CN115558082A - Spider silk bionic high-toughness polyurea and preparation method and coating thereof - Google Patents

Spider silk bionic high-toughness polyurea and preparation method and coating thereof Download PDF

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CN115558082A
CN115558082A CN202210951733.8A CN202210951733A CN115558082A CN 115558082 A CN115558082 A CN 115558082A CN 202210951733 A CN202210951733 A CN 202210951733A CN 115558082 A CN115558082 A CN 115558082A
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parts
portions
polyurea
toughness
spider silk
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CN115558082B (en
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陈威
吴泽文
周创
贺行洋
苏英
李铃
宋小康
赖志辉
李维和
陈顺
王迎斌
杨进
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Hubei University of Technology
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    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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Abstract

The embodiment of the invention discloses spider silk bionic high-toughness polyurea, which comprises the following components in parts by weight: 25 to 45 portions of polyamine organic compound, 15 to 40 portions of isocyanate, 0.1 to 2 portions of catalyst, 0.5 to 5 portions of amino acid compound, 0.1 to 10 portions of amine chain extender, 0.1 to 10 portions of neutralizer, 0.5 to 10 portions of inorganic metal nano material, 0.5 to 15 portions of organic silicon fluorine modifier, 0.1 to 5 portions of metal ion cross linker, 1 to 5 portions of dispersant, 0.5 to 10 portions of surfactant and 1 to 5 portions of solvent. The coating formed by the coating has super-strong toughness, excellent mechanical property and chemical durability, and can effectively inhibit the damage of external impact load to the coating.

Description

Spider silk bionic high-toughness polyurea and preparation method and coating thereof
Technical Field
The invention relates to the technical field of industrial coatings and functionalized polymers, in particular to spider silk bionic high-toughness polyurea and a preparation method and a coating thereof.
Background
With the continuous promotion of urbanization and modern industry and commerce, people pay more and more attention to protection in the fields of precision equipment, electronic instruments, important buildings and the like. The polyurea material has excellent mechanical and physical and chemical properties and high dynamic resistance, ultrahigh speed and explosive load resistance, so that the polyurea material is widely applied to the fields of chemical protection, explosion protection of surfaces of precision equipment parts and building structures, aviation protection and the like.
Polyurea (PUA) is a segmented block copolymer having a typical phase-separated microstructure formed by the reaction of a polyisocyanate with a polyamine (including a mixture of resins and chain extenders) to form urea linkages (-NH-CO-NH-). The hard segment comprises isocyanate and amine chain extender, self-assembles into a hard domain through intermolecular interaction, and is embedded in a continuous matrix of a flexible soft segment generated by long-chain diamine. A large number of groups with stronger polarity in the hard section, such as urea bonds, carbamate groups, ester groups and the like, can form a large number of hydrogen bonds with stronger acting force among molecular chains, so that the mechanical property of the polyurea material is improved. In recent years, the toughness (impact resistance) requirement of the protective coating is becoming more and more strict, and the conventional polyurea coating often has insufficient toughness to cause abrasion of the coating and cannot reach the normal service life.
The mechanical properties of the traditional polyurea elastomer coating are mainly derived from a segmented and blocked phase separation structure, wherein a hard segment comprises isocyanate and an amine chain extender, self-assembly into a hard domain is carried out through intermolecular interaction force, and the hard domain is embedded into a continuous matrix of a flexible soft segment generated by long-chain polyamine and plays a role in physical crosslinking. However, for the protection of some important equipments, the mechanical properties such as toughness, tensile strength and Young's modulus are far from sufficient
Therefore, in order to solve the above technical problems, it is necessary to develop a novel polyurea coating having superior toughness and excellent mechanical properties and chemical durability, which can effectively inhibit the damage of the coating caused by external impact load.
Disclosure of Invention
The invention aims to provide a spider silk bionic high-toughness polyurea and a preparation method and a coating thereof.
In order to achieve the above object, the present invention provides a spider silk bionic high-toughness polyurea, comprising, in parts by weight:
25 to 45 portions of polyamine organic compound, 15 to 40 portions of isocyanate, 0.1 to 2 portions of catalyst, 0.5 to 5 portions of amino acid compound, 0.1 to 10 portions of amine chain extender, 0.1 to 10 portions of neutralizer, 0.5 to 10 portions of inorganic metal nano material, 0.5 to 15 portions of organic silicon fluorine modifier, 0.1 to 5 portions of metal ion cross-linking agent, 1 to 5 portions of dispersant, 0.5 to 10 portions of surfactant and 1 to 5 portions of solvent.
Further, the polyamine organic compound is selected from one or more of biomass secondary amine, polyethyleneimine, polydopamine, polyacrylamide, amino-terminated polyether and polyaspartic acid ester; the biomass secondary amine comprises plant oil-based secondary amine selected from one or more of soybean oil-based secondary amine, peanut oil-based secondary amine, castor oil-based secondary amine and sesame oil-based secondary amine;
the isocyanate is selected from one or more of isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), hexamethylene Diisocyanate (HDI), HDI trimer, dicyclohexyl methane diisocyanate (HMDI), toluene Diisocyanate (TDI) and Lysine Diisocyanate (LDI);
the inorganic metal ion crosslinking agent is selected from ferric chloride (FeCl) 3 ) Ferrous chloride (FeCl) 2 ) Manganese dichloride (MnCl) 2 ) One or more of zinc oxide, aluminum chloride, aluminum sulfate nano-grade, chromium nitrate, aluminum isopropoxide, titanium acetylacetonate and zinc acetate;
the amino acid compound is selected from one or more of glycine, glutamic acid, serine, leucine, tyrosine, methionine, alanine, aspartic acid, glutamine, lysine and asparagine;
the amine chain extender is selected from one or more of levodopamine, ethylenediamine ethylene sodium sulfonate, 2, 6-diaminopyridine, isophorone diamine, 3, 6-diaminocarbazole, 1, 6-hexamethylene diamine, MOCA, diethylenetriamine (DETA), diethyltoluene diamine, diethylenetriamine and N-aminoethyl piperazine;
the organosilicon fluorine modifier is selected from 1H,2H perfluorododecyl triethoxysilane (HFDS), polytrifluoropropylmethylsiloxane (PTFPMS), 1H,2H perfluorododecyl trichlorosilane (PFDTS), KH-550, KH-560, octadecyltrichlorosilane (ODTS), phenyltrimethoxysilane (PTMS), trimethylchlorosilane (TMCS), chlorotrimethylsilane (Me) 3 SiCl), silicon sulfide rubber, heptafluoro-1, 2-tetrahydrodecyl dimethylchlorosilane (HFTD), methyl silicone resin (Al) one or more of silicone, 1, 3-Hexamethyldisilazane (HMDS), and methyltriethoxysilane;
the inorganic metal nano material is selected from nano ZnO, nano GaN and nano Al 2 O 3 Nano Fe 2 O 3 Nano NiO and nano ZrO 2 Nano GaAs, nano TiO 2 And nano CaCO 3 One or more of (a).
Further, the catalyst is selected from one or more of dibutyl tin dilaurate (DBTDL), stannous octoate, bismuth isooctanoate, bismuth laurate, bismuth neodecanoate, and bismuth naphthenate.
Further, the neutralizing agent is selected from one or more of Triethylamine (TEA), triisopropanolamine (triisopropanolamine), triethanolamine (TEOA), diethanolamine, dimethylethanolamine (DMEA), diethylethanolamine (DEEA), and 2-amino-2-methylpropanol.
Further, the dispersing agent is selected from one or more of ethanol, deionized water, acetone, butanone, sodium dodecyl sulfate and methyl amyl alcohol.
Further, the surfactant is selected from one or more of ethylene glycol, sodium dodecyl sulfate, sodium hexadecylbenzene sulfonate, sodium dodecyl benzene sulfonate, hexadecyl trimethyl ammonium bromide, sodium dioctyl sulfosuccinate, sodium stearate and polysorbate.
Further, the defoaming agent is selected from one or more of higher alcohols, polydimethylsiloxane, ethanol, silicone emulsion, lauryl phenylacetate, higher alcohol fatty acid ester complex, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene amine ether, polyoxypropylene glycerol ether and polyoxypropylene;
the leveling agent is selected from one or more of butyl cellulose, polyacrylic acid, diacetone alcohol, polydimethylsiloxane, polymethylphenyl siloxane, solvesso150 and carboxymethyl cellulose;
the solvent is selected from one or more of N, N-Dimethylformamide (DMF), acetone (AC), tetrahydrofuran (THF), 2-butanone, dimethyl sulfoxide (DMSO), isopropyl acetate, propylene glycol and pyridine.
The embodiment of the invention also provides a preparation method of the spider silk bionic high-toughness polyurea, which comprises the following steps:
dispersing the inorganic metal nano material in H 2 O 2 Stirring the solution, centrifuging, cleaning, drying, dispersing in a solvent, adding a surfactant to adjust the pH, ultrasonically dispersing, heating to 50-80 ℃, stirring for 3-5 hours, cooling, centrifuging and drying to obtain a surface-activated metal nano material;
uniformly mixing polyamine organic compounds, a catalyst, a solvent and isocyanate, heating in a water bath to 25-80 ℃, reacting for 2-4 h under stirring, adding an amine chain extender to perform chain extension reaction for 1-2 h, cooling to 25-50 ℃ when the content of the isocyanate in a detection system is not changed, adding an organic silicon fluorine modifier to modify for 1-2 h, continuously cooling to 0-25 ℃, adding a neutralizer to neutralize for 1-2 h, adding a metal ion crosslinking agent to react for 1-1.5 h, adding the surface-activated metal nano material to react for 1-2 h, and removing the solvent through reduced pressure distillation to obtain the spider silk bionic high-toughness polyurea.
The embodiment of the invention also provides a coating which is a film formed by coating and curing the spider silk bionic high-toughness polyurea.
One or more technical solutions in the embodiments of the present invention have at least the following technical effects or advantages:
1. according to the spider silk bionic high-toughness polyurea and the preparation method thereof provided by the embodiment of the invention, a highly crosslinked organic whole is formed by chemical bonds, coordination bonds, hydrogen bonds and intermolecular interaction force through the bonding action of the components such as isocyanate, polyamine organic compounds, metal ion cross-linking agents, chain extenders, silicon/fluorine modifiers, metal nano materials and the like, so that a coating formed by the prepared coating has excellent heat resistance, tensile property, bonding property, ageing resistance, acid and alkali resistance and hydrolysis resistance. The prepared polyurea coating is characterized in that amino acid organic matters such as glycine and alanine are grafted on a polyurea chain segment through simulating a spider silk structure to form beta-folded conformation and spiral conformation, so that the polymer coating has excellent elasticity and toughness. Transition metal ions are doped into the polyurea system to serve as a cross-linking agent, and a metal-polyurea complex or stronger covalent bonds are formed at hydrogen bond sites through the chelation between the metal ions and polar groups in the system, so that the toughening effect is achieved. The polyurea coating has the advantages that the regular/irregular distribution of amino acid chain segments in the molecular structure of the polyurea coating is cooperated with the coordination toughening effect of metal ions, so that the coating has super-strong toughness and tensile strength.
2. The bionic polyurea coating has moderate curing speed, simple synthesis process, no complicated and fussy links, lower preparation cost and contribution to realizing industrial production.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to derive other drawings without creative efforts.
FIG. 1 is a simplified structural representation of a spider silk biomimetic polyurea coating prepared according to examples 1-5 of the present invention;
FIG. 2 is a diagram of the bonding mechanism of the spider silk bionic polyurea coating prepared by the embodiments 1-5 of the invention applied to the field of concrete coating.
Detailed Description
The embodiments of the present invention will be described in detail below with reference to specific embodiments and examples, and the advantages and various effects of the embodiments of the present invention will be more clearly apparent therefrom. It should be understood by those skilled in the art that the detailed description and examples are intended to illustrate, but not limit, the embodiments of the invention.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood according to the meanings commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which embodiments of the invention belong. If there is a conflict, the present specification will control.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the examples of the present invention are commercially available or can be prepared by an existing method.
In order to solve the technical problems, the embodiment of the invention provides a technical scheme, and the general idea is as follows:
according to another exemplary embodiment of the present invention, there is provided a method for preparing a spider silk biomimetic high tenacity polyurea, the method comprising:
s1, dispersing the inorganic metal nano material in H 2 O 2 Stirring the solution, centrifuging, cleaning, drying, dispersing in a solvent, adding a surfactant to adjust the pH, ultrasonically dispersing, heating to 50-80 ℃, stirring for 3-5 hours, cooling, centrifuging and drying to obtain a surface-activated metal nano material;
the reaction equation involved is:
Figure RE-GDA0003968366960000051
0.5-10% of inorganic metal nano material and 0.5-10% of surfactant in parts by weight;
s2, mixing a polyamine organic compound, a catalyst, a solvent and isocyanate, heating the mixture in a water bath to 25-80 ℃, reacting for 2-4 h under stirring, adding an amine chain extender to perform chain extension reaction for 1-2 h, cooling the temperature to 25-50 ℃ when the content of the isocyanic acid radical in the detection system is not changed, adding an organic silicon fluorine modifier to modify for 1-2 h, continuously cooling to 0-25 ℃, adding a neutralizer to neutralize for 1-2 h, adding a metal ion crosslinking agent to react for 1-1.5 h, adding the surface-activated metal nano material dispersed by a dispersing agent (1-5 parts of the dispersing agent) to react for 1-2 h, and removing the solvent through reduced pressure distillation to obtain the spider silk bionic high-toughness polyurea.
25 to 45 portions of polyamine organic compound, 0.1 to 2 portions of catalyst, 1 to 5 portions of solvent, 15 to 35 portions of isocyanate, 0.1 to 10 portions of amine chain extender, 0.5 to 15 portions of organic silicon fluorine modifier, 0.1 to 10 portions of neutralizer, 0.1 to 5 portions of metal ion cross linker and 1 to 5 portions of dispersant;
and (3) performing biomimetic high-toughness polyurea on the spider silks. And finally, adding 0.1-3 parts of defoaming agent and 0.1-3 parts of flatting agent, uniformly mixing, uniformly coating the mixture on a polytetrafluoroethylene board, standing at normal temperature for 48 hours, and then putting the polytetrafluoroethylene board into a 70 ℃ oven to be cured for 36 hours to obtain the functionalized spider silk bionic high-toughness polyurea coating.
The details of the spider silk bionic high-toughness polyurea and the preparation method thereof according to the present application will be described below with reference to examples, comparative examples and experimental data.
The surface-activated metal nano material provided by the embodiment of the invention is prepared by the following method:
dispersing nano ZnO in H 2 O 2 Stirring in the solution for 30min, centrifuging, cleaning with acetone, centrifuging, and drying; dispersing the dried nano ZnO in deionized water, adding a surfactant, adjusting the pH to 6, performing ultrasonic dispersion for 30min, heating the reaction system to 65 ℃, mechanically stirring for 1.5h, cooling to room temperature, and performing centrifugal drying to obtain the surface-activated nano ZnO particles.
Example 1
A spider bionic high-toughness polyurea protective coating comprises the following components in parts by weight: 35 parts of polyaspartic acid ester, 35 parts of isophorone diisocyanate, 0.5 part of stannous octoate catalyst, 2 parts of chain extender 2, 6-diaminopyridine, 2 parts of glycine, 2 parts of neutralizing agent triethylamine, 3 parts of nano ZnO particles, 5 parts of organosilicon/fluorine modifying agent octadecyl trichlorosilane (ODTS), chlorinationIron (FeCl) 3 ) 1 part of metal cross-linking agent, 3 parts of dispersing agent, 5 parts of surfactant cetyl trimethyl ammonium bromide, 0.5 part of defoaming agent, 0.5 part of flatting agent and 2 parts of solvent.
The preparation method of the spider biomimetic high-toughness polyurea protective coating comprises the following steps: adding fully dried polyaspartic ester, stannous octoate catalyst, acetone solvent and isophorone diisocyanate with corresponding mass into a three-port reaction kettle with a nitrogen inlet and a nitrogen outlet respectively, reacting in a water bath at 65 ℃, stirring at medium speed for a certain time until the-NCO content reaches a theoretical value, adding chain extender 2, 6-diaminopyridine and glycine, detecting the content of the system isocyanate every 30min, cooling the reaction system to 35 ℃ until the content of the isocyanate does not change, adding organosilicon/fluorine modifier Octadecyltrichlorosilane (ODTS), modifying for 1h, continuously cooling, adding triethylamine, adding a metal ion crosslinking agent ferric chloride after neutralizing for 1h, reacting for 1h, adding metal ZnO nanoparticles modified by a surfactant cetyl trimethyl ammonium bromide, mechanically stirring for 45min, and removing the solvent by reduced pressure distillation to obtain the spider silk bionic polyurea with high toughness. And finally, adding additives such as a defoaming agent, a leveling agent and the like, uniformly mixing, uniformly coating the mixture on a polytetrafluoroethylene board, standing at normal temperature for 48 hours, and then putting in a 70 ℃ drying oven for curing for 36 hours to obtain the functionalized spider silk bionic high-toughness polyurea coating.
Example 2
A spider bionic type high-toughness polyurea protective coating comprises the following components in parts by weight: 35 parts of polyaspartic acid ester, 35 parts of isophorone diisocyanate, 0.5 part of stannous octoate catalyst, 2 parts of chain extender 2, 6-diaminopyridine, 2 parts of glutamic acid, 2 parts of triethylamine serving as neutralizing agent, 3 parts of nano ZnO particles, 5 parts of organosilicon/fluorine modifier Octadecyltrichlorosilane (ODTS), and iron chloride (FeCl) 3 ) 1 part of metal cross-linking agent, 3 parts of dispersing agent, 5 parts of surfactant cetyl trimethyl ammonium bromide, 0.5 part of defoaming agent, 0.5 part of flatting agent and 2 parts of solvent. The preparation method comprises the following steps: same as in example 8.
Example 3
A spider bionic high-toughness polyurea protective coating comprises the following components in parts by weight: 35 parts of polyaspartic acid ester, 35 parts of isophorone diisocyanate, 0.5 part of stannous octoate catalyst, 2 parts of chain extender 2, 6-diaminopyridine, 2 parts of glycine, 2 parts of neutralizer triethylamine and nano Fe 2 O 3 3 parts of particles, 5 parts of organosilicon/fluorine modifier Octadecyltrichlorosilane (ODTS), and ferric chloride (FeCl) 3 ) 1 part of metal cross-linking agent, 3 parts of dispersing agent, 5 parts of surfactant cetyl trimethyl ammonium bromide, 0.5 part of defoaming agent, 0.5 part of flatting agent and 2 parts of solvent. The preparation method comprises the following steps: same as in example 8.
Example 4
A spider bionic high-toughness polyurea protective coating comprises the following components in parts by weight: 35 parts of polyaspartic acid ester, 35 parts of isophorone diisocyanate, 0.5 part of stannous octoate catalyst, 2, 6-diaminopyridine as a chain extender, 2 parts of glycine, 2 parts of triethylamine as a neutralizing agent, 3 parts of nano ZnO particles, 5 parts of octadecyl trichlorosilane (ODTS) as an organosilicon/fluorine modifier, 1 part of zinc oxide metal cross-linking agent, 3 parts of dispersing agent, 5 parts of cetyl trimethyl ammonium bromide as a surfactant, 0.5 part of defoaming agent, 0.5 part of leveling agent and 2 parts of solvent. The preparation method comprises the following steps: same as in example 8.
Example 5
A spider bionic type high-toughness polyurea protective coating comprises the following components in parts by weight: 35 parts of polyaspartic acid ester, 35 parts of isophorone diisocyanate, 0.5 part of stannous octoate catalyst, 2, 6-diaminopyridine as a chain extender, 2 parts of glycine, 2 parts of triethylamine as a neutralizing agent, 3 parts of nano ZnO particles, 5 parts of heptafluoro-1, 2-tetrahydrodecyl dimethylchlorosilane (HFTD) as an organosilicon/fluorine modifier, 3 parts of a dispersing agent, 5 parts of cetyl trimethyl ammonium bromide as a surfactant, 0.5 part of a defoaming agent, 0.5 part of a leveling agent and 2 parts of a solvent. The preparation method comprises the following steps: same as in example 8.
Comparative example 1
A spider bionic type high-toughness polyurea protective coating comprises the following components in parts by weight: 35 parts of polyaspartic acid ester, 35 parts of isophorone diisocyanate, 0.5 part of stannous octoate catalyst, 2 parts of chain extender 2, 6-diaminopyridine, 2 parts of neutralizing agent triethylamine, 5 parts of organosilicon/fluorine modifier Octadecyltrichlorosilane (ODTS), 3 parts of dispersing agent, 0.5 part of defoaming agent, 0.5 part of flatting agent and 2 parts of solvent.
The preparation method of the spider bionic high-toughness polyurea protective coating comprises the following steps: respectively adding fully dried polyaspartic ester, stannous octoate catalyst, acetone solvent and isophorone diisocyanate with corresponding mass into a three-port reaction kettle with a mechanical stirrer, a reflux condenser pipe and a nitrogen inlet and outlet to react, heating in a water bath to 65 ℃, reacting for a certain time under medium-speed stirring until-NCO content reaches a theoretical value, adding chain extender 2, 6-diaminopyridine, detecting the content of isocyanate in the system every 30min, cooling the reaction system to 35 ℃ when the content of isocyanate does not change, adding organosilicon/fluorine modifier Octadecyltrichlorosilane (ODTS), modifying for 1h, continuously cooling, adding neutralizing agent triethylamine, and removing the solvent by reduced pressure distillation after neutralizing for 1h to obtain the spider silk bionic high-toughness polyurea. And finally, adding an antifoaming agent, a leveling agent and other additives, uniformly mixing, uniformly coating the mixture on a polytetrafluoroethylene board, standing at normal temperature for 48 hours, and then putting into a 70 ℃ oven for curing for 36 hours to obtain the functionalized spider silk bionic high-toughness polyurea coating.
Comparative example 2
A spider bionic type high-toughness polyurea protective coating comprises the following components in parts by weight: 25 parts of polyaspartic acid ester, 35 parts of isophorone diisocyanate, 0.5 part of stannous octoate catalyst, 2 parts of chain extender 2, 6-diaminopyridine, 2 parts of neutralizing agent triethylamine, 5 parts of organosilicon/fluorine modifier Octadecyltrichlorosilane (ODTS), 3 parts of dispersing agent, 0.5 part of defoaming agent, 0.5 part of flatting agent and 2 parts of solvent. The preparation method comprises the following steps: same as in example 1.
Comparative example 3
A spider bionic high-toughness polyurea protective coating comprises the following components in parts by weight: 45 parts of polyaspartic acid ester, 35 parts of isophorone diisocyanate, 0.5 part of stannous octoate catalyst, 2 parts of chain extender 2, 6-diaminopyridine, 2 parts of neutralizing agent triethylamine, 5 parts of organosilicon/fluorine modifier Octadecyltrichlorosilane (ODTS), 3 parts of dispersing agent, 0.5 part of defoaming agent, 0.5 part of flatting agent and 2 parts of solvent. The preparation method comprises the following steps: same as in example 1.
Comparative example 4
A spider bionic type high-toughness polyurea protective coating comprises the following components in parts by weight: 35 parts of polyaspartic acid ester, 15 parts of isophorone diisocyanate, 0.5 part of stannous octoate catalyst, 2 parts of chain extender 2, 6-diaminopyridine, 2 parts of neutralizing agent triethylamine, 5 parts of organosilicon/fluorine modifier Octadecyltrichlorosilane (ODTS), 3 parts of dispersing agent, 0.5 part of defoaming agent, 0.5 part of flatting agent and 2 parts of solvent. The preparation method comprises the following steps: same as in example 1.
Comparative example 5
A spider bionic type high-toughness polyurea protective coating comprises the following components in parts by weight: 35 parts of polyaspartic acid ester, 40 parts of isophorone diisocyanate, 0.5 part of stannous octoate catalyst, 2 parts of chain extender 2, 6-diaminopyridine, 2 parts of neutralizing agent triethylamine, 5 parts of organosilicon/fluorine modifier Octadecyltrichlorosilane (ODTS), 3 parts of dispersing agent, 0.5 part of defoaming agent, 0.5 part of flatting agent and 2 parts of solvent. The preparation method comprises the following steps: same as in example 1.
Comparative example 6
A spider bionic type high-toughness polyurea protective coating comprises the following components in parts by weight: 35 parts of polyaspartic acid ester, 35 parts of isophorone diisocyanate, 0.5 part of stannous octoate catalyst, 2 parts of chain extender 2, 6-diaminopyridine, 2 parts of glycine, 2 parts of triethylamine as a neutralizing agent, 5 parts of Octadecyltrichlorosilane (ODTS) as an organosilicon/fluorine modifier, 3 parts of dispersing agent, 0.5 part of defoaming agent, 0.5 part of flatting agent and 2 parts of solvent.
The preparation method of the spider biomimetic high-toughness polyurea protective coating comprises the following steps: respectively adding fully dried polyaspartic ester, stannous octoate catalyst, acetone solvent and isophorone diisocyanate with corresponding mass into a three-port reaction kettle with a mechanical stirrer, a reflux condenser pipe and a nitrogen inlet and outlet to react, heating in a water bath to 65 ℃, reacting for a certain time under medium-speed stirring until the-NCO content reaches a theoretical value, adding chain extender 2, 6-diaminopyridine and glycine, detecting the content of isocyanate in the system every 30min, cooling the reaction system to 35 ℃ until the content of isocyanate does not change, adding organosilicon/fluorine modifier Octadecyltrichlorosilane (ODTS), modifying for 1h, continuously cooling, adding triethylamine neutralizer, neutralizing for 1h, and removing the solvent through reduced pressure distillation to obtain the spider silk bionic high-toughness polyurea. And finally, adding an antifoaming agent, a leveling agent and other additives, uniformly mixing, uniformly coating the mixture on a polytetrafluoroethylene board, standing at normal temperature for 48 hours, and then putting into a 70 ℃ oven for curing for 36 hours to obtain the functionalized spider silk bionic high-toughness polyurea coating.
Comparative example 7
A spider bionic high-toughness polyurea protective coating comprises the following components in parts by weight: 35 parts of polyaspartic acid ester, 35 parts of isophorone diisocyanate, 0.5 part of stannous octoate catalyst, 2, 6-diaminopyridine as a chain extender, 2 parts of glycine, 2 parts of triethylamine as a neutralizing agent, 3 parts of nano ZnO particles, 5 parts of octadecyl trichlorosilane (ODTS) as an organosilicon/fluorine modifier, 3 parts of a dispersing agent, 0.5 part of a defoaming agent, 0.5 part of a leveling agent and 2 parts of a solvent.
The preparation method of the spider biomimetic high-toughness polyurea protective coating comprises the following steps: respectively adding fully dried polyaspartic ester, stannous octoate catalyst, acetone solvent and isophorone diisocyanate with corresponding mass into a three-port reaction kettle with a nitrogen inlet and a nitrogen outlet to react, heating in a water bath to 65 ℃, reacting for a certain time under medium-speed stirring until the-NCO content reaches a theoretical value, adding chain extender 2, 6-diaminopyridine and glycine, detecting the content of the isocyanate in the system every 30min, cooling the reaction system to 35 ℃ until the content of the isocyanate does not change, adding organosilicon/fluorine modifier Octadecyltrichlorosilane (ODTS), modifying for 1h, continuously cooling, adding triethylamine, adding the metal nanomaterial subjected to surface activation after neutralizing for 1h, mechanically stirring for 45min, and removing the solvent through reduced pressure distillation to obtain the spider silk bionic high-toughness polyurea. And finally, adding an antifoaming agent, a leveling agent and other additives, uniformly mixing, uniformly coating the mixture on a polytetrafluoroethylene board, standing at normal temperature for 48 hours, and then putting into a 70 ℃ oven for curing for 36 hours to obtain the functionalized spider silk bionic high-toughness polyurea coating.
Experimental example 1
For ease of comparison, the formulations of the polyurea coatings prepared in examples 1-5 and comparative examples 1-7 above are summarized in Table 1.
TABLE 1
Figure RE-GDA0003968366960000091
Figure RE-GDA0003968366960000101
The polyurea coatings prepared in the above examples 1 to 5 and comparative examples 1 to 7 were tested for their impact toughness, tensile strength, adhesion strength, water absorption, ultraviolet aging resistance, acid and alkali corrosion resistance, and abrasion resistance, respectively, and the test results are shown in table 2.
The respective performance parameters of the biomimetic polyurea coatings prepared in examples 1-5 and comparative examples 1-7 were determined according to the following methods:
impact toughness: the assay was carried out according to GB/T33144-2016.
Tensile strength: the measurement was carried out in accordance with GB/T16777-2008.
Water absorption: the assay was performed according to GB/T8810-2005.
Ultraviolet aging resistance: the measurement was carried out in accordance with GB/T16777-2008.
Bonding strength: the measurement was carried out according to GB/T16777-2008.
Acid and alkali resistance: the measurement was carried out according to GB/T16777-2008.
Wear resistance: the measurement was carried out according to GB/T1768-2006.
TABLE 2 mechanical property data table of spider bionic type high-toughness polyurea coating
Figure RE-GDA0003968366960000111
As can be seen from table 2:
in comparative examples 1 to 5, amino acid, nano ZnO particles, a metal ion crosslinking agent and a surfactant are not contained, and the obtained coating has the defects of low strength, insufficient toughness, poor water resistance, weak adhesion with a matrix, low wear resistance and the like in mechanical properties;
in the comparative example 6, the coating does not contain nano ZnO particles, metal ion cross-linking agents and surfactants, and the obtained coating has the defects of lower strength, low toughness and poor acid-base corrosion resistance;
in comparative example 7, the paint contains no metal ion crosslinking agent and surfactant, and has the defects of low strength, poor toughness and weak adhesion property in the mechanical property of the obtained paint;
the spider silk bionic polyurea coating prepared by the embodiment of the invention has high toughness, excellent aging resistance, acid and alkali resistance, water resistance, wear resistance and good bonding performance.
Finally, it should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the embodiments of the invention.
It will be apparent to those skilled in the art that various modifications and variations can be made in the embodiments of the present invention without departing from the spirit or scope of the embodiments of the invention. Thus, if such modifications and variations of the embodiments of the present invention fall within the scope of the claims of the embodiments of the present invention and their equivalents, the embodiments of the present invention are also intended to encompass such modifications and variations.

Claims (10)

1. The spider silk bionic high-toughness polyurea is characterized by comprising the following components in parts by weight:
25 to 45 portions of polyamine organic compound, 15 to 40 portions of isocyanate, 0.1 to 2 portions of catalyst, 0.5 to 5 portions of amino acid compound, 0.1 to 10 portions of amine chain extender, 0.1 to 10 portions of neutralizer, 0.5 to 10 portions of inorganic metal nano material, 0.5 to 15 portions of organic silicon fluorine modifier, 0.1 to 5 portions of metal ion cross linker, 1 to 5 portions of dispersant, 0.5 to 10 portions of surfactant and 1 to 5 portions of solvent.
2. The spider silk bionic high-toughness polyurea according to claim 1, wherein the spider silk bionic high-toughness polyurea comprises the following components in parts by weight:
32 to 40 parts of polyamine organic compound, 28 to 38 parts of isocyanate, 0.1 to 2 parts of catalyst, 0.5 to 5 parts of amino acid compound, 0.5 to 8 parts of amine chain extender, 0.1 to 8 parts of neutralizer, 0.5 to 10 parts of inorganic metal nano material, 0.5 to 15 parts of organic silicon fluorine modifier, 0.1 to 5 parts of metal ion cross linker, 1 to 5 parts of dispersant, 0.5 to 10 parts of surfactant and 1 to 5 parts of solvent.
3. A high-tenacity polyurea of the spider silk biomimetic type according to claim 1 or 2,
the polyamine organic compound is selected from one or more of biomass secondary amine, polyethyleneimine, polydopamine, polyacrylamide, amino-terminated polyether and polyaspartic ester; the biomass secondary amine comprises plant oil-based secondary amine selected from one or more of soybean oil-based secondary amine, peanut oil-based secondary amine, castor oil-based secondary amine and sesame oil-based secondary amine;
the isocyanate is selected from one or more of isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), hexamethylene Diisocyanate (HDI), HDI trimer, dicyclohexyl methane diisocyanate (HMDI), toluene Diisocyanate (TDI) and Lysine Diisocyanate (LDI);
the inorganic metal ion crosslinking agent is selected from ferric chloride (FeCl) 3 ) Ferrous chloride (FeCl) 2 ) Manganese dichloride (MnCl) 2 ) One or more of zinc oxide, aluminum chloride, aluminum sulfate nano-grade, chromium nitrate, aluminum isopropoxide, titanium acetylacetonate and zinc acetate;
the amino acid compound is selected from one or more of glycine, glutamic acid, serine, leucine, tyrosine, methionine, alanine, aspartic acid, glutamine, lysine and asparagine;
the amine chain extender is selected from one or more of levodopa, ethylenediamine sodium ethanesulfonate, 2, 6-diaminopyridine, isophorone diamine, 3, 6-diaminocarbazole, 1, 6-hexamethylene diamine, MOCA, diethylenetriamine (DETA), diethyltoluene diamine, diethylenetriamine and N-aminoethyl piperazine;
the organosilicon fluorine modifier is selected from 1H,2H perfluorododecyl triethoxysilane (HFDS), polytrifluoropropylmethylsiloxane (PTFPMS), 1H,2H perfluorododecyl trichlorosilane (PFDTS), KH-550, KH-560, octadecyltrichlorosilane (ODTS), phenyltrimethoxysilane (PTMS), trimethylchlorosilane (TMCS), chlorotrimethylsilane (Me) 3 SiCl), silicon sulfide rubber, heptafluoro-1, 2-tetrahydrodecyl dimethylchlorosilane (HFTD), methyl silicone resin (Al) one or more of silicone, 1, 3-Hexamethyldisilazane (HMDS), and methyltriethoxysilane;
the inorganic metal nano material is selected from nano ZnO, nano GaN and nano Al 2 O 3 Nano Fe 2 O 3 Nano NiO and nano ZrO 2 Nano GaAs, nano TiO 2 And nano CaCO 3 One or more of (a).
4. The spider silk biomimetic high-toughness polyurea according to claim 1 or 2, wherein the catalyst is selected from one or more of dibutyl tin dilaurate (DBTDL), stannous octoate, bismuth isooctanoate, bismuth laurate, bismuth neodecanoate, and bismuth naphthenate.
5. A spider silk biomimetic high tenacity polyurea according to claim 1 or 2, wherein the neutralizing agent is selected from one or more of Triethylamine (TEA), triisopropanolamine (triisopropanolamine), triethanolamine (TEOA), diethanolamine, dimethylethanolamine (DMEA), diethylethanolamine (DEEA), and 2-amino-2-methylpropanol.
6. A spider silk bionic high-toughness polyurea according to claim 1 or 2, wherein the dispersant is selected from one or more of ethanol, deionized water, acetone, butanone, sodium dodecyl sulfate and methyl amyl alcohol.
7. A high tenacity polyurea according to claim 1 or 2, wherein the surfactant is selected from one or more of ethylene glycol, sodium dodecyl sulphate, sodium hexadecyl benzene sulphonate, sodium dodecyl benzene sulphonate, hexadecyl trimethyl ammonium bromide, sodium dioctyl sulfosuccinate, sodium stearate and polysorbate.
8. The spider silk bionic high-toughness polyurea according to claim 1 or 2, wherein the defoaming agent is selected from one or more of high-carbon alcohol, polydimethylsiloxane, ethanol, emulsified silicone oil, lauryl phenylacetate, a high-carbon alcohol fatty acid ester compound, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene amine ether, polyoxypropylene glycerol ether and polyoxypropylene;
the leveling agent is selected from one or more of butyl cellulose, polyacrylic acid, diacetone alcohol, polydimethylsiloxane, polymethylphenyl siloxane, solvesso150 and carboxymethyl cellulose;
the solvent is selected from one or more of N, N-Dimethylformamide (DMF), acetone (AC), tetrahydrofuran (THF), 2-butanone, dimethyl sulfoxide (DMSO), isopropyl acetate, propylene glycol and pyridine.
9. A method for preparing a high tenacity, biomimetic spider silk type polyurea according to any of claims 1-8, characterized in that the method comprises:
dispersing the inorganic metal nano material in H 2 O 2 Stirring the solution, centrifuging, cleaning, drying, dispersing in a solvent, adding a surfactant to adjust the pH, ultrasonically dispersing, heating to 50-80 ℃, stirring for 3-5 hours, cooling, centrifuging and drying to obtain a surface-activated metal nano material;
uniformly mixing polyamine organic compounds, a catalyst, a solvent and isocyanate, heating in a water bath to 25-80 ℃, reacting for 2-4 h under stirring, adding an amine chain extender to perform chain extension reaction for 1-2 h, cooling to 25-50 ℃ when the content of the isocyanate in a detection system is not changed, adding an organic silicon fluorine modifier to modify for 1-2 h, continuously cooling to 0-25 ℃, adding a neutralizer to neutralize for 1-2 h, adding a metal ion crosslinking agent to react for 1-1.5 h, adding the surface-activated metal nano material to react for 1-2 h, and removing the solvent through reduced pressure distillation to obtain the spider silk bionic high-toughness polyurea.
10. A coating layer, characterized in that the coating layer is a film formed by coating and curing the spider silk bionic high-toughness polyurea of any one of claims 1 to 8.
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