CN-122011337-A - Sweat and seawater resistant wearable human body affinity poly (siloxane-urethane) material and preparation method thereof

CN122011337ACN 122011337 ACN122011337 ACN 122011337ACN-122011337-A

Abstract

The invention belongs to the technical field of polyurethane material preparation, and particularly relates to a sweat and seawater resistant wearable human body affinity poly (siloxane-urethane) material and a preparation method thereof. The small-molecule fluorine-containing dihydric alcohol is efficiently prepared through the mercapto-alkene click reaction, is introduced into a polyurethane system in the form of a chain extender, and the surface energy of the material is greatly reduced by utilizing the synergistic effect of fluorine-silicon atoms, so that the problem that the traditional polyurethane material is easy to erode is solved, and meanwhile, the synergistic repair of hydrogen bonds and covalent bonds is realized by introducing a certain dynamic covalent bond, so that the service life and the application field of the polyurethane material are prolonged. The polyurethane designed by the invention has excellent hydrophobic property and self-repairing property, and has good application value and prospect.

Inventors

LI NING
JI XIANGRUI
SHA XIANG
Diao Dongqi
Tong Xinlin
LIU HONGYAN
YANG GUOQUAN
Fan Xiqia
ZENG FANGLEI
TANG ZICHEN

Assignees

常州大学

Dates

Publication Date: 20260512
Application Date: 20260415

Claims (9)

1. A preparation method of sweat and seawater resistant wearable human body affinity poly (siloxane-urethane) material is characterized by comprising the following steps: (1) The fluorine-containing monomer reacts with the dihydric hydroxyl organic matters to prepare micromolecular fluorine-containing dihydric alcohol; (2) Dissolving hydroxyl-terminated polysiloxane and polyalcohol in N, N-dimethylformamide and transferring the mixture into a reaction bottle, dropwise adding isocyanate dissolved in the N, N-dimethylformamide into the reaction bottle by adopting a dropping funnel, and then adding a catalyst to perform catalytic reaction; (3) And (3) cooling the system in the step (2), adding small-molecule fluorine-containing dihydric alcohol and diaminoglyoxime, and continuing to react in a nitrogen atmosphere.
2. The method for preparing the sweat-and seawater-resistant wearable human-friendly poly (siloxane-urethane) material, as claimed in claim 1, characterized in that in the step (1), the preparation method of the small-molecule fluorine-containing dihydric alcohol comprises the steps of adding fluorine-containing monomers, dihydric organic matters and acetone into a beaker for dissolution, adding a photoinitiator, continuously irradiating 1h under ultraviolet light for initiating reaction, and drying the obtained product in a drying oven to obtain the small-molecule fluorine-containing dihydric alcohol.
3. The method for preparing the sweat and seawater resistant wearable human body compatible poly (siloxane-urethane) material according to claim 2, wherein the fluorine-containing monomer is 1H, 2H-perfluoro-1-hexene or 1H, 2H-perfluoro-1-decene, the dihydric hydroxyl organic compound is thioglycerol, and the molar ratio of the fluorine-containing monomer to the dihydric hydroxyl organic compound is 1.05-1.12:1.
4. The method for preparing a sweat and seawater resistant wearable human-friendly poly (siloxane-urethane) material according to claim 2, wherein the photoinitiator is benzoin dimethyl ether, 2-diethoxyacetophenone or 2-hydroxy-2-methylphenyl acetone.
5. The method of preparing a sweat and seawater resistant wearable human-friendly poly (siloxane-urethane) material of claim 1, wherein in step (2), the hydroxyl-terminated polysiloxane is hydroxyl-terminated polydimethylsiloxane and the polyol is polytetrahydrofuran ether glycol.
6. The method for preparing a sweat and seawater resistant wearable human-friendly poly (siloxane-urethane) material according to claim 1, wherein in the step (2), isocyanate is one of toluene diisocyanate, hexamethylene diisocyanate and diphenylmethane diisocyanate, and the molar ratio of polysiloxane, polyol and isocyanate is 0.5-1:1:4.1-5.1.
7. The method of preparing a sweat and seawater resistant wearable human-friendly poly (siloxane-urethane) material of claim 1, wherein in step (3), the catalyst is dibutyl tin dilaurate or stannous octoate.
8. The method for preparing a sweat and seawater resistant wearable human-friendly poly (siloxane-urethane) material according to claim 1, wherein in the step (3), the molar ratio of the small molecule fluorine-containing dihydric alcohol to the diaminoglyoxime to the isocyanate is 1-2:1:4.4-6.
9. A sweat and seawater resistant wearable human-friendly poly (siloxane-urethane) material prepared by the method of claim 1, wherein the poly (siloxane-urethane) material has the following structural formula: 。

Description

Sweat and seawater resistant wearable human body affinity poly (siloxane-urethane) material and preparation method thereof Technical Field The invention belongs to the technical field of polyurethane material preparation, and particularly relates to a sweat and seawater resistant wearable human body affinity poly (siloxane-urethane) material and a preparation method thereof. Background The polyurethane material is a polymer material with very wide application, can realize the property regulation and control of the material by adjusting the composition of raw materials, has the high elasticity and wear resistance of rubber and the processing formability of plastic, and is widely applied to the fields of paint, adhesive and the like, thus being an intangible universal material. However, polyurethane materials have poor hydrophobic properties due to their hydrophilic urethane linkages, and are susceptible to attack by aqueous solutions. In order to solve the problem, a micro/nano structure is constructed by adding nano filler to improve the hydrophobic property of the material, however, the method has the phenomenon of agglomeration caused by insufficient filler dispersibility, so that the mechanical property of the material is reduced, the microphase separation structure of the material is damaged, and the service life of the material is greatly reduced. Therefore, hydrophobic performance of the material is improved by introducing hydrophobic groups, for example Sun Lian, and the like, self-made high-performance fluorinated polyurethane and modified nano SiO 2 are taken as raw materials to prepare a high-wear-resistance superhydrophobic coating, hong Cheng Yu is prepared by introducing fluorinated siloxane (HTFSi) modified monomers containing two hydrophobic units of organic silicon and organic fluorine into a polyether aqueous polyurethane system through polycondensation reaction to prepare the fluorinated siloxane modified aqueous polyurethane material, and the material has the flexibility of a siloxane chain segment and low free energy characteristic of fluoroalkyl, so that a hydrophobic outer layer with low surface energy is formed on the surface of the material, and the hydrophobicity and the water resistance of the material are improved. However, since the price of fluorinated siloxanes is relatively high and the processing procedure is relatively cumbersome, it is difficult to achieve mass production. Disclosure of Invention Aiming at the defects of the prior art, the invention provides a sweat and seawater resistant wearable human body affinity poly (siloxane-urethane) material and a preparation method thereof, and solves the problem that most polyurethanes are easy to be corroded by aqueous solution. The prepared poly (siloxane-urethane) material is based on the synergistic effect of fluorine and silicon atoms, so that the material has good hydrophobic property and thermal stability, and meanwhile, certain self-repairing property is considered, and the service performance and service life of the material are ensured. The invention adopts the following technical scheme: the sweat and seawater resistant wearable human body compatible poly (siloxane-urethane) material is prepared by reacting hydroxyl terminated polysiloxane, polyalcohol and isocyanate to obtain prepolymer, and then adding small molecule fluorine-containing dihydric alcohol to react with diaminoglyoxime, and the specific preparation method comprises the following steps: (1) Adding fluorine-containing monomers, dihydric organic matters and acetone into a beaker, dissolving, adding a photoinitiator, continuously irradiating for 1 h under ultraviolet light to initiate reaction, and putting the obtained product into an oven to be dried to obtain the micromolecular fluorine-containing dihydric alcohol. Wherein the fluorine-containing monomer is 1H, 2H-perfluoro-1-hexene or 1H, 2H-perfluoro-1-decene, the dihydric hydroxyl organic matter is thioglycerol, the photoinitiator is benzoin dimethyl ether, 2-diethoxyacetophenone or 2-hydroxy-2-methyl phenyl acetone, the molar ratio of the fluorine-containing monomer to the dihydric hydroxyl organic matter is 1.05-1.12:1, and the photoinitiator accounts for 0.5% of the total mass of the raw materials. (2) Placing hydroxyl-terminated polysiloxane and polyol into an oven to remove water by 2h, dissolving the hydroxyl-terminated polysiloxane and polyol into N, N-dimethylformamide after water removal, adding the mixture into a three-necked flask filled with nitrogen, dropwise adding isocyanate dissolved in the N, N-dimethylformamide into the flask by adopting a dropping funnel, adding a catalyst and an organic solvent, and controlling the stirring speed to be 120-180 r/min to enable the mixture to react for 2 hours at 70-80 ℃ to obtain the viscous isocyanate-terminated polyurethane prepolymer. The hydroxyl-terminated polysiloxane is hydroxyl-terminated polydimethylsiloxane, the polyol is polytetrahydrofura