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1.
The crosslinked polyvinyl alcohol (CPVA) and alkyl chain grafted CPVA (CPVA‐g‐BGE) were prepared through the addition reaction of epoxy group of epichlorohydrin and butyl glycidyl ether (BGE) with the hydroxyl group of PVA. By FTIR and 1HNMR analysis, BGE was confirmed to be grafted onto the molecular chain of PVA successfully. By grafting with BGE, the area of the stress–strain curves of CPVA increased, and the elongation at break increased remarkably with little drop of the tensile strength. Much rougher fractured surface with folds was observed, indicating the increased toughness of CPVA. The relaxation peak corresponding to the glass transition temperature (Tg) of CPVA shifted to low temperature with increasing grafting ratio of BGE. When compared with CPVA, the crystallization ability of CPVA‐g‐BGE decreased, indicating that although the intermolecular hydrogen bonding of PVA was weakened by grafting with alkyl chain, appropriate intermolecular association of alkyl chain facilitated the formation of physical entanglement of molecular chains to strengthen and toughen the PVA matrix. Ink contact angles of CPVA‐g‐BGE decreased with increasing grafting ratio of BGE, indicating the increasing compatibility of CPVA with ink, which was advantageous for PVA to be used as surface sizing agent in papermaking. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

2.
Grafting of poly(ε‐caprolactone) (PCL) and poly(lactide) (PLA) chains on poly(vinyl alcohol) backbone (PVA degree of hydrolysis 99%) was investigated using MgH2 environmental catalyst and melt‐grown ring‐opening polymerization (ROP) of ε‐caprolactone (CL) and L ‐lactide (LA), that avoiding undesirable toxic catalyst and solvent. The ability of MgH2 as catalyst as well as yield of reaction were discussed according to various PVA/CL/MgH2 and PVA/LA/MgH2 ratio. PVA‐g‐PCL and PVA‐g‐PLA were characterized by 1H‐ and 13C‐NMR, DSC, SEC, IR. For graft copolymers easily soluble in tetrahydrofuran (THF) or chloroform, wettability and surface energy of cast film varied in relation with the length and number of hydrophobic chains. Aqueous solution of micelle‐like particles was realized by dissolution in THF then addition of water. Critical micelle concentration (CMC) decreased with hydrophobic chains. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

3.
Poly(N‐isopropylacrylamide‐co‐hydroxyethyl methacrylate) [P(NIPAM‐co‐HEMA)] copolymer was synthesized by controlled radical polymerization from respective N‐isopropylacrylamide (NIPAM) and hydroxyethyl methacrylate (HEMA) monomers with a predetermined ratio. To prepare the thermosensitive and biodegradable nanoparticles, new thermosensitive graft copolymer, poly(L ‐lactide)‐graft‐poly(N‐isoporylacrylamide‐co‐hydroxyethyl methacrylate) [PLLA‐g‐P(NIPAM‐co‐HEMA)], with the lower critical solution temperature (LCST) near the normal body temperature, was synthesized by ring opening polymerization of L ‐lactide in the presence of P(NIPAM‐co‐HEMA). The amphiphilic property of the graft copolymers was formed by the grafting of the PLLA hydrophobic chains onto the PNIPAM based hydrophilic backbone. Therefore, the graft copolymers can self‐assemble into uniformly spherical micelles ò about 150–240 nm in diameter as observed by the field emission scanning electron microscope and dynamic light scattering. Dexamethasone can be loaded into these nanostructures during dialysis with a relative high loading capacity and its in vitro release depends on temperature. Above the LCST, most of the drugs were released from the drug‐loaded micelles, whereas a large amount of drugs still remains in the micelles after 48 h below the LCST. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

4.
A series of novel cationic gemini surfactants with rigid amido groups inserted as the spacers, named C 12 ‐PPDA‐C 12 , C 14 ‐PPDA‐C 14 and C 16 ‐PPDA‐C 16 , were synthesized by a two‐step reaction with dimethyl terephthalate, N,N‐dimethyl propylene diamine and alkyl bromide as raw materials. The chemical structures of the prepared compounds were confirmed by IR, 1H and 13C NMR and element analysis. Surface activity properties of the synthesized compounds were investigated by surface tension, electrical conductivity and fluorescence. Increasing the number of carbon atoms in the hydrophobic alkyl chain, decreased the critical micelle concentration (CMC), surface tension at the CMC and the minimum surface area. Other relevant properties including foaming ability and emulsion stability were investigated. The results indicated that the synthesized gemini surfactants possess good surface properties, emulsifying properties and steady foam properties.  相似文献   

5.
The self‐aggregation behavior of catanionic surface active ionic liquids (SAIL), 1‐alkyl‐3‐methylimidazolium alkyl sulfates, [C4mim][C16SO4] and [C6mim][C14SO4], in aqueous solutions was explored by several techniques. These results were analyzed together with the concerning data of [C8mim][C12SO4] reported previously. The feature of these SAIL is that the total carbon number of the hydrophobic chains is kept constant, while only the length of the two hydrocarbon chains varies. Because of the different intermolecular and intramolecular interactions, the hydrophobic interaction of asymmetrical SAIL is enhanced, which explains the minimal CMC value of [C4mim][C16SO4]. Thermal motion of hydrocarbon chains at the air–water interface leads to higher Amin and lower Γmax values with the increasing asymmetry of two hydrophobic chains. The conductivity measurements reveal that the micellization process is spontaneous and entropy‐driven in the studied temperature range. This work indicates that the symmetry of alkyl chains can influence the aggregation behavior of [Cnmim][CmSO4] in aqueous solutions.  相似文献   

6.
Cellulose‐graft‐polyacrylamide and cellulose‐graft‐poly(N,N‐dimethylacrylamide) copolymers were prepared by single‐electron‐transfer living radical polymerization (SET‐LRP) in homogeneous medium. Cellulose macroinitiators for SET‐LRP, with different numbers of initiating sites along the cellulose backbone, were successfully synthesized by direct acylation of cellulose with 2‐bromoisobutyryl bromide in LiCl/dimethylacetamide. Dynamic light scattering revealed that cellulose macroinitiator molecules in dimethylsulfoxide (DMSO) exist primarily as individual chains with a certain amount of intermolecular aggregates. SET‐LRP of acrylamide and N,N‐dimethylacrylamide with the cellulose macroinitiators was carried out in DMSO solution. Formation of cellulose‐graft‐copolymers was confirmed using attenuated total reflectance Fourier transform infrared, 1H NMR and 13C NMR spectroscopy, and the products were water‐soluble. High content of poly(N,N‐dimethylacrylamide) in the copolymers enhanced the thermal stability relative to that of cellulose. Scanning electron microscopy studies of cellulose‐based particles formed from the copolymers using the aerosol flow reactor method revealed spherical nanoscale structures. Copyright © 2011 Society of Chemical Industry  相似文献   

7.
Novel thermoresponsive poly(vinyl alcohol)‐graft‐poly(N,N‐diethylacrylamide) (PVA‐g‐PDEAAm) copolymers were prepared by microwave‐assisted graft copolymerization using a potassium persulfate/N,N,N′,N′‐tetramethylethylenediamine (KPS/TEMED) initiator system. The structures of PVA‐g‐PDEAAm copolymers were characterized by 1H‐NMR, Fourier transform infrared spectroscopy, differential scanning calorimetry/thermogravimetric analysis, gel permeation chromatography, X‐ray diffraction, and scanning electron microscopy. The effects of various process parameters on grafting were systematically studied: microwave power, KPS, monomer and PVA concentrations, and ultraviolet irradiation. Under optimal conditions, the maximum grafting percent and graft efficiency were 101% and 93%, respectively. Furthermore, a lower critical temperature of copolymers was measured in the range 29–31 °C by ultraviolet spectroscopy. The swelling behavior of graft membranes was carried out at various temperatures, and the results showed that the swelling behavior of membranes was dependent on the temperature. In vitro cell culture studies using L929 fibroblast cells confirmed cell compatibility with the PVA‐g‐PDEAAm copolymer and its membrane, making them an attractive candidate for drug delivery systems. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45969.  相似文献   

8.
Poly(ethylene‐co‐propylene) (EPR) was functionalized to varying degrees with glycidyl methacrylate (GMA) by melt grafting processes. The EPR‐graft‐GMA elastomers were used to toughen poly(butylene terephthalate) (PBT). Results showed that the grafting degree strongly influenced the morphology and mechanical properties of PBT/EPR‐graft‐GMA blends. Compatibilization reactions between the carboxyl and/or hydroxyl of PBT and epoxy groups of EPR‐graft‐GMA induced smaller dispersed phase sizes and uniform dispersed phase distributions. However, higher degrees of grafting (>1.3) and dispersed phase contents (>10 wt%) led to higher viscosities and severe crosslinking reactions in PBT/EPR‐graft‐GMA blends, resulting in larger dispersed domains of PBT blends. Consistent with the change in morphology, the impact strength of the PBT blends increased with the increase in EPR‐graft‐GMA degrees of grafting for the same dispersion phase content when the degree of grafting was below 1.8. However, PBT/EPR‐graft‐GMA1.8 displayed much lower impact strength in the ductile region than a comparable PBT/EPR‐graft‐GMA1.3 blend (1.3 indicates degree of grafting). Morphology and mechanical results showed that EPR‐graft‐GMA 1.3 was more suitable in improving the toughness of PBT. SEM results showed that the shear yielding properties of the PBT matrix and cavitation of rubber particles were major toughening mechanisms. Copyright © 2006 Society of Chemical Industry  相似文献   

9.
Poly(vinyl alcohol) (PVA) is a water‐soluble and biomedical polymer. 2‐Acrylamido‐2‐methyl‐1‐propanesulfonic acid was grafted onto PVA using ammonium persulfate as radical initiator. The influences of synthesis conditions such as temperature, concentrations of initiator, PVA and monomer were investigated. Both the initial rate of grafting and the final percentage of grafting were increased by an increase in reaction temperature. The reaction kinetics were studied to determine the rate constants of the first‐order reactions. An activation energy of 16.3 kJ mol?1 was found for the grafting reaction. The graft copolymers were characterized by IR and intrinsic viscosity measurements. A proposed mechanism of the grafting reaction is discussed. Kinetics of the thermal degradation were studied using a thermogravimetric method and the order of thermal stabilities are given. The apparent activation thermodynamic parameters, Ea, ΔH*, ΔS* and ΔG* were determined and correlated to the thermal stabilities of the homo‐ and grafted polymers. © 2001 Society of Chemical Industry  相似文献   

10.
BACKGROUND: Hydrophobically associating water‐soluble polymers are of great interest because they possess unique rheological behaviour that results from the reversible association/dissociation process of their hydrophobic moieties. In this study, we focused on the structure of hydrophobic monomers related to the rheological and viscoelastic behaviours in semi‐dilute solutions of acrylamide polymers modified with small amounts of N‐alkyl‐ and N‐arylalkylacrylamides (0.5 and 1 mol%). RESULTS: Associative efficiency increases with the length of the graft alkyl chain, with its proportion in the copolymer and with the presence of an aromatic group at the end of the alkyl graft chain. Introduction of hydrophobic groups induces a slowing down of the dynamics of the system, particularly marked for copolymers containing phenyldecyl chains. CONCLUSION: At low frequencies, solutions behave as Newtonian liquids; at higher frequencies, solutions of strongly associative systems behave as a solid with a storage modulus higher than the loss modulus and little dependency on the frequency. The system is a transient network whose dynamics depend on entanglements and hydrophobic associations. The presence of the hydrophobic groups induces an increase of the final relaxation time, even more pronounced since these associations are strong. Copyright © 2008 Society of Chemical Industry  相似文献   

11.
Novel chiral polyamides with chiral environment in their main chains were obtained from aromatic diamine, 4,4′‐diaminodiphenylmethane (DADPM), and the D ‐isomer or the L ‐isomer of N‐α‐protected glutamic acid, such as N‐α‐benzyloxycarbonyl‐D ‐glutamic acid (Z‐D ‐Glu‐OH) or N‐α‐benzyloxycarbonyl‐L ‐glutamic acid (Z‐L ‐Glu‐OH), in the presence of triphenyl phosphite (TPP). Two types of newly prepared polyamide showed optical rotation, implying that there were asymmetric carbons in their main chains. Circular dichroism studies demonstrated that resulting chiral poly‐ amides took a helical structure. Optical resolution ability of those two types of polyamide was studied by adopting potential difference as a driving force for membrane transport. Membranes showed permselectivity toward racemic mixture of N‐α‐acetyltryptophan (Ac‐Trp). The permselectivity was dependent on the absolute configuration of diacid component. The permselectivity was expressed by diffusivity selectivity, which was determined by the presence of chiral helicity. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

12.
A straightforward strategy is described to synthesize poly(?‐caprolactone)‐graft‐poly(N‐isopropylacrylamide) (PCL‐g‐PNIPAAm) amphiphilic graft copolymers consisting of potentially biodegradable polyester backbones and thermoresponsive grafting chains. PCL with pendent chlorides was prepared by ring‐opening polymerization, followed by conversion of the pendent chlorides to azides. Alkyne‐terminated PNIPAAm was synthesized by atom transfer radial polymerization. Then, the alkyne end‐functionalized PNIPAAm was grafted onto the PCL backbone by a copper‐catalyzed azide–alkyne cycloaddition. PCL‐g‐PNIPAAm graft copolymers self‐assembled into spherical micelles comprised of PCL cores and PNIPAAm coronas. The critical micelle concentrations of the graft copolymers were in the range 7.8–18.2 mg L?1, depending on copolymer composition. Mean hydrodynamic diameters of micelles were in the range 65–135 nm, which increased as the length of grafting chains grew. PCL‐g‐PNIPAAm micelles were thermosensitive and aggregated upon heating. © 2014 Society of Chemical Industry  相似文献   

13.
The functionalization of poly(ester‐urethane) (PUR) surface was conducted using radiation‐induced grafting. A thermosensitive layer constructed from N‐isopropylacrylamide (NIPAAm) was introduced onto a polyurethane film and characterized using attenuated total reflection Fourier transform infrared and X‐ray photoelectron spectroscopies and contact angle measurements. Size exclusion chromatography was used to analyse the PUR‐graft‐PNIPAAm copolymers and homopolymers formed in solution. Additionally, reversible addition–fragmentation chain transfer (RAFT) polymerization was performed in order to obtain PNIPAAm‐grafted surfaces with well‐defined properties. Atomic force microscopy was used to evaluate the surfaces synthesized via conventional and RAFT‐mediated grafting methods. The results of various techniques confirmed the successful grafting of NIPAAm from PUR film. © 2015 Society of Chemical Industry  相似文献   

14.
To construct rapid C3H8 transport pathways in polymer matrix, alkyl chain‐functionalized graphene oxide (GO) was prepared via grafting octadecylamine (ODA) molecules and then embedded into polydimethylsiloxane (PDMS) matrix to obtain high‐efficiency mixed matrix membranes (MMMs). The incorporation of alkyl chains contributes to lowering the surface energy of GO nanosheets and providing higher affinity with PDMS matrix. Additionally, the alkyl chains on the surface of ODA‐functionalized GO nanosheets (ODA‐GO) are in favor of C3H8 adsorption, thus conferring continuous and specific transport pathways for C3H8. The optimized membrane with ODA‐GO loading of 0.3 wt% exhibits the C3H8 permeance of 1897 GPU and the C3H8/N2 ideal selectivity of 67, which are 50.2 and 72.5% higher than those of bare PDMS membrane, respectively. The simultaneous enhancement of C3H8 permeance and C3H8/N2 ideal selectivity indicates that ODA‐GO is an effective filler applied in MMMs for C3H8 recovery. © 2017 American Institute of Chemical Engineers AIChE J, 63: 3501–3510, 2017  相似文献   

15.
Water‐soluble polyphenol‐graft‐poly(ethylene oxide) (PPH‐g‐PEO) copolymers were prepared using grafting‐through methodology. Polyphenol chains were synthesized via enzymatic polymerization of phenols, and the graft chains were synthesized via living anionic polymerization of ethylene oxides. The polymers were characterized using gel permeation chromatography, static light scattering and 1H NMR, infrared and ultraviolet spectroscopies. The PPH‐g‐PEO graft copolymers are soluble in several common solvents, such as water, ethanol, N,N‐dimethylformamide, tetrahydrofuran and methylene dichloride. The solubility of the PPH‐g‐PEO graft copolymers is improved significantly compared with that of polyphenol. Copyright © 2009 Society of Chemical Industry  相似文献   

16.
Poly(vinyl alcohol) (PVA) was grafted on natural rubber (NR) latex particles (NR‐g‐PVA) using potassium persulfate to generate active radicals on both NR particle surface as well as PVA molecules. 1H‐ and 13C‐nuclear magnetic resonance spectroscopy suggested a possibly chemical attachment of PVA on the NR. The amount of graft‐PVA expressed in term of grafting percentage (%G) increased almost linearly with the amount of PVA adding to the NR latex. Measuring by dynamic light scattering, the particle size of NR‐g‐PVA particles was larger than the size of unmodified NR, also it increased with the molecular weight and %G of PVA. Transmission electron microscopy images of the NR‐g‐PVA latex particles revealed that the size of PVA‐grafted NR particle was enlarged by a layer of graft‐PVA surrounding the NR particle. Given by the graft‐PVA layer surrounding NR particles, the NR‐g‐PVA latex particles possessed better colloidal stability as lowering pH compared with the unmodified NR latex. Comparing with unmodified NR particles, the electrophoretic mobility of NR‐g‐PVA particles was lower due to the presence of graft‐PVA that shifted the shear plane further away from the surface of the particles. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

17.
Poly(vinyl alcohol)‐initiated microwave‐assisted ring opening polymerization of ε‐caprolactone in bulk was investigated, and a series of poly(vinyl alcohol)‐graft‐poly(ε‐caprolactone) (PVA‐g‐PCL) copolymers were prepared, with the degree of polymerization (DP) of PCL side chains and the degree of substitution (DS) of PVA by PCL being in the range of 3–24 and 0.35–0.89, respectively. The resultant comb‐like PVA‐g‐PCL copolymers were confirmed by means of FTIR, 1H NMR, and viscometry measurement. The introduction of hydrophilic backbone resulted in the decrease in both melting point and crystallization property of the PVA‐g‐PCL copolymers comparing with linear PCL. With higher microwave power, the DP of PCL side chains and DS of PVA backbone were higher, and the polymerization reaction proceeded more rapidly. Both the DP and monomer conversion increased with irradiation time, while the DS increased first and then remained constant. With initiator in low concentration, the DP and DS were higher, while the monomer was converted more slowly. Microwaves dramatically improved the polymerization reaction in comparison of conventional heating method. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104, 3973–3979, 2007  相似文献   

18.
The synthesis and structural analysis of glucosamide surfactants of the general formula CnH2n+1NH(CH2)2NHCO(CHOH)4CH2OH (n = 8, 10, 12) are described, and the surface activity properties of the surfactants are studied. N‐alkylethylenediamines were synthesized by the alkylation of the ethylenediamine with alkyl bromide. The glucosamide surfactants, N‐alkyl‐N′‐glucosylethylenediamine (CnGA), were prepared by amidation of the precursor diamine with d ‐gluconic acid δ‐lactone. They were structurally characterized by IR, 1H NMR and MS. They reduced the surface tension of water to approximately 26–27 mN m?1 at concentration levels of (0.5–1.6) × 10?3 mol L?1.  相似文献   

19.
In this study, 2‐hydroxyethyl methacrylate and N‐isopropyl acrylamide was block grafted onto the polypropylene macroporous membrane surface by photo‐induced reversible addition‐fragmentation chain transfer (RAFT) radical polymerization with benzyl dithiobenzoate as the RAFT agent. The degree of grafting of poly(2‐hydroxyethyl methacrylate) on the membrane surface increased with UV irradiation time and decreased with the chain transfer agent concentration increasing. The poly(2‐hydroxyethyl methacrylate)‐ grafted membranes were used as macro chain transfer agent for the further block graft copolymerization of N‐isopropyl acrylamide in the presence of free radical initiator. The degree of grafting of poly(N‐isopropyl acrylamide) increased with reaction time. Furthermore, the poly(2‐hydroxyethyl methacrylate)‐ grafted membrane with a degree of grafting of 0.48% (wt) showed the highest relative pure water flux and the best antifouling characteristics of protein dispersion. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

20.
In the current work, synthetic polyamide nylon fibers were modified via the strategy of surface molecular imprinting to develop enantio‐selective adsorbent fabrics for chiral recognition of d ‐phenyllactic acid (d‐ PhLA). The nylon fibers were first modified by grafting of polyacrylamide and then the incorporated amide groups were converted into functional amino groups via treatment with NaOCl (Hofmann degradation). The amino‐functionalized nylon fibers (Ny‐NH2) were interacted with the targeted d‐ PhLA enantiomer before crosslinking the amino‐containing grafted chains with glutaraldehyde crosslinker followed by leashing the template d‐ PhLA out of the formed surface polymeric matrix by lowering the pH to 1 to finally produce the desired enantio‐selective adsorbent fibers DP‐Ny. Different instrumental methods such as elemental analysis, Fourier transform infrared spectroscopy, XRD and TGA were employed to examine all the synthetic procedures. SEM was also utilized to observe the morphological appearances of both native and modified nylon fibers. Moreover, the optimum extraction of d‐ PhLA was found to occur at pH 7. Isotherm studies of the prepared DP‐Ny fibers obeyed the common Langmuir linear equation with qm values 130 ± 2 and 75 ± 1 mg g?1 in the case of d‐ PhLA and l‐ PhLA, respectively. Furthermore, the enantiomeric resolution of (±)‐PhLA racemate was successfully carried out by a column technique with enantiomeric excess reaching approximately 78%. © 2019 Society of Chemical Industry  相似文献   

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