Phase Behavior of Aqueous Solution of Poly(ethylene oxide)- Poly(propylene oxide) Alternating Multiblock Copolymer

[1] Kobayashi, J.; Okano, T. Design of Temperature-Responsive Polymer-Grafted Surfaces for Cell

Sheet Preparation and Manipulation. Bull. Chem. Soc. Jpn. 2019, 92, 817–824.

[2] Rikiyama, K.;Sanada, Y.; Watanabe, K.; Aida, M.; Katsumoto, Y. Unimer Structure and

Micellization of Poly(ethylene oxide)-Stereocontrolled Poly(N-isopropylacrylamide) Alternating

Multiblock Copolymers in Aqueous Solution. Macromolecules. 2019, 52, 7188-7196.

[3] Lutz, J. F. A controlled sequence of events. Nat. Chem. 2010, 2, 84–85.

[4] Keerl, M.; Richtering, W. Synergistic depression of volume phase transition temperature in

copolymer microgels. Colloid Polym. Sci. 2007, 285, 471–474.

[5] Maeda, Y.; Yamabe, M. A unique phase behavior of random copolymer of N-isopropylacrylamide

and N,N-diethylacrylamide in water. Polymer (Guildf). 2009, 50, 519–523.

[6] Engelis, N. G.; Anastasaki, A.; Nurumbetov, G.; Truong, N. P.; Nikolaou, V.; Shegiwal, A.;

Whittaker, M. R.; Davis, T. P.; Haddleton, D. M. Sequence-controlled methacrylic multiblock

copolymers via sulfur-free RAFT emulsion polymerization. Nat. Chem. 2017, 9, 171–178.

[7] Gody, G.; Barbey, R.; Danial, M.; Perrier, S. Ultrafast RAFT polymerization: Multiblock

copolymers within minutes. Polym. Chem. 2015, 6, 1502–1511.

[8] Gody, G.; Maschmeyer, T.; Zetterlund, P. B.; Perrier, S. Rapid and quantitative one-pot synthesis

of sequence-controlled polymers by radical polymerization. Nat. Commun. 2013, 4, 1–9.

[9] Simula, A.; Nikolaou, V.; Anastasaki, A.; Alsubaie, F.; Nurumbetov, G.; Wilson, P.; Kempe, K.;

Haddleton, D. M. Synthesis of well-defined α,ω-telechelic multiblock copolymers in aqueous

medium: In situ generation of α,ω-diols. Polym. Chem. 2015, 6, 2226–2233.

[10] Anastasaki, A.; Oschmann, B.; Willenbacher, J.; Melker, A.; Van Son, M. H. C.; Truong, N. P.;

Schulze, M. W.; Discekici, E. H.; McGrath, A. J.; Davis, T. P.; Bates, C. M.; Hawker, C. J. OnePot Synthesis of ABCDE Multiblock Copolymers with Hydrophobic, Hydrophilic, and SemiFluorinated Segments. Angew. Chemie - Int. Ed. 2017, 56, 14483–14487.

[11] Carroll, D. R.; Constantinou, A. P.; Stingelin, N.; Georgiou, T. K. Scalable syntheses of welldefined pentadecablock bipolymer and quintopolymer. Polym. Chem. 2018, 9, 3450–3454.

[12] Zhang, Q.; Anastasaki, A.; Li, G. Z.; Haddleton, A. J.; Wilson, P.; Haddleton, D. M. Sequencecontrolled multi-block glycopolymers to inhibit DC-SIGN-gp120 binding. Angew. Chemie - Int.

Ed. 2013, 52, 4435–4439.

[13] Alsubaie, F.; Anastasaki, A.; Wilson, P.; Haddleton, D. M. Sequence-controlled multi-block

copolymerization of acrylamides via aqueous SET-LRP at 0 °c. Polym. Chem. 2015, 6, 406–417.

[14] Zhang, Q.; Collins, J.; Anastasaki, A.; Wallis, R.; Mitchell, D. A.; Becer, C. R.; Haddleton, D. M.

Multiblock sequence-controlled glycopolymers via Cu(0)-LRP following efficient thiol-halogen,

thiol-epoxy and CuAAC reactions. Polym. Chem. 2014, 5, 3876–3883.

[15] Determan, M. D.; Cox, J. P.; Seifert, S.; Thiyagarajan, P.; Mallapragada, S. K. Synthesis and

42

characterization of temperature and pH-responsive pentablock copolymers. Polymer (Guildf).

2005, 46, 6933–6946.

[16] Determan, M. D.; Guo, L.; Thiyagarajan, P.; Mallapragada, S. K. Supramolecular self-assembly

of multiblock copolymers in aqueous solution. Langmuir 2006, 22, 1469–1473.

[17] Peleshanko, S.; Anderson, K. D.; Goodman, M.; Determan, M. D.; Mallapragada, S. K.; Tsukruk,

V. V. Thermoresponsive reversible behavior of multistimuli pluronic-based pentablock

copolymer at the air-water interface. Langmuir 2007, 23, 25–30.

[18] Lu, Y.; Chen, T.; Mei, A.; Chen, T.; Ding, Y.; Zhang, X.; Xu, J.; Fan, Z.; Du, B. Solution behaviors

and microstructures of PNIPAm-P123-PNIPAm pentablock terpolymers in dilute and

concentrated aqueous solutions. Phys. Chem. Chem. Phys. 2013, 15, 8276–8286.

[19] Zhou, Y.; Jiang, K.; Song, Q.; Liu, S. Thermo-induced formation of unimolecular and

multimolecular micelles from novel double hydrophilic multiblock copolymers of N,Ndimethylacrylamide and N-isopropylacrylamide. Langmuir 2007, 23, 13076–13084.

[20] Rikiyama, K.; Horiuchi, T.; Koga, N.; Sanada, Y.; Watanabe, K.; Aida, M.; Katsumoto, Y.

Micellization of poly(ethylene oxide)-poly(propylene oxide) alternating multiblock copolymers

in water. Polymer (Guildf). 2018, 156, 102–110.

[21] Muraoka, T.; Shima, T.; Hamada, T.; Morita, M.; Takagi, M.; Kinbara, K. Mimicking multipass

transmembrane proteins: Synthesis, assembly and folding of alternating amphiphilic multiblock

molecules in liposomal membranes. Chem. Commun. 2011, 47, 194–196.

[22] Alexandridis, P.; Holzwarth, J. F.; Hatton, T. A. Micellization of Poly(ethylene oxide)Poly(propylene oxide)-Poly(ethylene oxide) Triblock Copolymers in Aqueous Solutions:

Thermodynamics of Copolymer Association. Macromolecules 1994, 27, 2414–2425.

[23] Horiuchi, T.; Sakai, T.; Sanada, Y.; Watanabe, K.; Aida, M.; Katsumoto, Y. Association Behavior

of Poly(ethylene oxide)-Poly(propylene oxide) alternating multiblock copolymers in water

toward thermally induced phase separation. Langmuir 2017, 33, 14649–14656.

[24] Francuskiewicz, F. Polymer Fractionation. Springer, Berlin (1994).

[25] Saeki, S.; Kuwahara, N.; Nakata, M.; Kaneko, M. Upper and lower critical solution temperatures

in poly (ethylene glycol) solutions. Polymer (Guildf). 1976, 17, 685–689.

[26] Alexandridis, P.; Alan Hatton, T. Poly(ethylene oxide)poly(propylene oxide)poly(ethylene oxide)

block copolymer surfactants in aqueous solutions and at interfaces: thermodynamics, structure,

dynamics, and modeling. Colloids Surfaces A Physicochem. Eng. Asp. 1995, 96, 1–46.

[27] Watanabe, R.; Takaseki, K.; Katsumata, M.; Matsushita, D.; Ida, D.; Osa, M. Characterization of

poly(N,N-diethylacrylamide) and cloud points in its aqueous solutions. Polym. J. 2016, 48, 621–

628.

[28] Tong, Z.; Zeng, F.; Zheng, X.; Sato, T. Inverse molecular weight dependence of cloud points for

aqueous poly(N-isopropylacrylamide) solutions. Macromolecules 1999, 32, 4488–4490.

43

[29] Shultz, A. R.; Flory, P. J. Phase Equilibria in Polymer–Solvent Systems. J. Am. Chem. Soc. 1952,

74, 4760–4767.

[30] Hamada, F.; Fujisawa, K.; Nakajima, A. Lower Critical Solution Temperature in Linear

Polyethylene–n-Alkane Systems. Polym. J. 1973, 4, 316–322.

44

CHAPTER 4

General Conclusion

45

We investigated the properties of the aqueous solution of PEO–PPO AMB copolymer with

various molecular weight and different weight fraction of PEO.

The PEO–PPO AMB copolymers having a different weight fraction of PEO were prepared by a

dehydrated condensation reaction between α,ω‐diamino PPO and α,ω‐disuccinimidyl PEO

prepolymers. The copolymers with various molecular weights were obtained by precipitation

fractionation. The aqueous solution of the copolymer underwent a LCST‐type phase separation with

increasing temperature. The Tc of the aqueous solution of the copolymer decreased as the weight

fraction of PPO and the Mn of copolymer increased. These results suggest following:

(1) Tc of the aqueous solution of the PEO–PPO AMB copolymer is lower than that of PEO–PPO–

PEO triblock copolymer having similar PEO weight fraction. The result is caused by the Mw of

the PEO–PPO AMB copolymer which is much larger than that of the triblock copolymer.

(2) The hydrophobicity of the PEO–PPO AMB copolymer is correlated with the weight fraction of

PEO like as that of triblock copolymers.

(3) Shultz–Flory theory, which is proposed for homopolymer systems, is possibly applicable to the

AMB copolymer system.

These finding imply that the block design of the AMB copolymer has a potential to apply for designing

functional materials such as protein mimics.

46

公表論文

(1) Horiuchi, Tasuku; Sakai, Takamasa; Sanada, Yusuke; Watanabe, Keisuke; Aida, Misako;

Katsumoto, Yukiteru

Association Behavior of Poly(ethylene oxide)–Poly(propylene oxide) Alternating Multiblock

Copolymers in Water toward Thermally Induced Phase Separation.

Langmuir 2017, 33, 14649–14656.

(2) Horiuchi, Tasuku; Rikiyama, Kazuaki; Sakanaya, Kenji; Sanada, Yusuke; Watanabe, Keisuke;

Aida, Misako; Katsumoto, Yukiteru

Effect of Molecular Weight on Cloud Point of Aqueous Solution of Poly(ethylene oxide)–

Poly(propylene oxide) Alternating Multiblock Copolymer.

J. Oleo Sci. (in press)

47

参考論文

(1) Rikiyama, Kazuaki; Horiuchi, Tasuku; Koga, Naoyuki; Sanada, Yusuke; Watanabe, Keisuke;

Aida, Misako; Katsumoto, Yukiteru

Micellization of Poly(Ethylene Oxide)–Poly(Propylene Oxide) Alternating Multiblock

Copolymers in Water.

Polymer 2018, 156, 102–110.

48

...