Stereospecific Ring-Opening Metathesis Polymerization (ROMP) of Norbornene and Tetracyclododecene by Mo and W Initiators

Autenrieth, Benjamin; Schrock, Richard R.

doi:10.1021/acs.macromol.5b00161

Title: Stereospecific Ring-Opening Metathesis Polymerization (ROMP) of Norbornene and Tetracyclododecene by Mo and W Initiators

Journal Article · Tue Apr 07 00:00:00 EDT 2015 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.5b00161· OSTI ID:1557800

Autenrieth, Benjamin ^[1]; Schrock, Richard R. ^[1]

Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

Here we report the synthesis of >98% cis,isotactic and cis,syndiotactic polynorbornene (poly(NBE)) and poly(endo,anti-tetracyclododecene) (poly(TCD)). Cis,isotactic poly(NBE) and poly(TCD) were prepared employing Mo-based biphenolate imido alkylidene initiators, Mo(NR)(CHCMe₂Ph)(Biphen) (Biphen = e.g., 3,3'-(t-Bu)2-5,5'-6,6'-(CH₃)4-1,1'-biphenyl-2,2'-diolate), while cis,syndiotactic poly(NBE) and poly(TCD) were prepared employing W-based imido or oxo monoaryloxide pyrrolide (MAP) initiators, W(X)(CHR')(Pyrrolide)(OTer) (X = NR or O; OTer = a 2,6-terphenoxide). Addition of 1-hexene or coordinating solvents such as THF do not decrease the stereospecificity of the polymerization. Cis,iso and cis,syndio dyads can be distinguished through investigation of ¹H and ¹³C NMR spectra of the two polymers in a mixture. The polymers were hydrogenated to give isotactic and syndiotactic H-poly(NBE) and H-poly(TCD).

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Research Organization:: Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-86ER13564

OSTI ID:: 1557800

Journal Information:: Macromolecules, Vol. 48, Issue 8; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 55 works

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