A model for living radical polymerization

Otsu, Takayuki; Yoshida, Masatoshi; Tazaki, Toshinori

doi:10.1002/marc.1982.030030209

Cited by 465 publications

(304 citation statements)

References 28 publications

Supporting

Mentioning

299

Contrasting

Unclassified

Order By: Relevance

“…In early 1980s, Otsu reported a living radical polymerization of alkenes with this compound and described its action as inifer or iniferter which means that it acted as initiator, transfer agent and terminator 16 . The systems with thiuram disulfide as iniferter are usually characterized by the initial rapid growth and then a monotonous increase in molecular weight with conversion.…”

Section: System I Based On Reversible Recombination Of Growing Radicamentioning

confidence: 99%

“…R2N-C(S)-S" + Pn" -+ R2N-C(S)-S-Pn (reversible only with hv) (20) Growing radicals may also react with dithiocarbamates end groups in two different ways: by transfer process as suggested by Otsu 16 :…”

Section: R2n-c(s)-s-s-c(s)-nr2 2r2n-c(s)-s (18)mentioning

confidence: 99%

“…These initiators can be added in controlled amounts like in the polymerization with alkoxyamines as transfer agents 29 . The role of the initiator may be played by impurities or even by the product of decomposition of transfer agents (alkyl dithiocarbamates) 16 .…”

Section: R2n-c(s)-s-s-c(s)-nr2 2r2n-c(s)-s (18)mentioning

confidence: 99%

See 2 more Smart Citations

"Living" radical polymerization. 1. Possibilities and limitations

Greszta¹,

Mardare²,

1994

View full text Add to dashboard Cite

Section: System I Based On Reversible Recombination Of Growing Radicamentioning

confidence: 99%

Section: R2n-c(s)-s-s-c(s)-nr2 2r2n-c(s)-s (18)mentioning

confidence: 99%

See 1 more Smart Citation

"Living" radical polymerization. 1. Possibilities and limitations

Greszta¹,

Mardare²,

1994

View full text Add to dashboard Cite

“…the number of initiator fragments per one polymer molecule is always less than 2. So if we use initiators which have very high reactivities for chain transfer to the initiator and/or primary radical termination in order to avoid ordinary bimolecular terminations, it is expected to be obtained a polymer with two initiator fragments at its chain ends (eq 2). (2) Therefore, these radical polymerizations may simply be considered as an insertion reaction of monomer molecules into the R-R' bond of the initiator leading to a polymer with two initiator fragments at its chain ends, as well as the special case shown in eq 1. For initiators with these functions we proposed to call iniferter 1 in analogy with "inifer" named by Kennedl in cationic polymerization.…”

Section: The Concept Of Inifertermentioning

confidence: 99%

Polymer Design by Iniferter Technique in Radical Polymerization: Synthesis of AB and ABA Block Copolymers Containing Random and Alternating Copolymer Sequences

Otsu

Kuriyama

1985

Polym J

Self Cite

View full text Add to dashboard Cite

ABSTRACT:The iniferter technique was applied to synthesis of the AB and ABA block copolymers containing various random and alternating copolymer sequences. Benzyl N, Ndiethyldithiocarbamate (BDC), p-xylylene bis(N, N-diethyldithiocarbamate) (XDC) and 1,2,4,5-tetrakis(N, N-diethyldithiocarbamylmethyl)benzene (DDC) were used as mono-, bi-and tetrafunctional photoiniferters, respectively. The photopolymerizations with BDC and XDC proceeded via a living radical mechanism, and gave soluble mono-and bifunctional polymers (photoiniferters), respectively. However, DDC induced living radical polymerization of styrene with gelation. When various polymers and copolymers obtained by BDC and XDC were used as polymeric photoiniferters, the AB and ABA block copolymers containing random copolymer sequences were obtained in high yields. Similarly the alternating copolymerization of isobutyl vinyl ether with maleic anhydride in the presence of the alternating copolymers such as styrene and diisopropyl fumarate, which were obtained by BDC and XDC, as polymeric photoiniferters was found to give the AB and ABA block copolymers consisting of alternating copolymer sequences. DDC and the polymers and copolymers obtained by DDC could also act as an excellent cross-linking agent.KEY WORDS Radical Polymerization I Living Radical Polymerization I Initiator I Iniferter I Iniferter Technique I Polymer Design I Block Copolymer IThe structure control of the producing polymer, i.e., the reactivity control of the reacting monomer, in radical polymerization is now the most important problem to design and architect the polymer structure. To approach this purpose, we have recently proposed a concept of initiator-transfer agentterminator (iniferter) 1 for designing of the polymer chain end structure, and simultaneously a new model for living radical polymerization in homogeneous system by using iniferters such as phenylazotriphenylmethane2 and some organic sulfur compounds. 2 -5 These ideas are summarized briefly as follows.(R-R') is expressed by eq 1, if no chain transfer reactions occur and mutual termination proceeds only by recombination. The Concept of IniferterThe polymer formation in radical polymerization of vinyl monomers (M) initiated by an initiator (I) In this case, radical polymerization gives a polymer with two initiator fragments at its chain ends. However, in ordinary radical polymerization of many monomers, the termination by disproportionation and the chain transfer reactions have been known to occur importantly, i.e. the number of initiator fragments per one polymer molecule is always less than 2.So if we use initiators which have very high reactivities for chain transfer to the initiator and/or primary radical termination in order to avoid ordinary bimolecular terminations, it is expected to be 97

show abstract

“…A sufficiently large number of activation-deactivation cycles are required to achieve low polydispersity. In addition to thermal heating, photo irradiation has been utilized to control several LRP systems [4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19]. A restriction of the current systems is that the feasible wavelength is nearly fixed in each system.…”

Section: Introductionmentioning

confidence: 99%

Photo-Induced Living Radical Polymerization via Organic Catalysis

Goto

2015

J. Photopol. Sci. Technol.

View full text Add to dashboard Cite

Photo-controlled organocatalyzed living radical polymerization was developed. The polymerization was induced and controlled at desired wavelengths over a wide range of wavelengths (350-750 nm) by exploiting suitable catalysts. This polymerization was finely responsive to the irradiation power and wavelength. The polymer molecular weight and its distribution (M w /M n = 1.1-1.4) were well controlled for methacrylate monomers. The monomer scope encompassed various functional methacrylates, and their block copolymers were obtained. Applicability to a wide range of polymer designs is an advantage of this polymerization.

show abstract

A model for living radical polymerization

Cited by 465 publications

References 28 publications

"Living" radical polymerization. 1. Possibilities and limitations

"Living" radical polymerization. 1. Possibilities and limitations

Polymer Design by Iniferter Technique in Radical Polymerization: Synthesis of AB and ABA Block Copolymers Containing Random and Alternating Copolymer Sequences

Photo-Induced Living Radical Polymerization via Organic Catalysis

Contact Info

Product

Resources

About