CN115895411A - Preparation method and application of bi-component spray-coating self-repairing polyurea coating - Google Patents
Preparation method and application of bi-component spray-coating self-repairing polyurea coating Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 73
- 239000011248 coating agent Substances 0.000 title claims abstract description 70
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- 238000005507 spraying Methods 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
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- 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
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- 239000000203 mixture Substances 0.000 claims description 6
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- 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
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- 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
- 239000007921 spray Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 7
- 238000005536 corrosion prevention Methods 0.000 claims 1
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- 229910021389 graphene Inorganic materials 0.000 abstract description 11
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- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a preparation method and application of a double-component spray-coating self-repairing polyurea coating, which comprises the following specific steps: the component A is prepared by reaction of diisocyanate and a polymer with a double hydroxyl end capping, the component B is formed by mixing a post-crosslinking curing agent, a chain extender, a chain extension repairing agent and a catalytic repairing agent, the component A and the component B are mixed and then introduced into spraying equipment to be sprayed to prepare a coating, the coating is further cured by heating post-treatment to obtain a final coating, the prepared coating can be used in the fields of wear resistance, corrosion resistance, static resistance and the like, and meanwhile, the coating has self-repairing performance, and when mechanical damage is received, self-repairing can be realized by heating or near-infrared illumination. The performances of wear resistance, corrosion resistance, static resistance and the like of the composite material are further improved by introducing nano fillers such as silicon dioxide nano particles, basalt fibers, graphene oxide, graphene, carbon nano tubes or conductive carbon black and the like.
Description
Technical Field
The invention belongs to the field of self-repairing anti-coating layers, and particularly relates to a preparation method and application of a bi-component spray-coating self-repairing polyurea coating.
Background
The polyurea coating has excellent wear resistance, corrosion resistance and other performances, is widely applied to the field of corrosion resistance, and the service life of the polyurea coating can be prolonged by developing the polyurea coating with a self-repairing function. The common construction method of polyurea coatings is a two-component spray coating method. The paint has two components, has 100 percent of solid content, does not contain any Volatile Organic Compound (VOC), is environment-friendly, has no pollution construction, and is harmless to use in sanitary construction. Most of the reported polyurea materials are not suitable for two-component spraying construction at present, and the industrial application faces challenges.
CN113969096A discloses a high-strength room-temperature self-repairing polyurea coating material, the molecular structure of which comprises a hemithioacetal 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 mercapto compound with the functionality of more than or equal to 2 and an aldehyde 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, and obtaining an aldehyde-terminated poly-hemithioacetal 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, and obtaining an amino-terminated polyurea precursor; the invention utilizes dynamic reversible hemithioacetal group and urea bond group to realize the rapid room temperature self-repairing of the polyurea material; the mechanical property of the room temperature self-repairing polyurea material is improved by 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 hemithioacetal group, can dissociate to generate sulfydryl and aldehyde group, and realizes self-repairing under the action of hydrogen bond, and an organic solvent is required in the preparation process, so that the technology is not environment-friendly.
CN105400405A discloses a self-repairing organic silicon polyurethane/polyurea antifouling material, a method and application thereof. The material comprises: 40 to 95 percent of hydroxyl or amino terminated polysiloxane and 5 to 60 percent 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 does not contain reversible covalent bonds; the preparation by the solution method needs an organic solvent, and is not environment-friendly.
CN113337192A discloses a preparation method of a polyurea composite coating with wear resistance and self-repairing functions, which comprises the steps of firstly respectively preparing a polyurea component A and a polyurea component B, then mixing a fluoropolymer into the polyurea component B, uniformly dispersing to obtain a mixture, adding the polyurea component A and the mixture into connected spraying equipment, spraying the mixture on the surface of a metal substrate, and solidifying to obtain the composite coating; the fluorine polymer has a lubricating effect and a healing effect in a polyurea system in a mutual cooperation manner, so that the prepared composite coating has high mechanical strength and excellent wear resistance, and the self-repairing of the damaged part can be completed only by heating after the coating is damaged, so that the service life of the coated part is effectively prolonged. The technology realizes self-repairing by utilizing macromolecular chain migration in the fluoropolymer; and the preparation process contains the fluorine polymer, so that the environmental protection is poor.
In view of the defects, the invention provides a preparation method and application of a bi-component spray-coating self-repairing polyurea coating, and effectively solves the problems of pollution and poor practicability caused by the traditional process.
Disclosure of Invention
Aiming at the technical problems, the invention provides a preparation method of a bi-component self-repairing polyurea coating, the prepared coating has better mechanical property and self-repairing property, when mechanical damage is received, self-repairing can be realized through heating, and the service life of the coating is prolonged.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a bi-component self-repairing polyurea coating comprises the following specific steps:
(1) Preparation of component A: heating diisocyanate and dihydroxyl-terminated polymer at 60-100 ℃ for 2-4h to obtain a component A;
(2) Preparation of the component B: uniformly stirring and mixing the crosslinking curing agent, the chain extender, the chain extension repairing agent and the catalytic repairing agent to obtain a component B;
(3) Preparing a double-component self-repairing polyurea coating: and mixing the component A and the component B, introducing the mixture into spraying equipment for spraying to prepare the coating, controlling the gauge pressure of the component A and the gauge pressure of the component B to be 1200-1500 Psi, controlling the pressure difference between the component A and the component B to be less than 200Psi, heating the coating at 100 ℃ for 2 hours after the spraying is finished, and completely curing the coating to obtain the bi-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 rest 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 repairing agent is 2,2' - (methylenebis (sulfadiyl)) diethylamine.
Further, the catalytic repairing agent is copper chloride, and the content of the catalytic repairing agent accounts for 0.1-1% of the total mass of the whole coating.
Further, nano fillers such as silica nanoparticles, basalt fibers, graphene oxide, graphene, carbon nanotubes or conductive carbon black can be introduced into the component A or the component B.
The invention also discloses a bi-component spraying self-repairing polyurea coating prepared by any one of the preparation methods.
The invention also discloses application of the double-component spray-coating self-repairing polyurea coating in preparation of wear-resistant, corrosion-resistant and antistatic materials.
The invention has the following beneficial effects:
1) The chain extension repairing agent has a double-attack effect, the molecular weight of polyurea is increased through a chain extension function, reversible dynamic exchange can be generated on the sulfadiyl under a heating condition, and the chain extension repairing agent contributes to 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 rest functionality is hydroxyl. The primary amine and the secondary amine can react with isocyanate in the spraying process, and the residual hydroxyl groups can further react with the isocyanate in the later heating process, so that the polyurea coating can be crosslinked, and the problem that the spray head is blocked due to too fast reaction to cause foundation difficulty can be avoided.
3) The catalytic repairing agent is copper chloride and has double functions, when the catalytic repairing agent is heated and cured in a later period, copper ions can catalyze the translation of hydroxyl and isocyanate to ensure complete curing, and meanwhile, the copper ions can be coordinated with urea bonds and urethane bonds to contribute to a self-repairing process.
4) Based on reversible dynamic exchange among the sulfonamidodiyl groups, hydrogen bonds formed among urea bonds and coordination bonds formed by copper ions, the prepared coating has an excellent self-repairing function, and mechanical scratches of the coating can be repaired by heating when mechanical damage occurs.
5) The coating is prepared by a double-component spraying method, and is easy for 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 can be further improved by introducing nano-fillers such as silicon dioxide 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 tubes or conductive carbon black can be irradiated by a near infrared lamp, and scratch self-repairing is realized by utilizing the photo-thermal effect of the inorganic nano particles.
Drawings
FIG. 1 is an optical photograph of example 2 before and after repair;
FIG. 2 is a stress-strain curve 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 of 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 exemplary and is intended to provide further explanation of the disclosure. 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:
reacting 100g of polytetrahydrofuran with the molecular weight of 1000g/mol and 45g of isophorone diisocyanate at 80 ℃ for 3 hours to prepare a component A;
uniformly mixing 40g of base polyether ED-600,3g of 2,2' - (methylenebis (sulfonamido)) diethylamine, 1g of hydroxyethyl ethylenediamine and 1.2g of copper chloride by adopting a ball milling technology to prepare a component B;
adding the components A and B into connected spraying equipment for spraying by adopting an iron sheet as a base material; the gauge pressure of the component A and the gauge pressure of the component B are controlled to be 1200-1500 Psi, the pressure difference between the component A and the component B is controlled to be less than 200Psi, the spraying is finished, then the heating is carried out for 2 hours at the temperature of 100 ℃, and the polyurea coating is obtained after the complete curing.
Example 2:
a wound is scratched on the surface of the coating prepared in the example 1 by using a blade, the wound is heated at 140 ℃ for 30min, the change of the appearance of the wound is observed, the specific result is shown in detail in figure 1, and the scratch disappears after the coating in the example 2 is heated at 140 ℃ for 30min, which shows that the prepared coating has good self-repairing performance.
Example 3:
100g of polypropylene glycol with the molecular weight of 1000g/mol and 53g of 4,4' -dicyclohexylmethane diisocyanate react for 3 hours at 80 ℃ to prepare a component A;
uniformly mixing 40g of base polyether ED-600,3g of 2,2' - (methylenebis (sulfonamido)) diethylamine, 1g of hydroxyethyl ethylenediamine and 1g of copper chloride by adopting a ball milling technology to prepare a component B;
adding the component A and the component B into connected spraying equipment for spraying, and adopting a tetrafluoroethylene mould as a substrate; controlling the thickness of the coating to be about 1mm, controlling the gauge pressure of the component A and the component B to be between 1200 and 1500Psi, controlling the pressure difference between the component A and the component B to be less than 200Psi, heating the coating for 2 hours at 100 ℃ after the spraying is finished, and completely curing the coating to obtain the polyurea coating.
Example 4:
the coating in the embodiment 3 is peeled off from a tetrafluoroethylene mold, a sample strip is prepared by using a cutter, three quarters of the thickness of the sample strip is cut from the middle, the sample strip is butted again, and the sample strip is placed in a 120 ℃ oven for 6 hours to test the mechanical properties of the sample strip before and after repair, wherein the specific result is shown in figure 2, the coating material in the embodiment 4 is repaired at 120 ℃ for 6 hours, the mechanical properties of the material before and after repair are basically recovered, and the prepared coating material has good self-repair performance.
Example 5:
reacting 100g of polytetrahydrofuran with the molecular weight of 1000g/mol and 45g of isophorone diisocyanate at 80 ℃ for 3 hours to prepare a component A;
uniformly mixing 40g of polyether ED-600,1g of hydroxyethyl ethylenediamine and 1.2g of copper chloride by adopting a ball milling technology to prepare a component B;
adding the components A and B into connected spraying equipment for spraying by adopting an iron sheet as a substrate material; the gauge pressure of the component A and the gauge pressure of the component B are controlled to be 1200-1500 Psi, the pressure difference between the component A and the component B is controlled to be less than 200Psi, the spraying is finished, then the components are heated for 2 hours at 100 ℃, and the polyurea coating is obtained after the components are completely cured.
Example 6:
a wound is scratched on the surface of the coating prepared in example 5 by using a blade, the coating is heated at 140 ℃ for 30min, and the change of the appearance of the wound is observed, and the specific result is shown in fig. 3, only a small part of scratches disappear after the coating in example 6 is heated at 140 ℃ for 30min, which indicates that the chain extension repairing agent 2,2' - (methylenebis (sulfadiyl)) diethylamine is crucial to the repairing process, the coating with the chain extension repairing agent is not introduced, and the self-repairing performance is poor.
Example 7:
reacting 100g of polytetrahydrofuran with the molecular weight of 1000g/mol and 45g of isophorone diisocyanate at 80 ℃ for 3 hours to prepare a component A;
uniformly mixing 40g of base polyether ED-600,3g of 2,2' - (methylenebis (sulfonamido)) diethylamine and 1.2g of copper chloride by adopting a ball-milling technology to prepare a component B;
adding the components A and B into connected spraying equipment for spraying by adopting an iron sheet as a base material; the gauge pressure of the component A and the gauge pressure of the component B are controlled to be 1200-1500 Psi, the pressure difference between the component A and the component B is controlled to be less than 200Psi, and the polyurea coating is obtained after the spraying is finished and the polyurea coating is solidified at room temperature.
Example 8:
the coatings from examples 1 and 7 were prepared as test bars and tested for mechanical properties using tensile testing. 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 shows that the post-crosslinking curing agent provides significant improvements to the mechanical properties of the material.
Example 9:
100g of polypropylene glycol with the molecular weight of 1000g/mol and 53g of 4,4' -dicyclohexylmethane diisocyanate react for 3 hours at 80 ℃ to prepare a component A;
uniformly mixing 40g of base polyether ED-600,3g of 2,2' - (methylenebis (sulfonamido)) diethylamine, 1g of hydroxyethyl ethylenediamine, 1g of copper chloride and 0.5g of multi-arm carbon nano tube by adopting a ball milling technology to prepare a component B;
adding the component A and the component B into connected spraying equipment for spraying, and adopting a tetrafluoroethylene mould as a substrate; controlling the thickness of the coating to be about 1mm, controlling the gauge pressure of the component A and the component B pressure gauges to be between 1200 Psi and 1500Psi, controlling the pressure difference between the component A and the component B to be less than 200Psi, heating for 2 hours at 100 ℃ after spraying is finished, and completely curing to obtain the polyurea coating.
Example 10:
a wound was scratched with a blade on the surface of the coating prepared in example 5, and the change in the morphology of the wound was observed by illuminating under a near infrared lamp for 30 min. As shown in fig. 5, most of scratches disappeared after the coating in example 10 was irradiated under near infrared light for 30min, indicating that the prepared coating has good near infrared light-induced self-repair performance.
Claims (9)
1. A preparation method of a two-component spray-coating self-repairing polyurea coating comprises the following steps:
preparation of component A: prepared by reacting diisocyanate and a polymer terminated by a dihydroxyl group;
preparation of component B: the repairing agent is formed by mixing a crosslinking curing agent, a chain extender, a chain extension repairing agent and a catalytic repairing agent;
and mixing the component A and the component B, introducing the mixture into spraying equipment, spraying to prepare a coating, and heating for post-treatment and curing to obtain the bi-component spraying self-repairing polyurea coating.
The prepared coating has self-repairing performance and can be used in the field of corrosion prevention.
2. The production method 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. The production method according to claim 1, wherein:
the hydroxyl-terminated polymer is one or more of polytetrahydrofuran, polyethylene glycol, polypropylene glycol, polycaprolactone and polydimethylsiloxane, and has a molecular weight of 200-5000g/mol.
4. The production method according to claim 1, wherein:
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 rest functionalities are hydroxyl groups.
5. The production method according to claim 1, wherein:
the chain extender is one or a mixture of 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.
6. The production method according to claim 1, wherein:
the chain extension repairing agent is 2,2' - (methylene bis (sulfadiyl)) diethylamine.
7. The production method according to claim 1, wherein:
the catalytic repairing agent is copper chloride.
8. The two-component spray-coating self-repairing polyurea coating prepared by the preparation method of any one of claims 1 to 7.
9. Use of the two-component spray painted self-healing polyurea coating according to claim 8 for the production of corrosion-resistant materials.
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