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An Acid Test: Facile SI-ARGET-ATRP of Methacrylic Acid

Harm-Anton Klok, Piotr Mocny
2018
Article
Résumé

Atom transfer radical polymerization (ATRP) of methacrylic acid (MAA) is challenging. Herein is reported a study of conditions for facile surface-initiated ATRP by activator regenerated electron transfer (SI-ARGET-ATRP) growth of poly-methacrylic acid (PMAA) chains from a plasma polymer surface bearing surface-immobilized -bromoisobutyryl bromide, with no deoxygenation required. Factors that affect PMAA polymer growth off the surface under ARGET-ATRP conditions are systematically investigated, such as monomer/catalyst ratio, solvent, and, most importantly, addition of salts and change of pH. While the concentrations of the copper catalyst and acid affect grafting, the most pronounced effect arises from the concentration of chloride ions. Adding 0.1 m NaCl and acidifying the reaction solution to pH 3 offers the best trade-off between reaction rate and reproducibility; yielding approximate to 60nm thick PMAA graft polymers in 1 h under ambient conditions. Using this easily scalable recipe and surface analysis, the grafted polymers are verified to be pure PMAA and the graft coatings to be homogenous across a substrate of 100 mm diameter.

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Proximité ontologique
Chimie
Concepts associés (31)
Reaction rate
The reaction rate or rate of reaction is the speed at which a chemical reaction takes place, defined as proportional to the increase in the concentration of a product per unit time and to the decrease in the concentration of a reactant per unit time. Reaction rates can vary dramatically. For example, the oxidative rusting of iron under Earth's atmosphere is a slow reaction that can take many years, but the combustion of cellulose in a fire is a reaction that takes place in fractions of a second.
Polymérisation radicalaire
La polymérisation (par voie) radicalaire est un processus de polymérisation en chaîne qui, comme son nom l'indique, fait intervenir comme espèce active des radicaux. Elle fait intervenir des réactions d'amorçage, de propagation, de terminaison et de transfert de chaîne. Le site actif qui propage est un radical possédant une structure quasi plane au carbone terminal qui porte l'électron non apparié. L'assemblage du maillon suivant peut alors se faire par-dessus ou dessous aléatoirement.
Graft polymer
In polymer chemistry, graft polymers are segmented copolymers with a linear backbone of one composite and randomly distributed branches of another composite. The picture labeled "graft polymer" shows how grafted chains of species B are covalently bonded to polymer species A. Although the side chains are structurally distinct from the main chain, the individual grafted chains may be homopolymers or copolymers.
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