Synthesis of ABA triblock copolymers of norbornenes and 7-oxanorbornenes via living ring-opening metathesis polymerization using well-defined, bimetallic ruthenium catalysts

Marcus Weck, Peter Schwab, Robert H. Grubbs

Research output: Contribution to journalArticle

Abstract

Norbornene and 7-oxanorbornene derivatives were polymerized by ring-opening metathesis polymerization (ROMP) in a living manner by employing three new well-defined, bimetallic ruthenium catalysts (PR3)2Cl2Ru(=CH-p-C6H 4C(H)=)RuCl2(PR3)2 [R = Ph, 1; R = Cy (cyclohexyl), 2; R = Cyp (cyclopentyl), 3] as initiators to obtain ABA triblock copolymers with low polydispersities. 1-3 were synthesized via alkylidene transfer from 1,4-bis(α-diazomethyl)benzene to RuCl2(PPh3)3 and subsequent phosphine exchange. Reactions of 7-oxanorbornenes 5 and 6 or a silicon-containing norbornene 7 with 3 resulted in polymers with low polydispersities ranging from 1.10 to 1.22, while polymerizations initiated by 2 displayed higher polydispersities ranging from 1.20 to 1.35. Polymerizations of 5-7 catalyzed by 2 and 3 fulfill the requirements for a living polymerization. However, catalyst 1 is not reactive enough to polymerize functionalized norbornenes or 7-oxanorbornenes. The living polymerizations were successfully used to prepare three ABA triblock copolymers of monomers 5-7. In all cases, these ABA triblock copolymers have higher molecular weights than the homopolymers, and all polydispersities remained low.

Original languageEnglish (US)
Pages (from-to)1789-1793
Number of pages5
JournalMacromolecules
Volume29
Issue number5
StatePublished - Feb 26 1996

Fingerprint

Living polymerization
Ruthenium
Ring opening polymerization
Polydispersity
Block copolymers
Catalysts
phosphine
Polymerization
Silicon
Benzene
Homopolymerization
Polymers
Monomers
Molecular weight
Derivatives
2-norbornene

ASJC Scopus subject areas

  • Materials Chemistry

Cite this

Synthesis of ABA triblock copolymers of norbornenes and 7-oxanorbornenes via living ring-opening metathesis polymerization using well-defined, bimetallic ruthenium catalysts. / Weck, Marcus; Schwab, Peter; Grubbs, Robert H.

In: Macromolecules, Vol. 29, No. 5, 26.02.1996, p. 1789-1793.

Research output: Contribution to journalArticle

@article{0c95dcc07e5746a487fefeb9852390a7,
title = "Synthesis of ABA triblock copolymers of norbornenes and 7-oxanorbornenes via living ring-opening metathesis polymerization using well-defined, bimetallic ruthenium catalysts",
abstract = "Norbornene and 7-oxanorbornene derivatives were polymerized by ring-opening metathesis polymerization (ROMP) in a living manner by employing three new well-defined, bimetallic ruthenium catalysts (PR3)2Cl2Ru(=CH-p-C6H 4C(H)=)RuCl2(PR3)2 [R = Ph, 1; R = Cy (cyclohexyl), 2; R = Cyp (cyclopentyl), 3] as initiators to obtain ABA triblock copolymers with low polydispersities. 1-3 were synthesized via alkylidene transfer from 1,4-bis(α-diazomethyl)benzene to RuCl2(PPh3)3 and subsequent phosphine exchange. Reactions of 7-oxanorbornenes 5 and 6 or a silicon-containing norbornene 7 with 3 resulted in polymers with low polydispersities ranging from 1.10 to 1.22, while polymerizations initiated by 2 displayed higher polydispersities ranging from 1.20 to 1.35. Polymerizations of 5-7 catalyzed by 2 and 3 fulfill the requirements for a living polymerization. However, catalyst 1 is not reactive enough to polymerize functionalized norbornenes or 7-oxanorbornenes. The living polymerizations were successfully used to prepare three ABA triblock copolymers of monomers 5-7. In all cases, these ABA triblock copolymers have higher molecular weights than the homopolymers, and all polydispersities remained low.",
author = "Marcus Weck and Peter Schwab and Grubbs, {Robert H.}",
year = "1996",
month = "2",
day = "26",
language = "English (US)",
volume = "29",
pages = "1789--1793",
journal = "Macromolecules",
issn = "0024-9297",
publisher = "American Chemical Society",
number = "5",

}

TY - JOUR

T1 - Synthesis of ABA triblock copolymers of norbornenes and 7-oxanorbornenes via living ring-opening metathesis polymerization using well-defined, bimetallic ruthenium catalysts

AU - Weck, Marcus

AU - Schwab, Peter

AU - Grubbs, Robert H.

PY - 1996/2/26

Y1 - 1996/2/26

N2 - Norbornene and 7-oxanorbornene derivatives were polymerized by ring-opening metathesis polymerization (ROMP) in a living manner by employing three new well-defined, bimetallic ruthenium catalysts (PR3)2Cl2Ru(=CH-p-C6H 4C(H)=)RuCl2(PR3)2 [R = Ph, 1; R = Cy (cyclohexyl), 2; R = Cyp (cyclopentyl), 3] as initiators to obtain ABA triblock copolymers with low polydispersities. 1-3 were synthesized via alkylidene transfer from 1,4-bis(α-diazomethyl)benzene to RuCl2(PPh3)3 and subsequent phosphine exchange. Reactions of 7-oxanorbornenes 5 and 6 or a silicon-containing norbornene 7 with 3 resulted in polymers with low polydispersities ranging from 1.10 to 1.22, while polymerizations initiated by 2 displayed higher polydispersities ranging from 1.20 to 1.35. Polymerizations of 5-7 catalyzed by 2 and 3 fulfill the requirements for a living polymerization. However, catalyst 1 is not reactive enough to polymerize functionalized norbornenes or 7-oxanorbornenes. The living polymerizations were successfully used to prepare three ABA triblock copolymers of monomers 5-7. In all cases, these ABA triblock copolymers have higher molecular weights than the homopolymers, and all polydispersities remained low.

AB - Norbornene and 7-oxanorbornene derivatives were polymerized by ring-opening metathesis polymerization (ROMP) in a living manner by employing three new well-defined, bimetallic ruthenium catalysts (PR3)2Cl2Ru(=CH-p-C6H 4C(H)=)RuCl2(PR3)2 [R = Ph, 1; R = Cy (cyclohexyl), 2; R = Cyp (cyclopentyl), 3] as initiators to obtain ABA triblock copolymers with low polydispersities. 1-3 were synthesized via alkylidene transfer from 1,4-bis(α-diazomethyl)benzene to RuCl2(PPh3)3 and subsequent phosphine exchange. Reactions of 7-oxanorbornenes 5 and 6 or a silicon-containing norbornene 7 with 3 resulted in polymers with low polydispersities ranging from 1.10 to 1.22, while polymerizations initiated by 2 displayed higher polydispersities ranging from 1.20 to 1.35. Polymerizations of 5-7 catalyzed by 2 and 3 fulfill the requirements for a living polymerization. However, catalyst 1 is not reactive enough to polymerize functionalized norbornenes or 7-oxanorbornenes. The living polymerizations were successfully used to prepare three ABA triblock copolymers of monomers 5-7. In all cases, these ABA triblock copolymers have higher molecular weights than the homopolymers, and all polydispersities remained low.

UR - http://www.scopus.com/inward/record.url?scp=0001377632&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0001377632&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0001377632

VL - 29

SP - 1789

EP - 1793

JO - Macromolecules

JF - Macromolecules

SN - 0024-9297

IS - 5

ER -