Synthesis of Cyclic Polymers:  Ring-Expansion Reaction of Cyclic <i>S</i>-Dithioester with Thiiranes

Kudo, Hiroto; Makino, Shinya; Kameyama, and Atsushi; Nishikubo, Tadatomi

doi:10.1021/ma047642h

Cited by 67 publications

(47 citation statements)

References 13 publications

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“…Two reactive thermolabile SAC bonds in a cyclic aromatic bis(dithioester) were the structural prerequisites enabling the insertion of thiiranes (Scheme 60). 248 However, high molar masses were not obtained by this method.…”

Section: Reps Of Various Monomersmentioning

confidence: 91%

“…[244][245][246][247][248] They are based on four different classes of cyclic initiators, four different classes of monomers, and four different reaction mechanisms.…”

Section: Reps Of Various Monomersmentioning

confidence: 99%

“…The SANS method was preferentially used to measure the radii of gyration 59,61,[248][249][250] either from solutions of a protonated polymer in a deuterated solvent or from a solution of the deuterated polymer in a protonated solvent. A review article describing this method along with a handful of typical results was also published.…”

Section: Solution Propertiesmentioning

confidence: 99%

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Cyclic polymers: Synthetic strategies and physical properties

Kricheldorf

2009

J. Polym. Sci. A Polym. Chem.

397

442

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Syntheses of cyclic polymers including cyclic homopolymers, cyclic block copolymers, sun-shaped polymers, and tadpole polymers are discussed on the basis of a differentiation between synthetic methods and synthetic strategies (e.g., polycondensation, ring-ring equilibration, or ring-expansion polymerization). Furthermore, all synthetic methods are classified as kinetically or thermodynamically controlled reactions. Characteristic properties of cyclic polymers such as smaller hydrodynamic volume, lower melt viscosities, and higher thermostabilities are compared to the properties of their linear counterparts. Furthermore, the nanophase separation of cyclic diblock copolymers is discussed.

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Section: Reps Of Various Monomersmentioning

confidence: 91%

“…[244][245][246][247][248] They are based on four different classes of cyclic initiators, four different classes of monomers, and four different reaction mechanisms.…”

Section: Reps Of Various Monomersmentioning

confidence: 99%

See 1 more Smart Citation

Cyclic polymers: Synthetic strategies and physical properties

Kricheldorf

2009

J. Polym. Sci. A Polym. Chem.

397

442

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“…When the insertion reaction of PPS into CD (CD/PPS = 1/50) was carried out using TBAC catalyst, the corresponding large cyclic polysulfide with M n ¼ 42000, M w =M n ¼ 4:50 was obtained (Scheme 14). 53 This is a unique reaction system for the synthesis of cyclic polymers; the size of the cyclic polymers increased with the polymerization as it proceeded. It was also found that an intermolecular ester-exchange reaction occurred as an unexpected reaction during the insertion reaction of PPS into CD.…”

Section: Synthesis Of Polymers With Complex Architecturesmentioning

confidence: 99%

“…It was also found that an intermolecular ester-exchange reaction occurred as an unexpected reaction during the insertion reaction of PPS into CD. 53 …”

Section: Synthesis Of Polymers With Complex Architecturesmentioning

confidence: 99%

Novel Synthesis of Polymers with Well-Defined Structures Based on Selective Reaction of Cyclic Sulfides and Cyclic Ethers Catalyzed by Quaternary Onium Salts

Kameyama

Nishikubo

2009

Polym. J.

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Novel syntheses of polymers with well-defined structures were developed on the basis of the selective reactions of thiiranes and oxiranes with carboxylic esters or active chlorides using quaternary onium salts. (1) A new type of reactive polymers with pendant chloromethyl groups was synthesized by polyaddition of difunctional thiiranes or oxiranes with various organic dichlorides. (2) Polysulfides with controlled molecular weight and narrow molecular weight distribution were synthesized by ring-opening polymerization of thiiranes with carboxylic acid derivatives as initiators and quaternary onium salts as catalysts, in which acyl-groups transfer to the propagating center in each propagation step. The ring-opening polymerization of thiiranes has an advantage in the synthesis of specific shaped polymers such as star polymers and cyclic polymers. (3) Novel A-B type sequence-ordered copolymers were synthesized by alternating ring-opening polymerization of oxiranes withthiobutyrolactone, or of oxetane with cyclic carboxylic anhydrides. (4) Sequence-ordered polymers were successfully synthesized on the basis of a new concept-''transformation of polymer backbones'' using insertion of thiiranes and oxiranes into poly(S-thioester)s in the aforementioned reaction systems. The reaction mechanism and advantages of the reaction systems are also discussed.KEY WORDS: Ring-opening Reaction / Thiirane / Oxirane / Quaternary Onium Salts / Acyl Transfer / Sequence-ordered Polymers / Addition reactions of cyclic compounds such as cyclic ethers with certain reagents are useful synthetic methods for preparing polymeric materials. The addition reactions of oxiranes (epoxy) compounds have been used for syntheses of functional polymers from reactive polymers containing pendant oxirane groups.1 Epoxy resins with multiple oxirane groups are widely utilized with certain curing reagents to obtain thermal cured materials.2 These polymer syntheses are based on the addition reaction of oxiranes with such reagents as amines, carboxylic acids, etc. In general, the reactions provide mixtures of -addition and -addition products (mixtures of regio-isomers).3 Regioselective ring-opening reactions of oxiranes are important research subjects in synthetic organic chemistry, 4 but it has been thought that the reactions of oxiranes with the reagents mentioned are not suitable for precise syntheses of polymers with well-defined structures.Recently, we have developed synthetic methods for functional polymers and chemical modification of polymers based on the regioselective ring-opening reactions of oxiranes with carboxylic esters catalyzed by quaternary onium salts. 5 In a series of studies on ring-opening reaction of cyclic compounds with several reagents; we found novel regioselective reactions of thiiranes or oxiranes to be useful for syntheses of polymers with well-defined structures.A significant advantage of the addition reactions of thiiranes or oxiranes with the reagents is the selective formation ofaddition products without ring-opening polymeriza...

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Cyclic and Multicyclic Topological Polymers

Yamamoto

Tezuka

2011

Complex Macromolecular Architectures

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Synthesis of Cyclic Polymers: Ring-Expansion Reaction of Cyclic S-Dithioester with Thiiranes

Cited by 67 publications

References 13 publications

Cyclic polymers: Synthetic strategies and physical properties

Cyclic polymers: Synthetic strategies and physical properties

Novel Synthesis of Polymers with Well-Defined Structures Based on Selective Reaction of Cyclic Sulfides and Cyclic Ethers Catalyzed by Quaternary Onium Salts

Cyclic and Multicyclic Topological Polymers

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