CN113969096A - High-strength room-temperature self-repairing polyurea coating material and preparation method thereof - Google Patents
High-strength room-temperature self-repairing polyurea coating material and preparation method thereof Download PDFInfo
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Abstract
The invention 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: the method 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; step two: 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 invention realizes the rapid room temperature self-repairing of the polyurea material by utilizing the dynamic reversible hemithioacetal group and the urea bond group; 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.
Description
Technical Field
The invention relates to the field of polyurea elastomers, in particular to a high-strength room-temperature self-repairing polyurea coating material and a preparation method thereof.
Background
Polyurea is an elastomeric material formed by the reaction of an isocyanate component and an amino compound component. The polyurea is divided into pure polyurea and semi-polyurea, and the most basic characteristics of the polyurea are corrosion resistance, water resistance, wear resistance and the like. Because the curing reaction rate of the amino and the isocyanate is very fast, the most common method for preparing the polyurea material is spray molding, and the polyurea coating material can be prepared on various substrate materials. Reaction injection molding can also be used to prepare elastomeric polyurea coating materials. Polyurea elasticity is derived from hydrogen bonds between polymer chains, and can dissipate energy in the stretching process, so that the polyurea elastic material has good resilience. The polyurea coating is widely applied to the fields of water resistance, corrosion resistance, terrace and the like due to good physical and chemical properties such as tensile strength, elongation, flexibility and the like, good thermal stability and quick setting characteristics. With the development and application of polyurea coating in China, the application scene of the polyurea coating is continuously expanded. In practical application, it is found that in marine climate areas, especially in humid air rich in chloride ions, the polyurea coating still has insufficient protection performance on metals, and has the problems of non-durable corrosion resistance and short service life. Particularly, when the surface of the coating is mechanically damaged, the surface corrosion resistance of the coating is rapidly reduced, and the development of the polyurea coating material with self-repairing performance has important significance.
The graphene has a large specific surface area and a strong shielding effect, and can effectively prevent corrosive media from permeating into a coating through pores and cracks when being added into the polyurea coating as a filler. The graphene is added into the self-repairing polyurea coating as a filler, so that the original anti-corrosion performance can be maintained, the self-repairing polyurea coating also has the self-repairing performance, and a long-acting self-repairing anti-corrosion coating material can be developed.
The first prior art is as follows:
the invention provides a colorless and transparent room temperature self-repairing polyurea elastomer with high tensile property and tear resistance, wherein a repeating structural unit of the polyurea elastomer is shown as a formula I. The polymer is polymerizedThe urea elastomer is obtained by polymerizing the following raw materials as monomers: diisocyanate, difunctional polyetheramine, and trifunctional polyetheramine, wherein the difunctional polyetheramine: the molar ratio of the trifunctional polyether amine is (1-3): 1. the elongation at break of the polyurea elastomer provided by the invention is more than 1600 percent, the elongation at tear resistance is more than 800 percent, and the tear resistance is 12500J/m2Above, the light transmittance is as high as above 90%; the self-repairing efficiency of 6 hours of repair at 25 ℃ is up to more than 100 percent. The polyurea elastomer provided by the invention has excellent mechanical property, self-repairing capability and light transmittance, and has very wide application potential and prospect in the fields of photoelectric intelligent electronic equipment, transparent protective films, transparent electronic skins and the like.
The first prior art has the following defects:
the corrosion resistance is not involved, the self-repairing time is long, six hours are needed, the tearing resistance is emphasized, and the tensile strength at break is not mentioned.
The invention provides a self-repairing thermoplastic polyurea elastomer and a preparation method thereof. The preparation method of the self-repairing thermoplastic polyurea elastomer provided by the invention comprises the following steps: carrying out polymerization reaction on diamine A and diamine B and carbon dioxide to obtain a self-repairing thermoplastic polyurea elastomer; the diamine A is isophorone diamine; the diamine B is diamino oxaalkane of C4-C10. According to the invention, two specific diamines are adopted to react with carbon dioxide at the same time, wherein carbamido formed by reacting diamino oxaalkane of C4-C10 with carbon dioxide generates a regular hydrogen bond structure, carbamido formed by reacting asymmetric alicyclic diamine-isophorone diamine with carbon dioxide generates an irregular hydrogen bond structure, and the two hydrogen bond structures act together, so that the polyurea material has high strength, high toughness, good self-repairing performance and transparency.
The second prior art has the defects
The corrosion resistance is not involved, the self-repairing time is long, the room temperature repairing needs 24 hours, the tensile strength is low and is only 10.7MPa
Technical scheme of prior art III
The invention discloses a high-wear-resistance anticorrosive modified single-component polyurea coating and a preparation method thereof. The high-wear-resistance anticorrosive modified single-component polyurea coating comprises the following components in parts by weight: 35-40 parts of polytetrahydrofuran glycol, 8-12 parts of dicyclohexylmethane diisocyanate, 50-54 parts of dichloromethane, 2-3 parts of liquid antioxidant, 2-3 parts of ultraviolet absorbent, 2-3 parts of stabilizer, 1-2 parts of dibutyltin dilaurate, color paste and curing agent diethyl toluene diamine, wherein the volume ratio of the curing agent component to the non-color paste component is 1:31, and the weight parts of the color paste are 3-9 parts. The polyurea coating prepared by the invention innovatively uses dichloromethane as a diluent, obtains good dilution effect, and independently stores the curing agent component, so that the storage time of the polyurea coating is greatly prolonged.
Disadvantages of the third prior art
The corrosion-resistant effect is general, and the self-repairing performance is not achieved.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a high-strength room temperature self-repairing polyurea coating material and a preparation method thereof, and solves the problems that the traditional polyurea material does not have room temperature self-repairing performance, when the coating is applied as an anticorrosive coating and is mechanically damaged, the anticorrosive efficiency is reduced, the room temperature self-repairing polyurea material has long repairing time and poor mechanical performance, and the traditional polyurea material has general anticorrosive performance.
The technical scheme of the invention is as follows:
the molecular structure of the high-strength room-temperature self-repairing polyurea coating material comprises a hemithioacetal group and a urea group, and the molecular structural formula is as follows:
preferably, the method for preparing the high-strength room temperature self-repairing polyurea coating material comprises the following steps:
the method 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;
the mercapto compound having a functionality of 2 or more is: one or more of bis (3-mercaptopropionate) ethylene glycol, bis (2-mercaptoethyl) ether, pentaerythritol tetra-3-mercaptopropionate, 1, 4-butanediol bis (mercaptoacetic acid) and tetraethylene glycol bis (3-mercaptopropionate) are mixed
The aldehyde compound with the functionality of more than or equal to 2 is as follows: 5-bromoisophthalaldehyde, pyridine-2, 6-dicarbaldehyde, glutaraldehyde, succinaldehyde, o-phthalaldehyde, trialdehyde phloroglucinol, m-phthalaldehyde, and one or more of terephthalaldehyde
Step two: 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;
amino compounds having a functionality of 2 or more are: one or a mixture of more than one of p-phenylenediamine, o-phenylenediamine, m-phenylenediamine, 1, 6-hexamethylenediamine, 3-dimethoxybenzidine, p-xylylenediamine, triethylene tetramine, amino-terminated polycaprolactone, amino-terminated polypropylene glycol, amino-terminated polydimethylsiloxane, amino-terminated polyethylene glycol, amino-terminated polytetrahydrofuran, polyethylene glycol with side chain containing more than 2 amino groups, polydimethylsiloxane with side chain containing more than 2 amino groups, and polycaprolactone with side chain containing more than 2 amino groups
The isocyanate compound having a functionality of 2 or more is: one or a mixture of several of hexamethylene diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate trimer, tolylene diisocyanate, diphenylmethane diisocyanate, p-phenylene diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate trimer, dimethyl biphenyl diisocyanate and m-phenylene diisocyanate
Step three: mixing the precursor solutions obtained in the step 1 and the step 2, stirring and reacting for 1 hour, pouring into a mold, and volatilizing the solvent to obtain the polyurea material with the room-temperature self-repairing function;
step four: dispersing graphene oxide in a solvent, mixing the graphene oxide with the precursor solution obtained in the step 1 and the precursor solution obtained in the step 2, stirring for reaction for 1 hour, and spraying the mixture on the surface of a substrate by using a spray gun to obtain the graphene oxide/polyurea composite anticorrosive coating material with the room-temperature self-repairing function;
the graphene oxide is a single-layer or multi-layer graphene oxide, the diameter of the graphene oxide is 0.5-20 mu m, the thickness of the graphene oxide is 0.5-10nm, and the specific surface area of the graphene oxide is 20-800m2/g。
The mass fraction of the graphene oxide in the prepared graphene oxide/polyurea composite anticorrosive coating material is 0.5-20 wt%
Step five: and (3) dispersing graphene in a solvent, mixing the graphene with the precursor solution obtained in the step (1) and the precursor solution obtained in the step (2), stirring for reaction for 1 hour, pouring the mixture into a mold, and volatilizing the solvent to obtain the graphene/polyurea composite electrode material with the room-temperature self-repairing function.
The diameter of the graphene is 0.5-20 μm, the thickness is 0.5-10nm, and the specific surface area is 20-800m2/g。
The mass fraction of graphene in the prepared graphene/polyurea composite anticorrosive coating material is 3-25 wt%
The high-strength room-temperature self-repairing polyurea coating material and the preparation method have the following beneficial effects:
1) the urea bond in the prepared polyurea material can form a hydrogen bond, the hemithioacetal group has room temperature dynamic property, can be dissociated to generate a sulfydryl group and an aldehyde group, the two have synergistic effect, the material is endowed with a rapid room temperature self-repairing function, and when the material is damaged by machinery, the material can be automatically repaired within 1 hour.
2) The hydrogen bonds formed in the polyurea network structure not only contribute to the self-repairing process, but also contribute to the improvement of the mechanical properties of the material, and can be used as weak interaction to dissipate energy and improve the strength and toughness of the material.
3) Micro-phase separation can occur in the polyurea network structure, the toughening effect is achieved, the toughness and the mechanical strength of the polyurea material are improved, and the tensile strength of the polyurea material can reach 3-60 MPa.
4) The prepared polyurea material can be blended with graphene to prepare a composite material, and the prepared composite material also has a rapid room temperature self-repairing function.
5) The prepared polyurea composite material can be used for an anticorrosive coating, and when the material is mechanically scratched, the generated cracks can be automatically repaired to prevent further corrosion.
6) The polyurea material and the graphene oxide are blended to improve the anti-corrosion performance of the polyurea material, meanwhile, the graphene oxide/polyurea composite material also has a room-temperature self-repairing function, when the material is mechanically scraped, the generated cracks can be automatically repaired, and further corrosion is prevented.
7) The prepared graphene polyurea composite material can be used for electrode materials, when the materials are mechanically scraped, generated cracks can be automatically repaired, and the conductivity can be automatically recovered.
Drawings
FIG. 1 is a scheme showing the synthesis of a poly (hemithioacetal) precursor in example 1 of the present invention;
FIG. 2 is a synthesis scheme of a polyurea precursor in example 1 of the present invention;
FIG. 3 is a roadmap for a polyurea material according to example 1 of the present invention;
FIG. 4 is an optical picture of a polyurea material according to example 1 of the present invention;
FIG. 5 is a microscope photograph of example 2 of the present invention;
FIG. 6 is an optical picture of the iron plate of example 3 of the present invention when it was left in a sodium chloride solution for 72 hours;
FIG. 7 is a photomicrograph of example 5 of the present invention;
FIG. 8 is a Bode modulus resin of iron sheets coated with different coatings according to example 6 of the present invention after 24 hours in a sodium chloride solution;
FIG. 9 is a stress-strain curve of the original sample and the sample after repair in example 8 of the present invention;
FIG. 10 is a graph of the electrical resistance of composites of example 9 of the present invention with different graphene concentrations;
FIG. 11 is a graph showing the electrical resistance before and after repair of the composite material in example 10 of the present invention;
FIG. 12 is a molecular structure diagram of the high-strength room temperature self-repairing polyurea coating material of the present invention.
Detailed Description
The following description of the embodiments of the present invention is provided to facilitate the understanding of the present invention by those skilled in the art, but it should be understood that the present invention is not limited to the scope of the embodiments, and it will be apparent to those skilled in the art that various changes may be made without departing from the spirit and scope of the invention as defined and defined in the appended claims, and all matters produced by the invention using the inventive concept are protected.
The molecular structure of the high-strength room-temperature self-repairing polyurea coating material prepared by the invention contains hemithioacetal groups and urea groups, and the molecular structure diagram is shown as the following figure:
the specific synthesis method of the polyurea material is as follows:
1) 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;
2) 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;
3) mixing the precursor solutions obtained in the step 1 and the step 2, stirring and reacting for 1 hour, pouring into a mold, and volatilizing the solvent to obtain the polyurea material with the room-temperature self-repairing function;
4) dispersing graphene oxide in a solvent, mixing the graphene oxide with the precursor solution obtained in the step 1 and the precursor solution obtained in the step 2, stirring for reaction for 1 hour, and spraying the mixture on the surface of a substrate by using a spray gun to obtain the graphene oxide/polyurea composite anticorrosive coating material with the room-temperature self-repairing function;
5) and (3) dispersing graphene in a solvent, mixing the graphene with the precursor solution obtained in the step (1) and the precursor solution obtained in the step (2), stirring for reaction for 1 hour, pouring the mixture into a mold, and volatilizing the solvent to obtain the graphene/polyurea composite electrode material with the room-temperature self-repairing function.
The invention realizes the rapid room temperature self-repairing of the polyurea material by utilizing the dynamic reversible hemithioacetal group and the urea bond group; the mechanical property of the room-temperature self-repairing polyurea material is improved by utilizing phase separation; the graphene/polyurea composite anticorrosive coating and the electrode material with the rapid room-temperature self-repairing performance are prepared by compounding with graphene.
Example 1: 1g of m-phthalaldehyde and 1.4g of bis (3-mercaptopropionate) ethylene glycol are stirred and reacted in 2ml of tetrahydrofuran for 1 hour to obtain an aldehyde-terminated poly-hemithioacetal precursor. 2g of amino-terminated polypropylene glycol with the molecular weight of 2000g/mol and 0.17g of isophorone diisocyanate are stirred and reacted in 2ml of tetrahydrofuran for 1 hour to obtain an amino-terminated polyurea precursor. And mixing and stirring the two precursors for reaction for 2 hours, and curing in an oven at 80 ℃ for 24 hours to obtain the polyurea material.
Example 2: the polyurea material obtained in example 1 was scratched on the upper surface with a surgical blade, left at room temperature for 20min, and then the wound healing was observed with an optical microscope.
Example 3: and (3) mixing and stirring the two precursors in the embodiment 1 for reaction for 2 hours, spraying the mixture on an iron sheet, and drying. And scratching 2 iron sheets coated with the polyurea coating by using a blade respectively, directly placing one of the iron sheets into a 3.5 wt% sodium chloride solution, placing the other iron sheet into the 3.5 wt% sodium chloride solution after placing the other iron sheet for 1 hour at room temperature, and observing the color of the solution after three days to judge the anti-corrosion performance of the coating.
Example 4: 1g of bis (2-mercaptoethyl) ether and 1.2g of 5-bromo-m-phthalaldehyde are stirred and reacted in 2ml of tetrahydrofuran for 1 hour to obtain an aldehyde-terminated poly-hemithioacetal precursor. 2g of amino-terminated polydimethylsiloxane with the molecular weight of 800g/mol and 0.3g of toluene diisocyanate are stirred and reacted in 2ml of tetrahydrofuran for 1h to obtain an amino-terminated polyurea precursor. Dispersing 0.1g of graphene oxide in 96ml of tetrahydrofuran to obtain graphene oxide dispersion liquid, adding the two precursors into the dispersion liquid, stirring at room temperature to volatilize tetrahydrofuran, spraying the precursors onto an iron sheet after the tetrahydrofuran volatilizes 80%, and drying at room temperature to obtain the graphene oxide/polyurea anticorrosive coating.
Example 5: the coating prepared in example 3 was scratched on a wound with a scalpel blade, left at room temperature for 1 hour, and then its wound healing was observed with an optical microscope.
Example 6: the iron piece coated with the polyurea coating in example 3 and the iron piece coated with the graphene oxide polyurea composite coating in example 4 were placed in a 3.5 wt% sodium chloride solution for 24 hours, and after letting the iron pieces act as working electrodes, the electrochemical impedance spectrum at a frequency of 0.1Hz was measured using an electrochemical workstation and the bode modulus was calculated.
Example 7: 1g of 1, 4-butanediol bis (thioglycolic acid) and 0.4g of terephthalaldehyde react in 2ml of tetrahydrofuran for 1 hour under stirring to obtain an aldehyde-terminated poly-hemithioacetal precursor. 2g of amino-terminated polypropylene glycol with the molecular weight of 600g/mol and 0.6g of isophorone diisocyanate are stirred and reacted in 2ml of tetrahydrofuran for 1 hour to obtain an amino-terminated polyurea precursor. And mixing and stirring the two precursors for reaction for 2 hours, and curing in an oven at 80 ℃ for 24 hours to obtain the polyurea material.
Example 8: the sample of example 6 was cut into a dumbbell type test piece with a cutter, 80% of the thickness was cut down along the middle portion, the cut samples were aligned, left at room temperature for 24 hours, and the mechanical properties of the original sample and the repaired sample were tested.
Example 9: 1g of 1, 4-butanediol bis (thioglycolic acid) and 0.4g of terephthalaldehyde react in 2ml of tetrahydrofuran for 1 hour under stirring to obtain an aldehyde-terminated poly-hemithioacetal precursor. 2g of amino-terminated polypropylene glycol with the molecular weight of 600g/mol and 0.6g of isophorone diisocyanate are stirred and reacted in 2ml of tetrahydrofuran for 1 hour to obtain an amino-terminated polyurea precursor. Mixing and stirring the two precursors for reaction for 1h, adding graphene with different masses, stirring uniformly, putting the mixture into a tetrafluoroethylene mold, stirring at room temperature to volatilize tetrahydrofuran, drying to obtain the graphene/polyurea composite conductive material, wherein the mass fractions of the graphene in the composite material are respectively 3 wt%, 5 wt%, 7 wt% and 10 wt%, and testing the resistance of the composite material with different graphene concentrations.
Example 10: the conductive composite material having a graphene mass fraction of 10 wt% obtained in example 8 was cut out from the middle, and after joining, it was left at room temperature for 1 hour, and the electric resistance thereof was measured.
FIG. 1: scheme for synthesis of Poly-hemithioacetal precursor in example 1
FIG. 2: polyurea precursor Synthesis scheme in example 1
FIG. 3: polyurea Material route Pattern in example 1
FIG. 4: photomicrographs of the polyurea material of example 1
FIG. 5: photomicrograph of example 2
From fig. 5, the following conclusions can be drawn: the scratch of the prepared polyurea material disappears after the polyurea material is placed for 20 minutes at room temperature, which shows that the material has a rapid room-temperature self-repairing function
FIG. 6: photo of the iron plate of example 3 in sodium chloride solution for 72 hours
From fig. 6, the following conclusions can be drawn: the iron sheet with the scratched surface coating is seriously corroded in a sodium chloride solution, and the scratched iron sheet is put into the sodium chloride solution after being repaired for one hour at room temperature, so that the corrosion phenomenon basically does not occur, the coating has better corrosion resistance, the iron sheet can be automatically repaired when the coating is mechanically damaged, and meanwhile, the repaired coating still has better corrosion resistance
FIG. 7: photomicrograph of example 5
From fig. 5, the following conclusions can be drawn: after the prepared graphene oxide/polyurea composite material is placed at room temperature for 1 hour, scratches disappear, and the material has a rapid room-temperature self-repairing function.
FIG. 8: the Bode modulus values of the differently coated iron sheets of example 6 after 24 hours exposure to a sodium chloride solution
From fig. 8, the following conclusions can be drawn: the Bode modulus of the sample coated with the graphene oxide/polyurea composite coating is higher, which indicates that the addition of the graphene oxide can further improve the corrosion resistance of the polyurea material
FIG. 9: stress-strain curves for the original and repaired samples of example 8
From fig. 9, the following conclusions can be drawn: the tensile strength of the prepared room-temperature self-repairing polyurea material can reach 32MPa, the room-temperature self-repairing polyurea material can be repaired for 24 hours, and the mechanical property of the material can be recovered to more than 90% of that of an original sample.
FIG. 10: resistance of composite materials containing different graphene concentrations in example 9
From fig. 10, the following conclusions can be drawn: when the concentration of the graphene is 10%, the resistance of the composite material is 2000 omega, which shows that the composite material has good conductivity
FIG. 11: resistance before and after repair of the composite in example 10
From fig. 10, the following conclusions can be drawn: before and after the graphene/polyurea conductive composite material is repaired, the resistance is not changed, which shows that the conductivity of the material can be repaired while the mechanical damage is repaired.
Claims (2)
1. The molecular structure of the high-strength room-temperature self-repairing polyurea coating material is characterized by comprising a hemithioacetal group and a urea group, and the molecular structural formula is as follows:
2. the method for preparing the high-strength room temperature self-repairing polyurea coating material of claim 1, which is characterized by comprising the following steps:
the method 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;
step two: 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;
step three: mixing the precursor solutions obtained in the step 1 and the step 2, stirring and reacting for 1 hour, pouring into a mold, and volatilizing the solvent to obtain the polyurea material with the room-temperature self-repairing function;
step four: dispersing graphene oxide in a solvent, mixing the graphene oxide with the precursor solution obtained in the step 1 and the precursor solution obtained in the step 2, stirring for reaction for 1 hour, and spraying the mixture on the surface of a substrate by using a spray gun to obtain the graphene oxide/polyurea composite anticorrosive coating material with the room-temperature self-repairing function;
step five: and (3) dispersing graphene in a solvent, mixing the graphene with the precursor solution obtained in the step (1) and the precursor solution obtained in the step (2), stirring for reaction for 1 hour, pouring the mixture into a mold, and volatilizing the solvent to obtain the graphene/polyurea composite conductive material with the room-temperature self-repairing function.
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