CN115895411B - Preparation method and application of double-component spray self-repairing polyurea coating - Google Patents
Preparation method and application of double-component spray self-repairing polyurea coating Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 68
- 239000011248 coating agent Substances 0.000 title claims abstract description 65
- 229920002396 Polyurea Polymers 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000007921 spray Substances 0.000 title claims abstract description 10
- 238000005507 spraying Methods 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000005260 corrosion Methods 0.000 claims abstract description 8
- 230000003197 catalytic effect Effects 0.000 claims abstract description 7
- 238000004132 cross linking Methods 0.000 claims abstract description 7
- 239000004970 Chain extender Substances 0.000 claims abstract description 6
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 6
- 229920000642 polymer Polymers 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 18
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 15
- 229920000570 polyether Polymers 0.000 claims description 15
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical group Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 12
- -1 polydimethylsiloxane Polymers 0.000 claims description 9
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 claims description 7
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 238000007711 solidification Methods 0.000 claims description 6
- 230000008023 solidification Effects 0.000 claims description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 5
- 229960003280 cupric chloride Drugs 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- 150000003141 primary amines Chemical class 0.000 claims description 4
- 150000003335 secondary amines Chemical group 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 claims description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 2
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 claims description 2
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 2
- 239000009261 D 400 Substances 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- MOAAMPQMKNSCEL-UHFFFAOYSA-N N-phenylaniline toluene Chemical compound C1(=CC=CC=C1)NC1=CC=CC=C1.C1(=CC=CC=C1)C MOAAMPQMKNSCEL-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- WNYIBZHOMJZDKN-UHFFFAOYSA-N n-(2-acetamidoethyl)acetamide Chemical compound CC(=O)NCCNC(C)=O WNYIBZHOMJZDKN-UHFFFAOYSA-N 0.000 claims description 2
- UQVKNKXDSWRQJE-UHFFFAOYSA-N n-(3-acetamidophenyl)acetamide Chemical compound CC(=O)NC1=CC=CC(NC(C)=O)=C1 UQVKNKXDSWRQJE-UHFFFAOYSA-N 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- NMWCVZCSJHJYFW-UHFFFAOYSA-M sodium;3,5-dichloro-2-hydroxybenzenesulfonate Chemical compound [Na+].OC1=C(Cl)C=C(Cl)C=C1S([O-])(=O)=O NMWCVZCSJHJYFW-UHFFFAOYSA-M 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 16
- 229910021389 graphene Inorganic materials 0.000 abstract description 11
- 230000007797 corrosion Effects 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002041 carbon nanotube Substances 0.000 abstract description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002105 nanoparticle Substances 0.000 abstract description 4
- 230000003068 static effect Effects 0.000 abstract description 4
- 229920002748 Basalt fiber Polymers 0.000 abstract description 3
- 239000000945 filler Substances 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 abstract description 3
- 238000005286 illumination Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 230000008439 repair process Effects 0.000 description 6
- 238000000498 ball milling Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical group C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 239000004811 fluoropolymer Substances 0.000 description 3
- 229920002313 fluoropolymer Polymers 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 3
- 230000003373 anti-fouling effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229960004306 sulfadiazine Drugs 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920003226 polyurethane urea Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The application discloses a preparation method and application of a bi-component spray self-repairing polyurea coating, which comprises the following specific steps: the component A is prepared by reacting diisocyanate and a dihydroxyl-terminated polymer, the component B is prepared by mixing a post-crosslinking curing agent, a chain extender and a catalytic repairing agent, the component A and the component B are introduced into spraying equipment after being mixed and sprayed to prepare a coating, the coating is further cured after heating and post-treatment to obtain a final coating, and the prepared coating can be used in the fields of wear resistance, corrosion resistance, static resistance and the like, has self-repairing performance, and can realize self-repairing through heating or near infrared illumination when mechanical damage is received. The wear resistance, corrosion resistance, static resistance and other performances of the composite material are further improved by introducing nano fillers such as silica nano particles, basalt fibers, graphene oxide, graphene, carbon nanotubes or conductive carbon black.
Description
Technical Field
The application belongs to the field of sub self-repairing anti-coating layers, and particularly relates to a preparation method and application of a bi-component spray self-repairing polyurea coating.
Background
The polyurea coating has excellent wear resistance, corrosion resistance and other performances, is widely used in the corrosion resistance field, and can be developed to have a self-repairing function so as to prolong the service life. The usual construction method for polyurea coatings is a two-component spray method. The double-component, 100% solid content, does not contain any Volatile Organic Compounds (VOC), is environment-friendly, has no pollution to construction, and is harmless to use in sanitary construction. Most of the polyurea materials are not suitable for two-component spraying construction at present, and industrial application faces challenges.
CN113969096a discloses a high Jiang Shiwen self-repairing polyurea coating material, the molecular structure of which comprises a semi-thioacetal group and a urea group; the method for preparing the high-strength room temperature self-repairing polyurea coating material comprises the following steps: stirring a sulfhydryl compound with the functionality more than or equal to 2 and an aldehyde compound with the functionality more than or equal to 2 in a solvent according to a certain proportion until the viscosity is not increased any more, so as to obtain an aldehyde group-terminated polythioacetal precursor; stirring an amino compound with the functionality of more than or equal to 2 and an isocyanate compound with the functionality of more than or equal to 2 in a solvent according to a certain proportion until the viscosity is not increased any more, so as to obtain an amino-terminated polyurea precursor; the application utilizes the dynamic reversible semi-thioacetal group and the urea bond group to realize the rapid room temperature self-repair of the polyurea material; the mechanical property of the room temperature self-repairing polyurea material is improved by utilizing phase separation; graphene/polyurea anticorrosive coatings and conductive materials with rapid room temperature self-repairing performance are prepared by compounding graphene oxide/graphene. The technology utilizes the room temperature dynamic property of the semi-thioacetal group, can dissociate to generate sulfhydryl and aldehyde groups, and realizes self-repairing through the action of hydrogen bonds, and the preparation process needs to use an organic solvent, thus being not environment-friendly.
CN105400405a discloses a self-repairing organic silicon polyurethane/polyurea antifouling material, a method and application thereof. The material comprises: 40-95% of hydroxyl or amino terminated polysiloxane, 5-60% of diisocyanate and chain extender. The prepared antifouling material has the characteristics of high bonding strength, good mechanical property, good durability and scratch resistance, and also has simple self-repairing performance and good recoatability. The polyurea material disclosed by the application does not contain reversible covalent bonds; the preparation method is characterized by using a solution method, requiring an organic solvent, and being not environment-friendly.
CN113337192a discloses a method for preparing a polyurea composite coating with wear-resistant and self-repairing functions, which comprises the steps of preparing a polyurea a component and a polyurea B component respectively, mixing a fluoropolymer into the polyurea B component, uniformly dispersing to obtain a mixture, and adding the polyurea a component and the mixture into a connected spraying device to spray onto the surface of a metal substrate for solidification to obtain the composite coating; the fluoropolymer has a lubricating effect and a healing effect in a polyurea system, so that the prepared composite coating has high mechanical strength and excellent wear resistance, and can finish self-repairing of a damaged part only by heating after the coating is damaged, thereby effectively prolonging the service life of a coated part. The technology utilizes the migration of macromolecular chains in the fluoropolymer to realize self-repair; and the preparation process contains the fluorine polymer, so that the environmental protection performance is poor.
In view of the above-mentioned shortcomings, the application provides a preparation method and application of a bi-component spray self-repairing polyurea coating, which effectively solves the pollution problem and the poor practicability problem caused by the traditional process.
Disclosure of Invention
Aiming at the technical problems, the application provides a preparation method of a bi-component self-repairing polyurea coating, which has better mechanical property and self-repairing property, and can realize self-repairing by heating when mechanical damage is received, thereby prolonging the service life of the coating.
In order to achieve the above purpose, the present application adopts the following technical scheme:
a preparation method of a bi-component self-repairing polyurea coating comprises the following specific steps:
(1) And (3) preparation of the component A: heating diisocyanate and a dihydroxyl-terminated polymer at 60-100 ℃ for 2-4h to obtain a component A;
(2) And (3) preparation of a component B: the crosslinking curing agent, the chain extender and the catalytic repairing agent are uniformly stirred and mixed to obtain a component B;
(3) Preparation of a two-component self-healing polyurea coating: mixing the component A and the component B, introducing the mixture into spraying equipment at the same time, spraying to prepare a coating, controlling the gauge pressure of a component A and a component B in a range of 1200-1500 Psi and controlling the pressure difference of the component A and the component B below 200Psi, heating the mixture at 100 ℃ for 2 hours after the spraying is finished, and completely curing the mixture to obtain the double-component self-repairing polyurea coating.
Further, the diisocyanate is one or more of 4,4' -dicyclohexylmethane diisocyanate, isophorone diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, hexamethylene diisocyanate and diphenylmethane diisocyanate.
Further, the hydroxyl-terminated polymer is one or more of polytetrahydrofuran, polyethylene glycol, polypropylene glycol, polycaprolactone and polydimethylsiloxane, and the molecular weight is 200-5000g/mol.
Further, the crosslinking curing agent is a compound with the functionality of more than or equal to 3, wherein two functionalities are primary amine or secondary amine groups, and the residual functionality is hydroxyl.
Further, the chain extender is one or more of amino-terminated polyether D-230, amino-terminated polyether D-400, amino-terminated polyether ED-600, amino-terminated polyether D-1000, amino-terminated polyether D-2000, isophorone diamine, diacetyl m-phenylenediamine, N-dialkyl methyl diamine, diethyl toluene diamine, diacetyl ethylene diamine and dialkyl toluene diphenylamine.
Further, the chain extension repair agent is 2,2' - (methylenebis (sulfadiyl)) diethylamine.
Further, the catalytic repairing agent is copper chloride, and the content of the catalytic repairing agent is 0.1-1% of the total mass of the whole coating.
Furthermore, the A component or the B component can be further introduced with nano fillers such as silica nano particles, basalt fibers, graphene oxide, graphene, carbon nano tubes or conductive carbon black.
The application also discloses a double-component spray self-repairing polyurea coating prepared by any one of the preparation methods.
The application also discloses an application of the double-component spray self-repairing polyurea coating in preparation of wear-resistant, corrosion-resistant and antistatic materials.
The beneficial effects of the application are as follows:
1) The chain extension repairing agent has double-attack effect, the molecular weight of polyurea is increased through the chain extension function, and the sulfadiazine groups can be subjected to reversible dynamic exchange under the heating condition, so that the self-repairing agent contributes to the self-repairing performance.
2) The crosslinking curing agent is a compound with the functionality of more than or equal to 3, wherein two functionalities are primary amine or secondary amine groups, and the residual functionality is hydroxyl. Primary amine and secondary amine can react with isocyanate in the spraying process, and the residual hydroxyl groups can further react with isocyanate in the later heating process, so that the polyurea coating can be crosslinked, and the nozzle can not be blocked due to the too fast reaction, so that the foundation is difficult.
3) The catalytic repairing agent is copper chloride with dual functions, copper ions can catalyze the translation of hydroxyl and isocyanate during the later-stage heating and curing, so that the curing is complete, and simultaneously, copper ions can coordinate with urea bonds and carbamate bonds, thereby contributing to the self-repairing process.
4) The prepared coating has excellent self-repairing function based on reversible dynamic exchange between sulfadiazine groups, hydrogen bond formed between urea bonds and coordination bond formed by copper ions, and when mechanical damage occurs, the mechanical scratch of the coating can be repaired by heating.
5) The coating is prepared by a double-component spraying method, and is easy to realize industrial production and application
6) The prepared coating has the functions of corrosion resistance, wear resistance, static resistance and the like, and the performances of wear resistance, corrosion resistance, static resistance and the like of the coating can be further improved by introducing nano fillers such as silica nano particles, basalt fibers, graphene oxide, graphene, carbon nano tubes or conductive carbon black and the like into the component A or the component B.
7) The coating prepared by introducing graphene oxide, graphene, carbon nano tube or conductive carbon black can also realize scratch self-repairing by utilizing the photo-thermal effect of the inorganic nano particles through illumination of a near infrared lamp.
Drawings
FIG. 1 is an optical photograph of example 2 before and after repair;
FIG. 2 is a graph showing the stress-strain curves of the coating of example 4 before and after repair;
FIG. 3 is an optical photograph of example 6 before and after repair;
FIG. 4 is a stress-strain curve of the coating materials in examples 1 and 7;
FIG. 5 is an optical photograph of example 10 before and after repair.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the application. 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 this application belongs.
Example 1:
100g of polytetrahydrofuran with a molecular weight of 1000g/mol and 45g of isophorone diisocyanate are reacted at 80 ℃ for 3 hours to prepare a component A;
uniformly mixing 40g of polyether ED-600,3g of 2,2' - (methylenebis (sulfadiazine)) diethylamine, 1g of hydroxyethyl ethylenediamine and 1.2g of copper chloride by using a ball milling technology to prepare a component B;
adopting an iron sheet as a base material, and adding the components A and B into connected spraying equipment for spraying; the gauge pressure of the component A and the gauge pressure of the component B are controlled between 1200 Psi and 1500Psi, the pressure difference of the component A and the component B is controlled below 200Psi, and the component A and the component B are heated for 2 hours at 100 ℃ after spraying is finished, and the polyurea coating is obtained after complete solidification.
Example 2:
the surface of the coating prepared in example 1 was scratched with a blade, the coating was heated at 140 ℃ for 30min, the change of the appearance of the wound was observed, the specific result is shown in fig. 1, the scratch of the coating in example 2 was disappeared after heating at 140 ℃ for 30min, and the prepared coating was proved to have good self-repairing performance.
Example 3:
100g of polypropylene glycol with a molecular weight of 1000g/mol are reacted with 53g of 4,4' -dicyclohexylmethane diisocyanate at 80 ℃ for 3 hours to prepare a component A;
40g of polyether ED-600,3g of 2,2' - (methylenebis (sulfadiyl)) diethylamine, 1g of hydroxyethyl ethylenediamine and 1g of cupric chloride are uniformly mixed by adopting a ball milling technology to prepare a component B;
adding the components A and B into the connected spraying equipment for spraying, and adopting a tetrafluoroethylene mold as a substrate; the thickness of the coating is controlled to be about 1mm, the gauge pressure of the component A and the component B is controlled to be between 1200 and 1500Psi, the pressure difference of the component A and the component B is controlled to be below 200Psi, and the coating is heated for 2 hours at 100 ℃ after the spraying is finished, so that the polyurea coating is obtained after complete solidification.
Example 4:
the coating in example 3 was removed from the tetrafluoroethylene mold, a sample bar was prepared by a cutter, three quarters of the thickness of the sample bar was cut off from the middle, and the sample bar was re-butted, and the mechanical properties of the sample bar were tested for 6 hours at 120 ℃ in an oven, and the specific results are shown in fig. 2, and the mechanical properties of the coating material in example 4 were basically recovered at 120 ℃ for 6 hours before and after the repair, indicating that the prepared coating material had good self-repairing properties.
Example 5:
100g of polytetrahydrofuran with a molecular weight of 1000g/mol and 45g of isophorone diisocyanate are reacted at 80 ℃ for 3 hours to prepare a component A;
uniformly mixing 40g of base polyether ED-600,1g of hydroxyethyl ethylenediamine and 1.2g of copper chloride by adopting a ball milling technology to prepare a component B;
adopting an iron sheet as a base material, and adding the components A and B into connected spraying equipment for spraying; the gauge pressure of the component A and the gauge pressure of the component B are controlled between 1200 Psi and 1500Psi, the pressure difference of the component A and the component B is controlled below 200Psi, and the component A and the component B are heated for 2 hours at 100 ℃ after spraying is finished, and the polyurea coating is obtained after complete solidification.
Example 6:
the surface of the coating prepared in example 5 was scratched with a blade, the coating was heated at 140 ℃ for 30min, the change of the appearance of the wound was observed, and specific results are shown in fig. 3, and after the coating in example 6 was heated at 140 ℃ for 30min, only a small part of scratches disappeared, which indicates that the chain-extending repairing agent 2,2' - (methylenebis (sulfadiyl)) diethylamine was critical to the repairing process, and the self-repairing performance was poor without the coating into which the chain-extending repairing agent was introduced.
Example 7:
100g of polytetrahydrofuran with a molecular weight of 1000g/mol and 45g of isophorone diisocyanate are reacted at 80 ℃ for 3 hours to prepare a component A;
uniformly mixing 40g of base polyether ED-600,3g of 2,2' - (methylenebis (sulfadiazine)) diethylamine and 1.2g of cupric chloride by adopting a ball milling technology to prepare a component B;
adopting an iron sheet as a base material, and adding the components A and B into connected spraying equipment for spraying; the gauge pressure of the component A and the gauge pressure of the component B are controlled between 1200 Psi and 1500Psi, the pressure difference of the component A and the component B is controlled below 200Psi, and the polyurea coating is obtained after the spraying is completed and is fixed at room temperature.
Example 8:
the coatings of examples 1 and 7 were prepared as bars and tested for mechanical properties using a tensile test. As shown in fig. 4, the mechanical properties of the coating material in example 1 are significantly better than those of the coating material in example 7, which indicates that the mechanical properties of the post-crosslinking curing agent are significantly improved.
Example 9:
100g of polypropylene glycol with a molecular weight of 1000g/mol are reacted with 53g of 4,4' -dicyclohexylmethane diisocyanate at 80 ℃ for 3 hours to prepare a component A;
uniformly mixing 40g of polyether ED-600,3g of 2,2' - (methylenebis (sulfadiyl)) diethylamine, 1g of hydroxyethyl ethylenediamine, 1g of cupric chloride and 0.5g of multi-arm carbon nano tube by adopting a ball milling technology to prepare a component B;
adding the components A and B into the connected spraying equipment for spraying, and adopting a tetrafluoroethylene mold as a substrate; the thickness of the coating is controlled to be about 1mm, the gauge pressure of the component A and the component B is controlled to be between 1200 and 1500Psi, the pressure difference of the component A and the component B is controlled to be below 200Psi, and the coating is heated for 2 hours at 100 ℃ after the spraying is finished, so that the polyurea coating is obtained after complete solidification.
Example 10:
a wound was scratched on the surface of the coating prepared in example 5 with a blade, and the change in wound morphology was observed by irradiation with light under a near infrared lamp for 30 minutes. As shown in fig. 5, the scratch of the coating in example 10 largely disappears after the coating is irradiated for 30min under near infrared light, which indicates that the prepared coating has good near infrared light induced self-repairing performance.
Claims (4)
1. A preparation method of a two-component spray self-repairing polyurea coating comprises the following steps:
preparing a component A: is prepared by the reaction of diisocyanate and a dihydroxyl terminated polymer;
preparing a component B: the catalyst consists of a cross-linking curing agent, a chain extender repairing agent and a catalytic repairing agent which are mixed;
the components A and B are mixed and then introduced into spraying equipment, a coating is prepared after spraying, and a double-component spraying self-repairing polyurea coating is obtained after heating and post-treatment and solidification; wherein:
the polymer with the end capped by the double hydroxyl groups is one or more of polytetrahydrofuran, polyethylene glycol, polypropylene glycol, polycaprolactone and polydimethylsiloxane, and the molecular weight is 200-5000g/mol;
the crosslinking curing agent is a compound with the functionality degree more than or equal to 3, wherein two of the functionality degrees are primary amine or secondary amine groups, and the residual functionality degrees are hydroxyl groups;
the chain extension repairing agent is 2,2' - (methylenebis (sulfadiyl)) diethylamine;
the chain extender is one or more of amino-terminated polyether D-230, amino-terminated polyether D-400, amino-terminated polyether ED-600, amino-terminated polyether D-1000, amino-terminated polyether D-2000, isophorone diamine, diacetyl m-phenylenediamine, N-dialkyl methyl diamine, diethyl toluene diamine, diacetyl ethylene diamine and dialkyl toluene diphenylamine;
the catalytic repairing agent is cupric chloride.
2. The method of manufacturing according to claim 1, wherein:
the diisocyanate is one or more of 4,4' -dicyclohexylmethane diisocyanate, isophorone diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, hexamethylene diisocyanate and diphenylmethane diisocyanate.
3. A two-component spray-on self-healing polyurea coating prepared according to the preparation method of claim 1 or 2.
4. Use of a two-component spray-on self-healing polyurea coating according to claim 3 for the preparation of anti-corrosion materials.
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