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

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

刘正阳^1,,
时金凤¹,
赵娜¹,
李志波^{1, 2, ,}

1.
高分子科学与工程学院青岛科技大学
2.
化工学院, 山东青岛 266042

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
计量
- 文章访问数: 31
- HTML全文浏览量: 17
- PDF下载量: 8
- 被引次数: 0
出版历程
- 收稿日期: 2022-01-05
- 录用日期: 2022-03-21
- 网络出版日期: 2022-03-29

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

LIU Zhengyang^1
,,
SHI Jinfeng¹,
ZHAO Na¹,
LI Zhibo^{1, 2
, ,}

1.
College of Polymer Science and Engineering
2.
College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266042, China

摘要

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（T_g = −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。
- 有机磷腈碱 /
- 开环聚合 /
- 聚三氟丙基甲基硅氧烷 /
- 聚二乙基硅氧烷 /
- 低玻璃化转变温度
Abstract: In this contribution, the ring-opening copolymerization (ROP) of hexaethylcyclotrisiloxane (E3), and the ring-opening copolymerization E3 and 1,3,5-trimethyl-1,3,5-tri(3,3,3-trifluoropropyl) cyclotrisiloxane (F3) was catalyzed by organic cyclotrisiloxane base (CTPB) under mild conditions. CTPB showed high catalytic activity for the polymerization of E3 and F3. Linear polydiethylsiloxanes (PDES) and poly(diethyl-ran-trifluoropropyl methyl) siloxanes (PDES-ran-PTFPMS) with different trifluoropropyl methyl siloxane group (F) (mole fractions: 0～46%) were successfully synthesized. The composition and structure of the PDES-ran-PTFPMS copolysiloxanes were characterized in detail by gel permeation chromatography (GPC) and nuclear magnetic resonance (NMR), and the glass transition temperature (T_g) and crystallization behavior of the polymers were comprehensively analyzed by differential scanning calorimetry, and the water-oil contact angle of fluorine-containing polyethylsiloxane film was investigated by microscopic contact angle test. The chemical positions of the resonance peaks in the nuclear magnetic resonance spectrum (¹H-NMR and ²⁹Si-NMR) were analyzed, indicating that the PDES-ran-PTFPMS copolysiloxanes was successfully prepared. The results of differential scanning calorimeter (DSC) indicated that the crystallization of polydiethylsiloxane at low temperature can be entirely inhibited by the introduction of tri(3,3,3-trifluoropropyl)-methyl siloxane groups. The obtained PDES-ran-PTFPMS copolysiloxanes has a low glass transition temperature T_g (−134 ºC), has very excellent low temperature performance, and is an ideal precursor material for low temperature resistant rubber materials. When the contents of the methyl-tri(3,3,3-trifluoropropyl)siloxane group are higher than 6.0%, the crystallization behavior was inhibited. The results of contact angle test of fluorine-containing polyethylsiloxane film demonstrated that the introduction of tri(3,3,3-trifluoropropyl)-methyl siloxane groups into the PDES chain can effectively improve its hydrophobicity and decrease the oil wettability.
- organophosphazene base /
- ring-opening polymerization /
- polytrifluoropropylmethylsiloxane /
- polydiethylsiloxane /
- low glass transition temperature

HTML全文

图 1 PDES-ran-PTFPMS的合成示意图

Figure 1. Synthetic routes of PDES-ran-PTFPMS

下载: 全尺寸图片幻灯片

图 2 PDES-ran-PTFPMS共聚物的GPC曲线

Figure 2. GPC trances of PDES-ran-PTFPMS

下载: 全尺寸图片幻灯片

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

下载: 全尺寸图片幻灯片

图 4 PDES和PDES-ran-PTFPMS的DSC曲线

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

下载: 全尺寸图片幻灯片

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

下载: 全尺寸图片幻灯片

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

run	M	n（M）∶n（BnOH）∶n（CTPB）	c_M/（mol·L⁻¹）	t/min	Yield/%	M_n	Đ
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; M_n 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

run	n（E3）∶n（F3）∶n（BnOH）∶n（CTPB）	T/ºC	Yield/%	M_n	Đ	f_F/%
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; c_M= 2.6 mol/L; Yield is Determined by weight; M_n is determined by GPC at 40 ºC in THF relative to polystyrene standards; f_F is determined by ¹H-NMR, F stands for the unit of ―Si(CH₃)(CH₂CH₂CF₃)O―, E stands for the unit of ―Si(CH₃CH₂)₂O―, f_F=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

δ	Sequence
(−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

参考文献(32)

[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-T_g 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