CN-122011331-A - Preparation method of high-hydrophobicity corrosion-resistant fluorine-containing polyurea material

CN122011331ACN 122011331 ACN122011331 ACN 122011331ACN-122011331-A

Abstract

The invention discloses a preparation method of a fluorine-containing polyurea material with high hydrophobicity and corrosion resistance. The amino-terminated fluoropolymer is used as a raw material to carry out copolymerization reaction with an amino-containing oligomer, an amine compound and an isocyanate compound. Or an aminosilane oligomer and an aminosilane compound may be introduced and reacted with the above-mentioned amino group-containing oligomer or the like. The invention has simple process, mild condition and high efficiency, the fluorine content of the product section reaches more than 25%, the fluorine content of the surface is higher than 50%, and the introduction of fluorine-containing groups ensures that the hydrophobicity and the corrosion resistance of the material are obviously improved on the basis of retaining the original mechanical properties of polyurea. The requirements of long-term reliability and extreme protective performance under extreme working conditions are met, the construction limit caused by the rapid solidification of the traditional polyurea material is broken through, and the dual optimization of the material performance and the process feasibility is realized. The method is widely applied to the fields of marine engineering facility protection, chemical equipment protection, electronic and electrical equipment packaging, aerospace components and the like.

Inventors

LI DONGHAN
SHEN TONGTONG
GU ZHENZHEN
LI WANTONG
ZHAO XIN
LI KE
Chang Xiaohaohan

Assignees

沈阳化工大学

Dates

Publication Date: 20260512
Application Date: 20260325

Claims (10)

1. The preparation method of the fluorine-containing polyurea material with high hydrophobicity and corrosion resistance is characterized by comprising the following steps: (a) Adding a polar organic solvent into the amino-terminated fluorine-containing polymer to prepare the amino-terminated fluorine-containing polymer with the mass concentration of 16-25%, and stirring until the amino-terminated fluorine-containing polymer is completely dissolved; (b) Sequentially adding an amino-containing oligomer, an amine compound and an isocyanate compound into the solution (a) to react under the microwave radiation condition, wherein the microwave power adjustment range is 180-480 kW, the reaction temperature is controlled to be 40-80 ℃, the stirring rotation speed is set to be 150-300 rpm, and the reaction duration is 240-540 minutes; (c) After the reaction is finished, part of the solvent is removed by rotary evaporation, and then the polymer after rotary evaporation is placed in a freeze dryer, and residual solvent is thoroughly removed by low-temperature freezing and vacuum drying. Or in the step (a), after the amino-terminated fluorine-containing polymer is completely dissolved, sequentially adding the aminosilane oligomer and the aminosilane compound into a reaction bottle, and after uniformly stirring, executing the step (b) and the step (c); In the step (b), the molar ratio of the amino group in the amino-terminated fluorine-containing polymer to the oligomer containing the amino group, the isocyanate compound and the amine compound is 1:0.5-2:5-11.5:1-4.
2. The method according to claim 1, wherein the molar ratio of the amino-terminated fluoropolymer to the aminosilane oligomer to the aminosilane compound is 1:0.5 to 1.5:0.5 to 1.5.
3. The method according to claim 1, wherein the amino-terminated fluoropolymer has a number average molecular weight in the range of 0.5X 10 3 ~5×10 4 and contains fluorine atoms at the main chain or side chain carbon atoms and amino groups at the chain end.
4. The method of claim 1, wherein the amino-terminated fluoroolefin copolymer is selected from the group consisting of tetrafluoroethylene-vinylidene fluoride copolymer, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-vinyl fluoride copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, hexafluoroisobutylene-vinylidene fluoride copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, chlorotrifluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoromethyl vinyl ether copolymer, vinylidene fluoride-perfluoromethyl vinyl ether copolymer, perfluoroethyl vinyl ether-tetrafluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene terminal amino copolymer, vinylidene fluoride-perfluoroethyl vinyl ether copolymer, vinylidene fluoride-perfluoropropyl vinyl ether copolymer, trifluoroethylene-perfluoromethyl vinyl ether copolymer, vinylidene fluoride-perfluoromethyl vinyl ether amino copolymer, vinylidene fluoride-tetrafluoroethylene-perfluoroethyl vinyl ether terpolymer, vinylidene fluoride-perfluoromethyl vinyl ether terpolymer, vinylidene fluoride-tetrafluoroethylene-perfluoromethyl vinyl ether terpolymer; Or fluoroolefins and non-fluoroolefin copolymers selected from vinylidene fluoride-ethylene copolymer, chlorotrifluoroethylene-ethylene copolymer, tetrafluoroethylene-propylene copolymer, tetrafluoroethylene-ethylene copolymer, vinylidene fluoride-propylene copolymer, hexafluoropropylene-ethylene copolymer, vinylidene fluoride-butylene copolymer, hexafluoropropylene-butylene copolymer, chlorotrifluoroethylene-vinyl fluoride copolymer, perfluoromethyl vinyl ether-ethylene copolymer, hexafluoropropylene-vinyl fluoride copolymer, hexafluoroisobutylene-vinylidene fluoride copolymer, hexafluoropropylene-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-tetrafluoroethylene-propylene terpolymer.
5. The method according to claim 1, wherein the organic solvent is one or more compound organic solvent systems selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, acetone and ethyl acetate.
6. The method of claim 1, wherein the amine oligomer is one or more of a diamino polyether D-230, a diamino polyether D-400, a diamino polyether D-2000, a diamino polyether D-5000, a monoamine polyether M-600, a monoamine polyether M-1000, a monoamine polyether M-2070, a monoamine polyether M-3000, a modified diamino polyether SD-231, a modified diamino polyether SD-401, and a triamino polyether XTJ-542.
7. The method of claim 1, wherein the aminosilicone oligomer is one or more of an α, ω -bis (3-aminopropyl) polydimethylsiloxane, an α, ω -bis (aminoethylaminopropyl) polydimethylsiloxane, a side chain aminopropyl polydimethylsiloxane, an amino terminated polymethyltrifluoropropyl siloxane, an amino terminated polydimethylsiloxane-polyfluoroalkyl ether block copolymer, an amino terminated polymethylphenyl siloxane, an amino terminated long chain alkyl modified polydimethylsiloxane, an amino terminated epoxy modified polydimethylsiloxane.
8. The method of claim 1, wherein the aminosilane compound is one or more of γ -aminopropyl triethoxysilane, γ -aminopropyl trimethoxysilane, N-phenyl- γ -aminopropyl trimethoxysilane, N-ethyl- γ -aminopropyl trimethoxysilane, bis (γ -trimethoxysilylpropyl) amine, N-aminoethyl- γ -aminopropyl trimethoxysilane.
9. The method according to claim 1, wherein the isocyanate compound is one or more of isophorone diisocyanate, trifluoromethylbenzene isocyanate, hexamethylene diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate, 1, 4-cyclohexane diisocyanate, and lysine diisocyanate.
10. The method of claim 1, wherein the amine compound is one or more of hexamethylenediamine, ethylenediamine, isophoronediamine, metaphenylene diamine, polyetherdiamine, perfluoropolyether diamine, 3 '-difluorobenzidine, 4' -diaminodiphenylmethane, 3 '-dichloro-4, 4' -diaminodiphenylmethane.

Description

Preparation method of high-hydrophobicity corrosion-resistant fluorine-containing polyurea material Technical Field The invention relates to a preparation method of a fluorine-containing polyurea material with high hydrophobicity and corrosion resistance. Background The fluorine-containing polyurea material combines the advantages of the fluorine-containing polymer and the polyurea, and the introduction of the fluorine-containing group endows the polyurea with more excellent hydrophobicity, corrosion resistance and acid and alkali resistance, and simultaneously maintains the advantage of stronger mechanical properties of the polyurea, so that the fluorine-containing polyurea material becomes an indispensable high-performance material in the fields of marine engineering facility protection, chemical equipment protection, electronic and electrical equipment encapsulation, aerospace parts and the like. Research shows that the traditional polyurea material has poor performance under extreme environments. The material is easy to absorb water in a high humidity environment, the invasion of water molecules can damage the internal structure of the material, and the swelling and deformation are caused, so that the mechanical property and chemical stability of the material are reduced, and the service life of the material is shortened. Besides the defects of long-term weather resistance and corrosion resistance, the traditional polyurea material has obvious defects in the aspect of construction application, and the problem of too high reaction speed is particularly remarkable. Polyurea materials generally consist of an a-component (isocyanate component) and a B-component (amino compound component, including amino oligomers, amine compounds) which exhibit very short gel times during mixing. Although the characteristic gives advantages of rapid molding of the polyurea material, the polyurea material also has extremely high requirements on construction equipment and operation process, and the uniformity and compactness of the coating are difficult to ensure in complex surface or large-area operation. To systematically overcome the above-mentioned multiple limitations, researchers have begun to explore molecular-level modification designs for polyurea materials. Disclosure of Invention In order to overcome the defects, the invention synthesizes the fluorine-containing polyurea material with high hydrophobicity and corrosion resistance. The invention takes amino-terminated fluorine-containing polymer as raw material, and under mild condition, the amino-terminated fluorine-containing polymer is dissolved in organic solvent to carry out copolymerization reaction with amino-containing oligomer, amine compound and isocyanate compound. As a system expansion, aminosilane oligomer and aminosilane compound can be further introduced into the raw material system, and then the aminosilane oligomer and the components containing amino groups react to finally obtain the fluorine-containing polyurea material. The preparation process has the characteristics of mild conditions and high operation efficiency, and enhances the hydrophobicity and corrosion resistance of the material by improving the fluorine content. The obtained product is expected to be widely applied to the fields of marine engineering facility protection, chemical equipment protection, electronic and electrical appliance packaging, aerospace parts and the like by virtue of excellent comprehensive performance. The requirements of long-term reliability and extreme protective performance under extreme working conditions are met, the construction limit caused by the rapid solidification of the traditional polyurea material is broken through, and the dual optimization of the material performance and the process feasibility is realized. The invention aims at realizing the following technical scheme: the invention relates to a preparation method of a fluorine-containing polyurea material with high hydrophobicity and corrosion resistance, which specifically comprises the following steps: (a) Placing the amino-terminated fluorine-containing polymer into a reaction bottle, adding a polar organic solvent, preparing the amino-terminated fluorine-containing polymer with the mass concentration of 16-25%, and stirring the polymer until the polymer is completely dissolved; (b) And sequentially adding an oligomer containing amino, an amine compound and an isocyanate compound into the reaction bottle, and reacting under the condition of microwave radiation, wherein the microwave power adjustment range is 180-480 kW, and preferably 220-440 kW. The reaction temperature is controlled to be 40-80 ℃, preferably 40-60 ℃. The stirring speed is set to 150 to 300 rpm, preferably 180 to 250rpm. The reaction lasts for 240-540 minutes, preferably 300-480 minutes, and the molar ratio of the amino groups in the amino-terminated fluoropolymer to the amino-containing oligomer, isocyanate compound and amin