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磷腈碱催化开环聚合制备含氟聚乙基硅氧烷

刘正阳 时金凤 赵娜 李志波

刘正阳, 时金凤, 赵 娜, 等. 磷腈碱催化开环聚合制备含氟聚乙基硅氧烷[J]. 功能高分子学报,2022,35(5):1-8 doi: 10.14133/j.cnki.1008-9357.20220105001
引用本文: 刘正阳, 时金凤, 赵 娜, 等. 磷腈碱催化开环聚合制备含氟聚乙基硅氧烷[J]. 功能高分子学报,2022,35(5):1-8 doi: 10.14133/j.cnki.1008-9357.20220105001
LIU Zhengyang, SHI Jinfeng, ZHAO Na, LI Zhibo. Preparation of Fluorine-Containing Polyethylsiloxane by Ring-Opening Polymerization of Cyclic Siloxanes Catalyzed by Phosphazene Base[J]. Journal of Functional Polymers. doi: 10.14133/j.cnki.1008-9357.20220105001
Citation: LIU Zhengyang, SHI Jinfeng, ZHAO Na, LI Zhibo. Preparation of Fluorine-Containing Polyethylsiloxane by Ring-Opening Polymerization of Cyclic Siloxanes Catalyzed by Phosphazene Base[J]. Journal of Functional Polymers. doi: 10.14133/j.cnki.1008-9357.20220105001

磷腈碱催化开环聚合制备含氟聚乙基硅氧烷

doi: 10.14133/j.cnki.1008-9357.20220105001
基金项目: 山东省自然科学基金联合基金(No. ZR2020LFG014)
详细信息
    作者简介:

    刘正阳(1994—),男,山东潍坊人,硕士生,主要研究方向为聚硅氧烷的合成及改性工作。E-mail:792936920@qq.com

    通讯作者:

    李志波,E-mail:zbli@qust.edu.cn

  • 中图分类号: O633.4

Preparation of Fluorine-Containing Polyethylsiloxane by Ring-Opening Polymerization of Cyclic Siloxanes Catalyzed by Phosphazene Base

  • 摘要: 以有机环三磷腈碱(CTPB)作为催化剂,在温和条件下催化六乙基环三硅氧烷(E3)开环聚合(ROP),以及E3与1,3,5-三甲基-1,3,5-三(3,3,3-三氟丙基)环三硅氧烷(F3)开环共聚合,制备了聚二乙基硅氧烷(PDES)和含有不同三氟丙基甲基硅氧(F)单元摩尔分数(0~46%)的聚(二乙基-ran-三氟丙基甲基)硅氧烷(PDES-ran-PTFPMS)。采用凝胶渗透色谱、核磁共振(NMR)表征了聚合物的组成和结构,利用差示扫描量热(DSC)和微观接触角对聚合物的性质进行研究。结果表明:成功制得PDES-ran-PTFPMS。当F单元摩尔分数高于6%时,可以有效抑制PDES的低温结晶性,且PDES-ran-PTFPMS具有极低的玻璃化转变温度(Tg = −134 ºC)。含氟聚乙基硅氧烷薄膜的接触角测试结果表明,F单元的引入有效提高了聚乙基硅氧烷的疏水性及降低了油的浸润性。

     

  • 图  1  PDES-ran-PTFPMS的合成示意图

    Figure  1.  Synthetic routes of PDES-ran-PTFPMS

    图  2  PDES-ran-PTFPMS共聚物的GPC曲线

    Figure  2.  GPC trances of PDES-ran-PTFPMS

    图  3  PDES-ran-PTFPMS的(a)1H-NMR谱图和(b)29Si-NMR谱图

    Figure  3.  (a)1H-NMR and (b) 29Si-NMR spectra of PDES-ran-PTFPMS

    图  4  PDES和PDES-ran-PTFPMS的DSC曲线

    Figure  4.  DSC curves of PDES and PDES-ran-PTFPMS

    图  5  PDES和PDES-ran-PTFPMS的水/油接触角

    Figure  5.  Water/oil contact angles of PDES and PDES-ran-PTFPMS

    表  1  CTPB/BnOH催化E3和F3开环均聚合

    Table  1.   Homopolymerization of E3 or F3 catalyzed by CTPB/BnOH

    runMn(M)∶n(BnOH)∶n(CTPB)cM/(mol·L−1t/minYield/%MnĐ
    1 F3 100∶1∶0.0001 1.4 15 59 3.79×104 1.82
    2 F3 100∶1∶0.001 1.4 15 83 4.85×104 1.77
    3 E3 50∶1∶0.001 1.4 600 4
    4 E3 50∶1∶0.1 1.4 240 65 1.89×104 1.54
    5 E3 1000∶1∶1 2.8 30 87 1.67×105 1.80
    The polymerizations were carried out in toluene at room temperature (about 25 ºC); Yield is determined by weight; Mn is determined by GPC at 40 ºC in THF relative to polystyrene standards
    下载: 导出CSV

    表  2  CTPB/BnOH催化E3和F3共聚合

    Table  2.   Copolymerization of E3 and F3 catalyzed by CTPB/BnOH

    runn(E3)∶n(F3)∶n(BnOH)∶n(CTPB)T/ºCYield/%MnĐfF/%
    1 950∶50∶1∶2 25 49 8.39×104 1.57 6
    2 850∶150∶1∶1 25 10
    3 850∶150∶1∶1 80 55 6.02×104 1.61 18
    4 850∶150∶1∶2 25 72 1.32×105 1.52 14
    5 750∶250∶1∶2 25 47 1.00×105 1.58 26
    6 650∶350∶1∶2 25 60 1.12×105 1.61 37
    7 550∶450∶1∶2 25 56 9.12×104 1.59 46
    The polymerizations were carried out in toluene at room temperature (about 25 ºC) for 30 min; cM= 2.6 mol/L; Yield is Determined by weight; Mn is determined by GPC at 40 ºC in THF relative to polystyrene standards; fF is determined by 1H-NMR, F stands for the unit of ―Si(CH3)(CH2CH2CF3)O―, E stands for the unit of ―Si(CH3CH2)2O―, fF=n(F)/n(E+F)
    下载: 导出CSV

    表  3  PDES-ran-PTFPMS的三元序列

    Table  3.   Triad sequences for PDES-ran-PTFPMS

    δSequence
    (−23.1~−23.2)a EEE, ―Si(CH3CH2)2O―Si(CH3CH2)2O―Si(CH3CH2)2O―
    (−21.9~−22.9)a FEE, ―Si(CH3)(CH2CH2CF3)O―Si(CH3CH2)2O―Si(CH3CH2)2O― or
    EEF,― Si(CH3CH2)2O―Si(CH3CH2)2O―Si(CH3)(CH2CH2CF3)O―
    (−20.9~−21.8)a FEF, ―Si(CH3)(CH2CH2CF3)O―Si(CH3CH2)2O―Si(CH3)(CH2CH2CF3)O―
    (−20.2~−20.4)b EFE, ―Si(CH3CH2)2O―Si(CH3)(CH2CH2CF3)O―Si(CH3CH2)2O―
    (−19.4~−20.1)b FFE , ―Si(CH3)(CH2CH2CF3)O―Si(CH3)(CH2CH2CF3)O―Si(CH3CH2)2O― or
    EFF, ―Si(CH3CH2)2O―Si(CH3)(CH2CH2CF3)O―Si(CH3)(CH2CH2CF3)O―
    (−19.2~−19.3)b FFF, ―Si(CH3)(CH2CH2CF3)O―Si(CH3)(CH2CH2CF3)O―Si(CH3)(CH2CH2CF3)O―
    a Triad sequence centered on E unit; b Triad sequence centered on F unit
    下载: 导出CSV
  • [1] YILGÖR E, YILGÖR I. Silicone containing copolymers: Synthesis, properties and applications [J]. Progress in Polymer Science,2014,39(6):1165-1195. doi: 10.1016/j.progpolymsci.2013.11.003
    [2] MENG Y, CHU J F, XUE J J, LIU C H, WANG Z, ZHANG L Q. Design and synthesis of non-crystallizable, low-Tg polysiloxane elastomers with functional epoxy groups through anionic copolymerization and subsequent epoxidation [J]. RSC Advances,2014,4(59):31249-31260. doi: 10.1039/C4RA02293A
    [3] CHEN Z, ZHANG T J, ZHANG Y, REN Z J, ZHANG J M, YAN S K. Main chain copolysiloxanes with terthiophene and perylenediimide units: Synthesis, characterization and electrical memory [J]. Polymer Chemistry,2017,8(22):3515-3522. doi: 10.1039/C7PY00418D
    [4] REN Z J, YAN S K. Polysiloxanes for optoelectronic applications [J]. Progress in Materials Science,2016,83(2):383-416.
    [5] 张继华, 任灵, 赵云峰, 王立峰. 空间环境用耐低温硅橡胶密封材料研究 [J]. 航天器环境工程,2011,28(2):161-166. doi: 10.3969/j.issn.1673-1379.2011.02.012

    ZHANG J H, REN L, ZHAO Y F, WANG L F. Low-temperature seal materials made of silicon rubber for space use [J]. Spacecraft Environment Engineering,2011,28(2):161-166. doi: 10.3969/j.issn.1673-1379.2011.02.012
    [6] BEATTY C L, KARASZ F E. Transitions in poly(diethyl siloxane) [J]. Journal of Polymer Science: Polymer Physics Edition,1975,13:971-975. doi: 10.1002/pol.1975.180130509
    [7] INOMATA K, YAMAMOTO K, NOSE T. An X-ray diffraction study on crystalline and mesomorphic structures of poly(diethylsiloxane) [J]. Polymer Journal,2000,32(12):1044-1048. doi: 10.1295/polymj.32.1044
    [8] MOLENBERG A, MÖLLER M. Structure and phase transitions of poly(diethylsiloxane) [J]. Macromolecules,1997,30(26):8332-8337. doi: 10.1021/ma970786u
    [9] MILLER K J, GREBOWICZ J, WESSON J P, WUNDERLICH B. Conformations of poly(diethylsiloxane) and its mesophase transitions [J]. Macromolecules,1990,23(3):849-856. doi: 10.1021/ma00205a026
    [10] LI B, ZHANG Z D, MA D P, ZHAI Q Q, FENG S Y, ZHANG J. Preparation and kinetic analysis of room-temperature vulcanized methylethylsilicone rubbers [J]. Journal of Applied Polymer Science,2015,132(41):42656.
    [11] QU L L, HUANG G S, WANG Q, XIE Z J. Effect of diphenylsiloxane unit content on aggregation structure of poly(dimethylsiloxane-co-diphenylsiloxane) [J]. Journal of Polymer Science Part B:Polymer Physics,2008,46(1):72-79. doi: 10.1002/polb.21343
    [12] FEI H F, HAN X J, LIU B Z, GAO X Y, WANG Q, ZHANG Z J, XIE Z M. Synthesis of gradient copolysiloxanes by simultaneous copolymerization of cyclotrisiloxanes and mechanism for kinetics inverse between anionic and cationic ring-opening polymerization [J]. Journal of Polymer Science Part A:Polymer Chemistry,2016,54(6):835-843. doi: 10.1002/pola.27921
    [13] BREWER J R, TSUCHIHARA K, MORITA R, JONES J R, BLOXSIDGE J P, FUJISHIGE S. Poly(diethylsiloxane-co-ethylphenylsiloxane) and poly(diethylsiloxane-co-methylphenylsiloxane): Synthesis and characterization [J]. Polymer,1994,35(23):5118-5123. doi: 10.1016/0032-3861(94)90674-2
    [14] 刘立华, 杨始燕, 张志杰, 谢择民. 耐超低温硅橡胶的研制 [J]. 有机硅材料,2003,17(6):4-6. doi: 10.3969/j.issn.1009-4369.2003.06.002

    LIU L H, YANG S Y, ZHANG Z J, XIE Z M. Study on ultralow temperature resistance silicone rubber [J]. Silicome Material,2003,17(6):4-6. doi: 10.3969/j.issn.1009-4369.2003.06.002
    [15] LIU L H, YANG S Y, ZHANG Z J, WANG Q, XIE Z M. Synthesis and characterization of poly(diethylsiloxane) and its copolymers with different diorganosiloxane units [J]. Journal of Polymer Science Part A:Polymer Chemistry,2003,41(17):2722-2730. doi: 10.1002/pola.10822
    [16] BREWER J R, TSUCHIHARA K, MORITA R, JONES J R, BLOXSIDGE J P, KAGAO S, OTSUKI T, FUJISHIGE S. Poly(diethylsiloxane-co-diphenylsiloxane) and poly(diethylsiloxane-co-3, 3, 3-trifluoropropylmethylsiloxane): Synthesis, characterization and low-temperature properties [J]. Polymer,1994,35(23):5109-5117. doi: 10.1016/0032-3861(94)90673-4
    [17] 李敏, 韩龙, 郭旭虹, 王杰. 有机硅改性水性聚氨酯涂层的制备及其防污性能 [J]. 功能高分子学报,2021,34(4):379-386.

    LI M, HAN L, GUO X H, WANG J. Preparation and antifouling properties of silicon-modified waterborne polyurethane coatings [J]. Journal of Functional Polymers,2021,34(4):379-386.
    [18] YOU Y, CHEN J D, ZHENG A N, WEI D F, XU X, GUAN Y. Effect of silanol on the thermal stability of poly[methyl(trifluoropropyl)siloxane] [J]. Journal of Applied Polymer Science,2020,137(44):1-9.
    [19] LIU Y T, ZHU D, SUN J W, LI J, WU Y M, GAO C H. Synthesis and characterization of a novel fluorosilicone resin based on trifluoropropylalkoxylsilane [J]. Materials Chemistry and Physics,2019,224:40-46. doi: 10.1016/j.matchemphys.2018.11.077
    [20] LI X, CHEN B L, CAI W B, WANG T, WU Z, LI J D. Highly stable PDMS-PTFPMS/PVDF OSN membranes for hexane recovery during vegetable oil production [J]. RSC Advances,2017,7(19):11381-11388. doi: 10.1039/C6RA28866A
    [21] INDULEKHA K, BEHERA P K, RAJEEV R S, GOURI C, NINAN K N. Polyfluoroalkyl siloxanes with varying trifluoropropyl content: Synthesis, characterization and solvent resistance studies [J]. Journal of Fluorine Chemistry,2017,200:24-32. doi: 10.1016/j.jfluchem.2017.05.007
    [22] YUZHELEVSKII Y A, KAGAN Y G, FEDOSEYEVA N N. Activators of the anionic polymerization of cyclosiloxanes [J]. Polymer Science U. S. S. R.,1970,12(7):1800-1809. doi: 10.1016/0032-3950(70)90326-6
    [23] YUZHELEVSKII Y A, KAGAN Y G, TIMOFEYEVA N P, DOLETSKAYA T D, KLEBANSKII A L. Anionic polymerization of methyl (propyl) cyclosiloxanes [J]. Polymer Science U. S. S. R.,1971,13(1):208-216. doi: 10.1016/0032-3950(71)90238-3
    [24] LI B, CHNE S J, ZHANG J. Synthesis and characterization of vinyl-terminated copolysiloxanes containing 3, 3, 3-trifluoropropyl groups [J]. Polymer Chemistry,2012,3(9):2366-2376. doi: 10.1039/c2py20091k
    [25] YI L M, ZHAN X L, CHEN F Q, DU F, HAUNG L B. Synthesis and characterization of poly[styrene-b-methyl(3, 3, 3-trifluoropropyl)siloxane] diblock copolymers via anionic polymerization [J]. Journal of Polymer Science Part A:Polymer Chemistry,2005,43(19):4431-4438. doi: 10.1002/pola.20927
    [26] TSUCHIHARA K, FUJISHIGE S. Living polymerization of hexaethylcyclotrisiloxane [J]. Polymer Bulletin,1999,43(2):129-134.
    [27] VEITH C A, COHEN R E. Kinetic modelling and optimization of the trifluoropropylmethylsiloxane polymerization [J]. Journal of Polymer Science Part A:Polymer Chemistry,1989,27(4):1241-1258. doi: 10.1002/pola.1989.080270411
    [28] 夏爽, 刘小兵, 赵娜, 李玉全, 赵祺, 刘绍峰, 李志波. 环硅氧烷阴离子开环均聚及共聚研究进展 [J]. 高分子学报,2018(12):1482-1492. doi: 10.11777/j.issn1000-3304.2018.18165

    XIA S, LIU X B, ZHAO N, LI Y Q, ZHAO Q, LIU S F, LI Z B. Progress in Anionic ring-opening homo/co-polymerization of cyclosiloxanes [J]. Acta Polymerica Sinica,2018(12):1482-1492. doi: 10.11777/j.issn1000-3304.2018.18165
    [29] ZHAO N, REN C L, LI H K, LI Y X, LIU S F, LI Z B. Selective ring-opening polymerization of non-strained γ-butyrolactone catalyzed by a cyclic trimeric phosphazene base [J]. Angewandte Chemie: International Edition,2017,56(42):12987-12990. doi: 10.1002/anie.201707122
    [30] 时金凤, 赵娜, 符文鑫, 李志波. 基于可逆离子氢键构筑室温快速自修复聚硅氧烷弹性体 [J]. 功能高分子学报,2020,33(5):433-440.

    SHI J F, ZHAO N, FU W X, LI Z B. A stretchable and rapidly self-healable polysiloxane elastomer based on reversible ionic hydrogen bonds [J]. Journal of Functional Polymers,2020,33(5):433-440.
    [31] SHI J F, ZHAO N, XIA S, LIU S F, LI Z B. Phosphazene superbase catalyzed ring-opening polymerization of cyclotetrasiloxane toward copolysiloxanes with high diphenyl siloxane content [J]. Polymer Chemistry,2019,10(17):2126-2133. doi: 10.1039/C9PY00247B
    [32] FEI H F, GAO X Y, HAN X J, WANG Q, HU T, ZHANG Z J, XIE Z M. Synthesis, characterization, and properties of vinyl-terminated copolysiloxanes containing trifluoropropyl and 4-trifluoromethylphenyl groups [J]. Journal of Polymer Science Part A:Polymer Chemistry,2015,53(8):1023-1031. doi: 10.1002/pola.27530
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  • 收稿日期:  2022-01-05
  • 录用日期:  2022-03-21
  • 网络出版日期:  2022-03-29

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