Citation: Zhong-Fu Zhao, Pei-Ying Liu, Chun-Qing Zhang, Wei Liu, Yan-Hui Wang, Tao Tang, Yi-Fu Ding, Yan-Dong Zhang, Fan-Zhi Meng. Synthesis and Properties of SEPS-g-PEO Copolymers with Varying Branch Lengths[J]. Chinese Journal of Polymer Science, ;2018, 36(8): 934-942. doi: 10.1007/s10118-018-2104-0 shu

Synthesis and Properties of SEPS-g-PEO Copolymers with Varying Branch Lengths

a.
State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China
b.
State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
c.
Department of Mechanical Engineering, University of Colorado Boulder, Boulder, CO 80309-0427, USA

Corresponding author: Zhong-Fu Zhao, zfzhao@dlut.edu.cn Tao Tang, ttang@ciac.jl.cn
Received Date: 24 October 2017
Accepted Date: 19 December 2017
Available Online: 7 March 2018

Poly(ethylene oxide) (PEO) was controllably grafted from styrene-b-(ethylene-co-propylene)-b-styrene (SEPS) backbones by combining lithiation of styrenic units and living monomer-activated anionic ring-opening polymerization of ethylene oxide (EO) monomers with the aid of co-initiators triisobutyl aluminum. The as-synthesized SEPS-g-PEO copolymers were characterized by SEC, ¹H-NMR, FTIR, SAXS, AFM and DSC. When the branch length is relatively small, increase of PEO fraction leads to the increase of the correlation length between neighboring hard domains, but the degree of correlation reduces. When the branch length is relatively large, the phase-separated structures become random both in terms of size and spatial correlation, and macro-phase separated structures appear. The crystallization behavior of the PEO branches can be effectively inhibited in SEPS-g-PEO, so no significant crystallization takes place until the fraction of PEO branches is 20.1 wt%, which greatly promotes the rapid delivery of hydrophilic drugs in the hot-melting pressure-sensitive adhesives (HMPSAs) based on SEPS-g-PEO. Their cumulative release amount of a model drug could achieve 80%, more than twice the value in the HMPSAs based on linear PEO-containing styrenic block copolymers.
- Living anionic polymerization,
- SEPS-g-PEO copolymers,
- Phase structures,
- Drug delivery
1. [1]
  Xue, Z.; He, D.; Xie, X. Poly(ethylene oxide)-based electrolytes for lithium-ion batteries. J. Mater. Chem. A 2015, 3(38), 19218−19253 doi: 10.1039/C5TA03471J
2. [2]
  Bouchet, R.; Phan, T. N. T.; Beaudoin, E. D. Devaux; Davidson, P.; Bertin, D.; Denoyel, R. Charge transport in nanostructured PS-PEO-PS triblock copolymer electrolytes. Macromolecules 2014, 47(8), 2659−2665 doi: 10.1021/ma500420w
3. [3]
  Pulst, M.; Samiullah, M. H.; Baumeister, U.; Marko, P.; Jens, B.; Thomas, T.; Karsten, B.; Yury, G.; Detlef, R.; Jörg, K. Crystallization of poly(ethylene oxide) with a well-defined point defect in the middle of the polymer chain. Macromolecules 2016, 49(17), 6609−6620 doi: 10.1021/acs.macromol.6b01107
4. [4]
  Chen, X. C.; Oh, H. J.; Yu, J. F.; Jeffrey, K. Y.; Nikos, P.; Anand, S. P.; Steven, W. H.; Nitash, P. B. Block copolymer membranes for efficient capture of a chemotherapy drug. ACS Macro Lett. 2016, 5(8), 936−941 doi: 10.1021/acsmacrolett.6b00459
5. [5]
  Kim, J. M.; Kim, Y. J.; Park, W. I. Eliminating the trade-off between the throughput and pattern quality of sub nm directed selfassembly via warm solvent annealing. Adv. Funct. Mater. 2015, 25(2), 306−315 doi: 10.1002/adfm.v25.2
6. [6]
  Feng, C.; Pang, X.; He, Y.; Li, B.; Lin, Z. Robust route to unimolecular core-shell and hollow polymer nanoparticles. Chem. Mater. 2014, 26(20), 6058−6067 doi: 10.1021/cm503108z
7. [7]
  Chen, Y.; Yang, D.; Yoon, Y. J.; Pang, X.; Wang, Z.; Jung, J.; He, Y.; Harn, Y. W.; He, M.; Zhang, S.; Zhang, G.; Lin, Z. Hairy uniform permanently ligated hollow nanoparticles with precise dimension control and tunable optical properties. J. Am. Chem. Soc. 2017, 139, 12956−12967 doi: 10.1021/jacs.7b04545
8. [8]
  Feng, C.; Pang, X.; He, Y.; Chen, Y.; Zhang, G.; Lin, Z. A versatile strategy for uniform hybrid nanoparticles and nanocapsules. Polym. Chem. 2015, 6(29), 5190−5197 doi: 10.1039/C5PY00765H
9. [9]
  Bates, F. S.; Hillmyer, M. A.; Lodge, T. P. Multiblock polymers: panacea or dandora's box. Science 2015, 336(6080), 434−440
10. [10]
  Holden, G.; Kricheldorf, H. R.; Quirk, R. in "Handbook of thermoplastic elastomers Vol.1, Chapter 4" Munich: Germany, 2004, p. 36-37.
11. [11]
  Zhang, X, L.; Wu, H.; Guo, S. Y. The molecular structure of SEBS grafted with maleic anhydride through ultrasound initiation. Chinese J. Polym. Sci. 2015, 33(7), 988−999 doi: 10.1007/s10118-015-1645-8
12. [12]
  Shi, W.; Hamilton, A. L.; Delaney, K. T.; Fredrickson, G.H.; Kramer, E. J.; Ntaras, C.; Avgeropoulos, A.; Lynd, N. A. Creating extremely asymmetric lamellar structures via fluctuation-assisted unbinding of miktoarm star block copolymer alloys. J. Am. Chem. Soc. 2015, 137(19), 6160−6163 doi: 10.1021/jacs.5b02881
13. [13]
  Zhao, Y.; Su, B.; Chen, F. Evolution of unique nano-cylindrical structure in poly(styrene-b-isoprene-b-styrene) prepared under "dynamic packing injection moulding. Soft Matter 2015, 11(11), 2300−2307 doi: 10.1039/C4SM02463J
14. [14]
  Garate, H.; Goyanes, S.; D'Accorso, N. B. Controlling nanodomain morphology of epoxy thermosets modified with reactive amine-containing epoxidized poly(styrene-b-isoprene-b-styrene) block copolymer. Macromolecules 2014, 47(21), 7416−7423 doi: 10.1021/ma501496x
15. [15]
  Luo, M.; Seppala, J. E.; Albert, J. N. L. Manipulating nanoscale morphologies in cylinder-forming poly (styrene-b-isoprene-b-styrene) thin films using film thickness and substrate surface chemistry gradients. Macromolecules 2013, 46(5), 1803−1811 doi: 10.1021/ma302410q
16. [16]
  Garate, H.; Fascio, M. L.; Mondragon, I. Surfactant-aided dispersion of polystyrene-functionalized carbon nanotubes in a nanostructured poly(styrene-b-isoprene-b-styrene) block copolymer. Polymer 2011, 52(10), 2214−2220 doi: 10.1016/j.polymer.2011.03.032
17. [17]
  Garate, H.; Mondragon, I.; D'Accorso, N. B. Exploring microphase separation behavior of epoxidized poly(styrene-b-isoprene-b-styrene) block copolymer inside thin epoxy coatings. Macromolecules 2013, 46(6), 2182−2187 doi: 10.1021/ma4000144
18. [18]
  Song, J.; Remmers, S. J.; Shao, J.; Kolwijck, E.; Walboomers, X. F.; Jansen, J. A.; Leeuwenburgh, S. C.; Yang, F. Antibacterial effects of electrospun chitosan/poly(ethylene oxide) nanofibrous membranes loaded with chlorhexidine and silver. Nanomedicine: NBM 2016, 12(5), 1357−1364
19. [19]
  Villaluenga, I.; Xi, C. C.; Devaux, D. Nanoparticle-driven assembly of highly conducting hybrid block ccopolymer electrolytes. Macromolecules 2015, 48(2), 358−364 doi: 10.1021/ma502234y
20. [20]
  Yuan, R.; Teran, A. A.; Gurevitch, I. Ionic conductivity of low molecular weight block copolymer electrolytes. Macromolecules 2013, 46(3), 914−921 doi: 10.1021/ma3024552
21. [21]
  Chintapalli, M.; Le, T. N. P.; Venkatesan, N. R. Structure and ionic conductivity of polystyrene-block-poly(ethylene oxide) electrolytes in the high salt concentration limit. J. Mater. Sci. 1997, 43(5), 1734−1739
22. [22]
  Gosecki, M.; Gadzinowski, M.; Gosecka, M. Polyglycidol, its derivatives, and polyglycidol-containing copolymers—synthesis and medical applications. Polymers 2016, 8(6), 227 doi: 10.3390/polym8060227
23. [23]
  Rejsek, V.; Desbois, P.; Deffieux, A. Polymerization of ethylene oxide initiated by lithium derivatives via the monomer-activated approach: application to the direct synthesis of PS-b-PEO and PI-b-PEO diblock copolymers. Polymer 2010, 51(24), 5674−5679 doi: 10.1016/j.polymer.2010.09.061
24. [24]
  Zhang, J.; Sides, S.; Bates, F. S. Ordering of sphere forming SISO tetrablock terpolymers on a simple hexagonal lattice. Macromolecules 2012, 45(1), 256−265 doi: 10.1021/ma202196c
25. [25]
  Zhang, J.; Bates, F. S. Dodecagonal quasicrystalline morphology in a poly(styrene-b-isoprene-b-styrene-b-ethylene oxide) tetrablock terpolymer. J. Am. Chem. Soc. 2015, 134(18), 7636−7639
26. [26]
  Bates, F. S.; Bluemle, M.; Zhang, J. Phase behavior of multblock terpolymers. Aiche Meeting 2010.
27. [27]
  Chanpuriya, S.; Kim, K.; Zhang, J. A cornucopia of nanoscale ordered phases in sphere forming tetrablock terpolymers. ACS Nano 2016, 10(5), 4961−4972 doi: 10.1021/acsnano.6b00495
28. [28]
  Percec, V.; Ungar, G.; Peterca, M. Chemistry. self-assembly in action. Science 2006, 313(5783), 55−56 doi: 10.1126/science.1129512
29. [29]
  Meuler, A. J.; Fleury, G.; Hillmyer, M. A. Structure and mechanical properties of an O70 (Fddd) network-forming pentablock terpolymer. Macromolecules 2008, 41(15), 5809−5817 doi: 10.1021/ma800885s
30. [30]
  Zhao, Z.; Zhang, R.; Zhang, C. SISO-based hot-melt pressure-sensitive adhesives for transdermal delivery of hydrophilic drugs. Int. J. Adhes. Adhes. 2017, 74, 86−91 doi: 10.1016/j.ijadhadh.2016.11.003
31. [31]
  Yang, C.; Wang, S.; Ma, W. Highly stable poly(ethylene glycol)-grafting alkaline anion exchange membranes. J. Mater. Chem. A 2016, 4(10), 3886−3892 doi: 10.1039/C6TA00200E
32. [32]
  Chung, T. C.; Lu, H. L.; Ding, R. D. Synthesis of polyethylene-g-polystyrene and polyethylene-g-poly(p-methylstyrene) graft copolymers. Macromolecules 1997, 30(5), 1272−1278 doi: 10.1021/ma9614003
33. [33]
  Farrall M. J.; Frechet J. M. J. Bromination and lithiation: two important steps in the functionalization of polystyrene resins. J. Appl. Polym. Sci. 1990, 40(9-10), 1575−1582
34. [34]
  Wu, S.; Guo, Q.; Peng, S. Toughening epoxy thermosets with block ionomer complexes: A nanostructure- mechanical property correlation. Macromolecules 2012, 45(9), 3829−3840 doi: 10.1021/ma300458y
35. [35]
  Kripotou, S.; Psylla, C.; Kyriakos, K. Structure and crystallization behavior of poly(ethylene oxide) (PEO) chains in core-shell brush copolymers with poly(propylene oxide)-block-poly(ethylene oxide) side chains. Macromolecules 2016, 49(16), 5963−5977 doi: 10.1021/acs.macromol.6b00879
36. [36]
  Ashman, P. C.; Booth, C. Crystallinity and fusion of ethylene oxide/propylene oxide block copolymers: 1. type PE copolymers. Polymer 1975, 16(12), 889−896 doi: 10.1016/0032-3861(75)90209-8
37. [37]
  Beaudoin, E.; Phan, T. N.; Robinet, M. Effect of interfaces on the melting of PEO confined in triblock PS-b-PEO-b-PS copolymers. Langmuir 2013, 29(34), 10874−10880 doi: 10.1021/la401889h
38. [38]
  Lin, F.; Wu, C.; Cui, D. Synthesis and characterization of crystalline styrene-b-(ethylene-co-butylene)‐b‐styrene triblock copolymers. J. Polym. Sci., Part A: Polym. Chem. 2017, 55(7), 1243−1249 doi: 10.1002/pola.v55.7
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