Cu(0)-RDRP of 2-hydroxyethyl methacrylate in a non-polar solvent enables rapid synthesis of high-molecular weight homopolymers and direct access to amphiphilic copolymers

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61389013%3A_____%2F23%3A00567290" target="_blank" >RIV/61389013:_____/23:00567290 - isvavai.cz</a>

Výsledek na webu

<a href="https://www.sciencedirect.com/science/article/pii/S1381514823000123?via%3Dihub" target="_blank" >https://www.sciencedirect.com/science/article/pii/S1381514823000123?via%3Dihub</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1016/j.reactfunctpolym.2023.105509" target="_blank" >10.1016/j.reactfunctpolym.2023.105509</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Cu(0)-RDRP of 2-hydroxyethyl methacrylate in a non-polar solvent enables rapid synthesis of high-molecular weight homopolymers and direct access to amphiphilic copolymers

Popis výsledku v původním jazyce

2-Hydroxyethyl methacrylate (HEMA) is an important functional monomer affording (co)polymers with numerous applications in different fields. Nevertheless, we still lack a reliable polymerization method for the synthesis of well-defined, high-molecular weight (MW) HEMA homopolymers, as well as for controlled copolymerization of unprotected HEMA with lipophilic comonomers. Herein, we report that rapid and well-controlled (co)polymerization of HEMA can be achieved via metallic copper-mediated reversible-deactivation radical polymerization (Cu(0)-RDRP) in a non-polar solvent (1,4-dioxane) using a chlorine-based initiation/catalytic system. With purified HEMA monomer, this protocol affords very well-defined (Ɖ ≤ 1.26) HEMA homopolymers in an unprecedently wide range of molecular weights from 10,000 to 500,000. Conversely, the structurally analogous bromine-based initiation/catalytic system leads to an uncontrolled polymerization. The use of a non-polar solvent enables, for the first time, a direct access to low-dispersity HEMA-rich copolymers with non-polar comonomers, including highly lipophilic ones. This is demonstrated on the successful copolymerization of HEMA with an equimolar amount of 2-ethylhexyl methacrylate and of lauryl methacrylate, yielding well-defined amphiphilic copolymers at quantitative conversion. This work significantly expands the application scope of the HEMA monomer and demonstrates for the first time that Cu(0)-RDRP in a non-polar solvent is applicable also to comparatively polar monomers.

Název v anglickém jazyce

Cu(0)-RDRP of 2-hydroxyethyl methacrylate in a non-polar solvent enables rapid synthesis of high-molecular weight homopolymers and direct access to amphiphilic copolymers

Popis výsledku anglicky

2-Hydroxyethyl methacrylate (HEMA) is an important functional monomer affording (co)polymers with numerous applications in different fields. Nevertheless, we still lack a reliable polymerization method for the synthesis of well-defined, high-molecular weight (MW) HEMA homopolymers, as well as for controlled copolymerization of unprotected HEMA with lipophilic comonomers. Herein, we report that rapid and well-controlled (co)polymerization of HEMA can be achieved via metallic copper-mediated reversible-deactivation radical polymerization (Cu(0)-RDRP) in a non-polar solvent (1,4-dioxane) using a chlorine-based initiation/catalytic system. With purified HEMA monomer, this protocol affords very well-defined (Ɖ ≤ 1.26) HEMA homopolymers in an unprecedently wide range of molecular weights from 10,000 to 500,000. Conversely, the structurally analogous bromine-based initiation/catalytic system leads to an uncontrolled polymerization. The use of a non-polar solvent enables, for the first time, a direct access to low-dispersity HEMA-rich copolymers with non-polar comonomers, including highly lipophilic ones. This is demonstrated on the successful copolymerization of HEMA with an equimolar amount of 2-ethylhexyl methacrylate and of lauryl methacrylate, yielding well-defined amphiphilic copolymers at quantitative conversion. This work significantly expands the application scope of the HEMA monomer and demonstrates for the first time that Cu(0)-RDRP in a non-polar solvent is applicable also to comparatively polar monomers.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10404 - Polymer science

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2023

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Reactive and Functional Polymers

ISSN

1381-5148

e-ISSN

1873-166X

Svazek periodika

183

Číslo periodika v rámci svazku

February

Stát vydavatele periodika

NL - Nizozemsko

Počet stran výsledku

7

Strana od-do

105509

Kód UT WoS článku

000997355000001

EID výsledku v databázi Scopus

2-s2.0-85146054939