Polymerization Of Glycidyl Phenyl Ether Research Articles

Metal- and halogen-free one-pot synthesis of functional oligomers by tetra-n-butylammonium acetate/alcohol system

In this study, ring-opening polymerization of glycidyl phenyl ether (GPE) is performed using tetra-n-butylammonium acetate (n-Bu4NOAc) as a metal- and halogen-free initiator. Various alcohols are used as chain transfer agents (CTAs), of which ethanol yields oligo-GPE with a controlled number-average molecular weight (Mn) of relatively narrow polydispersity (Mw/Mn = 1.27–1.33). This polymerization system facilely affords various functional oligomers, including amphiphilic block copolymer, reactive oligomer, and branched oligomer from poly(ethylene glycol) methyl ether, allyl alcohol, and polyhydric alcohol as the respective CTAs. The terminal chain structures are confirmed via NMR and MALDI-TOF MS analysis.

Anionic Polymerization of an Amphiphilic Copolymer for Preparation of Block Copolymer Micelles Stabilized by π-π Stacking Interactions.

In this study, an amphiphilic copolymer that includes a core-forming block with phenyl groups was synthesized by living anionic polymerization of phenyl glycidyl ether (PheGE) on methoxy-polyethylene glycol (mPEG-b-PPheGE). Characterization of the copolymer revealed a narrow molecular distribution (PDI < 1.03) and confirmed the degree of polymerization of mPEG122-b-(PheGE)15. The critical micelle concentration of the copolymer was evaluated using an established fluorescence method with the aggregation behavior evaluated by dynamic light scattering and transmission electronic microscopy. The potential of the copolymer for use in drug delivery applications was evaluated in a preliminary manner including in vitro biocompatibility, loading and release of the hydrophobic anti-cancer drug doxorubicin (DOX). A stable micelle formulation of DOX was prepared with drug loading levels up to 14% (wt%), drug loading efficiencies > 60% (w/w) and sustained release of drug over 4 days under physiologically relevant conditions (acidic and neutral pH, presence of albumin). The high drug loading level and sustained release is attributed to stabilizing π-π interactions between DOX and the core-forming block of the micelles.

Dielectric Relaxations in Poly(glycidyl phenyl ether): Effects of Microstructure and Cyclic Topology

Cyclic and linear, isoregic and aregic, and isotactic and atactic poly(glycidyl phenyl ether) (PGPE) with molecular weights up to Mw = 5.5 kg/mol are synthesized by ring-opening polymerization of glycidyl phenyl ether. Initiation with tetrabutylammonium fluoride leads to isoregic linear polymers with ∼95% regular linkages, and initiation with B(C6F5)3 and B(C6F5)3/water leads to aregic cyclic and linear polymers, respectively, with ∼50% regular linkages as quantified by 13C NMR. Local, segmental, and chain dynamics in PGPE is investigated by broadband dielectric spectroscopy (10–2–106 Hz). The β-relaxation for linear PGPE is separated into two contributions arising from the motions of side groups and end groups with activation energies of 35.4 and 23.8 kJ/mol, respectively. The β-relaxation process for cyclic PGPE shows the same activation energy as that shown by the side-group contribution in linear PGPE, indicating that topology does not play a key role on the side-group local dynamics. Moreover, cyclic...

Ring-Opening Polymerization of Glycidyl Phenyl Ether Initiated by Tetra n -butylammonium Halides as Metal-Free Initiators and Application of Its Polymer System to Networked Polymers

Ring-Opening Polymerization of Glycidyl Phenyl Ether Initiated by Tetra n -butylammonium Halides as Metal-Free Initiators and Application of Its Polymer System to Networked Polymers

Controlled polymerization of epoxides: Metal‐free ring‐opening polymerization of glycidyl phenyl ether initiated by tetra‐n‐butylammonium fluoride in the presence of protic compounds

AbstractMetal‐free controlled ring‐opening polymerization of glycidyl phenyl ether (GPE) was achieved using tetra‐n‐butylammonium fluoride (Bu4NF) as an initiator in the presence of water and ethanol as chain transfer agents (CTAs). Number‐averaged molecular weight of poly(GPE) increased with an increase of [GPE]0/([Bu4NF]0 + [CTA]0) values, showing relatively narrow molecular weight distributions. NMR spectroscopic analysis exhibited a formation of ethoxy groups as well as FCH2 at the initiating polymer chain‐end when ethanol was used as the CTA in the polymerization. These results indicate that Bu4NF acts as a catalyst as well as the initiator for this polymerization system. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

Metal‐free ring‐opening polymerization of glycidyl phenyl ether initiated by tetra‐n‐butylammonium acetate and its application to the hydroxyl‐terminated telechelic polymer

Metal‐free ring‐opening polymerization of glycidyl phenyl ether initiated by tetra‐<i>n</i>‐butylammonium acetate and its application to the hydroxyl‐terminated telechelic polymer

Thermally induced cationic polymerization of glycidyl phenyl ether using novel xanthenyl phosphonium salts

The present study firstly describes the synthesis of novel, thermo-latent initiators based on xanthenyl phosphonium salts with different counter anions and phosphine moieties and secondly examines their efficiency in the bulk polymerization of glycidyl phenyl ether (GPE). The polymerization was performed with phosphonium salt initiators (I SbF6 ,I PF6 ,I AsF6 andI BF4 ) at ambient temperature to 200 °C for 1 h. The order of initiator activity wasI SbF6 >I PF6 >I AsF6 >I BF4 . To examine the effect of the phosphine moiety on the initiator activity, polymerization was carried out withI SbF6 (Ph3P) andII SbF6 (Bu3P) at ambient temperature to 170 °C for 1 h. The order of reactivity wasI SbF6 >II SbF6 . In general, the conversion percentage increased with increasing polymerization temperature. The thermal stability of these salts was measured by thermo gravimetric analysis (TGA). The solubility of phosphonium salts in various organic solvents and epoxy monomers was also investigated.

Novel dibenzocycloheptenyl phosphonium salts as thermolatent initiator in cationic polymerization

AbstractIn this study, novel thermolatent cationic initiators based on dibenzocycloheptenyl phosphonium salts (1a, 1b, 1c, 1d, 2a, and 3a) were synthesized and their efficiency was examined in bulk polymerization of glycidyl phenyl ether (GPE). The polymerization of GPE was performed with 1 mol % of dibenzocycloheptenyl triphenylphosphonium salts (1a–1d) with different counter anions (SbF6−, PF6−, AsF6−, and BF4−) at 25–200°C for 1 h. The order of initiator activity was found as 1a &gt; 1d &gt; 1b &gt; 1c. To examine the effect of phosphine moiety, the activity of 1a was compared with dibenzocycloheptenyl‐tri‐n‐butylphosphonium hexafluoroantimonate (2a). The order of initiator activity was observed as 1a &gt; 2a. The initiator activity of 1a was compared with that of 10,11‐dihydro‐dibenzocycloheptenyltriphenylphosphonium hexafluoroantimonate (3a) to understand the effect of extended conjugation in dibenzocycloheptenyl ring. In general, with the increase in the polymerization temperature, conversion (%) also increases. The solubility of initiators in various solvents and epoxy monomers was also examined. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Cationic Polymerization of Epoxides using Novel Xanthenyl Phosphonium Salts as Thermo-latent Initiator

The present article describes the effect of steric and electronic factors on the efficiency of initiators based on novel xanthenyl phosphonium salts for cationic polymerization of epoxide monomers. 2-substituted (IH, ICl, IMe, and IOMe) xanthenyl phosphonium hexafluoroantimonate were synthesized and characterized by NMR (1H, 13C and 31P) and IR spectroscopy. The order of initiator activity in polymerization of glycidyl phenyl ether (GPE), was found as IH> ICl>IMe>IOMe. To understand the effect of steric factor, the polymerization of cyclohexene oxide (CHO) was performed and the order of activity was found as ICl>IH>IMe >IOMe. All the initiators were found to be latent at ambient temperature and initiates polymerization on thermal initiation. The order of initiator activity was influenced by electronic and steric factors in the system. The thermal stability of these salts was measured by Thermo gravimetric analysis (TGA). The solubility of the initiators in various organic solvents and epoxy monomers is also discussed.

Metal-Free Ring-Opening Polymerization of Glycidyl Phenyl Ether by Tetrabutylammonium Fluoride

Metal-Free Ring-Opening Polymerization of Glycidyl Phenyl Ether by Tetrabutylammonium Fluoride

Homopolymerization of epoxy monomers initiated by 4-(dimethylamino)pyridine

The anionic epoxy homopolymerization initiated by tertiary amines, imidazoles, and ammonium salts is a complex reaction exhibiting two undesired characteristics for practical applications: (a) slow reaction rates with long induction periods, and (b) short primary chains due to the high rate of chain transfer reactions. Therefore, these systems have not found an important place in commercial applications. In this study, it is shown that using 4-(dimethylamino)pyridine (DMAP) as initiator of the polymerization of phenyl glycidyl ether (PGE) or diglycidyl ether of bisphenol A (DGEBA) enables to obtain high polymerization rates and longer primary chains than those generated using typical initiators. A critical molar ratio DMAP/epoxy groups was necessary to attain complete conversion. Networks resulting from the DMAP-initiated homopolymerization of DGEBA exhibited a high crosslink density and corresponding high values of the glass transition temperature (Tg = 160°C) and of the rubbery elastic modulus (higher than 100 MPa). An intense brown color of reaction products, associated with an absorption band with a maximum at 360 nm, was ascribed to the presence of initiator fragments with conjugated double bonds in chain ends. These results might revalorize the anionic homopolymerization of epoxy monomers for commercial applications. POLYM. ENG. SCI. 46:351–359, 2006. © 2006 Society of Plastics Engineers

Branched Architectures from Anhydride Cured Glycidylethers

Polymerization of phenylglycidylether (PGE) could be initiated by 1‐methylimidazole (1‐MI) and poly(N‐vinylimidazol) (PVI) in the melt to synthesize alternating polyesters composed of PGE and phthalic acid anhydride (PAA) as components. Linear chains, cross‐linked clusters, and networks were prepared with MI and comb molecules with PVI. The samples were characterized by common static and dynamic light scattering and combined SEC/LALLS/VISC analysis. The clusters from the pregel and postgel states were found to develop different internal structures with increasing network formation. The critical sol‐gel transition was studied and found to agree with percolation theory. The polymerization to comb molecules was accompanied by a partial depolymerization of PVI. The monomer VI synthesized linear polyesters, the substituents of PVI comb molecules. Both components appeared well separated in the chromatograms. The contraction of the comb dimensions is well described by star‐branch behavior with a weak tendency to ellipsoidal shapes that could be made visible by environmental scanning electron microcopy (ESEM) from films on mica. Dedicated to Professor John L. Stanford on the occasion of his 60th birthday.

Electron-beam curing of epoxy resins: Effect of alcohols on cationic polymerization

Electron-beam (e-beam) induced polymerization of epoxy resins proceeds via cationic mechanism in presence of suitable photoinitiator. Despite good thermal properties and significant processing advantages, epoxy-based composites manufactured using e-beam curing suffer from low compressive strength, poor interlaminar shear strength, and low fracture toughness. A detailed understanding of the reaction mechanism involving e-beam induced polymerization is required to properly address the shortcomings associated with e-beam curable resin systems. This work investigated the effect of hydroxyl containing materials on the reaction mechanism of e-beam induced cationic polymerization of phenyl glycidyl ether (PGE). The alcohols were found to play important roles in polymerization. Compared to hydroxyl group of aliphatic alcohol, phenolic hydroxyl group is significantly less reactive with the oxonium active centre, generated during e-beam induced polymerization of epoxy resin system.

Hydrazinium salts as thermally latent initiators in the polymerization of glycidyl phenyl ether

AbstractNovel hydrazinium salts, N,N‐dimethyl N‐benzyl N′‐benzyl N′‐benzoyl hydrazinium hexafluoroantimonate (2) and N,N‐dimethyl N‐benzyl N′‐(2‐propyl) N′‐benzoyl hydrazinium hexafluoroantimonate (3) were synthesized from hydrazinium salt (1) with the corresponding alcohol. Their initiator activities were examined in the polymerization of glycidyl phenyl ether (GPE). The polymerization of GPE did not proceed with 2 and 3 below 60 and 100°C but proceeded rapidly above those temperatures, respectively. It was found that 1–3 served as thermally latent initiators in the polymerization of GPE. The initiating species and terminating species were identified as the proton or alkyl cation and aminimide, respectively. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1439–1442, 2005

Novel anionic thermally latent initiating systems: Anionic polymerization of glycidyl phenyl ether with potassium tert‐butoxide/active methylene compounds

Novel thermally latent initiators were prepared in situ by the treatment of potassium tert-butoxide (tBuOK) with several active methylene compounds: diethyl malonate (1a), acetylacetone (1b), ethyl acetoacetate (1c), and ethyl phenylacetate (1d). Their activities for a thermally latent initiating system were examined in the polymerization of glycidyl phenyl ether (2 or GPE), and these tBuOK/1a–1d systems were found to serve as anionic thermally latent initiators. The activity order for the initiator was estimated as follows: tBuOK/1b ≫ tBuOK/1d > tBuOK/1a ≈ tBuOK/1c.

Benzylpyrazinium Salts as Thermally Latent Initiators in the Polymerization of Glycidyl Phenyl Ether: Substituent Effect on the Initiator Activity and Mechanistic Aspects

Benzylpyrazinium Salts as Thermally Latent Initiators in the Polymerization of Glycidyl Phenyl Ether: Substituent Effect on the Initiator Activity and Mechanistic Aspects

Novel Anionic Thermally Latent Initiating Systems: Controlled Anionic Polymerization of Glycidyl Phenyl Ether with Silylated Nucleophiles/Inorganic Fluoride Salts System

ADVERTISEMENT RETURN TO ISSUEPREVCommunication to the...Communication to the EditorNEXTNovel Anionic Thermally Latent Initiating Systems: Controlled Anionic Polymerization of Glycidyl Phenyl Ether with Silylated Nucleophiles/Inorganic Fluoride Salts SystemTetsuo Hino and Takeshi EndoView Author Information Department of Polymer Science and Engineering, Faculty of Engineering, Yamagata University, 4-3-16 Jonan, Yonezawa, Yamagata 992-8510, Japan Cite this: Macromolecules 2003, 36, 13, 4672–4674Publication Date (Web):May 30, 2003Publication History Received24 February 2003Revised15 April 2003Published online30 May 2003Published inissue 1 July 2003https://doi.org/10.1021/ma0301350Copyright © 2003 American Chemical SocietyRIGHTS & PERMISSIONSArticle Views353Altmetric-Citations10LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit Read OnlinePDF (51 KB) Get e-AlertsSUBJECTS:Anionic polymerization,Anions,Central nervous system,Polymerization,Substitution reactions Get e-Alerts

Substituted Cyclopropenium Salts as Photoinitiators for Cationic Polymerization of Glycidyl Phenyl Ether

A new series of triarylcyclopropenium tetrakis(pentafluorophenyl)gallates (I) were synthesized by anion exchange. These salts are photoacid generators from which we have measured the rates of acid release using the indicator Quinaldine Red (QR). Electron-donating substituents on the aromatic ring slow the rate of photoacid release. Cationic photopolymerization of glycidyl phenyl ether (GPE) was also examined. With 1 wt % triphenylcyclopropenium (TPCP) gallate, 90% of conversion of GPE was achieved within 20 min irradiation at 300 nm. The polymerization afforded polyGPE with Mw of 4100−8100. The initiating species was identified as a proton produced from photolysis of the triarylcyclopropenium cation.

Application of novel polymers with S‐alkylsulfonium salt moieties as alkylating agents and thermal latent cationic initiators

AbstractSulfonium‐containing polymers prepared from dibenzothiophene and diphenyl sulfide were applied as both alkylating agents and latent initiators for the cationic polymerization of glycidyl phenyl ether. The alkylation of acetonitrile proceeded smoothly with poly(S‐n‐octyl‐2‐vinyldibenzothiophenium tetrafluoroborate) (4; 64 mol % octyldibenzothiophenium tetrafluoroborate unit) to give N‐(n‐octyl)acetamide in an excellent yield on the basis of the starting octyldibenzothiophenium tetrafluoroborate unit in 4. The cationic polymerization of glycidyl phenyl ether was also carried out in the presence of poly(S‐methyl‐2‐vinyldibenzothiophenium tetrafluoroborate) or poly(S‐n‐octyl‐4‐vinyldiphenylsulfonium tetrafluoroborate) to confirm their moderate thermal latent activity. © 2001 John Wiley &amp; Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3928–3933, 2001

Synthesis of phosphate end‐functional polymers and application to thermally latent polymeric initiators

AbstractNovel phosphates, O‐p‐(hydroxymethyl)benzyl O,O‐diethyl phosphate (1) and O‐(2‐bromoisobutyryloxymethyl)benzyl O,O‐diethyl phosphate (2) were synthesized by the reaction of diethyl phosphorochloridate with 1,4‐benzenedimethanol and the successive reaction with 2‐bromoisobutyryl bromide in the presence of triethylamine and submitted to the polymerization of ϵ‐caprolactone and methyl methacrylate as the initiators. They afforded phosphate end‐functional poly(ϵ‐caprolactone) and poly(methyl methacrylate) with controlled molecular weights and polydispersity ratios by living ring‐opening polymerization and samarium‐induced polymerization. The polymerization of glycidyl phenyl ether (GPE) was carried out with the phosphate end‐functional polymers as the latent polymeric initiators in the presence of ZnCl2. The polymerization of GPE did not proceed below 90 °C, but it rapidly proceeded to afford poly(GPE) above the temperature. © 2001 John Wiley &amp; Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3832–3840, 2001