Citation: ZHANG Xiaosa, JI Shengxiang. Synthesis and Directed Self-assembly of Cylinder-Forming Poly(styrene-b-lactide) Block Copolymers[J]. Chinese Journal of Applied Chemistry, ;2018, 35(12): 1420-1426. doi: 10.11944/j.issn.1000-0518.2018.12.180075 shu

Synthesis and Directed Self-assembly of Cylinder-Forming Poly(styrene-b-lactide) Block Copolymers

ZHANG Xiaosa ^a,b ,
JI Shengxiang ^a,,

a.
Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
b.
University of Chinese Academy of Sciences, Beijing 100049, China

Corresponding author: JI Shengxiang, sji@ciac.ac.cn
Received Date: 19 March 2018
Revised Date: 19 April 2018
Accepted Date: 6 June 2018

Fund Project: the National Natural Science Foundation of China 51773201the Department of Science and Technology of Jilin Province 20160414032GHSupported by the National Natural Science Foundation of China(No.51773201), the Department of Science and Technology of Jilin Province(No.20160414032GH)

Figures(6)

Two cylinder-forming poly(styrene-b-lactide)s, poly(styrene-b-D, L-lactide)(PS-b-PDLLA) and poly(styrene-b-L-lactide))(PS-b-PLLA), with similar domain sizes(L_O) were synthesized using ring opening polymerization(ROP) of lactide monomers from hydroxy-terminated polystyrene(PS-OH) with zinc octoate(Sn(Oct)₂) as the catalyst and characterized by nuclear magnetic resonance spectroscopy(NMR), gel permeation chromatography(GPC), differential scanning calorimetry(DSC), thermal gravimetric analyzer(TGA) and small-angle X-ray scattering(SAXS). Thin films of PS-b-PDLLA and PS-b-PLLA were directed to assemble on hexagonal arrays of spot chemical patterns with a range of pattern periods(L_S) under thermal annealing. SEM analysis of the two assembled films revealed that long-range ordered perpendicularly-oriented hexagonal-array cylinders were obtained in both films. The range of L_S window for defect-free assembly of perpendicular cylinders was larger in PS-b-PDLLA films than that in PS-b-PLLA films, which is similar to the assembly behavior of lamellar-forming PS-b-PLA on stripe chemical patterns.
- poly (styrene-b-lactide),
- block copolymers,
- directed self-assembly,
- chemical pattern
1. [1]
  Ji S, Wan L, Liu C C. Directed Self-Assembly of Block Copolymers on Chemical Patterns:A Platform for Nanofabrication[J]. Prog Polym Sci, 2016,54/55:76-127. doi: 10.1016/j.progpolymsci.2015.10.006
2. [2]
  Bates F S, Fredrickson G H. Block Copolymer Thermodynamics-Theory and Experiment[J]. Annu Rev Phys Chem, 1990,41(1):525-557. doi: 10.1146/annurev.pc.41.100190.002521
3. [3]
  Park S, Wang J Y, Kim B. Solvent-Induced Transition from Micelles in Solution to Cylindrical Microdomains in Diblock Copolymer Thin Films[J]. Macromolecules, 2007,40(25):9059-9063. doi: 10.1021/ma071321z
4. [4]
  Park S, Kim B, Xu J. Lateral Ordering of Cylindrical Microdomains under Solvent Vapor[J]. Macromolecules, 2009,42(4):1278-1284. doi: 10.1021/ma802480s
5. [5]
  Lee D H, Park S, Gu W Y. Highly Ordered Nanoporous Template from Triblock Copolymer[J]. ACS Nano, 2011,5(2):1207-1214. doi: 10.1021/nn102832c
6. [6]
  Albalak R J, Thomas E L. Microphase Separation of Block Copolymer Solutions in a Flow Field[J]. J Polym Sci, Part B:Polym Phys, 1993,31(1):37-46. doi: 10.1002/polb.1993.090310106
7. [7]
  Koppi K A, Tirrell M, Bates F S. Shear Induced Isotropicto-Lamellar Transition[J]. Phys Rev Lett, 1993,70(10):1449-1452. doi: 10.1103/PhysRevLett.70.1449
8. [8]
  Chen Z R, Kornfield J A, Smith S D. Pathways to Macroscale Order in Nanostructured Block Copolymers[J]. Science, 1997,277(5330):1248-1253.
9. [9]
  Morkved T L, Lu M, Urbas A M. Local Control of Microdomain Orientation in Diblock Copolymer Thin Films with Electric Fields[J]. Science, 1996,273(5277):931-933. doi: 10.1126/science.273.5277.931
10. [10]
  Thurn-Albrecht T, Schotter J, Kästle G A. Ultrahigh-Density Nanowire Arrays Grown in Self-assembled Diblock Copolymer Templates[J]. Science, 2000,290(5499):2126-2129. doi: 10.1126/science.290.5499.2126
11. [11]
  Olszowka V, Hund M, Kuntermann V. Electric Field Alignment of a Block Copolymer Nanopattern:Direct Observation of the Microscopic Mechanism[J]. ACS Nano, 2009,3(5):1091-1096. doi: 10.1021/nn900081u
12. [12]
  Hashimoto T, Bodycomb J, Funaki Y. The Effect of Temperature Gradient on the Microdomain Orientation of Diblock Copolymers Undergoing an Order-Disorder Transition[J]. Macromolecules, 1999,32(3):952-954. doi: 10.1021/ma981249s
13. [13]
  Mita K, Takenaka M, Hasegawa H. Cylindrical Domains of Block Copolymers Developed via Ordering under Moving Temperature Gradient:Real-Space Analysis[J]. Macromolecules, 2008,41(22):8789-8799. doi: 10.1021/ma801750c
14. [14]
  Kim S O, Solak H H, Stoykovich M P. Epitaxial Self-Assembly of Block Copolymers on Lithographically Defined Nanopatterned Substrates[J]. Nature, 2003,424(6947):411-414. doi: 10.1038/nature01775
15. [15]
  Ruiz R, Kang H M, Detcheverry F A. Density Multiplication and Improved Lithography by Directed Block Copolymer Assembly[J]. Science, 2008,321(5891):936-939. doi: 10.1126/science.1157626
16. [16]
  Ji S, Nagpal U, Liu G. Directed Assembly of Non-equilibrium ABA Triblock Copolymer Morphologies on Nanopatterned Substrates[J]. ACS Nano, 2012,6(6):5440-5448. doi: 10.1021/nn301306v
17. [17]
  Cheng J, Mayes A M, Ross C A. Nanostructure Engineering by Templated Self-assembly of Block Copolymers[J]. Nat Mater, 2004,3(11):823-828. doi: 10.1038/nmat1211
18. [18]
  Chai J, Wang D, Fan X N. Assembly of Aligned Linear Metallic Patterns on Silicon[J]. Nat Nanotechnol, 2007,2(8):500-506. doi: 10.1038/nnano.2007.227
19. [19]
  Bita I, Yang J K W, Jung Y S. Graphoepitaxy of Self-assembled Block Copolymers on Two-Dimensional Periodic Patterned Templates[J]. Science, 2008,321(5891):939-943. doi: 10.1126/science.1159352
20. [20]
  Gamys C G, Schumers J, Mugemana C. Pore-Functionalized Nanoporous Materials Derived from Block Copolymers[J]. Macromol Rapid Commun, 2013,34(12):962-982. doi: 10.1002/marc.v34.12
21. [21]
  Zalusky A S, Olayo-Valles R, Wolf J H. Ordered Nanoporous Polymers from Polystyrene-Polylactide Block Copolymers[J]. J Am Chem Soc, 2002,124(43):12761-12773. doi: 10.1021/ja0278584
22. [22]
  Cummins C, Mokarian-Tanari P, Holmes J D. Selective Etching of Polylactic Acid in Poly(styrene)-block-Poly(D, L)Lactide Diblock Copolymer for Nanoscale Patterning[J]. J Appl Polym Sci, 2014,131(18)40798.
23. [23]
  Hou X, Li Q, Cao A. In Situ Aggregates of Enantiomeric Poly(styrene)-block-Poly(lactide) Diblock Copolymers via Stereocomplexation in a Non-selective Solvent[J]. Macromol Chem Phys, 2013,214(14):1569-1579. doi: 10.1002/macp.v214.14
24. [24]
  Hsueh H Y, Yao C T, Ho R M. Well-Ordered Nanohybrids and Nanoporous Materials from Gyroid Block Copolymer Templates[J]. Chem Soc Rev, 2015,44(7):1974-2018. doi: 10.1039/C4CS00424H
25. [25]
  Rzayev J, Hillmyer M A. Nanochannel Array Plastics with Tailored Surface Chemistry[J]. J Am Chem Soc, 2005,127(38):13373-13379. doi: 10.1021/ja053731d
26. [26]
  Wolf F F, Friedemann N, Frey H. Poly(lactide)-block-Poly(HEMA) Block Copolymers:An Orthogonal One-Pot Combination of ROP and ATRP, Using a Bifunctional Initiator[J]. Macromolecules, 2009,42(15):5622-5628. doi: 10.1021/ma900894d
27. [27]
  Mazarro R, Gracia I, Rodr guze J F. Kinetics of the Ring-Opening Polymerization of D, L-Lactide Using Zinc(Ⅱ) Octoate as Catalyst[J]. Polym Int, 2012,61(2):265-273. doi: 10.1002/pi.v61.2
28. [28]
  Ho R M, Chiang Y W, Tsai C C. Three-Dimensionally Packed Nanohelical Phase in Chiral Block Copolymers[J]. J Am Chem Soc, 2004,126(9):2704-2705. doi: 10.1021/ja039627i
29. [29]
  Li X, Liu Y, Wan L. Effect of Stereochemistry on Directed Self-assembly of Poly(styrene-b-lactide) Films on Chemical Patterns[J]. ACS Macro Lett, 2016,5(3):396-401. doi: 10.1021/acsmacrolett.6b00011
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