Synthesis and properties of cyclic olefin polymers by ring-opening metathesis (co)polymerization of α-methyl-substituted norbornene lactones

Kiyohara, Sae; Miyasako, Narumi; Ota, Yoshiya; Matsuoka, Shin‐ichi; Suzuki, Masato

doi:10.1039/d2py01020h

Cited by 7 publications

(11 citation statements)

References 35 publications

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“…endo -Tricyclo[4.2.2.0 2,5 ]deca-3,9-diene-7,8-dicarboxylic anhydride, 11,12 2 , 10 endo -NBLs, and exo -NBLs 31–33 were synthesized according to previously reported procedures.…”

Section: Methodsmentioning

confidence: 99%

“…We have previously reported the synthesis and properties of COPs through a ring-opening metathesis (co) polymerization of norbornene lactones (NBLs). 31,32 The resulting COPs show good solubility, high thermal stability, and low birefringence. Given the extensive studies on the ROMP of ester-functionalized NB monomers for versatile applications, we have focused on ester-functionalized TDD monomers, 4-oxa-endo-tetracyclo[5.4.2.0 2,6 .0 8,11 ]trideca-9,12-dien-3-one (1) and endo-endo-tricyclo[4.2.2.0 2,5 ]deca-3,9-diene-7,8-dicarboxylate (2) (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

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Ring-opening metathesis polymerization of ester-functionalizedendo-tricyclo[4.2.2.0^2,5]deca-3,9-dienes and thermal properties of the resulting polymers

et al. 2023

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“…endo -Tricyclo[4.2.2.0 2,5 ]deca-3,9-diene-7,8-dicarboxylic anhydride, 11,12 2 , 10 endo -NBLs, and exo -NBLs 31–33 were synthesized according to previously reported procedures.…”

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Ring-opening metathesis polymerization of ester-functionalizedendo-tricyclo[4.2.2.0^2,5]deca-3,9-dienes and thermal properties of the resulting polymers

et al. 2023

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“…The design of the monomer structure and the copolymer sequence are critical for the resulting COP properties, and polycyclic polymer structures are required to obtain a high glass-transition temperature ( T g ) of around 150 °C. Various COPs have been produced from polycyclic NB derivatives, including conventional hydrocarbons (dicyclopentadienes, − tetracyclododecenes, − and others), ester-, , imide-, epoxy-substituted NBs, anthracene-derived NBs, NB lactones (NBL), , and cyclopropane-containing norbornadiene dimers (NBDDs) …”

Section: Introductionmentioning

confidence: 99%

“…Endo -/ exo -isomerism practically affects the polymerization rate as well as T g , and thus, this is also an important factor for the precise control of the properties of (co)polymers. Endo -isomers are polymerized slower than exo -isomers because of the steric hindrance and/or chelation to the metal catalyst at the polymer terminals. − Endo -isomeric polymers show higher T g values than exo -isomers; − ,, however, it is unclear how the structural difference affects their physical properties. In this context, we previously proposed that the higher T g and lower solubility of endo -isomers are due to more regularly arranged structures of endo -isomers, as indicated by sharper X-ray diffraction (XRD) patterns based on the analysis of the polymers derived from the four isomers ( exo - exo -, exo - endo -, endo - exo -, and endo - endo -) of NBDDs …”

Section: Introductionmentioning

confidence: 99%

Spiro-Fluorene-Containing Cyclic Olefin Polymers

Ishii,

Ota,

Matsuoka

et al. 2023

ACS Appl. Polym. Mater.

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For application to optical polymer materials with a high refractive index and low birefringence as well as high thermal stability and low hygroscopicity, we have performed the ring-opening metathesis (co)polymerization (ROMP, ROMCP) of fluorene-based norbornene (NB) monomers, spiro[fluorene-9,4′-tricyclo[5.2.1.0 2,6 ]dec-8en] (endo-1 and exo-1) and subsequent hydrogenation to produce spiro-fluorenecontaining cyclic olefin polymers. The living ROMP and the kinetics of the ROMCP with NB were investigated. A series of hydrogenated endo-and exo-isomeric polymers, Hpoly( 1) and H-poly(1-co-NB), with random, gradient, and block sequences, were synthesized and characterized. They are highly soluble in common organic solvents due to their large fractional free volume, as indicated by broad X-ray diffraction patterns. The glass-transition temperatures (T g ) of Hpoly(1-co-NB) significantly increased with the content of 1 up to 273 °C [H-poly(endo-1)]. The endo-isomeric polymers exhibited significantly higher T g values and slightly lower solubility than their exo-counterparts, probably because of the slightly smaller fractional free volume of the endo-isomers. The refractive indexes of H-poly(1)s are as high as 1.61, and the stress-optical coefficients in the rubbery state (C R ) of H-poly(1-co-NB) are less than zero. These low birefringences and large fractional free volumes are derived from the bulky spiro-fluorene moiety oriented vertically to the polymer main chain.

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“…Cyclic olefin copolymers (COCs) always show high transparency, outstanding chemical resistance, and dimensional stability. [1][2][3][4][5][6][7] Furthermore, COCs display lower moisture absorption, better radiation resistance and lower birefringence compared to the common optical plastics as polymethylmethacrylate (PMMA) and polycarbonate (PC). [8][9][10][11][12] Therefore, COCs could be employed as an ideal alternative of PMMA and PC in various fields.…”

Section: Introductionmentioning

confidence: 99%

Simultaneously improving of thermal resistance and mechanical performances of cyclic olefin copolymers by incorporation of bulky adamantane side group

Deng

Wang

et al. 2023

J of Applied Polymer Sci

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Due to the low toxicity, excellent thermal resistance, optical performances and dielectric properties, cyclic olefin copolymers (COCs) could be widely applied in manufacturing of food and medicine package, optical components, electronic device, and so forth. However, most of the commoditized COCs possessing glass transition temperatures (T g s) higher than 150 C always show non-ignorable mechanical brittleness. Herein, a bulky cyclic olefin, 5-norboenene-2,3-dicarboxylicacid-adamantan-1-yl ester (NBDAE), was synthesized by one step reaction in high yields and subsequently employed to copolymerize with cis-cyclooctene (COE), affording a series of COCs bearing bulky adamantane side group. Due to the incorporation of the bulky norbornene derivative (NBDAE), the obtained COCs exhibited high T g s (up to 216 C) and transparency (higher than 90%), even at relatively low NBDAE incorporations. As expected, the NBDAE-COE copolymers also showed improved mechanical properties compared to commercialized Zeonex ® 330R (Stress at break: 39.1 MPa, strain at braek: 2.3%). Most of the synthesized COCs showed thermal decomposition temperatures (T d s) higher than 300 C and did not decompose under maintaining at 250 C for 1 h. Considering the performances mentioned above, the prepared COCs would show more greatly potential application in various fields.

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Synthesis and properties of cyclic olefin polymers by ring-opening metathesis (co)polymerization of α-methyl-substituted norbornene lactones

Abstract: Previously, we prepared new cyclic olefin polymers (COPs) by performing a ring-opening metathesis polymerization (ROMP) of endo- and exo-norbornene lactones (NBLs) and then hydrogenation. In this study, we produced new...

Cited by 7 publications

References 35 publications

Ring-opening metathesis polymerization of ester-functionalizedendo-tricyclo[4.2.2.0^2,5]deca-3,9-dienes and thermal properties of the resulting polymers

Ring-opening metathesis polymerization of ester-functionalizedendo-tricyclo[4.2.2.0^2,5]deca-3,9-dienes and thermal properties of the resulting polymers

Spiro-Fluorene-Containing Cyclic Olefin Polymers

Simultaneously improving of thermal resistance and mechanical performances of cyclic olefin copolymers by incorporation of bulky adamantane side group

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Synthesis and properties of cyclic olefin polymers by ring-opening metathesis (co)polymerization of α-methyl-substituted norbornene lactones

Abstract: Previously, we prepared new cyclic olefin polymers (COPs) by performing a ring-opening metathesis polymerization (ROMP) of endo- and exo-norbornene lactones (NBLs) and then hydrogenation. In this study, we produced new...

Cited by 7 publications

References 35 publications

Ring-opening metathesis polymerization of ester-functionalizedendo-tricyclo[4.2.2.02,5]deca-3,9-dienes and thermal properties of the resulting polymers

Ring-opening metathesis polymerization of ester-functionalizedendo-tricyclo[4.2.2.02,5]deca-3,9-dienes and thermal properties of the resulting polymers

Spiro-Fluorene-Containing Cyclic Olefin Polymers

Simultaneously improving of thermal resistance and mechanical performances of cyclic olefin copolymers by incorporation of bulky adamantane side group

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Ring-opening metathesis polymerization of ester-functionalizedendo-tricyclo[4.2.2.0^2,5]deca-3,9-dienes and thermal properties of the resulting polymers

Ring-opening metathesis polymerization of ester-functionalizedendo-tricyclo[4.2.2.0^2,5]deca-3,9-dienes and thermal properties of the resulting polymers