Reactivity in radical polymerization ofN-substituted maleimides and thermal stability of the resulting polymers

Otsu, Takayuki; Matsumoto, Akikazu; Kubota, Toru; Mori, Shigeki

doi:10.1007/bf00983962

Cited by 144 publications

(57 citation statements)

References 17 publications

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“…The degradation is due to decarboxylation, decomposition of the ester groups and to successive degradation of simpler degradation products. The results obtained by TGA are in accordance with the literature data [18].…”

Section: Resultssupporting

confidence: 91%

Synthesis and Radical Polymerization of N-(3-Acetyl-4-Carboxy-Phenyl)-Maleimide

Hulubei¹,

Morariu²

2000

High Performance Polymers

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Abstract.A new functional monomer derivative of p-aminosalicylic acid, N-(3-acetyl-4-carboxy-phenyl)-maleimide, was synthetized and polymerized with azobisisobutyronitrile as initiator at 60 • C in various solvents. The obtained structures were confirmed by IR, 1 H-NMR and elemental analysis. The molecular weights and the polydispersity values of the polymers were determined in the ranges (3.4-5.9)×10 3 and 1.28-1.60 respectively, by gel permeation chromatography. The activation energy of the monomer polymerization in tetrahydrofuran was calculated as 26.11 kcal mol −1 . The x-ray analysis shows, in all cases, the existence of two characteristic diffraction maxima (d i , d o ), and the influence of the length and size of the aromatic substituents on these maxima are discussed. Functional polymers members of the salicylic acid family would lead to polymers which should show chelation, catalytic, thermochromic or photochromic properties.

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Section: Resultssupporting

confidence: 91%

Synthesis and Radical Polymerization of N-(3-Acetyl-4-Carboxy-Phenyl)-Maleimide

Hulubei¹,

Morariu²

2000

High Performance Polymers

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“…[1][2][3][4][5][6] The RMIs also copolymerize with electron-donating monomers, such as styrene, vinyl ethers, and olefins, to give alternating copolymers with excellent thermal stability and a high glass transition temperature (T g ). [7][8][9][10][11] Especially, the copolymerization of the RMIs with isobutene provided an alternating copolymer with excellent thermal stability, high transparency, and high modulus and strength.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of Thermoresistant Maleimide Copolymers and their Crosslinked Polymers

Yamamoto

Okamura

Matsukawa

et al. 2014

J. Photopol. Sci. Technol.

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We fabricated thermosetting maleimide polymers with excellent thermal and optical properties by the sequence-controlled radical copolymerization of N-allylmaleimide (AMI) and N-(2-ethylhexyl)maleimide (EHMI) with diisobutylene (DIB) and postpolymerization reactions. The AAB-type maleimides/DIB copolymers randomly containing an allyl group in the side chain were thermally or photochemically cured using pentaerythritol tetrakis(3-mercaptobutyrate) as a polyfunctional thiol by thiol/ene reaction. The organic-inorganic hybrid was also fabricated by the thiol/ene reaction of the maleimide copolymers containing allyl side groups combined with surface-modified silica nanoparticles. The produced organic-inorganic hybrid was dispersed in tetrahydrofuran. The transparent films of the maleimide copolymers containing the hybrid were obtained by casting and drying. The crosslinked polymers and the organic-inorganic hybrid obtained in this study exhibited excellent thermal stability as well as the high transparency.

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“…The radical polymerization and copolymerization of N-phenylmaleimide (PhMI, 1) and the thermal properties of the resulting polymers have been extensively studied in order to obtain thermally stable vinyl polymers. [1][2][3] At the same time, various kinds of PhMI derivatives have also been synthesized and polymerized. [4][5][6][7][8][9][10][11][12] When alkyl substituents were introduced in the N-phenyl group, the polymers were soluble in non-polar solvents and showed an excellent thermal decomposition property, while poly(1) was soluble in limited kinds of polar solvents.…”

mentioning

confidence: 99%

“…For example, the T g values were reported to be 139, 126, 124, and 154 C for poly(RMI-alt-IB)s with 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, and 1-methyl-2-hydroxyethyl groups as N-substituents, respectively. 22 In the present study, the alternating copolymers of N-(substituted phenyl)maleimides (XPhMIs), such as N-(hydroxyphenyl)-maleimides (2)(3)(4) and N-(4-carboxyphenyl)maleimide (5), with IB [poly(XPhMI-alt-IB)s] were synthesized, as shown in Scheme 1. The effects of hydroxy and carboxy groups on their thermal properties were investigated on the basis of the results of thermal analysis, temperature-controlled IR spectroscopy, and theoretical calculations.…”

mentioning

confidence: 99%

Thermal Properties of N-Phenylmaleimide-Isobutene Alternating Copolymers Containing Polar Groups to Form Intermolecular and Intramolecular Hydrogen Bonding

Omayu

Matsumoto

2008

Polym J

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We have demonstrated that the alternating copolymers obtained from N-phenylmaleimides having hydroxy and carboxy substituents and isobutene show excellent thermal stabilities; namely, onset temperatures of decomposition higher than 350 C and glass transition temperatures higher than 220 C, depending on the structure and position of the polar groups in the N-phenyl group. The obtained copolymers were soluble in organic solvents, such as dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, and acetone, and transparent and brittle films were obtained by casting from their acetone solutions. The role of intermolecular hydrogen bonding for an increase in the glass transition temperature by the introduction of the polar groups was investigated by temperature-controlled IR spectroscopy. The formation of intramolecular hydrogen bonding for the N-2-hydroxyphenyl derivative was also revealed. The molecular conformations were discussed on the basis of the results of DFT calculations for the model compounds of the repeating unit in the copolymers. Recently, new thermo-resistant polymers with a high transparency attract a great interest as key materials for optoelectronic applications. The radical polymerization and copolymerization of N-phenylmaleimide (PhMI, 1) and the thermal properties of the resulting polymers have been extensively studied in order to obtain thermally stable vinyl polymers.1-3 At the same time, various kinds of PhMI derivatives have also been synthesized and polymerized. [4][5][6][7][8][9][10][11][12] When alkyl substituents were introduced in the N-phenyl group, the polymers were soluble in non-polar solvents and showed an excellent thermal decomposition property, while poly(1) was soluble in limited kinds of polar solvents. 13,14 On the other hand, the introduction of polar substituents resulted in the formation of polymers with poor solubility. For example, thermally stable polymers were synthesized by the polymerization of N-(hydroxyphenyl)-, N-(carboxyphenyl)-, and N-(trifluoromethylphenyl)maleimides, but they were insoluble or had a very limited solubility in solvents. 4,[15][16][17] In 1996, Doi and coworkers reported that the alternating copolymerization of N-alkylmaleimides (RMI) with isobutene (IB) [poly(RMI-alt-IB)] produces high molecular weight copolymers with excellent thermal properties, as well as excellent mechanical and optical properties.18-21 Poly(RMI-alt-IB)s are soluble in a larger number of organic solvents and had a moderate softening temperature. The processing of poly-(RMI-alt-IB)s can be easily carried out for the fabrication of polymer films, sheets, and molded products. Recently, we synthesized the alternating copolymers of RMIs containing a functional group, such as hydroxy and carboxy groups, combined with IB, and revealed the role of the intermolecular hydrogen bond of the functional groups in the thermal properties of the obtained copolymers. 22 We demonstrated that poly(RMI-alt-IB)s containing hydroxy and carboxy groups showed high glass transition temperature (T g )...

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Reactivity in radical polymerization ofN-substituted maleimides and thermal stability of the resulting polymers

Cited by 144 publications

References 17 publications

Synthesis and Radical Polymerization of N-(3-Acetyl-4-Carboxy-Phenyl)-Maleimide

Synthesis and Radical Polymerization of N-(3-Acetyl-4-Carboxy-Phenyl)-Maleimide

Synthesis and Characterization of Thermoresistant Maleimide Copolymers and their Crosslinked Polymers

Thermal Properties of N-Phenylmaleimide-Isobutene Alternating Copolymers Containing Polar Groups to Form Intermolecular and Intramolecular Hydrogen Bonding

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