Atom Transfer Radical Polymerization (ATRP) of Methyl Methacrylate using a Functional Initiator Bearing an Amino‐Adamantane

Kavitha, A. Amalin; Singha, Nikhil K.

doi:10.1002/macp.200900094

Cited by 14 publications

(11 citation statements)

References 47 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…A noticeable exception to this general behavior was reported for polymers produced by ATRP of methyl methacrylate using an initiator bearing an adamantyl group (Kavitha & Singha, ), and generated as intact bromine‐terminated cationic adducts during MALDI with nearly no other side‐products. It was concluded that the adamantyl group attached to PMMA improved thermal stability and raised the glass transition temperature of the polymers, as indicated by thermogravimetric analysis and differential scanning calorimetry experiments.…”

Section: Maldi‐ms Of Atrp Polymersmentioning

confidence: 94%

MALDI of synthetic polymers with labile end‐groups

Charles

2013

Mass Spectrometry Reviews

View full text Add to dashboard Cite

Mass spectrometry is increasingly used in the field of synthetic polymers as a fast and accurate technique for end-group analysis. More particularly, matrix-assisted laser desorption/ionization (MALDI) has gained much popularity because it allows quite simple mass spectra to be obtained, displaying a single distribution for each polymeric species present in the sample, in contrast to electrospray ionization (ESI) which readily promotes multiple charging for most polymers. A soft ionization process, ensuring the integrity of the species upon transfer into gas phase ions, is however mandatory for polymer end-group analysis since information about the chain terminations mainly rely on the m/z values measured for polymer adducts. As compared to ESI, MALDI is sometimes suspected to be a quite "hard" ionization technique, leading to spontaneous dissociation of ionized species either in the source or during their flight time. This issue is of particular concern for polymers carrying so-called fragile end-groups arising from their mode of synthesis. In particular, controlled radical polymerization (CRP) processes, one of the most important advances in the field of polymer science during the last 20 years, allow the production of polymers with well-defined molecular distribution and low polydispersities, but they are all based on the low dissociation energy of the chemical bond between the last monomer and the terminating group. As a result, if macromolecules are activated while being ionized, this end-group is prone to fragmentation and ions measured in the mass spectra do no longer reflect the original chain composition. However, different results are reported in the literature about the ability of MALDI to generate intact ions from CRP synthetic polymers. This article reviews MALDI MS data reported for synthetic polymers produced by atom transfer radical polymerization (ATRP), reversible addition-fragmentation transfer polymerization (RAFT), and nitroxide-mediated polymerization (NMP), the three most studied CRP techniques. The general principle of each polymerization process, which defines the structure of the end-groups in both targeted macromolecules and species arising from eventual side-reactions, is first briefly presented. An overview of MALDI data reported for samples obtained upon polymerization of different monomers are then commented for each polymerization techniques with regards to the success of the ionization method to generate intact cationic adducts and its propensity to distinguish in-source fragments from polymerization side-products.

show abstract

Section: Maldi‐ms Of Atrp Polymersmentioning

confidence: 94%

MALDI of synthetic polymers with labile end‐groups

Charles

2013

Mass Spectrometry Reviews

View full text Add to dashboard Cite

show abstract

“…Adamantane (3.3.1.1 1,2 ) decane is a thermodynamically stable, highly symmetrical, tricyclic, bulky, and diamond-like cage hydrocarbon structure with three structures that consist of a three-fused chair conformation of a cyclohexane ring in a diamond lattice [19][20][21][22]. Recently, adamantane-containing polymers have been given much attention because they are expected not only to have high free volume but also to improve thermal stability, mechanical strength, optical property, and low dielectric property.…”

Section: Introductionmentioning

confidence: 99%

“…Recently, adamantane-containing polymers have been given much attention because they are expected not only to have high free volume but also to improve thermal stability, mechanical strength, optical property, and low dielectric property. Therefore, the effects of adamantyl unit on the physical and chemical properties, such as thermal, stiffness, optical, and electrical properties, have been widely investigated [22][23][24][25][26][27][28][29][30]. From these functions, the wide applications of adamantane-containing polymer materials, such as photo resistance [31,32], thermal stability and transparency [28,33], adhesion [30], separation of membrane materials [34][35][36] have been investigated.…”

Section: Introductionmentioning

confidence: 99%

Effect of OH group on the water vapor sorption property of adamantane-containing polymer membranes

Kanehashi

Konishi

Takeo

et al. 2013

Journal of Membrane Science

View full text Add to dashboard Cite

“…Adamantane is a bulky diamond‐like, cage‐type structure that is composed of three fused cyclohexane rings arranged in a chair conformation, which results in a large structure (volume higher than 150 Å). This material is expected to possess high thermal stability, mechanical strength, low dielectric constant, and gas permeation properties . However, homopolymer permeability has not been reported because self‐standing thin membranes of adamantane homopolymer are difficult to obtain given that adamantyl groups rigidize the polymer main chain.…”

Section: Introductionmentioning

confidence: 99%

Thermal and gas permeation properties of copolymers derived from 3‐methacryloxypropyltris(trimethylsiloxy)silane and adamantyl group‐containing methacrylate derivatives

Ando

Yoshida

Nakagawa

et al. 2015

J of Applied Polymer Sci

View full text Add to dashboard Cite

Novel copolymer membranes derived from three types of adamantyl group‐containing methacrylate derivatives and 3‐methacryloxypropyltris(trimethylsiloxy)silane (SiMA) were synthesized via free radical polymerization. The thermal and permeation properties of these copolymer membranes were investigated. Copolymer membranes with less than 11.9 mol % adamantane content exhibited good membrane forming abilities that are suitable for permeation measurement. The decomposition temperature of all copolymers increased up to approximately 40–80°C with increasing adamantane content compared with poly(SiMA). Moreover, the glass transition temperature (Tg) of all copolymers increased up to approximately 46–60°C with increasing adamantane content compared with the theoretical value, which was estimated from Fox equation. 1‐Adamantyl methacrylate copolymer had the highest fractional free volume among the three types of adamantly group‐containing methacrylate derivatives. The gas permeability coefficient of this copolymer increased by 22–45% with increasing adamantane content compared with that of poly(SiMA). © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43129.

show abstract

Atom Transfer Radical Polymerization (ATRP) of Methyl Methacrylate using a Functional Initiator Bearing an Amino‐Adamantane

Cited by 14 publications

References 47 publications

MALDI of synthetic polymers with labile end‐groups

MALDI of synthetic polymers with labile end‐groups

Effect of OH group on the water vapor sorption property of adamantane-containing polymer membranes

Thermal and gas permeation properties of copolymers derived from 3‐methacryloxypropyltris(trimethylsiloxy)silane and adamantyl group‐containing methacrylate derivatives

Contact Info

Product

Resources

About