Novel substituted epoxide initiators for the carbocationic polymerization of isobutylene

Puskás, Judit E.; Brister, LB; Michel, Armin; Lanzendörfer, Michael G.; Jamieson, D. R.; Pattern, W. G.

doi:10.1002/(sici)1099-0518(20000201)38:3<444::aid-pola8>3.0.co;2-b

Cited by 48 publications

(55 citation statements)

References 14 publications

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“…[71] Multiple initiation by HES resulted in a star polymer with an average of 5.2 arms per molecule. [67] Epoxides are readily available or can be synthesized very easily, and are cost-efficient. Therefore they are attractive initiators for potential commercial living carbocationic polymerization processes.…”

Section: B) New Initiators For Carbocationic Polymerizationmentioning

confidence: 99%

Macromolecular Engineering via Carbocationic Polymerization: Branched Structures, Block Copolymers and Nanostructures

Puskás¹,

Antony

Kwon

et al. 2001

Macromol. Mater. Eng.

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This article features macromolecular engineering via carbocationic polymerization, the focus of research of the recently established Macromolecular Engineering Research Centre (MERC) at the University of Western Ontario. The fundamental philosophy of MERC is interdisciplinary research with a strong industrial orientation, while emphasizing the quest for fundamental understanding of polymerization processes and polymer structure‐property relationships. First, a brief overview of living polymerizations in general, and living carbocationic polymerizations in particular will be given. This latter technique is of interest because some monomers (e. g., isobutylene) can be polymerized by cationic techniques only, to yield polymers with unique properties (e. g., polyisobutylene with superior chemical and oxidative stability, low permeability and high damping). This will be followed by an overview of our research strategy and a summary of our latest results. These include the development of a fiber‐optic mid‐FTIR method for the real‐time monitoring of low temperature polymerization processes, the discovery that selected epoxides initiate effectively the living carbocationic polymerization of isobutylene, fundamental studies into the mechanism and kinetics of living carbocationic polymerization, and the design and synthesis of various polymer architectures (e. g., branched homo‐ and block copolymers) with improved properties and nanostructured phase morphologies.

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Section: B) New Initiators For Carbocationic Polymerizationmentioning

confidence: 99%

Macromolecular Engineering via Carbocationic Polymerization: Branched Structures, Block Copolymers and Nanostructures

Puskás¹,

Antony

Kwon

et al. 2001

Macromol. Mater. Eng.

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“…The substituted epoxides were commercially available or simply obtained by the reaction of their corresponding olefins with purified m-chloroperoxybenzoic acid. 69 Clearly, the easy synthesis renders these initiators very attractive for carbocationic polymerizations.…”

Section: One-step Hydroxyl-functionalization Of Pib By Living Initiatmentioning

confidence: 99%

“…69,70,75 The competitive reaction mechanism shown in Scheme 11 was proposed, according to which I eff was defined by the competition between S N 1 and S N 2 mechanistic pathways. The carbenium ions forming in the S N 1 pathway initiated the carbocationic polymerization of IB, whereas the initiator reacting in the S N 2 pathway was "lost" in terms of carbocationic activity.…”

Section: One-step Hydroxyl-functionalization Of Pib By Living Initiatmentioning

confidence: 99%

“…These side reactions were evidenced by in situ FTIR monitoring. 69,70,75 Because I eff is defined as the percentage of the initiator that yields carbocations to induce IB polymerization, the relative proportion of the simultaneous reactions in the epoxy ring-opening reaction was apparently influenced by the epoxide structure. The effect of the chemical structure of styrene-based epoxides (SE) on the initiation was subsequently investigated.…”

Section: One-step Hydroxyl-functionalization Of Pib By Living Initiatmentioning

confidence: 99%

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Polyisobutylene‐based biomaterials

Puskás

Chen

Dahman

et al. 2004

J. Polym. Sci. A Polym. Chem.

119

121

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This article highlights the biomaterial-related research of the Macromolecular Engineering Research Centre (MERC). The MERC group concentrated on polyisobutylene (PIB)-based biomaterials. In this article, first the unique properties of PIB are discussed, followed by a review of PIB-based potential biomaterials. MERC's systematic research program aimed to develop novel PIB-based biomaterials is then highlighted, including surface modification and biocompatibility studies.

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“…In polymer research this real-time in situ technique also showed to be an excellent monitoring tool, as reactions can be analysed without complicated reactor modifications or expensive deuterated monomers in order to reveal the reaction kinetics and mechanism [7][8][9][10][11][12][13][14][15].…”

Section: Introductionmentioning

confidence: 99%

Reaction Kinetics and Intermediate Determination of Solid Acid Catalysed Liquid-phase Hydrolysis Reactions: A Real-time in situ ATR FT-IR Study

2006

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The appearance of catalyst-reactant interactions observed in on-line ATR FT-IR spectra of Nafion/silica catalysed esterification and etherification reactions of 1-octanol was investigated. It was assessed by variation of catalyst and solvent that the catalyst-reactant band is a result of the reaction of silica with 1-octanol, yields Si-O-R functionalities. Based on off-line TPD-MS and TGA characterisation of the used solid catalyst powder, the formation of Si-O-R linkages on the SiO 2 surface was confirmed. This demonstrates conclusively that in specific liquid-phase reactions, on-line analysis of intermediate species adsorbed on heterogeneous catalysts is possible. Using on-line particle analyzers, it was assessed that the absorptions were not the result of severe attrition of the catalyst particles in the course of the reaction, but apparently the result of apolar interactions of the particles with the diamond crystal.

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Novel substituted epoxide initiators for the carbocationic polymerization of isobutylene

Cited by 48 publications

References 14 publications

Macromolecular Engineering via Carbocationic Polymerization: Branched Structures, Block Copolymers and Nanostructures

Macromolecular Engineering via Carbocationic Polymerization: Branched Structures, Block Copolymers and Nanostructures

Polyisobutylene‐based biomaterials

Reaction Kinetics and Intermediate Determination of Solid Acid Catalysed Liquid-phase Hydrolysis Reactions: A Real-time in situ ATR FT-IR Study

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