Synthesis, characterization, and properties of crystalline poly(<i>endo</i>‐dicyclopentadiene) resin made via cis‐ and isoselective bulk ring‐opening metathesis polymerization

Hayano, Shigetaka; Sugawara, Takuo; Tsunogae, Yasuo

doi:10.1002/pola.21421

Cited by 14 publications

(15 citation statements)

References 29 publications

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“…Hydrogenated ring-opened poly(cycloolefin)s have been attracting intensive interest from academia and industry because of their superior properties such as optical properties, heat resistance, moisture resistance, chemical resistance, and electric property. , In particular, the stereospecific ring-opening metathesis polymerization (ROMP) of cycloolefins has been studied well in the past decade. In the course of exploring the stereospecific ROMP, we succeeded in obtaining the hydrogenated polymers of norbornene (NB) as well as dicyclopentadiene (DCP) and tetracyclododecene having a wide range of stereoregularities. − Schrock and Autenrieth reported cis-syndiospecific and cis-isospecific ROMPs of various NB derivatives. , It is very significant, from the viewpoint of the development of polymers with superior properties, to comprehensively compile the structural characteristics of the various stereoregular poly(cycloolefin)s. In the present study, we have focused on the detailed structural analysis of the stereoregular H-poly(NB)s.…”

Section: Introductionmentioning

confidence: 99%

Influence of Tacticity on the Crystal Structures of Hydrogenated Ring-Opened Poly(norbornene)s

Nakama¹,

Hayano²,

Tashiro

2021

Macromolecules

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The crystal structures of highly crystalline isotactic and syndiotactic hydrogenated poly(norbornene)s [Hpoly(NB)s], synthesized by the stereospecific ring-opening metathesis polymerizations of norbornene followed by complete hydrogenation, have been determined for the first time on the basis of the X-ray diffraction data analyses. The similarity and difference of the chain conformation and the chain packing mode in the crystal lattice have been clarified among the three kinds of H-poly(NB) samples (syndiotactic, isotactic, and atactic species). The molecular chains were found to take essentially the planar zigzag conformation at room temperature with slight torsional angle fluctuations around the skeletal C−C bonds. The cyclopentylene rings were found to protrude from the plane of the skeletal polymer chain in various different ways depending on the tacticity, resulting in the difference of the whole shape of the chains and then the difference of the chain packing structure. The melting point was found to be different depending on the tacticity: 178, 148, and 134 °C for the isotactic, atactic, and syndiotactic H-poly(NB)s, respectively. The difference in the thermal behavior has been discussed qualitatively on the basis of these structural pieces of information.

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Section: Introductionmentioning

confidence: 99%

Influence of Tacticity on the Crystal Structures of Hydrogenated Ring-Opened Poly(norbornene)s

Nakama¹,

Hayano²,

Tashiro

2021

Macromolecules

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“…One type of reaction that has become very popular over the last several years is ring-opening metathesis polymerization (ROMP), initiated by organometallic carbenes. [27][28][29][30][31][32][33] Most of the welldefined ROMP catalysts are grouped in the category of either Grubbs [34][35][36] or Schrock-type [37][38][39] complexes, named after their Nobel laureate inventors. 40,41 The former show great practicality because of their high reactivity, functional group tolerance, and air/moisture insensitivity.…”

Section: Introductionmentioning

confidence: 99%

“…One type of reaction that has become very popular over the last several years is ring‐opening metathesis polymerization (ROMP), initiated by organometallic carbenes 27–33. Most of the well‐defined ROMP catalysts are grouped in the category of either Grubbs34–36 or Schrock‐type37–39 complexes, named after their Nobel laureate inventors 40, 41.…”

Section: Introductionmentioning

confidence: 99%

Ring‐opening metathesis polymerization of a modified linseed oil with varying levels of crosslinking

Mauldin

Haman

Sheng

et al. 2008

J. Polym. Sci. A Polym. Chem.

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A commercial norbornyl-functionalized linseed oil, blended with a bicyclic norbornene-based crosslinking agent (at loadings ranging from 0 to 50 wt %) undergoes ring-opening metathesis polymerization with the 1st generation Grubbs' catalyst to form a biorenewable polymer network. Comonomers are characterized, the thermal and mechanical properties of the cured systems are investigated by dynamic mechanical analysis, and thermal decomposition is evaluated by thermogravimetric analysis. The resin is shown to consist of a modified linseed oil and small oligomers of cyclopentadiene. Broad tan d peaks suggest inhomogeneous phase morphologies, which result in complex crosslinking behaviors. The thermal stability of the polymers increases with increasing crosslinker content. V V C 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6851-6860, 2008

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“…Polyolefins with cyclic units in the main chain, which have been synthesized by the copolymerization of conventional olefins with cycloolefins, have been developed because of their excellent properties, good transparency, high glass‐transition temperature ( T g ), low water absorption, and so on 1–39. An alternative synthetic route of polyolefins containing cyclic units is the ring‐opening metathesis polymerization of norbornene or norbornene derivatives following a hydrogenation reaction 40–47. This process is commercially used to synthesize amorphous cycloolefin polymers for optical materials 48, 49.…”

Section: Introductionmentioning

confidence: 99%

Copolymerization of propylene and disubstituted diallylsilanes involving intramolecular cyclization with stereoselective zirconocene catalysts

Naga

2006

J. Polym. Sci. A Polym. Chem.

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The copolymerization of propylene and disubstituted diallylsilanes [(CH 2 ¼ ¼CHÀ ÀCH 2 À À) 2 R 2 Si (R ¼ CH 3 or C 6 H 5 )] was investigated with isoselective and syndioselective zirconocene catalysts with methylaluminoxane as a cocatalyst. The syndioselective catalyst showed a higher reactivity for disubstituted diallylsilanes than the isoselective catalysts. Diallyldimethylsilane was incorporated into the polymer chain via cyclization insertion preferentially and formed 3,5-disubstituted dimethylsilacyclohexane units in the polypropylene main chain. In the copolymerization with diallyldiphenylsilane, diallyldiphenylsilane was copolymerized via both cyclization insertion and 1,2-insertion, which formed a pendant allyl group. The structures of isolated silacyclohexane units, determined by 13 C NMR and distortionless enhancement by polarization transfer spectroscopy, proved that the 1,2-insertion of diallylsilanes proceeded with enantiomorphic site control; however, the diastereoselectivity of the cyclization reaction was independent of the stereoselectivity of the catalysts used, and cis-silacyclohexane units were mainly formed. V V C 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6083-6093, 2006

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Synthesis, characterization, and properties of crystalline poly(endo‐dicyclopentadiene) resin made via cis‐ and isoselective bulk ring‐opening metathesis polymerization

Cited by 14 publications

References 29 publications

Influence of Tacticity on the Crystal Structures of Hydrogenated Ring-Opened Poly(norbornene)s

Influence of Tacticity on the Crystal Structures of Hydrogenated Ring-Opened Poly(norbornene)s

Ring‐opening metathesis polymerization of a modified linseed oil with varying levels of crosslinking

Copolymerization of propylene and disubstituted diallylsilanes involving intramolecular cyclization with stereoselective zirconocene catalysts

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