Page 60 - 201903

·406· 精细化工 FINE CHEMICALS 第 36 卷

由表 6 可见，随着聚硅氧烷含量的增加，水和 [5] Zhu Jianqin (朱建琴), Dai Wenqi (戴文琪), Li Xiangyu (郦向宇).
Synthesis and application of siloxane-modified aliphatic aqueous
乙二醇在水性聚氨酯膜上的接触角先增大后基本不 polyurethane finishing agents for synthetic leather[J]. Plastics
变，这可能是聚硅氧烷本身的结构所致。随着聚硅 Additives (塑料助剂), 2017, 124: 16-19.
[6] Hao Lifen (郝丽芬), Pei Mengmeng (裴萌萌), Xu Wei (许伟).
氧烷加入量的增多，Si—CH 3 基团迁移到膜表面也 Synthesis of fluoroalkyl-terminated hyperbranched polyurethane
nanohybrid latex and its waterproofing application on fabric[J].
增多，膜的表面呈现疏水性，而有机硅又含有亲水 Journal of Shaanxi University of Science Technology(陕西科技大学
性 PEO 链段，在加入量较多时，Si—CH 3 基团迁移 学报), 2018, 36(3): 23-28.
[7] Zhang Ruofei (张若飞), Chen Xianping (陈县萍), Cheng Shiqiang
到表面的同时会使亲水性 PEO 链段也迁移到表面， (程诗强), et al. Research progress of waterborne polyurethane
疏水基团和亲水基团的共同作用，导致水性聚氨酯 adhesives and their application in automotive interior[J].
Adhesion(粘接), 2018, 39(2): 24-28.
膜的水接触角先增大后不变。随着聚硅氧烷的加入， [8] Huang Yiping ( 黄毅萍 ), Xu Gewen ( 许戈 文 ). Waterborne
2
水性 聚氨 酯膜 的表 面能 从 40.16 mJ/m 降到 polyurethane and its application[M]. Beijing: Chemical Industry
Press (化学工业出版社), 2015.
2
27.27 mJ/m 。当聚硅氧烷质量分数达到 5%时，表面 [9] Yang F, Zhu L, Han D, et al. Effects of fluorine and silicon
components on the hydrophobicity failure behavior of acrylic
能基本保持不变，这一结果与 XPS 测定的表面硅含 polyurethane coatings[J]. Journal of Coatings Technology and
量变化相吻合，说明表面能的降低与表面有机硅链 Research, 2017, 14(3): 691-699.
[10] Hui B, Ye L. Highly heat-resistant silicon-containing polyurethane-
段含量变化一致。 imide copolymers: Synthesis and thermal mechanical stability[J].
European Polymer Journal, 2017, 91: 337-353.
3 结论 [11] Zheng G, Lu M, Rui X, et al. Surface and bulk properties of
waterborne polyurethane modified with fluorinated siloxane[J].
Journal of Applied Polymer Science, 2018, 135(28): 46473.
（1）本文将聚硅氧烷和异氰酸酯作为第一步反 [12] Ge Shoushou (葛硕硕), Zhang Pingbo (张萍波), Jiang Pingping (蒋
平平). Preparation and properties of castor-oil-based polyurethane
应，成功合成了聚硅氧烷改性水性聚氨酯。聚硅氧 modified by polyether-polysiloxanePolyols[J]. China plastics(中国塑
烷的加入，对水性聚氨酯乳液的稳定性、粒径影响 料), 2017, 31(6): 28-35.
[13] Go C W, Yang J H, Kwak D, et al. Waterborne polyurethane
甚微。 modified with silicone macromer and the nylon airbag coated with
（2）随着聚硅氧烷的加入，红外衰减全反射光 it[J]. Textile Research Journal, 2016, 86(19): 2015-2021.
[14] Yu Chenxi (余晨曦), Zhao Chen (赵晨), Chen Zhenghan (陈政翰).
谱和透射光谱可以表明，Si—CH 3 基团迁移到膜表 Linear Polysiloxane modified polyether polyurethane/epoxy resin
interpenetrating polymer networks[J]. Polymer Materials Science and
面。XPS 测试表明，当聚硅氧烷质量分数在 5%时， Engineering(高分子材料科学与工程), 2017, 33(1): 125-129.
硅在水性聚氨酯膜表面的迁移量达到饱和。通过不 [15] Standardization Administration of the People's Republic of China (中
国国家标准化管理委员会). Methods of test for package stability of
同接触角测试得到水性聚氨酯膜的表面能，当有机 paints: GB 6753. 3-1986[S]. Beijing: Standards Press of China (北
硅质量分数达到 5%时，水性聚氨酯膜的表面能达到 京: 中国标准出版社), 1986: 1-4.
[16] Shalel-Levanon S, Marmur A, Kim H D, et al. Validity and accuracy
2
27.27 mJ/m 。这一结果与 XPS 测定的表面硅含量变 in evaluating surface tension of solids by additive approaches[J].
Journal of Colloid and Interface Science, 2003, 262(2): 489-499.
化一致。
[17] Li Q, Ye J, Qiu T, et al. Synthesis of waterborne polyurethane
（3）聚硅氧烷的加入改善了水性聚氨酯膜的热 containing alkoxysilane side groups: Study on spacer linkages[J].
Journal of Applied Polymer Science, 2018, 135(36): 46628.
学性能和力学性能。WPU2 的拉伸强度最大达到 [18] Rahman M M, Hasneen A, Kim H D, et al. Preparation and properties
31.81 MPa，断裂伸长率为 1023%。WPU6 的 100% of polydimethylsiloxane (PDMS)/polytetramethyleneadipate glycol
(PTAd)-based waterborne polyurethane adhesives: Effect of PDMS
定伸模量最低为 1.79 MPa。 molecular weight and content[J]. Journal of Applied Polymer
通过对水性聚氨酯表面硅迁移含量与表面能的 Science, 2012, 125(1): 88-96.
[19] Yu Xuekang (余学康), Chen Xin (陈昕), Wang Wusheng (王武生).
研究相结合，可以得到有机硅对表面能的影响，这 Preparation and characterization of organosilicone modified
对未来研究水性聚氨酯表面性能提供了更近一步的 waterborne polyurethane dispersion [J]. Paint & Coatings Industry
(涂料工业), 2017, 47(3): 44-48.
理论分析。 [20] Xu Gewen ( 许戈文 ), Huang Yiping ( 黄毅 萍 ). Waterborne
polyurethane material [M]. Beijing : Chemical Industry Press(化学工
业出版社), 2007.
参考文献： [21] Du Y, Zhang J, Zhou C. Synthesis and properties of waterborne
[1] Yang G, Song J, Hou X. Fabrication of highly hydrophobic polyurethane-based PTMG and PDMS as soft segment[J]. Polymer
two-component thermosetting polyurethane surfaces with silica Bulletin, 2016, 73(1): 293-308.
nanoparticles [J]. Applied Surface Science, 2018, 439: 772-779. [22] Xiahou Guolun (夏侯国论), Liu Weiqu (刘伟区), Tan Jianquan(谭建
[2] Zhang Y, Shao L, Dong D, et al. Enhancement of water and organic 权). Preparation and properties of polyurethane elastomer composites
solvent resistances of a waterborne polyurethane film by incorporating modified by polydimethylsiloxane and organic-montmorillonite [J].
liquid polysulfide[J]. RSC Advances, 2016, 6(21): 17163-17171. Acta Polymerica Sinica(高分子学报), 2014 (4): 444-450.
[3] Jofre-Reche J A, García-Pacios V, Costa V, et al. Role of the [23] Cakić S M, Ristić I S, Krakovský I, et al. Crystallization and thermal
interactions between carbonate groups on the phase separation and properties in waterborne polyurethane elastomers: Influence of mixed
properties of waterborne polyurethane dispersions prepared with soft segment block[J]. Materials Chemistry and Physics, 2014,
copolymers of polycarbonate diol [J]. Progress in Organic Coatings, 144(1/2): 31-40.
2015, 88: 199-211. [24] Huang Q, Lu H, Deng B, et al. Effect of hard segments on the
[4] Patel C J, Mannari V. Air-drying bio-based polyurethane dispersion thermal and mechanical behaviour of a novel hybrid silicon
from cardanol: Synthesis and characterization of coatings[J]. thermoplastic elastomer[J]. Materials Research Express, 2017, 4(7):
Progress in Organic Coatings, 2014, 77(5): 997-1006. 075305.