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1.
Niyazi Bicak Mustafa Gazi Giancarlo Galli Emo Chiellini 《Journal of polymer science. Part A, Polymer chemistry》2006,44(23):6708-6716
We report application of copper‐mediated atom transfer radical polymerization in graft copolymerization of glycidyl methacrylate (GMA) from N‐bromosulfonamide groups on polystyrene‐divinyl benzene (PS‐DVB) microspheres (210–420 μm). The surface initiator groups were introduced by simple modification of crosslinked PS‐DVB (10% mol/mol) beads in three steps: (i) chlorosulfonation, (ii) sulfamidation with propylamine, and (iii) bromination. Initiation from surface‐bound N‐bromosulfonamide groups showed first‐order kinetics (k = 1.04 × 10?4 s?1 in toluene at 70 °C) and gave poly(GMA) graft chains linked to the surface by hydrolytically stable sulfonamide bonds. High graft yields were attained (up to 294.4% within 21 h) while retaining the epoxy groups. Epoxy content of the resulting product (5.41 mmol g?1) revealed an average 17 GMA repeating units in the graft per initiation site. Taking advantage of the hydrolytic stability of sulfonamide linkages and well‐known reactivity of the epoxy groups on dangling chains, “the hair‐like structure” of the polymer beads prepared can be considered when devising more efficient functional polymers as catalysts or reagent carriers. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6708–6716, 2006 相似文献
2.
Marko Zupan Peter Krajnc Stojan Stavber 《Journal of polymer science. Part A, Polymer chemistry》1996,34(12):2325-2331
Crosslinked chloromethylated polystyrene ( 1 ) and crosslinked copoly(styrene-p-nitro-phenylacrylate) ( 3 ) readily reacted with 1,1-dimethylhydrazine, but the course of the reaction was strongly dependent on the structure of the backbone. Monofunctionalization was observed with chloromethylated polystyrene ( 1 ) giving the 1,1,1-dimethylhydrazinium chloride derivative ( 2 ), while high degree of additional crosslinking took place with crosslinked copoly(styrene-p-nitrophenylacrylate) ( 3 ), and additional crosslinking was also observed in functionalization with N-aminopiperidine and N-aminomorpholine. The additional crosslinking suggested a higher backbone mobility in acrylate beads ( 3 ) compared to chloromethylated polystyrene ( 1 ). The type of transformation and the degree of additional crosslinking also depended on the starting crosslinking of copoly(styrene-p-nitrophenylacrylate) ( 3; 3a , 2% DVB; 3b , 4% DVB; 3c , 10% DVB). Replacement of p-nitrophenol groups in copoly(styrene-p-nitrophenylacrylate) ( 3 ) with hydrazino units resulted in enhanced swelling abilities of the hydrazine derivatives ( 4, 5, 6 ) in methanol, dimethylformamide, and chloroform, while formation of the hydrazinium chloride derivative ( 2 ) from chloromethylated polystyrene ( 1 ) caused enhancement of swelling in methanol but diminished it in toluene. The degree of crosslinking of copoly(styrene-p-nitrophenylacrylate) ( 3 ) also influenced the swelling abilities of 3 and its hydrazino derivatives, being higher with 2% cross-linked resins and lower with 4% and 10% crosslinked resins. © 1996 John Wiley & Sons, Inc. 相似文献
3.
Joo-Young Park Jang-Joo Kim Kyung-Hoon Kim Jeong-Yeol Moon Dae-Won Park 《Reaction Kinetics and Catalysis Letters》2001,74(1):29-40
The synthesis of phenoxymethyl ethylene carbonate from carbon dioxide and phenyl glycidyl ether was investigated in a semi-batch
reactor using crosslinked polystyrene beads containing pendant quaternary ammonium salts as catalysts. The catalysts were
prepared by suspension copolymerization of styrene, divinylbenzene (DVB) and vinylbenzyl chloride (VBC), followed by quaternization
using trialkylamines. The influence of VBC and DVB concentration, the structure of trialkylamine, and the type of solvent,
on the catalytic behavior are discussed. A kinetic study was also carried out to better understand the reaction steps.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
4.
A flexible poly(dimethyl siloxane) diacrylate (PDMSDA) crosslinker was synthesized using different molecular weights of poly(dimethyl siloxane) (PDMS, M
n
=550, 1,700, 4,000 g/mol). The monodisperse polystyrene (PS) particles crosslinked with various contents of PDMSDA were prepared by dispersion polymerization, and applied as seed particles in the seeded polymerization. The crosslinking density of the PS particles was determined from the rate of transport of the monomer molecules to the crosslinked seed particles. It was confirmed that the monomer swelling capacity of seed particles and final morphological changes of polymer beads were determined significantly by the crosslinking density of the seed particles. In addition, the morphological change was not observed without the oligomer swelling step in the seeded polymerization due to the hydrophobic property of PDMS. When highly crosslinked seed particles were used in the seeded polymerization, peculiar morphology (doublet structure) of polymer beads appeared. 相似文献
5.
Dezhong Zou Liquing Sun J. J. Aklonis R. Salovey 《Journal of polymer science. Part A, Polymer chemistry》1992,30(7):1463-1475
Monodisperse crosslinked polystyrene (PS) and polymethacrylate (PMA) beads of sizes greater than 1 μm in diameter are prepared by particle nucleation onto pre-existing polymer seeds in a multistage emulsion polymerization, in the absence of emulsifier. An adequate seed number concentration, which decreases with increasing seed size, is necessary to achieve monodisperse beads. Monodisperse multicomposition beads are prepared by polymerizing styrene onto PMA seeds, but not by polymerizing methyl methacrylate onto PS seeds. Phase separation in growing seed particles or surface polymerization following free radical capture may lead to the formation of asymmetric shaped particles. 相似文献
6.
Xiaoqing Zhang Masahiko Shimoda Akinobu Toyoda 《Journal of Polymer Science.Polymer Physics》1994,32(8):1399-1406
The molecular motion of crosslinked polyepichlorohydrin (PECH) is studied qualitatively by NMR techniques. The results of temperature dependence of 1H T2 and T1 indicate that the crosslinking (crosslink density < 3%) restricts molecular motions of the polymer even far above its Tg. The 1H T1 minimum, corresponding to the large-scale chain-motion of crosslinked PECH, shifts to higher temperatures with increasing crosslink density. 1H T2 data also show that the crosslinking hinders free chain motions of the polymer above its Tg. The 13C T1 relaxation time is sensitive to such motional changes as well. 13C linewidths of crosslinked PECHs vary with the crosslink density in both the swollen state and the solid state. The mechanism of 13C linewidth broadening of crosslinked polymers is discussed in detail. In the case of PECH, the linewidth broadening is caused by changing molecular environment due to crosslinking (such as presence of various chemical shift structures and freezing effects in conformational environment as chain mobility decreases), rather than increasing correlation times, which shorten the relaxation time (T2) of polymer chains. © 1994 John Wiley & Sons, Inc. 相似文献
7.
Takashi Sasaki Shoko Kawagoe Hajime Mitsuya Satoshi Irie Kensuke Sakurai 《Journal of Polymer Science.Polymer Physics》2006,44(17):2475-2485
Glass transition of core/shell capsules consisting of calcium carbonate whisker as a core and crosslinked polystyrene as a shell was studied by differential scanning calorimetry. The thickness of the crosslinked shell was in the range of 26–81 nm. The crosslinked shells were revealed to show higher glass transition temperatures (Tg) than the corresponding bulk values. It was revealed that a thicker shell exhibits a lower Tg than a thinner shell, and that capsules without core (hollow capsules) exhibit lower Tg's than the corresponding core/shell capsules. These results suggest that the interfacial molecular interaction plays a role in the segmental relaxation, which is responsible for the glass transition. The difference in Tg between the core/shell and hollow samples was reduced when a coupling agent, methacrylic acid 3‐(trimethoxysilyl)propyl ester, was not included. This also suggests the interfacial effect on Tg. However, the results still suggest that the enhancement of Tg for the present crosslinked shells is not only due to the interfacial effect but also to the effects of chain configuration and heterogeneous crosslink. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2475–2485, 2006 相似文献
8.
Composites with a matrix of poly(2-hydroxyethyl methacrylate) (PHEMA) and 10% by volume of various crosslinked PHEMA polymer fillers (prepared by copolymerization with 0.1, 0.4, 1.0, and 20.0% by weight of ethylenedimethacrylate) of particle size about 1 μm were prepared. Some polymer matrixes were prepared from soluble branched PHEMA (Hydron S), and others by copolymerization, in the presence of the filler with 0.4 and 1.0% of ethylenedimethacrylate as a crosslinking agent. In the case of the uncrosslinked matrix, a linear polymer–crosslinked polymer system, resulted; in the case of the crosslinked matrix, a composite heterogeneous network was formed (in the latter case, the particles of the filler were swollen with monomer during the crosslinking polymerization). Stress–strain, equilibrium, and ultimate characteristics were measured at 3, 10, 25, 40, 60, and 80°C on samples swollen to equilibrium in water (Tg ≈ ?50°C) and at 80, 110, and 140°C on dry samples (Tg ≈ 100°C). Depending on experimental conditions, above all on the distance from the main transition region and on whether the polymer is dry or swollen, it was found that the measured hydrophilic composite systems behaves as a filled system (with the polymer filler acting mostly as solid particles, irrespective of the crosslink density) or as a system with crosslink density fluctuations (where both networks, the matrix and the filler, contribute roughly additively to the properties of the system), or finally as defect heterogeneous systems (where the properties depend primarily on the character of the polymer–filler interface). 相似文献
9.
Dezhong Zou J. J. Aklonis R. Salovey 《Journal of polymer science. Part A, Polymer chemistry》1992,30(11):2443-2449
Monodisperse polymethacrylonitrile beads of varied size and crosslink density are prepared by emulsion copolymerization of methacrylonitrile and allylmethacrylate in the absence of emulsifier. The particle size is very sensitive to polymerization temperature and initiator concentration. Because of a nitrile group effect, the maximum conversion varies with reaction conditions. The highest conversion obtained was 82%. © 1992 John Wiley & Sons, Inc. 相似文献
10.
11.
Masayoshi Okubo Tomoaki Nakagawa Tsuyoshi Yamashita Morio Tsuji 《Macromolecular Symposia》1995,92(1):83-95
Three kinds of micron-sized monodispersed polystyrene (PS)/ poly(styrene - divinylbenzene) composite particles were produced by two kinds of seeded copolymerizations of styrene (S) and divinylbenzene (DVB) (PS seed/ (S+DVB)=2/1, wt. ratio; S/DVB=1/1, molar ratio) in the presence of about 2 μm-sized monodispersed PS particles, and their morphologies were examined. One was produced by a seeded dispersion copolymerization where almost monomers and initiators exist in an ethanol/water (12.6/4.0, w/w) medium. The others two were produced by seeded copolymerizations with the dynamic swelling method where almost monomers exist in the monomer-swollen particles using 2, 2'-azobisisobutyronitrile in monomer-swollen PS seed particles or using 4, 4'-azobis (4-cyanopentanoic acid) in an ethanol/water (7/43, w/w) medium. In the former polymerization, the produced composite particles had a high dense crosslinked shell, whereas in the latter two polymerizations, they did the comparatively homogeneous crosslinked structures. 相似文献
12.
A new chelating polymer support has been prepared by suspension copolymerization of synthesized N,N'-bis(3-allyl salicylidene)ethylenediamine monomer Schiff base (N,N'-BSEDA) with styrene (St) and divinylbenzene (DVB) using azobisisobutyronitrile (AIBN) as initiator in the presence of poly(vinyl alcohol). The content and complexation ability of monomer Schiff base (N,N'-BSEDA) for cobalt(Ⅱ) ions in prepared crosslinked polymer beads have shown dependence on the amount of DVB used in reaction mixture. The amount of monomer Schiff base (N,N '-BSEDA) in crosslinked beads showed a substantial decreasing trend at high concentration of DVB in the reaction mixture (> 1.5 mol dm-3), hence the efficiency of complexation (EC%) and cobaltⅡion loading (EL%) of polymer beads showed a decreasing trend. The structure of monomer Schiff base (N,N'-BSEDA) and its cobalt(Ⅱ)complex on polymer support was elucidated by IR, UV and magnetic measurements. The catalytic activity of polymer bound cobalt(Ⅱ)Schiff base complex was evaluated by analyzing kinetic data of decomposition of hydrogen peroxide in the presence of either supported cobalt(Ⅱ)complex or free cobalt(Ⅱ)complex. The activation energy for the decomposition of hydrogen peroxide by polymer supported cobalt complex was found to be low (33.37 kJ mol-1) in comparison with unsupported cobalt(Ⅱ)complex (56.35 kJ mol-1). On the basis of experimental observations, reaction steps are proposed and a suitable rate expression derived. 相似文献
13.
Takuya Ogawa Sang‐Do Lee Masashi Murakami 《Journal of polymer science. Part A, Polymer chemistry》2002,40(3):416-422
Thermally stable polysilylenemethylenes (PSMs) with siloxane crosslinking moieties were successfully synthesized by chlorodephenylation of preformed poly(methylphenylsilylenemethylene) (PMPSM) and subsequent in situ alcoholysis/hydrolysis/condensation reactions. The simplified process and mild reaction conditions are quite advantageous. The crosslink density of these materials can be adjusted by the degree of chlorodephenylation, although an alkoxysilyl group remains to some extent. The resulting crosslinked PSMs have well defined structures in which the backbone is composed of MePhSiCH2 and Me(MeO)SiCH2 as well as Me(O1/2)SiCH2 as a crosslinking moiety. The resulting crosslinked PSMs exhibited glass‐transition temperatures ranging from 15 to 20 °C, whereas that of linear PMPSM was 22 °C. The crosslinked PSMs remained unchanged in weight below 300 °C, suggesting that they are thermally stable up to that temperature. The good solvent resistance caused by crosslinking as well as high thermal stability of these materials allow us to design new PSM‐based polymer blends and preceramic polymers. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 416–422, 2002 相似文献
14.
H. T. Van De Grampel A. G. M. Santing Y. Y. Tan G. Challa 《Journal of polymer science. Part A, Polymer chemistry》1992,30(5):787-796
The effect of crosslinked poly(methacrylic acid) (c-PMAA) on the polymerization of N-vinylimidazole in aqueous solution was studied using UV, calorimetry, SEM, and TEM. It was established that synthetic lightly crosslinked PMAA samples behaved intermediate between rigid crosslinked PMAA particles functioning as microreactors, and linear conventional PMAA, where template and conventional polymerization in the surrounding solution are integrated. A modified calorimetric technique was used to measure monomer conversion, and to correct for the rapid adsorption process. Rate enhancements up to a factor of 4 were obtained for the c-PMAA's, which were lower than those obtained for linear conventional PMAA, and which slightly decreased with increasing crosslink density of the samples. Template complexes possessed a platelet-like morphology similar to template complexes obtained for linear PMAA. 相似文献
15.
Synthesis of insoluble polystyrene‐supported flavins and their catalysis in aerobic reduction of olefins
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Yukihiro Arakawa Risa Kawachi Yoshihiko Tezuka Keiji Minagawa Yasushi Imada 《Journal of polymer science. Part A, Polymer chemistry》2017,55(10):1706-1713
2′,4′‐p‐Vinylbenzylideneriboflavin ( 2′,4′‐PVBRFl ) was prepared as a flavin‐containing monomer and copolymerized with divinylbenzene and styrene or its p‐substituted derivatives such as 4‐acetoxystyrene, 4‐vinylbenzyl alcohol, and 4‐vinylbenzoic acid to give the corresponding non‐functionalized and functionalized PS‐DVB‐supported flavins PS(H)‐DVB‐Fl , PS(OAc)‐DVB‐Fl , PS(CH2OH)‐DVB‐Fl , and PS(COOH)‐DVB‐Fl , respectively. PS(OH)‐DVB‐Fl was also prepared by hydrolysis of PS(OAc)‐DVB‐Fl under basic conditions. These novel flavin‐containing insoluble polymers exhibited characteristic fluorescence in solid state, except PS(OH)‐DVB‐Fl , and different catalytic activities in aerobic reduction of olefins by in situ generated diimide from hydrazine depending on their pendant functional group. For example, PS(H)‐DVB‐Fl was found to be particularly effective for neutral hydrophobic substrates, which could be readily recovered by a simple filtration and reused more than 10 times without loss in catalytic activity. On the other hand, PS(OH)‐DVB‐Fl and PS(COOH)‐DVB‐Fl proved to be highly active for phenolic substrates known to be less reactive in the reaction with conventional non‐supported flavin catalysts. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 1706–1713 相似文献
16.
Thodoris Tsoukatos Stergios Pispas Nikos Hadjichristidis 《Journal of polymer science. Part A, Polymer chemistry》2001,39(2):320-325
Star‐branched polystyrenes, with polydispersity indices of 1.15–1.56 and 4–644 equal arms, were synthesized by the reaction of 2,2,6,6‐tetramethylpiperidin‐1‐yloxy (TEMPO)‐capped polystyrene (PS‐T) with divinylbenzene (DVB). The characterization of PS‐T and the final star polymers was carried out by size exclusion chromatography, low‐angle laser light scattering, and viscometry. The degree of branching of the star polymers depended on the DVB/PS‐T ratio and the PS‐T molecular weight. An asymmetric (or miktoarm) star homopolymer of the PSnPS′n type was made by the reaction of the PSn symmetric star, which had n TEMPO molecules on its nucleus and consisted of a multifunctional initiator, with extra styrene. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 320–325, 2001 相似文献
17.
Artificial red cells with crosslinked hemoglobin membranes 总被引:1,自引:0,他引:1
Thomas A. Davis William J. Asher Herbert W. Wallace 《Applied biochemistry and biotechnology》1984,10(1-3):123-132
Artificial cells containing concentrated hemoglobin (Hb) solution were prepared by interfacial polymerization of Hb with glutaraldehyde
(GA) in liquid membrane capsules (LMC). A solution containing 30% of Hb was emulsified in mineral oil as red cell-size microdroplets,
and this emulsion was dispersed in an aqueous phase containing glutaraldehyde to form LMC. The LMC were semipermeable templates
that held the microdroplets of Hb in suspension while GA diffused through the oil to the microdroplet surfaces. The GA crosslinked
Hb at the surface of each microdroplet to form an artificial red-cell membrane encapsulating Hb solution. A water-soluble
surfactant was used to eject the cells from the LMC and suspend them in saline.
Several surfactants were evaluated. Cell size was controlled by agitation speed during preparation of the original emulsion.
Cells of 2.52 = ±1.69 μm were prepared. The encapsulated Hb retained capacity to bind and release O2. The cells had aP
50 of 8.9 torr (1200 Pa) and a capacity of 0.55 cc O2/g of total Hb, indicating that the crosslinked portion of the Hb did not contribute to O2 transport. 相似文献
18.
P. W. Kwant 《Journal of polymer science. Part A, Polymer chemistry》1979,17(5):1331-1338
The study of copolymerization of styrene with small amounts (≤0.04 wt %) of divinylbenzenes (DVB) offers advantages over similar studies made at high DVB concentrations. A simple set of equations can be used to describe the kinetics of copolymerization at low DVB concentrations. Experimental data show that the copolymerization constants (r2) for the copolymerization of the first double bonds of m- and p-DVB (monomer 1) with styrene (monomer 2) are 0.85 and 0.43, respectively. In contrast to findings at higher DVB concentrations these constants do not change during the first half of the polymerization. After 50% conversion an autoacceleration effect reduces the selectivity of the growing polystyrene radical. The copolymerization constants for the second double bonds of m- and p-DVB during the first half of the polymerization are estimated as 1. 相似文献
19.
Dr. Lei Jiang Dr. Yinran Wang Dr. Hanyang Sun Tingting Fu Prof. Zhaomin Hou Prof. Fang Guo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(62):e202202113
The precise control of monomer sequence and stereochemistry in copolymerization is of much interest and importance for the synthesis of high performance materials, but studies toward this goal have met with only limited success to date. The coordination polymerization of diphenylphosphinostyrene (p-StPPh2 and o-StPPh2) and its copolymerization with styrene (St) by (C5Me4SiMe3)Sc(CH2C6H4NMe2-o)2 have been achieved for the first time to afford a new series of phosphine functionalized syndiotactic polystyrene. By the design of the polymer structure, the copolymer of o-StPPh2 and St (poly(o-StPPh2-alt-St)-b-sPS) containing o-StPPh2 and St atactic alternating copolymer block and syndiotactic polystyrene block (sPS) showed excellent thermal stability and chemical resistance. The simple combination of the triphenylphosphine and syndiotactic polystyrene realized the stable immobilization of metal nanoparticles to afford highly robust metal@poly(o-StPPh2-alt-St)-b-sPS nanocatalysts at high temperature and various atmospheres. The Cu@poly(o-StPPh2-alt-St)-b-sPS catalyst can serve as a highly efficient heterogeneous catalyst for the synthesis of quinoline derivatives by acceptorless dehydrogenative coupling of o-aminobenzylalcohol with ketones. 相似文献
20.
Sung Chul Hong Ursula Rief Marc Oliver Kristen 《Macromolecular rapid communications》2001,22(17):1447-1454
Gel‐type poly(styrene‐co‐divinylbenzene) beads (PS bead) were used as a carrier to encapsulate metallocene catalysts through a simple swelling‐shrinking procedure. The catalytic species were homogeneously distributed in the PS bead particle. The catalyst exhibited high and stable ethylene polymerization and ethylene/1‐hexene copolymerization activity affording uniform spherical polymer particles (1 mm). Polymerization rate profiles exhibited slow initiation and stable increase in polymerization activity with time. 相似文献