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Synthesis of Polyisobutylene-Based Block Copolymers with Precisely Controlled Architecture by Living Cationic Polymerization

  • Chapter
New Synthetic Methods

Part of the book series: Advances in Polymer Science ((POLYMER,volume 167))

Abstract

During the last two decades we have witnessed the discovery and development of living cationic polymerization. As a result of persistent growth in this field, today living cationic polymerization is an equal counterpart of anionic living polymerization although the latter has a considerably longer history. Living cationic polymerization is an indispensable tool for the preparation of a wide variety of homo-, block-, graft- and functional polymers. This chapter reviews recent efforts in cationic macromolecular engineering with emphasis on fundamental concepts and advanced technologies for polyisobutylene block copolymer synthesis. For block copolymer synthesis by the simple sequential monomer addition technique rationalization is given for the selection of polymerization conditions and monomer addition order. The application of non-(homo)polymerizable monomers such as 1,1-diarylethylenes and furan analogues, coupled with changes in the synthetic approaches for various block copolymer architectures, is described in terms of three categories; cap**, coupling, and living coupling reactions. These appear to be versatile synthetic tools for numerous linear di- and triblock copolymers, and block copolymers with non-linear architectures. Finally, current developments in the combination of different polymerization mechanisms are illustrated.

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Abbreviations

AA′B:

Poly[(A)-s-(A′)-s-(B)] three-arm star-block copolymer

A2B:

Poly[(A)2-s-(B)] three-arm star-block copolymer

A2B2 :

Poly[(A)2-s-(B)2] four-arm star-block copolymer

ABC linear:

Poly[(A)-b-(B)-b-(C)] linear triblock copolymer

ABC star:

Poly[(A)-s-(B)-s-(C)] three-arm star-block copolymer

AcNMe2 :

N,N-Dimethylacetamide

AROP:

Anionic ring-opening polymerization

BDPEP:

2,2-Bis[4-(1-phenylethenyl)phenyl]propane

BDTEP:

2,2-Bis[4-(1-tolylethenyl)phenyl]propane

B eff :

Blocking efficiency

BFPF:

2,5-Bis[1-(2-furanyl)-1-methylethyl]-furan

2-Bu3SnFu:

2-tert-Butylstannylfuran

ε-CL:

ε-Caprolactone

CMC:

Critical micelle concentration

DFP:

2,2-Difurylpropane

DiαMeSt-Cl:

2-Chloro-2,4-diphenyl-4-methylpentane (adduct of α-methylstyrene dimer and hydrogen chloride)

DMFu:

Difurylmethane

DPE:

1,1-Diphenylethylene

DPn:

Number-average degree of polymerization

DSC:

Differential scanning calorimetry

DTBP:

2,6-Di-tert-butylpyridine

DTE:

1,1-Ditolylethylene

DVB:

Divinylbenzene

FMF:

2,5-Bis-(2-furylmethyl)furan

GPC:

Gel permeation chromatography

GTP:

Group transfer polymerization

HES:

Hexaepoxy squalene

Hex:

Hexane

IB:

Isobutylene

IB-IB-Cl:

Isobutylene-isobutylene end capped with chloride

IBVE:

Isobutyl vinyl ether

K cd :

Equilibrium constant of cap**/decap** equilibrium

k c :

Rate constant of cap**

k d :

Rate constant of decap**

K e :

Apparent equilibrium constant

K i :

Equilibrium constant of ionization

MDDPE:

1,3-Bis(1-phenylethenyl)benzene

MeChx:

Methylcyclohexane

MeCl:

Methyl chloride

αMeSt:

α-Methylstyrene

MeVE:

Methyl vinyl ether

MMA:

Methyl methacrylate

Mn :

Number-average molecular weight

N :

Nucleophilicity parameter

NMR:

Nuclear magnetic resonance (spectroscopy)

R cr :

Rate of crossover to a second monomer

R p :

Rate of homopolymerization of a second monomer

St:

Styrene

pClαMeSt:

p-Chloro-α-methylstyrene

pClSt:

p-Chlorostyrene

PDDPE:

1,4-Bis(1-phenylethenyl)benzene

PIB:

Polyisobutylene

PIB-DPE+ :

1,1-Diphenylethylene capped polyisobutylene carbocation

PIBVE:

Poly(isobutyl vinyl ether)

pMeSt:

p-Methylstyrene

PαMeSt:

Poly(α-methylstyrene)

PMeVE:

Poly(methyl vinyl ether)

PMMA:

Poly(methyl methacrylate)

Poly(ε-CL-b-IB-b-ε-CL):

Poly(ε-caprolactone-block-isobutylene-block-ε-caprolactone) copolymer

Poly(IB-b-ε-CL):

Poly(isobutylene-block-ε-caprolactone) copolymer

Poly(IB-b-St):

Poly(isobutylene-block-styrene) copolymer

Poly(IB-b-IBVE):

Poly(isobutylene-block-isobutyl vinyl ether) copolymer

Poly(IB-b-αMeSt):

Poly(isobutylene-block-α-methylstyrene) copolymer

Poly(IB-b-MeVE):

Poly(isobutylene-block-methyl vinyl ether) copolymer

Poly(IB-b-MMA):

Poly(isobutylene-block-methyl methacrylate) copolymer

Poly(IB-b-tBMA):

Poly(isobutylene-block-tert-butyl methacrylate) copolymer

Poly(IB-b-PVL):

Poly(isobutylene-block-pivalolactone) copolymer

Poly(IB-s-IB′-s-MeVE):

Poly(isobutylene-star-isobutylene′-star-methyl vinyl ether) three-arm star-block copolymer

Poly(αMeSt-b-IB):

Poly(α-methylstyrene-block-isobutylene) copolymer

Poly(PVL-b-IB-b-PVL):

Poly(pivalolactone-block-isobutylene-block-pivalolactone) triblock copolymer

Poly(αMeSt-b-IB-b-αMeSt):

Poly(α-methylstyrene-block-isobutylene-block-α-methylstyrene) triblock copolymer

Poly(MMA-b-IB-b-MMA):

Poly(methyl methacrylate-block-isobutylene-block-methyl methacrylate) triblock copolymer

Poly(St-b-IB):

Poly(styrene-block-isobutylene) copolymer

Poly(pClαMeSt-b-IB):

Poly(p-chloro-α-methylstyrene-block-isobutylene) copolymer

Poly(pMeSt-b-IB-b-pMeSt):

Poly(p-methylstyrene-block-isobutylene-block-p-methylstyrene) triblock copolymer

Poly(St-b-IB-b-St):

Poly(styrene-block-isobutylene-block-styrene) triblock copolymer

PpClαMeSt:

Poly(p-chloro-α-methylstyrene)

PPVL:

Poly(pivalolactone)

PVL:

Pivalolactone

PSt:

Polystyrene

-St-IB-Cl:

Dormant polymer end with styrene as the penultimate and isobutylene as the ultimate monomer unit

t1/2 :

Half-life time of living chain ends

tBuDiCumCl:

5-tert-Butyl-1,3-bis-(1-chloro-1-methylethyl)-benzene

T g :

Glass transition temperature

[TiCl4]free :

Concentration of free and uncomplexed TiCl4

T m :

Melting temperature

TMPCl:

2-Chloro-2,4,4-trimethylpentane

TPE:

Thermoplastic elastomer

σ:

Tensile strength

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Acknowledgments

Financial support from National Science Foundation (DMR-9502777 and DMR-9806418), the Exxon Chemical Co. and Dow Corning Corp. is gratefully acknowledged.

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  1. Younghwan Kwon

    Present address: Department of Chemical Engineering, Daegu University, Gyeongsan, Gyeongbuk, 712-714, Korea

Authors and Affiliations

  1. Polymer Science Program, Department of Chemistry, University of Massachusetts Lowell, One, University Avenue, Lowell, MA, 01854, USA

    Younghwan Kwon & Rudolf Faust

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Kwon, Y., Faust, R. (2004). Synthesis of Polyisobutylene-Based Block Copolymers with Precisely Controlled Architecture by Living Cationic Polymerization. In: New Synthetic Methods. Advances in Polymer Science, vol 167. Springer, Berlin, Heidelberg. https://doi.org/10.1007/b12306

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  • DOI: https://doi.org/10.1007/b12306

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