Citation: Lue Xiang, Wen Zhu, Mei-lin Long, Ke Zhang, Yong-ming Chen. Synthesis of Triblock Bottlebrush Copolymer and Its Solution Self-assembly to Form Porous Nanoparticles[J]. Acta Polymerica Sinica, ;2018, 0(7): 917-929. doi: 10.11777/j.issn1000-3304.2018.18043 shu

Synthesis of Triblock Bottlebrush Copolymer and Its Solution Self-assembly to Form Porous Nanoparticles

Lue Xiang ^1,3 ,
Wen Zhu ¹ ,
Mei-lin Long ¹ ,
Ke Zhang ^1,3,, ,
Yong-ming Chen ^2,,

1.
Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190
2.
School of Materials Science and Engineering, Sun Yat-Sen University, Key Laboratory for Polymeric Composite and Functional Materials of Ministry of Education, Guangzhou 510275
3.
School of Chemical Science, University of Chinese Academy of Sciences, Beijing 100049

Corresponding author: Ke Zhang, kzhang@iccas.ac.cn Yong-ming Chen, chenym35@mail.sysu.edu.cn
Received Date: 5 February 2017
Revised Date: 9 March 2017
Available Online: 7 May 2018

A triblock bottlebrush copolymer, poly(N,N-dimethyl acrylamide)-block-(polyacrylate-graft- (polystyrene-alternate-poly(L-lactide)))-block-poly(N,N-dimethyl acrylamide) (PDMA-b-(PA-g-(PS-alt-PLLA))-b-PDMA), was prepared with an amphiphilic coil-rod-coil macromolecular structure based on the combination of reversible addition-fragmentation chain transfer polymerization (RAFT), copper-catalyzed azide-alkyne cycloaddition reaction (CuAAC), and ring-opening polymerization (ROP). For the formation of the triblock bottlebrush copolymer, RAFT was used to prepare the well-defined triblock copolymer main chain of PDMA-b-PA-b-PDMA. CuAAC was then employed to graft the PS side chains onto the reactive PA block to form the triblock bottlebrush copolymer PDMA-b-(PA-g-PS)-b-PDMA with PS side chains. The in situ ROP of L-lactide to graft PLLA from PA block finally produced the triblock bottlebrush copolymer of PDMA-b-(PA-g-(PS-alt-PLLA))-b-PDMA with V-shaped side chains of PS and PLLA. In this macromolecule, PDMA formed the hydrophilic coil blocks while the bottlebrush polymer of PA-g-(PS-alt-PLLA) formed the hydrophobic rod block. Self-assembly of the amphiphilic PDMA-b-(PA-g-(PS-alt-PLLA))-b-PDMA was subsequently investigated in selective solvents. Due to the unique coil-rod-coil molecular structure, this triblock bottlebrush copolymer self-assembled into sheet-like micelles or vesicles in the selective solvents of THF/methanol or THF/ethanol, respectively. In these self-assemblies, the coil hydrophilic PDMA block formed the dispersing shell to keep their dispersion while the rigid hydrophobic bottlebrush block aggregated into the sheet-like cores to maintain stability of the self-assemblies. The PS and PLLA side chains with V-shaped structure along the middle blocks microphase-separated inside the aggregated micellar sheet or vesicle wall, in which the isolated PLLA microdomain was surrounded by the continuous PS microdomain. Furthermore, the selective hydrolysis of PLLA microdomain left the nanopores inside the cores of micelles and vesicles. It has been demonstrated the hydrolysis rate was heavily depended on the morphology of the self-assemblies, where the hydrolysis of PLLA microdomains of sheet-like micelles was much faster than that of the corresponding vesicles.
- Bottlebrush copolymer,
- Block copolymer,
- Microphase separation,
- Porous nanoparticles,
- Solution self-assembly
1. [1]
  Zhang M F, Müller A H E. J Polym Sci, Part A: Polym Chem,2005, 43(16): 3461-3481 doi: 10.1002/(ISSN)1099-0518
2. [2]
  Sheiko S S, Sumerlin B S, Matyjaszewski K. Prog Polym Sci, 2008, 33(7): 759-785 doi: 10.1016/j.progpolymsci.2008.05.001
3. [3]
  Verduzco R, Li X Y, Peseka S L, Steinc G E. Chem Soc Rev, 2015, 44(8): 2405-2420 doi: 10.1039/C4CS00329B
4. [4]
  Müllner M, Müller A H E. Polymer, 2016, 98: 389-401 doi: 10.1016/j.polymer.2016.03.076
5. [5]
  Feng C, Li Y J, Yang D, Hu J H, Zhang X H, Huang X Y. Chem Soc Rev, 2011, 40(3): 1282-1295 doi: 10.1039/B921358A
6. [6]
  Djalali R, Li S Y, Schmidt M. Macromolecules, 2002, 35(11): 4282-4288 doi: 10.1021/ma0113733
7. [7]
  Huang K, Rzayev J. J Am Chem Soc, 2009, 131(19): 6880-6885 doi: 10.1021/ja901936g
8. [8]
  Müllner M. Macromol Chem Phys, 2016, 217(20): 2209-2222 doi: 10.1002/macp.v217.20
9. [9]
  Johnson J A, Lu Y Y, Burts A O, Lim Y H, Finn M G, Koberstein J T, Turro N J, Tirrell D A, Grubbs R H. J Am Chem Soc, 2011, 133(3): 559-566 doi: 10.1021/ja108441d
10. [10]
  Johnson J A, Lu Y Y, Burts A O, Xia Y, Durrell A C, Tirrell D A, Grubbs R H. Macromolecules, 2010, 43(24): 10326-10335 doi: 10.1021/ma1021506
11. [11]
  Yuan J Y, Xu Y Y, Walther A,Bolisetty S, Schumacher M, Schmalz H, Ballauff M, Müller A H E. Nat Mater, 2008, 7(9): 718-722 doi: 10.1038/nmat2232
12. [12]
  Yuan J Y, Xu Y Y, Müller A H E. Chem Soc Rev, 2011, 40(2): 640-655 doi: 10.1039/c0cs00087f
13. [13]
  Daniel W F M, Burdynska J, Vatankhah-Varnoosfaderani M, Matyjaszewski K, Paturej J, Rubinstein M, Dobrynin A V, Sheiko S S. Nat Mater, 2016, 15(2): 183-189 doi: 10.1038/nmat4508
14. [14]
  Miyake G M, Piunova V A,Weitekamp R A, Grubbs R H. Angew Chem Int Ed, 2012, 51(45): 11246-11248 doi: 10.1002/anie.201205743
15. [15]
  Macfarlane R J, Kim B, Lee B, Weitekamp R A, Bates C M, Lee S F, Chang A B, Delaney K T, Fredrickson G H, Atwater H A, Grubbs R H. J Am Chem Soc, 2014, 136(50): 17374-17377 doi: 10.1021/ja5093562
16. [16]
  Bolton J, Bailey T S, Rzayev J. Nano Lett, 2011, 11(3): 998-1001 doi: 10.1021/nl103747m
17. [17]
  Song D P, Shahin S, Xie W T, Mehravar S, Liu X H, Li C, Norwood R A, Lee J H, Watkins J J. Macromolecules, 2016, 49(14): 5068-5075 doi: 10.1021/acs.macromol.6b00926
18. [18]
  Sun G R, Cho S H, Clark C, Verkhoturov S V, Eller M J, Li A, Pavia-Jimenez A, Schweikert E A, Thackeray J W, Trefonas P, Wooley K L. J Am Chem Soc, 2013, 135(11): 4203-4206 doi: 10.1021/ja3126382
19. [19]
  Neiser M W, Muth S, Kolb U, Harris J R, Okuda J, Schmidt M. Angew Chem Int Ed, 2004, 43(24): 3192-3195 doi: 10.1002/(ISSN)1521-3773
20. [20]
  Li Z, Ma J, Cheng C, Zhang K, Wooley K L. Macromolecules,2010, 43(3): 1182-1184 doi: 10.1021/ma902513n
21. [21]
  Li Z, Ma J, Lee N S, Wooley K L. J Am Chem Soc, 2011, 133(5): 1228-1231 doi: 10.1021/ja109191z
22. [22]
  Fenyves R, Schmutz M, Horner I J, Bright F V, Rzayev J. J Am Chem Soc, 2014, 136(21): 7762-7770 doi: 10.1021/ja503283r
23. [23]
  Zehm D, Laschewsky A, Gradzielski M, Prevost S, Liang H, Rabe J P, Schweins R, Gummel J. Langmuir, 2010, 26(5): 3145-3155 doi: 10.1021/la903087p
24. [24]
  Schappacher M, Deffieux A. Science, 2008, 319(5869): 1512-1515 doi: 10.1126/science.1153848
25. [25]
  Luo H Y, Santos J L, Herrera-Alonso M. Chem Commun, 2014, 50(5): 536-538 doi: 10.1039/C3CC46834H
26. [26]
27. [27]
  Gröschel A H, Schacher F H, Schmalz H, Borisov O V, Zhulina E B, Walther A, Müller A H E. Nat Commun, 2012, 3: 710 doi: 10.1038/ncomms1707
28. [28]
  Sun G R, Cui H G, Lin L Y, Lee N S, Yang C, Neumann W L, Freskos J N, Shieh J J, Dorshow R B, Wooley K L. J Am Chem Soc, 2011, 133(22): 8534–8543 doi: 10.1021/ja200182t
29. [29]
  Kubowicz S, Baussard J F, Lutz J F, Thünemann A F, Berlepsch H V, Laschewsky A. Angew Chem Int Ed, 2005, 44 (33): 5262-5265 doi: 10.1002/(ISSN)1521-3773
30. [30]
  Hanisch A, Gröschel A H, Förtsch M, Drechsler M, Jinnai H, Ruhland T M, Schacher F H, Müller A H E. ACS Nano, 2013, 7(5): 4030–4041 doi: 10.1021/nn400031u
31. [31]
  Saito N, Liu C, Lodge T P, Hillmyer M A. ACS Nano, 2010, 4(4): 1907–1912 doi: 10.1021/nn9016873
32. [32]
  Asano I, So S, Lodge T P. J Am Chem Soc, 2016, 138 (14): 4714–4717 doi: 10.1021/jacs.6b01697
33. [33]
  Qiu H B, Hudson Z M, Winnik M A, Manners I. Science, 2015, 347 (6228): 1329−1332 doi: 10.1126/science.1261816
34. [34]
  Chen Y C, Zhang K, Wang X J, Zhang F W, Zhu J H, Mays J W, Wooley K L, Pochan D J. Macromolecules, 2015, 48 (16): 5621–5631 doi: 10.1021/acs.macromol.5b00752
35. [35]
  Gröschel A H, Müller A H E. Nanoscale, 2015, 7(28): 11841-11876 doi: 10.1039/C5NR02448J
36. [36]
  Moughton A O, Hillmyer M A, Lodge T P. Macromolecules, 2012, 45(1): 2-19 doi: 10.1021/ma201865s
37. [37]
  Shi Y, Zhu W, Yao D D, Long M L, Peng B, Zhang K, Chen Y M. ACS Macro Lett, 2014, 3(1): 70-73 doi: 10.1021/mz400619g
38. [38]
  Long M L, Shi Y, Zhang K, Chen Y M. Macromol Rapid Commun, 2016, 37(7): 605-609 doi: 10.1002/marc.v37.7
39. [39]
  Zhu H, Deng G H, Chen Y M. Polymer, 2008, 49(2): 405-411 doi: 10.1016/j.polymer.2007.11.037
40. [40]
  Zhao P, Liu L X, Feng X Q, Wang C, Shuai X T, Chen Y M. Macromol Rapid Commun, 2012, 33(16): 1351-1355 doi: 10.1002/marc.201200172
41. [41]
  Zhao P, Yan Y C, Feng X Q, Liu L X, Wang C, Chen Y M. Polymer, 2012, 53(10): 1992-2000 doi: 10.1016/j.polymer.2012.02.055
42. [42]
  Yan Y C, Shi Y, Zhu W, Chen Y M. Polymer, 2013, 54(21): 5634-5642 doi: 10.1016/j.polymer.2013.08.036
43. [43]
  Shi Y, Wang X F, Graff R W, Phillip W A, Gao H F. J Polym Sci, Part A: Polym Chem, 2015, 53(2): 239-248 doi: 10.1002/pola.27307
44. [44]
  Gao H F, Matyjaszewski K. J Am Chem Soc, 2007, 129(20): 6633-6639 doi: 10.1021/ja0711617
45. [45]
  Golas P L, Matyjaszewski K. Chem Soc Rev, 2010, 39(4): 1338-1354 doi: 10.1039/B901978M
46. [46]
  Farah S, Anderson D G, Langer R. Adv Drug Deliv Rev, 2016, 107:367-392 doi: 10.1016/j.addr.2016.06.012
47. [47]
  Choi P. Macromol Rapid Commun, 2002, 23(8): 484-487 doi: 10.1002/1521-3927(20020501)23:8<484::AID-MARC484>3.0.CO;2-K
48. [48]
49. [49]
  Ruzette A V, Tence-Girault S, Leibler L, Chauvin F, Bertin D, Guerret O, Gerard P. Macromolecules, 2006, 39(17): 5804-5814 doi: 10.1021/ma060541u
50. [50]
  Ozdemir C, Guener A. Eur Polym J, 2007, 43(7): 3068-3093 doi: 10.1016/j.eurpolymj.2007.02.022
51. [51]
  Fathi-Azarbayjani A, Abbasi M, Vaez-Gharamaleki J, Jouyban A. J Mol Liq, 2016, 215: 339-344 doi: 10.1016/j.molliq.2015.12.005
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通讯作者: 陈斌, bchen63@163.com

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沈阳化工大学材料科学与工程学院沈阳 110142

Synthesis of Triblock Bottlebrush Copolymer and Its Solution Self-assembly to Form Porous Nanoparticles

南开大学师唯/华北电力大学（保定）刘景维：二维配位聚合物中有序的亲锂冠醚位点用于无枝晶锂沉积

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通讯作者: 陈斌, bchen63@163.com