Synthesis of Poly(alcohol)s by Hydroboration/Oxidation of Poly(methylallene) Prepared by π-Allylnickel-Catalyzed Living Coordination Polymerization

Kino, Tomohiro; Tomita, Ikuyoshi

doi:10.1007/s00289-005-0435-9

Polym. Bull.

2005

DOI: 10.1007/s00289-005-0435-9

|View full text |Cite

Synthesis of Poly(alcohol)s by Hydroboration/Oxidation of Poly(methylallene) Prepared by π-Allylnickel-Catalyzed Living Coordination Polymerization

Tomohiro Kino

Ikuyoshi Tomita

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...

Citation Types

Supporting

Mentioning

Contrasting

Year Published

2006

2017

Publication Types

Select...

Article6

Relationship

Self Cite1

Independent5

Authors

Journals

Cited by 10 publications

(1 citation statement)

References 21 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In fact, this living polymerization can be applied to monomers bearing diverse functional groups such as alkyl, aryl, alkoxy, carboalkoxy, hydroxy and amide to produce welldefined polymers bearing the corresponding functional groups. [33][34][35][36][37][38][39][40][41][42][43][44][45][46][47] Additionally, this living polymerization can be carried out in protic polar media such as alcohols without any deactivations of the growing species. 47 In this paper, we describe the results of the π-allylnickelcatalyzed living dispersion polymerization of allene derivatives that enables the precision synthesis of well-defined polymer microspheres.…”

mentioning

confidence: 99%

Well-defined polymer microspheres formed by living dispersion polymerization: precisely functionalized crosslinked polymer microspheres from monomers possessing cumulated double bonds

et al. 2016

Self Cite

View full text Add to dashboard Cite

The precise method for synthesizing well-defined polymer microspheres via π-allylnickel-catalyzed living coordination polymerization of allene derivatives under dispersion polymerization conditions is described. The π-allylnickel-catalyzed living coordination polymerization of allene derivatives such as phenoxyallene was carried out in protic solvents such as methanol in the presence of stabilizers such as polyvinylpyrrolidone to produce polymer microspheres with a narrowly dispersed diameter distribution (D w /D n ) at a high yield. For example, polymer microspheres with a number-average diameter (D n ) of 1.10 μm and D w /D n of 1.01 were obtained at a yield of 97%; these microspheres are composed of a polymer with a controlled molecular weight (M n = 11 700) and narrow molecular weight distribution (M w /M n = 1.06). The size of the resulting polymer microspheres proved to be affected by polymerization conditions such as the initial monomer concentrations, monomer structures, polymerization media and stabilizers. Unlike conventional dispersion polymerization systems, the use of a bifunctional monomer, 1,4-diallenoxybenzene, for this living dispersion polymerization successfully produced well-defined crosslinked living polymer microspheres that exhibited high solvent tolerance. The postpolymerization of functional allene monomers in the living dispersion polymerization was also successful, resulting in functionalized polymer microspheres that could be applied in solid-phase organic synthesis and solid-supported transition metal catalysis. NPG Asia Materials (2016) 8, e307; doi:10.1038/am.2016; published online 9 September 2016 INTRODUCTION Polymer microspheres are frequently applied in scientific and industrial fields such as coatings, electronics, biomedical engineering and organic synthesis. [1][2][3][4][5][6] Precision synthesis of polymer microspheres with a regulated size, a narrow size distribution and surface functionality is very important for the further development of polymer microspheres for advanced applications. The crosslinking of polymer microspheres is also likely to be very important for achieving sufficient reagent resistance, thermal stability and good mechanical properties. 7 Among the heterogeneous polymerization techniques, dispersion polymerization is an effective method for obtaining polymer microspheres with narrowly dispersed diameter distributions. 8,9 Dispersion polymerization is defined as a heterogeneous polymerization process that starts from a homogeneous solution of all the starting materials (i.e., the monomer, initiator and stabilizer), whereas the polymer microspheres precipitate out during the progress of the polymerization. 10 Accordingly, the polymerization should be carried out in good solvents for the monomers but poor solvents for the polymers being formed. To establish precision dispersion polymerization, the living anionic polymerization of styrene was studied in hydrocarbon solvents. [11][12][13] Although this technique successfully provides narrowly dispersed polym...

show abstract

mentioning

confidence: 99%

Well-defined polymer microspheres formed by living dispersion polymerization: precisely functionalized crosslinked polymer microspheres from monomers possessing cumulated double bonds

et al. 2016

Self Cite

View full text Add to dashboard Cite

show abstract

Polymerization and copolymerization of functionalized 2‐alkoxy‐1‐methylenecyclopropanes to form new polymers having alkoxy substituents

Takeuchi

Inoue

Ishimaru

et al. 2008

J. Polym. Sci. A Polym. Chem.

View full text Add to dashboard Cite

The polymers with functionalized alkoxy groups and with narrow molecular weight distribution (Mw/Mn < 1.12) are obtained from the living polymerization of 2‐alkoxy‐1‐methylenecyclopropanes using π‐allylpalladium complex, [(PhC3H4)Pd(μ‐Cl)]2, as the initiator. The polymers with oligoethylene glycol groups in the alkoxy substituent are soluble in water, and hydroboration of the CC double bond and ensuing addition of the OH groups to CN bond of alkyl isocyanate produce the polymers with urethane pendant groups. The reaction decreases solubility of the polymer in water significantly. Di‐ and triblock copolymers of the 2‐alkoxy‐1‐methylenecyclopropanes are prepared by consecutive addition of the two or three 2‐alkoxy‐1‐methylenecyclopropane monomers to the Pd initiator. The polymers which contain both hydrophobic butoxy or tert‐butoxy group and hydrophilic oligoethylene glycol group dissolve in water and/or organic solvents, depending on the substituents. The 1H NMR spectrum of poly(1a‐b‐1h) ((CH2C(CH2)CHOBu)n(CH2C(CH2)CH(OCH2CH2)3OMe)m) in D2O solution exhibits peaks because of the butoxy and CH2 hydrogen in decreased intensity, indicating that the polymer forms micelle particles containing the hydrophilic segments in their external parts. Aqueous solution of the polymer with a small amount of DPH (DPH = 1,6‐diphenyl‐1,3,5‐hexatriene) shows the absorbance due to DPH at concentration of the polymer higher than 5.82 × 10−5 g mL−1. Other block copolymers such as poly(1b‐b‐1h) and poly(1a‐b‐1g) also form the micelles that contain DPH in their core. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 959–972, 2009

show abstract

Synthesis of PS-b-PPOA-b-PS triblock copolymer via sequential free radical polymerization and ATRP

Ding

Guo

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

View full text Add to dashboard Cite

A novel ABA triblock copolymer comprising double‐bond‐containing poly(phenoxyallene) (PPOA) and polystyrene (PS) segments was synthesized by sequential conventional free radical polymerization and atom transfer radical polymerization (ATRP) via the site transformation strategy. A new bifunctional initiator containing azo and Br‐containing ATRP initiating groups was prepared using 2‐bromopropionyl chloride, hydroquinone, and 4,4′‐azobis(4‐cyanopentanoic acid) as starting materials. Conventional free radical homopolymerization of phenoxyallene with cumulated double bond was performed in toluene to provide a polyallene‐based macroinitiator bearing ATRP initiating groups at both ends, which is stable under UV irradiation and free radical circumstances. PS‐b‐PPOA‐b‐PS triblock copolymer was then obtained by bulk ATRP of styrene initiated by PPOA‐based macroinitiator. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 1366–1372

show abstract

scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.

Contact Info

hi@scite.ai

10624 S. Eastern Ave., Ste. A-614

Henderson, NV 89052, USA

Blog Terms and Conditions API Terms Privacy Policy Contact Cookie Preferences Do Not Sell or Share My Personal Information

Made with 💙 for researchers

Part of the Research Solutions Family.

Synthesis of Poly(alcohol)s by Hydroboration/Oxidation of Poly(methylallene) Prepared by π-Allylnickel-Catalyzed Living Coordination Polymerization

Cited by 10 publications

References 21 publications

Well-defined polymer microspheres formed by living dispersion polymerization: precisely functionalized crosslinked polymer microspheres from monomers possessing cumulated double bonds

Well-defined polymer microspheres formed by living dispersion polymerization: precisely functionalized crosslinked polymer microspheres from monomers possessing cumulated double bonds

Polymerization and copolymerization of functionalized 2‐alkoxy‐1‐methylenecyclopropanes to form new polymers having alkoxy substituents

Synthesis of PS-b-PPOA-b-PS triblock copolymer via sequential free radical polymerization and ATRP

Contact Info

Product

Resources

About