Synthesis and Properties of SEPS-<italic style="font-style: italic">g</italic>-PEO Copolymers with Varying Branch Lengths

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

doi:10.1007/s10118-018-2104-0

Your Location：

Home >

Browse articles >

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

ARTICLE | Updated：2021-02-18

- Synthesis and Properties of SEPS-g-PEO Copolymers with Varying Branch Lengths
- Synthesis and Properties of SEPS-g-PEO Copolymers with Varying Branch Lengths
- Chinese Journal of Polymer Science 2018年36卷第8期页码：934-942
- Affiliations：
  
  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
- Author bio：
  
  zfzhao@dlut.edu.cn (Z.F.Z)
  ttang@ciac.jl.cn (T.T.)
- Funds：
  
  This work was financially supported by the National Natural Science Foundation of China (Nos. 51673034 and 51233005) and the Open Research Fund of State Key Laboratory of Polymer Physics and Chemistry (Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, No. 110000R088).
- DOI：10.1007/s10118-018-2104-0
  中图分类号：
Scan for full text
Zhong-Fu Zhao, Pei-Ying Liu, Chun-Qing Zhang, 等. Synthesis and Properties of SEPS-g-PEO Copolymers with Varying Branch Lengths[J]. Chinese Journal of Polymer Science, 2018,36(8):934-942.

Zhong-Fu Zhao, Pei-Ying Liu, Chun-Qing Zhang, et al. Synthesis and Properties of SEPS-g-PEO Copolymers with Varying Branch Lengths[J]. Chinese Journal of Polymer Science, 2018,36(8):934-942.
Zhong-Fu Zhao, Pei-Ying Liu, Chun-Qing Zhang, 等. 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.

Zhong-Fu Zhao, Pei-Ying Liu, Chun-Qing Zhang, et al. 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.

摘要

Abstract

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,1,H-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.

关键词

Keywords

Living anionic polymerizationSEPS-g-PEO copolymers Phase structuresDrug delivery

references

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/C5TA03471Jhttp://doi.org/10.1039/C5TA03471J .

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/ma500420whttp://doi.org/10.1021/ma500420w .

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.6b01107http://doi.org/10.1021/acs.macromol.6b01107 .

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.6b00459http://doi.org/10.1021/acsmacrolett.6b00459 .

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.v25.2http://doi.org/10.1002/adfm.v25.2 .

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/cm503108zhttp://doi.org/10.1021/cm503108z .

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.7b04545http://doi.org/10.1021/jacs.7b04545 .

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/C5PY00765Hhttp://doi.org/10.1039/C5PY00765H .

Bates, F. S.; Hillmyer, M. A.; Lodge, T. P . Multiblock polymers: panacea or dandora's box . Science , 2015 . 336 (6080 ):434 -440. .

Holden, G.; Kricheldorf, H. R.; Quirk, R. in "Handbook of thermoplastic elastomers Vol.1, Chapter 4" Munich: Germany, 2004, p. 36-37.

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/s10118-015-1645-8http://doi.org/10.1007/s10118-015-1645-8 .

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.5b02881http://doi.org/10.1021/jacs.5b02881 .

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/C4SM02463Jhttp://doi.org/10.1039/C4SM02463J .

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/ma501496xhttp://doi.org/10.1021/ma501496x .

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/ma302410qhttp://doi.org/10.1021/ma302410q .

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.2011.03.032http://doi.org/10.1016/j.polymer.2011.03.032 .

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/ma4000144http://doi.org/10.1021/ma4000144 .

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. .

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/ma502234yhttp://doi.org/10.1021/ma502234y .

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/ma3024552http://doi.org/10.1021/ma3024552 .

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. .

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/polym8060227http://doi.org/10.3390/polym8060227 .

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.2010.09.061http://doi.org/10.1016/j.polymer.2010.09.061 .

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/ma202196chttp://doi.org/10.1021/ma202196c .

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. .

Bates, F. S.; Bluemle, M.; Zhang, J. Phase behavior of multblock terpolymers. Aiche Meeting 2010.

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.6b00495http://doi.org/10.1021/acsnano.6b00495 .

Percec, V.; Ungar, G.; Peterca, M . Chemistry. self-assembly in action . Science , 2006 . 313 (5783 ):55 -56 . DOI:10.1126/science.1129512http://doi.org/10.1126/science.1129512 .

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/ma800885shttp://doi.org/10.1021/ma800885s .

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.2016.11.003http://doi.org/10.1016/j.ijadhadh.2016.11.003 .

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/C6TA00200Ehttp://doi.org/10.1039/C6TA00200E .

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/ma9614003http://doi.org/10.1021/ma9614003 .

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. .

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/ma300458yhttp://doi.org/10.1021/ma300458y .

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.6b00879http://doi.org/10.1021/acs.macromol.6b00879 .

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)90209-8http://doi.org/10.1016/0032-3861(75)90209-8 .

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/la401889hhttp://doi.org/10.1021/la401889h .

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.v55.7http://doi.org/10.1002/pola.v55.7 .

浏览量

Downloads

CSCD

文章被引用时，请邮件提醒。

Submit

工具集

关联资源

A Redox-responsive Prodrug Nanogel of TLR7/8 Agonist for Improved Cancer Immunotherapy

Controlling Membrane Phase Separation of Polymersomes for Programmed Drug Release

Characterization of a Multi-responsive Magnetic Graphene Oxide Nanocomposite Hydrogel and Its Application for DOX Delivery

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

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

DOI：10.1007/s10118-018-2104-0

摘要

Abstract

关键词

Keywords

references