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1.
A series of microspheres composed of methyl methacrylate (MMA) and N-(2-hydroxypropyl)methacrylamide (HPMA), and/or 2-(methacryloyloxy)ethyl phosphorylcholine (MPC), i.e., binary copolymer microspheres [poly(HPMA-co-MMA)KPS and poly(HPMA-co-MMA)ABIP] and ternary ones [poly(HPMA/MPC-co-MMA)KPS and poly(HPMA/MPC-co-MMA)ABIP], were prepared by emulsifier-free emulsion copolymerization using potassium peroxodisulfate (KPS) or 2,2′-azobis[2-(imidazolin-2-yl)propane] dihydrochloride (ABIP) as initiators. The decrease in ζ-potential of the polymer microspheres is caused by the addition of the HPMA and/or MPC moieties. Equilibrium water content of poly(HPMA-co-MMA)ABIP showed a remarkable swelling change with a change in response to temperature: the hydrated conformation at 28°C and the dehydrated one at above 40°C. The adsorption of protein on the polymer microspheres also changed in response to change in temperature. The ternary polymer microspheres effectively suppressed the adsorption both of Alb and Glo, less than binary ones. A series of polymer microspheres are expected to apply as a novel drug carrier with both thermosensitive and nonthrombogenic functions. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 3349–3357, 1997  相似文献   

2.
An interpenetrating polymer network (IPN) based on poly(N-butyl 2-ethynylpyridinum bromide) (PB2EPB) and polycarbonate-urethane (PCU) has been prepared and characterized. The simultaneous full IPNs of PCU and PB2EPB have two glass transition temperatures corresponding to those of the linear chain blends measured by DSC. This suggests immiscibility of the two networks in the IPNs. The IPNs display a multiphase morphology which is confirmed by SEM observation. The full IPNs exhibit excellent solvent resistance, good thermal stability and good mechanical properties. High UV absorption of these materials extending to the visible range and beyond indicates that the polyacetylene network is extensively conjugated. The electrical conductivity of the IPNs increases linearly with increasing polyacetylene content reaching 10-4 S/cm. © 1996 John Wiley & Sons, Inc.  相似文献   

3.
As part of our continuing studies concerned with the elucidation of the crosslinking polymerization mechanism leading to interpenetrating polymer network (IPN) formation, in which IPNs consist of both polymethacrylates and polyurethane (PU) networks, this article explores the polyaddition crosslinking reactions of multifunctional poly(methyl methacrylate‐co‐2‐methacryloyloxyethyl isocyanate) [poly(MMA‐co‐MOI)] [MMA/MOI = 90/10] with various diols leading to PU network formation. Thus, the equimolar polyaddition crosslinking reactions of poly(MMA‐co‐MOI) with ethylene glycol (EG), 1,6‐hexane diol, and 1,10‐decane diol (DD) were carried out in N‐methyl pyrrolidone at a 0.25 mol/L isocyanate group concentration at 80 °C. The second‐order rate constants decreased from EG to DD. The deviation of the actual gel point from the theoretical one was smaller from EG to DD. The intrinsic viscosity of resulting prepolymer demonstrated almost no variation with progressing polymerization for the EG system, whereas it gradually increased with conversion for the DD system. Close to the gel point conversion it increased rather drastically for both systems. The swelling ratio of resulting gel was higher from EG to DD. These are discussed mechanistically in terms of the significant occurrence of intramolecular cyclization and intramolecular crosslinking reactions leading to shrinkage of the molecular size. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3243–3248, 2003  相似文献   

4.
Second harmonic generation (SHG) was used to measure the temperature dependence of the reorientation activation volume of the side-chain copolymer poly(disperse red 1 methacrylate-co-methyl methacrylate) (DR1-MMA). The decay of the SHG signal from poled films of DR1-MMA was recorded at hydrostatic pressures up to 3060 atm and at different temperatures between 25°C below the glass transition temperature (Tg) to 35°C above it. The activation volume, ΔV*, decreased with increasing temperature. The data suggests that the coupling between chromophore reorientation and the long-range motion of the polymer is stronger for the DR1-MMA side-chain system than in previously measured guest–host systems. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2793–2803, 1998  相似文献   

5.
Five ionic imidazolium based monomers, namely 1‐vinyl‐3‐ethylimidazolium bis(trifluoromethylsulfonyl)imide (ILM1), 1‐vinyl‐3‐(diethoxyphosphinyl)‐propylimidazolium bis(trifluoromethylsulfonyl)imide (ILM2), 1‐[2‐(2‐methyl‐acryloyloxy)‐propyl]‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide (ILM3), 1‐[2‐(2‐methyl‐acryloyloxy)‐undecyl]‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide (ILM4), 1‐vinyl‐3‐ethylimidazolium dicyanamide (ILM5) were prepared and used for the synthesis of linear polymeric ionic liquids (PILs), crosslinked networks with polyethyleneglycol dimethacrylate (PEGDM) and interpenetrating polymer networks (IPNs) based on polybutadiene (PB). The ionic conductivities of IPNs prepared using an in situ strategy were found to depend on the ILM nature, Tg and the ratio of the other components. Novel ionic IPNs are characterized by increased flexibility, small swelling ability in ionic liquids (ILs) along with high conductivity and preservation of mechanical stability even in a swollen state. The maximum conductivity for a pure IPN was equal to 3.6 × 10?5 S/cm at 20 °C while for IPN swollen in [1‐Me‐3‐Etim] (CN)2N σ reached 8.5 × 10?3 S/cm at 20 °C or 1.4 × 10?2 S/cm at 50 °C. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4245–4266, 2009  相似文献   

6.
New step‐growth graft block copolymers were synthesized. These two‐sided comb copolymers consisted of a poly(amic ester) (PAE) backbone and pendant poly(propylene oxide) (PPO) grafts. The copolymers were made via a macromonomer approach, in which the 4,6‐bischlorocarbonyl isophthalic acid bis[poly(propylene oxide)] ester macromonomer was synthesized through the reaction of hydroxyl‐terminated PPO oligomers with pyromellitic dianhydride and oxalyl chloride. This macromonomer was subsequently used in step‐growth polymerization with comonomers 4,6‐bischlorocarbonyl isophthalic acid diethyl ester, 2,5‐bischlorocarbonyl terephthalic acid diethyl ester, and 2,2‐bis[4‐ (4‐aminophenoxy)phenyl] hexafluoropropane, and this yielded PPO‐co‐PAE graft copolymers. Accordingly, we report the synthesis and characterization of the PPO oligomer, the PPO macromonomer, and their corresponding PPO‐co‐PAE graft copolymers. Graft copolymers with PPO concentrations of 3–26 wt % were synthesized. These polymers were thermally cured to produce polyimide/PPO composites. The thermolysis of these polyimide/PPO composites yielded porous polyimide films with porosities ranging of 4–22.5%. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2266–2275, 2005  相似文献   

7.
Poly[isobutyl methacrylate‐co‐butanediol dimethacrylate‐co‐3‐methacrylylpropylheptaisobutyl‐T8‐polyhedral oligomeric silsesquioxane] [P(iBMA‐co‐BDMA‐co‐MA‐POSS)] nanocomposites with different crosslink densities and different polyhedral oligomeric silsesquioxane (MA‐POSS) percentages (5, 10, 15, 20, and 30 wt %) were synthesized by radical‐initiated terpolymerization. Linear [P(iBMA‐co‐MA‐POSS)] copolymers were also prepared. The viscoelastic properties and morphologies were studied by dynamic mechanical thermal analysis, confocal microscopy, and transmission electron microscopy (TEM). The viscoelastic properties depended on the crosslink density. The dependence of viscoelastic properties on MA‐POSS content at a low BDMA loading (1 wt %) was similar to that of linear P(iBMA‐co‐MA‐POSS) copolymers. P(iBMA‐co‐1 wt % BDMA‐co‐10 wt % MA‐POSS) exhibited the highest dynamic storage modulus (E′) values in the rubbery region of this series. The 30 wt % MA‐POSS nanocomposites with 1 wt % BDMA exhibited the lowest E′. However, the E′ values in the rubbery region for P(iBMA‐co‐3 wt % BDMA‐co‐MA‐POSS) nanocomposites with 15 and 30 wt % MA‐POSS were higher than those of the parent P(iBMA‐co‐3 wt % BDMA) resin. MA‐POSS raised the E′ values of all P(iBMA‐co‐ 5 wt % BDMA‐co‐MA‐POSS) nanocomposites in the rubbery region above those of P(iBMA‐co‐5 wt % BDMA), but MA‐POSS loadings < 15 wt % had little influence on glass‐transition temperatures (Tg's) and slightly reduced Tg values with 20 or 30 wt % POSS. Heating history had little influence on viscoelastic properties. No POSS aggregates were observed for the P(iBMA‐co‐1 wt % BDMA‐co‐MA‐POSS) nanocomposites by TEM. POSS‐rich particles with diameters of several micrometers were present in the nanocomposites with 3 or 5 wt % BDMA. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 355–372, 2005  相似文献   

8.
At the start of our research program concerned with the elucidation of the crosslinking polymerization mechanism leading to interpenetrating polymer network (IPN) formation, in which IPNs consist of both polymethacrylates and polyurethane (PU) networks, this article deals with the polyaddition crosslinking reaction leading to PU network formation. Therefore, 2‐methacryloyloxyethyl isocyanate (MOI) was radically copolymerized with methyl methacrylate (MMA) in the presence of CBr4 as a chain‐transfer agent. The resulting poly(MMA‐co‐MOI)s, having pendant isocyanate (NCO) groups as novel multifunctional polyisocyanates, were used for polyaddition crosslinking reactions with ethylene glycol as a typical diol. The second‐order rate constants depended on both the functionality of poly(MMA‐co‐MOI) and the NCO group concentration. The actual gel points were compared with the theoretical ones calculated according to Macosko's equation; the deviation of the actual gel point from the theoretical value became more remarkable for a greater functionality of poly(MMA‐co‐MOI) and at a lower NCO group concentration or at a lower poly(MMA‐co‐MOI) concentration. These are discussed mechanistically, with consideration given to the significance of intramolecular cyclization and intramolecular crosslinking reactions leading to the shrinkage of the molecular size of the prepolymer, along with the data of the intrinsic viscosities of resulting prepolymers and the swelling ratios of resulting gels. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 606–615, 2003  相似文献   

9.
This article reports on the synthesis of a novel amphiphilic polyhedral oligomeric silsesquioxane (POSS) end-capped poly(2-(2-methoxyethoxy)ethyl methacrylate)-co-oligo(ethylene glycol) methacrylate) (POSS-P(MEO2MA-co-OEGMA)). These thermoresponsive organic–inorganic hybrid polymers exhibit critical phase transition temperature in water, which can be finely tuned by changing the feed ratio of OEGMA and MEO2MA. The lower critical solution temperature (LCST) of POSS-P(MEO2MA-co-OEGMA) increases from 31 to 59 °C with the increasing of OEGMA content. Dynamic light scattering (DLS) and transmission electron microscopy (TEM) studies show that these polymers can self-assemble into spherical micelles with the thermosensitive block into the corona and the POSS forming the core, and larger aggregates are formed when the temperature values are above their LCSTs. These thermoresponsive polymers POSS-P(MEO2MA-co-OEGMA) with self-assembly behavior and tunable tempetature-responsive property have the potential applications in material science and biotechnology.  相似文献   

10.
The synthesis and characterization of pseudo or semi- and full-interpenetrating polymer networks (IPNs) of poly(2,6-dimethyl-1,4-phenylene oxide) and polydimethylsiloxane were performed. We observed that in full IPNs, the elasticity of the IPN samples increased very drastically, as the composition of polydimethylsiloxane increased (i.e. 0–60%) while the tensile strength (TS) and the glass transition temperature (Tg) decreases. The pseudo IPNs appeared to consist of two phases while the full IPNs of lower siloxane content were miscible.  相似文献   

11.
Novel polyesterurethane/poly(ethylene glycol) dimethacrylate (PEGDMA) interpenetrating networks (IPNs) with good shape‐memory properties were synthesized using solvent casting method. The star‐shaped oligo[(rac‐lactide)‐co‐glycolide] was coupled with isophorone diisocyanate to form a polyesterurethane network (PULG), and PEGDMA was photopolymerized to form another polyetheracrylate network. IPNs were transparent and gel content exceeded 92%. The values of strain fixity rate and strain recovery rate were above 93%. PULG and PEGDMA networks in IPNs were amorphous and did not show any characteristic diffraction peaks in X‐ray diffraction spectra. Only one glass transition temperature (Tg) of the IPNs between Tg of PEGDMA and PULG was observed, which was proportional to PEGDMA content. PULG and PEGDMA networks were miscible when PEGDMA content was below 50 wt %. The hydrophilicity, transition temperatures, and mechanical properties of IPNs could be conveniently adjusted through variation of network compositions to match the promising potential clinical or medical applications. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 768–775, 2007  相似文献   

12.
刘守信 《高分子科学》2016,34(8):965-980
A double thermoresponsive ABC-type triblock copolymer(poly(ethyleneglycol)-block-poly(2-(2-methoxyethoxy) ethyl methacrylate)-block-poly(2-(2-methoxy ethoxy) ethyl methacrylate-co-oligo(ethylene glycol) methyl ether methacrylate, PEG-b-PMEO_2MA-b-P(MEO_2MA-co-OEGMA)) was designed and synthesized by reversible additionfragmentation chain transfer polymerization(RAFT). The ABC-type triblock copolymer endowed a thermal-induced twostep phase transition at 29 and 39 °C, corresponding to the thermosensitive properties of PMEO_2 MA and P(MEO_2MA-coOEGMA) segments, respectively. The two-step self-assembly of copolymer solutions was studied by UV transmittance measurement, dynamic light scattering(DLS), transmission electron microscopy(TEM) and so on. The triblock copolymers showed the distinct thermosensitive behavior with respect to transition temperatures, aggregate type and size, which was correlated to the degree of polymerization of thermosensitive blocks and the molar fraction of OEGMA in the P(MEO_2MAco-OEGMA) segments. In addition, micelles could further aggregate to form the hydrogel by the self-associate of PEG chains under the abduction of the concentration and temperature. The transition from sol to gel was investigated by a test tube inverting method and dynamic rheological measurement.  相似文献   

13.
In this article we review the synthesis and morphology and the physical and mechanical properties of two-component interpenetrating polymer networks (IPNs) from polyurethane and epoxy polymers; the corresponding pseudo-IPNs and grafted IPNs are also discussed. A comparison was made of full IPNs, pseudo-IPNs, grafted IPNs, and related homopolymers by examining their mechanical properties, mechanical spectra, and electron microscopy on an investigation of the effects of interpenetration or permanent entanglement in the IPN and related systems. This interpenetration has resulted in improved compatibility between the two polymer systems and has caused a decrease in the degree of phase separation. An observed shift in the dynamic glass transition temperatures (Tgs) of the two components which yielded a single IPN Tg further substantiates our results.  相似文献   

14.
Colloidal crystallization of copolymer-grafted silica containing ferrocenyl groups in organic solvents and effects of ferrocenyl groups on effective refractive index of colloidal crystal systems were investigated. Poly(ferrocenyl metharylate (FeMA)-co-methyl methacrylate (MMA)-grafted silica gave colloidal crystallization in dimethylformamide and acetonitrile. The colloidal crystals exhibited characteristic coloration due to cooperative effects of specific absorption at 400–500 nm by ferrocenyl group and transmission of 700–800-nm light through the crystals. It was observed that effective refractive index of colloidal crystals systems of poly(FeMA-co-MMA)-grafted silica was higher than that of poly(MMA)-grafted silica. Normalized effective refractive index of the system linearly increased with mole fraction of FeMA in grafted copolymer. However, poly(FeMA-block-MMA) did not bring effective increase of the index because of bias formation of ferrocenyl group on silica.  相似文献   

15.
Poly(methyl acrylate‐co‐methyl methacrylate) [P(MA‐co‐MMA)] nanocomposite film containing 1 wt % of montmorillonite (MMT) exhibited unusual higher ductility, higher strain recovery ratio after creep, and higher modulus and strength compared to neat P(MA‐co‐MMA) as they were cast from their individual latices fabricated by soap‐free emulsion polymerization. The fortified mechanical properties were attributed to the MgO components of exfoliated MMT nanoplatelets being grafted by P(MA‐co‐MMA) chains as verified by FTIR and XPS spectroscopies, which to the best of our knowledge is the first time in the literature providing the direct evidence for the polymer chains grafting onto the exfoliated MMT. TEM investigation of the stretched nanocomposite film revealed that the microcracks in the nanocomposite film appeared mainly in the bulk region of polymer matrix, implying that the interfacial strength between P(MA‐co‐MMA) and its grafted MMT nanoplatelets was higher than the cohesion strength of P(MA‐co‐MMA). © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5891–5897, 2009  相似文献   

16.
Recent DC conductivity measurements on iodine-doped full and psuedo IPNs of poly (carbonate-urethane) (PCU) and natural rubber (NR) reveal that these materials possess a modest conductivity. Both such full and pseudo IPNs (with linear NR chains) are single-phased materials if the NR is of sufficiently high molecular weight derived from Brazilian Manihot glaziovii. On iodine doping the electrical conductivity rises eight orders of magnitude of both the full IPN (to ca. 10?5S cm?1) and the pseudo IPN (to ca. 10?4 S cm?1). A simple theory based on the assumption that conduction occurs essentially along the linear NR chains, composing a percolation cluster, in the iodine-doped pseudo IPNs of PCU and NR accounts for the observed electrical conductivity dependence on temperature, iodine molality, and weight fraction of NR. As temperature decreases the DC conductivity falls and the material becomes essentially an insulator. At sufficiently low temperature (ca. 115 K) this trend reverses and the DC conductivity rises by two orders of magnitude with further decreasing temperature up to that of liquid helium. © 1994 John Wiley & Sons, Inc.  相似文献   

17.
Poly(2,6‐dimethyl‐1,4‐phenylene oxide)/polyamide 6 (PPO/PA6) blends were reactively compatibilized by maleic anhydride (MA) grafted PPO (PPO‐g‐MA) and reinforced by short glass fibers (SGF) via melt extrusion. An observation of the SGF‐polymer interface by scanning electronic microscope (SEM) together with etching techniques indicated that the PPO‐g‐MA played a decisive role in the adhesion of polymers to SGF. The rheological behavior was investigated by capillary rheometer, and the addition of PPO‐g‐MA, and SGF could increase the viscosity of the PPO/PA6 blends. The analysis of fiber orientation and distribution in the PPO/PA6/SGF composites showed PPO‐g‐MA favored to the random dispersion of SGF. The statistic analysis of SGF length showed that PPO‐g‐MA was helpful to maintain the fiber length during melt‐processing. For the composites at a given SGF content of 30 wt %, the addition of PPO‐g‐MA increased the tensile strength from 59.4 MPa to 97.1 MPa and increased SGF efficiency factor from 0.028 to 0.132. The experimental data were consistent with the theoretical predictions of the extension of Kelly‐Tyson model for tensile strength. The fracture toughness of the composites was investigated by single edge notch three‐point bending test. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2188–2197, 2009  相似文献   

18.
Hydrogels responsive to both temperature and pH have been synthesized in the forms of sequential interpenetrating networks (IPNs) of N‐isopropylacrylamide (NIPAAm) and sodium acrylate (SA) and compared with the crosslinked random copolymers of N‐isopropylacrylamide and SA. Whereas the stimuli‐sensitive behaviors of copolymer hydrogels were strongly dependent on the ionic SA contents, the IPN hydrogels exhibited independent swelling and thermal behaviors of each network component. The sequences and media in the synthesis of IPNs influenced the swelling capacities of the IPNs, but not the temperature or pH ranges at which the swelling changes occurred. In IPNs, a more expanded primary gel network during the synthesis of the secondary network contributed to the better swelling of the final IPNs. Both the swelling and thermal behaviors of the IPNs suggest that poly(N‐isopropylacrylamide) and poly(sodium acrylate) are phase separated regardless of their synthesis conditions. The presence of the poly(sodium acrylate) network did not influence the temperature or the extent of phase transition of the poly(N‐isopropylacrylamide) network in the IPNs, but did improve the thermal stability of the IPNs. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3293–3301, 2004  相似文献   

19.
The first example of organostibine mediated controlled/living random copolymerization of styrene (St) and methyl methacrylate (MMA) was achieved by heating a solution of St/MMA/organostibine mediator at 100 °C or St/MMA/organostibine mediator/AIBN with various monomer feed ratios at 60 °C. The addition of AIBN significantly decreased the reaction temperature and enhanced the rate of copolymerization. The structure of poly(St-co-MMA) was verified by 1H NMR. The reactivity ratios at 60 °C were determined by the extended Kelen-Tüd?s method to be γSt = 0.40 and γMMA = 0.44. The ln([M]0/[M]) increased linearly with increasing reaction time. The number-average molecular weights of poly(St-co-MMA) increased linearly with conversion. Poly(St-co-MMA) with expected number-average molecular weight and low polydispersity index was formed. The living characteristic was further confirmed by chain-extension of poly(St-co-MMA) to form poly(St-co-MMA)-b-PMMA.  相似文献   

20.
We report the synthesis and characterization of interpenetrating polymer networks (IPNs) exhibiting nonlinear optical (NLO) properties. The network consists of aliphatic polycarbonate urethane (PCU) and poly(methyl methacrylate-co-N,N-disubstituted urea), with a nonlinear optical (NLO) chromophore incorporated into N,N-disubstituted urea. The full IPNs have only one Tg, as determined by differential scanning calorimetry (DSC), together with scanning electron microscopy (SEM) observations, suggest a single phase morphology. The thin films of IPNs are transparent and the unpoled samples produced second harmonic generation (SHG) signals at room temperature. This result indicates that the NLO chromophore is oriented noncentrosymmetrically during the IPN formation process and is tightly held between the permanent entanglements of the two component networks of the IPN. © 1996 John Wiley & Sons, Inc.  相似文献   

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