Preparation of end-?-allylnickel macroinitiator from poly(ethylene glycol) allenyl methyl ether and its application to the living coordination polymerization of isonitriles

Taguchi, Masanori; Tomita, Ikuyoshi; Yoshida, Yasuhiko; Endo, Takeshi

doi:10.1002/1099-0518(20010215)39:4<495::aid-pola1018>3.0.co;2-a

Cited by 14 publications

(11 citation statements)

References 14 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…A block copolymer containing both PEG and poly( 1 ) segments was prepared by the polymerization of 1 from a macroinitiator possessing PEG segment (Scheme 1b). The macroinitiator was obtained by the reaction of a PEG allenyl methyl ether ( M n = 5,000) with an excess amount of [(π‐allyl)NiOCOCF 3 ] 2 /2 PPh 3 , as we described previously for the synthesis of PEG‐ block ‐poly(isocyanide) . The polymerization of 1 proceeded smoothly, resulting in the quantitative conversion and the product thus obtained exhibited a unimodal narrowly dispersed elution peak at the higher molecular weight region in SEC (Figure ).…”

Section: Resultsmentioning

confidence: 99%

“…The macroinitiator was prepared as we described . That is, a toluene solution of Ni(COD) 2 (0.10 M, 0.50 ml, 0.050 mmol), a toluene solution of allyl trifluoroacetate (1.0 M, 0.060 ml, 0.060 mmol), and a toluene solution of PPh 3 (1.0 M, 0.060 ml, 0.060 mmol) were added to a nitrogen‐substituted two‐necked flask and the mixture was kept stirring at ambient temperature for 5 min.…”

Section: Methodsmentioning

confidence: 99%

“…In the laboratory of the coauthors, the allylnickel‐catalyzed living polymerization of allene derivatives has been studied, in which a wide variety of allene monomers including both nonpolar and polar functional groups can be polymerized in a living mechanism in both polar and non‐polar polymerization media . In addition, this living polymerization can be applied to the synthesis of copolymers of plural allenes, and allenes with other monomers such as butadiene and isocyanides . On the basis of the living polymerization of allenes, it would be also possible to produce functional thin films with unique nanostructures, which are suitable for wide applications.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Synthesis of well‐defined block copolymer composed of flexible amphiphilic poly(ethylene glycol) and hydrophobic liquid crystalline segments by living coordination polymerization of allene derivatives and its application to thin film with perpendicularly oriented cylindrical nanostructure

Sakai

Nishiyama

Inagi

et al. 2019

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

Self Cite

View full text Add to dashboard Cite

A block copolymer composed of a flexible polar poly(ethylene glycol) (PEG) and a less polar liquid crystalline poly(allene) segments is prepared by the living coordination polymerization of an allene derivative possessing transazobenzene-containing mesogenic substituent by the use of a π-allylnickel macroinitiator bearing PEG segment. The thin film of the block copolymer is prepared by the spin coating of its solution onto mica or silicon wafer which proves to possess perpendicularly oriented nanocylindrical microphase separated structures as supported by the differential calorimetric, polarized optical microscopic, grazing-incidence small-angle X-ray scattering, transmission electron microscope, and atomic force microscope measurements.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Synthesis of well‐defined block copolymer composed of flexible amphiphilic poly(ethylene glycol) and hydrophobic liquid crystalline segments by living coordination polymerization of allene derivatives and its application to thin film with perpendicularly oriented cylindrical nanostructure

Sakai

Nishiyama

Inagi

et al. 2019

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

Self Cite

View full text Add to dashboard Cite

show abstract

“…With the advent of this living coordination polymerization, some well‐defined polyallene‐based chiral polymers were developed from allene derivatives possessing chiral substituent40 and block copolymers of allene derivatives could be prepared by using two stages of monomer feeding due to the stability of living π‐allylnickel end group 41. Furthermore, polyallene bearing pendent hydroxyls was synthesized via the direct living coordination polymerization of allene derivative containing hydroxyl42 and the copolymers of allene derivatives with butadiene, isocyano monomers or PEG were also reported 43. However, well‐defined polyallene‐based copolymers prepared via vinyl monomers could not be obtained by this kind of Ni‐catalyzed living polymerization due to their different polymerization mechanisms.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of a well‐defined polyallene‐based amphiphilic graft copolymer via sequential living coordination polymerization and SET‐LRP

Dai

et al. 2013

J. Polym. Sci. A Polym. Chem.

View full text Add to dashboard Cite

A well-defined amphiphilic graft copolymer, poly (6-methyl-1,2-heptadien-4-ol)-g-poly(2-(dimethylamino)ethyl methacrylate) (PMHDO-g-PDMAEMA), has been synthesized by the combination of living coordination polymerization, single electron transfer-living radical polymerization (SET-LRP), and the grafting-from strategy. PMHDO backbone containing double bonds and pendant hydroxyls was first prepared by [(g 3 -allyl)-NiOCOCF 3 ] 2 -initiated living coordination polymerization of 6methyl-1,2-heptadien-4-ol (MHDO) followed by treating the pendant hydroxyls with 2-chloropropionyl chloride to give PMHDO-Cl macroinitiator. SET-LRP of 2-(dimethylamino)ethyl methacrylate (DMAEMA) was performed in THF/H 2 O using PMHDO-Cl as macroinitiator and CuCl/Me 6 TREN as catalytic system to afford the well-defined PMHDO-g-PDMAEMA graft copolymer with a narrow molecular weight distribution (M w / M n ¼ 1.28). The grafting density was as high as 92%. The critical micelle concentration (cmc) in water was determined by fluorescence probe technique and the micellar morphology was preliminarily explored by transmission electron microscopy.

show abstract

“…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

Preparation of end-?-allylnickel macroinitiator from poly(ethylene glycol) allenyl methyl ether and its application to the living coordination polymerization of isonitriles

Cited by 14 publications

References 14 publications

Synthesis of well‐defined block copolymer composed of flexible amphiphilic poly(ethylene glycol) and hydrophobic liquid crystalline segments by living coordination polymerization of allene derivatives and its application to thin film with perpendicularly oriented cylindrical nanostructure

Synthesis of well‐defined block copolymer composed of flexible amphiphilic poly(ethylene glycol) and hydrophobic liquid crystalline segments by living coordination polymerization of allene derivatives and its application to thin film with perpendicularly oriented cylindrical nanostructure

Synthesis of a well‐defined polyallene‐based amphiphilic graft copolymer via sequential living coordination polymerization and SET‐LRP

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

Contact Info

Product

Resources

About