Mechanism for peroxide cross-linking of EPDM rubber from MAS 13C NMR spectroscopy

R.A. Orza; P.C.M.M. Magusin; V.M. Litvinov; M. Duin, van; M.A.J. Michels

doi:10.1021/ma9016482

Mechanism for peroxide cross-linking of EPDM rubber from MAS 13C NMR spectroscopy

R.A. Orza
, P.C.M.M. Magusin
, V.M. Litvinov
, M. Duin, van
, M.A.J. Michels

Soft Matter and Biological Physics

Research output: Contribution to journal › Article › Academic › peer-review

61 Citations (Scopus)

Abstract

Detailed information about the chemical role of the third monomer 5-ethylidene-2-norbonene (ENB) in EPDM during peroxide cross-linking has been obtained by use of MAS 13C NMR spectroscopy and 1H NMR T2 relaxometry. Advanced 13C NMR techniques like INADEQUATE and TOCSY applied to a special EPDM grade with 13C-labeled ENB reveal a large number of new aliphatic and olefinic signals as well as indications for oxidation. The ENB unit is involved in cross-linking reactions not only (i) via addition of macroradicals to the pendent ENB unsaturation yielding aliphatic cross-link structures but also (ii) via combination of ENB-derived allyl radicals resulting in cross-link structures with intact unsaturation. The latter represents a novel pathway in the mechanism for peroxide curing of EPDM.

Original language	English
Pages (from-to)	8914-8924
Journal	Macromolecules
Volume	42
Issue number	22
DOIs	https://doi.org/10.1021/ma9016482
Publication status	Published - 2009

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title = "Mechanism for peroxide cross-linking of EPDM rubber from MAS 13C NMR spectroscopy",

abstract = "Detailed information about the chemical role of the third monomer 5-ethylidene-2-norbonene (ENB) in EPDM during peroxide cross-linking has been obtained by use of MAS 13C NMR spectroscopy and 1H NMR T2 relaxometry. Advanced 13C NMR techniques like INADEQUATE and TOCSY applied to a special EPDM grade with 13C-labeled ENB reveal a large number of new aliphatic and olefinic signals as well as indications for oxidation. The ENB unit is involved in cross-linking reactions not only (i) via addition of macroradicals to the pendent ENB unsaturation yielding aliphatic cross-link structures but also (ii) via combination of ENB-derived allyl radicals resulting in cross-link structures with intact unsaturation. The latter represents a novel pathway in the mechanism for peroxide curing of EPDM.",

author = "R.A. Orza and P.C.M.M. Magusin and V.M. Litvinov and \{Duin, van\}, M. and M.A.J. Michels",

year = "2009",

doi = "10.1021/ma9016482",

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volume = "42",

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journal = "Macromolecules",

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T1 - Mechanism for peroxide cross-linking of EPDM rubber from MAS 13C NMR spectroscopy

AU - Orza, R.A.

AU - Magusin, P.C.M.M.

AU - Litvinov, V.M.

AU - Duin, van, M.

AU - Michels, M.A.J.

PY - 2009

Y1 - 2009

N2 - Detailed information about the chemical role of the third monomer 5-ethylidene-2-norbonene (ENB) in EPDM during peroxide cross-linking has been obtained by use of MAS 13C NMR spectroscopy and 1H NMR T2 relaxometry. Advanced 13C NMR techniques like INADEQUATE and TOCSY applied to a special EPDM grade with 13C-labeled ENB reveal a large number of new aliphatic and olefinic signals as well as indications for oxidation. The ENB unit is involved in cross-linking reactions not only (i) via addition of macroradicals to the pendent ENB unsaturation yielding aliphatic cross-link structures but also (ii) via combination of ENB-derived allyl radicals resulting in cross-link structures with intact unsaturation. The latter represents a novel pathway in the mechanism for peroxide curing of EPDM.

AB - Detailed information about the chemical role of the third monomer 5-ethylidene-2-norbonene (ENB) in EPDM during peroxide cross-linking has been obtained by use of MAS 13C NMR spectroscopy and 1H NMR T2 relaxometry. Advanced 13C NMR techniques like INADEQUATE and TOCSY applied to a special EPDM grade with 13C-labeled ENB reveal a large number of new aliphatic and olefinic signals as well as indications for oxidation. The ENB unit is involved in cross-linking reactions not only (i) via addition of macroradicals to the pendent ENB unsaturation yielding aliphatic cross-link structures but also (ii) via combination of ENB-derived allyl radicals resulting in cross-link structures with intact unsaturation. The latter represents a novel pathway in the mechanism for peroxide curing of EPDM.

U2 - 10.1021/ma9016482

DO - 10.1021/ma9016482

M3 - Article

SN - 0024-9297

VL - 42

SP - 8914

EP - 8924

JO - Macromolecules

JF - Macromolecules

IS - 22

ER -

Mechanism for peroxide cross-linking of EPDM rubber from MAS 13C NMR spectroscopy

Abstract

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