CN115558082B - Spider silk bionic type high-toughness polyurea, preparation method and coating thereof - Google Patents
Spider silk bionic type high-toughness polyurea, preparation method and coating thereof Download PDFInfo
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- C08G18/753—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
- 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 application discloses a spider silk bionic type high-toughness polyurea, which comprises the following components in parts by weight: 25-45 parts of polyamine organic compound, 15-40 parts of isocyanate, 0.1-2 parts of catalyst, 0.5-5 parts of amino acid compound, 0.1-10 parts of amine chain extender, 0.1-10 parts of neutralizer, 0.5-10 parts of inorganic metal nano material, 0.5-15 parts of organosilicon fluorine modifier, 0.1-5 parts of metal ion cross-linking agent, 1-5 parts of dispersing agent, 0.5-10 parts of surfactant and 1-5 parts of solvent. Through intermolecular forces between polar/nonpolar groups of the organic-inorganic compound, the coating is highly crosslinked to form a compact network structure through chemical bonds, hydrogen bonds, metal coordination bonds and the like, so that the coating formed by the coating has super toughness, excellent mechanical properties and chemical durability, and can effectively inhibit damage of external impact load to the coating.
Description
Technical Field
The application relates to the technical field of industrial coatings and functionalized polymers, in particular to a spider silk bionic type high-toughness polyurea, a preparation method thereof and a coating.
Background
With the continuous advancement of urban 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-chemical properties and very high dynamic resistance, superhigh speed and explosion load resistance, so that the polyurea material is widely applied to the fields of chemical protection, explosion protection of the 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 reacting a polyisocyanate with a polyamine (comprising a mixture of a resin and a chain extender) to form urea linkages (-NH-CO-NH-). The hard segments comprise isocyanate and amine chain extenders which self-assemble into hard domains by intermolecular interactions embedded in a continuous matrix of flexible soft segments formed from long chain diamines. And a large number of groups with stronger polarity in the hard segment, such as urea bonds, carbamate groups, ester groups and the like, can form a large number of strong acting force hydrogen bonds among molecular chains, so that the mechanical property of the polyurea material is promoted to be improved. In recent years, the requirements of people on toughness (impact resistance) of protective coatings are also becoming more and more severe, and conventional polyurea coatings often wear out the coating due to insufficient toughness, so that the normal service life of the coating cannot be achieved.
The mechanical properties of the traditional polyurea elastomer coating mainly come from the phase separation structure of segmented blocks, wherein the hard segments comprise isocyanate and amine chain extender, the hard segments are self-assembled into hard domains through intermolecular interaction force and then are embedded into a continuous matrix of flexible soft segments generated by long-chain polyamine, and the hard domains play a physical crosslinking role. However, the mechanical properties such as toughness, tensile strength and Young's modulus are far from adequate for protection of some important equipment
Therefore, in order to solve the above-mentioned technical problems, there is a need to develop a novel polyurea coating having super toughness and excellent mechanical properties and chemical durability, which can effectively suppress damage to the coating by external impact load.
Disclosure of Invention
The application aims to provide a spider silk bionic type high-toughness polyurea, a preparation method and a coating thereof, wherein the spider silk bionic type high-toughness polyurea is formed by highly crosslinking chemical bonds, hydrogen bonds, metal coordination bonds and the like through intermolecular forces between polar/nonpolar groups of organic-inorganic compounds, so that the coating formed by the coating has super toughness and excellent mechanical properties and chemical durability, and the damage of external impact load to the coating can be effectively inhibited.
In order to achieve the above object, the present application provides a spider silk bionic type high-toughness polyurea, which comprises, in parts by weight:
25-45 parts of polyamine organic compound, 15-40 parts of isocyanate, 0.1-2 parts of catalyst, 0.5-5 parts of amino acid compound, 0.1-10 parts of amine chain extender, 0.1-10 parts of neutralizer, 0.5-10 parts of inorganic metal nano material, 0.5-15 parts of organosilicon fluorine modifier, 0.1-5 parts of metal ion cross-linking agent, 1-5 parts of dispersing agent, 0.5-10 parts of surfactant and 1-5 parts of solvent.
Further, the polyamine organic compound is selected from one or more of secondary biomass amine, polyethyleneimine, polydopamine, polyacrylamide, amino terminated polyether and polyaspartate; the biomass secondary amine comprises a vegetable oil-based secondary amine, and is selected from one or more of a soybean oil-based secondary amine, a peanut oil-based secondary amine, a castor oil-based secondary amine and a 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, dicyclohexylmethane diisocyanate (HMDI), toluene Diisocyanate (TDI) and Lysine Diisocyanate (LDI);
the inorganic metal ion cross-linking 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, chromium nitrate, aluminum isopropoxide, titanium acetylacetonate and zinc acetate;
the amino acid compound is 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 L-dopamine, ethylenediamine sodium ethanesulfonate, 2, 6-diaminopyridine, isophorone diamine, 3, 6-diaminocarbazole, 1, 6-hexamethylenediamine, MOCA, diethylenetriamine (DETA), diethyltoluenediamine, diethylenetriamine and N-aminoethylpiperazine;
the organosilicon fluorine modifier is selected from 1H,2H perfluoro dodecyl triethoxy silane (HFDS), poly trifluoro propyl methyl siloxane (PTFPMS), 1H,2H perfluoro dodecyl trichlorosilane (PFDTS), KH-550, KH-560, octadecyl trichlorosilane (ODTS), phenyl trimethoxy silane (PTMS), trimethyl chlorosilane (TMCS), chlorotrimethylsilane (Me) 3 SiCl), vulcanized silicone rubber, heptafluoro-1, 2-tetrahydrodecyl dimethyl chlorosilane (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 Nano CaCO 3 One or more of the following.
Further, the catalyst is selected from one or more of dibutyl tin dilaurate (DBTDL), stannous octoate, bismuth iso-octoate, bismuth laurate, bismuth neodecanoate, and bismuth naphthenate.
Further, the neutralizing agent is selected from one or more of Triethylamine (TEA), 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 hexadecyl benzene sulfonate, sodium dodecyl benzene sulfonate, cetyltrimethylammonium bromide, sodium dioctyl succinate sulfonate, sodium stearate and polysorbate.
Further, the defoamer is selected from one or more of higher alcohols, polydimethylsiloxane, ethanol, emulsified silicone oil, lauryl phenylacetate, higher alcohol fatty acid ester compound, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene alcohol amine ether, polyoxypropylene glycerol ether and polyoxypropylene;
the leveling agent is one or more selected from butyl cellulose, polyacrylic acid, diacetone alcohol, polydimethylsiloxane, polymethylphenylsiloxane, 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 application also provides a preparation method of the spider silk bionic type high-toughness polyurea, which comprises the following steps:
dispersing the inorganic metal nano material in H 2 O 2 Stirring, centrifuging, cleaning and drying, dispersing in solvent, adding surfactant to regulate pH, ultrasonic dispersing, heating to 50-80 deg.c, stirring for 3-5 hrThen cooling, centrifuging and drying to obtain the surface-activated metal nano material;
uniformly mixing polyamine organic compound, catalyst, solvent and isocyanate, heating in water bath to 25-80 ℃, reacting for 2-4 h under stirring, adding amine chain extender, performing chain extension reaction for 1-2 h, cooling to 25-50 ℃ when the isocyanate content of the detection system is no longer changed, adding organosilicon fluorine modifier for modification for 1-2 h, continuously cooling to 0-25 ℃, adding neutralizer for neutralization for 1-2 h, adding metal ion cross-linking agent for reacting for 1-1.5 h, adding surface-activated metal nano-material for reacting for 1-2 h, and distilling under reduced pressure to remove solvent to obtain the spider silk bionic high-toughness polyurea.
The embodiment of the application also provides a coating, which is formed by coating and curing the spider silk bionic type high-toughness polyurea.
One or more technical solutions in the embodiments of the present application at least have the following technical effects or advantages:
1. according to the spider silk bionic type high-toughness polyurea and the preparation method thereof provided by the embodiment of the application, through the bonding action of isocyanate, polyamine organic compounds, metal ion crosslinking agents, chain extenders, silicon/fluorine modifiers, metal nano materials and other components, a highly crosslinked organic whole is formed through chemical bonds, coordination bonds, hydrogen bonds and intermolecular interaction forces, so that a coating formed by the prepared coating has excellent heat resistance, tensile property, adhesive property, ageing resistance, acid and alkali resistance and hydrolysis resistance. The prepared polyurea coating grafts amino acid organic matters such as glycine, alanine and the like onto a polyurea chain segment through simulating a spider silk structure to form a beta-sheet conformation and a spiral conformation, so that the polymer coating is endowed with excellent elasticity and toughness. And transition metal ions are doped into the polyurea system as a cross-linking agent, and metal-polyurea complex or stronger covalent bonds are formed at hydrogen bond sites through chelation between the metal ions and polar groups in the system, so that the toughening effect is achieved. The regular/irregular distribution of the amino acid chain segments in the molecular structure of the polyurea coating cooperates with the coordination toughening effect of metal ions, so that the coating has super toughness and tensile strength.
2. The bionic polyurea coating has moderate curing speed, simple synthesis process, no complex and complicated links, low preparation cost and contribution to realizing industrial production.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a simplified schematic illustration of the spider silk biomimetic polyurea coating prepared in examples 1-5 of the present application;
FIG. 2 is a graph showing the bonding mechanism of the spider silk bionic polyurea coating prepared in examples 1-5 of the application applied to the field of concrete coating.
Detailed Description
The advantages and various effects of the embodiments of the present application will be more clearly apparent from the following detailed description and examples. Those skilled in the art will appreciate that these specific implementations and examples are provided to illustrate, but not limit, examples of the present application.
Throughout the specification, unless specifically indicated otherwise, the terms used herein should be understood in accordance with the meanings commonly used in the art. Thus, 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 application belong. In case of conflict, the present specification will control.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the examples of the present application are commercially available or may be prepared by existing methods.
The technical scheme provided by the embodiment of the application aims to solve the technical problems, and the overall thought is as follows:
according to another exemplary embodiment of the present application, there is provided a method for preparing a spider silk biomimetic high-toughness polyurea, the method comprising:
step S1, dispersing the inorganic metal nano material in H 2 O 2 Stirring, centrifuging, cleaning and drying the solution, dispersing in a solvent, adding a surfactant to adjust the pH, performing ultrasonic dispersion, heating to 50-80 ℃, stirring for 3-5 hours, cooling, centrifuging and drying to obtain the surface-activated metal nanomaterial;
the reaction equation involved is:
0.5-10% of inorganic metal nano material and 0.5-10% of surfactant in parts by weight;
s2, uniformly mixing a polyamine organic compound, a catalyst, a solvent and isocyanate, heating in a water bath to 25-80 ℃, reacting for 2-4 hours under stirring, adding an amine chain extender, performing chain extension reaction for 1-2 hours, cooling to 25-50 ℃ when the isocyanate content of a detection system is no longer changed, adding an organosilicon fluorine modifier for modification for 1-2 hours, continuously cooling to 0-25 ℃, adding a neutralizer for neutralization for 1-2 hours, adding a metal ion crosslinking agent for reacting for 1-1.5 hours, adding a dispersing agent (1-5 parts of a dispersing agent) for dispersing the surface-activated metal nano material, reacting for 1-2 hours, and distilling under reduced pressure to remove the solvent to obtain the spider silk bionic high-toughness polyurea.
25-45 parts of polyamine organic compound, 0.1-2 parts of catalyst, 1-5 parts of solvent, 15-35 parts of isocyanate, 0.1-10 parts of amine chain extender, 0.5-15 parts of organosilicon fluorine modifier, 0.1-10 parts of neutralizer, 0.1-5 parts of metal ion cross-linking agent and 1-5 parts of dispersing agent;
and (3) the spider silk bionic type high-toughness polyurea. And finally, adding 0.1-3 parts of defoaming agent and 0.1-3 parts of leveling agent, uniformly mixing, uniformly coating the mixture on a polytetrafluoroethylene plate, standing for 48 hours at normal temperature, and then placing the mixture in a 70 ℃ oven for curing for 36 hours to obtain the functionalized spider silk bionic type high-toughness polyurea coating.
The spider silk bionic type high-toughness polyurea and the preparation method thereof are described in detail below by combining examples, comparative examples and experimental data.
The surface-activated metal nano material provided by the embodiment of the application is prepared by adopting the following method:
dispersing nano ZnO in H 2 O 2 Stirring 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
The spider bionic type high-strength and 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 modifier octadecyl trichlorosilane (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 leveling agent and 2 parts of solvent.
The preparation method of the spider bionic type high-strength and high-toughness polyurea protective coating comprises the following steps: adding fully dried polyaspartic acid ester, stannous octoate catalyst, acetone solvent and corresponding mass of isophorone diisocyanate into a three-port reaction kettle equipped with a mechanical stirrer, a reflux condenser pipe and a nitrogen inlet and outlet respectively, reacting in the reaction kettle filled with nitrogen, heating to 65 ℃ in a water bath, 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 isocyanate content of the system every 30min, cooling the reaction system to 35 ℃ when the isocyanate content is not changed, adding organosilicon/fluorine modifier octadecyl trichlorosilane (ODTS), modifying for 1h, continuing cooling, adding neutralizing agent triethylamine, adding metal ion cross-linking agent ferric chloride for reacting for 1h after neutralizing for 1h, then adding metal nano ZnO particles modified by surfactant cetyl trimethyl ammonium bromide, mechanically stirring for 45min, and distilling off the solvent under reduced pressure to obtain the silk bionic high-toughness polyurea. And finally adding an external agent such as a defoaming agent, a leveling agent and the like, uniformly mixing, uniformly coating the mixture on a polytetrafluoroethylene plate, standing the mixture at normal temperature for 48 hours, and then placing the mixture in a 70 ℃ oven for curing for 36 hours to obtain the functionalized spider silk bionic type high-toughness polyurea coating.
Example 2
The spider bionic type high-strength and 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 neutralizing agent triethylamine, 3 parts of nano ZnO particles, 5 parts of organosilicon/fluorine modifier octadecyl trichlorosilane (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 leveling agent and 2 parts of solvent. The preparation method comprises the following steps: the same as in example 8.
Example 3
The spider bionic type high-strength and 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 octadecyl trichlorosilane (ODTS) as an organosilicon/fluorine modifier 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 leveling agent and 2 parts of solvent. The preparation method comprises the following steps: the same as in example 8.
Example 4
The spider bionic type high-strength and 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 modifier octadecyl trichlorosilane (ODTS), 1 part of zinc oxide metal cross-linking agent, 3 parts of dispersing agent, 5 parts of surfactant hexadecyl trimethyl ammonium bromide, 0.5 part of defoamer, 0.5 part of flatting agent and 2 parts of solvent. The preparation method comprises the following steps: the same as in example 8.
Example 5
The spider bionic type high-strength and 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 modifier heptafluoro-1, 2-tetrahydrodecyl dimethyl chlorosilane (HFTD), 3 parts of dispersing agent, 5 parts of surfactant hexadecyl 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: the same as in example 8.
Comparative example 1
The spider bionic type high-strength and 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 octadecyl trichlorosilane (ODTS), 3 parts of dispersing agent, 0.5 part of defoaming agent, 0.5 part of leveling agent and 2 parts of solvent.
The preparation method of the spider bionic type high-strength and high-toughness polyurea protective coating comprises the following steps: adding fully dried polyaspartic acid ester, stannous octoate catalyst, acetone solvent and corresponding mass of isophorone diisocyanate into a three-port reaction kettle equipped with a mechanical stirrer, a reflux condenser pipe and a nitrogen inlet and outlet respectively, reacting in the reaction kettle filled with nitrogen, heating to 65 ℃ in a water bath, reacting for a certain time under medium-speed stirring until the-NCO content reaches a theoretical value, adding a chain extender 2, 6-diaminopyridine, detecting the isocyanate content of the system every 30min, cooling the reaction system to 35 ℃ until the isocyanate content is not changed, adding an organosilicon/fluorine modifier octadecyl trichlorosilane (ODTS), modifying for 1h, continuing cooling, adding a 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 external agent such as a defoaming agent, a leveling agent and the like, uniformly mixing, uniformly coating the mixture on a polytetrafluoroethylene plate, standing the mixture at normal temperature for 48 hours, and then placing the mixture in a 70 ℃ oven for curing for 36 hours to obtain the functionalized spider silk bionic type high-toughness polyurea coating.
Comparative example 2
The spider bionic type high-strength and 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 octadecyl trichlorosilane (ODTS), 3 parts of dispersing agent, 0.5 part of defoaming agent, 0.5 part of leveling agent and 2 parts of solvent. The preparation method comprises the following steps: the same as in example 1.
Comparative example 3
The spider bionic type high-strength and 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 octadecyl trichlorosilane (ODTS), 3 parts of dispersing agent, 0.5 part of defoaming agent, 0.5 part of leveling agent and 2 parts of solvent. The preparation method comprises the following steps: the same as in example 1.
Comparative example 4
The spider bionic type high-strength and 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 octadecyl trichlorosilane (ODTS), 3 parts of dispersing agent, 0.5 part of defoaming agent, 0.5 part of leveling agent and 2 parts of solvent. The preparation method comprises the following steps: the same as in example 1.
Comparative example 5
The spider bionic type high-strength and 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 octadecyl trichlorosilane (ODTS), 3 parts of dispersing agent, 0.5 part of defoaming agent, 0.5 part of leveling agent and 2 parts of solvent. The preparation method comprises the following steps: the same as in example 1.
Comparative example 6
The spider bionic type high-strength and 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, 5 parts of organosilicon/fluorine modifier octadecyl trichlorosilane (ODTS), 3 parts of dispersing agent, 0.5 part of defoaming agent, 0.5 part of leveling agent and 2 parts of solvent.
The preparation method of the spider bionic type high-strength and high-toughness polyurea protective coating comprises the following steps: adding fully dried polyaspartic acid ester, stannous octoate catalyst, acetone solvent and corresponding mass of isophorone diisocyanate into a three-port reaction kettle equipped with a mechanical stirrer, a reflux condenser pipe and a nitrogen inlet and outlet respectively, reacting in the reaction kettle filled with nitrogen, heating to 65 ℃ in a water bath, 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 isocyanate content of the system every 30min, cooling the reaction system to 35 ℃ until the isocyanate content is not changed, adding organosilicon/fluorine modifier octadecyl trichlorosilane (ODTS), modifying for 1h, continuing 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 external agent such as a defoaming agent, a leveling agent and the like, uniformly mixing, uniformly coating the mixture on a polytetrafluoroethylene plate, standing the mixture at normal temperature for 48 hours, and then placing the mixture in a 70 ℃ oven for curing for 36 hours to obtain the functionalized spider silk bionic type high-toughness polyurea coating.
Comparative example 7
The spider bionic type high-strength and 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 modifier octadecyl trichlorosilane (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 type high-strength and high-toughness polyurea protective coating comprises the following steps: adding fully dried polyaspartic acid ester, stannous octoate catalyst, acetone solvent and corresponding mass of isophorone diisocyanate into a three-port reaction kettle equipped with a mechanical stirrer, a reflux condenser pipe and a nitrogen inlet and outlet respectively, reacting in the reaction kettle filled with nitrogen, heating to 65 ℃ in a water bath, 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 isocyanate content of the system every 30min, cooling the reaction system to 35 ℃ until the isocyanate content is not changed, adding organosilicon/fluorine modifier octadecyl trichlorosilane (ODTS), modifying for 1h, continuing cooling, adding neutralizing agent triethylamine, adding surface-activated metal nano material after neutralizing for 1h, mechanically stirring for 45min, and distilling to remove the solvent under reduced pressure to obtain the spider silk bionic high-toughness polyurea. And finally adding an external agent such as a defoaming agent, a leveling agent and the like, uniformly mixing, uniformly coating the mixture on a polytetrafluoroethylene plate, standing the mixture at normal temperature for 48 hours, and then placing the mixture in a 70 ℃ oven for curing for 36 hours to obtain the functionalized spider silk bionic type 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
The polyurea coatings prepared in examples 1 to 5 and comparative examples 1 to 7 were respectively tested for impact toughness, tensile strength, adhesive strength, water absorption, ultraviolet aging resistance, acid and alkali corrosion resistance, abrasion resistance, and other performance parameters, and the test results are shown in table 2.
The various performance parameters of the prepared biomimetic polyurea coatings of examples 1-5 and comparative examples 1-7 were determined as follows:
impact toughness: the measurement was carried out according to the GB/T33144-2016 standard.
Tensile strength: the measurement was carried out according to GB/T16777-2008 standard.
Water absorption rate: the measurement was carried out according to GB/T8810-2005 standard.
Ultraviolet aging resistance: the measurement was carried out according to GB/T16777-2008 standard.
Adhesive strength: the measurement was carried out according to GB/T16777-2008 standard.
Acid and alkali resistance: the measurement was carried out according to GB/T16777-2008 standard.
Abrasion resistance: the measurement was carried out according to GB/T1768-2006 standard.
Table 2 mechanical property data sheet of spider bionic type high strength and toughness polyurea coating
As can be seen from table 2:
in comparative examples 1 to 5, the coating obtained does not contain amino acid, nano ZnO particles, metal ion cross-linking agent and surfactant, and has the defects of low strength, insufficient toughness, poor water resistance, weak adhesion with a substrate, low wear resistance and the like;
in comparative example 6, the coating obtained without nano ZnO particles, metal ion cross-linking agent and surfactant has the disadvantages of low strength, low toughness and poor acid and alkali corrosion resistance;
in comparative example 7, the metal ion crosslinking agent and the surfactant are not contained, and the obtained coating has the defects of low strength, poor toughness and weak bonding performance in mechanical properties;
the spider silk bionic polyurea coating prepared by the embodiment of the application has high strength and toughness, excellent ageing resistance, acid and alkali resistance, water resistance, wear resistance and good bonding performance.
Finally, it is also 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 application 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. It is therefore intended that the following claims be interpreted as including the preferred embodiment and all such alterations and modifications as fall within the scope of the embodiments of the application.
It will be apparent to those skilled in the art that various modifications and variations can be made to the embodiments of the present application without departing from the spirit or scope of the embodiments of the application. Thus, the embodiments of the present application are intended to include such modifications and alterations insofar as they come within the scope of the embodiments of the application as claimed and the equivalents thereof.
Claims (10)
1. The spider silk bionic type high-toughness polyurea is characterized by comprising the following components in parts by weight:
25-45 parts of polyamine organic compound, 15-40 parts of isocyanate, 0.1-2 parts of catalyst, 0.5-5 parts of amino acid compound, 0.1-10 parts of amine chain extender, 0.1-10 parts of neutralizer, 0.5-10 parts of surface activated metal nano material, 0.5-15 parts of organosilicon fluorine modifier, 0.1-5 parts of metal ion cross-linking agent, 1-5 parts of dispersing agent and 1-5 parts of solvent; the preparation method of the surface-activated metal nano material comprises the following steps:
dispersing inorganic metal nano material in H 2 O 2 Stirring, centrifuging, cleaning, drying, dispersing in solvent, adding surfactant, and concoctingAfter pH, ultrasonic dispersion is carried out, after the temperature is raised to 50-80 ℃, stirring is carried out for 3-5 hours, cooling, centrifuging and drying are carried out, and the surface activated metal nano material is obtained, wherein the inorganic metal ion cross-linking agent is one or more selected from ferric chloride, ferrous chloride, manganese dichloride, zinc oxide, aluminum chloride, chromium nitrate, aluminum isopropoxide, titanium acetylacetonate and zinc acetate; the organosilicon fluorine modifier is selected from 1H,2H perfluoro dodecyl triethoxy silane, poly trifluoro propyl methyl siloxane, 1H,2H perfluoro dodecyl trichlorosilane, KH-550, KH-560, octadecyl trichlorosilane, phenyl trimethoxy silane, trimethylchlorosilane, chlorotrimethylsilane, vulcanized silicone rubber, heptafluoro-1, 2-tetrahydrodecyl dimethyl chlorosilane one or more of methyl silicone, 1, 3-hexamethyldisilazane, and methyltriethoxysilane.
2. The spidroin-type high-toughness polyurea of claim 1, wherein the spidroin-type high-toughness polyurea comprises, in parts by weight:
32-40 parts of polyamine organic compound, 28-38 parts of isocyanate, 0.1-2 parts of catalyst, 0.5-5 parts of amino acid compound, 0.5-8 parts of amine chain extender, 0.1-8 parts of neutralizer, 0.5-10 parts of surface activated metal nano material, 0.5-15 parts of organosilicon fluorine modifier, 0.1-5 parts of metal ion cross-linking agent, 1-5 parts of dispersing agent and 1-5 parts of solvent.
3. A spidroin-simulated high-toughness polyurea as claimed in claim 1 or 2, wherein,
the polyamine organic compound is selected from one or more of secondary biomass amine, polyethyleneimine, polydopamine, polyacrylamide, amino-terminated polyether and polyaspartic ester; the biomass secondary amine comprises a vegetable oil-based secondary amine, and is selected from one or more of a soybean oil-based secondary amine, a peanut oil-based secondary amine, a castor oil-based secondary amine and a sesame oil-based secondary amine;
the isocyanate is selected from one or more of isophorone diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, HDI trimer, dicyclohexylmethane diisocyanate, toluene diisocyanate and lysine diisocyanate;
the amino acid compound is 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 L-dopamine, ethylenediamine sodium ethanesulfonate, 2, 6-diaminopyridine, isophorone diamine, 3, 6-diaminocarbazole, 1, 6-hexamethylenediamine, MOCA, diethylenetriamine, diethyltoluenediamine, diethylenetriamine and N-aminoethylpiperazine;
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 Nano CaCO 3 One or more of the following.
4. A spidroin bionic high tenacity polyurea according to claim 1 or 2, wherein the catalyst is selected from one or more of dibutyl tin dilaurate, stannous octoate, bismuth iso-octoate, bismuth laurate, bismuth neodecanoate and bismuth naphthenate.
5. A spidroin bionic high tenacity polyurea according to claim 1 or 2, wherein the neutralizing agent is selected from one or more of triethylamine, triisopropanolamine, triethanolamine, diethanolamine, dimethylethanolamine, diethylethanolamine and 2-amino-2-methylpropanol.
6. A spidroin bionic high tenacity polyurea according to claim 1 or 2, wherein the dispersing agent is selected from one or more of ethanol, deionized water, acetone, butanone and methylpentanol.
7. A spidroin-biomimetic high-toughness polyurea according to claim 1 or 2, wherein the surfactant is selected from one or more of sodium dodecyl sulphate, sodium hexadecyl benzene sulphonate, sodium dodecyl benzene sulphonate, cetyltrimethyl ammonium bromide, sodium dioctyl succinate sulphonate, sodium stearate and polysorbate.
8. A spidroin-biomimetic high-toughness polyurea according to claim 1 or 2, wherein the solvent is selected from one or more of N, N-dimethylformamide, acetone, tetrahydrofuran, 2-butanone, dimethyl sulfoxide, isopropyl acetate and pyridine.
9. A method of preparing the spidroin-simulated high toughness polyurea according to any one of claims 1 to 8, comprising:
dispersing inorganic metal nano material in H 2 O 2 Stirring, centrifuging, cleaning and drying the solution, dispersing in a solvent, adding a surfactant, adjusting the pH value to 6, performing ultrasonic dispersion, heating to 50-80 ℃, stirring for 3-5 hours, cooling, centrifuging and drying to obtain the surface-activated metal nanomaterial;
uniformly mixing polyamine organic compound, catalyst, solvent and isocyanate, heating in water bath to 25-80 ℃, reacting for 2-4 h under stirring, adding amine chain extender and amino acid compound for chain extension reaction for 1-2 h, cooling to 25-50 ℃ when the isocyanate content of the detection system is no longer changed, adding organosilicon fluorine modifier for modification for 1-2 h, continuously cooling to 0-25 ℃, adding neutralizer for neutralization for 1-2 h, adding metal ion cross-linking agent for reaction for 1-1.5 h, adding the surface-activated metal nano material dispersed by a dispersing agent for reaction for 1-2 h, and carrying out reduced pressure distillation to remove the solvent to obtain the spider silk bionic high-toughness polyurea.
10. A coating, characterized in that the coating is a capsule formed by coating and curing the spider silk bionic type high-toughness polyurea according to any one of claims 1-8.
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