molar ratio of 1.0. Compared with the contribution of St/MAH‐g‐PP to the peeling strength between the PP and polyamide (PA) layer for a PP/PA laminated film, the introduction of 1‐decene/MAH‐g‐PP increased the peeling strength from 180 g/15 mm to 250 g/15 mm. 1‐Decene inhibited the chain scission behavior of PP. 1‐Decene reacted with MAH to form a 1‐decene/MAH copolymer or the Alder‐ene reaction product before the two monomers grafted onto PP. The grafting of the reactive product onto PP greatly improved the grafting degree of MAH. What is more, because of the similar chemical structures of 1‐decene and PP, the affinity of 1‐decene with PP was higher than that of St. Compared with St, the introduction of less 1‐decene led to a higher grafting degree and higher peeling strength. Therefore, we concluded that 1‐decene was more effective for improving the grafting degree of MAH onto PP. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

7.
Functionalization of polypropylene (PP) during melt extrusion has been explored extensively. In this study, two different radical initiators were employed and compared in grafting acyclic halamine precursors to PP. 2,4‐Diamino‐6‐diallylamino‐1,3,5‐triazine (NDAM) was grafted onto PP during a melt‐extrusion process using either 2,5‐dimethyl‐2,5‐(tert‐butylperoxy)hexyne (DTBHY) or dicumyl peroxide (DCP) as initiator. The results confirmed the radical graft copolymerization of the monomer onto the PP backbone during the reactive extrusion process. It was revealed that, at low monomer concentration, when peroxide initiator concentration was increased, polymer chain scission became dominant. DCP was more efficient than DTBHY as an initiator in the graft polymerization. After exposure to chlorine bleach, the grafted structures could be easily transformed into N‐halamines, which provided powerful, durable and regenerable antibacterial activities against Escherichia coli and Staphylococcus aureus. It is concluded that both DCP and DTBHY could be used as radical initiators in reactive extrusion to graft certain vinyl monomers to PP. The NDAM‐grafted PP could provide expected antibacterial function after chlorination of the grafted product in a chlorine bleach solution. The modified PP showed great potential for use in medical devices and non‐woven textiles. Copyright © 2009 Society of Chemical Industry  相似文献   

8.
Acrylic acid (AAc) and 2‐hydroxyethyl methacrylate (HEMA) mixtures were simultaneously grafted onto the surfaces of polydimethylsiloxane (PDMS) films using a two‐step oxygen plasma treatment (TSPT). The first step of this method includes: oxygen plasma pretreatment of the PDMS films, immersion in HEMA/AAc mixtures, removal from the mixtures, and drying. The second step was carried out by plasma copolymerization of preadsorbed reactive monomers on the surfaces of dried pretreated films. The effects of pretreatment and polymerization time length, monomer concentration, and ratio on peroxide formation and graft amount were studied. The films were characterized by attenuated total reflection Furrier transformer infrared (ATR‐FTIR) spectroscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), zeta potential, surface tension, and water contact angle measurements. The ATR‐FTIR spectrum of the modified film after alkaline treatment showed the two new characteristic bands of PHEMA and PAAc. Both increase the polar part of surface tension (γp) after grafting and the evaluation of surface charge at pH 1.8, 7, and 12 confirmed the presence of polar groups on the surface of grafted films with a mixture of HEMA/AAc. Morphological studies using both AFM and SEM evaluation illustrated various amounts of grafted copolymer on the surface of PDMS films. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007  相似文献   

9.
Grafting of acrylic acid and glycidyl methacrylate onto low density polyethylene (LDPE) was performed by using a corotating twin‐screw extruder. The effects of residence time and concentration of initiator and monomers on degree of grafting and gel content of grafting LDPE were studied systematically. Paraffin, styrene, p‐benzoquinone, triphenyl phosphite, tetrachloromethane, and oleic acid were added to try to decrease the extent of crosslinking of LDPE. 4‐hydroxyl‐2,2,6,6‐tetramethyl‐1‐piperidinyloxy (4‐hydroxyl‐TEMPO) and dipentamethylenethiuram tetrasulfide were also tried to inhibit crosslinking reaction of LDPE during its extruding grafting process. It was found that p‐benzoquinone, triphenyl phosphite and tetrachloromethane were good inhibitors for crosslinking of LDPE. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 535–543, 2001  相似文献   

10.
Radiation grafting of 2-hydroxyethyl methacrylate (HEMA) and methoxytetraethyleneglycol methacrylate (M4G) on low crystallinity poly(4-methylpentene-1) (TPX) has been investigated. Grafting yield increased with increasing pre-irradiation dose, grafting temperature, and monomer concentration. Grafting rate depends on length of molecular chain in the monomers and decreases with increasing chain length. The grafting yields of electron beam irradiated samples were higher than those of γ-irradiated ones because of higher radical concentration. Tensile strength of the grafted film in the dried state increased and the elongation at break decreased with increasing degree of grafting. On the other hand, in the wet state, the tensile strength and elongation at break decreased with increasing the degree of grafting due to the lack of hydrogen bonds between the grafted chains caused by increased water absorption.  相似文献   

11.
The tert‐butoxy radical‐facilitated grafting of methyl methacrylate (MMA) onto commercial polypropylene (PP) pellets and fiber was investigated in heterogeneous conditions similar to practical systems. Free‐radical grafting of several other monomers onto PP fiber was also investigated. Also, preliminary data from the grafting of MMA onto poly(ethylene terephthalate) pellets is presented. The PP‐graft‐PMMA residues were detected by solid‐state 13C‐NMR and photoacoustic IR spectroscopy. There was a good correlation between the degree of grafting (DG) determined from these spectroscopic techniques and the results from gravimetric methods. A maximum grafting efficiency of over 50% was found, whereas DG (20%) remained constant at various PP pellet, initiator, and monomer concentrations. However, at relatively low PP fiber concentrations, the DG was 27%; the increase was most likely due to the greater surface area of the fiber. There was also a reduction in DG (14%) at relatively low initiator concentrations. The reaction conditions were altered to favor grafting by the addition of more polymer substrate. When the ratio of tert‐butoxy radicals to PP was decreased, more of the substrate remained unmodified, and empirical calculations showed the formation of grafts with up to 40 monomer units. At high initiator concentrations, calculations showed that the graft residues were 1–2 units long. Therefore, variation of the polymer, initiator, and monomer concentrations was shown to have a significant effect on grafting. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 898–915, 2002  相似文献   

12.
A new antithrombosis dialytic membrane with a hydrophilic–hydrophobic microphase structure was prepared by preirradiation grafting of β‐hydroxyethyl methacrylate (HEMA) and styrene (St) onto ethylene–vinyl acetate (EVA). The influence of some effects, such as preirradiation dose, dose rate, grafting reaction temperature, reaction time, and monomer component, on the degree of grafting was determined, and the properties of the grafted films were investigated. Compared with the conventional EVA‐grafted hydrophilic monomer, the EVA films grafted with HEMA and St have superior antithrombogenicity; the antithrombogenicity and permeability of EVA‐g‐(HEMA‐co‐St) were 30 and 20 times higher than those of the ungrafted films, respectively, when the volume ratio (HEMA versus St) was about 7:3. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1321–1327, 2000  相似文献   

13.
m‐Isopropenyl‐α, α‐dimethylbenzyl isocyanate (m‐TMI) was grafted on isotactic polypropylene (PP) using di‐cumyl peroxide as a reaction initiator under varying reaction conditions to yield m‐TMI‐g‐PP coupling agent with four sets of grafting yield and molecular weight. Grafting yield of the synthesized m‐TMI‐g‐PP were 1.80%, 2.01%, 9.05%, and 8.86% and molecular weight of the corresponding grafted polymer were 129,225; [Correction made here after initial online publication.] 187,240; 124,130; and 180,838, respectively. Rubberwood flour reinforced polypropylene composites were prepared using these coupling agents and tested for mechanical properties. m‐TMI‐g‐PP coupling agent with 9.09% grafting and 124230 Mw was found to give the highest tensile and flexural strengths. Flexural modulus of the coupled composites was higher than uncoupled composites. Interfacial region of the composites characterized by scanning electron microscope (SEM) suggest effective wetting of fiber by PP in the case of coupled composites. The effect of fiber loading on composites indicates continuous increment in tensile and flexural strengths in coupled composites. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44196.  相似文献   

14.
1,6‐Hexanediol diacrylate (HDDA), pentaerythrithyl tetramethacrylate (PETMA), and triallyl‐isocyanurate (TAIC) were used as representative monomers to modify polypropylene (PP) in the presence of dicumyl peroxide (DCP) in a mixer. Fourier transformed infrared spectroscopy (FTIR) results confirmed that all the three polyfunctional monomers have been grafted on PP backbone. The shape of torque curves suggested the occurrence of grafting and/or crosslinking structure. The rheological behaviors of HDDA modified PP showed the highest G′ and lowest tan δ at low frequency, shear‐thinning shifted to lower frequency in η*–ω plot, as well as more deviation from semicircle characteristic of linear PP at high viscosity in Cole–Cole plot. And, the improvement of the mechanical properties followed the order as below: TAIC < PETMA < HDDA. Meanwhile, the foamability of the modified PP samples was also investigated. The cellular structure and morphology of the obtained foams were observed by scanning electron microscopy (SEM), and the results indicated that the foamability of the three modified PPs followed the same order, demonstrating HDDA modified PP foam possessed the highest cell density and expansion ratio, and the most well‐defined closed cell structure and uniformly cellular morphology. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1675–1681, 2013  相似文献   

15.
The polypropylene‐polyhedral oligomeric silsesquioxane (PP‐POSS) organic–inorganic hybrids were obtained and studied. The hybrids were prepared by grafting of POSS on PP chains during a reactive melt‐blending of polypropylene (iPP), maleic anhydride functionalized PP (PP‐g‐MA), and amine‐functionalized POSS (aminopropylheptaisobutyl‐POSS, ambPOSS, aminopropylheptaisooctyl‐POSS, amoPOSS, or aminoethylaminopropylheptaisobutyl‐POSS, am2bPOSS), taking advantage of the high efficiency of amino‐anhydride reaction in the molten state. The structure, morphology, and physical properties of the obtained hybrids and blends were studied by means of wide‐ and small‐angle X‐ray scattering, dynamic scanning calorimetry, scanning electron microscopy, dynamic mechanical thermal analysis, as well as tensile and impact experiments. The influence of POSS chemical structure and grafting degree on the morphological characteristics and mechanical properties was investigated. It was found that grafting of POSS cages on PP chains leads to the POSS dispersion on the molecular level. On contrary, when POSS was mixed with plain iPP any grafting of POSS on iPP chains was impossible, which resulted in phase‐separated blend with crystallites of POSS dispersed in iPP matrix. The mechanical tests revealed that modification of polypropylene by grafting with POSS molecules does not affect significantly its mechanical properties, both static and dynamic, except ultimate strain, which is markedly lower in hybrids and their blends than in plain iPP. Also the impact properties of PP were practically not improved by modification with POSS. POLYM. COMPOS., 34:929–941, 2013. © 2013 Society of Plastics Engineers  相似文献   

16.
Comparative analysis was conducted to learn the grafting of itaconic acid (IA) and glycidyl methacrylate (GMA) onto polypropylene (PP) in the course of reactive extrusion. Seven organic peroxides, which satisfactorily dissolve in PP, but do not dissolve in the monomer, were used to initiate free‐radical reactions. The grafting of IA and GMA onto PP initiated by certain peroxides gave approximately equal amounts of grafted product. It was learned that the nature of peroxide initiators is decisive for grafting efficiency and degree of macromolecular degradation. To ensure a high yield of grafted product, it is advisable to use peroxides, which have thermodynamic affinity with PP and the temperature range of decomposition of which corresponds to the thermal regime of reactive extrusion. Di(tert‐butyl peroxy‐isopropyl)‐benzene (P‐14) appeared to meet for the most these requirements for grafting both GMA and IA. Grafting is accompanied by β‐decomposition of the chains irrespective of the type of peroxide and monomer used; hence, the MFI increases. A considerable rise in MFI was observed at a minimum peroxide concentration (0.1wt %). Degradation of PP during modification eases its crystallization from the melt. In this case the crystallization temperature is 5 to 8.5°C higher than of the original PP, and the crystallinity degree increases by 20 to 60%. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 64–72, 2002  相似文献   

17.
Hydrophilic polymer/sodium montmorillonite (Na‐MMT) hybrid nanomaterials were prepared via surface‐initiated redox polymerization of 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid (PAMPS‐g‐MMT), acrylamide (PAAm‐g‐MMT) and styrenesulfonic acid sodium salt (PSSA‐g‐MMT) from surface of aminopropyl‐functionalized sodium montmorillonite (AMMT) dispersed in an aqueous medium. Cerium(IV) ammonium nitrate/nitric acid and aminopropyl groups on the surface of AMMT were used as oxidant and reducing groups, respectively. AMMT was prepared by covalently attaching 3‐aminopropyltriethoxysilane onto the surface of Na‐MMT. Hydrophilic monomers (AMPS, AAm and SSA) were then grafted onto AMMT dispersed in water via redox initiation at 40 °C. Structure, morphology and thermal properties of the AMMT, PAMPS‐g‐MMT, PAAm‐g‐MMT and PSSA‐g‐MMT hybrid materials were characterized using Fourier transform infrared (FTIR), X‐ray diffraction (XRD) and thermogravimetric (TGA) analyses, respectively. FTIR results indicated that hydrophilic monomers were successfully grafted onto the surface of MMT. Grafting amounts of the hydrophilic polymers were estimated from TGA thermograms to be 28.8, 118.8 and 14.4% for PAMPS, PAAm and PSSA, respectively. XRD patterns showed an exfoliated morphology for PAMPS‐ and PAAm‐grafted MMT hybrid nanomaterials and an intercalated/exfoliated morphology for the PSSA‐grafted MMT one. The effect of the nature of hydrophilic monomer on the grafting efficiency is discussed in detail. © 2013 Society of Chemical Industry  相似文献   

18.
Polypropylene dialysis membranes were prepared using cobalt-60 gamma radiation to directly graft 2-hydroxyethyl methacrylate (HEMA) onto polypropylene (PP) membranes. The surface structures of both the grafted membranes and the PP membrane were observed by using FTIR–PAS and ESCA methods. The X-ray diffraction diagrams of the PP and PP-g-HEMA membranes indicated a transformation process of the β-form toward the α-form crystallinity with increasing degree of grafting. The SEM data of the membrane grafted under a low grafting temperature showed many spheres of PHEMA embedded in the PP matrix, whose size was well distributed and increased with the degree of grafting. The influences of the degree of grafting and grafting temperature on the permeabilities of PP-g-HEMA membranes toward urea and creatinine were studied in a dialyzer. In all cases, the PP-g-HEMA membrane obtained under higher grafting temperature showed higher permeability toward those solutes. The permeation coefficients of urea and creatinine through the PP-g-HEMA membrane obtained at 59°C were about 10.4 and 28.8 times that through the PP membrane, respectively. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68:83–89, 1998  相似文献   

19.
Acrylic acid (AA)‐g‐polypropylene (PP) membranes were prepared by grafting AA on to a microporous PP membrane via plasma‐induced graft polymerization. The grafting of AA to the PP membrane was investigated using Fourier transform infrared spectroscopy (FTIR). Pore‐filling of the membranes was confirmed by field emission‐scanning electron microscopy (FESEM) and energy dispersing X‐ray (EDX). Ion exchange capacity (IEC), membrane electric resistance, transport number and water content were measured and analyzed as a function of grafting reaction time. The prepared AA‐g‐PP membranes showed moderate electrochemical properties as a cation‐exchange membrane. In particular, membranes with a degree of grafting of 155% showed good electrical properties, with an IEC of 2.77 mmol/g dry membrane, an electric resistance of 0.4 Ω cm2 and a transport number of 0.96. Chronopotentiometric measurements indicated that AA‐g‐PP membranes, with a high IEC had a sufficient conducting region in the membrane. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007  相似文献   

20.
Novel sulfobetaines were synthesized from two urethanes derived from 2,4‐tolylene diisocyanate (TDI) blocked with 2‐hydroxyethyl methacrylate (HEMA) and either N,N‐dimethylaminopropylamine (DMAPA) or N,N‐dimethylaminoethanolamine (DMAEA). The first‐stage reaction of TDI with HEMA was carried out in petroleum ether heterogeneously with the precipitation of the intermediate monoadduct product in the reaction solution. The second stage is a homogeneous reaction of the monoadduct with the blocking agent, DMAPA or DMAEA, in tetrahydrofuran (THF). In both reactions, an inhibitor, hydroquinone, and a catalyst, dibutyltin diacetate (DBDAc), were used. The tertiary amine urethanes were quaternized by 1,3‐propane sultone to form the two novel sulfobetaines. The results of the elemental analysis of those products along with their 1H‐NMR and IR spectra indicated that these materials were, indeed, the compounds expected. The products dissolved in strongly polar organic solvents. The copolymerization of these two monomers with comonomers such as styrene, methyl methacrylate, acrylamide, and HEMA was investigated. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3447–3459, 2001  相似文献   

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