Regiospecific Radical Polymerization of a Tetrasubstituted Ethylene Monomer with Molecular Oxygen for the Synthesis of a New Degradable Polymer

Matsumoto, Akikazu; Taketani, Shuji

doi:10.1021/ja0580385

Cited by 52 publications

(48 citation statements)

References 15 publications

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“…A mechanism for the regiospecific 1,4-propagation of the MCP monomers via a radical reaction process was discussed based on the results of DFT calculations as well as the precise structure determination of the model oligomers. Recently, the regiospecific radical polymerizations were reported for the copolymerization of diene monomers with nonvinyl monomers, such as molecular oxygen 64,65 and sulfur dioxide. 66,67 The regiospecific radical polymerization is still one of the most important and challenging topics as well as the sequence-and stereocontrol of polymers using a radical polymerization process.…”

Section: ■ Conclusionmentioning

confidence: 99%

Controlled Radical Polymerization of 3-Methylenecyclopentene with N-Substituted Maleimides To Yield Highly Alternating and Regiospecific Copolymers

Yamamoto

Matsumoto

2013

Macromolecules

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High-molecular-weight diene copolymers with a regiospecific repeating structure were produced in a high yield during the alternating radical copolymerization of N-substituted maleimides (RMIs) and 3-methylenecyclopentene (MCP) as the cyclic 1,3-diene monomer including a reactive exomethylene moiety. The eminent copolymerization reactivity of MCP was in contrast to the predominant occurrence of the Diels−Alder reaction of isoprene with the RMIs rather than copolymerization. The highly alternating structure of the copolymers was confirmed based on the monomer reactivity ratios for the copolymerization of MCP (M 1 ) and N-phenylmaleimide (PhMI, M 2 ), r 1 = 0.010 and r 2 = 0.0080. A mechanism for the highly controlled 1,4-regiospecific propagation, which consists of the addition of an RMI radical to the exomethylene group of MCP and subsequent 1,4-regiospecific propagation, was supported by the DFT calculations using model reactions as well as the precise structure determination of oligomers produced during telomerization in the presence of 1-butanethiol as a chain transfer agent. The resulting copolymers exhibited no weight-loss under 340°C during heating in a nitrogen atmosphere and their glass transition temperature was over the wide temperature range of 66−159°C, depending on the structure of the N-alkyl substituents. The transparent and flexible films were fabricated by a casting method. The optical properties of the films were as follows: the visible light transmittance over 95% at 380 nm, the refractive indices of 1.54−1.58, and the Abbe number of 42−45. ■ INTRODUCTIONTransparent polymer materials with a thermal stability are one of the key materials for various application fields, such as electronics, optoelectronics, and photonics. 1−11 The transparent and heat-resistant polymers are industrially fabricated by condensation polymerization and metal-catalyzed polymerization processes, as seen in most cases of the mass-production of polycarbonates and cycloolefin polymers as the transparent polymers and polyimides as the high-temperature polymers. 12 A radical chain polymerization process has a significant number of merits for the fabrication of polymeric materials due to the formation of high-molecular-weight polymers from commodity monomers, the design of polymer sequences using controlled polymerizations, and finely tunable polymer structures and properties by copolymerization. 13−15 The radical copolymerization of electron-accepting N-substituted maleimides (RMIs) with electron-donating olefins readily produces high-molecularweight and alternating copolymers in a high yield. 16−19 Especially, the copolymers of the RMIs with isobutene 20,21 and other olefins 22−26 exhibited an excellent thermal stability, transparency, high strength, and high modulus. In contrast, very few studies have reported the radical copolymerization with conjugated 1,3-dienes 27−29 because diene compounds and the RMIs predominantly give Diels-Adler adducts, 30 not copolymers. A maleimide moiety is favorably used as a reactive funct...

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Section: ■ Conclusionmentioning

confidence: 99%

Controlled Radical Polymerization of 3-Methylenecyclopentene with N-Substituted Maleimides To Yield Highly Alternating and Regiospecific Copolymers

Yamamoto

Matsumoto

2013

Macromolecules

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“…In this so-called homolytic displacement reaction, the peroxide is split into two alkoxyl radicals, one of which forms an epoxide, whereas the other induces cleavage between the carbons bearing the alkoxyl radical and the peroxide group to form the two aldehydes benzaldehyde and formaldehyde in a chain reaction. Related chemistry is characterized with other starting materials (31,32). The overall outcome of carbon chain cleavage of peroxide-linked polymers into aldehydes triggered further interest in the dimerization or oligomerization of fatty acid derivatives during autoxidation.…”

Section: New Insights From Novel Products: Evidence For Intermoleculamentioning

confidence: 99%

Routes to 4-Hydroxynonenal: Fundamental Issues in the Mechanisms of Lipid Peroxidation

Schneider

Porter

Brash

2008

Journal of Biological Chemistry

238

205

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Although investigation of the toxicological and physiological actions of ␣/␤-unsaturated 4-hydroxyalkenals has made great progress over the last 2 decades, understanding of the chemical mechanism of formation of 4-hydroxynonenal and related aldehydes has advanced much less. The aim of this review is to discuss mechanistic evidence for these non-enzymatic routes, especially of the underappreciated intermolecular pathways that involve dimerized and oligomerized fatty acid derivatives as key intermediates. These cross-molecular reactions of fatty acid peroxyls have also important implications for understanding of the basic initiation and propagation steps during lipid peroxidation and the nature of the products that arise.

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“…13 Therefore, it is expected as the new kind of degradable polymer with significant potential in the fields of adhesion, coating, environment, and medicinal chemistry. We already reported some preliminary results regarding the syntheses of environmentally friendly PP that avoid the evolution of volatile and toxic degradation products, 13,14 water-soluble PP which exhibit an LCST (lower critical solution temperature)-type phase separation, 15 degradable PP gels using bifunctional diene monomers, 16 and poly(lactic acid) with a branched or network structure containing PP repeating units as the thermally degradable junctions. 17 The highly controlled regiostructure of the PP chain is necessary for controlling the degradation and its reaction products.…”

Section: Introductionmentioning

confidence: 99%

Regiospecific Structure, Degradation, and Functionalization of Polyperoxides Prepared from Sorbic Acid Derivatives with Oxygen

et al. 2006

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We have fabricated degradable polyperoxides (PP) consisting of well-controlled 5,4-repeating units using various sorbic acid derivatives and molecular oxygen by an alternating radical copolymerization process. The PP obtained from the sorbic esters decompose via a radical chain reaction mechanism, leading to the formation of controlled low-molecular-weight products. In contrast, PP from some amide derivatives include an irregular chain structure, resulting in a more complicated degradation behavior. The theoretical calculations account for the selectivity in the two-step regiospecific propagation depending on the monomer structure. We have demonstrated the synthesis of functional PP based on two methods: one is the copolymerization of functional diene monomers with oxygen, and the other is the polymer reaction of PP including an azide group with a functional alcohol.

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Regiospecific Radical Polymerization of a Tetrasubstituted Ethylene Monomer with Molecular Oxygen for the Synthesis of a New Degradable Polymer

Cited by 52 publications

References 15 publications

Controlled Radical Polymerization of 3-Methylenecyclopentene with N-Substituted Maleimides To Yield Highly Alternating and Regiospecific Copolymers

Controlled Radical Polymerization of 3-Methylenecyclopentene with N-Substituted Maleimides To Yield Highly Alternating and Regiospecific Copolymers

Routes to 4-Hydroxynonenal: Fundamental Issues in the Mechanisms of Lipid Peroxidation

Regiospecific Structure, Degradation, and Functionalization of Polyperoxides Prepared from Sorbic Acid Derivatives with Oxygen

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