Controlled Synthesis of Polymer Brushes by “Living” Free Radical Polymerization Techniques

Husseman, Marc; Malmström, Eva; McNamara, Mary; Mate, Mathew; Mecerreyes, David; Benoit, Didier; Hedrick, James L.; Mansky, P.; Huang, E.; Russell, Thomas P.; Hawker, Craig J.

doi:10.1021/ma981290v

Cited by 909 publications

(889 citation statements)

References 19 publications

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“…NMRP and ATRP-methods have been successfully applied for the polymerization of various monomers in grafting-from manner [23,24]. Binary polymer brushes certainly are a powerful tool to the preparation of versatile switchable surfaces (coatings) for numerous applications.…”

Section: Discussionmentioning

confidence: 99%

NMRP and ATRP Double Initiators for the Formation of Binary Polymer Brushes via Grafting-From Methods

Thiessen

Wolff

2011

Designed Monomers and Polymers

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New ATRP and NMRP initiator molecules were synthesized, which were grafted on silica wafer surfaces and served for initiating the formation of polymer brushes via the grafting-from method. Two of the new initiators bore ATRP and NMRP moieties in the same molecule. These double initiators were used to produce binary polymer brushes with switchable surface properties: styrene was first polymerized via ATRP at 40 • C and 4-vinylpyridine was polymerized thereafter at 110 • C via NMRP. The brushes achieved in this way exhibited smooth surfaces differing in the thickness of the brush layers by less than 10% (at different areas of the wafers) and could be switched from hydrophobic to hydrophilic and vice versa.

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Section: Discussionmentioning

confidence: 99%

NMRP and ATRP Double Initiators for the Formation of Binary Polymer Brushes via Grafting-From Methods

Thiessen

Wolff

2011

Designed Monomers and Polymers

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“…This approach yields well-defined grafted polymer. However, the deposited layers have low densities and their thickness is limited (100 nm [47]) due to the steric hindrance during grafting and diffusion processes [48][49][50][51]. The "grafting from" method consists in polymerization directly from the surface.…”

Section: Brush Structurementioning

confidence: 99%

“…Several techniques are based on this process. Surface-initiated polymerization (SIP) based on radical chemistry is commonly used [47,51,52]. "Grafting from" techniques yield higher grafted layer densities and overcome thickness limitations.…”

Section: Brush Structurementioning

confidence: 99%

“…It is also possible to control thickness and graft density separately, by modulating the reaction time and stoichiometric ratio, respectively [57,58]. In addition, ATRP is known to be versatile and easy to perform (mild conditions) [51,58,59]. While high temperatures make the reaction time shorter, some studies also show a slight reduction of the polydispersity [60].…”

Section: Grafting Techniques 321 Atom Transfer Radical Polymerizatmentioning

confidence: 99%

“…The direct characterization of grafted polymer through the "grafting from" method is difficult. Generally, a sacrificial initiator is used, assuming that the polymer growth is similar on the surface and in the medium [51,52,58,59,[82][83][84][85]. Another method is to use reversible or breakable surface bonds in order to detach and study the grafted polymer [86].…”

Section: Grafting Techniques 321 Atom Transfer Radical Polymerizatmentioning

confidence: 99%

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PNIPAM grafted surfaces through ATRP and RAFT polymerization: Chemistry and bioadhesion

Conzatti

Cavalié

Combes

et al. 2017

Colloids and Surfaces B: Biointerfaces

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a b s t r a c tBiomaterials surface design is critical for the control of materials and biological system interactions. Being regulated by a layer of molecular dimensions, bioadhesion could be effectively tailored by polymer surface grafting. Basically, this surface modification can be controlled by radical polymerization, which is a useful tool for this purpose. The aim of this review is to provide a comprehensive overview of the role of surface characteristics on bioadhesion properties. We place a particular focus on biomaterials functionalized with a brush surface, on presentation of grafting techniques for "grafting to" and "grafting from" strategies and on brush characterization methods. Since atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain transfer (RAFT) polymerization are the most frequently used grafting techniques, their main characteristics will be explained. Through the example of poly(N-isopropylacrylamide) (PNIPAM) which is a widely used polymer allowing tuneable cell adhesion, smart surfaces involving PNIPAM will be presented with their main modern applications.

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Initiators, Free‐Radical

Myers

2001

Kirk-Othmer Encyclopedia of Chemical Technology

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Most commercial free‐radical applications employ initiators such as peroxides and azo compounds. Lesser amounts of carbon–carbon initiators and photoinitiators and high‐energy ionizing radiation are also used commercially to generate free radicals. The chemical initiators are substances possessing labile oxygen–oxygen, carbon–nitrogen, or carbon–carbon covalent bonds that under certain thermal, chemical, or photochemical conditions undergo homolytic scission of the labile bond to produce free radicals. The free radicals produced are useful in many industrial chain reactions, eg, halogenations, additions to carbon–carbon double bonds, polymerizations of vinyl monomers, grafting reactions, curing of rubbers and unsaturated polymers, cross‐linking of polyolefins, modification of polyolefins, and reactive processing. In this article free‐radical initiator decomposition pathways are reviewed. Initiator reactivity is related to chemical structure and to first‐order decomposition parameters such as temperature, frequency factor, and activation energy. Reactivity of derived free radicals is also related to structure and to the occurrence of secondary reactions such as β‐scission and induced decomposition. The energy and the chemical properties of the free radicals determine commercial utility; thus the interrelation of initiators, their kinetics, and the radicals produced provide guidelines for initiator selection.

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Controlled Synthesis of Polymer Brushes by “Living” Free Radical Polymerization Techniques

Cited by 909 publications

References 19 publications

NMRP and ATRP Double Initiators for the Formation of Binary Polymer Brushes via Grafting-From Methods

NMRP and ATRP Double Initiators for the Formation of Binary Polymer Brushes via Grafting-From Methods

PNIPAM grafted surfaces through ATRP and RAFT polymerization: Chemistry and bioadhesion

Initiators, Free‐Radical

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