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1.
Cellulosic absorbents for water were synthesized by photografting (λ > 300 nm) acrylic acid (AA) onto fiberous carboxymethyl cellulose (CMC, degree of substitution [DS] = 0.1–0.4) at 30°C in the presence of N,N′-methylenebisacrylamide as a crosslinker. The CMC sample was pretreated with hydrogen peroxide in the presence of sulfuric acid to prepare CMC peroxides with a peracid type as a polymeric photoinitiator. The peroxides were active for the photografting and AA could be grafted onto CMC with percent graftings higher than 150% by photoirradiation of 10 min at 30°C. The amount of water absorbed increased with increasing percent grafting of AA and DS of CMC. The amount was reduced considerably when the absorbents were prepared by the photografting of AA onto crosslinked CMC in the absence of the crosslinker. Graft copolymers which display a decreasing water absorbency as a function of temperature were prepared by two methods: In the first synthesis method, AA and N-isopropylacrylamide (NIPAAm) binary monomers were graft-copoly-merized onto CMC samples using photoinitiation. In the second method, photografting of AA was followed by a second-step photografting of NIPAAm to produce a terpolymer with two types of side chains of differing repeat unit composition on the CMC substrate. Graft copolymers formed by both methods showed decreasing water absorbency as temperature increased with losses in water absorbency of up to about 60% as the temperature was increased above 30°C. Effects of NIPAAm composition and corsslinker content in the graft copolymers on the decreasing water absorbency as a function of temperature were also examined. © 1996 John Wiley & Sons, Inc.  相似文献   

2.
Photografting (λ > 300 nm) of N‐isopropylacrylamide (NIPAAm) and glycidyl methacrylate (GMA) binary monomers (NIPAAm/GMA) on low‐density polyethylene film (thickness = 30 μm) was investigated at 60°C using mixed solvent consisting of water and an organic solvent such as acetone. Xanthone was used as a photoinitiator by coating it on the film surfaces. A maximum percentage of grafting was observed at a certain concentration of acetone in the mixed solvent, which was commonly observed for both ratios of NIPAAm/GMA, 8/2 and 7/3. Based on the photografting of NIPAAm/GMA on xanthone‐coated film, monomer reactivity ratios of NIPAAm (r1) and GMA (r2) were calculated using the Fineman–Ross method. The values were 0.31 ± 0.1 and 4.8 ± 0.2 for the water solvent system, while they were 0.96 ± 0.1 and 4.9 ± 0.1 for the mixed solvent system. NIPAAm/GMA‐grafted films with a homogeneous distribution of grafted chains were formed by photografting using water and mixed solvents. The NIPAAm/GMA‐grafted films exhibited temperature‐responsive characters, whereas the grafted films showed a reversible change in the degree of swelling between 0 and 50°C, respectively. Epoxy groups in the grafted poly(NIPAAm/GMA) chains could be aminated with ethylenediamine in N,N′‐dimethylformamide at 70°C for 3 h. Complexes of the aminated NIPAAm/GMA‐grafted chains with cupric ion exhibited catalytic activity for the decomposition of hydrogen peroxide at 20 to 50°C. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2469–2475, 2005  相似文献   

3.
The effects of a mixed solvent consisting of water and organic solvents such as acetone and methanol on the photografting (λ > 300 nm) of N‐isopropylacrylamide (NIPAAm) on linear low‐density polyethylene film (thickness = 30 μm) was investigated at 30°C and 60°C. Xanthone, which had been coated on the film, was used as a photoinitiator. The photografting initiated even in the system at 30°C by using a longer irradiation time. It was found that the maximum percentage of grafting was attained at a certain concentration of organic solvent in the mixed solvent, which shifted to a lower concentration of organic solvent in the system at 60°C compared with the system at 30°C. It was found that the grafted chains of the sample prepared in the system with the higher polymerization temperature and the use of mixed solvent penetrated into the center of the film compared with the sample prepared in the system with the lower polymerization temperature and use of a water solvent. Moreover, the NIPAAm‐grafted films exhibited temperature responsiveness, swelling and shrinking in water at 0°C and 50°C, respectively. The extent of this characteristic was found to be closely related to the location of the grafted chains in film substrate, which was measured by an attenuated total reflection infrared spectroscope and a scanning electron microscope. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 458–463, 2003  相似文献   

4.
Photografting (λ > 300 nm) of methacrylic acid (MAA) on low-density polyethylene (PE) film (thickness = 30 and 60 μm), on which xanthone photoinitiator was coated earlier, was investigated at 60°C in the presence of polyfunctional monomers such as N,N′-methylenebisacrylamide (MBAAm) and trimethylol propane triacrylate (TMPTA). Addition of the polyfunctional monomers (0.01 and 0.1 wt %) to the grafting system largely accelerated the photografting, and the magnitude of the enhancement was larger for TMPTA than MBAAm. MBAAm component was incorporated into PE substrate and/or MAA-grafted chains through the grafting reaction. Double bonds of the introduced polyfunctional component seemed to act as a new site for the grafting initiation, leading to the promoted grafting. The polyfunctional monomer did not affect distribution of the grafted chains in the cross section of the resultant MAA-grafted film, which was measured by electron probe microanalysis. Wettability of the MAA-grafted PE film was not influenced by the addition of MBAAm, but water absorbency was reduced by using a higher concentration of MBAAm. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1635–1641, 1997  相似文献   

5.
Factors affecting photografting (λ > 300 nm) of methacrylic acid on low-density polyethylene film were investigated in liquid-phase system with water. Benzophenone was used as a sensitizer by coating it on the film surface. Factors examined were monomer concentration (1.3 wt% to 10.0 wt%), polymerization temperature (30°C to 70°C), and film thickness (30 μm and 80 μm). It was found that grafted polymer is formed preferentially as compared with homopolymer under conditions such as monomer concentration higher than 6.0 wt%, polymerization temperature higher than 50°C, and film thickness of 30 μm. The structure of the grafted samples obtained in the above systems was characterized by the grafted chains distributing over the film and the flat appearance of film surface. In the grafting systems using the monomer concentration lower than 6.0 wt%, the polymerization temperature lower than 50°C, and the film thickness of 80 μm, homopolymer was formed predominantly. The resultant grafted chains localized mainly on the film surface, which appeared to be grainy.  相似文献   

6.
An investigation was carried out on estimation of hydrophilicity, wettability and water-absorptivity, and surface analysis by X-ray photoelectron spectroscopy of the low- and high-density polyethylene (LDPE and HDPE) plates photografted with methacrylic acid (MAA) and acrylic acid (AA) at different monomer concentrations or temperatures. Wettability of the MAA-grafted LDPE and HDPE plates increased with grafted amounts, and became constant when the substrate surfaces were fully covered with the grafted polymer chains. On the other hand, for the AA-grafted LDPE and HDPE plates, wettability had the maximum value, and then gradually decreased against the grafted amount probably due to aggregation of grafted PAA chains, although the surfaces were covered with grafted PAA chains at lower grafted amounts compared with grafted PMAA chains. Water-absorptivity sharply increased at lower grafted amounts due to formation of shorter grafted polymer chains for photografting at lower monomer concentrations or due to restriction of the location of grafting to the outer surface region for photografting at lower temperatures. Therefore, for photograftings of AA or onto the HDPE plates, the substrate surfaces were covered with grafted polymer chains and the grafted layers formed possessed higher water-absorptivity at lower grafted amounts. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

7.
Photografting (λ > 300nm) of acrylamide on ethylene-vinyl alcohol copolymer film (vinyl alcohol unit = 56 mol%, film thickness = 20μm) was investigated at 60°C in water medium, where photoinitiators were coated on the film earlier. The percent grafting decreased in the order of xanthone ≈ benzophenone > anthraquinone > benzoyl peroxide. The graft efficiencies in each sensitized system were less than 30%, showing a predominant formation of homopolymer. Grafting of acrylamide on the film was also initiated in systems with and without photoirradiation when ceric salt was used as an initiator. Based on electron probe microanalysis of the grafted films, the grafted chains of the sample prepared by photografting were distributed inside the film, while those of the sample prepared by ceric salt-initiated grafting without photoirradiation were located mainly on the film surface. The grafted films prepared by the former system exhibited a higher moisture permeability than those prepared by the latter system.  相似文献   

8.
Photografting of N-isopropylacrylamide (NIPAAm) on ethylene–vinyl alcohol copolymer films (thickness = 15,20, and 25 μm) and low-and high-density polyethylene films (thickness = 30 μm) was carried out at 60°C in a water medium. Xanthone was used as a photoinitiator by coating it on the film samples. The resultant NIPAAm-grafted films exhibited a temperature-responsive character, which was evaluated by measuring a dimensional change of the grafted films. The grafted films swelled and shrank in water at temperatures lower and higher than around 30°C, respectively. The character was found to be reversible between 0 and 50°C. It was observed that the extent of the character is largely influenced by film thickness, location of NIPAAm-grafted chains, and crystallinity of film substrate. © 1994 John Wiley & Sons, Inc.  相似文献   

9.
Polyethylene (PE) film was treated by corona discharge and then grafted with N-isopropylacrylamide (NIPAAm) for modification of the surface. The grafted amount was determined by gravimetry and the surface morphology was observed by using a scanning electron microscope. The surface analysis was carried out with a x-ray photoelectron spectroscopy and electron probe microanalysis. It was clarified that grafting was limited surface and there was no change of the surface morphology after grafting. The water absorption at various temperature under the absolute humidity (11.4 g/cm3) and the leakage of electrostatic charge from PE film were measured. PolyNIPAAm that was introduced onto PE surface has hydrophilic-hydrophobic transition properties at the 32°C in the atmospheric condition. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1773–1779, 1998  相似文献   

10.
The physical properties of poly(vinyl chloride) (PVC) and poly(N‐isopropylacrylamide) [poly(NIPAAm)] blend systems, and their corresponding graft copolymers such as PVC‐g‐NIPAAm, were investigated in this work. The compatible range for PVC–poly(NIPAAm) blend systems is less than 15 wt % poly(NIPAAm). The water absorbencies for the grafted films increase with increase in graft percentage. The water absorbencies for the blend systems increase with increase in poly(NIPAAm) content within the compatible range for the blends, but the absorbencies decrease when the amount of poly(NIPAAm) is more than the compatible range in the blend system. The tensile strengths for the graft copolymers are larger than the corresponding blends. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 170–178, 2000  相似文献   

11.
Photografting of methacrylic acid (MAA) on low‐density polyethylene film (thickness = 30 μm), on which xanthone photoinitiator was coated earlier, in the presence of polyfunctional monomers such as N,N′‐methylenebisacrylamide, ethylene glycol dimethacrylate, and trimethylol propane triacrylate was examined at 60°C in water/acetone (3:1 v/v) mixture solvent. The photografting was retarded at the earlier stage of polymerization, and then accelerated when small amounts of the polyfunctional monomers (1–3 mol % of MAA monomer used) were added to the system. Addition of the polyfunctional monomers did not affect distribution of the grafted chains in the cross section of the resultant MAA‐grafted PE film, which was measured by electron probe microanalysis. The MAA‐grafted samples were subjected to adsorption of cupric ions at 25°C for 24 h in the system of pH = 5. The adsorption was considerably suppressed for the grafted samples prepared at the earlier stage of polymerization in the system with the polyfunctional monomers. The phenomenon was discussed in terms of the formation of crosslinked and branched structures in the MAA‐grafted chains depending on the polymerization stage in the system with polyfunctional monomers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1262–1268, 2006  相似文献   

12.
Effect of hydroquinone (HQ) on photografting of methacrylic acid (MAA) on low-density polyethylene film (thickness = 30 μm) sensitized with xanthone was investigated at 60°C in water medium. Both the formation of grafted polymer and homopolymer were retarded by HQ. The contact angle of water on the MAA-grafted polyethylene films (sample with HQ) prepared in the system with HQ was larger than that of the grafted films (sample without HQ) prepared in the system without HQ. Based on electron probe microanalysis of the grafted films, it was found that distribution of grafted chains in the direction of film thickness is different between the both grafted films. Namely, the grafted chains of the sample with HQ distributed in the inside of the film compared with those of the sample without HQ. The difference in the distribution of grafted chains between the grafting systems with and without HQ was discussed in terms of effect of HQ on the photodecomposition of MAA-grafted chains and the subsequent initiation of polymerization by radicals due to the photodecomposition.  相似文献   

13.
The photografting of methacrylic acid (MAA) on a linear low‐density polyethylene film (thickness = 30 μm) under air and nitrogen atmospheres was investigated at 60°C in mixed solvents consisting of water and an organic solvent, with xanthone as a photoinitiator. The organic solvents used were acetone, methanol, tetrahydrofuran, and dioxane. A maximum percentage of grafting occurred at a certain concentration of the organic solvent in the mixed solvent. This was observed for the systems under both air and nitrogen. The grafting reaction under air exhibited an induction period, but the rate of grafting after the period was greater than that under nitrogen. The formation of poly(ethylene peroxide)s by photoirradiation seemed to be a factor for the accelerated photografting under air. On the basis of attenuated total reflection infrared spectroscopy and scanning electron microscopy of the grafted film, the MAA‐grafted chains of the sample prepared under air tended to penetrate more deeply inside the film than those of the sample prepared under nitrogen. The resulting grafted films exhibited a pH‐responsive character: the grafted films shrank in an acidic medium but swelled in alkaline medium. This was evaluated from measurements of dimensional changes in the grafted films. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 992–998, 2003  相似文献   

14.
The photografting of methacrylic acid (MAA) onto high‐density polyethylene (HDPE) initiated by aliphatic ketones (acetone, butanone, and cyclohexanone) in aqueous solutions with different pH values adjusted by adding different amount of mineral acids was reported. Acids significantly enhanced the photografting yield, and the extent of grafting generally increased with decreasing pH value. The effect of pH value on the grafting reactions varied with the acid used. The grafting of MAA onto HDPE surface was confirmed with FTIR and SEM characterizations. The water absorbency of the grafted p‐MAA varied with the extent of grafting. When the extent of grafting was less than 2000–3000 μg/cm2, grafted p‐MAA absorbed about 25–30% water, whereas at higher extent of grafting, it absorbed about 50% water. The mechanism of the acid enhancement of the photografting of MAA initiated by aliphatic ketones in aqueous solutions is believed to be attributed to the change of the solubility of monomer in the solution and the conformation of grafted chains, both are favorable for accelerating grafting reactions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

15.
This study was divided into two sections. In the first part, we used ultraviolet (UV) rays in the wavelength range 300–400 nm to remove the hydrogen atom from polyethylene (PE) and worked with a hydrophilic monomer to complete the grafting action. In the second part, we used the best conditions derived from the previous film grafting and applied them to fibers to achieve excellent adhesion for application in composite materials. For the handling process of the PE film, we initially used acrylamide (AM) as the monomer and then added acetone and benzophenone (BP) to form a reactive solution for the advanced photografting process. In general, the optimum concentrations of the monomer solutions obtained from the photografting of PE films were 2 mol/L of AM and 0.2 mol/L of BP. The UV irradiation time was fixed at 30 min. The optimum grafting conditions achieved in the first part of this research were applied in the photografting process for the PE fiber bundles in the second part. The unsaturated polyester (UP) resins were spread over the outer surfaces of the modified fibers. This was done to strengthen and increase the interface between the UP resins and the modified PE fiber. During the curing experiment of the grafted fiber bundles in the resin coatings, the best material quality was obtained under the following conditions: hardener content = 0.85% (relative to the UP resin weight), oven temperature = 80°C, and time frame = 5 h. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

16.
Acetaldehyde could act as a very effective photoinitiator for water‐borne photografting. The photografting of methacrylic acid (MAA) onto polyethylene initiated by acetaldehyde in aqueous solutions was reported. Acetaldehyde had higher photoinitiation efficiency than acetone and formaldehyde. The extent of grafting varied with the acetaldehyde content in the solution and it showed the maximum when the content of acetaldehyde was about 10 w/w %. The extent of grafting firstly increased with the increase of monomer concentration till 2 mol/L and then kept constant or slightly decreased. ATR‐FTIR characterizations of the grafted samples proved the successful grafting of MAA onto PE, and the calculated carbonyl indexes were in accord with the results obtained by the gravimetric method. The water absorbency of the grafted samples increased almost linearly with the extent of grafting. The difference in the photoinitiation efficiencies of acetaldehyde, acetone and formaldehyde was discussed through their differences in the n‐π* transitions in water and the photoinitiation process. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

17.
This study investigated the activity of trypsin that had been covalently immobilized onto acrylic acid (AA)– and methacrylic acid (MAA)–grafted polyethylene (PE) plates—PE–g–PAA and PE–g–PMAA—using a water‐soluble carbodiimide as a coupling agent, as a function of the immobilized amount, the grafted amount, the pH value on immobilization, and the pH value and temperature at the activity measurement. The activity of trypsin immobilized on the PE–g–PAA plates at pH 6.0 decreased with an increase in the immobilized amount because of the crowding of trypsin molecules in the vicinity of the surfaces of the grafted PAA layers. The increase in the grafted amount resulted in a decrease in the activity of immobilized trypsin because of a decrease in the diffusivity of BANA molecules caused by the formation of dense grafted PAA layers for the PE–g–PAA plates and led to the increased activity because of the increase in the hydrophilicity of the whole grafted layers for the PE–g–PMAA plates. The activity of trypsin immobilized on the PE–g–PAA and PE–g–PMAA plates at pH 6 increased with an increase in the pH value, probably because of the expansion of trypsin‐carrying grafted PAA and PMAA chains and the increased diffusivity of Nα‐benzoyl‐DL ‐arginine‐nitroanilide hydrochloride molecules in the grafted layers. The optimum temperature of the activity of immobilized trypsin shifted to 50°C from 30°C for native trypsin. Immobilized trypsin was reusable without any denaturation and isolation at temperatures ranging from 20°C to 60°C and pH values ranging from 6 to 10. Trypsin immobilized on a PE–g–PAA plate had 95% of the remaining activity in relation to native trypsin at 30°C after preservation in a pH 7.8 buffer at 4°C over 6 months. These results made clear that alkaline and thermal stability, reusability, and storage stability can be much improved by the covalent coupling of trypsin on PE–g–PAA and PE–g–PMAA plates. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3574–3581, 2003  相似文献   

18.
An investigation was carried out on the application of dilute chitosan solutions modified by a tyrosinase‐catalyzed reaction with 3,4‐dihydroxyphenetylamine (dopamine) to the adhesion of low‐density polyethylene (LDPE) and high‐density polyethylene (HDPE) plates photografted with carboxyl‐group‐containing hydrophilic monomers, such as methacrylic acid (MAA) and acrylic acid (AA). In the case where photografting was carried out at lower monomer concentrations or at lower temperatures, the adhesive strength sharply increased with lower grafted amounts. A sharp increase in the adhesive strength was found to be due to the formation of shorter grafted polymer chains at lower monomer concentrations and/or the restriction of the location of grafting to the outer surface region at lower temperatures. In addition, the adhesive strength also sharply increased at even lower grafted amounts for photografting onto the HDPE plates and/or that of AA because the location of grafting was restricted to the outer surface region. For the AA‐grafted LDPE and HDPE plates, substrate breaking was observed. This was attributed to the coverage of the substrate surfaces with grafted poly(acrylic acid) chains at lower grafted amounts and a high water absorptivity of the grafted layer. X‐ray photoelectron spectroscopy (XPS) analysis of the grafted LDPE plates incubated in a dopamine solution containing tyrosinase suggested that the increase in the adhesive strength was caused by the penetration of enzymatically modified chitosan solutions in the grafted layers and the subsequent reaction of quinone derivatives enzymatically generated with grafted polymer chains. In addition, the surface analysis of the failed surfaces by XPS showed that as the adhesive strength increased, the location of failure was shifted from the interface between the layers mixed with enzymatically modified chitosan materials and grafted polymer chains to the inside the grafted layer containing enzymatically modified chitosan materials. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

19.
Chemical composition, morphology, and crystalline structure of low density polyethylene (LDPE) films surface grafted with acrylic acid (AA) using corona discharge were studied by attenuated total reflection infrared (ATR-IR), electron spectroscopy for chemical analysis (ESCA), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and wide angle X-ray diffraction (WAXD) techniques. The grafted film surface is covered with grafted chains. After grafting for 3.0 h in 20% aqueous solution of AA, the depth of the grafted layer is more than 10 nm. A grain structure was observed on the grafted surfaces which was probably caused by the isolated dispersion of active sites generated by corona discharge, and these active sites initiated the graft copolymerization. However, surfaces of grafted films were smoother than that of ungrafted ones. DSC curves of grafted films show a small peak at about 100°C due to vaporization of adsorbed water. The longer the graft copolymerization time, i.e. the higher the graft degree of AA on LDPE, the higher the amount of adsorbed water. The position of each peak in WAXD patterns, crystal axial length, crystal plane distance and crystal grain size remain almost unchanged during the graft copolymerization time of 2.0 h. However, when the graft copolymerization time reaches 3.0 h, twin peaks at about 21.4° and 22.0° are observed, indicating that a different crystal form is formed at longer copolymerization time, i.e. at a higher graft degree.  相似文献   

20.
Novel dual temperature‐ and pH‐sensitive poly(acrylic acid‐co‐N‐isopropylacrylamide), AA/NIPAAm, hydrogels were successfully prepared by chemical crosslinking with crosslinkers. Copolymers of AA/NIPAAm were crosslinked in the presence of different mol % of N,N‐methylene bisacrylamide (MBA) and melamine triacrylamide (MAAm) as crosslinkers by bulk radical polymerization. The resultant xerogels were characterized by extracting the soluble fractions and measuring the equilibrium water content. Lower critical solution transition temperatures (LCST) were measured by DSC. The properties of crosslinked AA/NIPAAm series are evaluated in terms of compositional drift of polymerization, heterogeneous crosslinking, and chemical structure of the relevant components. Soluble fractions of the crosslinked networks were reduced by varying the MAAm and MBA concentrations. The influence of environmental conditions such as temperature and pH on the swelling behavior of these polymeric gels was investigated. The swelling behaviors of the resulting gels show pH sensitivity. The prepared MAAm type AA/NIPAAm hydrogels exhibited a more rapid deswelling rate than MBA type AA/NIPAAm hydrogels in ultra pure water in response to abrupt changes from 20°C to 50°C. The results of this study provide valuable information regarding the development of dual stimuli‐sensitive hydrogels with fast responsiveness. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

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