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Synthesis and thermoresponsive property of end-functionalized poly(N-isopropylacrylamide) with pyrenyl group

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Title: Synthesis and thermoresponsive property of end-functionalized poly(N-isopropylacrylamide) with pyrenyl group
Authors: Duan, Qian Browse this author
Miura, Yutaka Browse this author
Narumi, Atsushi Browse this author
Shen, Xiande Browse this author
Sato, Shin-Ichiro Browse this author →KAKEN DB
Satoh, Toshifumi Browse this author →KAKEN DB
Kakuchi, Toyoji7 Browse this author →KAKEN DB
Authors(alt): 覚知, 豊次7
Keywords: aggregation
atom transfer radical polymerization (ATRP)
inclusion complex
Issue Date: 1-Feb-2006
Publisher: Wiley Periodicals, Inc., A Wiley Company
Journal Title: Journal of Polymer Science Part A: Polymer Chemistry
Volume: 44
Issue: 3
Start Page: 1117
End Page: 1124
Publisher DOI: 10.1002/pola.21208
Abstract: N-Isopropylacrylamide (NIPAM) was polymerized using 1-pyrenyl 2-chloropropionate (PyCP) as the initiator and CuCl/tris[2-(dimethylamino)ethyl]amine (Me6TREN) as the catalyst system. The polymerizations were performed using the feed ratio of [NIPAM]0/[PyCP]0/[CuCl]0/[Me6TREN]0 = 50/1/1/1 in DMF/water of 13/2 at 20 ーC to afford an end-functionalized poly(N-isopropylacrylamide) with the pyrenyl group (Py-PNIPAM). The characterization of the Py-PNIPAM using matrix-assisted laser desorption ionization time-of-flight mass spectrometry provided the number-average molecular weight (Mn,MS). The lower critical solution temperature (LCST) for the liquid-solid phase transition was 21.7, 24.8, 26.5, and 29.3 ーC for the Py-PNIPAMs with the Mn,MS's of 3000, 3400, 4200, and 5000, respectively; hence, the LCST was dramatically lowered with the decreasing Mn,MS. The aqueous Py-PNIPAM solution below the LCST was characterized using a static laser light scattering (SLS) measurement to determine its molar mass, Mw,SLS. The aqueous solutions of the Py-PNIPAMs with the Mn,MS's of 3000, 3400, 4200, and 5000 showed the Mw,SLS of 586,000, 386,000, 223,000, and 170,000, respectively. Thus, lowering the LCST for Py-PNIPAM should be attributable to the formation of the PNIPAM aggregates. The LCST of 21.7 ーC for Py-PNIPAM with the Mn,MS of 3000 was effectively raised by adding β-cyclodextrin (β-CD) and reached the constant value of 26 ーC above the molar ratio of [β-CD]/[Py-PNIPAM] = 2/1, suggesting that β-CD formed an inclusion complex with pyrene in the chain-end to disturb the formation of PNIPAM aggregates, thus raising the LCST.
Rights: Copyright © 2006 John Wiley & Sons, Inc., JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY, vol.44-3, p. 1117-1124
Type: article (author version)
Appears in Collections:工学院・工学研究院 (Graduate School of Engineering / Faculty of Engineering) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)

Submitter: 覺知 豊次

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