注册 English

官能化聚四氢呋喃-b-聚异丁烯-b-聚四氢呋喃三嵌段共聚物的合成与性能

张方 ,  张航天 ,  杨甜 ,  孔波 ,  郭安儒 ,  章琦 ,  吴一弦

downloadPDF
引用本文: 张方, 张航天, 杨甜, 孔波, 郭安儒, 章琦, 吴一弦. 官能化聚四氢呋喃-b-聚异丁烯-b-聚四氢呋喃三嵌段共聚物的合成与性能[J]. 高分子学报, 2020, 51(1): 98-116. doi: 10.11777/j.issn1000-3304.2020.19151 shu
Citation:  Fang Zhang, Hang-tian Zhang, Tian Yang, Bo Kong, An-ru Guo, Qi Zhang, Yi-xian Wu. Synthesis and Property of Novel Functionalized Polytetrahydrofuran-b-polyisobutylene-b-polytetrahydrofuran Triblock Copolymers[J]. Acta Polymerica Sinica, 2020, 51(1): 98-116. doi: 10.11777/j.issn1000-3304.2020.19151 shu

官能化聚四氢呋喃-b-聚异丁烯-b-聚四氢呋喃三嵌段共聚物的合成与性能

  • 北京化工大学 化工资源有效利用国家重点实验室 生物医用材料北京实验室　北京 100029

    • 通讯作者: E-mail: wuyx@mail.buct.edu.cn
摘要: 采用2-氯-2,4,4-三甲基戊烷或对二枯基氯为引发剂和TiCl4或FeCl3为共引发剂，引发异丁烯(IB)可控/活性正离子聚合与官能端基转化，设计合成不同分子量及窄分子量分布的端基官能化聚异丁烯，如双端烯丙基溴官能化聚异丁烯(Br-PIB-Br)或双端烯丙基胺官能化聚异丁烯(H2N-PIB-NH2). 采用烯丙基溴/高氯酸银体系引发四氢呋喃(THF)开环聚合，合成聚四氢呋喃活性链(PTHF+). 进一步通过将IB可控/活性正离子聚合与THF可控/活性正离子开环聚合2种方法相结合，设计合成2种新型官能化聚四氢呋喃-b-聚异丁烯-b-聚四氢呋喃(PTHF-b-PIB-b-PTHF)三嵌段共聚物：(1)以上述Br-PIB-Br为大分子引发剂，在AgClO4作用下引发THF活性正离子开环聚合，采用水终止活性链端，设计合成双端为羟基的HO-PTHF-b-PIB-b-PTHF-OH三嵌段共聚物(简称：FIBF-OH)；(2)以上述合成的PTHF+活性链与H2N-PIB-NH2链端胺基发生高效亲核取代反应，设计合成中间链段连接点含―NH―官能基团的PTHF-b-HN-PIB-NH-b-PTHF三嵌段共聚物(简称：FIBF-NH). 在上述三嵌段共聚物中，极性PTHF链段与非极性PIB链段的热力学不相容，导致其呈现明显的微相分离，且微观形态与共聚组成相关. PTHF均聚物易结晶，在上述共聚物中由于PTHF链段单端受限致其结晶性减弱. 三嵌段共聚物分子链的中间连接点含―NH―官能基团，具有更强的氢键作用，促进PTHF链段重排并结晶，易形成更紧密的超分子网络结构，导致即使在PTHF链段相对分子量为0.7 kg·mol−1时仍具有较强的结晶性，且结晶熔融温度明显提高. 此外，由于FIBF-NH中形成超分子网络结构，使材料具有优异的自修复性能，材料表面的切痕在常温下10 min 后可以完全自愈合. 本文设计合成的新型官能化PTHF-b-PIB-b-PTHF三嵌段共聚物兼具有PTHF与PIB的优良性能，在生物医用、智能修复等功能材料领域具有潜在的应用前景.

English


    1. [1]

      Campbell C G, Ummadisetty S, Storey R F. Macromolecules, 2016, 49: 7642 − 7652 doi: 10.1021/acs.macromol.6b01754

    2. [2]

      Wu Guanying(武冠英), Wu Yixian(吴一弦). Controlled Cationic Polymerization and its Application(控制阳离子聚合及其应用). Beijing(北京): Chemical Industry Press(化学工业出版社), 2005. 436

    3. [3]

      Kennedy J P, Macrechal E. Carbocationic polymerization. New York: John Wiley & Sons, 1982. 59

    4. [4]

      Faust R, Kennedy J P. Polym Bull, 1986, 15(4): 317 − 323

    5. [5]

      Bahadur M, Shaffer T D, Ashbaugh J R. Macromolecules, 2000, 33(26): 9548 − 9552 doi: 10.1021/ma000064u

    6. [6]

      Hadjikyriacou S, Acar M, Faust R. Macromolecules, 2004, 37(20): 7543 − 7547 doi: 10.1021/ma049082s

    7. [7]

      Qiu Y X, Wu Y X, Gu X L, Xu X, Wu G Y. Eur Polym J, 2005, 41: 349 − 358 doi: 10.1016/j.eurpolymj.2004.10.003

    8. [8]

      Xu X, Wu Y X, Qiu Y X, Dong C L, Wu G Y, Wang H. Eur Polym J, 2006, 42: 2791 − 2800 doi: 10.1016/j.eurpolymj.2006.06.028

    9. [9]

      Liu Xun(刘迅), Wu Yixian(吴一弦), Zhang Chenglong(张成龙), Zhang Bei(张蓓), Li Yan(李艳), Xu Xu(徐旭), Wu Guanying(武冠英). Acta Polymerica Sinica(高分子学报), 2007, (3): 255 − 261 doi: 10.3321/j.issn:1000-3304.2007.03.009

    10. [10]

      Li Y, Wu Y X, Xu X, Liang L H, Wu G Y. J Polym Sci, Part A: Polym Chem, 2007, 45(14): 3053 − 3061 doi: 10.1002/pola.22061

    11. [11]

      Qiu Yingxin(邱迎昕), Wu Yixian(吴一弦), Cui Yu(崔宇), Ye Xiaolin(叶晓林), Wu Guanying(武冠英). Acta Polymerica Sinica(高分子学报), 2007, (2): 190 − 197 doi: 10.3321/j.issn:1000-3304.2007.02.017

    12. [12]

      Zhang C L, Wu Y X, Xu X, Li Y, Feng L, Wu G Y. J Polym Sci, Part A: Polym Chem, 2008, 46: 936 − 946 doi: 10.1002/pola.22437

    13. [13]

      Lin Tao(林涛), Wu Yixian(吴一弦), Ye Xiaolin(叶晓林), Zhang Laibao(张来宝), Huang Qigu(黄启谷), Wu Guanying(武冠英). Acta Polymerica Sinica(高分子学报), 2008, (2): 129 − 135 doi: 10.3321/j.issn:1000-3304.2008.02.006

    14. [14]

      Liang Lihu(梁立虎), Wu Yixian(吴一弦), Li Yan(李艳), Xu Riwei(徐日炜), Yang Waitai(杨万泰), Wu Guanying (武冠英). Acta Polymerica Sinica(高分子学报), 2008, (12): 1166 − 1174 doi: 10.3321/j.issn:1000-3304.2008.12.008

    15. [15]

      Zhang C L, Wu Y X, Meng X Y, Huang Q, Wu G Y, Xu R W. Chinese J Polym Sci, 2009, 27(4): 551 − 559 doi: 10.1142/S0256767909004230

    16. [16]

      Zhang Bei(张蓓), Wu Yixian(吴一弦), Li Yan(李艳), Liu Xun(刘迅), Xu Xu(徐旭), Wu Guanying(武冠英). Acta Polymerica Sinica(高分子学报), 2009, (11): 1040 − 1046

    17. [17]

      Li Y, Wu Y X, Liang L H, Li Y, Wu G Y. Chinese J Polym Sci, 2010, 28(1): 55 − 62 doi: 10.1007/s10118-010-8216-9

    18. [18]

      Liu Q, Wu Y X, Zhang Y, Yan P F, Xu R W. Polymer, 2010, 51(25): 5960 − 5969 doi: 10.1016/j.polymer.2010.10.012

    19. [19]

      Vasilenko I V, Frolov A N, Kostjuk S V. Macromolecules, 2010, 43(13): 5503 − 5507 doi: 10.1021/ma1009275

    20. [20]

      Zhang L B, Wu Y X, Zhou P, Wu G Y, Yang W T, Yu D S. Chinese J Polym Sci, 2011, 29(3): 360 − 367 doi: 10.1007/s10118-011-1042-x

    21. [21]

      Liu Q, Wu Y X, Yan P F, Zhang Y, Xu R W. Macromolecules, 2011, 44: 1866 − 1875 doi: 10.1021/ma1027017

    22. [22]

      Yan P F, Guo A R, Liu Q, Wu Y X. J Polym Sci, Part A: Polym Chem, 2012, 50: 3383 − 3392 doi: 10.1002/pola.26126

    23. [23]

      Zhang L B, Wu Y X, Zhou P, Xu R W. Polym Adv Technol, 2012, 23: 522 − 528 doi: 10.1002/pat.1908

    24. [24]

      Kumar R, Dimitrov P, Bartelson K J, Emert J, Faust R. Macromolecules, 2012, 45(21): 8598 − 8603 doi: 10.1021/ma3017585

    25. [25]

      Bartelson K J, De P, Kumar R, Emert J, Faust R. Polymer, 2013, 54(18): 4858 − 4863 doi: 10.1016/j.polymer.2013.07.024

    26. [26]

      Guo A R, Yang X J, Yan P F, Wu Y X. J Polym Sci, Part A: Polym. Chem, 2013, 51: 4200 − 4212 doi: 10.1002/pola.26834

    27. [27]

      Kumar R, Zheng B, Huang, K W, Emert J, Faust R. Macromolecules, 2014, 47(6): 1959 − 1965 doi: 10.1021/ma500042f

    28. [28]

      Yang X J, Guo A R, Xu H C, Wu Y X. J Appl Polym Sci, 2015, 132: 42232 − 42244

    29. [29]

      Kostjuk S V, Vasilenko I V, Shiman D I, Frolov A N, Gaponik L V. Macromol Symp, 2015, 349(1): 94 − 103 doi: 10.1002/masy.201400016

    30. [30]

      Vasilenko I V, Berezianko I A, Shiman D I, Shiman D I, Kostjuk S V. Polym Chem, 2016, 7(36): 5615 − 5619 doi: 10.1039/C6PY01325B

    31. [31]

      Wu Yixian(吴一弦), Zhou Qi(周琦), Du Jie(杜杰), Wang Nan(王楠). Acta Polymerica Sinica(高分子学报), 2017, (7): 1047 − 1057 doi: 10.11777/j.issn1000-3304.2017.17045

    32. [32]

      Yang S X, Fan Z Y, Zhang F Y, Li S H, Wu Y X. Chinese J Polym Sci, 2019, 37: 919 − 929 doi: 10.1007/s10118-019-2329-6

    33. [33]

      De P, Faust R. Macromolecules, 2006, 39(22): 7527 − 7533 doi: 10.1021/ma061463d

    34. [34]

      Ojha U, Rajkhowa R, Agnihotra S R, Faust R. Macromolecules, 2008, 41(11): 3832 − 3841 doi: 10.1021/ma7027209

    35. [35]

      Deodhar T J, Keszler B L, Kennedy J P. J Polym Sci, Part A: Polym Chem, 2017, 55(10): 1784 − 1789 doi: 10.1002/pola.28529

    36. [36]

      Nugay T, Deodhar T, Nugay N, Kennedy J P. J Polym Sci, Part A: Polym Chem, 2018, 56(11): 1140 − 1145 doi: 10.1002/pola.28993

    37. [37]

      Sipos L, Som A, Rudolf Faust R. Biomacromolecules, 2005, 6: 2570 − 2582 doi: 10.1021/bm050299j

    38. [38]

      Bouchekif H, Som A, Sipos L, Faust R. J Macromol Sci, Part A: Pure Appl Chem, 2007, 44: 359 − 366 doi: 10.1080/10601320601187986

    39. [39]

      Kleinedler J J, Foley J D, Alexander J S, Roerig S C, Hebert V Y, Dugas T R. J Biomed Mater Res B, 2011, 99B(2): 266 − 275 doi: 10.1002/jbm.b.31894

    40. [40]

      McDermott M K, Kim C S, Saylor D M, Patwardhan D V. J Biomed Mater Res B, 2013, 101: 1191 − 1199 doi: 10.1002/jbm.b.32930

    41. [41]

      Fittipaldi M, Rodriguez L A, Damley-Strnad A, Grace L R. Mater Des, 2015, 86: 6 − 13 doi: 10.1016/j.matdes.2015.07.070

    42. [42]

      Toth K, Nugay N, Kennedy J P. J Polym Sci, Part A: Polym Chem, 2016, 54(15): 2361 − 2369 doi: 10.1002/pola.28109

    43. [43]

      Moralesa B, Kaskarb O, Grace L R. Mater Today Commun, 2018, 17: 278 − 288 doi: 10.1016/j.mtcomm.2018.09.019

    44. [44]

      Wu Y B, Li K, Xiang D, Zhang M, Yang D, Zhang J H, Mao J, Wang H, Guo W L. Appl Surf Sci, 2018, 445: 8 − 15 doi: 10.1016/j.apsusc.2018.03.048

    45. [45]

      James G K, Robson F S, William L J, Kenneth A M. Polymer, 2008, 49: 5045 − 5052 doi: 10.1016/j.polymer.2008.08.045

    46. [46]

      Bonduelle C V, Karamdoust S, Gillies E R. Macromolecules, 2011, 44: 6405 − 6415 doi: 10.1021/ma2009996

    47. [47]

      Li S, He J L, Zhang M Z, Wang H R, Ni P H. Polym Chem, 2016, 7: 1773 − 1781 doi: 10.1039/C5PY02017D

    48. [48]

      Malins E L, Waterson C, Becer C R. RSC Adv, 2016, 6: 71773 − 71780 doi: 10.1039/C6RA15346A

    49. [49]

      Castano M, Alvarez1 A, Becker M L, Puskas J E. Express Polym Lett, 2016, 10(8): 693 − 700 doi: 10.3144/expresspolymlett.2016.62

    50. [50]

      Zhang H F, Banerjee S, Faust R, Hadjichristidis N. Polym Chem, 2016, 7: 1217 − 1220 doi: 10.1039/C5PY01892G

    51. [51]

      Askes S H C, Pomp W, Hopkins S L, Kros A, Wu S, Schmidt T, Bonnet S. Small, 2016, 12(40): 5579 − 5590 doi: 10.1002/smll.201601708

    52. [52]

      Askes S H C, Bossert N, Bussmann J, Talens V S, Meijer M S, Kieltyka R E, Kros A, Bonnet S, Heinrich D. Biomaterials, 2018, 168: 54 − 63 doi: 10.1016/j.biomaterials.2018.03.037

    53. [53]

      Campbell C G, Storey R F. Macromolecules, 2018, 51: 6430 − 6439 doi: 10.1021/acs.macromol.8b01258

    54. [54]

      Fu Y H, Madrahimov S T, Bergbreiter D E. J Polym Sci, Part A: Polym Chem, 2018, 56: 1860 − 1867 doi: 10.1002/pola.29069

    55. [55]

      Kerscher B, Trötschler T M, Pásztói B, Gröer S, Szabó A, Iván B, Mülhaupt R. Macromolecules, 2019, 52: 3306 − 3318 doi: 10.1021/acs.macromol.9b00296

    56. [56]

      Yang B, Abel B A, McCormick C L, Storey R F. Macromolecules, 2017, 50: 7458 − 7467 doi: 10.1021/acs.macromol.7b01655

    57. [57]

      Du Y Q, Li C M, Jin J, Li C, Jiang W. Colloids Surf B, 2018, 161: 73 − 82 doi: 10.1016/j.colsurfb.2017.10.035

    58. [58]

      Wei Mengjuan(魏梦娟), Guo Anru(郭安儒), Wu Yixian(吴一弦). Acta Polymerica Sinica(高分子学报), 2017, (3): 118 − 127

    59. [59]

      Wei Mengjuan(魏梦娟), Zhang Qi(章琦), Zhang Hangtian(张航天), Wu Yixian(吴一弦). Acta Polymerica Sinica(高分子学报), 2018, (4): 464 − 474 doi: 10.11777/j.issn1000-3304.2017.17130

    60. [60]

      Gao Y Z, Chang T X, Wu Y X. Carbohyd Polym, 2019, 219: 201 − 209 doi: 10.1016/j.carbpol.2019.04.087

    61. [61]

      Theiler S, Diamantouros S E, Jockenhoevel S, Keul H, Moeller M. Polym Chem, 2011, 2(10): 2273 − 2283 doi: 10.1039/c1py00262g

    62. [62]

      Guo A R, Yang W X, Yang F, Yu R, Wu Y X. Macromolecules, 2014, 47(16): 5450 − 5461 doi: 10.1021/ma501060y

    63. [63]

      Jikei M, Aikawa Y, Matsumoto K. High Perform Polym, 2016, 28(9): 1015 − 1023 doi: 10.1177/0954008315613423

    64. [64]

      Meyer W, Engelhardt S, Novosel E, Elling B, Wegener M, Krüger H. J Funct Biomater, 2012, 3(2): 257 − 268 doi: 10.3390/jfb3020257

    65. [65]

      Cheng Liang(程亮), Li Jianda(李健达), Ma Jun(马骏), Su Junping(苏军平), Wei Shifeng(卫世锋), Liu Xu(刘旭). Guangzhou Chemical Industry(广州化工), 2018, 46(19): 114 − 115

    66. [66]

      Hourston D J, Williams G D, Satguru R, Padget J C, Pears D. J Appl Polym Sci, 1999, 74: 556 − 566 doi: 10.1002/(SICI)1097-4628(19991017)74:3<556::AID-APP10>3.0.CO;2-D

    67. [67]

      Rasolonjatovo B, Gomez J P, William M, Gonçalves C, Huin C, Bennevault-Celton V, Gall T L, Montier T, Lehn P, Cheradame H, Midoux P, Guégan P. Biomacromolecules, 2015, 16: 748 − 756 doi: 10.1021/bm5016656

    68. [68]

      Zhang Qi(章琦), Wei Mengjuan(魏梦娟), Deng Jinrui(邓金睿), Wu Yixian(吴一弦). Acta Polymerica Sinica(高分子学报), 2018, (9): 70 − 79

    69. [69]

      Almeida A D, Nébouy M, Baeza G P. Macromolecules, 2019, 52(3): 1227 − 1240 doi: 10.1021/acs.macromol.8b01689

    70. [70]

      Jewrajka S K, Yilgor E, Yilgor I, Kennedy J P. J Polym Sci, Part A: Polym Chem, 2009, 47(1): 38 − 48 doi: 10.1002/pola.23118

    71. [71]

      Jewrajka S K, Kang J, Erdodi G, Kennedy J P, Yilgor E, Yilgor I. J Polym Sci, Part A: Polym Chem, 2009, 47(11): 2787 − 2797 doi: 10.1002/pola.23361

    72. [72]

      Erdodi G, Kang J, Kennedy J P, Yilgor E, Yilgor I. J Polym Sci, Part A: Polym Chem, 2009, 47(20): 5278 − 5290 doi: 10.1002/pola.23577

    73. [73]

      Kang J, Erdodi G, Kennedy J P, Yilgor E, Yilgor I. J Polym Sci, Part A: Polym Chem, 2009, 47(22): 6180 − 6190 doi: 10.1002/pola.23661

    74. [74]

      Ojha U, Kulkarni P, Faust R. Polymer, 2009, 50(15): 3448 − 3457 doi: 10.1016/j.polymer.2009.05.025

    75. [75]

      Erdodi G, Kang J, Kennedy J P. J Polym Sci, Part A: Polym Chem, 2010, 48(11): 2361 − 2371 doi: 10.1002/pola.24003

    76. [76]

      Cozzens D, Ojha U, KulkarniP, Faust R, Desai S. J Biomed Mater Res A, 2010, 95(3): 774 − 782 doi: 10.1002/jbm.a.32897

    77. [77]

      Ojha U, Faust R. J Biomed Mater Res A, 2010, 47(3): 186 − 191

    78. [78]

      Cozzens D, Ojha U, Kulkarni P, Faust R, Desai S. Abstr Papers Am Chem Soc, 2010, 51(2): 31 − 32

    79. [79]

      Kang J, Erdodi G, Brendel C M, Ely D, Kennedy J P. J Polym Sci, Part A: Polym Chem, 2010, 48(10): 2194 − 2203 doi: 10.1002/pola.23989

    80. [80]

      Cozzens D, Luk A, Ojha U, Ruths M, Faust R. Langmuir, 2011, 27(23): 14160 − 14168 doi: 10.1021/la202586j

    81. [81]

      Wei X Y, Bagdi K, Ren L, Shah P, Seethamraju K, Faust R. Polymer, 2013, 54(6): 1647 − 1655 doi: 10.1016/j.polymer.2013.01.029

    82. [82]

      Kulkarni P, Ojha U, Wei X Y, Gurung N, Seethamraju K, Faust R. J Appl Polym Sci, 2013, 130(2): 891 − 897 doi: 10.1002/app.39236

    83. [83]

      Wei X Y, Shah P N, Bagdi K, Seethamraju K, Faust R. J Macromol Sci Part A: Pure Appl Chem, 2014, 51(1): 6 − 15 doi: 10.1080/10601325.2014.850617

    84. [84]

      Kang J, Kennedy J P. J Polym Sci, Part A: Polym Chem, 2015, 53(1): 1 − 4 doi: 10.1002/pola.27447

    85. [85]

      Mishra A, Seethamraju K, Delaney J, Willoughby P, Faust R. J Biomed Mater Res A, 2015, 103(12): 3798 − 3806 doi: 10.1002/jbm.a.35523

    86. [86]

      Banerjee S, Shah P N, Jeong Y, Chang T, Seethamraju K, Faust R. J Chromatogr A, 2015, 1376: 98 − 104 doi: 10.1016/j.chroma.2014.12.022

    87. [87]

      Nugay N, Toth K, Kekec N C, Nugay T, Kennedy J P. J Polym Sci, Part A: Polym Chem, 2016, 54(17): 2760 − 2765 doi: 10.1002/pola.28158

    88. [88]

      Storey R F, Chisholm B J, Brister L B. Macromolecules, 1995, 28(12): 4055 − 4061 doi: 10.1021/ma00116a002

    89. [89]

      Feldman K E, Kade M J, Meijer E W, Hawker C J, Kramer E J. Macromolecules, 2011, 42: 9072 − 9081

    90. [90]

      Liu Xiao(刘晓), Li Shengran(李晟冉), Wu Yixian(吴一弦). Acta Polymerica Sinica(高分子学报), 2017, (11): 84 − 92

    91. [91]

      Chang Tianxiao(常添笑), Zhang Hangtian(张航天), Lu Congjie(卢聪杰), Wu Yixian(吴一弦). Acta Polymerica Sinica(高分子学报), 2018, (6): 700 − 711 doi: 10.11777/j.issn1000-3304.2017.17290

    92. [92]

      Gao Y Z, Chang T X, Wu Y X. Appl Surf Sci, 2019, 483: 1027 − 1036 doi: 10.1016/j.apsusc.2019.03.103

  • 加载中
WeChat 扫一扫看文章
计量
  • PDF下载量:  0
  • 文章访问数:  2209
  • HTML全文浏览量:  212
文章相关
  • 发布日期:  2020-01-01
  • 收稿日期:  2019-08-10
  • 修回日期:  2019-09-09
通讯作者: 陈斌, bchen63@163.com
  • 1. 

    沈阳化工大学材料科学与工程学院 沈阳 110142

  1. 本站搜索
  2. 百度学术搜索
  3. 万方数据库搜索
  4. CNKI搜索

/

返回文章

All Rights Reserved by the Chinese Chemical Society   中国化学会 版权所有 京ICP备05002797号

本系统由北京仁和汇智信息技术有限公司开发    技术支持: info@rhhz.net