Amphiphilic model conetworks of polyisobutylene methacrylate and 2-(dimethylamino)ethyl methacrylate prepared by the combination of quasiliving carbocationic and group transfer polymerizations

Theoni K. Georgiou, Costas S. Patrickios, Peter Werner Groh, B. Iván

Research output: Contribution to journalArticle

68 Citations (Scopus)

Abstract

A series of amphiphilic polymer conetworks (APCN) of the hydrophobic polyisobutylene methacrylate macromonomer (PIBMA) and the ionizable hydrophilic 2-(dimethylamino)ethyl methacrylate (DMAEMA) were synthesized by combining, for the first time, two controlled polymerization methods, quasiliving carbocationic polymerization (QLCCP) and group transfer polymerization (GTP). First, isobutylene (IB) was polymerized by QLCCP, and the resulting IB 7-mer (PIB) was modified to yield PIBMA with exact chain end-functionality of 1.0. Subsequently, PIBMA was successfully polymerized sequentially by GTP with DMAEMA (comonomer) and ethylene glycol dimethacrylate (EGDMA, cross-linker) using a bifunctional GTP initiator, 1,4-bis(methoxytrimethylsiloxymethylene)cyclohexane. Amphiphilic conetworks with linear segments of well-defined molecular weights (model conetworks) and a randomly cross-linked conetwork with linear segments characterized by a broad size distribution between the cross-links were prepared. Four of the model conetworks were based on poly(PIBMA-b-DMAEMA-b- PIBMA) triblock copolymers and two were based on poly(DMAEMA-b-PIBMA-b-DMAEMA) triblock copolymers of different degrees of polymerization (DP). Another conetwork was prepared from statistical copolymer chains. For comparison, four more networks, two of them based on DMAEMA homopolymers and two others based on copolymers of DMAEMA and methyl methacrylate, were also synthesized in the course of this study. Gel permeation chromatography and 1H NMR analyses indicated that the precursors to all the networks had the desired molecular weights and compositions. The degrees of swelling (DS) of the conetworks in tetrahydrofuran, n-hexane, and acidic water depended on the DP and the composition of the polymer chains between the EGDMA cross-links, while the DSs in neutral water were very low and almost constant because of the low degree of ionization of DMAEMA units in the conetworks in this solvent. These results show that the swelling behavior of the DMAEMA-PIBMA and DMAEMA-MMA conetworks can be controlled by the length and the composition of the chains between the cross-links, by the solvent polarity and the pH in a broad range.

Original languageEnglish
Pages (from-to)2335-2343
Number of pages9
JournalMacromolecules
Volume40
Issue number7
DOIs
Publication statusPublished - Apr 3 2007

Fingerprint

Methacrylates
Polymerization
Block copolymers
Swelling
Copolymers
Chemical analysis
Molecular weight
2-(dimethylamino)ethyl methacrylate
polyisobutylene
Gel permeation chromatography
Polymers
Cyclohexane
Ethylene glycol
Homopolymerization
Hexane
Ionization
Water
Nuclear magnetic resonance

ASJC Scopus subject areas

  • Materials Chemistry

Cite this

Amphiphilic model conetworks of polyisobutylene methacrylate and 2-(dimethylamino)ethyl methacrylate prepared by the combination of quasiliving carbocationic and group transfer polymerizations. / Georgiou, Theoni K.; Patrickios, Costas S.; Groh, Peter Werner; Iván, B.

In: Macromolecules, Vol. 40, No. 7, 03.04.2007, p. 2335-2343.

Research output: Contribution to journalArticle

@article{1aa7ac6f4751451b8788edc8da3cbb4e,
title = "Amphiphilic model conetworks of polyisobutylene methacrylate and 2-(dimethylamino)ethyl methacrylate prepared by the combination of quasiliving carbocationic and group transfer polymerizations",
abstract = "A series of amphiphilic polymer conetworks (APCN) of the hydrophobic polyisobutylene methacrylate macromonomer (PIBMA) and the ionizable hydrophilic 2-(dimethylamino)ethyl methacrylate (DMAEMA) were synthesized by combining, for the first time, two controlled polymerization methods, quasiliving carbocationic polymerization (QLCCP) and group transfer polymerization (GTP). First, isobutylene (IB) was polymerized by QLCCP, and the resulting IB 7-mer (PIB) was modified to yield PIBMA with exact chain end-functionality of 1.0. Subsequently, PIBMA was successfully polymerized sequentially by GTP with DMAEMA (comonomer) and ethylene glycol dimethacrylate (EGDMA, cross-linker) using a bifunctional GTP initiator, 1,4-bis(methoxytrimethylsiloxymethylene)cyclohexane. Amphiphilic conetworks with linear segments of well-defined molecular weights (model conetworks) and a randomly cross-linked conetwork with linear segments characterized by a broad size distribution between the cross-links were prepared. Four of the model conetworks were based on poly(PIBMA-b-DMAEMA-b- PIBMA) triblock copolymers and two were based on poly(DMAEMA-b-PIBMA-b-DMAEMA) triblock copolymers of different degrees of polymerization (DP). Another conetwork was prepared from statistical copolymer chains. For comparison, four more networks, two of them based on DMAEMA homopolymers and two others based on copolymers of DMAEMA and methyl methacrylate, were also synthesized in the course of this study. Gel permeation chromatography and 1H NMR analyses indicated that the precursors to all the networks had the desired molecular weights and compositions. The degrees of swelling (DS) of the conetworks in tetrahydrofuran, n-hexane, and acidic water depended on the DP and the composition of the polymer chains between the EGDMA cross-links, while the DSs in neutral water were very low and almost constant because of the low degree of ionization of DMAEMA units in the conetworks in this solvent. These results show that the swelling behavior of the DMAEMA-PIBMA and DMAEMA-MMA conetworks can be controlled by the length and the composition of the chains between the cross-links, by the solvent polarity and the pH in a broad range.",
author = "Georgiou, {Theoni K.} and Patrickios, {Costas S.} and Groh, {Peter Werner} and B. Iv{\'a}n",
year = "2007",
month = "4",
day = "3",
doi = "10.1021/ma062307+",
language = "English",
volume = "40",
pages = "2335--2343",
journal = "Macromolecules",
issn = "0024-9297",
publisher = "American Chemical Society",
number = "7",

}

TY - JOUR

T1 - Amphiphilic model conetworks of polyisobutylene methacrylate and 2-(dimethylamino)ethyl methacrylate prepared by the combination of quasiliving carbocationic and group transfer polymerizations

AU - Georgiou, Theoni K.

AU - Patrickios, Costas S.

AU - Groh, Peter Werner

AU - Iván, B.

PY - 2007/4/3

Y1 - 2007/4/3

N2 - A series of amphiphilic polymer conetworks (APCN) of the hydrophobic polyisobutylene methacrylate macromonomer (PIBMA) and the ionizable hydrophilic 2-(dimethylamino)ethyl methacrylate (DMAEMA) were synthesized by combining, for the first time, two controlled polymerization methods, quasiliving carbocationic polymerization (QLCCP) and group transfer polymerization (GTP). First, isobutylene (IB) was polymerized by QLCCP, and the resulting IB 7-mer (PIB) was modified to yield PIBMA with exact chain end-functionality of 1.0. Subsequently, PIBMA was successfully polymerized sequentially by GTP with DMAEMA (comonomer) and ethylene glycol dimethacrylate (EGDMA, cross-linker) using a bifunctional GTP initiator, 1,4-bis(methoxytrimethylsiloxymethylene)cyclohexane. Amphiphilic conetworks with linear segments of well-defined molecular weights (model conetworks) and a randomly cross-linked conetwork with linear segments characterized by a broad size distribution between the cross-links were prepared. Four of the model conetworks were based on poly(PIBMA-b-DMAEMA-b- PIBMA) triblock copolymers and two were based on poly(DMAEMA-b-PIBMA-b-DMAEMA) triblock copolymers of different degrees of polymerization (DP). Another conetwork was prepared from statistical copolymer chains. For comparison, four more networks, two of them based on DMAEMA homopolymers and two others based on copolymers of DMAEMA and methyl methacrylate, were also synthesized in the course of this study. Gel permeation chromatography and 1H NMR analyses indicated that the precursors to all the networks had the desired molecular weights and compositions. The degrees of swelling (DS) of the conetworks in tetrahydrofuran, n-hexane, and acidic water depended on the DP and the composition of the polymer chains between the EGDMA cross-links, while the DSs in neutral water were very low and almost constant because of the low degree of ionization of DMAEMA units in the conetworks in this solvent. These results show that the swelling behavior of the DMAEMA-PIBMA and DMAEMA-MMA conetworks can be controlled by the length and the composition of the chains between the cross-links, by the solvent polarity and the pH in a broad range.

AB - A series of amphiphilic polymer conetworks (APCN) of the hydrophobic polyisobutylene methacrylate macromonomer (PIBMA) and the ionizable hydrophilic 2-(dimethylamino)ethyl methacrylate (DMAEMA) were synthesized by combining, for the first time, two controlled polymerization methods, quasiliving carbocationic polymerization (QLCCP) and group transfer polymerization (GTP). First, isobutylene (IB) was polymerized by QLCCP, and the resulting IB 7-mer (PIB) was modified to yield PIBMA with exact chain end-functionality of 1.0. Subsequently, PIBMA was successfully polymerized sequentially by GTP with DMAEMA (comonomer) and ethylene glycol dimethacrylate (EGDMA, cross-linker) using a bifunctional GTP initiator, 1,4-bis(methoxytrimethylsiloxymethylene)cyclohexane. Amphiphilic conetworks with linear segments of well-defined molecular weights (model conetworks) and a randomly cross-linked conetwork with linear segments characterized by a broad size distribution between the cross-links were prepared. Four of the model conetworks were based on poly(PIBMA-b-DMAEMA-b- PIBMA) triblock copolymers and two were based on poly(DMAEMA-b-PIBMA-b-DMAEMA) triblock copolymers of different degrees of polymerization (DP). Another conetwork was prepared from statistical copolymer chains. For comparison, four more networks, two of them based on DMAEMA homopolymers and two others based on copolymers of DMAEMA and methyl methacrylate, were also synthesized in the course of this study. Gel permeation chromatography and 1H NMR analyses indicated that the precursors to all the networks had the desired molecular weights and compositions. The degrees of swelling (DS) of the conetworks in tetrahydrofuran, n-hexane, and acidic water depended on the DP and the composition of the polymer chains between the EGDMA cross-links, while the DSs in neutral water were very low and almost constant because of the low degree of ionization of DMAEMA units in the conetworks in this solvent. These results show that the swelling behavior of the DMAEMA-PIBMA and DMAEMA-MMA conetworks can be controlled by the length and the composition of the chains between the cross-links, by the solvent polarity and the pH in a broad range.

UR - http://www.scopus.com/inward/record.url?scp=34247260401&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=34247260401&partnerID=8YFLogxK

U2 - 10.1021/ma062307+

DO - 10.1021/ma062307+

M3 - Article

AN - SCOPUS:34247260401

VL - 40

SP - 2335

EP - 2343

JO - Macromolecules

JF - Macromolecules

SN - 0024-9297

IS - 7

ER -