Synthesis of well-defined PPV containing block polymers with precise endgroup control by a dual-initiator strategy

Inge Cosemans, Joke Vandenbergh, Laurence Lutsen, Dirk Vanderzande, Thomas Junkers

Research output: Contribution to journalArticleResearchpeer-review

15 Citations (Scopus)

Abstract

Poly(2,5-bis(2-ethylhexyloxy)p-phenylene vinylene)-b-poly(tert-butyl acrylate) (BEH-PPV-b-P(t-BuA)) block copolymers with various block compositions have been synthesized by a dual initiator strategy. PPV polymerizations are performed via the anionic polymerization mode of the so-called sulfinyl precursor synthesis route with a dedicated initiator carrying a moiety that is able to reinitiate polymer chains under the conditions of a single electron transfer living radical polymerization (SET-LRP). In order to prove that such a route can be taken, a detailed study on the initiator efficiency in the anionic polymerization based on post-mortem analysis of materials with ESI-MS is presented. Low molecular weight PPVs in the range of 2000 Da are synthesized by means of high initiator to monomer concentrations with the use of two differently functionalized anionic initiators. Almost quantitative incorporation of the initiator in the alpha position of the chains is confirmed. Block copolymers are subsequently obtained from a BEH-PPV building block with an apparent Mn of 5300 g mol-1. Block copolymers with apparent Mn between 6800 and 25000 g mol-1 are synthesized. Hydrolysis of the acrylate ester block yields amphiphilic block copolymers with a poly(acrylic acid) block, which can be self-assembled in methanolic solution to form micelles with a mean diameter of 81 nm. The micelles respond to changes in pH and ionic strength, leading to significant expansion of the micelles in both cases.

Original languageEnglish
Pages (from-to)3471-3479
Number of pages9
JournalPolymer Chemistry
Volume4
Issue number12
DOIs
Publication statusPublished - 21 Jun 2013
Externally publishedYes

Cite this

Cosemans, Inge ; Vandenbergh, Joke ; Lutsen, Laurence ; Vanderzande, Dirk ; Junkers, Thomas. / Synthesis of well-defined PPV containing block polymers with precise endgroup control by a dual-initiator strategy. In: Polymer Chemistry. 2013 ; Vol. 4, No. 12. pp. 3471-3479.
@article{eb786fd1909c40d49b23ecc0b4030f55,
title = "Synthesis of well-defined PPV containing block polymers with precise endgroup control by a dual-initiator strategy",
abstract = "Poly(2,5-bis(2-ethylhexyloxy)p-phenylene vinylene)-b-poly(tert-butyl acrylate) (BEH-PPV-b-P(t-BuA)) block copolymers with various block compositions have been synthesized by a dual initiator strategy. PPV polymerizations are performed via the anionic polymerization mode of the so-called sulfinyl precursor synthesis route with a dedicated initiator carrying a moiety that is able to reinitiate polymer chains under the conditions of a single electron transfer living radical polymerization (SET-LRP). In order to prove that such a route can be taken, a detailed study on the initiator efficiency in the anionic polymerization based on post-mortem analysis of materials with ESI-MS is presented. Low molecular weight PPVs in the range of 2000 Da are synthesized by means of high initiator to monomer concentrations with the use of two differently functionalized anionic initiators. Almost quantitative incorporation of the initiator in the alpha position of the chains is confirmed. Block copolymers are subsequently obtained from a BEH-PPV building block with an apparent Mn of 5300 g mol-1. Block copolymers with apparent Mn between 6800 and 25000 g mol-1 are synthesized. Hydrolysis of the acrylate ester block yields amphiphilic block copolymers with a poly(acrylic acid) block, which can be self-assembled in methanolic solution to form micelles with a mean diameter of 81 nm. The micelles respond to changes in pH and ionic strength, leading to significant expansion of the micelles in both cases.",
author = "Inge Cosemans and Joke Vandenbergh and Laurence Lutsen and Dirk Vanderzande and Thomas Junkers",
year = "2013",
month = "6",
day = "21",
doi = "10.1039/c3py00303e",
language = "English",
volume = "4",
pages = "3471--3479",
journal = "Polymer Chemistry",
issn = "1759-9954",
publisher = "The Royal Society of Chemistry",
number = "12",

}

Synthesis of well-defined PPV containing block polymers with precise endgroup control by a dual-initiator strategy. / Cosemans, Inge; Vandenbergh, Joke; Lutsen, Laurence; Vanderzande, Dirk; Junkers, Thomas.

In: Polymer Chemistry, Vol. 4, No. 12, 21.06.2013, p. 3471-3479.

Research output: Contribution to journalArticleResearchpeer-review

TY - JOUR

T1 - Synthesis of well-defined PPV containing block polymers with precise endgroup control by a dual-initiator strategy

AU - Cosemans, Inge

AU - Vandenbergh, Joke

AU - Lutsen, Laurence

AU - Vanderzande, Dirk

AU - Junkers, Thomas

PY - 2013/6/21

Y1 - 2013/6/21

N2 - Poly(2,5-bis(2-ethylhexyloxy)p-phenylene vinylene)-b-poly(tert-butyl acrylate) (BEH-PPV-b-P(t-BuA)) block copolymers with various block compositions have been synthesized by a dual initiator strategy. PPV polymerizations are performed via the anionic polymerization mode of the so-called sulfinyl precursor synthesis route with a dedicated initiator carrying a moiety that is able to reinitiate polymer chains under the conditions of a single electron transfer living radical polymerization (SET-LRP). In order to prove that such a route can be taken, a detailed study on the initiator efficiency in the anionic polymerization based on post-mortem analysis of materials with ESI-MS is presented. Low molecular weight PPVs in the range of 2000 Da are synthesized by means of high initiator to monomer concentrations with the use of two differently functionalized anionic initiators. Almost quantitative incorporation of the initiator in the alpha position of the chains is confirmed. Block copolymers are subsequently obtained from a BEH-PPV building block with an apparent Mn of 5300 g mol-1. Block copolymers with apparent Mn between 6800 and 25000 g mol-1 are synthesized. Hydrolysis of the acrylate ester block yields amphiphilic block copolymers with a poly(acrylic acid) block, which can be self-assembled in methanolic solution to form micelles with a mean diameter of 81 nm. The micelles respond to changes in pH and ionic strength, leading to significant expansion of the micelles in both cases.

AB - Poly(2,5-bis(2-ethylhexyloxy)p-phenylene vinylene)-b-poly(tert-butyl acrylate) (BEH-PPV-b-P(t-BuA)) block copolymers with various block compositions have been synthesized by a dual initiator strategy. PPV polymerizations are performed via the anionic polymerization mode of the so-called sulfinyl precursor synthesis route with a dedicated initiator carrying a moiety that is able to reinitiate polymer chains under the conditions of a single electron transfer living radical polymerization (SET-LRP). In order to prove that such a route can be taken, a detailed study on the initiator efficiency in the anionic polymerization based on post-mortem analysis of materials with ESI-MS is presented. Low molecular weight PPVs in the range of 2000 Da are synthesized by means of high initiator to monomer concentrations with the use of two differently functionalized anionic initiators. Almost quantitative incorporation of the initiator in the alpha position of the chains is confirmed. Block copolymers are subsequently obtained from a BEH-PPV building block with an apparent Mn of 5300 g mol-1. Block copolymers with apparent Mn between 6800 and 25000 g mol-1 are synthesized. Hydrolysis of the acrylate ester block yields amphiphilic block copolymers with a poly(acrylic acid) block, which can be self-assembled in methanolic solution to form micelles with a mean diameter of 81 nm. The micelles respond to changes in pH and ionic strength, leading to significant expansion of the micelles in both cases.

UR - http://www.scopus.com/inward/record.url?scp=84887413825&partnerID=8YFLogxK

U2 - 10.1039/c3py00303e

DO - 10.1039/c3py00303e

M3 - Article

AN - SCOPUS:84887413825

VL - 4

SP - 3471

EP - 3479

JO - Polymer Chemistry

JF - Polymer Chemistry

SN - 1759-9954

IS - 12

ER -