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  • 1995-1999  (3,277)
  • 1950-1954
  • 1997  (3,277)
  • Polymer and Materials Science  (3,277)
  • Nuclear reactions
  • 101
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 3299-3304 
    ISSN: 0887-624X
    Keywords: acyclic diene polycondensation (ADP) ; diallyldimethylsilane ; diallyldiphenylsilane ; rhodium and ruthenium catalysts ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Acyclic diene polycondensation (ADP) of diallyldiorganosilanes (CH2=CHCH2)2SiR2 (where R = Me, Ph), in the presence of various ruthenium and rhodium complexes, led predominantly to linear silylene-propenylene oligomers. Ruthenium catalysts (e.g. RuCl2(PPh3)3, RuHCl(CO)(PPh3)3, and RuCl(SiMe3)(CO)(PPh3)2) were found to be more efficient than the rhodium ones. The reaction proceeds via preliminary catalytic isomerization of allylsilane to silyl-1-propenes followed by their oligococondensation. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3299-3304, 1997
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  • 102
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 3327-3329 
    ISSN: 0887-624X
    Keywords: saccharin ; anaerobic adhesives ; polarography ; cyclic voltammetry ; copper(II) ions ; iron(III) ions ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract.
    Additional Material: 2 Ill.
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  • 103
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 3331-3333 
    ISSN: 0887-624X
    Keywords: oxidoreductase ; horseradish peroxidase ; free-radical polymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract.
    Additional Material: 1 Ill.
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  • 104
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 3335-3338 
    ISSN: 0887-624X
    Keywords: polyisoimide powder ; suspension polymerization poly(amic acid) suspension ; poly(pyromellitimide) ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract.
    Additional Material: 2 Ill.
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  • 105
    ISSN: 0887-624X
    Keywords: aliphatic-aromatic ; polyamide ; catalyzed reactivity ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The relationship between the structure and reactivity of aliphatic-aromatic polyamides in the presence of CuI in an inert atmosphere was probed by reacting a family of benzamides with varying degrees of substitution on the amide nitrogen. Experiments with benzamide, N-methylbenzamide, N,N-dimethylbenzamide, N-hexylbenzamide, and N,N-dihexylbenzamide allowed comparison of primary, secondary, and tertiary benzamides and identification of the degradation pathways influenced by CuI. The presence of copper iodide enhanced the reactivity of all of the benzamides. Loadings as low as 0.5% led to higher conversion and increased recoverable product yields. Reaction path selectivities were also affected by the addition of CuI. The selectivity to benzene increased for all reactants, and the pathway leading to N-alkylation increased for the reaction of NHB. In all, these results revealed three major reaction pathways influenced by CuI: (1) N—C bond cleavage; (2) N—H bond cleavage; and (3) removal of the amide functional group from the aromatic ring. Kinetic results and visible color changes suggested a direct interaction of CuI with the reactant benzamide. Three electron-rich sites on the reactant benzamide, namely, the lone pairs on the carbonyl oxygen, the lone pair on the amide nitrogen and the aromatic ring, are likely sites of interaction of Cu+. Models invoking the subsequent reaction of complexes formed from Cu+ ion interaction at each of these sites account for the observed products well. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3305-3322, 1997
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  • 106
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 3339-3339 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract.
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  • 107
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 3341-3347 
    ISSN: 0887-624X
    Keywords: styrene polymerization ; p-chlorostyrene polymerization ; p-methylstyrene polymerization ; living carbocationic ; common ion effect ; kinetics ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of common anion producing salt, tetrabutylammonium chloride (n-Bu4NCl), on the livingness and kinetics of styrene (St), p-chlorostyrene (pClSt), and p-methylstyrene (pMeSt) polymerization initiated by the 2-chloro-2,4,4-trimethylpentane (TMPCl)/TiCl4 system has been investigated. Uncontrolled (conventional) carbocationic polymerization of St and p MeSt can be converted to living polymerization by the use of n-Bu4NCl. Under similar conditions the polymerization of p ClSt is living even in the absence of n-Bu4NCl, although the molecular weight distribution (MWD) of the polymer becomes narrower in the presence of this salt. The apparent rates of polymerizations decrease in the presence of n-Bu4NCl in proportion with the concentration of the salt. The rate of living polymerization of p ClSt is noticeably lower than that of St, while that of p MeSt is higher. The apparent rate constants, kpA, of these polymerizations have been determined, and the effects of the electron donating p Me- and electron withdrawing p Cl-substituents relative to the rate of St polymerization have been analyzed. [For part LXI, see J. Si and J. P. Kennedy, Polym. Bull., 33, 651 (1994)]. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3341-3347, 1997
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  • 108
    Electronic Resource
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 3359-3363 
    ISSN: 0887-624X
    Keywords: hydrazinodeoxycellulose ; adsorption ; heavy metal ions ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Nitrogen-containing cellulose derivatives hydrazinodeoxycellulose (HDC) and carboxyalkyl hydrazinodeoxycelluloses (α- and β-CAHDCs) were prepared from 6-chlorodeoxycellulose (CDC). Their adsorption of divalent transition metal ions was determined from dilute aqueous solutions and compared with that of aminoalkyl celluloses (AmACs) reported previously. HDC scarcely adsorbs metal ions in the pH range of 1-2, whereas α- and β-CAHDCs adsorb metal ions in this pH range. However, the adsorption of metal ions on HDC increases rapidly with increasing pH and HDC more effectively adsorbs metal ions than α- and β-CAHDCs in weakly acidic conditions. The ability to adsorb Cu2+ ions was in the order of AmAC (carbon number in the diamine moiety m = 2) 〉 HDC 〉 α-CAHDC 〉 β-CAHDC in the weakly acidic region. These adsorbents selectively adsorb Cu2+ ions from the solutions containing other metal ions such as Mn2+, Co2+, and Ni2+, and the Irving-Williams series is obeyed in these adsorbent/metal ion systems. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3359-3363, 1997
    Additional Material: 3 Ill.
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  • 109
    ISSN: 0887-624X
    Keywords: N-(2-hydroxypropyl)methacrylamide ; methyl methacrylate ; 2-(methacryloyloxy)ethyl phosphorylcholine ; emulsion polymerization ; thermosensitive polymer microspheres ; hydrogel ; protein adsorption ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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
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  • 110
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 3365-3376 
    ISSN: 0887-624X
    Keywords: cyclopolymerization ; ferrocenophane ; cyclophane polymer ; poly(vinylferrocene) ; non-conjugated conducting polymer ; polymer electrochemistry ; redox active polymer ; metallocene polymer ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Radical cyclopolymerization of 3-phenyl[5]ferrocenophane-1,5-dimethylene (2) and copolymerization with styrene gave polymers (3 and 4) with [3]ferrocenophane moieties pendant to the backbone. Cyclic voltammetry (CV) on polymer 3 in CH2Cl2 showed two oxidation waves at -0.13 and +0.05 V (versus ferrocene/ferrocenium) and CV on copolymer 4 showed one oxidation potential at -0.03 V. CV on 3 in dimethylacetamide showed only one oxidation potential at -0.10 V. Near-IR spectroscopy of partially oxidized 3 showed a broad intervalence band at ca. 2000 nm, indicative of low-energy barriers to electron hopping. Conductivity measurements on 3 and poly(vinylferrocene) (PVFc) oxidatively doped with iodine vapors under an argon atmosphere showed a maximum conductivity ca. 5 × 10-5 S/cm before the samples cracked, while 4 exhibited a maximum conductivity of 1.6 × 10-6 S/cm. On iodine doping under ambient conditions, polymers 3, 4, and PVFc showed maximum conductivities of 7.6 × 10-4, 9.5 × 10-5, and 5.5 × 10-5 S/cm, respectively. Conductivity measurement were also performed on samples of 3+BF4- with oxidation levels ranging from 8 to 56%. Conductivities of these samples ranged from ca. 10-10 to 10-9 S/cm under vacuum and ca. 10-6 S/cm under ambient conditions, indicating that atmospheric moisture has a strong effect on the conductivity. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3365-3376, 1997
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  • 111
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 3377-3384 
    ISSN: 0887-624X
    Keywords: N-vinylalkylamide ; N-vinylisobutyramide ; thermosensitive hydrogels ; swelling transition ; free radical polymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A novel thermosensitive poly(N-vinylisobutyramide)(polyNVIBA) hydrogel was prepared by the copolymerization of N-vinylisobutyramide (NVIBA) with butylene-bis-NVA(B-BNVA) as a crosslinker in a high yield. The swelling transition behavior was examined in comparison with poly(N-isopropylacrylamide)(polyNIPAAm) hydrogel. The resulting polyNVIBA hydrogel clearly showed a swelling transion in water at ca. 41°C. To control the transition temperature (Tt) of the gel, crosslinked copolymers of NVIBA and N-vinylacetamide (NVA) were prepared and compared with copolymers of N-isopropylacrylamide(NIPAAm) and NVA. The incorporation of NVA led to a higher swelling transition temperature. Tt of poly(NVIBA-co-NVA) gels was almost the same as those in water-soluble poly(NVIBA-co-NVA). The responses for a swelling transition of polyNVIBA and poly(NVIBA-co-NVA) gels were sharp in comparison to polyNIPAAm gels. PolyNVIBA and poly(NVIBA-co-NVA) gels desorbed 98% of water above Tt. The characteristic and the mechanism of the phase transition on the hydrogels were discussed. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3377-3384, 1997
    Additional Material: 6 Ill.
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  • 112
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 3393-3401 
    ISSN: 0887-624X
    Keywords: gel permeation chromatography ; star polymer ; block copolymer ; butadiene ; styrene ; silicon tetrachloride ; light scattering ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A novel GPC calculation method has been developed for characterizing star-shaped styrene-butadiene block copolymers (SBS). This method enables us to determine the degree of branching (number of arms per molecule) of the synthesized polymer without the need of a priori measurement of the true molecular weights of the SBS star polymer and its linear polymeric arm. To illustrate the simplicity of this method, nearly monodispersed three-arm and four-arm model star polymers have been purposely synthesized by linking living diblock polymeric arms of the polystyrene-block-polybutadiene type with silicon tetrachloride as the multifunctional linking agent. The good agreement between the degree of branching calculated from the GPC chromatogram and that actually measured by MALL (multiple angle laser light scattering) has corroborated the validity of the calculation method. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3393-3401, 1997
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  • 113
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 3403-3408 
    ISSN: 0887-624X
    Keywords: star-shaped ; poly(THF) ; ion-coupling ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The prepoly(tetrahydrofuran) [poly(THF)] capped with hydroxyl and tetrahydrothiophenium groups was prepared using tetrahydrothiophene to terminate the living cationic polymerization of THF initiated by BF3·OEt2 and epichlorohydrin (ECH) at low conversion. Well-defined star-shaped poly(THF) polyols were synthesized by an ion-coupling reaction of the prepoly(THF) with tri- or tetrafunctional benzenecarboxylates, respectively, and this process proceeded by precipitation when the solution of the prepolymer in THF was added to an aqueous solution containing an excess of the corresponding coupling reagent. GPC studies showed that all of the carboxylate groups of every coupling reagent molecule took part in the ion-coupling reaction simultanously. This was confirmed by IR spectra. Almost all of the prepolymers were coupled to form star polymers after repeating the precipitation four times. 1H-NMR illustrated that both the star-shaped polymers and the prepolymers contained primary and secondary hydroxyl end groups. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3403-3408, 1997
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  • 114
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 3385-3391 
    ISSN: 0887-624X
    Keywords: 4,4′-(2,3-naphthalenedioxy)dibenzoic acid ; polyamides ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A novel aromatic dicarboxylic acid monomer, 4,4′-(2,3-naphthalenedioxy)-dibenzoic acid (3), was prepared by the fluorodisplacement reaction of p-fluorobenzonitrile with 2,3-dihydroxynaphthalene in N,N-dimethylformamide (DMF) in the presence of potassium carbonate followed by alkaline hydrolysis of the intermediate dinitrile. A series of novel aromatic polyamides containing ortho-linked aromatic units in the main chain were synthesized by the direct polycondensation of diacid 3 and a variety of aromatic diamines using triphenyl phosphite and pyridine as condensing agents in the N-methyl-2-pyrrolidone (NMP) solution containing dissolved calcium chloride. The resulting polyamides had inherent viscosities higher than 0.74 and up to 2.10 dL/g. All of these polyamides were soluble in polar solvents, such as NMP, DMF, N,N-dimethylacetamide (DMAc), and dimethyl sulfoxide. Transparent, flexible, and tough films could be cast from their DMAc or NMP solutions. The solvent-cast films had high tensile strengths and moduli. Extensions to break were relatively low, except for the polymers derived from 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane and 3,4′-oxydianiline, which had elongations of 82 and 62%, respectively. Except for the polyamide based on p-phenylenediamine, all the other polyamides were amorphous in nature. All the polymers are thermally stable to temperatures in excess of 450°C in either air or nitrogen atmosphere. The polymers exhibited glass transition temperatures ranging from 183 to 260°C and decomposition temperatures (10% weight loss) ranging from 462-523°C in air and 468-530°C in nitrogen. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3385-3391, 1997
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  • 115
    ISSN: 0887-624X
    Keywords: polyesters ; bulk copolyesterification ; o-phthalic anhydride ; oleic acid ; trimethylolpropane ; 13C-NMR spectroscopy ; 1H-NMR spectroscopy ; structural analysis ; trimethylolpropane esterification degree ; volumetry ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A detailed structural analysis of the copolyesterification in bulk without any external catalyst at 160°C between o-phthalic anhydride (P), oleic acid (O), and trimethylolpropane (T) with a mol ratio ([—COOH]/[—OH]) = 0.70 has been carried out by high resolution 13C nuclear magnetic resonance (13C-NMR) (DMSO-d6 and CDCl3 solutions), 1H nuclear magnetic resonance (1H-NMR) (CDCl3 solution), and by volumetry. The use of CDCl3 as NMR solvent has allow us to identify several signals that have been assigned to trimethylolpropane monoesters with different esterification degrees in the o-phthalate residue. Identically, we have detected signals assignable to monoesters at the chain ends in structures with different chain lengths. These monoesterified structures have been also confirmed by analyzing samples modified by the diazomethane addition. These modified samples have been also used to determine free acid groups as their methoxylic derivatives by 1H-NMR in CDCl3 solution. We have not observed any detectable signs of gelation nor products produced by secondary reactions. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3409-3429, 1997
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  • 116
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 3431-3440 
    ISSN: 0887-624X
    Keywords: lactide ; polylactide ; polymerization ; mechanism ; stannous octoate ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ring-opening polymerization of lactide cyclic monomers in the bulk in the presence of tin(II) 2-ethylhexanoate (stannous octoate or SnOct2) was reexamined under conditions allowing for the end group characterization of growing chains by high-resolution 1H-NMR. Data collected for low values of the monomer/initiator (M/I) ratio showed that the DL-lactide ring was opened to yield lactyl octoate-terminated short chains. A cationic-type mechanism involving co-initiation by octanoic acid was proposed to account for experimental findings. The formation of a side product, hydroxytin(II) lactate (HTL), was found which appeared able to initiate lactide polymerization and to yield a high molecular weight PLA50 polymer. However the polymerization with stannous octoate was faster than the HTL one. Anyhow, data suggested that both SnOct2 and HTL are likely to act simultaneously as initiators during the polymerization of lactides in the presence of SnOct2. A complete reaction scheme was proposed to account for the presence of the various compounds likely to be formed under these conditions. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3431-3440, 1997
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  • 117
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 3441-3449 
    ISSN: 0887-624X
    Keywords: phase separation ; metathesis polymerization ; ADMET ; block polymers ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Segmented oligomers consisting of polyoctenylene hard segments and unsaturated polytetrahydrofuran soft segments were prepared using acyclic diene metathesis (ADMET) copolymerization techniques. These are the first such segmented materials prepared via metathesis chemistry. Two different molecular weight α,ω-poly(tetrahydrofuran)diene soft segment monomers of the structure [CH2=CH(CH2)4[O(CH2)4]-nO(CH2)4CH=CH2] (1) were synthesized by the cationic living polymerization of tetrahydrofuran (THF). Trifluoromethanesulfonic anhydride, (CF3SO2)2O (triflic anhydride) (2), was employed as the initiator, followed by in situ bis-functionalization with 5-hexen-1-ol, [CH2=CH(CH2)4OH] (3), to yield soft segment dienes with vinyl end groups. The functionality of these soft segment monomers was approximately 1.9. These telechelic monomers possessed sufficient functionality to be homopolymerized or copolymerized with 1,9-decadiene (4) to generate well phase separated, segmented oligomers exhibiting hard segment/soft segment thermal behavior. The segmented copolymers were characterized by 1H-NMR, 13C-NMR, and IR spectroscopy, elemental analysis, and TGA and DSC analysis. Average molecular weights were determined by gel permeation chromatography (GPC) and end-group analysis. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3441-3449, 1997
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  • 118
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 3451-3456 
    ISSN: 0887-624X
    Keywords: PBO ; rigid-rod polymer ; multidimensional polymer ; thermooxiative stability ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two- and three-dimensional rigid-rod polymers containing benzobisoxazole structures were prepared through the polycondensation in polyphosphoric acid of 4-[5-amino-6-hydroxybenzoxazol-2-yl]benzoic acid (ABA) with trimesic acid and 1,3,5,7-tetrakis(4-carboxylatophenyl)adamantane, respectively. Thermal properties of the polymers were determined by differential scanning calorimetry, thermogravimetric/mass spectral analysis, and isothermal aging studies. The multidimensional polymers exhibited lower solution viscosities and lower thermooxidative stabilities than the one-dimensional polymer generated by the homopolymerization of ABA under identical reaction conditions. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3451-3456, 1997
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  • 119
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 3457-3466 
    ISSN: 0887-624X
    Keywords: PBO ; rigid-rod polymer ; multidimensional polymer ; compressive strength ; fiber morphology ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A high-torque rheometer was used to facilitate the polycondensation of 4-[5-amino-6-hydroxybenzoxazol-2-yl]benzoic acid (ABA) with trimesic acid and 1,3,5,7-tetrakis(4-carboxylatophenyl)adamantane to yield two- and three-dimensional benzobisoxazole polymers, respectively. Although the resultant polymer dopes exhibited improved homogeneity compared to polymer dopes previously prepared in glassware, improved polymer solution viscosities were not achieved. Fibers spun from the two- and three-dimensional polymers did not show a significant increase in compressive strength compared to fibers of the linear or one-dimensional benzobisoxazole polymer derived from the homopolymerization of ABA. Morphological studies of the polymer fibers and films by wide-angle X-ray scattering and scanning electron microscopy strongly indicated more lateral disorder and a more isotropic character for the three-dimensional structures compared to the one-dimensional structures. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3457-3466, 1997
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  • 120
    ISSN: 0887-624X
    Keywords: 1H-NMR ; 13C-NMR ; ethyl α-benzoyloxymethylacrylate ; methyl methacrylate ; copolymers ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Proton and Carbon-13 NMR spectra of ethyl α-benzoyloxymethylacrylate (E)-methyl methacrylate (M) copolymers were analyzed in terms of sequence distribution and stereoregularity of monomer units. The copolymers were prepared by free radical polymerization in benzene at 50°C. The methoxy region of the M proton signal resonance was found to be sensitive to the copolymer composition for M-centred sequences. The carbon-13 NMR spectra of the EM copolymers, in particular the carbonyl signal resonances of carbomethoxy and carboethoxy groups, are discussed in terms of M- and E-centred configurational sequences. The experimental values were in excellent agreement with those calculated taken into account the terminal copolymerization model and Bernoullian distribution of stereoregularity with the statistical parameters determined from reactivity ratios rE = 0.32 and rM = 1.34 and the coisotacticity parameters σMM = 0.22, σEE = 0.70, and σME = σEM = σ = 0.30. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3483-3493, 1997
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  • 121
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 3467-3482 
    ISSN: 0887-624X
    Keywords: surface modification ; photograft polymerization ; PTFE ; benzophenone ; diphenyl ketyl radical anion ; acrylic acid ; acrylamide ; PEG monoacrylate ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The objective of this study was to explore and optimize the photograft polymerization of acrylate monomers and macromonomers upon premodified poly(tetrafluoroethylene) (PTFE) substrates, with a view toward applying these grafted materials as biomaterials. PTFE films were photochemically reduced by exposure to short wavelength ultraviolet (UV) light in the presence of the reducing agents, i.e., diphenyl ketyl radical anion, generated from a solution of benzophenone and sodium hydride in dimethylformamide (Noh et al., J. Polym. Sci. A, Polym. Chem., 35, 1499 (1997)). The photochemically reduced PTFE films were subsequently modified by photograft polymerization of acrylic acid, acrylamide, and poly(ethylene glycol) monoacrylate (PEG-Ac) by employing long wavelength UV irradiation with benzil dimethyl ketal as an initiator. The photochemically reduced PTFE films were good substrates for photograft polymerization, leading to surfaces with chemical compositions close to those of the respective homopolymers as determined by electron spectroscopy for chemical analysis. Photograft polymerization of PEG-Ac on the photochemically reduced surface was also explored with different concentrations (1, 2, 4, 6, and 8%; v/v) and molecular weights (200, 400, 1000, and 2000 g/mol) of PEG-Ac, different durations (5, 10, and 20 min) of long wavelength UV irradiation, and different concentrations (0.1, 0.2, 0.4, and 0.8%; v/v) of benzil dimethyl ketal. Higher concentrations and lower molecular weights of PEG-Ac generally led to more extensive photograft polymerization, whereas the concentration of benzil dimethyl ketal and duration of UV irradiation did not substantially influence the extent of photograft polymerization. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3467-3482, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 3517-3525 
    ISSN: 0887-624X
    Keywords: peroxide ; vinylsilane ; grafting ; polymers ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The peroxide-initiated grafting of vinyltrimethoxysilane (VTMS) onto dodecane has been examined as a model for grafting onto polyethylene. At 160°C, 2% v/v VTMS and 0.08% v/v initiator, the monomer was grafted onto dodecane with a 59% conversion and an average of 2.37 VTMS grafts per dodecane. These values were obtained by separation of the grafted material through reduced pressure distillation then characterization with FTIR and NMR spectroscopy, mass spectrometry, and gel permeation chromatography. NMR studies strongly indicate that the multiple grafts consist predominantly of multiple single grafts rather than homopolymer grafts. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3517-3525, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 3527-3536 
    ISSN: 0887-624X
    Keywords: poly(carboxybetaine) ; cationic polyelectrolyte ; NMR spectra ; solubility ; moisture regain properties ; solution property ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two types of carboxybetaines and their corresponding cationic monomers and polymers are synthesized in this study. Comparing the chemical shifts of the methylene groups in the cationic monomers and carboxybetaines in both 1H- and 13C-NMR spectra reveal that the respective methylene groups are clearly distinguished from their chemical shifts in 1H- and 13C-NMR spectra. The solubilities, moisture regain properties, and solution properties of the poly(carboxybetaine)s and cationic polymers are investigated in relation to their molecular structures. Because the cationic polymers were ionized in an aqueous solution, the cationic polymers were more soluble than the poly(carboxybetaine). For the various functional groups of poly(carboxybetaine)s and cationic polymers, the order of tendency for moisture regain is —COO— 〉 —CONH—. Results obtained from the reduced viscosity for cationic poly(TMMPAMS) are reversed from that for zwitterionic poly(DMAEAPL). © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3527-3536, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 3507-3515 
    ISSN: 0887-624X
    Keywords: thermoplastic elastomers ; polyglycidylmethacrylate ; polybutadiene ; block copolymers ; anionic polymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New block copolymers of the ABA type, where B stands for polybutadiene (PBD) and A for polyglycidylmethacrylate(PGMA), poly(methylmethacrylate(MMA)-co-GMA) and PMMA-b-PGMA, respectively, have been successfully synthesized by using the diadduct of tert-butyllithium (tert-BuLi) to meta-diisopropenylbenzene (m-DIB) as a difunctional initiator. The PBD midblock has been synthesized in a cyclohexane/diethylether (100/6, v/v) mixture at room temperature, whereas the methacrylate outer blocks have been synthesized in a cyclohexane/diethylether/THF (100/6/150, v/v/v) mixture at -78°C. Block copolymers of a very narrow molecular weight distribution (1.10) have been analyzed by differential scanning calorimetry (DSC), transmission electron microscopy (TEM), and tensile testing. These materials are phase separated and can exhibit tensile strength up to 22 MPa together with very high elongation at break (1500%). © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3507-3515, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 3495-3506 
    ISSN: 0887-624X
    Keywords: segmented copolymers ; cycloaliphatic polyesters ; PDMS ; melt polymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: High molecular weight poly(dimethylsiloxane)/semicrystalline cycloaliphatic polyester segmented copolymers based on dimethyl-1,4-cyclohexane dicarboxylate were prepared and characterized. The copolymers were synthesized using a high trans content isomer that afforded semicrystalline morphologies. Aminopropyl-terminated poly(dimethylsiloxane) (PDMS) oligomers of controlled molecular weight were synthesized, end capped with excess diester to form a diester-terminated oligomer, and incorporated via melt transesterification step reaction copolymerization. The molecular weight of the polysiloxane and chemical composition of the copolymer were systematically varied. The polysiloxane segment was efficiently incorporated into the copolymers via an amide link and its structure was unaffected by low concentrations of titanate transesterification catalyst, as shown by control melt experiments. The homopolymer and copolymers were characterized by solution, thermal, mechanical, and surface techniques. The segmented copolymers were microphase separated as determined by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and by transmission electron microscopy (TEM). It was demonstrated that relatively short poly(dimethylsiloxane) segment lengths and compositions were required to maintain single phase melt polymerization conditions. This was, in fact, the key to the successful preparation of these materials. The copolymers derived from short poly(dimethylsiloxane) segments demonstrated good mechanical properties, melt viscosities representative of single phase polymer melts, and were easily compression molded into films. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3495-3506, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 3537-3541 
    ISSN: 0887-624X
    Keywords: radical polymerization ; captodative olefin ; methyl α-trifluoroacetoxy-acrylate ; alternating copolymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Radical homo- and copolymerizations of methyl α-trifluoroacetoxyacrylate (MTFAA) are studied by using azo initiators at 40 and 60°C. The rate of the homopolymerization of MTFAA was lower than that of methyl α-acetoxyacrylate. Monomer reactivity ratios (r), and Q and e values were estimated to be r1 = 0.03, r2 = 0.27, Q1 = 0.65, and e1 = 1.38 from the copolymerization of MTFAA (M1) and styrene (M2) at 60°C. Preferential crosspropagation was observed in particular in the copolymerization of MTFAA and α-methylstyrene. The influence of replacing the hydrogens of the acetoxy moiety of the acyloxyacrylate with the fluorines upon the copolymerization reactivity is discussed on the basis of the 13C-NMR chemical shift of various acyloxyacrylates. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3537-3541, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 3553-3559 
    ISSN: 0887-624X
    Keywords: hyaluronic acid ; crosslinking ; glutaraldehyde ; biodegradation ; IR spectra ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Hyaluronic acid (HA) was chemically crosslinked with glutaraldehyde (GA) to produce water-insoluble films having low water contents when brought into contact with water. The crosslinking reaction was performed using uncrosslinked HA films in acetone-water mixtures. This method could produce water-insoluble HA films with water contents as low as 60 wt % when subjected to swelling with phosphate-buffered saline of pH 7.4 at 37°C. This 60 wt % water content was lower than any values for HA ever reported. There was an optimal HCl concentration around 0.01N for the HA crosslinking with GA in acetone - water mixtures. To get information on the crosslinking mechanism, alginic acid, which possesses hydroxyl and carboxyl groups in one molecule, similar to HA, and poly(vinyl alcohol) (PVA) and amylopectin, which possess only hydroxyl groups, were subjected to crosslinking with GA. PVA and amylopectin were also found to become water-insoluble after reaction with GA. On the basis of the infrared spectra of these crosslinked films, it was concluded that intermolecular formation of hemiacetal bonds with GA between the hydroxyl groups belonging to different HA molecules led to crosslinking. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3553-3559, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 3575-3583 
    ISSN: 0887-624X
    Keywords: latexes ; dispersion polymerization ; styrene ; PEO macromonomer ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The particle sizes and their size distributions of latexes from the dispersion polymerization of styrene using a small amount of ω-methoxy poly(ethylene oxide)n undecyl-α-methacrylate macromonomer (PEO-R-MA-40) as a polymerizable stabilizer in ethanol-water media have been studied. Monodisperse or/and nearly monodisperse latex particles from 0.1 to 1 μm in diameter were readily obtained. The diameter of latex particles follows the relationship Dvad ∝ θ0.33 [PEO-R-MA-40]-0.60 [styrene]01.02 [AIBN]o-0.09, where θ is the fractional conversion of styrene. Except for the styrene concentration dependency, this relationship is in excellent agreement with the model developed by Paine11 and modified by Kawaguchi et al.13 When the surface composition of the grafted PEO macromonomer on the latex particles exceeded 16% as analyzed by X-ray photoelectron spectroscopy (XPS), the particles were nearly monodisperse. In terms of polymerization, this occurred around 18% conversion of styrene. Beyond this critical state of polymerization, the latex particles grew bigger with more PEO macromonomer-styrene copolymers situated on the particle surface. The effect of various factors on the particle size distribution is also discussed. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3575-3583, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 3585-3593 
    ISSN: 0887-624X
    Keywords: poly(methylstyrene) ; catalytic oxidation ; functional latex particles ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Surface-functionalized cationic poly(methylstyrene) (PMS) latex particles containing aldehyde and carboxylic acid groups were successfully achieved via an emulsion polymerization of 3(4)-methylstyrene in the presence of cetyltrimethylammonium bromide, followed by an in-situ oxidation catalyzed by copper chloride and tert-butyl hydroperoxide (t-BuOOH). Factors such as the type of metal catalyst, oxidant, and their concentration strongly affected the rate of oxidation. Step addition of t-BuOOH resulted in both a higher degree of oxidation and a more uniform distribution of particle size of the functionalized PMS as compared to the batch addition method. The effect of organic solvent was found to be insignificant, and the oxidation could still proceed in its absence. The particle sizes increased significantly during the oxidation but could be controlled by using crosslinked PMS latexes. Finally, the versatility of this oxidation process was demonstrated by oxidation of the polymer with a solid loading as high as 28%. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3585-3593, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 3613-3615 
    ISSN: 0887-624X
    Keywords: anionic polymerization ; kinetics ; mechanism ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 3595-3601 
    ISSN: 0887-624X
    Keywords: polyisobutene ; polystyrene ; ABA-type block copolymers ; controlled/“living” radical polymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A general method for the transformation of “living” carbocationic into “living” radical polymerization, without any modification of chain ends, is reported for the preparation of ABA block copolymers. For example, α,ω-difunctional polyisobutene, capped with several units of styrene, Cl-St-PIB-St-Cl, prepared cationically (Mn = 7800, Mw/Mn = 1.31) was used as an efficient difunctional macroinitiator for homogeneous “living” atom transfer radical polymerization to prepare triblock copolymers with styrene, PSt-PIB-PSt (Mn = 28,800, Mw/Mn = 1.14), methyl acrylate, PMA-PIB-PMA (Mn = 31,810, Mw/Mn = 1.42), isobornyl acrylate, PIBA-PIB-PIBA (Mn = 33,500, Mw/Mn = 1.21), and methyl methacrylate, PMMA-PIB-PMMA (Mn = 33,500, Mw/Mn = 1.47). © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3595-3601, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 3617-3617 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 3603-3611 
    ISSN: 0887-624X
    Keywords: PVA ; acrylic acid ; methacrylic acid ; 2-vinyl-4,4-dimethyl-azlactone ; acrylamides ; GPC ; light scattering ; photochemistry ; contact lenses ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(vinyl alcohol) (PVA) was partially modified by polymer analogous reaction with acrylic and methacrylic acid and with 2-vinyl-4,4-dimethyl-azlactone to obtain water-soluble polymers with pendant (meth)acrylate and acrylamide groups. Aqueous solutions of these polymers were crosslinked by UV-irradiation within seconds to form transparent networks with potential for use in contact lenses. The water content of these hydrogels was studied as a function of polymer molecular weight, the acetate, (meth)acrylate, and methacrylamide contents and irradiation conditions. The hydrogels showed good mechanical properties, even at low crosslinker (〈5 mol %) and high water contents (60-80%). The formation kinetics and stability of aggregates, investigated by combined GPC/light-scattering measurements of samples annealed and/or stored at different temperatures (-20 to 100°C), give insight into PVA secondary structures. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3603-3611, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 3619-3625 
    ISSN: 0887-624X
    Keywords: NMR ; structure ; porperties ; poly(MMA-co-VP) ; hydrogels ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1H- and 13C-NMR techniques were used to study the microscopic structure of NMA/VP copolymer hydrogels. Evidence was obtained for a plasticization effect of MMA chains by VP. An original 1H-NMR approach revealed the existence of several types of water with various degree of bounding to the polymer network, a conclusion that is corroborated by a complementary 13C-NMR study. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3619-3625, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 3627-3636 
    ISSN: 0887-624X
    Keywords: conducting polymers ; electropolymerization ; 3,4-(ethylenedioxy)thiophene (EDOT) ; didecylfluorene ; electrochromism ; EQCM ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The monomers bis(2-thienyl)-9,9-didecylfluorene, BTDF, and bis(3,4-(ethylenedioxy)thien-2-yl)-9,9-didecylfluorene, BEDOT-DF, have been synthesized and electropolymerized to the corresponding conducting polymers. The potential for the electropolymerization of BTDF was found to be dependent on the solvent composition. In CH2Cl2, polymer film deposition is achieved only at potentials higher than 1.3 V vs. Ag/Ag+, while in a 30/70 mixture of CH2Cl2/CH3CN the polymerization is efficient at 0.9 V. BEDOT-DF polymerizes at significantly lower potentials and more rapidly than BTDF. The electron-donating alkoxy substituents of the EDOT units lead to stabilization of the cation radical intermediates allowing the electropolymerization to proceed at 0.55 V. The neutral polymers are insoluble in common organic solvents and are stable to 300°C under nitrogen. Upon oxidation, both polymers show two intragap transitions at intermediate doping levels due to the formation of bipolaronic states and the oxidized polymers exhibit conductivities up to 10-4 S/cm. The redox-stimulated ion transport characteristics, studied by the electrochemical quartz crystal microbalance (EQCM) indicates that the electrolyte anions are the dominant mobile species. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3627-3636, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 1-8 
    ISSN: 0887-624X
    Keywords: Ziegler-Natta catalysts ; propene ; polymerization ; zirconocene ; methylalumoxane ; homogeneous catalysts ; supported catalysts ; morphology ; copolymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The isoselective propene polymerization using the supported catalyst SiO2/MAO/Me2Si(2-Me-Benz[e]Ind)2ZrCl2/AlR3 was investigated and compared with propene polymerization using the corresponding homogeneous catalyst system. The influence of propene concentration, polymerization medium, temperature, comonomer, and external aluminium alkyls on polymerization kinetics and polypropene properties such as molecular mass, stereo- and regioselectivity, morphology, and bulk density was studied. © 1997 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 17-25 
    ISSN: 0887-624X
    Keywords: polyisoprene ; dibromoethane ; bromoethane ; polyisoprene bromine-terminated ; coupling reaction ; lithium-bromine exchange reaction ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The coupling reaction of polyisoprenyllithium with 1,2-dibromoethane (DBE) gives a multimodal molecular weight distribution (MWD). Species with molecular weights three and four times (P3, P4) higher than the base polymer (P) are present beside the main expected one with double molecular weight (P2). The relative abundancies of P1, P2, P3, and P4 depend on the experimental conditions. Gas-phase chromatographic analysis carried out during the coupling reaction show the presence of ethylene whose formation is related to a lithium-bromine exchange reaction competing with direct alkylation. The lithium-bromine exchange reaction is more effective at T 〈 80°C and results in the formation of allyl bromide-terminated polyisoprene, while direct alkylation is effective at T 〉 100°C and yields alkyl bromide chain ends. The allylic and alkylic bromides react differently with the remaining polyisoprenyllithium: the former adds only to polyisoprenyllithium yielding P2, while the later also yields P3 and P4 through radical reactions. © 1997 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 55-67 
    ISSN: 0887-624X
    Keywords: VPi ; ADMVN ; AIBN ; syndiotacticity-rich HMW PVA ; PVA microfibrillar fiber ; Pn ; saponification ; PVPi ; conversion ; initiation rate ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Vinyl pivalate (VPi) was polymerized in bulk by ultraviolet-ray initiation at low temperatures using 2,2′-azobis(2,4-dimethylvaleronitrile) (ADMVN) and 2,2'-azobis(isobutyronitrile) (AIBN) as photoinitiators. High molecular weight (HMW) poly(vinyl pivalate) (PVPi), having a number-average degree of polymerization (Pn) of 13,000-28,000, was obtained at conversions below 30% and converted by saponification to a syndiotacticity-rich HMW poly(vinyl alcohol) (PVA) microfibrillar fiber with Pn of 7300-18,300, syndiotactic diad (S-diad) and triad contents of ∼ 64% and ∼ 39%, respectively, and crystal melting temperature (Tm) of ∼ 249°C. ADMVN gave higher Pn than AIBN. On the other hand, conversion was smaller with the former than with the latter, and it was found that the initiation rate of ADMVN was lower than that of AIBN. Pn of PVA was constant while Pn of the precursor PVPi increased with increasing conversion. The syndiotacticity, Tm and thermal stability of PVA obtained from PVPi were much superior to those of PVA derived from poly(vinyl acetate) prepared under the same polymerization conditions. Polymerization of VPi at lower temperatures gave PVA with higher syndiotacticity. © 1997 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 91-95 
    ISSN: 0887-624X
    Keywords: photoconductivity ; bridged polymeric phthalocyanine ; one-dimensional structure ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A novel polymer with quasi-one-dimensional structure of 4,4′-diamino-diphenyl ether bridged polymeric silicon phthalocyanine (I) is synthesized by the condensation polymerization of 4,4′-diamino-diphenyl ether (DDE) monomer and dichloride silicon phthalocyanine (Cl2SiPc) monomer. The structure of the polymer (I) is identified by IR subtraction and UV/VIS spectroscopy and elemental analysis. The photoconductivity of the polymer I with quasi-one-dimensional structure is better than that of not only the parent Cl2SiPc reactant, but also other polymeric phthalocyanines without one-dimensional structures, and showing one-dimensional effect of molecular structure. © 1997 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 137-142 
    ISSN: 0887-624X
    Keywords: supramolecular architecture ; cascade molecule ; photochemistry ; phenylazido ; ultraviolet irradiation ; wettability ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A novel supramolecularly assembled surface architectural method was developed, which involved a self-assembling process of amphiphilic molecules and a subsequent photochemical process. The specially designed molecules were cascade “tree” molecules composed of a phenylazido group as root, an aliphatic hydrocarbon chain as stem, and two or three tris(hydroxymethyl)aminomethane groups as leaves. Using a horizontal lifting method, unimolecular assemblies which formed at an air/water interface were transferred to polyethylene (PE) surfaces. Upon ultraviolet irradiation, these molecules were covalently fixed on the surfaces due to the photochemical reactivity of the phenylazido group. Treated surfaces became wettable with water, indicating that hydrophilic hemispheres were located at the outer surface region of the PE surfaces. Bimolecular assemblies composed of cascade molecules and noncascade molecules with a hydroxyl group at a terminus exhibited lower advancing and receding contact angles and reduced hysteresis than those of unimolecular ones, indicating that these bimolecular assemblies have a well-structured molecular organization with a high degree of packing. © 1997 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 193-195 
    ISSN: 0887-624X
    Keywords: N-cyclohexylacrylamide ; reactivity ratios ; sequence length ; copolymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract.
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  • 142
    ISSN: 0887-624X
    Keywords: combination of ziegler-natta and metallocene catalysts ; half metallocene catalysts supported on magnesium dichloride ; activation by ordinary alkylaluminums ; improvement of catalyst isospecificity by electron donors ; microstructure of isotactic polypropene ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several kinds of MgCl2-supported half titanocene (XTiCl3; X = cyclopentadienyl, pentamethylcyclopentadienyl, indenyl, and heptamethylindenyl) catalysts were prepared and applied to propene polymerization using Al(i-Bu)3a as cocatalyst. It was confirmed from the catalyst analysis that the ligand (X) is attached to titanium even after the reaction with Al(i-Bu)3. When polymerization was conducted without any external donor, those catalysts predominantly gave atactic PP. However, addition of a suitable monofunctional Lewis base like ethylbenzoate caused to change the stereospecificity of polymer from aspecific into highly isospecific. On the other hand, the use of a bifunctional donor like di-n-butylphthalate killed the activity almost completely. The isotactic PP was found to have a microstructure similar to that obtained with metallocene catalysts. © 1997 John Wiley & Sons, Inc.
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  • 143
    ISSN: 0887-624X
    Keywords: acid-catalyzed polycondensation ; L-aspartic acid ; 6-aminocaproic acid ; o-phosphoric acid ; poly(succinimide-co-6-aminocaproic acid) ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polycondensation of L-aspartic acid (ASP) with 6-aminocaproic acid (ACA) using o-phosphoric acid produced poly(succinimide-co-6-aminocaproic acid). The yield of the MeOH-insoluble copolymer decreased from 99 to 52% and that of the MeOH-soluble one increased from 9 to 47%, with increasing molar ratio of ACA in the monomer feed. The compositions of the succinimide (SCI) unit in the MeOH-insoluble and -soluble copolymers tended to be higher than those of ASP in the monomer feed. The copolymers with the 35 mol % SCI units or above were soluble in DMSO, DMF, and conc-H2SO4, but those with the 20 and 21 mol % SCI units were soluble only in conc-H2SO4. The melting temperature appeared for the copolymers with less than 76 mol % SCI units. Poly(succinimide-co-6-aminocaproic acid) was easily hydrolyzed to yield poly(aspartic acid-co-6-aminocaproic acid), and it exhibited biodegradability toward activated sludge. © 1997 John Wiley & Sons, Inc.
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  • 144
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 319-327 
    ISSN: 0887-624X
    Keywords: polyimide alternating copolymers ; N,N′-bis-(4-anilino)-1,2,4,5-benzene ; bis(dicarboximide) ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: N,N′-Di-(4-anilino)-1,2,4,5-benzene bis(dicarboximide) was prepared in a three-step synthesis and purified by heating the resulting solid to 200°C. Condensation of the diamino-diimide with several dianhydrides (BPDA, BTDA, and 6-FDA) yielded polyamic acid-imides that could be either thermally or chemically cured to the corresponding alternating copolyimides. Imidization of the polyamic acid-imide to the final polyimide was monitored by FTIR for samples coated on silicon wafers before being thermally cured. Polyimides prepared by chemical imidization were found by thermogravimetric analysis to be stable to temperatures of 600°C. © 1997 John Wiley & Sons, Inc.
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  • 145
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 795-798 
    ISSN: 0887-624X
    Keywords: gels ; swelling ; quinones ; sulfhydryl compounds ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Interactions of sulfhydryl compounds and quinone derivatives with poly(4-vinylpyridine) gels have been studied. Adsorption of long-chain sulfhydryl compounds onto gels causes the gel to swell, whereas oxidation of the adsorbed sulfhydryl compound to disulfide by a quinone derivative results in the gel shrinking. The higher the donating ability of the sulfhydryl compound, the stronger its interaction with a quinone derivative and thus the faster the removal from the gels, as revealed by HPLC. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 795-798, 1997
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  • 146
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 817-822 
    ISSN: 0887-624X
    Keywords: graft polymerization ; chain transfer ; allylthio group ; N-vinyl-2-pyrrolidinone ; 2-hydroxyethyl methacrylate ; turbidity titration ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 147
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 799-806 
    ISSN: 0887-624X
    Keywords: allyl crosslinkers ; poly(acrylic acid) ; NMR ; superabsorbent ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several new crosslinkers have been synthesized for evaluation in superabsorbent polymers. These crosslinkers are allyl endcapped polyethylene glycols (PEG) of 200, 600, and 3400 molecular weight. A branched polyethylene oxide of 600 molecular weight, initiated with glycerin, was also synthesized as a trifunctional crosslinker. The allyl functionality was chosen because it is less reactive during radical polymerization than acrylate crosslinkers, an attribute that was necessary to achieve a more uniform gel network. A synthesis route was devised to make the crosslinkers in high purity and yield. The purity of the crosslinkers was determined by 13C NMR, liquid chromatography, and size exclusion chromatography. Gels that were produced with the allyl crosslinkers gave excellent soluble polymer levels and swelling characteristics. The mechanism of incorporation of the allyl functionality was determined to be exclusively vinyl polymerization rather than through hydrogen abstraction. This was determined using NMR spectroscopy, monitoring the polymerization of a model system consisting of acrylic acid and allylacetate. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 799-806, 1997
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  • 148
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 827-858 
    ISSN: 0887-624X
    Keywords: emulsion polymerization ; branched chains ; molecular weight distribution ; compartmentalization ; gel formation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A kinetic model for evaluating the degree of polymerization of a branched polymer produced in emulsion is developed. Only chain branching occurring through chain transfer to polymer has been considered. The model accounts for chain compartmentalization and, when coupled to a model able to describe the evolution of the polymerization system, allows to evaluate the cumulative properties of the produced polymer both in the pre- and post-gel phases. The difficulties related to the description of a heterogeneous polymer chain population and of gel formation are overcome by using the “numerical fractionation” technique. A parametric analysis of both instantaneous and cumulative properties is reported and discussed, with special attention to the role of radical compartmentalization in determining the molecular weight properties of an emulsion produced polymer. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 827-858, 1997
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  • 149
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 965-973 
    ISSN: 0887-624X
    Keywords: graft copolymerization ; polybutadiene ; SBS ; methyl methacrylate ; BPO ; AIBN ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: When a solution containing both styrene-butadiene block copolymer (SBS) and methyl methacrylate is treated with an initiator both homopolymerization of the methyl methacrylate and graft copolymerization of the methyl methacrylate onto the SBS occur. The amount of graft copolymerization depends upon the time and temperature of the reaction, the concentrations of all species, and the identity of the solvent and initiator. The combination of benzoyl peroxide in chloroform gives the highest graft yield and the reaction occurs by removal of an allylic hydrogen from the SBS by the initiator radical and subsequent addition of monomer units to that site; there is a significant solvent effect. Both AIBN and BPO function by the removal of an allylic hydrogen atom from SBS; BPO is able to effect this reaction relatively easily while AIBN can remove the hydrogen atom only with great difficulty and to a limited extent. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 965-974, 1997
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  • 150
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 747-750 
    ISSN: 0887-624X
    Keywords: laser ; radical ; surface graft polymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A laser-induced surface graft polymerization method is reported in which surface radicals generated upon laser irradiation initiated radical polymerization. The radical concentrations generated upon excimer laser irradiation under vacuum on poly-(ethylene terephthalate) film surfaces were measured using a radical scavenger, 1,1-diphenyl-2-picrylhydrazyl. The density of surface radicals increased with laser fluence at low fluences but decreased at high fluences. Upon laser irradiation and subsequent treatment with gaseous N,N-dimethylacrylamide, surface graft polymerization occurred. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 747-750, 1997
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  • 151
    ISSN: 0887-624X
    Keywords: thermotropic polyesters ; synthesis ; characterization ; nematic ; biphase ; high glass transition temperatures ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of wholly aromatic, thermotropic polyesters, derived from 3,3′-bis(phenyl)-4,4′-biphenol (DPBP), nonlinear 4,4′-benzophenone dicarboxylic acid (4,4′-BDA), and various linear comonomers, were prepared by the melt polycondensation reaction and characterized for their thermotropic properties by a variety of experimental techniques. The homopolymer of DPBP with 4,4′-BDA had a fusion temperature (Tf) at 265°C, exhibited a nematic phase, and had a liquid crystalline range of 105°C. All of the copolyesters of DPBP with 4,4′-BDA and either 30 mol % 4-hydroxybenzoic acid (HBA), 6-hydroxy-2-naphthoic acid (HNA), or 50 mol % terephthalic acid (TA), 2,6-naphthalenedicarboxylic acid (2,6-NDA) had low Tf values in the range of 220-285°C, exhibited a nematic phase, and had accessible isotropization transitions (Ti) in the range of 270-420°C, respectively. Their accessible Ti values would enable one to observe a biphase structure. Each of the copolymers with HBA or HNA had a much broader range of liquid crystalline phase. In contrast, each of the copolymers with TA or 2,6-NDA had a relatively narrow range of liquid crystalline phase. Each of these polyesters had a glassy, nematic morphology that was confirmed with the DSC, PLM, WAXD, and SEM studies. As expected, they had higher glass transition temperatures (Tg) in the range of 161-217°C than those of other liquid crystalline polyesters, and excellent thermal stabilities (Td) in the range of 494-517°C, respectively. Despite their noncrystallinity, they were not soluble in common organic solvents with the exception that the homopolymer and its copolymer with TA had limited solubility in CHCl3. However, they were soluble in the usual mixture of p-chlorophenol/1,1,2,2-tetrachloroethane (60/40 by weight) with the exception of the copolymer with 2,6-NDA. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 769-785, 1997
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  • 152
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 813-816 
    ISSN: 0887-624X
    Keywords: nonlinear block copolymers ; A(AB)2, A(AB)3, and (AB)3A(BA)3 ; anionic polymerization ; chlorosilanes ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 153
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 859-878 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The behavior of catalytic chain transfer in semi-batch emulsion polymerization has been studied for two monomers, viz, methyl and n-butyl methacrylate. Two different catalytic chain transfer reagents were used with different water solubilities: cobaloxime boron fluoride (COBF), which was found to partition approximately equally between organic and aqueous phases, and tetra-phenyl cobaloxime boron fluoride (COPhBF), which was found to reside predominantly in the organic phase. The difference in hydrophilicity between the two transfer agents was found to affect the polymerization mechanism. COBF exhibited superior transfer behavior in all cases, whereas the restricted mobility of the COPhBF had a deleterious effect on the efficiency of the transfer mechanism. The best results were achieved under monomer flooded conditions using COBF. MALDI-TOF mass spectrometry analysis shows catalytic chain transfer to be the dominant mechanism initiating and stopping chain growth as none of the chains appear to have initiator fragment end groups. Analysis of copolymers by MALDI-TOF mass spectrometry reveals both molecular weight and composition data. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 859-878, 1997
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  • 154
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 1105-1124 
    ISSN: 0887-624X
    Keywords: liquid crystalline ; epoxy ; kinetic ; curing ; smectic ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The curing kinetics of a system containing 4,4′-diglycidyloxy-α-methylstilbene (DOMS) and different functionality amines, N-ethylaniline (NEA), aniline, benzenesulfonamide (BSA), and sulfanilamide (SAA), have been studied by differential scanning calorimetry (DSC) under isothermal conditions. The phase transformations during curing of the systems have been monitored by a crosspolarized optical microscope equipped with a hot-stage and photo detector. It has been found that the growth of a nematic liquid crystal structure does not cause a discrepancy from the autocatalytic model for the reactions between aniline and epoxy. There is no liquid crystalline structure formed for the systems containing NEA or BSA, which follow the autocatalytic kinetic models within the temperature range of 120-150°C. For the curing reactions between DOMS and SAA, there is a big deviation from the autocatalytic model when the liquid crystals transfer from a nematic structure to a smectic structure. Unlike the usual decrease of reaction rate resulting from diffusion in a heterogeneous reaction, the reaction rate is enhanced. A modified kinetic model has been constructed for this reaction system by introducing a pseudoconcentration term caused from the liquid crystalline structure formation. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1105-1124, 1997
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  • 155
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 1157-1166 
    ISSN: 0887-624X
    Keywords: copolymerization ; polyketone ; carbon monoxide ; norbornadiene ; palladium catalyst ; hydrogenation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Carbon monoxide (CO) and norbornadiene (NBD) with Pd(CH3CN)4(BF4)2 were copolymerized under various conditions at 50°C. Elemental analysis, infrared spectra, UV, Raman, and NMR spectra showed that the copolymers contained both ketone and unsaturated ring structures. Bidentate nitrogen ligands and phosphorus ligands proved to be more effective at stabilizing catalytic activity than monodentate arsenic ligands or phosphorus ligands. Methanol, protic acid, and an oxidant served as the coinitiator and chain transfer agent, respectively. X-ray diffraction analysis showed the copolymer to be partially crystalline. Thermogravimetric analysis showed that the TG curve for the NBD/CO copolymer has two stages with two maxima peaks at 251 and 470°C. This phenomenon was probably due to increased instability of the copolymers as CO content is increased. Hydrogenation of norbornadiene/CO copolymer with LiAlH4 and Pd/C in THF yields a hydroxyl-containing polymer and norbornene/CO copolymer, respectively. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1157-1166, 1997
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  • 156
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 1173-1180 
    ISSN: 0887-624X
    Keywords: chemical composition distribution ; liquid chromatography ; porous polymer beads ; HPLC ; monodisperse particles ; poly(isobutylene-co-4-methylstyrene) ; bromination ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: High-performance liquid chromatography (HPLC) has been used to complement size-exclusion (gel permeation) chromatography (SEC) for the characterization of functional polymers. Whereas SEC is unable to detect compositional changes, HPLC in an appropriate interacting medium can provide detailed information on compositional changes occurring during chemical modification of a polymer. The method has been demonstrated using a normal-phase column consisting of porous monodisperse 10 μm poly(2,3-dihydroxypropyl methacrylate-co-ethylene dimethacrylate) beads that have a homogeneous coverage of aliphatic hydroxyl groups for the analysis of brominated poly(isobutylene-co-4-methylstyrene). Differences of well below 1 mol % of bromomethylstyrene units are easily detected and quantified. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1173-1180, 1997
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  • 157
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 1329-1332 
    ISSN: 0887-624X
    Keywords: poly(N-isopropylacrylamide) ; thermosensitive polymer ; hydrogenation ; catalyst ; platinum ; ultrafine particles ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract.
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  • 158
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 1338-1338 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract.
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  • 159
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 1399-1407 
    ISSN: 0887-624X
    Keywords: phenol-formaldehyde resin; ; novolac ; GPC ; molecular weight averages ; NMR ; hydrodynamic volume ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The number- and weight-average molecular weights of several statistical and high ortho novolac resins were determined using gel permeation chromatography (GPC). The standards used were pure compounds having between 2 and 12 phenol units bridged via methylene linkages. Three series of compounds were studied: (i) those with methylene linkages substituted in only the ortho positions relative to the phenolic hydroxyl group; (ii) those in which all para positions, together with sufficient ortho positions, were used to synthesize the compounds; and (iii) those in which the methylene linkages were substituted at a mixture of ortho and para positions. Such compounds, having known molecular architecture and units similar to the segments of industrial novolac resins, provide for a more exact measurement of the molecular weight than do the commonly used poly(styrene) standards. Using these new standards the number average molecular weights of the resins determined by GPC were in good agreement with the average molecular weight obtained by 1H-NMR spectra of the resins, particularly for low molecular weight resins. GPC analysis of higher molecular weight resins tends to underestimate the molecular weights because of complications introduced by hydrogen bonding. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1399-1407, 1997
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  • 160
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 1431-1442 
    ISSN: 0887-624X
    Keywords: poly(silmethylene) ; in situ polymerization ; polymer blend ; thermal stability ; dynamic mechanical properties ; graft copolymers ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(diphenylsilmethylene) (PDPSM)/poly(methylphenylsilmethylene) (PMPSM) binary polymer blends were synthesized by in situ ring-opening polymerization of 1,1,3,3-tetraphenyl-1,3-disilacyclobutane in PMPSM. Three catalytic methods as well as a noncatalytic method were employed. Radical initiators such as an organic peroxide or azo-compound proved to be the effective catalysts in addition to copper compounds. Blend samples were characterized in detail by DSC, dynamic mechanical analysis, solvent extraction, and microscopic observation to clarify the relationship between the preparative method and the properties of these polymer blends. It is strongly suggested that a part of PMPSM is converted into an insoluble form via formation of PDPSM-PMPSM block or graft copolymers in the case of the in situ copper-catalyzed polymerization in xylene. The formation of block or graft copolymers is also suggested for samples prepared by the in situ bulk polymerization in the presence of a radical initiator. However, PMPSMs simultaneously underwent molecular weight decrease and insolubilization probably due to polymer chain scission and crosslinking, respectively, when the latter method was employed using PMPSM with very high molecular weight. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1431-1442, 1997
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  • 161
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 1461-1467 
    ISSN: 0887-624X
    Keywords: hybrid biomaterials ; grafting ; hydrogek ; membranes ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We employed an ozone-induced grafting process to prepare membrane-hydrogel hybrid biomaterials. Exposure of isotactic polypropylene to ozone resulted in surface oxidation, as detected by ESCA, and the formation of peroxides and hydroperoxides. The amount of oxygen-bearing moieties, as detected by FT-IR, was increased when a microporous membrane with a large surface area was used. Ozonation for an extended period of time, 1-2 h, resulted in a degradation of microporous PP, observed with SEM as an enlargement of pores and brittle characteristics of the material. The molecular weight of PP was dramatically reduced after as little as 5 min of ozonation. Exposure to ozone for longer periods of time contributed to further reductions of the molecular weight and gradual modification of chemical composition of polypropylene, restricted, however, to the surface or intercrystalline amorphous regions. It was possible to graft 2-hydroxyethylmethacrylate (HEMA) to the ozonated samples, such that the graft copolymer acted as continiuous matrix consequently linked to and reinforced by the PP crystals. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1461-1467, 1997
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  • 162
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 1499-1514 
    ISSN: 0887-624X
    Keywords: PTFE ; surface modification ; benzophenone ; UV light ; diphenyl ketyl radical anion ; benzhydrol anion ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(tetrafluoroethylene) (PTFE) films were surface modified in a solution of benzophenone and sodium hydride in dry dimethylformamide by ultraviolet (UV) light irradiation. The extent of surface modification was characterized after durations of UV light irradiation from 5-20 min at temperatures from 19-60°C. The modified films were analyzed by electron spectroscopy for chemical analysis, diffuse reflectance ultraviolet-visible light spectroscopy, attenuated total reflection Fourier transform infrared spectroscopy, dynamic contact angle measurement, and low-voltage scanning electron microscopy. PTFE surfaces produced by this modification demonstrated extensive defluorination, oxygen incorporation, surface unsaturation, and reduction in both advancing and receding dynamic water contact angles in a manner that was more extensive at long durations of irradiation and at high temperatures. Morphological damage depended upon treatment conditions, but extensive surface modification could be obtained without substantial morphological damage to PTFE films. Control experiments indicated that the surface modification proceeded by photoexcitation of either diphenyl ketyl radical anion or benzhydrol anion, the products of reaction of benzophenone with sodium hydride. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1499-1514, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 1563-1570 
    ISSN: 0887-624X
    Keywords: cyclobutane ; ring-opening polymerization ; alternating copolymer ; dimethyl 1,1-dicyanoethylene-2,2-dicarboxylate ; vinyl ether ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: For an extension of the work on the ring-opening polymerizations of cyclobutane adducts of strong donor olefins and strong acceptor olefins yielding novel alternating copolymers of those olefins, the ring-opening polymerization of the cyclobutane adduct 3 of dimethyl 1,1-dicyanoethylene-2,2-dicarboxylate (DDED) and ethyl vinyl ether (EVE) is investigated. Cyclobutane 3 reacted with methanol and acetic acid at ambient temperature to yield the corresponding ring-opened adducts. The polymerizations of 3 were carried out with anionic initiators, tertiary amines, ammonium halides, and Lewis acids, respectively, according to the polymerization methods of the cyclobutane adduct 1 of tetracyanoethylene (TCNE) and EVE. All these polymerization catalysts except for ammonium halides were effective for the polymerization of 3, yielding alternating copolymers of DDED and EVE. The chain transfer reactions of the polymerization with anionic initiators are also discussed on the basis of a model reaction. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1563-1570, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 1549-1562 
    ISSN: 0887-624X
    Keywords: polyethylene ; γ-irradiation ; crosslinking ; NMR ; alkanes ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Long-chain linear alkanes have been used as model compounds for polyethylene in an attempt to identify the chemical nature of crosslinks formed in polyethylene when it undergoes γ-irradiation in the presence of acetylene. IR and UV spectral analysis of alkanes and polyethylene following acetylene-sensitized irradiation shows the formation of vinyl, trans-vinylene, and diene groups. A correlation of the conditions of formation suggests that in polyethylene the vinyl groups are restricted to amorphous regions, diene groups are restricted to the crystalline regions, and trans-vinylene groups are formed in both regions. There is no information on the nature of crosslinks. 13C-NMR analysis of alkanes following irradiation of molten alkanes in the presence of 13C-enriched acetylene has shown that a range of saturated alphatic structures are formed by inclusion of acetylene molecules in the alkane structure. They include ethyl branches, γ-branches,—CH(CH3)—, and —CH2—CH2— branches as the major species; the latter two are potential crosslink sites in the irradiation of polyethylene. In addition, the NMR analysis confirmed that the C atoms of the vinyl groups come from acetylene molecules and those of the trans-vinylene groups come from alkane molecules. Data on irradiation of the alkanes in the crystalline state showed that acetylene inclusion in the alkane structure is minimal under these conditions. The principal finding of this work is that acetylene can be incorporated as saturated aliphatic crosslinks in the amorphous regions of polyethylene during high-energy irradiation. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1549-1561, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 1605-1610 
    ISSN: 0887-624X
    Keywords: emulsion polymerization ; core-shell particles ; acetal functionality ; immunoassays ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of core-shell type polystyrene monodisperse particles with surface acetal groups was carried out by a two-step emulsion polymerization process. In a first step, the core was synthesized by batch emulsion polymerization of styrene (St), and in the second step, the shell was polymerized by batch emulsion terpolymerization of styrene, methacrylic acid (MAA), and methacrylamidoacetaldehyde dimethyl acetal (MAAMA), using the seed obtained previously. With the aim of analyzing the effect of the thickness of the shell, the pH of the reaction medium and the weight ratio of the termonomers to prepare the shell, on the amount of the functionalized groups, several core-shell type latex particles were synthesized by two-step emulsion polymerization in a batch reactor. The latexes were characterized by TEM and conductimetric titration to obtain the particle size distribution and the amount of carboxyl and acetal groups on the surface, respectively. Looking for the applicability of the synthesized latexes in immunoassays, IgG a-CRP rabbit antibody was covalently bonded to the surface of the particles synthesized in neutral medium. The complex latex-protein was immunologically active against the CRP antigen. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1605-1610, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 1681-1687 
    ISSN: 0887-624X
    Keywords: photopolymerization of MMA ; morpholine-chlorine C-T complex ; polymerization kinetics ; kinetic nonideality ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polymerization of methyl methacrylate (MMA) was kinetically studied under photo condition using near UV visible light at 40°C and employing morpholine (MOR)-chlorine (Cl2) charge transfer (C-T) complex as the photoinitiator. The rate of polymerization (Rp) was dependent on morpholine/chlorine mole ratio; the 1 : 2 (MOR-Cl2) C-T complex acted as the latent initiator complex, C, which underwent further complexation with the monomer molecules to give the actual initiator complex, I. Using 1 : 2 (MOR-Cl2) C-T complex as the latent initiator, the initiator exponent evaluated for bulk photopolymerization of MMA was 0.071 and monomer exponent determined from studies of photopolymerization in benzene diluted system was 1.10. Benzoquinone behaved as a strong inhibitor and the polymers tested positive for the incorporation of chlorine atom end groups. Polymerization followed a radical mechanism. Kinetic nonideality as revealed by low (≪0.5) initiator exponent and a monomer exponent of greater than unity were explained in terms of primary radical termination effect. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1681-1687, 1997
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  • 167
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    Keywords: liquid polysulfide polymer ; hydrazine ; sodium trisulfide ; 1,1′-[methylenebis(oxy)]-bis-[2-chloroethane] ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Liquid polysulfide polymers with the thiol groups on the end of the chains and of the average molecular weight of 7000-510 g mol-1 have been obtained by the reaction of BClE and Na2S3, i.e., Na2S2.5 in the presence of hydrazine. The average molecular weight of the obtained polymers depends on the quantity of hydrazine used for the syntheses. With the aim to obtain polymers of the similar average molecular weight it is necessary to use on average 0.5 mol of hydrazine per polymer segment less if Na2S2.5 is used instead of Na2S3. The sulfur content in the obtained polymers is on average less than 2 sulfur atoms per polymer segment and amounts to 1.90 sulfur atoms when Na2S3 is used and is 1.76 sulfur atoms per polymer segment when Na2S2.5 is used for the synthesis. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1369-1373, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 1389-1398 
    ISSN: 0887-624X
    Keywords: benzylamines ; benzoxazines ; curving ; HMTA ; NMR ; novolac resins ; xylenols ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It is proposed that the reactions of hexamethylenetetramine (HMTA) with 2,4-xylenol and with 2,6-xylenol occur by different pathways. The rate of reaction and the final product distribution depend on the initial xylenol : HMTA ratio and are different in the two systems. Measured by HMTA consumption, with 2,4-xylenol the reaction rate increased with increasing xylenol : HMTA ratios, whereas with 2,6-xylenol the rate of reaction decreased with increasing 2,6-xylenol : HMTA ratio. In systems which contain both 2,4- and 2,6-xylenol, a strong preference for reaction of the HMTA with the ortho site of 2,4-xylenol was noted. This preference was apparent even in mixtures in which 2,6-xylenol was present in greater amounts than 2,4-xylenol. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1389-1398, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 1381-1387 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Samarium poly(oxamide) polyanions, formed quantitatively in situ by the reductive coupling polymerization of aromatic diisocyanates with samarium (II) iodide/hexamethylphosphoramide (HMPA) system, were directly used as the polymeric initiators in the graft polymerization with some electrophilic monomers. The graft polymerization of ∊-caprolactone (CL) with several polyanions derived from bifunctional isocyanates, including tolylene 2,6-diisocyanate, o-tolidine diisocyanate and diphenylmethane diisocyanate, provided the corresponding graft copolymers in one-pot, indicating that the polyanion could work as a new type of reactive polymer. Several factors such as reaction temperature and time and the amount of HMPA and CL affected the behavior of the present polymerization system, and the graft copolymer was obtained quantitatively under the appropriate conditions. The results of the graft polymerizations of tert-butyl methacrylate and methyl methacrylate with the polyanion were also presented. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1381-1387, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 1453-1459 
    ISSN: 0887-624X
    Keywords: enzymatic polymerization ; oxidative polymerization ; alkylphenol ; peroxidase ; polyphenol ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Enzymatic oxidative polymerization of p-alkylphenols using horseradish peroxidase as catalyst has been carried out in two polymerization solvent systems: a mixture of phosphate buffer (pH 7) and 1,4-dioxane, and a reverse micellar solution, yielding powdery polymeric materials. The polymer yield was much dependent upon the type of alkyl group in the monomer as well as the solvent type. In case of the polymerization of umbranched alkylphenols in the aqueous 1,4-dioxane, the polymer yield increased with increasing chain length of the alkyl group from 1 to 5, and the yield of the polymer from hexyl or heptylphenol was almost the same as that of the pentyl derivative. The relationship between the type of substituent and the polymer yield in the reverse micellar system was different from that in the aqueous 1,4-dioxane; the highest yield was achieved from ethylphenol. The resulting polymers had molecular weight of several thousands. The polymer was estimated to be composed from a mixture of phenylene and oxyphenylene units from IR analyses. TG measurement exhibited that the polymer had relatively high thermal stability. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1453-1459, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 1487-1497 
    ISSN: 0887-624X
    Keywords: spirobichroman ; dietheramine ; polyamides ; polyimides ; poly(amide-imide)s ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A novel spirobichroman unit containing dietheramine, 6,6′-bis(4-aminophenoxy)-4,4,4′,4′,7,7′-hexamethyl-2,2′-spirobichroman (3), was prepared by the nucleophilic substitution of 6,6′-dihydroxy-4,4,4′,4′,7,7′-hexamethyl-2,2′-spirobichroman with p-chloronitrobenzene in the presence of K2CO3 followed by hydrazine catalytic reduction of the intermediate dinitro compound. A series of polyimides were synthesized from diamine 3 and various aromatic dianhydrides by a conventional two-stage procedure through the formation of poly(amic-acid)s followed by thermal imidization. The intermediate poly(amic-acid)s had inherent viscosities of 1.00-2.78 dL/g. All the poly-(amic-acid)s could be thermally cyclodehydrated into flexible and tough polyimide films, and some polyimides were soluble in polar solvents such as N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), and N,N-dimethylformamide (DMF). These polyimides had glass transition temperatures (Tg) in the range of 236-256°C, and 10% weight loss occurred up to 450°C. Furthermore, a series of polyamides and poly(amide-imide)s with inherent viscosities of 0.71-2.29 dL/g were prepared by direct polycondensation of the diamine 3 with various aromatic dicarboxylic acids and imide ring-containing dicarboxylic acids by means of triphenyl phosphite and pyridine. All the polyamides and poly(amide-imide)s were readily soluble in polar solvents such as DMAc, and tough and flexible films could be cast from their DMAc solutions. These polymers had glass transition temperatures in the range of 137-228°C and 10% weight loss temperatures in the range of 419-443°C in air and 404-436°C in nitrogen, respectively. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1487-1497, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 2041-2047 
    ISSN: 0887-624X
    Keywords: carbazole cyclic tetramer ; carbazole main-chain polymer ; Knoevenagel polycondensation ; nonlinear optical materials ; photorefractive materials ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The efficient synthesis of a novel cyclic carbazole tetramer and carbazole main-chain polymer via the Knoevenagel condensation has been developed. The carbazole cyclic tetramer could be obtained in a high yield by a one-stage Knoevenagel condensation of 3,6-diformyl-9-heptylcarbazole and 3,6-bis(cyanoacetoxymethyl)-9-heptylcarbazole in tetrahydrofuran (THF) without the use of the high-dilution principle. The corresponding carbazole main-chain polymer could also be obtained as a main product by a two-stage Knoevenagel polycondensation. Detailed structural characterization of this novel oligomer by spectroscopy and elemental analysis confirmed the cyclic structure. The corresponding main-chain polymer with large molecular weight was found to be amorphous by differential scanning calorimetry. Studies on the nonlinear optical and photorefractive properties of these materials are in progress. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2041-2047, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 2049-2053 
    ISSN: 0887-624X
    Keywords: chitin ; reversible gel ; hydrogel ; carboxylmethyl-gel ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A novel, reversible, water-swellable chitin gel has been produced by the carboxymethylation of a dry chitin film. The property of this material is that unlike carboxymethyl-chitin, it takes up water but is not soluble and retains a degree of rigidity even when wet. The degree of swelling depends on the reaction conditions and alkali (sodium or potassium hydroxide) used as a co-reactant during the carboxymethylation. Upon drying, the gel returns to its dry film form. This water uptake and loss is cyclic, which is a desirable property in certain applications and is a tremendous advantage in the handling of this material. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2049-2053, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 2097-2103 
    ISSN: 0887-624X
    Keywords: palladium catalyst ; allene derivatives ; nucleophile bearing aryl halides moieties ; multibranched polymer ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A novel polymerization method of allene derivatives with nucleophiles bearing aryl halide moieties (A-B type) is described. By the polymerization of hexylallene with malonates bearing an aryl iodide part, polymers consisting both of internal and exomethylene (exo) double bonds were obtained by mean of the coupling reaction of three different components in high yields. On the other hand, a polymer obtained from phenylallene was selectively composed of internal double bonds (E and Z). By the reaction of hexylallene with a malonate bearing two aryl halide moieties (A-B2 type), a multibranched polymer was also obtained. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2097-2103, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 521-526 
    ISSN: 0887-624X
    Keywords: poly(aryl ether ketone) ; naphthalene derivatives ; fluorinated ; Ullmann ether synthesis ; Friedel-Crafts acylation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The new monomer 2,2-bis[4-(4-{4-fluorobenzoyl}-1-naphthoxy)phenyl]hexafluoropropane (2) was synthesized in a two-step reaction sequence. 2,2-his[4-(1-naphthoxy)phenyl]-hexafluoropropane (1) was prepared using the Ullmann ether synthesis reaction of 4,4-(hex-afluoroisopropylidiene)diphenol with 1-bromonaphthalene. Friedel-Crafts acylation of 1 with 4-fluorobenzoyl chloride in methylene chloride containing dimethylsulfone selectively afforded 2 in 82% yield. The polycondensation of 2 with various bisphenols in DMAc in the presence of an excess of potassium carbonate as a condensation reagent was carried out at 165°C to quantitatively afford the corresponding fluorinated poly(aryl ether ketone)s containing 1,4-naphthalene moieties. Thermal analysis of the polymers showed them to have Tgs ranging from 194 to 230°C and to be thermally stable in air up with initial weight losses at about 500°C. In addition, these novel polymers exhibited excellent solubility in organic solvents including NMP, DMAc, and chloroform. © 1997 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 547-555 
    ISSN: 0887-624X
    Keywords: diphenylmethane-4,4′-di(methylthiopropionic acid) ; melt polycondensation ; linear polyesters containing sulfur ; physico-chemical properties ; thermal behavior ; kinetic parameter ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The new linear polyesters containing sulfur in the main chain were obtained by melt polycondensation of diphenylmethane-4,4′-di(methylthiopropionic acid) with ethanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-propanediol, 1,3-butanediol, and 2,2′-oxydiethanol. Low-molecular weights, low-softening temperatures and, very good solubility in organic solvents are their characteristics. The structure of all polyesters was determined by elemental analysis, FT-IR and 1H-NMR spectroscopy, and x-ray diffraction analysis. The thermal behavior of these polymers was examined by differential thermal analysis (DTA), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). The kinetics of polyesters formation by uncatalyzed melt polycondensation was studied in a model system: diphenylmethane-4,4′-di(methylthiopropionic acid) and 1,4-butanediol or 2,2′-oxydiethanol at 150, 160, and 170°C. Reaction rate constants (k3) and activation parameters (ΔG≠, ΔH≠, ΔS≠) from carboxyl group loss were determined using classical kinetic methods. © 1997 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 587-591 
    ISSN: 0887-624X
    Keywords: polydiacetylene ; dipropargylfluorene ; oxidative coupling ; thermal cure ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 613-624 
    ISSN: 0887-624X
    Keywords: anti head-to-head 7-hydroxycoumarin dimer ; anti head-to-tail 7-hydroxy-4-methylcoumarin dimer ; polyurethane ; photocleavage ; photopolymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Six polyurethanes containing coumarin dimer components in the main chain have been prepared by polyaddition of diisocyanates with anti head-to-head 7-hydroxycoumarin dimer or anti head-to-tail 7-hydroxy-4-methylcoumarin dimer. 7-Acetoxycoumarin and 7-acetoxy-4-methylcoumarin were first prepared and then photodimerized under 350 nm UV light to give anti head-to-head 7-acetoxycoumarin dimer and anti head-to-tail 7-acetoxy-4-methylcoumarin dimer, respectively. After hydrolyzing under acidic conditions to 7-hydroxycoumarin dimer and anti head-to-head 7-hydroxycoumarin dimer, they were polymerized with aliphatic and aromatic diisocyanates in N,N-dimethylacetamide to give the polyurethanes. Addition of dibutyltin dilaurate (T-12) as catalyst increases the polymer yield with the viscosity remaining almost unchanged. It was also found that lithium chloride enhances both the yield and viscosity of the polyurethanes by increasing their solubility possibly through complexation. The polyurethanes are symmetrically photocleaved at cyclobutane rings under 254 nm UV light to dicoumarins. Reversible photodimerization of the photocleaved compounds have also been investigated under 300 and 350 nm UV light. The polyurethanes from aromatic diisocyanates or with 4-methyl substituent exhibit greater reactivity in the photocleavage reaction. © 1997 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 689-694 
    ISSN: 0887-624X
    Keywords: aminimide ; thermal latent initiator ; anionic polymerization ; epoxide ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1,1-Dimethyl-1-(2-hydroxypropyl)amine p-substituted benzimide (“aminimide”) derivatives were prepared by the reaction of p-substituted methyl benzoates with equimolar amounts of 1,1-dimethylhydrazine and propylene oxide. These ylide compounds are shown to be useful as thermally latent initiators for the polymerization of glycidyl phenyl ether (GPE). Bulk polymerization of GPE with 3 mol % of these aminimides was carried out at 40-150°C for 8 h, showing ≥ 100°C was required for an effective rate. No consumption of the monomer could be observed at temperatures lower than 80°C. p-Methoxy substituted 1 showed the largest thermal latency among four aminimides tested. The activities of the aminimides increased with an increase of electron-donating ability of the substituents on the benzene ring, according to the following order: 1 (p-MeO) 〉 2(p-Me) 〉 3(H) 〉 4(p-NO2). © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 689-694, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 715-720 
    ISSN: 0887-624X
    Keywords: samarium iodide ; polyaddition ; ketyl radical ; polymeric alcohol ; electron transfer ; reductive coupling ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Hydrophilic polymers having both oligo(oxyethylene) moieties and tertiary alcohol units in the main chain were prepared by the radical polyaddition of the dike-tones with distyryl compounds by using samarium(II) iodide as an electron transfer agent. Polyaddition of 4,4′-(1,4-phenylene)bis-2-butanone or 6,9-dioxatetradeca-2,13-dione with distyryl compounds such as 1,15-di(4-ethenylphenyl)-2,5,8,11,14-pentaoxapentadecane, 1,18-di(4-ethenylphenyl)-2,5,8,11,14,17-hexaoxaoctadecane, or 1,21-di(4-ethenylphenyl)-2,5,8,11,14,17,20-heptaoxaheneicosane resulted in the formation of the corresponding polymeric alcohols in moderate yields (46-75%). The produced polymers showed high solubility in common solvents, and their molecular weights estimated by GPC (THF, polystyrene standard) were 5200-8100. No serious difference in the molecular weight of the polymer between after and before the treatment with cerium ammonium nitrate indicated that the produced polymers were inert under the oxidative condition where oxidative cleavage of the main chain of poly(vinyl alcohol) takes place. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 715-720, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 751-757 
    ISSN: 0887-624X
    Keywords: controlled synthesis ; glycopolymer ; pendant D-glucosamine residue ; vinyl ether ; living polymerization ; cationic polymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: D-glucosamine-containing glycopolymers with well-controlled structure were synthesized by living cationic polymerization. To this end, D-glucosamine-containing vinyl ether (VE) of the type [CH2(=)CH(OCH2CH2OR)] was prepared, where R denotes a 3,4,6-tri-O-acetyl-2-deoxy-2-phthalimide-β-D-glucopyranoside, i.e., the hydroxyl and amino groups in D-glucosamine residues are protected by acetyl and phthaloyl groups, respectively. It was found that (1) the efficient living cationic polymerization of VE monomer is achieved by a combination of ethylaluminum dichloride (EtAlCl2) with an adduct of trifluoroacetic acid (TFA) and isobutyl VE (IBVE) [CH3CH(OiBu)OCOCF3] (i.e., TFA/EtAlCl2 initiating system); and (2) the polymerization in toluene at the elevated temperature (0°C) is most suitable to proceed the homogeneous polymerization over the whole conversion range. The molecular weight distribution of the resulting polymers was very narrow (\documentclass{article}\pagestyle{empty}\begin{document}$ {\bar M}_w/{\bar M}_n \sim 1.1 $\end{document}). Quantitative deprotection of the resulting precursor polymers was successfully achieved with hydrazine monohydrate to afford the corresponding water-soluble polymers with pendant D-glucosamine residues. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 751-757, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 807-811 
    ISSN: 0887-624X
    Keywords: miniemulsion ; droplet nucleation ; oil-soluble initiator ; water-soluble inhibitor ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 823-826 
    ISSN: 0887-624X
    Keywords: MgCl2-supported dichlorobis (β-diketonato) titanium catalyst ; activated by ordinary trialkylaluminums ; propene polymerization ; effect of ethylbenzoate ; catalyst isospecificity ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 889-899 
    ISSN: 0887-624X
    Keywords: carbamoylphosphonate monomers ; carbamoylphosphonate polymers ; m-TMI ; organophosphorus polymers ; uranyl nitrate-polymer complex ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A monomer, diethyl α,α-dimethyl-m-isopropenylbenzyl carbamoylphosphonate, has been prepared by the base-catalyzed reaction of the isocyanate m-TMI (α,α-dimethyl-m-isopropenylbenzylisocyanate) with diethyl phosphite. The structure of the carbamoylphosphonate monomer and its styrene copolymer was confirmed spectroscopically, and the nature of the hydrogen bondings in the —NHC(=O)P(=O)(OR)2 unit in the monomer and copolymer is discussed in detail. A bulk polymerization of the carbamoylphosphonate is very slow and tends to yield a crosslinked product, but a solution polymerization produced the soluble copolymers. The Tg(midpoint) of the homo-polymer is low, 67°C, and its capacity to complex UO2(NO3)2 is very high, 28 wt % (19 mol %). © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 889-899, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 2157-2165 
    ISSN: 0887-624X
    Keywords: poly(p-phenylenebenzobis(thiazole)) ; poly(p-phenylenebenzobis(oxazole)) ; film ; molecular composite ; benzocyclobutene ; phase separation ; interlayer integrity ; tensile strength ; tensile modulus ; delamination resistance ; film density ; coefficient of thermal expansion ; thermal stability ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Films consisting of a rigid-rod polymer and thermoset resin matrixes were prepared. Poly{(benzo[1,2-d : 5,4-d′]bis(oxazole-2,6-diyl))-1,4-phenylene} (PBO) in polyphosphoric acid (PPA) was blended with 2,6-bis(4-benzocyclobutene) benzo[1,2-d : 5,4-d′]bis(oxazole) (1), and films were extruded from these solutions. The coagulated films were soluble in methanesulfonic acid (MSA). After heat treatment at 300°C, the films became insoluble in MSA. Crosslinked films were homogeneous and did not show phase segregation between the two components. These were composite films at the molecular level. Transmission electron microscopy (TEM) showed enhanced interlayer integrity and reduced microfibril separation for the molecular composite films as compared to normal PBO film. These films had significantly better torsion and tension delamination resistance. The incorporation of a second component did not sacrifice the tensile properties of PBO film. Thermal stability of these composite films was only slightly lower than that of normal PBO film. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2157-2165, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 2183-2192 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The hydrolytic degradation of technical poly(ethylene terephthalate) (PET) was investigated by means of different methods such as size-exclusion chromatography (SEC), viscometry, light-scattering, thin-layer chromatography, end-group titration, and matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS). The long-term degradation was simulated by exposing PET filament yarns to aqueous neutral conditions at 90°C for up to 18 weeks. By means of MALDI-MS and thin-layer chromatography, the formation of different oligomers was obtained during polymer degradation. As expected, an ester scission process was found generating acid terminated oligomers (H-[GT]m-OH) and T-[GT]m-OH and ethylene glycol terminated oligomers (H-[GT]m-G), where G is an ethylene glycol unit and T is a terephthalic acid unit. Additionally, the scission of the ester bonds during the chemical treatment led to a strong decrease in the number of cyclic oligomers ([GT]m). The occurrence of di-acid terminated species demonstrated a high degree of degradation. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2183-2192, 1997
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  • 187
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 2193-2206 
    ISSN: 0887-624X
    Keywords: multicomponent ; latex ; interpenetrating polymer networks ; IPN ; core/shell ; morphology ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of novel structured latex particles with interpenetrating polymer network (IPN) cores and glassy SAN shells were developed in an attempt to investigate the feasibility of these polymers as both toughening and damping agents in thermoplastics. The IPN cores were composed of one impact part (polybutadiene based) and one damping part (acrylic based, with Tg around +10°C). The particle morphologies of these polymers were determined by TEM. The glass transitions and mechanical behavior of the polymers were characterized from DMS. The effect of different components on the final core/shell particle morphologies and mechanical properties was studied. The mechanical behavior of core/shell particles with IPN cores was also compared with that of separate core/shell and multilayered core/shell particles. In addition, normal core/shell synthesis (rubbery part first then the glassy part) and inverted core/shell synthesis (glassy part first then the rubbery part) were performed to provide another access for morphology control. It was found that the core/shell latex particles with poly(butyl acrylate) based copolymers are more miscible than poly(ethylhexyl methacrylate)-based copolymers. The high grafting efficiency of poly(butyl acrylate) plays an important role in governing phase miscibility. The latex particles synthesized by the inverted core/shell mode showed higher miscibility than the normal synthesized ones. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2193-2206, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 2253-2258 
    ISSN: 0887-624X
    Keywords: electroluminescence ; thin film ; PPV ; light-emitting diode ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(2-(2′-ethylhexylthio)-5-methoxy-1,4-phenylenevinylene) (PMEHTPV) was synthesized in thin films via a water-soluble precursor polymer and characterized with thermogravimetric analysis (TGA), FT-IR, and elemental analysis, etc. The PMEHTPV film could be stretched up to 10 times and showed conductivity of 0.13 Scm-1 when doped with FeCl3. The 2-ethylhexylthio group resulted in blue-shifted absorption and emission compared to those of poly(2-2′-ethylhexyloxy-5-methoxy-1,4-phenylenevinylene) (MEH-PPV). The relative quantum efficiency of the device made by PMEHTPV was 20 times higher than that of MEH-PPV. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2253-2258, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 2259-2266 
    ISSN: 0887-624X
    Keywords: poly(m-phenylene) ; selective coupling ; regiocontrolled polymer ; oxidative coupling polymerization ; thermal stability ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(4,6-di-n-butoxy-1,3-phenylene) (6) was prepared by oxidative coupling polymerization of 1,3-di-n-butoxybenzene (1) or 2,2′,4,4′-tetra-n-butoxy biphenyl (3). Polymerizations were conducted in nitrobenzene in the presence of FeCl3 at room temperature and produced polymers with number-average molecular weights up to 42,000. The effects of various factors, such as amount of FeCl3 and reaction temperature and time were studied. The structure of polymer 6 was characterized by 270 MHz 1H- and 68.5 MHz 13C-NMR spectroscopies and was estimated to consist of almost completely 1,3-linkage. The regiocontrolled polymer was readily soluble in common organic solvents. Thermogravimetric analysis of polymer 6 showed 10% weight loss at 390°C in nitrogen. © 1997 John Wiley & Sons, Inc. J Polym Chem 35: 2259-2266, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 2273-2280 
    ISSN: 0887-624X
    Keywords: 1,4-bis(p-carboxyphenoxy)naphthyl ; aromatic polyamides ; solubility ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new aromatic dicarboxylic acid, 1,4-bis (p-carboxyphenoxy)naphthyl (3), was synthesized by the reaction of p-fluorobenzonitrile with 1,4-naphthalenediol, followed by hydrolysis. Aromatic polyamides having inherent viscosities of 1.27-2.22 dL/g were prepared by the triphenyl phosphite activated polycondensation of diacid 3 with various aromatic diamines. Most of the resulting polymers showed an amorphous nature and were readily soluble in a variety of organic solvents including N,N-dimethyl-acetamide (DMAc), N-methyl-2-pyrrolidone (NMP), and m-cresol. Transparent, tough, and flexible films of these polymers could be cast from the DMAc or NMP solutions. The cast films had tensile strengths ranging from 64-104 MPa, elongations-at-break from 6 to 10%, and initial moduli from 1.52 to 2.14 GPa. These polyamides had glass transition temperatures in the range of 195 to 240°C. Almost all polymers were thermally stable up to 400°C, with 10% weight loss being recorded above 480°C in air and nitrogen atmospheres. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2273-2280, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 2289-2294 
    ISSN: 0887-624X
    Keywords: polyimide ; clay ; hybrid ; synthetic mica ; montmorillonite ; saponite ; hectrite ; permeability ; thermal expansion ; storage elastic modulus ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polyimide-clay hybrid films with four different sizes of clay minerals have been synthesized to investigate the effect of the size of clay minerals to the properties of the hybrids. Hectrite, saponite, montmorillonite, and synthetic mica were used as clay minerals. Those clays consist of stacked silicate sheets about 460 Å (hectrite), 1650 Å (saponite), 2180 Å (montmorillonite), and 12300 Å (synthetic mica) in length, 10 Å in thickness. The longer the length of clay mineral was, the more effectively properties of polyimide were improved. In the case of polyimide-mica hybrid, only 2 wt % addition of synthetic mica brought permeability coefficients of water vapor to value less than one-tenth of that of ordinary unfilled polyimide, and thermal expansion coefficient was lowered at the level of 60% of the original one. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2289-2294, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 2295-2309 
    ISSN: 0887-624X
    Keywords: sol-gel process ; poly(ε-caprolactone) ; bioglass ; ceramer ; hybrid material ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The hydroxyl or vinyl end-groups of linear or three-arm star-shaped poly(ε-caprolactone) (PCL) chains have been derivatized into triethoxysilane groups reactive in the sol-gel process. New transparent hybrid materials that combine tetraethylorthosilicate (TEOS) and PCL known for biodegradability and biocompatibility have accordingly been prepared. The sol-gel process is, however, limited by the early vitrification of the reactive system. However, thermal posttreatment can overcome these diffusional and/or kinetic limitations as assessed by a set of analytical methods. The thermal stability of PCL is improved by incorporation into the silica network. Conversely, the thermal stability of the ceramer depends on the effective PCL content. The extent of PCL incorporation into the silica network depends on PCL molecular weight, number, and reactivity of the PCL functional groups. IR spectroscopy has shown that hydrogen bonding occurs between the ester groups of PCL and residual OH groups of the silicate component. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2295-2309, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 2333-2345 
    ISSN: 0887-624X
    Keywords: dicyclopentenyl acrylate/ethyl acrylate ; photopolymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The crosslinking efficiency and kinetics of a solid acrylic copolymer DCPA/EA (dicyclopentenyl acrylate/ethyl acrylate) matrix were investigated in the presence of pentaerythritol tetrakis (2-mercaptoacetate) (PETMP) or pentaerythritol tri- and tetraacrylates used as multifunctional crosslinking agents. The reaction of thiol and acrylate addition was sensitized by benzophenone (BP). The crosslinking efficiency of the DCPA/EA - BP - PETMP copolymer system, illuminated at high wavelengths (λ 〉 310 nm), was compared with that of the DCPA/EA matrix alone and the 2-component system copolymer DCPA/EA-BP. The concentrations of photosensitizer and crosslinking agent were varied from 1 to 10 mass %. The kinetics of tetrafunctional thiol addition and cyclopentene (pendant group of the DCPA/EA matrix) disappearance was followed through Fourier transform infrared (FTIR) and by determining the gel content. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2333-2345, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 2355-2364 
    ISSN: 0887-624X
    Keywords: photoresist ; polysilane ; base-developable resist ; phenylhydroxysilane ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(phenylhydrosilane) becomes soluble in a 2.38% tetramethylammoniumhydroxide aqueous solution after exposure to UV light. This is the first report that the polysilanes not bearing acidic groups can be developed with dilute basic aqueous solutions. Addition of 3,3′,4,4′-tetra(t-butylperoxycarbonyl)benzophenone increases the resist sensitivity. The reaction mechanism is as follows: PS1 photodecomposes to form silyl compounds having SiOH groups, which become soluble in an aqueous base solution, because these silane compounds bearing SiOHs are acidic. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2355-2364, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 2379-2386 
    ISSN: 0887-624X
    Keywords: nylon synthesis ; copolyamide ; solution polycondensation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Copolyamides based on poly(m-phenylene isophthalamide) and poly-(p-phenylene terephthalamide), to which 1,6-diaminohexane units were regularly inserted every 3 or 5 phenylene monomer units, were synthesized. The copolymers were obtained by condensation of individually prepared diamino- and dicarboxylic-building blocks via the Yamazaki-;Higashi reaction. Solubility of the copolyamides are discussed in relation with the structure. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2379-2386, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 2371-2378 
    ISSN: 0887-624X
    Keywords: living radical polymerization ; chlorostyrene ; MTEMPO ; BPO ; thermal stability ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Radical polymerization of 2-, 3-, and 4-chlorostyrenes (ClSts) was investigated with benzoyl peroxide (BPO) as an initiator, in the presence of 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl (MTEMPO). The polymerization was performed in bulk for 3.5 h at 95°C and then continued for a defined time at 125°C to give the corresponding poly(ClSt)s with narrow polydispersity in high yield. It was found that the polymerization proceeded in accordance with a living mechanism in all cases, because the molecular weight of the resulting polymers was proportional to the conversion, and inversely proportional to the initial concentration of MTEMPO. Furthermore, the polymers obtained from 2- and 3-ClSts quantitatively act as initiators for the polymerization in the living radical manner, of styrene to give the corresponding block copolymers, except for poly(4-ClSt). The thermal stability of the living poly(ClSt)s was found to decrease in the order of 2- 〉 3- 〉 4-ClSt on the basis of the results of their postpolymerizations. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2371-2378, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 2387-2394 
    ISSN: 0887-624X
    Keywords: inorganic-organic hybrid ; diacetylene ; silicon ; boron ; thermooxidative stability ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of inorganic-organic linear diacetylenic hybrid polymers (5a-e) were prepared by the polycondensation reaction of 1,4-dilithiobutadiyne with 1,4-bis(dimethylchlorosilyl)benzene and/or 1,7-bis(tetramethylchlorodisiloxane)-m-carborane. Their structures were characterized using FTIR, and 13C and 1H NMR spectroscopies, and their thermal and oxidative properties were evaluated by DSC and TGA analyses. The hybrid polymers exhibited solubility in common organic solvents and were viscous liquids or low melting solids at room temperature. Broad prominent exotherms, attributed to reaction of the diacetylenic units, were observed by DSC in the 306°C to 354°C temperature range. When 5a-e were analyzed by TGA to 1000°C under nitrogen, weight retention between 79 and 86% were obtained. Ageing studies, performed at elevated temperatures in air on a thermoset and a ceramic obtained from polymer 5b, showed this system to have excellent thermal and oxidative stability. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2387-2391, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 2323-2331 
    ISSN: 0887-624X
    Keywords: bisnadimide ; ring-opening metathesis polymerization ; 5-norbornene 2,3-dicarboximide ; nadic anhydride ; thermal stability ; char yield ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The article deals with synthesis, characterization, and polymerization of 5-norbornene-2,3-dicarboximide end-capped resins (bisnadimides) based on 4,4′-diaminodiphenylether, 1,4/1,3-bis(4′-aminophenoxy) benzene, 2,2′-bis[4-(4′-aminophenoxy)phenyl]propane, and bis[4-(4′-aminophenoxy)phenyl]sulphone. Both exo and endo bisnadimides were prepared by reacting the aromatic diamines with exo or endo nadic anhydride in glacial acetic acid at 120°C. The exo or endo bisnadimides could be distinguished on the basis of differences observed in IR or 1H-NMR spectra. Both thermal (in solid state) and metathetical polymerization (using WCl6/tetramethyltin catalyst and chlorobenzene solvent) of bisnadimides was carried out. Only exo bisnadimides could be polymerized using metathesis reaction whereas thermal polymerization of both endo and exo bisnadimide could be successfully carried out at 300°C in static air atmosphere. The polymers were highly crosslinked and insoluble in common organic solvents. The polymers obtained by metathesis polymerization were light brown in color whereas those obtained by thermal polymerization were dark brown in color. Thermal stability of the thermally polymerized exo or endo bisnadimides was comparable. These polymers were stable up to 400°C and decomposed in a single step above this temperature. The char yield at 800°C depended on the structure of the polymer and was in the 39-56% range. The polymers formed by metathesis polymerization showed a 1-3% weight loss in the temperature range 226-371°C and decomposed in a single step above 440°C. The char yields were higher in these polymers (53-71%) compared to those obtained by thermal polymerization. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2323-2331, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 2395-2402 
    ISSN: 0887-624X
    Keywords: internal acetylene ; crosslinking ; polyimide ; thermally curable ; high modulus ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 4,4′-Diaminodiphenylacetylene (p-intA) was reacted with 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA), 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA) and pyromellitic dianhydride (PMDA) in N-methyl-2-pyrrolidone (NMP) to give poly(amic acid) solution of moderate to high viscosity. Thermal imidization gave polyimide having acetylene units that are linked para to the aromatic connecting unit. Polyimide having acetylene units that are linked meta to the aromatic connecting unit also was prepared utilizing 3,3′-diaminodiphenylacetylene (m-intA) for comparison. The crosslinking behavior of the acetylene units was observed with DSC. Exotherm due to the crosslinking of the para-linked acetylene units appeared at ca. 340 to 380°C depending on the structure of polyimide, whereas meta-linked acetylene units appeared at lower temperature as 340-350°C. After thermal treatment at high temperature such as 350 or 400°C, the amount of the exotherm became smaller and finally disappeared on DSC, confirming the progress of crosslinking. Dynamic mechanical properties of the polyimide films show that glass transition temperature increased with higher heat treatment, also confirming the progress of crosslinking. Tensile properties of the polyimide films showed that rigid polyimide films consisting of p-intA with BPDA or PMDA have considerably higher modulus than those consisting of m-intA. Cold-drawing of the poly(amic acid) followed by imidization gave much higher modulus in the case of rigid polyimide. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2395-2402, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 2513-2520 
    ISSN: 0887-624X
    Keywords: polyvinylamine ; cinnamoylated polymers ; photocrosslinking ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Vinylamine copolymers prepared by the Hofmann reaction were functionalized by amidification with cinnamoyl chloride. The resulting photosensitive polymers, which are the nitrogen analogues of poly(vinylcinnamate), can be prepared with various contents of cinnamamide side groups. The polymers exhibit a marked hydrophilicity and undergo efficient crosslinking upon exposure to 250-300 nm UV light. The sensitivity S expressed in cm2·J-1 was shown to be higher for a given content, τ, in cinnamamide groups expressed in mol·g-1 when the residual vinyl amine units are in the ammonium form. The dependence of S upon τ was of the second order for the free base form of the photopolymers, but a higher order with S approximately proportional to τ3 for the hydrochloride form of the photosensitive polymers. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2513-2520, 1997
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