Synthesis of End-Functionalized Poly(norbornenes) and Poly(ethylidene norbornenes) Using a Pd(II) Catalyst in Combination with Chain Transfer Agents

Han, Xing-Wang; Daugulis, Olafs; Brookhart, Maurice

doi:10.1021/acs.organomet.1c00333

Synthesis of End-Functionalized Poly(norbornenes) and Poly(ethylidene norbornenes) Using a Pd(II) Catalyst in Combination with Chain Transfer Agents

Journal Article · Wed Jul 14 00:00:00 EDT 2021 · Organometallics

DOI:https://doi.org/10.1021/acs.organomet.1c00333· OSTI ID:1825482

^[1]; ^[2]; Brookhart, Maurice ^[2]

Univ. of Houston, TX (United States); University of Houston
Univ. of Houston, TX (United States)

Synthesis of end-functionalized poly(norbornene)s (PNBs) and poly(ethylidenenorbornene)s (PENBs) were prepared using the palladium catalyst ^tBu₃PPdMeCl/NaBAr^f in combination with chain transfer agents (CTAs) 4-penten-1-ol and 10-undecenal. These CTAs produce polymers end-capped with -OH and -CHO groups, respectively, in high yields with M_n values in the range of 6K to 17K, depending on the molar ratio of the CTA: monomer. End-functionalized PNBs and PENBs with precisely controlled Mn values and very narrow molecular weight distributions were accessed by using 4-penten-1-ol and 10-undecenal as chain-terminating agents following living polymerizations in which monomer is completely consumed. The utility of the aldehyde-functionalized polymers is illustrated via coupling to a dye molecule and by synthesis of ambiphilic diblock copolymers, PNB-b-PEG and PENB-b-PEG.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Houston, TX (United States)

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

Grant/Contract Number:: SC0021403

OSTI ID:: 1825482

Journal Information:: Organometallics, Journal Name: Organometallics Journal Issue: 15 Vol. 40; ISSN 0276-7333

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Polymerization
aldehydes
catalysts
hydrocarbons
norbornene
palladium
polymers

Synthesis of End-Functionalized Poly(norbornenes) and Poly(ethylidene norbornenes) Using a Pd(II) Catalyst in Combination with Chain Transfer Agents

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