Anti-corrosive, weatherproof and self-healing polyurethane developed from hydrogenated hydroxyl-terminated polybutadiene toward surface-protective applications

doi:10.1007/s11706-022-0598-4

Front. Mater. Sci.

2022, Vol. 16

Issue (2) : 220598 https://doi.org/10.1007/s11706-022-0598-4

RESEARCH ARTICLE

Anti-corrosive, weatherproof and self-healing polyurethane developed from hydrogenated hydroxyl-terminated polybutadiene toward surface-protective applications

Yuanyuan LIU¹, Xin DU¹, Hui WANG¹, Yu YUAN¹, Liuhe WEI^1,², Xingjiang LIU^1,², Ailing SUN^1,²(

), Yuhan LI^1,²(

)

¹. College of Chemistry and Green Catalysis Center, Zhengzhou University, Zhengzhou 450001, China
². Zhengzhou Key Laboratory of Elastic Sealing Materials, Zhengzhou 450001, China

Download: PDF(5269 KB) HTML
Export: BibTeX | EndNote | Reference Manager | ProCite | RefWorks

Abstract

Self-healing polyurethane (PU) faces aging deterioration due to active dynamic bonds, which remain a challenging predicament for practical use. In this work, a novel strategy is developed to address this predicament by leveraging the hydrophobicity and gas barrier of hydrogenated hydroxyl-terminated polybutadiene (HHPB). The dynamic oxime-carbamate bonds derived from 2, 4-pentanedione dioxime (PDO) enable the elastomer to exhibit surface self-repairability upon applied mild heat and achieve ~99.5% mechanical self-healing efficiency. The mechanical properties remained nearly intact after 30-d exposure to thermal oxidation, xenon lamp, acids, bases, and salts. Gas permeability, positron annihilation lifetime spectroscopy (PALS), and contact angle measurements reveal the pivotal role of gas barrier, free volume, and hydrophobicity in blocking undesirable molecules and ions which effectively protects the elastomer from deterioration. HHPB-PU also exhibits excellent adhesion to steel substrate. The shear strength achieves (3.02 ± 0.42) MPa after heating at 80 °C for 4 h, and (3.06 ± 0.2) MPa after heating at 130 °C for 0.5 h. Regarding its outstanding anti-corrosive and weatherproof performances, this self-healable elastomer is a promising candidate in surface-protective applications.

Keywords hydrogenated hydroxyl-terminated polybutadiene hydrophobicity anti-aging performance self-healing surface protection

Corresponding Author(s): Ailing SUN,Yuhan LI

About author:

Miaojie Yang and Mahmood Brobbey Oppong contributed equally to this work.

Issue Date: 09 May 2022

Cite this article:

Yuanyuan LIU,Xin DU,Hui WANG, et al. Anti-corrosive, weatherproof and self-healing polyurethane developed from hydrogenated hydroxyl-terminated polybutadiene toward surface-protective applications[J]. Front. Mater. Sci., 2022, 16(2): 220598.

URL:

https://academic.hep.com.cn/foms/EN/10.1007/s11706-022-0598-4
https://academic.hep.com.cn/foms/EN/Y2022/V16/I2/220598

Fig.1 (a) Synthetic route of HHPB-PU elastomer. (b) Photographs showing blade-scratched film repaired upon hot airflow (up) and microscopic photos displaying the repair of scratch interface (below).

Fig.2 (a) Stress?strain curves of original HHPB-PU sample and samples healed for 6 h at different temperatures. (b) Self-healing efficiency for 6 h at different temperatures. (c) Stress?strain curves of original and healed HHPB-PU samples with different healing time at 80 °C. (d) Self-healing efficiency with different healing time at 80 °C. (e) ¹H NMR chemical shift monitoring the process of substituting PDO with benzylamine. (f) Evolution of molecular weight of HHPB-PU elastomer during the substitution process. (g) Variable-temperature FTIR monitoring the variation of dynamic bonds. (h) Storage modulus (G′) and loss modulus (G″) of HHPB-PU obtained from rheology measurements at different temperatures.

Fig.3 Transmittance of HHPB-PU elastomer before and after (a) heat aging and (b) xenon aging. Transmittance of PTMEG-PU elastomers before and after (c) heat aging and (d) xenon aging. (e) Transmittance of PPG-PU elastomers before and after heat aging. (f) A photograph showing the PPG-PU film after xenon aging.

Fig.4 Stress?strain curves of HHPB-PU elastomers before and after (a) heat aging and (b) xenon aging. Stress?strain curves of PTMEG-PU elastomers before and after (c) heat aging and (d) xenon aging. (e) GPC information of PTMEG-PU. (f) Photographs showing PPG-PU specimens before and after heat aging.

Fig.5 Stress?strain curves of HHPB-PU specimens before and after soaking in (a) 5% NaOH, (b) 5% H₂SO₄ and (c) 5% NaCl solution. (d) Photographs displaying appearance of pristine and corroded HHPB-PU specimens. Stress?strain curves of PTMEG-PU specimens before and after soaking in (e) 5% NaOH, (f) 5% H₂SO₄ and (g) 5% NaCl solution. (h) Photographs displaying appearance of pristine and corroded PTMEG-PU specimens.

Fig.6 (a) Pressure plotting to time from gas permeability measurements. (b) One-dimensional (1D) SAXS results and (c) two-dimensional (2D) SAXS images. (d) Photographs showing contact angles of HHPB-PU elastomer to 5% H₂SO₄, 5% NaOH and 5% NaCl solutions. (e) Comparison of contact angles for the three elastomers. (f) Comparison of water absorptions for the three elastomers. (g) An illustrative model showing the mechanism of anti-aging corrosion resistance.

Tab.1 PALS results of HHPB-PU, PTMEG-PU and PPG-PU elastomers

Fig.7 (a) Force?displacement curves of HHPB-PU elastomer bonded to different substrates treated at 80 °C for 4 h and (b) corresponding shear strength. (c) Force?displacement curves of HHPB-PU elastomer bonded to different substrates treated at 130 °C for 30 min and (d) corresponding shear strength. (e) Photograph showing scratched HHPB-PU film stuck on paint-coated steel after heat treatment. (f) Shear strength for HHPB-PU film to paint-coated steel.

1	R H Aguirresarobe , S Nevejans , B Reck . et al.. Healable and self-healing polyurethanes using dynamic chemistry. Progress in Polymer Science, 2021, 114 : 101362 https://doi.org/10.1016/j.progpolymsci.2021.101362
2	P Chakma , D Konkolewicz . Dynamic covalent bonds in polymeric materials. Angewantde Chemie International Edition, 2019, 58( 29): 9682– 9695 https://doi.org/10.1002/anie.201813525
3	A D Drozdov , J D Christiansen . Thermo-mechanical behavior of elastomers with dynamic covalent bonds. International Journal of Engineering Science, 2020, 147 : 103200 https://doi.org/10.1016/j.ijengsci.2019.103200
4	J B Hou , X Q Zhang , D Wu . et al.. Tough self-healing elastomers based on the host-guest interaction of polycyclodextrin. ACS Applied Materials & Interfaces, 2019, 11( 12): 12105– 12113 https://doi.org/10.1021/acsami.9b00626
5	S Nevejans , N Ballard , M Fernández . et al.. The challenges of obtaining mechanical strength in self-healing polymers containing dynamic covalent bonds. Polymer, 2019, 179 : 121670 https://doi.org/10.1016/j.polymer.2019.121670
6	Y Peng , Y Yang , Q Wu . et al.. Strong and tough self-healing elastomers enabled by dual reversible networks formed by ionic interactions and dynamic covalent bonds. Polymer, 2018, 157 : 172– 179 https://doi.org/10.1016/j.polymer.2018.09.038
7	Z Wang , S Gangarapu , J Escorihuela . et al.. Dynamic covalent urea bonds and their potential for development of self-healing polymer materials. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2019, 7( 26): 15933– 15943 https://doi.org/10.1039/C9TA02054C
8	F Li , Z Xu , H Hu . et al.. A polyurethane integrating self-healing, anti-aging and controlled degradation for durable and eco-friendly E-skin. Chemical Engineering Journal, 2021, 410 : 128363 https://doi.org/10.1016/j.cej.2020.128363
9	Z Liu , P Hong , Z Huang . et al.. Self-healing, reprocessing and 3D printing of transparent and hydrolysis-resistant silicone elastomers. Chemical Engineering Journal, 2020, 387 : 124142 https://doi.org/10.1016/j.cej.2020.124142
10	Y Nurhamiyah , A Amir , M Finnegan . et al.. Wholly biobased, highly stretchable, hydrophobic, and self-healing thermoplastic elastomer. ACS Applied Materials & Interfaces, 2021, 13( 5): 6720– 6730 https://doi.org/10.1021/acsami.0c23155
11	L Zhang , H Xiong , Q Wu . et al.. Constructing hydrophobic protection for ionic interactions toward water, acid, and base-resistant self-healing elastomers and electronic devices. Science China Materials, 2021, 64( 7): 1780– 1790 https://doi.org/10.1007/s40843-020-1558-6
12	P Galvez , S Lopez de Armentia , J Abenojar . et al.. Effect of moisture and temperature on thermal and mechanical properties of structural polyurethane adhesive joints. Composite Structures, 2020, 247 : 112443 https://doi.org/10.1016/j.compstruct.2020.112443
13	K Yang , Z Ge , M Zhang . et al.. Deep eutectic solvent based adhesive with dynamic adhesion, water-resistant and NIR-responsive retrieval properties. Chemical Engineering Journal, 2022, 439 : 135646 https://doi.org/10.1016/j.cej.2022.135646
14	T Li , Z Xie , J Xu . et al.. Design of a self-healing cross-linked polyurea with dynamic cross-links based on disulfide bonds and hydrogen bonding. European Polymer Journal, 2018, 107 : 249– 257 https://doi.org/10.1016/j.eurpolymj.2018.08.005
15	L Lyu , D Li , Y Chen . et al.. Dynamic chemistry based self-healing of asphalt modified by diselenide-crosslinked polyurethane elastomer. Construction & Building Materials, 2021, 293 : 123480 https://doi.org/10.1016/j.conbuildmat.2021.123480
16	M Zhang , F Zhao , Y Luo . Self-healing mechanism of microcracks on waterborne polyurethane with tunable disulfide bond contents. ACS Omega, 2019, 4( 1): 1703– 1714 https://doi.org/10.1021/acsomega.8b02923
17	B Xu , F Han , X Pei . et al.. Concise and efficient self-healing cross-linked polyurethanes via the blocking/deblocking reaction of oxime urethanes. Industrial & Engineering Chemistry Research, 2021, 60( 30): 11095– 11105 https://doi.org/10.1021/acs.iecr.1c01446
18	L Zhang , Z Liu , X Wu . et al.. A highly efficient self-healing elastomer with unprecedented mechanical properties. Advanced Materials, 2019, 31( 23): 1901402 https://doi.org/10.1002/adma.201901402
19	Z Liu , L Zhang , Q Guan . et al.. Biomimetic materials with multiple protective functionalities. Advanced Functional Materials, 2019, 29( 28): 1901058 https://doi.org/10.1002/adfm.201901058
20	F Ji , J Li , G Zhang . et al.. Alkaline monomer for mechanical enhanced and self-healing hydrogels based on dynamic borate ester bonds. Polymer, 2019, 184 : 121882 https://doi.org/10.1016/j.polymer.2019.121882
21	X Lei , Y Huang , S Liang . et al.. Preparation of highly transparent, room-temperature self-healing and recyclable silicon elastomers based on dynamic imine bond and their ion responsive properties. Materials Letters, 2020, 268 : 127598 https://doi.org/10.1016/j.matlet.2020.127598
22	P Wang , L Yang , B Dai . et al.. A self-healing transparent polydimethylsiloxane elastomer based on imine bonds. European Polymer Journal, 2020, 123 : 109382 https://doi.org/10.1016/j.eurpolymj.2019.109382
23	H Zhang , D Wang , W Liu . et al.. Recyclable polybutadiene elastomer based on dynamic imine bond. Journal of Polymer Science Part A: Polymer Chemistry, 2017, 55( 12): 2011– 2018 https://doi.org/10.1002/pola.28577
24	B Gyarmati , Á Némethy , A Szilágyi . Reversible disulphide formation in polymer networks: a versatile functional group from synthesis to applications. European Polymer Journal, 2013, 49( 6): 1268– 1286 https://doi.org/10.1016/j.eurpolymj.2013.03.001
25	O R Cromwell , J Chung , Z Guan . Malleable and self-healing covalent polymer networks through tunable dynamic boronic ester bonds. Journal of the American Chemical Society, 2015, 137( 20): 6492– 6495 https://doi.org/10.1021/jacs.5b03551
26	F Xie , T Zhang , P Bryant . et al.. Degradation and stabilization of polyurethane elastomers. Progress in Polymer Science, 2019, 90 : 211– 268 https://doi.org/10.1016/j.progpolymsci.2018.12.003
27	J Kang , D Son , G N Wang . et al.. Tough and water-insensitive self-healing elastomer for robust electronic skin. Advanced Materials, 2018, 30( 13): 1706846 https://doi.org/10.1002/adma.201706846
28	Y Liu , J Zheng , X Zhang . et al.. Mussel-inspired and aromatic disulfide-mediated polyurea-urethane with rapid self-healing performance and water-resistance. Journal of Colloid and Interface Science, 2021, 593 : 105– 115 https://doi.org/10.1016/j.jcis.2021.03.003
29	W B Ying , Z Yu , D H Kim . et al.. Waterproof, highly tough, and fast self-healing polyurethane for durable electronic skin. ACS Applied Materials & Interfaces, 2020, 12( 9): 11072– 11083 https://doi.org/10.1021/acsami.0c00443
30	K J Li , C Wang , T T Zheng . et al.. Towards high performance anti-aging diolefin elastomers based on structure healing strategy. Polymer, 2020, 186 : 122076 https://doi.org/10.1016/j.polymer.2019.122076
31	W Li , X Liu , A Sun . et al.. Exploring piperazine for intrinsic weather-proof, robust and self-healable poly(urethane urea) toward surface and tire protection. Polymer, 2021, 227 : 123829 https://doi.org/10.1016/j.polymer.2021.123829
32	X Liu , X Liu , W Li . et al.. Engineered self-healable elastomer with giant strength and toughness via phase regulation and mechano-responsive self-reinforcing. Chemical Engineering Journal, 2021, 410 : 128300 https://doi.org/10.1016/j.cej.2020.128300
33	Y C Jean . Positron annihilation spectroscopy for chemical analysis: a novel probe for microstructural analysis of polymers. Microchemical Journal, 1990, 42( 1): 72– 102 https://doi.org/10.1016/0026-265X(90)90027-3
34	G Galland , T M Lam . Permeability and diffusion of gases in segmented polyurethanes: structure–properties relations. Journal of Applied Polymer Science, 1993, 50( 6): 1041– 1058 https://doi.org/10.1002/app.1993.070500613
35	M Pegoraro , L Zanderighi , A Penati . et al.. Polyurethane membranes from polyether and polyester diols for gas fractionation. Journal of Applied Polymer Science, 1991, 43( 4): 687– 697 https://doi.org/10.1002/app.1991.070430406
36	K H Hsieh , C C Tsai , S M Tseng . Vapor and gas permeability of polyurethane membranes. Part I. Structure–property relationship. Journal of Membrane Science, 1990, 49( 3): 341– 350 https://doi.org/10.1016/S0376-7388(00)80647-X

[1]	Zai-Meng QIU, Fen ZHANG, Jun-Tong CHU, Yu-Chao LI, Liang SONG. Corrosion resistance and hydrophobicity of myristic acid modified Mg--Al LDH/Mg(OH)₂ steam coating on magnesium alloy AZ31[J]. Front. Mater. Sci., 2020, 14(1): 96-107.
[2]	Zhicun WANG, Xiaoman HAN, Yixi WANG, Kenan MEN, Lin CUI, Jianning WU, Guihua MENG, Zhiyong LIU, Xuhong GUO. Facile preparation of low swelling, high strength, self-healing and pH-responsive hydrogels based on the triple-network structure[J]. Front. Mater. Sci., 2019, 13(1): 54-63.
[3]	Na YI,Shanhu BAO,Huaijuan ZHOU,Yunchuan XIN,Aibin HUANG,Yining MA,Rong LI,Ping JIN. Preparation of microstructure-controllable superhydrophobic polytetrafluoroethylene porous thin film by vacuum thermal-evaporation[J]. Front. Mater. Sci., 2016, 10(3): 320-327.
[4]	Rong-Chang ZENG,Xiao-Ting LI,Zhen-Guo LIU,Fen ZHANG,Shuo-Qi LI,Hong-Zhi CUI. Corrosion resistance of Zn–Al layered double hydroxide/ poly(lactic acid) composite coating on magnesium alloy AZ31[J]. Front. Mater. Sci., 2015, 9(4): 355-365.
[5]	Qian-Feng XU, Jian-Nong WANG, . Superhydrophobic and transparent coatings prepared by self-assembly of dual-sized silica particles[J]. Front. Mater. Sci., 2010, 4(2): 180-188.

Viewed

Full text

Abstract

Cited

Shared

Discussed