Syntheses of Poly(ethylene oxide) Macromonomers Carrying Tertiary Amine and Quaternary Ammonium End Groups

Senyo, Takamichi; Atago, Yuji; Liang, Huanan; Shen, Renhua; Ito, Koichi

doi:10.1295/polymj.35.513

Cited by 7 publications

(10 citation statements)

References 16 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[6][7][8][9] Tetramethylene glycol monovinyl ether (TMGV) (VE-C 4 -OH) and di(ethylene glycol) monovinyl ether (DEGV) (VE-(EO) 2 -H) were purified by distillation over CaH 2 under vacuum. Poly(ethylene oxide) (PEO) with a molecular weight of 1000 g Á mol À1 was obtained from Kisida Chem.…”

Section: Methodsmentioning

confidence: 99%

“…[6][7][8][9] Preparation of an a-vinyloxytetramethyleneoxy-o-methacryloyl-PEO macromonomer (VE-C4-PEO-MA) follows as an example. Ampoules containing TMGV (1.7 mL, 13.8 mmol), EO (13 mL, 265 mmol), KC 10 H 8 /THF (4.3 mmol/11 mL), THF (80 mL), and a washing solution (solution of the disodium salt of a-methylstyrene tetramer in THF) were fitted into a flask attached with a breakable seal, the flask was evacuated, baked over an oxygen-free flame, and sealed off from the vacuum line.…”

Section: Preparation Of Peo Macromonomersmentioning

confidence: 99%

“…[5] Based on this work, we very recently reported a simple method to prepare such hetero-functional PEO macromonomers by taking advantage of the living anionic polymerization of EO. [6][7][8][9] Here we start with a functional alcohol, F-OH, and partially alkoxidate with potassium naphthalene, to initiate Summary: a,o-Hybrid (hetero-telechelic) poly(ethylene oxide) (PEO) macromonomers carrying both cationic and radical or anionic polymerizable vinyl end groups were newly synthesized by the living anionic polymerization of ethylene oxide (EO) initiated with partially K-alkoxidated vinylic alcohols such as the monovinyl ether of tetramethylene glycol or di(ethylene glycol) and p-vinylbenzyl alcohol (VBA), followed by reaction with methacryloyl chloride (MAC). They possess a couple of a-and o-end groups that can polymerize concurrently or selectively by radical and/or cationic or anionic mechanism.…”

Section: Introductionmentioning

confidence: 99%

“…In this manner we have prepared a-p-vinylphenylalkyl-o-hydroxy-, [6] a-dimethylamino-omethacryloyl-, [7,10] a-p-vinylbenzyl-o-dimethylaminoethyl-, [8] and a-3-thienylethyl-o-methacryloyl-ended PEO macromonomers. [9] The last one was shown to polymerize selectively by oxidative and radical mechanisms through the thienyl and methacryloyl end groups, respectively.…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Synthesis of Well‐Defined Hybrid Macromonomers of Poly(ethylene oxide) and Their Reactivity in Photoinitiated Polymerization

Murakami

Senyo

et al. 2004

Macro Chemistry & Physics

Self Cite

View full text Add to dashboard Cite

Summary: α,ω‐Hybrid (hetero‐telechelic) poly(ethylene oxide) (PEO) macromonomers carrying both cationic and radical or anionic polymerizable vinyl end groups were newly synthesized by the living anionic polymerization of ethylene oxide (EO) initiated with partially K‐alkoxidated vinylic alcohols such as the monovinyl ether of tetramethylene glycol or di(ethylene glycol) and p‐vinylbenzyl alcohol (VBA), followed by reaction with methacryloyl chloride (MAC). They possess a couple of α‐ and ω‐end groups that can polymerize concurrently or selectively by radical and/or cationic or anionic mechanism. The reactivity of the radical and cationic species formed upon photolysis of benzophenone and triphenylsulfonium tetrafluoroborate towards these end groups were studied by means of 1H NMR analysis following the disappearance of the respective olefinic groups. Studies with macromomonomers and model compounds revealed that photoexcited benzophenone abstracts hydrogen atoms from the PEO backbone to form radicals without added hydrogen donors. In the case of the sulfonium salt, both radical and cationic species are formed, which react with the respective functional groups. It was also shown that vinyl ether moieties react more readily than the methacrylate in both radical and cationic processes.The general synthetic strategy followed for the preparation of the hybrid PEO macromonomers studied here.magnified imageThe general synthetic strategy followed for the preparation of the hybrid PEO macromonomers studied here.

show abstract

Section: Methodsmentioning

confidence: 99%

Section: Preparation Of Peo Macromonomersmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Synthesis of Well‐Defined Hybrid Macromonomers of Poly(ethylene oxide) and Their Reactivity in Photoinitiated Polymerization

Murakami

Senyo

et al. 2004

Macro Chemistry & Physics

Self Cite

View full text Add to dashboard Cite

show abstract

“…18,19 Polymerization of EO and SO Polymerization was conducted under high vacuum with a conventional breakable seal technique. 18,19 First, EO (14 mL, 287 mmol) was polymerized in THF (130 mL in total) with potassium 2-methoxyethoxide (6.9 mmol) at 40 • C. The dispersion of the initiator became transparent in a few hours after heating, indicating the progress of polymerization. After polymerization for 24 h, an aliquot was poured into hexane.…”

Section: Methodsmentioning

confidence: 99%

Syntheses of Poly(ethylene oxide-b-styrene oxide) Macromonomers and Their Application to Emulsion and Dispersion Copolymerizations with Styrene

Imai

Kawaguchi

Ito

2003

Polym J

Self Cite

View full text Add to dashboard Cite

ABSTRACT:Poly(ethylene oxide-b-styrene oxide) macromonomers carrying p-vinylbenzyl ether end group were prepared by sequential anionic polymerization of ethylene oxide and styrene oxide with potassium 2-methoxyethoxide, followed by reaction with p-vinylbenzyl bromide to the end-group functionality up to 85%. The macromonomers have been successfully applied to emulsion and dispersion copolymerizations with styrene to afford monodisperse polymeric microsheres in water and in methanol-water (9/1 v/v) mixture, respectively. Incorporation of the macromonomer into the particle is more effective, so resulting in smaller particle size, in the emulsion than in the dispersion system. The particle size in the latter system decreased with the macromonomer concentration in accord with a previously proposed power-law theory and with the chain length of the styrene oxide block.KEY WORDS Macromonomers / Ethylene Oxide / Styrene Oxide / Block / p-Vinylbenzyl EndGroup / Emulsion / Dispersion / Amphiphilic macromonomers find increasing concern in view of their potential use for preparation of polymeric microspheres of submicron to micron size by emulsion and dispersion copolymerizations with a hydrophobic monomer in water and alcoholic media, respectively, without conventional surfactants ('soapfree'). They are usually composed of hydrophilic polymer chains (tails) and the hydrophobic polymerizable end groups (heads), which copolymerize in situ with a substrate hydrophobic monomer to afford graft copolymers. So they serve as effective stabilizers firmly (covalently) attached on the particle surfaces in such a manner that the hydrophobic heads act as anchors while the hydrophilic tails work as steric stabilizers against flocculation. So far a lot of macromonomers have been reported for design of various kinds of polymer microspheres. [1][2][3][4][5] In design of such macromonomers, considerable attention has been paid for control of hydrophiliclyophilic balance (HLB). To our experience, properly hydrophobically enhanced heads as well as properly long hydrophilic tails appear to be important in fine size control and stability of the microspheres to be obtained. In case of poly(ethylene oxide) (PEO) macromonomers with styryl or methacrylate end groups, introduction of some alkylene spacers 6-9 has been successful in this regard. Also interesting is the amphiphilic macromonomer of block copolymer type, 10-14 in which hydrophilic segments are connected through hydrophobic segments to polymerizable end groups. Examples include block macromonomers from poly(2-oxazoline)s, 10, 11 PEO-b-polystyrene (PSt), 12 PEO-bpoly(butylene oxide), In extension of our PEO macromonomer studies, in this paper we discuss preparation of PEO-bpoly(styrene oxide) (PSO) macromonomers with pvinylbenzyl (VB) end groups for use in emulsion and dispersion copolymerization with styrene. Here we expected that PSO segments with VB would provide good balance with the hydrophilic PEO chains for particle size control. The surface properties of PEO-b-PSO block copolymer...

show abstract

Novel Hydrogel Membrane Based on Copoly(hydroxyethyl methacrylate/p‐vinylbenzyl‐poly(ethylene oxide)) for Biomedical Applications: Properties and Drug Release Characteristics

Bayramoğlu

Arıca

et al. 2005

Macromolecular Bioscience

Self Cite

View full text Add to dashboard Cite

The aim of this study was to synthesize and characterize a novel biocompatible polymeric membrane system and demonstrate its potential use in various biomedical applications. Synthetic hydrogels based on poly(hydroxyethyl methacrylate), poly(HEMA), have been widely studied and used in biomedical fields. A novel copolymer hydrogel was prepared in the membrane form using 2-hydroxyethyl methacrylate monomer (HEMA) and a macromonomer p-vinylbenzyl-poly(ethylene oxide) (V-PEO) via photoinitiated polymerization. A series of poly(HEMA/V-PEO) copolymer membranes with different compositions was prepared. The membranes were characterized using infrared, thermal and SEM analysis. The thermal stabilities of the copolymer membranes were found to be lowered by an increase in the ratio of macromonomer (V-PEO) in the membrane structure. Because of the incorporation of PEO segments, the copolymers exhibited significantly higher hydrophilic surface properties than pure poly(HEMA), as demonstrated by contact angle measurements. Equilibrium swelling studies were conducted to investigate the swelling behavior of the membranes. The equilibrium water uptake was reached in about 4 h. Moreover, the blood protein adsorption and platelet adhesion were significantly reduced on the surface of the PEO containing copolymer membranes compared to control pure poly(HEMA). Drug release experiments were performed in a continuous release system using model drug (vancomycin) loaded copoly(HEMA/V-PEO) membranes. A specific poly(HEMA/V-PEO) membrane formulation possessing the highest PEO content (with a HEMA:V-PEO (mmol:mmol) feed ratio of 112:1 and loaded with 40 mg antibiotic/g polymer) released about 81% of the total loaded drug in 24 h at pH 7.4. This membrane composition provided the best results and can be considered as a potential candidate for a transdermal antibiotic carrier and various biomedical and biotechnological applications.

show abstract

Syntheses of Poly(ethylene oxide) Macromonomers Carrying Tertiary Amine and Quaternary Ammonium End Groups

Cited by 7 publications

References 16 publications

Synthesis of Well‐Defined Hybrid Macromonomers of Poly(ethylene oxide) and Their Reactivity in Photoinitiated Polymerization

Synthesis of Well‐Defined Hybrid Macromonomers of Poly(ethylene oxide) and Their Reactivity in Photoinitiated Polymerization

Syntheses of Poly(ethylene oxide-b-styrene oxide) Macromonomers and Their Application to Emulsion and Dispersion Copolymerizations with Styrene

Novel Hydrogel Membrane Based on Copoly(hydroxyethyl methacrylate/p‐vinylbenzyl‐poly(ethylene oxide)) for Biomedical Applications: Properties and Drug Release Characteristics

Contact Info

Product

Resources

About