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1.
Hyung Soon Park Joo Hee Cho Junghun Suh 《Journal of polymer science. Part A, Polymer chemistry》1997,35(14):2935-2942
Three molecules of 5-(bromoacetyl)salicylate ( 1 ) complexed to uranyl UO ion were crosslinked with branchy poly(ethylenimine) (PEI) in DMSO by alkylation of amino groups of PEI with 1, leading to the formation of UO2(Sal) PEI. Upon demetalation of UO2(Sal) PEI with HCl, apo(Sal) PEI was obtained. Based on the pH dependence of log Kf for UO2(Sal) PEI, it was concluded that each uranyl binding site in UO2(Sal) PEI or apo(Sal) PEI contains three salicylate moieties. In terms of the equilibrium constant for formation of the uranyl complex, apo(Sal) PEI was found to be comparable to or better than the previously reported effective uranophiles. In terms of the rates for the formation of the uranyl complex, however, apo(Sal) PEI was far superior to those other uranophiles. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2935–2942, 1997 相似文献
2.
James C. W. Chien Phillipe L. Bres 《Journal of polymer science. Part A, Polymer chemistry》1986,24(10):2483-2505
Polymerizations of ethylene by the MgCl2/ethylbenzoate/p-cresol/AlEt3 TiCl4-AlEt3/methyl-p-toluate (CW-catalyst) have been studied. The initially formed active site concentration, [Ti] has a maximum value of 50% of total titanium at 50°C and lower values at other temperatures. The Ti decays rapidly to Ti sites with conc. ca. 10 mol %/mol Ti. The rate constants for four chain transfer processes have been obtained at 50°C: for transfer with AlEt3, k = 2.1 × 10?4 s?1 and k = 4.8 × 10?4 s?1; for transfer with monomer, k = 3.6 × 10?3 (M s)?1 and K = 8.3 × 10?3 (M s)?1; for β-hydride transfer, k = 7.2 × 10?4 s?1 and k = 4.9 × 10?4 s?1; and transfer with hydrogen, k = 4.0 × 10?3 torr1/2 s? and k = 5.1 × 10?3 torr1/2 s?1. The rate constants for the termination assisted by hydrogen is k = 1.7 (M1/2 torr1/2 S)?1. If monomer is assisting termination as was observed for propylene polymerization, then k = 7.8 (M3/2 s)?1. Values of all the rate constants can be higher or lower at other temperatures. Detailed comparisons were made with the results of propylene polymerizations. There are more than four times as many Ti active sites for ethylene polymerization than there are for stereospecific polymerization of propylene; the difference is more than a factor of two for the Ti sites. Certain rate constants are nearly the same for both monomers while others are markedly different. Some of the differences can be explained by stereoelectronic effects. 相似文献
3.
Toshikazu Sakaguchi Kenichi Yumoto Yuichi Shida Masashi Shiotsuki Fumio Sanda Toshio Masuda 《Journal of polymer science. Part A, Polymer chemistry》2006,44(17):5028-5038
Poly(diphenylacetylene)s having various silyl groups are soluble in common solvents, from whose membranes poly(diphenylacetylene) membranes can be obtained by desilylation. The oxygen permeability coefficients of the desilylated polymers are quite different from one another (120–3300 barrers) irrespective of the same polymer structure. When bulkier silyl groups are removed, the oxygen permeability increases to larger extents. Poly[1-aryl-2-p-(trimethylsilyl)phenylacetylene]s are soluble in common solvents, and afford free-standing membranes. These Si-containing polymer membranes are desilylated to give the membranes of poly[1-aryl-2-phenylacetylene]s. Both of the starting and desilylated polymers show very high thermal stability and high gas permeability. 1-Phenyl-2-p-(t-butyldimethylsiloxy)phenylacetylene polymerizes into a high-molecular-weight polymer. This polymer is soluble in common organic solvents to provide a free-standing membrane. Desilylation of this membrane yields a poly(diphenylacetylene) having free hydroxyl groups, which is the first example of a highly polar group-carrying poly(diphenylacetylene). The P/P and P/P permselectivity ratios of poly(1-phenyl-2-p-hydroxylphenylacetylene) membrane are as large as 47.8 and 45.8, respectively, while keeping relatively high P of 110 barrers. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5028–5038, 2006 相似文献
4.
James C. W. Chien Tsunle Ang 《Journal of polymer science. Part A, Polymer chemistry》1986,24(9):2217-2230
Decene-1 was polymerized with the CW catalyst and fractionated by precipitation technique. Light-scattering and viscometric measurements on these fractions established the relationship [η] = 5.19 × 10?3 M . The unperturbed mean square end-to-end distance is (〈R〉/M)1/2 = (6.17 ± 0.34) × 10?9. Light-scattering data is consistent with a relatively stiff molecule with length of L = 1.75 × 10?5 cm for poly(decene-1) with MW = 397,000. Its mean square radius of gyration 〈R〉 is 2.79 × 10?11 cm.2 The ratio of L2/〈R〉 = 11 is close to the theoretical ratio of 12 for this kind of macromolecule. 相似文献
5.
Koji Ishizu Masataka Nunomura Takashi Fukutomi 《Journal of polymer science. Part A, Polymer chemistry》1987,25(4):1163-1175
Soluble microgels with several pendant vinyl groups were synthesised by radical copolymerization of methyl methacrylate (MMA) with p-divinyl benzene (p-DVB). The competitive reactions of intermolecular and intramolecular crosslinkings of these microgels were carried out at 40°C in the presence of 1-buten-3-ol as a degradative chain transfer agent. The rate constant of intermolecular crosslinking (k) was estimated by GPC (gel permeation chromatography) analysis on the polymer produced from intermolecular propagation between bimolecules. The k depended strongly on the internal structure of microgels. Network formation was discussd inclusive of informations for the rate constant of intramolecular crosslinking (k). 相似文献
6.
Norio Tsubokawa Yu Jian Yasuo Sone 《Journal of polymer science. Part A, Polymer chemistry》1988,26(10):2715-2724
The cationic ring-opening polymerization of oxepane was found to be initiated by carbon black having acylium perchlorate (CO+CIO) groups, which were introduced by the reaction of acyl chloride groups with silver perchlorate. It was confirmed that polyoxepane, i.e., poly(oxyhexamethylene), was propagated from CO+CIO groups on carbon black and effectively grafted on the surface. The rate of the polymerization and the percentage of grafting of poly(oxyhexamethylene) remarkably increased by the addition of epichlorohydrin (ECH) as a promoter: the percentage of grafting in the presence of ECH increased to about 100% with an increase in conversion. Furthermore, CO+CIO groups on carbon black have an ability to initiate the cationic ring-opening copolymerization of oxepane with ECH to give poly(oxepane-co-ECH) with various composition. The ring-opening copolymerization of oxepane with phthalic anhydride was also initiated by CO+CIO groups to give polyether ester, i.e., poly(hexamethylene phthalate) containing poly(oxyhexamethylene) sequence. In the copolymerization, polyether or polyether ester was effectively grafted from carbon black based on the propagation of these polymers from CO+CIO groups. 相似文献
7.
The electrosynthesis of polyparaphenylene films (PPP) by oxidation of benzene or biphenyl on a Pt electrode was studied in different organic media. Film formation was possible only if the solvent had acidic properties according to the Lewis concept, and if the water content of this medium was less than 5 × 10?2M. Addition of an excess of P2O5 or CuCl2 into the medium increased the acidity and improved the adherence and the homogeneity of the films considerably. PPP films were electroactive and conductive if the electrolysis was carried out in the presence of salts containing BF, SbF, PF anions; they were insulating with perchlorate salts. IR analysis of these polymers showed highly crosslinked structures and the chains were constituted of about 10 para coupled phenyl moieties. 相似文献
8.
The diffusion coefficient of oxygen in poly(2-hydroxyethyl methacrylate) has been explicitly measured using an optical technique based on fluorescence quenching. This measurement represents the first explicit determination of D in PHEMA. A diffusion coefficient of oxygen in PHEMA of 1.36 × 10?7 cm2/s at 20°C was obtained from this measurement. This value is shown to agree well with permeability data for PHEMA, the free volume theory of diffusion, and with values of D that have been explicitly measured in other methacrylate hydrogels. 相似文献
9.
Makiko Seno Mizuki Maeda Tsuneyuki Sato 《Journal of polymer science. Part A, Polymer chemistry》2000,38(14):2572-2578
The effect of fullerene (C60) on the radical polymerization of vinyl acetate (VAc) with dimethyl 2,2′‐azobisisobutyrate (MAIB) in benzene was investigated kinetically and by means of ESR. C60 was found to act as an effective inhibitor in the present polymerization. All C60 molecules used were incorporated into poly(VAc) during polymerization. The relationship of induction period and initiation rate reveals that a C60 molecule can trap 15 radicals formed in the polymerization system. The polymerization rate (Rp) after the induction period is given by Rp = k [MAIB]0.6 [VAc]2.0 (60 °C), which is similar to that observed in the absence of C60. Stable fullerene radical (C) was observed in the polymerization system by ESR. The C concentration increased with time and was then saturated. The saturation time well corresponds to the induction period observed in the polymerization. About 20% of C60 molecules added could survive as stable C. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2572–2578, 2000 相似文献
10.
V. Percec A. D. Asandei Q. Zheng 《Journal of polymer science. Part A, Polymer chemistry》2000,38(19):3631-3655
(S)‐1‐Cyano‐2‐methylpropyl‐4′‐{[4‐(8‐vinyloxyoctyloxy)benzoyl]oxy}biphenyl‐ 4‐carboxylate [ (S)‐11 ] and (R)‐1‐cyano‐2‐methylpropyl‐4′‐{[4‐(8‐vinyloxyoctyloxy)benzoyl]oxy}biphenyl‐4‐carboxylate [( R)‐11 ] enantiomers, both greater than 99% enantiomeric excess, and their corresponding homopolymers, poly[ (S)‐11 ] and poly[ (R)‐11 ], with well‐defined molecular weights and narrow molecular weight distributions were synthesized and characterized. The mesomorphic behaviors of (S)‐11 and poly[ (S)‐11 ] are identical to those of (R)‐11 and poly[ (R)‐11 ], respectively. Both (S)‐11 and (R)‐11 exhibit enantiotropic SA, S, and SX (unidentified smectic) phases. The corresponding homopolymers exhibit SA and S phases. The homopolymers with a degree of polymerization (DP) less than 6 also show a crystalline phase, whereas those with a DP greater than 10 exhibit a second SX phase. Phase diagrams were investigated for four different pairs of enantiomers, (S)‐11 /( R)‐11 , (S)‐11 /poly[ (R)‐11 ], and poly[ (S)‐11 ]/poly[ (R)‐11 ], with similar and dissimilar molecular weights. In all cases, the structural units derived from the enantiomeric components are miscible and, therefore, isomorphic in the SA and S phases over the entire range of enantiomeric composition. Chiral molecular recognition was observed in the SA and SX phases of the monomers but not in the SA phase of the polymers. In addition, a very unusual chiral molecular recognition effect was detected in the S phase of the monomers below their crystallization temperature and in the S phase of the polymers below their glass‐transition temperature. In the S phase of the monomers above the melting temperature and of the polymers above the glass‐transition temperature, nonideal solution behavior was observed. However, in the SA phase the monomer–polymer and polymer–polymer mixtures behave as an ideal solution. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3631–3655, 2000 相似文献
11.
Toshiyuki Hamano Toshio Masuda Toshinobu Higashimura 《Journal of polymer science. Part A, Polymer chemistry》1988,26(9):2603-2612
Copolymerization of 1-(trimethylsilyl)-1-propyne (MeC ≡ CSiMe3) with several aromatic and aliphatic disubstituted acetylenes (MeC ≡ CPh, n-BuC ≡ CPh, 2-octyne, and 4-octyne) were examined by using Ta and Nb catalysts. The TaCl5–Ph3Bi catalyst was effective in copolymerization with the aromatic acetylenes, whereas the NbCl5–Ph3Bi catalyst was preferable in copolymerization with the aliphatic acetylenes. The copolymerization products were not mixtures of homopolymers but copolymers. The relative reactivity of monomer tended to decrease with increasing steric effect of monomer: 2-octyne > MeC ≡ CSiMe3 > 4-octyne > MeC ≡ CPh > n-BuC ≡ CPh. The copolymers of MeC ≡ CSiMe3 with MeC ≡ CPh [copoly(TMSP/PP)s] had high molecular weight (M w > 1 × 106), and provided thermally stable tough films. With increasing MeC ≡ CPh content of copoly(TMSP/PP), the oxygen permeability coefficient (P) decreased, while the separation factor (P/P) increased. 相似文献
12.
Tsuyoshi Kiyotsukuri Naoto Tsutsumi Koichi Ayama Minoru Nagata 《Journal of polymer science. Part A, Polymer chemistry》1987,25(6):1591-1602
Silicon containing polyamides were prepared by melt polycondensation method with a 1,3-bis(3-aminopropyl)tetramethyldisiloxane and aliphatic dicarboxylic acids having various numbers of methylene groups. Only one endothermic peak appeared in the DTA curve of the quenched sample for polyamides having an even number of methylene groups in the repeating unit. Two endothermic peaks, however, appeared for the sample kept for a week in dry air at ambient temperature after quenching: the peak at the higher temperature is called peak I; and the peak at the lower one, peak II. By heat treatment at the higher temperature, peak II shifted to a higher temperature and increased its peak area, and peak I decreased its peak area while keeping its temperature unchanged. This behavior suggests the existence of two types of crystalline states. The peak temperature of peak I alternatively decreased with the increase of the number of methylene groups. The Young's modulus and the tensile strength increased with increase of annealing time at ambient temperature. The solubilities in various solvents, the resistance to alkali solution, and the thermal stability were acceptable. Both the permeation coefficient of oxygen (P) and the separation ratio (P/P) increased with the increase of silicon content in the repeating unit. 相似文献
13.
Katherine B. Aubrecht Karen Chang Marc A. Hillmyer William B. Tolman 《Journal of polymer science. Part A, Polymer chemistry》2001,39(2):284-293
In quest of new, single‐site catalysts for cyclic ester polymerizations, a series of mononuclear yttrium(III) complexes of N,N′‐bis(trimethylsilyl)benzamidinate ([LTMS]−) and hindered N,N′‐bis‐(2,6‐dialkylaryl)toluamidinates ([LEt]−, aryl = Et2C6H3, and [LiPr]−, aryl = iPr2C6H3) were synthesized and characterized by X‐ray diffraction: LY(μ‐Cl)2Li(TMEDA) ( 1 ), LY(OC6H2tBu2Me) ( 2 ), LY(OC6H3Me2)2Li(THF)4 ( 3 ), LY(μ‐OtBu)2Li(THF) ( 4 ), LiPrY[N(SiMe2H)2]2(THF) ( 5 ), LY(THF)(Cl)(μ‐Cl)Li(THF)3 ( 6 ), and LY[N(SiMe2H)2] ( 7 ). Coordination numbers ranging from five to seven were observed, and they appeared to be controlled by the steric bulk of the supporting amidinate and alkoxide, phenoxide, or amide coligands. Complexes 2 – 5 and 7 are active catalysts for the polymerization of D,L ‐lactide (e.g., with 2 and added benzyl alcohol, 1000 equiv of D,L ‐lactide were polymerized at room temperature in less than 1 h, with polydispersities less than 1.5). The neutral complexes 2 , 5 , and 7 were more effective than the anionic complexes 3 and 4 . In addition, the presence of the more hindered amidinate ligands [LEt]− and [LiPr]− on yttrium‐amides slowed the polymerizations ( 7 < 5 < Y[N(SiMe2H)2]3). © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 284–293, 2001 相似文献
14.
Gorkem Yilmaz Selim Beyazit Yusuf Yagci 《Journal of polymer science. Part A, Polymer chemistry》2011,49(7):1591-1596
The free radical promoted cationic polymerization cyclohexene oxide (CHO), was achieved by visible light irradiation (λinc = 430–490 nm) of methylene chloride solutions containing thioxanthone‐fluorene carboxylic acid (TX‐FLCOOH) or thioxanthone‐carbazole (TX‐C) and cationic salts, such as diphenyliodonium hexafluorophosphate (Ph2I+PF) or silver hexafluorophosphate (Ag+PF) in the presence of hydrogen donors. A feasible initiation mechanism involves the photogeneration of ketyl radicals by hydrogen abstraction in the first step. Subsequent oxidation of ketyl radicals by the oxidizing salts yields Bronsted acids capable of initiating the polymerization of CHO. In agreement with the proposed mechanism, the polymerization was completely inhibited by 2,2,6,6‐tetramethylpiperidinyl‐1‐oxy and di‐2,6‐di‐tert‐butylpyridine as radical and acid scavengers, respectively. Additionally polymerization efficiency was directly related to the reduction potential of the cationic salts, that is, Ag+PF (E = +0.8 V) was found to be more efficient than Ph2I+PF (E = ?0.2 V). In addition to CHO, vinyl monomers such as isobutyl vinyl ether and N‐vinyl carbazole, and a bisepoxide such as 3,4‐epoxycyclohexyl‐3′,4′‐epoxycyclohexene carboxylate, were polymerized in the presence of TX‐FLCOOH or TX‐C and iodonium salt with high efficiency. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献
15.
Yun‐Hi Kim Seong‐Kuk Ahn Hyung Sun Kim Soon‐Ki Kwon 《Journal of polymer science. Part A, Polymer chemistry》2002,40(23):4288-4296
Two new pyromellitic dianhydrides, 1,4‐bis(4′‐t‐butylphenyl) pyromellitic dianhydride and 1,4‐bis(4′‐trimethylsilylphenyl) pyromellitic dianhydride, were synthesized via Suzuki coupling, oxidation, and dehydration. A series of new organosoluble polyimides were prepared from the obtained pyromellitic dianhydride and various aromatic diamines by the conventional polycondensation reaction followed by chemical imidization, as well as high‐temperature, one‐step polymerization. The structures of the dianhydrides and polymers were identified with various spectroscopies. The inherent viscosities of the resulting polymers were 0.62–1.89 dL/g. The synthesized polyimides showed good solubility in various organic solvents such as N‐methyl‐2‐pyrrolidinone, N,N‐dimethylacetamide, and p‐chlorophenol. These polymers had glass‐transition temperatures of 230–260 °C. Thermogravimetric analysis showed that all the polymers were stable, with 10% weight losses recorded above 490 °C in nitrogen. The polyimide films had good mechanical properties and high oxygen permselectivity to nitrogen. The oxygen permeability coefficient (P) and the permselectivity of oxygen to nitrogen (P/P) of the films were 13–56 barrer and 3.7–5.5, respectively. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4288–4296, 2002 相似文献
16.
Dan Chen Wei Lu Ganhong Du Liming Jiang Jun Ling Zhiquan Shen 《Journal of polymer science. Part A, Polymer chemistry》2012,50(20):4191-4197
A new kind of polymeric chemosensor containing chiral naphthaldimine moiety in the side chain was synthesized by the reversible addition‐fragmentation chain transfer polymerization of N‐{[2‐(4‐vinylbenzyloxy)‐1‐naphthyl]‐methylene}‐(S)‐2‐phenylglycinol (VNP). The resulting polymers (PVNP) showed high selectivity for hydrogen sulfate relative to other anions including F?, Cl?, Br?, H2PO, CH3CO, and NO in tetrahydrofuran (THF) solution as judged from UV?vis, fluorescence, and circular dichroism spectrophotometric titrations. Compared with its monomer, the polymer has proven to be more attractive for detection of HSO in terms of sensitivity and reproducibility. Upon addition of the anion it gives remarkable spectral responses concomitant with detectable color change from colorless to pale yellow. Furthermore, the HSO‐induced CD or fluorescence signal can be totally reversed with addition of base and eventually recovered the initial state, leading to a reproducible molecular switch with two distinguished “on” and “off” states. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
17.
18.
James C. W. Chien Zdenek Salajka 《Journal of polymer science. Part A, Polymer chemistry》1991,29(9):1253-1263
Syndiospecific polymerization of styrene was catalyzed by monocyclopentadienyltributoxy titanium/methylaluminoxane [CpTi (OBu)3/MAO]. The atactic and syndiotactic polystyrenes were separated by extracting the former with refluxing 2-butanone. The activity and syndiospecificity of the catalyst were affected by changes in catalyst concentration and composition, polymerization temperature, and monomer concentration. Extremely high activity of 5 × 107 g PS (mol Ti mol S h)?1 with 99% yield of the syndiotactic product were achieved. The concentration of active species, [C*], has been determined by radiolabeling. The amount of the syndiospecific and nonspecific catalytic species, [C] and [C] respectively, correspond to 79 and 13% of the CpTi(OBu)3. The rate constants of propagation for C and C at 45°C are 10.8 and 2.0 (M s)?1, respectively, the corresponding rate constants for chain transfer to MAO are 6.2 × 10?4 and 4.3 × 10?4s?1. There was no deactivation of the catalytic species during a batch polymerization. The rate constant of chain transfer with monomer is 6.7 × 10?2 (M s)?1; the spontaneous β-hydride transfer rate constant is 4.7 × 10?2 s?1. The polymerization activity and stereospecificity of the catalyst are highest at 45°C, both decreasing with either higher or lower temperature. The stereoregular polymer have broad MW distributions, M?w/M?n = 2.8–5.7, and up to three crystalline modifications. The Tm of the s-PS polymerized at 0–90°C decreased from 261.8 to 241°C indicating thermally activated monomer insertion errors. The styrene polymerization behaviors were essentially insensitive to the dielectric constant of the medium. 相似文献
19.
Takashi Nozaki James C. W. Chien 《Journal of polymer science. Part A, Polymer chemistry》1991,29(12):1807-1817
Solvay type S –VCl3 catalyst has 7% of catalytically active vanadium sites ([C*]) with kp (rate constant of propagation) = 31 (M s)?1 for ethylene polymerization. Addition of a comonomer, propylene of 4-methylpentene-1 (4-MP) significantly raised the ethylene polymerization activity. S –VCI3 catalyst has very small amounts of catalytically active vanadium for propylene polymerizations: [C] = 0.19% with kp,i = 857 (M s)?1 and [C] = 0.45% with kp,a = 23 (M s)?1 for isospecific and nonspecific sites, respectively. Addition of a conomer, ethylene or 4-MP. lowered the propylene polymerization activity. S –VCI3 is more easily reduced to the divalent ion by AIR3 than S –TiCl3. Methyl-p-toluate moderates the reducting power of AIR3; it increase the productivity and stereoselectivity of the S –YiCl3 catalyst, VCI3 supported on MgCl2 (CW–V catalyst) has enhanced rate constant of propylene polymerization but has the opposite effects on the S –TiCl3 Catalyst. VCI3 supported on MgCl2 (CW–V catalyst) has enhances rate constant of propylene polymerization but only a minute fraction of the supported vanadiums are catalytically active: [C] = 0.019% and kp,i = 1580 (Ms)?1, [C] = 0.057% and kp,i = 58 (M s)?1. This is compared with far greater number of catalytically active titanium sites in the TiCl3 supported on MgCl2 catalyst: [C] = 6% and kp,i = 200 (M s)?1, [C] = 6% and kp,a = 16(M s)?1. Therefore, both the S –VCI3 and CW–V catalysts are highly stereoselective but low in efficiency with respect to the utilization of the vanadium ion in the catalysis. 相似文献
20.
Thermal Behaviour and Crystal Structure of YAl3Cl12 We determined the thermodynamic data of YAl3Cl12 ΔH = ?739.9 ± 3 kcal/mol and S = 136.1 ± 4 cal/K · mol by total pressure measurements and ΔH = ?739.1 ± 1.6 kcal/mol by solution calorimetry. Using DTA-investigations we established the phase diagram in the system AlCl3–YCl3. The crystal structure was refined on the basis of single crystal data (P31 12; Z = 3; a = 1 046.8(2); c = 1 562.3(3) pm). 相似文献