Spontaneous copolymerization and diels‐alder reaction of 1,3‐cyclohexadiene with citraconic anhydride

Nagai, Katsutoshi; Yonezawa, Hajime

doi:10.1002/pol.1983.130210208

Cited by 7 publications

(4 citation statements)

References 21 publications

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“…On the other hand, 1,3-dienes, such as butadiene (BD), isoprene, cyclopentadiene, and furan, readily react with MAn to yield Diels–Alder adducts, but not alternating copolymers. In fact, we found very few reports about the radical copolymerization of 1,3-diene monomers with MAn in the literature . Thus, the directivity of MAn to Diels–Alder reactions is an obstacle for the copolymerization with 1,3-dienes, while Diels–Alder polymer reaction is one of the most convenient and reliable methods for the synthesis of self-healing materials, bioconjugated functional polymers, well-controlled polymer architectures, and controlled polymer networks .…”

Section: Introductionmentioning

confidence: 99%

Radical Alternating Copolymerization of Twisted 1,3-Butadienes with Maleic Anhydride as a New Approach for Degradable Thermosetting Resin

et al. 2014

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We report a novel approach for the synthesis of a readily curable and degradable resin by the radical alternating copolymerization of 1,3-diene monomers with maleic anhydride. 2,4-Dimethyl-1,3-pentadiene predominantly produced an alternating copolymer rather than a Diels–Alder adduct during the reaction with maleic anhydride. We revealed the most stable conformation as a twisted diene structure of 2,4-dimethyl-1,3-pentadiene and the other methyl-substituted dienes by DFT calculations, while a completely planar structure was preferred for the s-cis and s-trans conformers of the nonsubstituted butadiene. The highly alternating repeating structure of the produced copolymers was revealed based on the NMR analysis and copolymerization reactivity ratios. The alternating copolymers including an anhydride moiety and a carbon-to-carbon double bond in each repeating unit was conveniently used for the thermosetting, subsequent degradation, and polymer–surface modification by postpolymerization reactions such as epoxy curing and oxidative ozonolysis.

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Section: Introductionmentioning

confidence: 99%

Radical Alternating Copolymerization of Twisted 1,3-Butadienes with Maleic Anhydride as a New Approach for Degradable Thermosetting Resin

et al. 2014

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“…Diels–Alder reactions require a diene and a dieneophile, usually a single double bond . Although maleic anhydride reacts readily with a range of dienes, the substitution of a proton with an electron donating group such as the methyl in citraconic anhydride or in fact the polymer chain in pSMA, significantly decreases the reactivity of the dienophile . Danishefsky’s diene is known to be one of the most electron-rich dienes and therefore one of the most effective for electron-deficient dieneophiles .…”

Section: Resultsmentioning

confidence: 99%

“…23 Although maleic anhydride reacts readily with a range of dienes, the substitution of a proton with an electron donating group such as the methyl in citraconic anhydride or in fact the polymer chain in pSMA, significantly decreases the reactivity of the dienophile. 24 Danishefsky's diene is known to be one of the most electron-rich dienes and therefore one of the most effective for electron-deficient dieneophiles. 25 Addition of this diene (in excess) to pSMA at elevated temperatures resulted in a successful Diels−Alder reaction (pSMADD), as illustrated by the MALDI−ToF−MS spectrum (Figure 8), which shows the successful addition of Danishefsky's diene (DD) to pSMA.…”

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confidence: 99%

End-Functional Styrene–Maleic Anhydride Copolymers via Catalytic Chain Transfer Polymerization

et al. 2012

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Styrene−maleic anhydride copolymers have been successfully synthesized using catalytic chain transfer polymerization employing the low spin [bis(difluoroboryl)dimethylglyoximato]cobalt(II) (COBF) complex. By partially replacing styrene with α-methylstyrene (while maintaining the amount of maleic anhydride at 50 mol %) over a range of ratios, it was shown that the rate of reaction and molar mass decreases with increasing α-methylstyrene content. The polymers were characterized using MALDI−ToF−MS and 1 H− 13 C gHMQC NMR to determine the end groups, which in the presence of α-methylstyrene was an α-methylstyrene unit with a vinylic functionality. For styrene−maleic anhydride copolymers, the end group was determined to be predominantly maleic anhydride with a vinylic functionality. Considering the fact that in a styrene−maleic anhydride copolymerization the propagating radicals are predominantly of a styrenic nature, this was a very surprising result, suggesting that the maleic anhydride radicals undergo a chain transfer reaction, which is orders of magnitude faster than that of styrenic radicals. This conclusion was supported by high-level ab initio quantum chemical calculations, which showed that hydrogen abstraction from the maleic anhydride radical is 40 kJ/mol more exothermic than that from a styrene radical. The chain transfer constant of COBF was determined for the different ratios of styrene and α-methylstyrene. It was found to increase 2 orders of magnitude from a purely styrene−maleic anhydride to a purely α-methylstyrene−maleic anhydride copolymer. Diels−Alder and thiol−ene reactions were performed on the vinylic end groups as postpolymerization modification reactions, as well as graft copolymerization reactions of the macromonomers with styrene and butyl acrylate.

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“…Recently, we reported a new type of readily curable and degradable thermosetting resin, which was synthesized by radical alternating copolymerization of maleic anhydride (MAn) and diene monomers and subsequent epoxy curing as post-polymerization reaction 16) . For a long time, it has been accepted that 1,3-diene compounds, such as butadiene, isoprene, cyclopentadiene, and furan, react with MAn to yield Diels-Alder adducts in a high yield, rather than alternating copoly-mers 17,18) . In fact, there are very few reports on the radical copolymerization of 1,3-diene monomers with MAn in the literature 19,20) .…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Degradable Thermosetting Resin Using MaleicAnhydride/Diene Copolymers and Difunctional Crosslinkers

Tsujii¹,

Lou²,

Nagashima³

et al. 2015

Journal of the Adhesion Society of Japan

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We report the synthesis of a readily curable and degradable resin using an alternating copolymer of maleic anhydride and 2,4-dimethyl-1,3-pentadiene. The anhydride moiety of the alternating copolymer reacted with difunctional compounds, such as diepoxy, diol, and diamine derivatives as the crosslinkers, to produce network polymers by thermal curing. The subsequent ozone degradation of these thermosetting resins induced the cleavage of a carbon-to-carbon double bond in the polymer main chains, leading to the re-solubilization and surface modification of the crosslinked polymer materials.

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Spontaneous copolymerization and diels‐alder reaction of 1,3‐cyclohexadiene with citraconic anhydride

Cited by 7 publications

References 21 publications

Radical Alternating Copolymerization of Twisted 1,3-Butadienes with Maleic Anhydride as a New Approach for Degradable Thermosetting Resin

Radical Alternating Copolymerization of Twisted 1,3-Butadienes with Maleic Anhydride as a New Approach for Degradable Thermosetting Resin

End-Functional Styrene–Maleic Anhydride Copolymers via Catalytic Chain Transfer Polymerization

Synthesis of Degradable Thermosetting Resin Using MaleicAnhydride/Diene Copolymers and Difunctional Crosslinkers

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