Synthesis and Characterization of Fluorinated Polyurethane Containing Carborane in the Main Chain: Thermal, Mechanical and Chemical Resistance Properties

Ning Li; Fang-Lei Zeng; Yu Wang; De-Zhi Qu; Chun Zhang; Juan Li; Jin-Zhao Huo; Yong-Ping Bai

doi:10.1007/s10118-018-2014-1

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Synthesis and Characterization of Fluorinated Polyurethane Containing Carborane in the Main Chain: Thermal, Mechanical and Chemical Resistance Properties

PAPERS | Updated：2021-02-18

- Synthesis and Characterization of Fluorinated Polyurethane Containing Carborane in the Main Chain: Thermal, Mechanical and Chemical Resistance Properties
- Chinese Journal of Polymer Science Vol. 36, Issue 1, Pages: 85-97(2018)
- Affiliations：
  
  a.School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001, China
  b.School of Materials Science & Engineering, Beijing Institute of Technology, Beijing 100081, China
  c.School of Materials Engineering, Yancheng Institute of Technology, Yancheng 224000, China
  d.Foshan NanHai Gotop Packaging Material Co., Ltd, Foshan 528225, China
- Author bio：
  
  Yong-Ping Bai, E-mail baifengbai@hit.edu.cn
- Funds：
- DOI：10.1007/s10118-018-2014-1
  CLC：
- Received：20 May 2017，
  
  Accepted：15 July 2017，
  
  Online First：18 September 2017，
  
  Published：05 January 2018
- Accepted：
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Ning Li, Fang-Lei Zeng, Yu Wang, et al. Synthesis and Characterization of Fluorinated Polyurethane Containing Carborane in the Main Chain: Thermal, Mechanical and Chemical Resistance Properties[J]. Chinese Journal of Polymer Science, 2018, 36(1): 85-97.
DOI：

Ning Li, Fang-Lei Zeng, Yu Wang, et al. Synthesis and Characterization of Fluorinated Polyurethane Containing Carborane in the Main Chain: Thermal, Mechanical and Chemical Resistance Properties[J]. Chinese Journal of Polymer Science, 2018, 36(1): 85-97. DOI： 10.1007/s10118-018-2014-1.

摘要

Abstract

In this study

two fluorinated polyurethanes (FPU) containing carborane groups in the main chains were firstly designed and synthesized

via

the reaction of hexamethylene diisocyanate trimer (HDI trimer) with fluorinated polyesters (CFPETs) having hydroxyl-terminated carborane groups at room temperature. The structures of carborane fluorinated polyesters (CFPETs) and polyurethanes (CFPUs) were characterized by gel permeation chromatography (GPC)

Fourier transform infrared (FTIR) spectroscopy and nuclear magnetic resonance (NMR) measurements. The thermal stability

mechanical properties

Shore A hardness

solvent resistance and acid-alkali resistance of the carborane fluorinated polyurethane films were also studied. Thermogravimetric analysis (TGA) tests manifested that the introduction of carborane groups into the main chain of fluorinated polyurethane endowed the obtained fluorinated polyurethane with excellent thermal stability. The thermal decomposition temperature of carborane fluorinated polyurethane (CFPU) increased by 190℃ compared with that of the carborane-free fluorinated polyurethane (FPU). Even at 800℃

CFPU showed the char yield of 66.5%

which was higher than that of FPU (34.3%). The carborane-containing fluorinated polyurethanes also showed excellent chemical resistance and prominent mechanical property even after the cured films being immersed into Jet aircraft oil or 37% HCl for 168 h or at high temperature (700℃). It is found that the structural characteristics of carborane group and the compacted structure of CFPU effectively improve the thermal stability

mechanical property

solvent resistance and acid-alkali resistance of the carborane-free fluorinated polyurethane. These excellent properties make CFPU as the useful raw materials to prepare the high temperature resistant coatings or adhesives for automotive engines

engine or fuel tank of aircraft and other equipment working in high-temperature or high concentrations of acid-alkali environments.

关键词

Keywords

references

T. Takakura , M. Kato , M. Yamabe . Synthesis and characterization of fluorine-containing segmented poly(urethane-urea)s . Macromol. Chem. Phys. , 1990 . 191 ( 3 ): 625 - 632 . .

C. L. Wu , S. H. Chiu , H. T. Lee , M. C. Suen . Synthesis and properties of biodegradable polycaprolactone/polyurethanes using fluoro chain extenders . Polym. Adv. Technol. , 2016 . 27 ( 5 ): 665 - 676 . DOI: 10.1002/pat.v27.5 http://doi.org/10.1002/pat.v27.5 .

Z. Ge , X. Zhang , J. Dai , W. Li , Y. Luo . Synthesis, characterization and properties of a novel fluorinated polyurethane . Eur. Polym. J. , 2009 . 45 ( 2 ): 530 - 536 . DOI: 10.1016/j.eurpolymj.2008.11.008 http://doi.org/10.1016/j.eurpolymj.2008.11.008 .

E. Alyamac , M. D. Soucek . Acrylate-based fluorinated copolymers for high-solids coatings . Prog. Org. Coat. , 2011 . 71 ( 3 ): 213 - 224 . DOI: 10.1016/j.porgcoat.2011.02.015 http://doi.org/10.1016/j.porgcoat.2011.02.015 .

T. Dikić , S. J. F. Erich , W. Ming , H. P. Huinink , P. C. Thüne , R. A. T. M. van Benthem , G. With . Fluorine depth profiling by high-resolution 1D magnetic resonance imaging . Polymer , 2007 . 48 ( 14 ): 4063 - 4067 . DOI: 10.1016/j.polymer.2007.05.017 http://doi.org/10.1016/j.polymer.2007.05.017 .

X. Wang , J. Hu , Y. Li , J. Zhang , Y. Ding . The surface properties and corrosion resistance of fluorinated polyurethane coatings . J. Fluorine. Chem. , 2015 . 176 14 - 19 . DOI: 10.1016/j.jfluchem.2015.04.002 http://doi.org/10.1016/j.jfluchem.2015.04.002 .

O. Smirnova , A. Glazkov , A. Yarosh , A. Sakharov . Fluorinated polyurethanes, synthesis and properties . Molecules , 2016 . 21 ( 7 ): DOI: 10.3390/molecules21070904 http://doi.org/10.3390/molecules21070904 .

L. Li , X. Wang , Z. Li , W. Bi , Y. Li , Y. Qi , Q. Dong . The synthesis and curing kinetics study of a new fluorinated polyurethane with fluorinated side chains attached to soft blocks . New J. Chem. , 2016 . 40 ( 1 ): 596 - 605 . DOI: 10.1039/C5NJ01772F http://doi.org/10.1039/C5NJ01772F .

F. Yu , L. Cao , Z. Meng , N. Lin , X. Y. Liu . Crosslinked waterborne polyurethane with high waterproof performance . Polym. Chem. , 2016 . 7 ( 23 ): 3913 - 3922 . DOI: 10.1039/C6PY00350H http://doi.org/10.1039/C6PY00350H .

X. Zhao , J. Ding , L. Ye . Structure and solvent-resistant property of fluorinated polyurethane elastomer . Fluor. Chem. , 2014 . 159 38 - 47 . DOI: 10.1016/j.jfluchem.2013.12.012 http://doi.org/10.1016/j.jfluchem.2013.12.012 .

M. Shin , Y. Lee , M. Rahman , H. Kim . Synthesis and properties of waterborne fluorinated polyurethane-acrylate using a solvent-/emulsifier-free method . Polymer , 2013 . 54 ( 18 ): 4873 - 4882 . DOI: 10.1016/j.polymer.2013.07.005 http://doi.org/10.1016/j.polymer.2013.07.005 .

J. Li , X. Zhang , Z. Liu , W. Li , J. Dai . Studies on waterborne polyurethanes based on new medium length fluorinated diols . J. Fluor. Chem. , 2015 . 175 12 - 17 . DOI: 10.1016/j.jfluchem.2015.02.015 http://doi.org/10.1016/j.jfluchem.2015.02.015 .

B. Ou , M. Chen , R. Huang , H. Zhou . Preparation and application of novel biodegradable polyurethane copolymer . RSC Adv. , 2016 . 6 ( 52 ): 47138 - 47144 . DOI: 10.1039/C6RA03064E http://doi.org/10.1039/C6RA03064E .

J. M. Park , Y. H. Lee , H. Park , H. D. Kim . Preparation and properties of UV-curable fluorinated polyurethane acrylates . J. Appl. Polym. Sci. , 2014 . 131 ( 16 ): http://www.chemie.de/fachpublikationen/700829/preparation-and-properties-of-uv-curable-fluorinated-polyurethane-acrylates.html http://www.chemie.de/fachpublikationen/700829/preparation-and-properties-of-uv-curable-fluorinated-polyurethane-acrylates.html , .

Z. Wang , Z. Hou , Y. Wang . Fluorinated waterborne shape memory polyurethane urea for potential medical implant application . J. Appl. Polym. Sci. , 2013 . 127 ( 1 ): 710 DOI: 10.1002/app.37862 http://doi.org/10.1002/app.37862 .

H. W. Engels , H. G. Pirkl , R. Albers , R. W. Albach , J. Krause , A. Hoffmann , J. Dormish . Polyurethanes:versatile materials and sustainable problem solvers for today's challenges . Angew. Chem. Int. Ed. , 2013 . 52 ( 36 ): 9422 - 9441 . DOI: 10.1002/anie.v52.36 http://doi.org/10.1002/anie.v52.36 .

Y. Wang , Y. Bai . The functionalization of fluoroelastomers:approaches, properties, and applications . RSC Adv. , 2016 . 6 ( 59 ): 53730 - 53748 . DOI: 10.1039/C6RA05816G http://doi.org/10.1039/C6RA05816G .

H. Yeganeh , M. A. Shamekhi . Poly(urethane-imide-imide), a new generation of thermoplastic polyurethane elastomers with enhanced thermal stability . Polymer , 2004 . 45 ( 2 ): 359 - 365 . DOI: 10.1016/j.polymer.2003.11.006 http://doi.org/10.1016/j.polymer.2003.11.006 .

P. I. Kordomenos , J. E. Kresta , K. C. Frisch . Kinetics of the thermal dissociation of model urethane, oxazolidone, and isocyanurate block copolymers . Macromolecules , 1987 . 20 ( 9 ): 2077 - 2083 . DOI: 10.1021/ma00175a006 http://doi.org/10.1021/ma00175a006 .

Y. Ma , Q. Y. Tang , J. Zhu , L. H. Wang , C. Yao . Fluorescent and thermal properties of siloxane-polyurethanes based on 1, 8-naphthalimide . Chin. Chem. Lett. , 2014 . 25 ( 5 ): 680 - 686 . DOI: 10.1016/j.cclet.2014.01.048 http://doi.org/10.1016/j.cclet.2014.01.048 .

A. Kausar , S. Zulfiqar , M. I. Sarwar . High performance segmented polyurethanes derived from a new aromatic diisocyanate and polyol . Polym. Degrad. Stab. , 2013 . 98 ( 1 ): 368 - 686 . DOI: 10.1016/j.polymdegradstab.2012.09.004 http://doi.org/10.1016/j.polymdegradstab.2012.09.004 .

C. E. Yuan , M. Z. Rong , M. Q. Zhang . Self-healing polyurethane elastomer with thermally reversible alkoxyamines as crosslinkages . Polymer , 2014 . 55 ( 7 ): 1782 - 1791 . DOI: 10.1016/j.polymer.2014.02.033 http://doi.org/10.1016/j.polymer.2014.02.033 .

Y. Wang , K. Kou , Z. Li , G. Wu , Y. Zhang , A. Feng . Synthesis, characterization, and thermal properties of benzoxazine monomers containing allyl groups . High. Perform. Polym. , 2016 . 28 ( 10 ): 1235 - 1245 . DOI: 10.1177/0954008315623353 http://doi.org/10.1177/0954008315623353 .

I. J. Sugden , D. F. Plant , R. G. Bell . Thermal rearrangement mechanisms in icosahedral carboranes and metallocarboranes . Chem. Commun. , 2013 . 49 ( 10 ): 975 - 977 . DOI: 10.1039/C2CC37520F http://doi.org/10.1039/C2CC37520F .

M. Tsuji . On attempts at generation of carboranyl carbocation . J. Org. Chem. , 2003 . 68 ( 25 ): 9589 - 9597 . DOI: 10.1021/jo035090f http://doi.org/10.1021/jo035090f .

Grimes, R. N., in "Carboranes", Second Edition., Elsevier, New York, 2011, Chapter 9, p. 301

A. F. Armstrong , J. F. Valliant . The bioinorganic and medicinal chemistry of carboranes:from new drug discovery to molecular imaging and therapy . Dalton. Trans. , 2007 . 38 4240 - 4251 . http://www.ncbi.nlm.nih.gov/pubmed/17893811 http://www.ncbi.nlm.nih.gov/pubmed/17893811 , .

T. Xing , K. Zhang . Syntheses of novel soluble carborane polyimides with ultrahigh thermal stability . Polym. Int. , 2015 . 64 ( 12 ): 1715 - 1721 . DOI: 10.1002/pi.2015.64.issue-12 http://doi.org/10.1002/pi.2015.64.issue-12 .

X. Huang , Q. Zhang , Z. Meng , J. Gu , X. Jia , K. Xi . Greatly enhanced thermo-oxidative stability of polybenzoxazine thermoset by incorporation of m -carborane . J. Polym. Sci., Part A:Polym. Chem. , 2015 . 53 ( 8 ): 973 - 980 . DOI: 10.1002/pola.v53.8 http://doi.org/10.1002/pola.v53.8 .

M. C. Parrott , J. F. Valliant , A. Adronov . Thermally induced phase transition of carborane-functionalized aliphatic polyester dendrimers in aqueous media . Langmuir , 2006 . 22 ( 12 ): 5251 - 5255 . DOI: 10.1021/la0529355 http://doi.org/10.1021/la0529355 .

X. Men , Y. Cheng , G. Chen , J. Bao , J. Yang . Curing behaviour and thermal properties of epoxy resin cured byaromatic diamine with carborane . High. Perform. Polym. , 2015 . 27 ( 4 ): 497 - 509 . DOI: 10.1177/0954008314557049 http://doi.org/10.1177/0954008314557049 .

S. C. Qi , G. Han , H. R. Wang , N. Li , X. A. Zhang , S. L. Jiang , Y. F. Lu . Synthesis and characterization of carborane bisphenol resol phenolic resins with ultrahigh char yield . Chinese J. Polym. Sci. , 2015 . 33 ( 11 ): 1606 - 1617 . DOI: 10.1007/s10118-015-1712-1 http://doi.org/10.1007/s10118-015-1712-1 .

Y. Luo , Y. Lu , N. Li , Y. Li , X. Zhang , S.C. Qi . Synthesis, structure, and properties of segmented carborane-containing polyurethanes . Appl. Polym. Sci. , 2015 . 132 ( 28 ): 42227 - 42238 . http://www.chemie.de/fachpublikationen/787961/synthesis-structure-and-properties-of-segmented-carborane-containing-polyurethanes.html?WT.mc_id=ca0438 http://www.chemie.de/fachpublikationen/787961/synthesis-structure-and-properties-of-segmented-carborane-containing-polyurethanes.html?WT.mc_id=ca0438 , .

Y. M. Jiang , Y. F. Lv , Y. Li , S.C. Qi . Synthesis, characterization and thermal properties of carborane-siloxane polymers . Polym. Mater. Sci. Eng. , 2014 . 30 ( 9 ): 1 - 4 . http://en.cnki.com.cn/Article_en/CJFDTotal-GFZC201409001.htm http://en.cnki.com.cn/Article_en/CJFDTotal-GFZC201409001.htm , .

S. Qi , H. Wang , G. Han , Z. Yang , X. A. Zhang , S. Jiang , Y. Lu . Synthesis, characterization, and curing behavior of carborane-containing benzoxazine resins with excellent thermal and thermo-oxidative stability . J. Appl. Polym. Sci. , 2016 . 133 ( 23 ): 43488 - 43499 . http://www.chemeurope.com/en/publications/925767/synthesis-characterization-and-curing-behavior-of-carborane-containing-benzoxazine-resins-with-excellent-thermal-and-thermo-oxidative-stability.html http://www.chemeurope.com/en/publications/925767/synthesis-characterization-and-curing-behavior-of-carborane-containing-benzoxazine-resins-with-excellent-thermal-and-thermo-oxidative-stability.html , .

J. Li , Y. Lu , Y. Liu , Y. Li , X. Zhang , S. Qi . Synthesis, characterization, curing and properties of carboxyl-terminated liquid fluoropolymers . Polym-Plast. Technol. , 2014 . 53 ( 1 ): 46 - 53 . DOI: 10.1080/03602559.2013.843688 http://doi.org/10.1080/03602559.2013.843688 .

N. Li , F. Zeng , D. Qu , J. Zhang , L. Shao , Y. Bai . Synthesis and characterization of carborane-containing polyester withexcellent thermal and ultrahigh char yield . J. Appl. Polym. Sci. , 2016 . 133 ( 46 ): 44202 - 44213 . http://www.chemeurope.com/en/publications/994157/synthesis-and-characterization-of-carborane-containing-polyester-with-excellent-thermal-and-ultrahigh-char-yield.html http://www.chemeurope.com/en/publications/994157/synthesis-and-characterization-of-carborane-containing-polyester-with-excellent-thermal-and-ultrahigh-char-yield.html , .

Li, J., "Study on functional liquid fluoroelastomer", Thesis, Beijing University of Chemical Technology, 2013

S. Wang , X. Jing , Y. Wang , J. Si . High char yield of aryl boron-containing phenolic resins:the effect of phenylboronic acid on the thermal stability and carbonization of phenolic resins . Polym. Degrad. Stab. , 2014 . 99 1 - 11 . DOI: 10.1016/j.polymdegradstab.2013.12.011 http://doi.org/10.1016/j.polymdegradstab.2013.12.011 .

J. W. Fergus , W. L. Worrell . Silicon-carbide/boron-containing coatings for the oxidation protection of graphite . Carbon , 1995 . 33 ( 4 ): 537 - 543 . DOI: 10.1016/0008-6223(94)00178-3 http://doi.org/10.1016/0008-6223(94)00178-3 .

C. Martin , J. C. Ronda , V. Cadiz . Boron-containing novolac resins as flame retardant materials . Polym. Degrad. Stab. , 2006 . 91 ( 4 ): 747 - 754 . DOI: 10.1016/j.polymdegradstab.2005.05.025 http://doi.org/10.1016/j.polymdegradstab.2005.05.025 .

Y. Liu , G. Hsiue , Y. Chiu , R. Jeng . Phosphorus containing epoxy for flame retardant Ⅱ:Curing reaction of bis-(3-glycidyloxy) phenylphosphine oxide . J. Appl. Polym. Sci. , 2015 . 61 ( 10 ): 1789 - 1796 . http://www.ingentaconnect.com/content/bpl/app/1996/00000061/00000010/art00020 http://www.ingentaconnect.com/content/bpl/app/1996/00000061/00000010/art00020 , .

M. Dogan , A. Yilmaz , E. Bayraml . Synergistic effect of boron containing substances on flame retardancy and thermal stability of intumescent polypropylene composites . Polym. Degrad. Stab. , 2010 . 95 ( 12 ): 2584 - 2588 . DOI: 10.1016/j.polymdegradstab.2010.07.033 http://doi.org/10.1016/j.polymdegradstab.2010.07.033 .

R. B. King . Three-dimensional aromaticity in deltahedral boranes and carboranes . Russ. Chem. B , 1993 . 42 ( 8 ): 1283 - 1291 . DOI: 10.1007/BF00699915 http://doi.org/10.1007/BF00699915 .

I. V. Glukhov , K. A. Lyssenko , A. A. Korlyukova. , M. Y. Antipina . Carboranes:chemical concepts derived from the AIM study of the experimental and theoretical electron density distribution functions . Faraday Discuss. , 2007 . 135 203 - 215 . DOI: 10.1039/B605811F http://doi.org/10.1039/B605811F .

N. Li , F. Zeng , Y. Wang , D. Qu , W. Hu , Y. G. Luan , S. Dong , J. J. Zhang , Y. P. Bai . Fluorinated polyurethane based on liquid fluorine elastomer (LFH) synthesis via two-step method:the critical value of thermal resistance and mechanical properties . RSC Adv. , 2017 . 7 30970 - 30978 . DOI: 10.1039/C7RA04509C http://doi.org/10.1039/C7RA04509C .

M. Fan , S. L. Sun , Y. Q. Qiu , X. D. Liu , Z. M. Su . DFT study on the second-order nonlinear optical property of 12-vertex close-carborane derivatives . Int. J. Quantu. Chem. , 2011 . 111 ( 5 ): 1039 - 1042 . DOI: 10.1002/qua.v111.5 http://doi.org/10.1002/qua.v111.5 .

J. Y. Lu , Y. M. Du , H. Wang , J. Y. Li , W. Q. Wang , J. W. Zhang , Y. N. Xue , J. Lv . A novel coronavirus associated with severe acute respiratory syndrome . Syn. Chem. , 2015 . 23 ( 9 ): 883 - 890 . http://www.nejm.org/doi/full/10.1056/NEJMoa030781 http://www.nejm.org/doi/full/10.1056/NEJMoa030781 , .

S. C. Qi , Y. S. Wang , G. Han , Z. Yang , X. A. Zhang , S. L. Jiang , Y. F. Lv . Characterization and high temperature resistance of diglycidyl ether of carborane bisphenol . Acta Polymerica Sinica (in Chinese) , 2015 . ( 8 ): 921 - 926 . http://en.cnki.com.cn/Article_en/CJFDTotal-GFXB201508006.htm http://en.cnki.com.cn/Article_en/CJFDTotal-GFXB201508006.htm , .

Y. Y. Jiang , Y. F. Lv , Y. Li , S.C. Qi . Synthesis, characterization and thermal properties of carborane-siloxane polymers . Polym. Mater. Sci. Eng. , 2014 . 30 ( 9 ): 1 - 4 . http://en.cnki.com.cn/Article_en/CJFDTotal-GFZC201409001.htm http://en.cnki.com.cn/Article_en/CJFDTotal-GFZC201409001.htm , .

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