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  • 1
    Electronic Resource
    Electronic Resource
    Synthesis and activity of aryl benzyl methyl sulfonium salts as cationic initiators: Effect of substituent on aryl group (1991)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 29 (1991), S. 1845-1851 
    Details
    ISSN: 0887-624X
    Keywords: sulfonium salt ; cationic initiator ; effect of substituent ; cationic polymerization ; glycidyl phenyl ether ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Benzyl o-, m-, and p-substituted phenyl methyl sulfonium salts (2b-2g) were synthesized and their activities as cationic initiators were evaluated in the bulk polymerization of phenyl glycidyl ether (PGE). Especially, their activities were estimated with respect to the effect of substituents on the aryl groups. In the polymerizations of PGE with a series of benzyl p-substituted phenyl methyl sulfonium salts, the order of their activities was found to be 2c (CH3OCOO) 〉 2b (CH3COO) 〉 2d (CH3O) ∼ 2a (HO). In particular, 2c was the most active initiator of all, capable of initiating the polymerization of PGE even at room temperature. In the polymerizations with 2a, 2e (m-Cl), 2f (o-CH3), and 2g (m-CH3), the activity of 2e was the highest of all while those of 2a, 2f, and 2g were almost the same. These results strongly suggested that the electron-withdrawing group placed on the aryl group undoubtedly enhanced the activity of the sulfonium salts as the cationic initiators.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1991.080291302
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  • 2
    Electronic Resource
    Electronic Resource
    Cationic polymerization of γ-methyl- and α-methylphenylallene (1992)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 30 (1992), S. 583-587 
    Details
    ISSN: 0887-624X
    Keywords: α-methylphenylallene ; γ-methylphenylallene ; cationic polymerization ; Lewis acid ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The cationic polymerizations of γ-methylphenylallene (1) and α-methylphenylallene (2) were carried out with some Lewis acids at 25 and 0°C in dichloromethane to obtain the corresponding polymers through allyl cations, respectively. Tin (IV) chloride was found to be an effective catalyst for the cationic polymerization of both allenes 1 and 2 compared with other Lewis acids. Thus, in the polymerization of 1, methanol-insoluble polymer was only obtained using Tin (IV) chloride, and M̄n of methanol-insoluble polymer obtained by Tin (IV) chloride was the highest in the polymerization of 2. From the analysis of 1H- and 13C-NMR spectra of the obtained polymers, the polymer from 1 consisted of two kinds of units polymerized by each double bonds of allene 1, whereas the polymer from 2 consisted of only one unit polymerized by terminal double bond of allene 2. Moreover, effect of solvent on the cationic polymerizations of 1 and 2 were discussed.
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1992.080300409
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  • 3
    Electronic Resource
    Electronic Resource
    Alkyl halide-initiated cationic polymerization of cyclic carbonate (1993)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 31 (1993), S. 581-584 
    Details
    ISSN: 0887-624X
    Keywords: cyclic carbonate ; polycarbonate ; cationic polymerization ; ring-opening polymerization ; alkyl halide ; decarboxylation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1993.080310232
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  • 4
    Electronic Resource
    Electronic Resource
    γ-poly(glutamic acid) as an initiator of cationic polymerization of N-vinylcarbazole and N-vinyl-2-pyrrolidone (1993)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 31 (1993), S. 3193-3198 
    Details
    ISSN: 0887-624X
    Keywords: γ-poly(glutamic acid) ; biosynthesized polymer ; cationic polymerization ; initiator ; N-vinylcarbazole ; N-vinyl-2-pyrrolidone ; carboxyl group ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The cationic polymerization of vinyl monomers initiated by biosynthesized γ-poly(glutamic acid) (γ-PGA) powder surface was carried out in a heterogeneous system. It was found that the polymerization of N-vinylcarbazole (NVC) and N-vinyl-2-pyrrolidone (NVPD) is initiated by γ-PGA powder. The grafting of polymers onto γ-PGA surface was scarcely observed. The apparent activation energy of the polymerization of NVC and NVPD was estimated to be 20.2 and 24.8 kJ/mol, respectively. The polymerization was totally inhibited by the addition of triethylamine and pyridine, but not hydroquinone. The polymerization rate in nitrobenzene was larger than that in toluene. These results indicated the cationic nature of the polymerization. γ-PGA treated with KOH did not show the initiating activity of the polymerization. Therefore, carboxyl groups on γ-PGA powder surface play an important role in the initiation of the polymerization. It may be suggested that the polymerization is initiated by proton addition to monomer from carboxyl groups on γ-PGA powder surface and the propagation proceeds with carboxylate anion on the surface as counter ion. © 1993 John Wiley & Sons, Inc.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1993.080311304
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  • 5
    Electronic Resource
    Electronic Resource
    Photocrosslinking of polymers containing cationically polymerizable groups in the side-chain by sulfonium salts (1992)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 30 (1992), S. 933-936 
    Details
    ISSN: 0887-624X
    Keywords: photocrosslinking ; vinylether ; sulfonium salt ; cationic polymerization ; swelling ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1992.080300525
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  • 6
    Electronic Resource
    Electronic Resource
    Oxoaminium salts as initiators for cationic polymerization of vinyl monomers (1993)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 31 (1993), S. 1505-1512 
    Details
    ISSN: 0887-624X
    Keywords: oxoaminium salt ; cationic polymerization ; cationic initiator ; vinyl monomers ; block copolymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Oxoaminium salt (1), derived from 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO, 2) by one-electron oxidation, could be an initiator for cationic polymerization of vinyl monomers such as isobutyl vinyl ether (IBVE), 2,3-dihydrofuran, p-methoxystyrene, N-vinyl pyrrolidone, etc., to give the corresponding polymers, when 1 had a low nucleophilic counter anion. Formation of the adducts of 1 and IBVE as well as 1H-NMR and IR data suggested the formation of polymers containing N—O—C structure as the polymer head group. In the polymerization of IBVE, the effects of solvent and concentration of 1 were little observed, however the polymerization rate was dependent on temperature. Furthermore, the thermal reaction of the polymers obtained, which were regarded as prepolymers for block copolymerization and polymeric initiators for radical polymerization, was studied. For example, poly(2-benzylidene-1,3-dioxane) obtained by the polymerization of 2-benzylidene-1,3-dioxane with oxoaminium hexafluoroantimonate (1, X = SbF6) was employed as an initiator for radical polymerization of MMA to give its block copolymer with PMMA. © 1993 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1993.080310620
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  • 7
    Electronic Resource
    Electronic Resource
    Regioselective cationic ring-opening polymerization of 4-methylene-2-styryl-1,3-dioxolane (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 983-985 
    Details
    ISSN: 0887-624X
    Keywords: 4-methylene-1,3-dioxolane ; cationic polymerization ; regioselectivity ; vinyl ether ; ring-opening ; isomerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1994.080320520
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  • 8
    Electronic Resource
    Electronic Resource
    Photocrosslinking of copolymers of vinyloxyethyl methacrylate-styrene initiated by sulfonium salts. II. Photocrosslinking behaviors (1992)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 30 (1992), S. 2569-2576 
    Details
    ISSN: 0887-624X
    Keywords: photocrosslinking ; vinylether ; sulfonium salt ; cationic polymerization ; swelling ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Vinylether was used as a cationically polymerizable moiety and incorporated into sidechain of polymers as copolymers of vinyloxyethyl methacrylate (VEM) and styrene (St). Photoirradiation of the copolymers containing a small amount of benzyl(4-hydroxyphenyl) methylsulfonium salt (BSS) resulted in a high crosslinking density as evidenced by a low degree of swelling, which is ascribed to the high reactivity of the vinyloxy moieties. The sensitivity of this photoreaction is significantly high because of a large kinetic chain length of the cationic polymerization of vinylethers, while copolymers of glycidyl methacrylate and St showed crosslinking to much less extent when irradiated under the same condition. The ability of other sulfonium salts, (4-hydroxyphenyl) methyl(4-nitrobenzyl) sulfonium salt and (4-hydroxyphenyl) methyl(1-naphthylmethyl)sulfonium salt, to induce photocrosslinking was also examined. © 1992 John Wiley & Sons, Inc.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1992.080301211
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  • 9
    Electronic Resource
    Electronic Resource
    Cationic polymerization of 2-isopropenyl-4-methylene-1,3-dioxolane in the presence of nucleophilic compounds (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 199-201 
    Details
    ISSN: 0887-624X
    Keywords: 4-methylene-1,3-dioxolane ; nucleophilic compound ; vinyl ether ; ring-opening polymerization ; cationic polymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1994.080320124
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  • 10
    Electronic Resource
    Electronic Resource
    Cationic polymerization behavior of seven-membered cyclic sulfite (1997)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 3673-3682 
    Details
    ISSN: 0887-624X
    Keywords: seven-membered cyclic sulfite ; cationic polymerization ; desulfoxylation ; volume expansion ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cationic ring-opening polymerization behavior of a seven-membered cyclic sulfite (1) was examined. 1 was prepared by the reaction of 1,4-butanediol with SOCl2 in 58% yield. The cationic polymerization of 1 was carried out at 0, 25, 60, or 100°C with trifluoromethanesulfonic acid (TfOH), methyl trifluoromethanesulfonate (TfOMe), BF3 · OEt2, SnCl4, methyl p-toluenesulfonate (TsOMe), or MeI as an initiator in bulk under a nitrogen atmosphere to afford the polymer with M̄n 1000-10,400. The order of activities of the initiators for 1 was as follows, TfOH ≅ TfOMe 〉 SnCl4 〉 BF3 · OEt2 〉 TsOMe ≅ MeI. The polymerization of 1 with TfOMe afforded a poly(sulfite) below 25°C, but afforded a polymer containing an ether unit at 60°C, which was formed by a desulfoxylation. The higher the activity of the initiator was, the more easily the desulfoxylation occurred. We expected volume expansion on polymerization because cyclic sulfites have large dipole moment values, but it turned out that 1 showed 4.34% shrinkage on polymerization. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3673-3682, 1997
    Additional Material: 10 Ill.
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