CN114752246B - Hollow multi-shell core-shell material, preparation method thereof and explosion-proof polyurea - Google Patents

Hollow multi-shell core-shell material, preparation method thereof and explosion-proof polyurea Download PDF

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CN114752246B
CN114752246B CN202210347492.6A CN202210347492A CN114752246B CN 114752246 B CN114752246 B CN 114752246B CN 202210347492 A CN202210347492 A CN 202210347492A CN 114752246 B CN114752246 B CN 114752246B
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zinc
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王宝柱
李永岗
苏坤
王昊翔
张天华
刘丽媛
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Qingdao Air++ New Materials Co ltd
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Abstract

The invention provides a hollow multi-shell core-shell material, which comprises hollow multi-shell zinc-nickel oxide microspheres and ferric hydroxide nanowires positioned on the surfaces of the hollow multi-shell zinc-nickel oxide microspheres. In the invention, the multistage shell structure has good buffering effect on stress, has stronger rigidity and strength in hollow structural materials under the micrometer scale, can bear higher load stress, and can also play a role in transmitting force when a composite material sample is acted by external force, thereby generating silver lines and deformation, absorbing energy in a part of acting force process to prevent the generation and expansion of destructive cracks, and finally realizing the aims of toughening and enhancing the mechanical properties of the composite material. The growth of the iron oxyhydroxide nanowire avoids the aggregation of the metal oxide microsphere with a hollow structure, and in addition, the iron oxyhydroxide can react with the active group of the polyurea, so that the performance of the composite material is improved.

Description

Hollow multi-shell core-shell material, preparation method thereof and explosion-proof polyurea
Technical Field
The invention relates to the technical field of coatings, in particular to a hollow multi-shell core-shell material, a preparation method thereof and explosion-proof polyurea.
Background
The spray polyurea material has the characteristics of no solvent, environmental protection, high mechanical strength, quick construction and the like, and is widely applied to the fields of submarine pipelines, underground pipeline corrosion prevention, storage tank corrosion prevention, concrete protection, water prevention, military skin, chassis protection and the like. The coating is applied to the field of military anti-bullet and anti-explosion protection materials, and besides the coating is required to have ultrahigh physical strength, the coating is required to have good tear resistance under high-speed impact, but the conventional polyurea product is difficult to meet the requirements.
The polyurea has multiple formulas and wide application fields, and different formulas and preparation methods are suitable for the application fields according to the application of the polyurea. The current conventional solutions are to add special fillers to polyurea resin systems or to use pure polyurea systems and to improve performance by increasing the hard segment content. The physical blending method has poor dispersibility, polyurea is difficult to spray after filler is added, the filler is excessively added, the filler and the resin are easily separated by the material under high-speed impact, and the strength of the coating film is sharply reduced under high-speed impact; the hardness of the material is greatly improved although the strength of the material is improved by increasing the hard segment content of the resin, so that the low-temperature flexibility of the material is poor, and the material loses the anti-explosion effect in a low-temperature environment.
Disclosure of Invention
The invention aims to provide a hollow multi-shell core-shell material, which can improve the low-temperature flexibility of a polyurea material when being used as a polyurea filler, thereby improving the anti-bouncing and anti-explosion effects at low temperature.
The invention provides a hollow multi-shell core-shell material, which comprises hollow multi-shell zinc-nickel oxide microspheres and ferric hydroxide nanowires positioned on the surfaces of the hollow multi-shell zinc-nickel oxide microspheres.
Preferably, the hollow multi-shell zinc-nickel oxide microsphere is a hollow 4-shell zinc-nickel oxide microsphere.
Preferably, the molar ratio of zinc to nickel in the hollow multi-shell zinc-nickel oxide microsphere is 1:1.
Preferably, the granularity of the hollow multi-shell zinc-nickel oxide microsphere is 200-1000 nm.
Preferably, the mass ratio of the hollow multi-shell zinc-nickel oxide microspheres to the iron oxyhydroxide nanowires is 2:1.
The invention provides a preparation method of a hollow multi-shell core-shell material, which comprises the following steps:
carrying out esterification reaction on 2-methylimidazole and citric acid to obtain imidazole ester;
mixing the imidazole ester with soluble zinc salt and soluble nickel salt for loading to obtain zinc-nickel@imidazole ester composite phase microspheres;
drying the zinc-nickel@imidazole ester composite phase microspheres to obtain zinc-nickel bimetallic powder;
performing heat treatment on the zinc-nickel bimetallic powder in air to obtain hollow multi-shell zinc-nickel oxide microspheres;
dispersing the hollow multi-shell zinc-nickel oxide microspheres in ferrous salt aqueous solution to perform in-situ oxidation and hydrolysis reaction to obtain the hollow multi-shell core-shell material.
Preferably, the 2-methylimidazole is 10-20 parts by mass, the citric acid is 10-20 parts by mass, the soluble nickel salt is 5-10 parts by mass, the soluble zinc salt is 5-10 parts by mass, and the ferrous salt is 5-10 parts by mass.
Preferably, the esterification reaction time is 2 hours;
the mixing time is 12h, and the loading time is 12h;
the temperature of the heat treatment is 600 ℃, and the heat preservation time of the heat treatment is 2h.
Preferably, the time of the in situ oxidation and hydrolysis reaction is 20 hours.
The invention provides an explosion-proof polyurea which comprises a component A and a component B and is characterized by comprising the following components in parts by mass: 50-100 parts of polyol, 10-30 parts of hollow multi-shell core-shell material and 150-250 parts of isocyanate, wherein the hollow multi-shell core-shell material is the hollow multi-shell core-shell material according to the technical scheme or the hollow multi-shell core-shell material obtained by the preparation method according to the technical scheme;
the component B comprises the following components in parts by mass: 30 to 60 parts of amino-terminated polyether, 20 to 50 parts of polyol, 1 to 2 parts of coupling agent, 20 to 40 parts of chain extender, 0 to 1 part of catalyst, 1 to 5 parts of water scavenger and 1 to 5 parts of color paste.
The invention provides a hollow multi-shell core-shell material, which comprises hollow multi-shell zinc-nickel oxide microspheres and ferric hydroxide nanowires positioned on the surfaces of the hollow multi-shell zinc-nickel oxide microspheres. In the invention, the multistage shell structure has good buffering effect on stress, has stronger rigidity and strength in hollow structural materials under the micrometer scale, can bear higher load stress, and can also play a role in transmitting force when a composite material sample is acted by external force, thereby generating silver lines and deformation, absorbing energy in a part of acting force process to prevent the generation and expansion of destructive cracks, and finally realizing the aims of toughening and enhancing the mechanical properties of the composite material. Compared with solid nano particles, the hollow multi-shell microsphere has lower density, larger area of surface/interface stress effect, and higher rigidity and strength due to the multi-stage stress buffering effect, so that the hollow multi-shell microsphere can show better mechanical property for the composite material, and the mechanical property of the polyurea material is improved when the hollow multi-shell microsphere is used for the polyurea material. Furthermore, the growth of the iron oxyhydroxide nanowires avoids the agglomeration of the metal oxide microspheres with hollow structures. In addition, the hollow metal oxide microsphere is an inorganic material, is slightly influenced by low-temperature change, has long length, can react with active groups of polyurea to form a chemical single bond, can rotate freely in space, and improves the low-temperature flexibility of a high-molecular material after reacting with the polyurea. The surface modification is not only beneficial to the uniform dispersion of the hollow multi-shell bimetallic oxide microsphere in the resin matrix, but also can enhance the effective combination of organic/inorganic two phases. In addition, the physical properties of the polyurea, such as tensile properties, tear resistance and elongation at break, can be improved by hydrogen bonding with polar groups in the polyurea or by physical crosslinking. The chemical reaction is different from modification in a physical blending mode, the spraying construction effect of polyurea is not affected, and the solid filler can not block the gun.
Drawings
FIG. 1 is a partial transmission electron microscope image of a core-shell material obtained in example 1 of the present invention;
FIG. 2 is a view of a particle-bulk transmission electron microscope of the core-shell material obtained in example 1 of the present invention;
FIG. 3 is a transmission electron microscope image of the core-shell material obtained in comparative example 3 of the present invention.
Detailed Description
The invention provides a hollow multi-shell core-shell material, which comprises hollow multi-shell zinc-nickel oxide microspheres and ferric hydroxide nanowires positioned on the surfaces of the hollow multi-shell zinc-nickel oxide microspheres.
The core of the hollow multi-layer core-shell material provided by the invention is a hollow multi-shell zinc-nickel oxide microsphere, the multi-layer shell structure can play a good role in buffering stress, and the hollow structure under the micrometer scale has stronger mechanical property. Compared with solid nano particles, the hollow multi-shell zinc-nickel oxide microsphere has lower density, larger surface/interface stress effect area and higher rigidity and strength due to the multi-stage stress buffering effect. The hollow multi-shell zinc-nickel oxide microsphere has very strong rigidity and strength, when being used as a filler to be compounded into a high polymer material, the hollow multi-shell zinc-nickel oxide microsphere can bear higher load stress, and simultaneously, when a composite material sample is acted by external force, the hollow multi-shell zinc-nickel oxide microsphere can also play a role in transferring force, thereby generating silver lines and deformation, absorbing energy in a part of acting force process to prevent the generation and expansion of destructive cracks, and finally realizing the aim of toughening and enhancing the mechanical property of the composite material. The iron oxyhydroxide nanowire wrapped outside the core can avoid aggregation of the zinc-nickel oxide microsphere, can react with active groups of polyurea when used as a polyurea coating filler, is favorable for uniform dispersion of the zinc-nickel oxide microsphere, and can effectively combine inorganic filler and an organic matrix through chemical bonding and physical adsorption, thereby improving the properties of the polyurea coating, such as tensile property, tearing resistance and elongation at break.
The hollow multi-shell core-shell material provided by the invention comprises hollow multi-shell zinc-nickel oxide microspheres, and the molar ratio of zinc to nickel in the hollow multi-shell zinc-nickel oxide microspheres is preferably 1:1. In one embodiment of the invention, the multi-shell zinc-nickel oxide microspheres are preferably 4-shell zinc-nickel oxide microspheres. In the present invention, the particle size of the hollow multi-shell zinc nickel oxide microsphere is preferably 200 to 1000nm, and may be specifically 200, 300, 400, 500, 600, 700, 800, 900 or 1000nm in embodiments. In the invention, the density of the hollow multi-shell zinc-nickel oxide microsphere is preferably 0.5g/cm 3 。
The hollow multi-shell core-shell material provided by the invention comprises a hydroxyl ferric oxide nanowire positioned on the surface of the hollow multi-shell zinc-nickel oxide microsphere. In the invention, the mass ratio of the hollow multi-shell zinc-nickel oxide microsphere to the iron oxyhydroxide nanowire is preferably 2:1. In the present invention, the diameter of the iron oxyhydroxide nanowire is preferably 30nm, and the length is preferably 300nm.
The invention provides a preparation method of the hollow multi-shell core-shell material, which comprises the following steps:
carrying out esterification reaction on 2-methylimidazole and citric acid to obtain imidazole ester;
mixing the imidazole ester with soluble zinc salt and soluble nickel salt for loading to obtain zinc-nickel@imidazole ester composite phase microspheres;
drying the zinc-nickel@imidazole ester composite phase microspheres to obtain zinc-nickel bimetallic powder;
performing heat treatment on the zinc-nickel bimetallic powder in air to obtain hollow multi-shell zinc-nickel oxide microspheres;
dispersing the hollow multi-shell zinc-nickel oxide microspheres in ferrous salt aqueous solution to perform in-situ oxidation and hydrolysis reaction to obtain the hollow multi-shell core-shell material.
The invention carries out esterification reaction on 2-methylimidazole and citric acid to obtain imidazole ester. In the present invention, the esterification reaction is carried out in a solvent system, preferably methanol. In one embodiment of the present invention, 2-methylimidazole is preferably dissolved in methanol to give a 2-methylimidazole solution; and adding citric acid into the 2-methylimidazole solution to perform esterification reaction to obtain imidazole ester. In the present invention, the 2-methylimidazole, methanol and citric acid are preferably 10 to 20 parts by mass, 100 parts by mass and 10 to 20 parts by mass, respectively. In a specific embodiment of the present invention, the mass part of the 2-methylimidazole may be specifically 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 parts; the citric acid can be specifically 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 parts by mass.
In the present invention, the esterification reaction is preferably carried out at room temperature; the time of the esterification reaction is preferably 2 hours. In the examples of the present invention, the esterification reaction is preferably carried out under stirring, and the method of stirring is not particularly limited, and stirring means well known to those skilled in the art, such as magnetic stirring, may be employed.
And mixing the imidazole ester with soluble zinc salt and soluble nickel salt for loading to obtain the zinc-nickel@imidazole ester composite phase microsphere. After the esterification reaction, the invention preferably does not carry out post-treatment, and the obtained esterification reaction feed liquid is continuously reacted. In a specific embodiment of the invention, after the esterification reaction, soluble zinc salt and soluble nickel salt are added into the obtained esterification reaction feed liquid to carry out loading.
In the present invention, the soluble zinc salt is preferably zinc nitrate and the soluble nickel salt is preferably nickel nitrate. In the present invention, the soluble zinc salt is preferably 5 to 10 parts by mass, and may be specifically 5, 6, 7, 8, 9 or 10 parts by mass in the embodiment of the present invention. In the present invention, the soluble nickel salt is preferably 5 to 10 parts by mass, and may be specifically 5, 6, 7, 8, 9 or 10 parts in the embodiment of the present invention.
In the present invention, the load is preferably stirred before standing. In an embodiment of the invention, the loading is performed at room temperature; the stirring time is preferably 12 hours, and the standing time is preferably 12 hours. The stirring method of the present invention is not particularly limited, and stirring means well known to those skilled in the art, such as magnetic stirring, may be employed.
After the loading, the method preferably carries out solid-liquid separation on the obtained loading system, and the obtained precipitate is washed to obtain the zinc-nickel@imidazole ester composite phase microsphere. The method of the present invention is not particularly limited, and may be a solid-liquid separation method known to those skilled in the art, such as centrifugation. In the present invention, the washing is preferably methanol washing, preferably 3 times.
After the zinc-nickel@imidazole ester composite phase microspheres are obtained, the zinc-nickel@imidazole ester composite phase microspheres are dried to obtain zinc-nickel bimetallic powder. In the present invention, the drying is preferably vacuum drying, the temperature of the vacuum drying is preferably 60 ℃, and the time of the vacuum drying is preferably 12 hours.
And after the zinc-nickel bimetallic powder is obtained, carrying out heat treatment on the zinc-nickel bimetallic powder in air to obtain the hollow multi-shell zinc-nickel oxide microsphere. The apparatus used for the heat treatment is not particularly limited, and heat treatment apparatuses well known to those skilled in the art may be used, for example, a tube furnace may be used, and in particular, in one embodiment, the zinc-nickel bimetal powder is placed in an alumina boat and transferred to the tube furnace.
In the present invention, the temperature of the heat treatment is preferably 600 ℃, and the rate of raising the temperature to the temperature of the heat treatment is preferably 5 ℃/min; the holding time of the heat treatment is preferably 2 hours. In the invention, a framework (the structural schematic diagram is shown as a formula I) of a shell layer is generated by air atmosphere heat treatment, zinc nitrate and nickel nitrate are oxidized into zinc oxide and nickel oxide to be loaded on the framework, and the non-uniform shrinkage caused by the unbalanced heat treatment leads the metal oxide to be separated in the shell layer, so that the hollow multi-shell zinc-nickel oxide microsphere is finally obtained.
Figure BDA0003577374980000061
In the formula I, M represents metal.
After the heat treatment, the obtained heat treatment product is preferably naturally cooled to obtain the hollow multi-shell zinc-nickel oxide microsphere.
After the hollow multi-shell zinc-nickel oxide microspheres are obtained, dispersing the hollow multi-shell zinc-nickel oxide microspheres in ferrous salt aqueous solution to perform in-situ oxidation and hydrolysis reaction to obtain the hollow multi-shell core-shell material. In the present invention, the ferrous salt is preferably ferrous sulfate. In the present invention, the ferrous salt is preferably 5 to 10 parts by mass, and in the embodiment of the present invention, it may be specifically 5, 6, 7, 8, 9 or 10 parts by mass. The mass fraction of water in the aqueous ferrous salt solution is preferably 100 parts of water.
In the invention, the hollow multi-shell zinc-nickel oxide microspheres are dispersed in ferrous salt aqueous solution to obtain microsphere dispersion liquid. In the present invention, the dispersion is preferably performed at room temperature; the dispersing time is preferably 20 hours; the dispersion is preferably carried out under stirring. The stirring method of the present invention is not particularly limited, and stirring methods well known to those skilled in the art may be employed.
After the dispersion, the present invention preferably washes the obtained dispersion system with water to obtain a core-shell material precursor.
The invention preferably dries the core-shell material to obtain the hollow multi-shell core-shell material. In the present invention, the drying is preferably vacuum drying, the temperature of the vacuum drying is preferably 60 ℃, and the time of the vacuum drying is preferably 12 hours.
In the invention, hollow multi-shell zinc-nickel oxide microspheres are uniformly dispersed in ferrous sulfate aqueous solution. In this process, ferrous ions are oxidized to ferric ions, which hydrolyze in water to form ferric oxyhydroxide. The metal oxide microsphere is used as a nucleus, the hydroxyl ferric oxide nanowire grows on the surface of the metal oxide microsphere, the length and the density of the hydroxyl ferric oxide nanowire on the surface of zinc oxide are controlled by adjusting the hydrolysis time, and the hydroxyl ferric oxide nanowire can grow longer and have larger density by prolonging the reaction time. In the embodiment of the present invention, the time of the in-situ oxidation and hydrolysis reaction is preferably 2 to 200 hours, and may be specifically 2, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190 or 200 hours, so that the iron oxyhydroxide nanowires having a length of 50 to 600nm can be obtained.
The invention provides an explosion-proof polyurea which comprises a component A and a component B and is characterized by comprising the following components in parts by mass: 50-100 parts of polyol, 10-30 parts of hollow multi-shell core-shell material and 150-250 parts of isocyanate;
the component B comprises the following components in parts by mass: 30 to 60 parts of amino-terminated polyether, 20 to 50 parts of polyol, 1 to 2 parts of coupling agent, 20 to 40 parts of chain extender, 0 to 1 part of catalyst, 1 to 5 parts of water scavenger and 1 to 5 parts of color paste.
The explosion-proof polyurea provided by the invention comprises an A component, wherein the A component is isocyanate prepolymer, and in the invention, the A component comprises 50-100 parts of polyol, and in the embodiment of the invention, the A component can be specifically 50, 60, 70, 80, 90 or 100 parts. In the present invention, the polyhydric alcohol is preferably one or more of polyoxypropylene glycol, polytetrahydrofuran ether glycol, polycaprolactone glycol, polyester glycol and polycarbonate glycol; when several, it may be specifically 2, 3, 4 or 5. In the present invention, the average molecular weight of the polyol is preferably between 400 and 1500; the water content of the polyol is preferably less than or equal to 0.5%; the acid value of the polyol is preferably 0.8mg KOH/g or less.
In the invention, the A component comprises 10-30 parts of hollow multi-shell core-shell material, and in the embodiment of the invention, the A component can be specifically 10, 15, 20, 25 or 30 parts. The hollow multi-shell core-shell material is the hollow multi-shell core-shell material according to the above technical scheme, and will not be described herein.
In the present invention, the A component comprises 150 to 250 parts of polyisocyanate, and in embodiments may be in particular positions 150, 160, 170, 180, 190, 200, 210, 220, 230, 240 or 250 parts. The polyisocyanates are used in such amounts that the-NCO mass% of the A component is 14 to 17%, which may in particular be 14, 15, 16 or 17%. In the present invention, the polyisocyanate is preferably a diisocyanate, more preferably one or more of diphenylmethane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, methylcyclohexyl diisocyanate, cyclohexanedimethylene and isocyanate, xylylene diisocyanate and 1, 4-cyclohexanediisocyanate; when several, it may be specifically 2, 3, 4, 5, 6 or 7.
In the present invention, the A component is an isocyanate prepolymer, and the isocyanate prepolymer preferably has a-NCO mass% of 14 to 17%, and may specifically be 14, 15, 16 or 17%.
In the present invention, the preparation method of the a component preferably comprises the steps of:
mixing polyol and hollow multi-shell core-shell material, and vacuum dehydrating to obtain dehydrated materials;
and mixing the dehydrated material with polyisocyanate for reaction to obtain the component A.
The invention adopts an in-situ polymerization method to add the filler into the polyurea matrix to prepare the polyurea composite material, so that the filler is uniformly dispersed in the polymer together.
The invention mixes the polyol and the hollow multi-shell core-shell material, wherein the mixing is preferably heating the polyol, and adding the hollow multi-shell core-shell material into the heated polyol. In the present invention, the heating is stirring heating. In the present invention, the temperature of the heating is preferably 95 to 105 ℃, and in embodiments may be specifically 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, or 105 ℃.
In the present invention, the time of the vacuum dehydration is preferably 5 to 7 hours, and may be specifically 5, 6 or 7 hours in the embodiment; the temperature of the vacuum dehydration is preferably 95 to 105 ℃, and in embodiments may be specifically 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, or 105 ℃. The invention preferably dehydrates the polyol and hollow multi-shell core-shell material to a moisture content of less than or equal to 0.5%.
After the vacuum dehydration, the invention mixes the dehydrated material obtained with polyisocyanate to react, thus obtaining the component A. The invention preferably releases vacuum after the vacuum dehydration, and reduces the temperature of the material to below 50 ℃ to obtain dehydrated material. In the present invention, the temperature of the cooling may be specifically 50, 45 ℃ or normal temperature.
In the present invention, the temperature of the reaction is preferably 90 ℃ or less, and in embodiments may be specifically 90, 85, 80, 75, or 70 ℃; the reaction time is preferably 3 to 4 hours, in particular 3, 3.5 or 4 hours in the examples.
The invention preferably determines the-NCO value of the reaction mass and then discharges the reaction mass to give component A. The method for determining the-NCO value of the present invention is not particularly limited and may be carried out using measurement protocols well known to those skilled in the art.
The explosion-proof polyurea provided by the invention comprises a component B, wherein the component B comprises 30-60 parts of amino-terminated polyether, and can be specifically 30, 35, 40, 45, 50, 55 or 60 parts in an embodiment. In the present invention, the amino-terminated polyether preferably comprises a polyfunctional amino-terminated polyether, more preferably comprises one or more of a difunctional amino-terminated polyether and a trifunctional amino-terminated polyether. In the present invention, the difunctional amine-terminated polyether is preferably JEFFAMINE D2000 or D4000; the trifunctional amine-terminated polyether is preferably JEFFAMINE T-3000 or T-5000.
In the present invention, the B component includes 20 to 50 parts of polyol, and may be specifically 20, 25, 30, 35, 40, 45 or 50 parts in embodiments. In the present invention, the polyhydric alcohol is preferably one or more of polyoxypropylene glycol, polytetrahydrofuran ether glycol, polycaprolactone glycol, polyester glycol and polycarbonate glycol; when several, it may be specifically 2, 3, 4 or 5. In the present invention, the average molecular weight of the polyol is preferably between 400 and 1500; the water content of the polyol is preferably less than or equal to 0.5%; the acid value of the polyol is preferably 0.8mg KOH/g or less.
In the present invention, the B component includes 1 to 2 parts of a coupling agent, and may be specifically 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2 parts in embodiments. In the present invention, the coupling agent is preferably one or more of a silane coupling agent, a borate coupling agent, an aluminate coupling agent, a bimetal coupling agent and a phosphate coupling agent. In the present invention, the silane coupling agent is preferably KH-550, KH-560, KH-570, A-151, A-172, A-1160, A-1120, KH-590, A-186, A-143, A-150, SI-400 or KH-480.
In the present invention, the B component comprises 20 to 40 parts of a chain extender, which in embodiments may be specifically 20, 25, 30, 35 or 40 parts. In the present invention, the chain extender preferably includes 3, 5-dimethylthiotoluenediamine (E-300), 2, 4-diamino-3, 5-dimethylthiochlorobenzene (TX-2), 4' -bis-secondary butylaminodiphenyl methane (Unilink 4200), N, -one or more of dialkylphenylenediamine, 2, 4-diamino-3-methylsulfanyl-5-propyltoluene (TX-3), 3' -dimethyl-4, 4' -diaminodicyclohexylmethane, 4, -di-sec-butylamino dicyclohexylmethane, 3, -dimethyl-4, -di-sec-butylamino-dicyclohexylmethane, trimethylhexamethylenediamine and hydrogenated MDA; when several, it may be specifically 2, 3, 4, 5, 6, 7, 8, 9 or 10.
In the present invention, the B component includes 0 to 1 part of a catalyst, and may be specifically 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1 part in embodiments. In the present invention, the catalyst preferably comprises one or more of bismuth isooctanoate, zinc isooctanoate, triethylene diamine, dimorpholinodiethyl ether, tetrabutyl borate and tetraisopropyl borate; when several, it may be specifically 2 kinds of 2 kinds, 3 kinds, 4 kinds, 5 kinds, 6 kinds or 7 kinds.
In the present invention, the B component preferably includes 1 to 5 parts of a water scavenger, and in embodiments, may be specifically 1, 2, 3, 4, or 5 parts. In the present invention, the water scavenger is preferably a molecular sieve, and the molecular sieve is preferably 3a or 4a in size.
In the invention, the component B comprises 1 to 5 parts of color paste, and can be 1, 2, 3, 4 or 5 parts in particular in the embodiment. The color paste is not particularly limited, and general color paste in the polyurethane field is adopted, and the color can comprise red, yellow, blue, green, white or black color paste; the water content of the color paste is preferably less than or equal to 0.5 percent.
In the present invention, the isocyanate index of the A-component and the B-component is preferably 1.05 to 1.10.
In the present invention, the preparation method of the B component preferably includes the steps of:
mixing, grinding and filtering amine-terminated polyether, polyol, a coupling agent, a chain extender, a catalyst, a water removing agent and color paste to obtain a component B.
The apparatus for preparing the B component is not particularly limited in the present invention, and apparatuses for preparing a polyurea B component known to those skilled in the art may be employed.
The fineness of the grinding is not particularly limited, and the grinding is carried out until the fineness of the polyurea coating is well known to a person skilled in the art; in the present invention, the grinding may be performed in a sand mill.
In an embodiment of the present invention, the filtration may be specifically a copper mesh filtration, and the pore size of the copper mesh is preferably 200 mesh.
In the invention, the volume ratio of the component A to the component B is preferably 1:1; when in use, the component A and the component B are preferably uniformly mixed according to the volume ratio of 1:1 and then sprayed.
The hollow multi-shell core-shell material, the preparation method thereof and the anti-explosion polyurea provided by the invention are further described below with reference to examples, comparative examples and drawings, but the hollow multi-shell core-shell material, the preparation method and the anti-explosion polyurea are not to be considered as limiting the protection scope of the invention.
Example 1
Preparing hollow multi-shell zinc-nickel oxide microspheres: 10 parts of 2-methylimidazole is ultrasonically dissolved in 100 parts of methanol, 10 parts of citric acid is dropwise added, the mixture is magnetically stirred at room temperature for 2 hours to obtain imidazole ester, 5 parts of nickel nitrate and 5 parts of zinc nitrate are continuously added, the mixture is magnetically stirred at room temperature for 12 hours, and the mixture is kept stand at room temperature for 12 hours. And collecting the precipitate through centrifugation, washing the precipitate with methanol for three times to obtain zinc-nickel@imidazole ester composite phase microspheres, and then drying the microspheres in a vacuum drying oven at 60 ℃ for 12 hours to obtain zinc-nickel bimetallic powder. And (3) placing the zinc-nickel bimetal powder in an alumina firing boat, transferring the zinc-nickel bimetal powder into a tube furnace, heating to 600 ℃ at a heating rate of 5 ℃/min, preserving heat in air for 2 hours, and naturally cooling to obtain the hollow multi-shell zinc-nickel oxide microspheres.
5 parts of ferrous sulfate is taken to be dissolved in 100 parts of water, 10 parts of the hollow multi-shell zinc-nickel oxide microsphere is dispersed in ferrous sulfate water solution, and the mixture is stirred for 20 hours at room temperature, washed with water and then dried for 12 hours at 60 ℃ in a vacuum drying oven, so that the hollow multi-shell zinc-nickel oxide@iron oxyhydroxide core-shell material is obtained.
The obtained core-shell material is subjected to transmission electron microscope scanning analysis, and the results are shown in fig. 1 and 2, and as can be seen from fig. 1 and 2, the surface of the core-shell material prepared by the embodiment is distributed with ferric hydroxide nanowires.
Preparing a polyurea material A component: 100 parts of PTMEG1000 is stirred and heated to 95 ℃, 10 parts of the hollow multi-shell zinc-nickel oxide@iron oxyhydroxide core-shell material is added under the vacuum of-0.1 MPa, the dehydration is carried out for 5 to 7 hours, the vacuum is released, the temperature is reduced to below 50 ℃, 200 parts of MDI-50 is added, the reaction is carried out for 3 hours at 90 ℃, and the discharge is carried out after the determination of the minus NCO value of 16%, thus obtaining the component A.
Preparing a component B of a polyurea material: sequentially adding 30 parts of amine-terminated polyether D2000, 20 parts of PTMEG1000, 2 parts of silane coupling agent A171, 35 parts of chain extender E100, 0.1 part of catalyst bismuth isooctanoate, 5 parts of 3A molecular sieve and 1 part of color paste into a storage tank of a high-speed dispersing machine, stirring at room temperature for 15-30 min, grinding to reach the fineness qualified through a sand mill, and filtering and packaging through a 200-mesh copper filter screen to obtain a component B.
The component A and the component B with the volume ratio of 1:1 are uniformly mixed by a spraying machine and sprayed on the surface of a steel plate, the coating is placed in an environment with the temperature of (25+/-2) DEG C and the humidity of (50+/-5)%, and after curing for 7 days, the performance is as follows according to GB 23446: the tensile strength is 36.5MPa, the elongation at break is 180%, the tearing strength is 133N/mm, and the low-temperature flexibility is-60 ℃.
Example 2
Preparing hollow multi-shell zinc-nickel oxide microspheres: dissolving 20 parts of 2-methylimidazole in 100 parts of methanol by ultrasonic, dropwise adding 20 parts of citric acid, magnetically stirring at room temperature for 2 hours to obtain imidazole ester, continuously adding 8 parts of nickel nitrate and 8 parts of zinc nitrate, magnetically stirring at room temperature for 12 hours, and standing at room temperature for 12 hours. And collecting the precipitate through centrifugation, washing the precipitate with methanol for three times to obtain zinc-nickel@imidazole ester composite phase microspheres, and then drying the microspheres in a vacuum drying oven at 60 ℃ for 12 hours to obtain zinc-nickel bimetallic powder. And (3) placing the zinc-nickel bimetal powder in an alumina firing boat, transferring the zinc-nickel bimetal powder into a tube furnace, heating to 600 ℃ at a heating rate of 5 ℃/min, preserving heat in air for 2 hours, and naturally cooling to obtain the hollow multi-shell zinc-nickel oxide microspheres.
8 parts of ferrous sulfate is taken to be dissolved in 100 parts of water, 10 parts of the hollow multi-shell zinc-nickel oxide microsphere is dispersed in ferrous sulfate aqueous solution, and the hollow multi-shell zinc-nickel oxide microsphere is stirred for 20 hours at room temperature, washed with water, and then dried for 12 hours at 60 ℃ in a vacuum drying oven to obtain the hollow multi-shell zinc-nickel oxide@iron oxyhydroxide core-shell material.
Preparing a polyurea material A component: 150 parts of PTMEG1000 is stirred and heated to 95 ℃, 30 parts of hollow multi-shell zinc-nickel oxide@iron oxyhydroxide core-shell material is added under the vacuum of-0.1 MPa, dehydration is carried out for 5 hours, vacuum is released, the temperature is reduced to below 50 ℃, 200 parts of MDI-50 is added, reaction is carried out for 4 hours at 90 ℃, after the reaction is finished, the-NCO value is measured to be 14%, and then the material is discharged, thus obtaining the component A.
Preparing a component B of a polyurea material: 50 parts of amine-terminated polyether D2000, 20 parts of PTMEG650, 1 part of borate coupling agent KR-TTS, 20 parts of chain extender Unilink4200, 1 part of 4A molecular sieve and 4 parts of color paste are sequentially put into a storage tank of a high-speed dispersing machine, stirred for 15min at room temperature, and then ground by a sand mill until the fineness is qualified, and filtered and packaged by a 200-mesh copper filter screen to obtain a component B.
The component A and the component B with the volume ratio of 1:1 are uniformly mixed by a spraying machine and sprayed on the surface of a steel plate, the coating is placed in an environment with the temperature of (25+/-2) DEG C and the humidity of (50+/-5)%, and after curing for 7 days, the performance is as follows according to GB 23446: tensile strength 40MPa, elongation at break 150%, tear strength 145N/mm, and low-temperature flexibility-60 ℃.
Comparative example 1
Preparation of zinc-nickel oxide microspheres: 5 parts of nickel nitrate and 5 parts of zinc nitrate were dissolved in 100 parts of methanol, and reacted under magnetic stirring at room temperature for 12 hours, and allowed to stand at room temperature for 12 hours. And collecting the precipitate through centrifugation, washing the precipitate with methanol three times to obtain zinc-nickel bimetallic microspheres, and then drying the zinc-nickel bimetallic microspheres in a vacuum drying oven at 60 ℃ for 12 hours to obtain zinc-nickel bimetallic powder. And (3) placing the zinc-nickel bimetal powder in an alumina firing boat, transferring the powder into a tube furnace, heating to 600 ℃ at a heating rate of 5 ℃/min, preserving heat in air for 2 hours, and naturally cooling to obtain the solid zinc-nickel oxide microspheres.
5 parts of ferrous sulfate is taken to be dissolved in 100 parts of water, 10 parts of solid zinc-nickel oxide microspheres are dispersed in ferrous sulfate aqueous solution, stirred for 20 hours at room temperature, washed with water, and then dried for 12 hours at 60 ℃ in a vacuum drying oven, thus obtaining the solid zinc-nickel oxide@iron oxyhydroxide core-shell material.
Preparing a polyurea material A component: 100 parts of PTMEG1000 are stirred and heated to 95 ℃, 10 parts of solid zinc nickel oxide@iron oxyhydroxide core-shell material is added under the vacuum of-0.1 MPa, dehydration is carried out for 5-7 h, vacuum is released, the temperature is reduced to below 50 ℃, 200 parts of MDI-50 are added, reaction is carried out for 3h at 90 ℃, and the discharge is carried out after the determination of the-NCO value of 16% to obtain the component A.
Preparing a component B of a polyurea material: sequentially adding 30 parts of amine-terminated polyether D2000, 20 parts of PTMEG1000, 2 parts of silane coupling agent A171, 35 parts of chain extender E100, 0.1 part of catalyst bismuth isooctanoate, 5 parts of 3A molecular sieve and 1 part of color paste into a storage tank of a high-speed dispersing machine, stirring at room temperature for 15-30 min, grinding to reach the fineness qualified through a sand mill, and filtering and packaging through a 200-mesh copper filter screen to obtain a component B.
Uniformly mixing the component A and the component B in a volume ratio of 1:1 by a spraying machine, spraying the mixture on the surface of a steel plate, placing the coating in an environment with the temperature of (25+/-2) DEG C and the humidity of (50+/-5)%, and curing for 7 days, wherein the test performance is as follows: tensile strength 19.5MPa, elongation at break 220%, tear strength 73N/mm, and low-temperature flexibility-40 ℃.
Comparative example 2
Preparation of zinc-nickel oxide microspheres: 10 parts of 2-methylimidazole is ultrasonically dissolved in 100 parts of methanol, 10 parts of citric acid is dropwise added, the mixture is magnetically stirred at room temperature for 2 hours to obtain imidazole ester, 5 parts of nickel nitrate and 5 parts of zinc nitrate are continuously added, the mixture is magnetically stirred at room temperature for 12 hours, and the mixture is kept stand at room temperature for 12 hours. And collecting the precipitate through centrifugation, washing the precipitate with methanol for three times to obtain zinc-nickel@imidazole ester composite phase microspheres, and then drying the microspheres in a vacuum drying oven at 60 ℃ for 12 hours to obtain zinc-nickel bimetallic powder. And (3) placing the zinc-nickel bimetal powder in an alumina firing boat, transferring the zinc-nickel bimetal powder into a tube furnace, heating to 600 ℃ at a heating rate of 5 ℃/min, preserving heat in air for 2 hours, and naturally cooling to obtain the hollow multi-shell zinc-nickel oxide microspheres.
Preparing a polyurea material A component: 100 parts of PTMEG1000 is stirred and heated to 95 ℃, 10 parts of the hollow multi-shell zinc-nickel oxide microsphere is added under the vacuum of-0.1 MPa, the dehydration is carried out for 5 to 7 hours, the vacuum is released, the temperature is reduced to below 50 ℃, 200 parts of MDI-50 is added, the reaction is carried out for 3 hours at 90 ℃, and the discharge is carried out after the determination of the minus NCO value of 16 percent, thus obtaining the component A.
Preparing a component B of a polyurea material: sequentially adding 30 parts of amine-terminated polyether D2000, 20 parts of PTMEG1000, 2 parts of silane coupling agent A171, 35 parts of chain extender E100, 0.1 part of catalyst bismuth isooctanoate, 5 parts of 3A molecular sieve and 1 part of color paste into a storage tank of a high-speed dispersing machine, stirring at room temperature for 15-30 min, grinding to reach the fineness qualified through a sand mill, and filtering and packaging through a 200-mesh copper filter screen to obtain a component B.
The component A and the component B with the volume ratio of 1:1 are uniformly mixed by a spraying machine and sprayed on the surface of a steel plate, the coating is placed in an environment with the temperature of (25+/-2) DEG C and the humidity of (50+/-5)%, and after curing for 7 days, the performance is as follows according to GB 23446: the tensile strength is 33.8MPa, the elongation at break is 170%, the tearing strength is 116N/mm, and the low-temperature flexibility is-40 ℃.
Comparative example 3
A hollow multi-shell zinc nickel oxide @ iron oxyhydroxide core-shell material was prepared following the protocol of example 1, except that ferrous sulfate was replaced with ferrous chloride. The length of the obtained core-shell material surface hydroxyl ferric oxide nanowire is shorter, as shown in fig. 3, and comparing fig. 3 with fig. 1 and fig. 2, the length of the nanowire on the core-shell material surface represented in fig. 3 is shorter.
The core-shell material obtained in the comparative example is used as one of the components to replace the core-shell material in the example 1, so as to prepare the polyurea coating, and the performance according to GB23446 test is as follows: the tensile strength is 29.3MPa, the elongation at break is 170%, the tearing strength is 103N/mm, and the low-temperature flexibility is-50 ℃.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (8)

1. An explosion-proof polyurea comprises a component A and a component B, and is characterized in that the component A comprises the following components in parts by mass: 50-100 parts of polyol, 10-30 parts of hollow multi-shell core-shell material and 150-250 parts of isocyanate, wherein the hollow multi-shell core-shell material comprises hollow multi-shell zinc-nickel oxide microspheres and ferric hydroxide nanowires positioned on the surfaces of the hollow multi-shell zinc-nickel oxide microspheres;
the preparation method of the hollow multi-shell core-shell material comprises the following steps:
esterifying 2-methylimidazole and citric acid in a solvent system to obtain imidazole ester, wherein the solvent is methanol;
mixing the imidazole ester with soluble zinc salt and soluble nickel salt for loading to obtain zinc-nickel@imidazole ester composite phase microspheres;
drying the zinc-nickel@imidazole ester composite phase microspheres to obtain zinc-nickel bimetallic powder;
performing heat treatment on the zinc-nickel bimetallic powder in air to obtain hollow multi-shell zinc-nickel oxide microspheres;
dispersing the hollow multi-shell zinc-nickel oxide microspheres in ferrous salt aqueous solution to perform in-situ oxidation and hydrolysis reaction to obtain the hollow multi-shell core-shell material;
the component B comprises the following components in parts by mass: 30 to 60 parts of amino-terminated polyether, 20 to 50 parts of polyol, 1 to 2 parts of coupling agent, 20 to 40 parts of chain extender, 0 to 1 part of catalyst, 1 to 5 parts of water scavenger and 1 to 5 parts of color paste.
2. The explosion-proof polyurea of claim 1, wherein the hollow multi-shell zinc-nickel oxide microsphere is a hollow 4-shell zinc-nickel oxide microsphere.
3. The explosion-proof polyurea of claim 1, wherein the hollow multi-shell zinc-nickel oxide microsphere has a molar ratio of zinc to nickel of 1:1.
4. An explosion-proof polyurea according to any one of claims 1 to 3, wherein the hollow multi-shell zinc nickel oxide microspheres have a particle size of 200 to 1000nm.
5. The explosion-proof polyurea of claim 1, wherein the mass ratio of the hollow multi-shell zinc nickel oxide microspheres to the iron oxyhydroxide nanowires is 2:1.
6. The explosion-proof polyurea according to claim 1, wherein the 2-methylimidazole is 10-20 parts by mass, the citric acid is 10-20 parts by mass, the soluble nickel salt is 5-10 parts by mass, the soluble zinc salt is 5-10 parts by mass, and the ferrous salt is 5-10 parts by mass.
7. The explosion-proof polyurea of claim 1, wherein the esterification reaction time is 2 hours;
the mixing time is 12h, and the loading time is 12h;
the temperature of the heat treatment is 600 ℃, and the heat preservation time of the heat treatment is 2h.
8. The explosion-proof polyurea of claim 1, wherein the in situ oxidation and hydrolysis reaction time is 20 hours.
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