Ring-Opening Metathesis Polymerization of Functionalized Cyclooctenes by a Ruthenium-Based Metathesis Catalyst

Hillmyer, Marc A.; Laredo, Walter R.; Grubbs, Robert H.

doi:10.1021/ma00122a043

Cited by 203 publications

(221 citation statements)

References 10 publications

(21 reference statements)

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“…This result was not observed during the ROMP of 5-chloro or 5-bromo substituted COE [33][34][35], which suggests polymers of 1 and 10 are prone to halide elimination to generate conjugated dienes, possibly facilitated by the Ru catalyst.…”

Section: Polymer Synthesis and Characterizationmentioning

confidence: 87%

“…In all cases, the reaction mixture turned a brown color within a few minutes, suggesting deactivation of the Ru catalyst. The failure of 5 or 6 was not surprising, as compounds containing nitrile groups or primary amines are known to deactivate the Ru catalysts [33,36,37,61,62]. However, the monomers bearing acetamide (16) and urea (17) functional groups did not polymerize either.…”

Section: Polymer Synthesis and Characterizationmentioning

confidence: 99%

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Functionalized regio-regular linear polyethylenes from the ROMP of 3-substituted cyclooctenes

et al. 2014

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We demonstrated that the ring-opening metathesis polymerization (ROMP) of 3-substituted cyclooctenes bearing polar substituents allows the synthesis of highly regio-and stereo-regular polymers. A series of polyalkenamers with 90-99 % head-to-tail/trans configuration were synthetized in good yields (33-87 % yield). Upon saturation of the backbone using diimide, these polymers represent a class of linear polyethylene derivatives where the polar side chain is located on every eighth carbon. The thermal properties of both the saturated and unsaturated polymers depend strongly on the size and polarity of the functional side groups. The results presented here demonstrate that the 3-substituted cyclooctenes can be used not only for the synthesis of precisely functionalized polyethylene derivatives, but also to participate in the ringopening metathesis copolymerization with unfunctionalized cyclic olefins to generate copolymers with tunable properties.

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Section: Polymer Synthesis and Characterizationmentioning

confidence: 87%

Section: Polymer Synthesis and Characterizationmentioning

confidence: 99%

Functionalized regio-regular linear polyethylenes from the ROMP of 3-substituted cyclooctenes

et al. 2014

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“…ROMP of the 5-substituted cyclooctene monomers gave regio-and stereoirregular polymers consistent with previous literature. 1,9 Unsaturated polymers were then hydrogenated using a diimide generated in situ by the thermolysis of p-toluenesulfonyl hydrazide. 17 The hydrogenation was quantitative according to the 1 H NMR spectrum, where the peaks in the olefinic region between 5.43 and 5.27 ppm were absent, and the allylic methylene protons of the end groups originally at 2.03-1.74 ppm shifted upfield (Fig.…”

Section: Synthesis and Polymerization Of Mmec And Bec Monomersmentioning

confidence: 99%

“…[5][6][7] Indeed, these catalysts have been referred to by some as empyrean. 8 One of us (MAH) has been enamored with ROMP of substituted cyclooctenes for over two decades 9 and ceases to be amazed at the possibilities to control polyolefin structure and function through monomer synthesis and (co)polymerization using ROMP. More recently, we have been working on the compatibilization of polyolefins and poly(methyl methacrylate) (PMMA) using either graft or block polymers prepared using cyclooctenes and its derivatives through a ROMP/hydrogenation protocol.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and utility of ethylene (meth)acrylate copolymers prepared by a tandem ring‐opening polymerization hydrogenation strategy

Onbulak

Wang

Brutman

2017

J. Polym. Sci. Part A: Polym. Chem.

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One new and one established functional cyclooctene were prepared and (co)polymerized using ring-opening metathesis polymerization. The resulting polymers were hydrogenated to yield the corresponding functional polyolefins that were structurally equivalent to copolymers of ethylene and either methyl methacrylate, t-butyl acrylate, or acrylic acid after deprotection. The copolymers that incorporate methyl methacrylate into the backbone were used as compatibilizers for poly(methyl methacrylate)/polyethylene blends. The copolymers that incorporate t-butyl acrylate into the backbone yielded elastomers that could be thermally crosslinked. V C 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 3117-3126 KEYWORDS: compatibilization; copolymer; methyl methacrylate; ROMP; thermoset polyolefins INTRODUCTION The ring-opening metathesis polymerization (ROMP) of functionalized cyclooctenes (COEs) followed by hydrogenation of the olefinic groups in the polymer backbone is a powerful method for the preparation of functionalized polyolefins. Many 3-substituted COEs provide regiospecific polymers 1 while 4-and 5-substituted COEs typically give regioirregular polymers. The broad utility of this approach to materials useful for a wide variety of interesting applications has been clearly demonstrated in the literature. [2][3][4] The success of these approaches can be in large part attributed to the robust nature of ruthenium-based metathesis catalysts developed by Robert H. Grubbs and coworkers. [5][6][7] Indeed, these catalysts have been referred to by some as empyrean. 8

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“…The resulting compounds of the general formula Cl 2 Ru(CHR)(PR 3 / 2 (R D Ph, CHCPh 2 /, nowadays well known as the rst-generation Grubbs catalyst, can be prepared in high yields. Ruthenium-based Grubbs catalysts turned out to be highly efcient in the ROMP of various substituted cyclic ole ns such as norbornenes, bicyclo[3.2.0]heptene [155], 7-oxanorbornenes [156], in the presence of cationic surfactants [157], as well as for low-strain ole ns such as cyclooctenes [158]. Phosphine exchange from the parent bis(triphenylphosphine) systems into the more reactive bis(tricyclohexylphosphines) may be performed either consecutively or in situ.…”

Section: Ru-based Systemsmentioning

confidence: 99%

Transition metal-based polymer chemistry: a critical micro-review

Buchmeiser¹

2002

Designed Monomers and Polymers

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Abstract-This micro-review summarizes mainly recent (i.e. mostly later than 1995) and important developments in transition metal-catalyzed polymerization and their impact on polymer synthesis. It is not intended to be entirely comprehensive, yet will focus on signi cant improvements or interesting aspects in certain areas of polymer chemistry. For this particular reason, not all transition metal-based polymerizations will be fully covered. Instead, besides providing a 'snapshot' of the state of the art, it was a major intention to outline the main advantages and disadvantages of certain important polymerizations in a critical, yet hopefully objective way.

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Ring-Opening Metathesis Polymerization of Functionalized Cyclooctenes by a Ruthenium-Based Metathesis Catalyst

Cited by 203 publications

References 10 publications

Functionalized regio-regular linear polyethylenes from the ROMP of 3-substituted cyclooctenes

Functionalized regio-regular linear polyethylenes from the ROMP of 3-substituted cyclooctenes

Synthesis and utility of ethylene (meth)acrylate copolymers prepared by a tandem ring‐opening polymerization hydrogenation strategy

Transition metal-based polymer chemistry: a critical micro-review

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