Hydrocarbon-Soluble Piperazine-Containing Dilithium Anionic Initiator for High Cis-1,4 Isoprene Polymerization

Alison R. Schultz, Sachin Bobade, Philip J. Scott, Timothy Edward Long

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

The synthesis of 1,4-bis[4-(1-phenylethenyl)benzyl] piperazine and subsequent reaction with sec-butyllithium enables a novel piperazine-containing difunctional organolithium initiator for the living anionic polymerization of isoprene. Piperazine provides a polar unit within the difunctional initiator, promoting ion dissociation and miscibility with hydrocarbon solvents, and enabling the formation of well-defined polyisoprene homopolymers with predictable molecular weights and controlled microstructure. In situ Fourier transform infrared spectroscopy monitors the dilithium initiator formation and the anionic polymerization of isoprene, revealing kinetic insight into this synthetic method. Furthermore, sequential monomer addition with styrene affords poly(styrene-block-isoprene-block-styrene) triblock copolymers with controlled molecular weights and narrow polydispersities. This novel initiator facilitates the synthesis of thermoplastic elastomers with desired cis-1,4 microstructure in polydienes.

Original languageEnglish
Article number1700201
JournalMacromolecular Chemistry and Physics
Volume219
Issue number1
DOIs
Publication statusPublished - 2018 Jan 5
Externally publishedYes

Fingerprint

Isoprene
Styrene
initiators
Hydrocarbons
Anionic polymerization
polymerization
hydrocarbons
Polymerization
Molecular weight
styrenes
molecular weight
Polyisoprenes
Thermoplastic elastomers
Microstructure
Living polymerization
Polydispersity
Homopolymerization
polyisoprenes
microstructure
Block copolymers

Keywords

  • anionic polymerization
  • block copolymers
  • in situ FTIR
  • piperazine
  • polyisoprene

ASJC Scopus subject areas

  • Condensed Matter Physics
  • Physical and Theoretical Chemistry
  • Polymers and Plastics
  • Organic Chemistry
  • Materials Chemistry

Cite this

Hydrocarbon-Soluble Piperazine-Containing Dilithium Anionic Initiator for High Cis-1,4 Isoprene Polymerization. / Schultz, Alison R.; Bobade, Sachin; Scott, Philip J.; Long, Timothy Edward.

In: Macromolecular Chemistry and Physics, Vol. 219, No. 1, 1700201, 05.01.2018.

Research output: Contribution to journalArticle

Schultz, Alison R. ; Bobade, Sachin ; Scott, Philip J. ; Long, Timothy Edward. / Hydrocarbon-Soluble Piperazine-Containing Dilithium Anionic Initiator for High Cis-1,4 Isoprene Polymerization. In: Macromolecular Chemistry and Physics. 2018 ; Vol. 219, No. 1.
@article{dcc47dec8cf342cd8671cb40eb6ed067,
title = "Hydrocarbon-Soluble Piperazine-Containing Dilithium Anionic Initiator for High Cis-1,4 Isoprene Polymerization",
abstract = "The synthesis of 1,4-bis[4-(1-phenylethenyl)benzyl] piperazine and subsequent reaction with sec-butyllithium enables a novel piperazine-containing difunctional organolithium initiator for the living anionic polymerization of isoprene. Piperazine provides a polar unit within the difunctional initiator, promoting ion dissociation and miscibility with hydrocarbon solvents, and enabling the formation of well-defined polyisoprene homopolymers with predictable molecular weights and controlled microstructure. In situ Fourier transform infrared spectroscopy monitors the dilithium initiator formation and the anionic polymerization of isoprene, revealing kinetic insight into this synthetic method. Furthermore, sequential monomer addition with styrene affords poly(styrene-block-isoprene-block-styrene) triblock copolymers with controlled molecular weights and narrow polydispersities. This novel initiator facilitates the synthesis of thermoplastic elastomers with desired cis-1,4 microstructure in polydienes.",
keywords = "anionic polymerization, block copolymers, in situ FTIR, piperazine, polyisoprene",
author = "Schultz, {Alison R.} and Sachin Bobade and Scott, {Philip J.} and Long, {Timothy Edward}",
year = "2018",
month = "1",
day = "5",
doi = "10.1002/macp.201700201",
language = "English",
volume = "219",
journal = "Macromolecular Chemistry and Physics",
issn = "1022-1352",
publisher = "Wiley-VCH Verlag",
number = "1",

}

TY - JOUR

T1 - Hydrocarbon-Soluble Piperazine-Containing Dilithium Anionic Initiator for High Cis-1,4 Isoprene Polymerization

AU - Schultz, Alison R.

AU - Bobade, Sachin

AU - Scott, Philip J.

AU - Long, Timothy Edward

PY - 2018/1/5

Y1 - 2018/1/5

N2 - The synthesis of 1,4-bis[4-(1-phenylethenyl)benzyl] piperazine and subsequent reaction with sec-butyllithium enables a novel piperazine-containing difunctional organolithium initiator for the living anionic polymerization of isoprene. Piperazine provides a polar unit within the difunctional initiator, promoting ion dissociation and miscibility with hydrocarbon solvents, and enabling the formation of well-defined polyisoprene homopolymers with predictable molecular weights and controlled microstructure. In situ Fourier transform infrared spectroscopy monitors the dilithium initiator formation and the anionic polymerization of isoprene, revealing kinetic insight into this synthetic method. Furthermore, sequential monomer addition with styrene affords poly(styrene-block-isoprene-block-styrene) triblock copolymers with controlled molecular weights and narrow polydispersities. This novel initiator facilitates the synthesis of thermoplastic elastomers with desired cis-1,4 microstructure in polydienes.

AB - The synthesis of 1,4-bis[4-(1-phenylethenyl)benzyl] piperazine and subsequent reaction with sec-butyllithium enables a novel piperazine-containing difunctional organolithium initiator for the living anionic polymerization of isoprene. Piperazine provides a polar unit within the difunctional initiator, promoting ion dissociation and miscibility with hydrocarbon solvents, and enabling the formation of well-defined polyisoprene homopolymers with predictable molecular weights and controlled microstructure. In situ Fourier transform infrared spectroscopy monitors the dilithium initiator formation and the anionic polymerization of isoprene, revealing kinetic insight into this synthetic method. Furthermore, sequential monomer addition with styrene affords poly(styrene-block-isoprene-block-styrene) triblock copolymers with controlled molecular weights and narrow polydispersities. This novel initiator facilitates the synthesis of thermoplastic elastomers with desired cis-1,4 microstructure in polydienes.

KW - anionic polymerization

KW - block copolymers

KW - in situ FTIR

KW - piperazine

KW - polyisoprene

UR - http://www.scopus.com/inward/record.url?scp=85040201214&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85040201214&partnerID=8YFLogxK

U2 - 10.1002/macp.201700201

DO - 10.1002/macp.201700201

M3 - Article

VL - 219

JO - Macromolecular Chemistry and Physics

JF - Macromolecular Chemistry and Physics

SN - 1022-1352

IS - 1

M1 - 1700201

ER -