CN113429868A - Modified polyurethane coating and preparation method thereof - Google Patents
Modified polyurethane coating and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a modified polyurethane coating, and belongs to the technical field of polyurethane coatings. According to the invention, the material performance is improved by modifying the aminated graphene oxide and boric acid and performing hyperbranched grafting, and then the material is blended and compounded with the defoaming agent and the flatting agent to obtain the modified polyurethane coating, so that the problem of poor mechanical performance of the polyurethane coating is solved. Through a chemical grafting mode, organic functional groups such as amino, boric acid group, hyperbranched polyborate and polyurethane and organic polymers are covalently bonded on the surface of the graphene oxide, so that the application range of the graphene oxide is effectively expanded, and the mechanical strength and the thermal stability of the polyurethane coating are integrally improved.
Description
Technical Field
The invention belongs to the technical field of polyurethane coatings, and particularly relates to a modified polyurethane coating and a preparation method thereof.
Background
Polyurethane refers to a polymer having urethane groups in the backbone of the macromolecule. Because the groups contained in the polyurethane molecule are strong polar groups and the macromolecule also contains polyether or polyester flexible chain segments, the polyurethane has higher mechanical strength and oxidation stability, higher flexibility and rebound resilience, excellent oil resistance, solvent resistance, water resistance and fire resistance, and is widely applied to the aspects of coatings, adhesives and the like.
In recent years, with the increasing awareness of environmental protection, environmental-friendly water-based resins have become a hot point of research. The waterborne polyurethane coating is a coating which takes waterborne polyurethane resin as a base material and water as a dispersion medium, has better comprehensive performance, is safe and environment-friendly, and is increasingly widely applied in the fields of coatings, adhesives, printing ink, sealants, surface treating agents and the like. However, the mechanical properties (strength, modulus), heat resistance and the like of the latex film of the polyurethane are not comparable to those of the traditional solvent-based polyurethane, so that the further wide application of the waterborne polyurethane is limited.
Graphene is a novel two-dimensional nano material, the basic structural unit is a six-ring formed by sp2 hybridized carbon atoms, the thickness is only one carbon atom, the graphene is nearly transparent, and the graphene has the characteristics of high specific surface, high heat resistance, high strength and the like. However, the graphene is very easy to agglomerate in a system due to the huge surface energy of the graphene to form a graphite-like structure, the unique performance of the graphene is lost, and the compatibility of the system is influenced.
Patent document CN104861643B discloses a preparation method of a graphene/aqueous polyurethane composite material, firstly, an improved Hummers method is adopted to prepare a graphene oxide aqueous dispersion; then reducing the modified graphene oxide by using ethylenediamine to obtain a modified graphene aqueous solution; then, synthesizing a linear polyurethane prepolymer by using diisocyanate, oligomer dihydric alcohol and a chain extender; and finally, adding a neutralizer into the linear polyurethane prepolymer for neutralization, and blending the modified graphene aqueous solution with the modified graphene aqueous solution to obtain the graphene/waterborne polyurethane composite material. However, the reduced graphene in the system cannot be dispersed in a single layer and is agglomerated in the composite material, so that the leveling property and the mechanical property of the composite material are influenced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a modified polyurethane coating and a preparation method thereof, which solve the problem of poor mechanical strength of the polyurethane coating, and simultaneously the prepared coating also has excellent thermal stability.
In order to achieve the purpose, the invention adopts the following technical scheme:
the modified polyurethane coating comprises the following preparation raw materials in parts by weight:
preferably, the defoaming agent is tributyl phosphate.
Preferably, the leveling agent is polyvinyl alcohol.
The invention also provides a preparation method of the modified polyurethane coating, which comprises the following steps: weighing the defoaming agent, the flatting agent and the modified polyurethane emulsion according to the proportion, adding the weighed materials into deionized water, and performing ultrasonic dispersion uniformly to obtain the modified polyurethane coating.
Preferably, the preparation of the modified polyurethane emulsion comprises the following steps:
(1) preparation of aminated graphene oxide: weighing graphene oxide and methyl isobutyl ketone, ultrasonically mixing uniformly, adding gamma-aminopropyltriethoxysilane, reacting for 8-24 hours at 70-95 ℃ in a nitrogen atmosphere, and after the reaction is finished, performing centrifugal separation and precipitation treatment to obtain aminated graphene oxide;
(2) preparing boric acid modified graphene oxide: adding the aminated graphene oxide prepared in the step (1) into dimethylbenzene, uniformly mixing by ultrasonic, then adding boric acid, uniformly stirring, heating to 60-80 ℃, reacting for 4-10 h in a nitrogen atmosphere, and filtering, washing and drying after the reaction is finished to obtain boric acid modified graphene oxide;
(3) preparing hyperbranched modified graphene oxide: adding the boric acid modified graphene oxide prepared in the step (2) into N-methyl-2-pyrrolidone, ultrasonically mixing uniformly, adding 4,4' -dihydroxybiphenyl and ferric trichloride, stirring uniformly, then reacting for 6-18 h at 70-110 ℃ in a nitrogen atmosphere, adding boric acid after the reaction is finished, starting hyperbranched polymerization reaction by taking dimethylbenzene as a water-carrying agent, and settling, washing, purifying and drying after the reaction is finished to obtain hyperbranched modified graphene oxide;
(4) preparing modified polyurethane emulsion: and (3) adding the hyperbranched modified graphene oxide prepared in the step (3), copper acetate, pyridine triethylamine and amine-terminated polyurethane into dichloromethane, uniformly stirring, then reacting for 12-36 h under the nitrogen atmosphere at room temperature, and filtering, washing and drying after the reaction is finished to obtain the modified polyurethane emulsion.
Further preferably, the mass ratio of the gamma-aminopropyltriethoxysilane, the graphene oxide and the methyl isobutyl ketone in the step (1) is 0.5-3: 1-5: 100.
more preferably, the mass ratio of the aminated graphene oxide to the boric acid in step (2) is 100: 14 to 35.
Further preferably, the mass ratio of the boric acid modified graphene oxide, 4' -dihydroxybiphenyl, ferric trichloride and boric acid in step (3) is 100: 120-250: 15-32: 180-360.
Preferably, the hyperbranched polymerization reaction in the step (3) is carried out for 10-20 h at 150-170 ℃, and then for 12-24 h at 200-220 ℃.
Preferably, in the step (4), the mass ratio of copper acetate, pyridine triethylamine, boric acid-terminated hyperbranched polyborate modified graphene oxide to amine-terminated polyurethane is 3-6: 3-6: 2-5: 100.
compared with the prior art, the invention has the following beneficial technical effects:
(1) according to the modified polyurethane coating provided by the invention, the graphene oxide and the polyurethane matrix are connected through the hyperbranched polyborate, so that the graphene oxide and the polyurethane matrix have good interface compatibility, the graphene oxide is uniformly dispersed in the polyurethane matrix, and the agglomeration phenomenon of the graphene oxide is avoided; evenly dispersed graphene oxide acts as the effect of chemical crosslinking point in the base member, when polyurethane composite coating receives the exogenic action, the base member can produce the crackle, the microcrack can receive the hindrance of graphene oxide on the way of extension, because graphene oxide specific surface is great and intensity is higher, make the propagation of crackle hindered and the passivation, and absorb a large amount of impact energy, simultaneously, graphene oxide can also transfer impact stress to hyperbranched polyborate and polyurethane complex crosslinked network through chemical crosslinking point, the phenomenon of stress concentration has been reduced, thereby the mechanical properties such as tensile, impact strength of composite coating have been improved effectively.
(2) According to the modified polyurethane coating provided by the invention, hyperbranched polyborate molecules grafted on the surface of graphene oxide generate cavities in a cross-linked network, and the cavities can absorb a large amount of plastic deformation work when the polyurethane composite coating is impacted by external force, so that the toughness of the polyurethane composite coating is effectively improved.
(3) According to the modified polyurethane coating provided by the invention, due to the existence of the graphene oxide, the crosslinking degree of a polyurethane composite coating matrix is greatly improved, the hyperbranched polyborate grafted on the surface of the graphene oxide reacts a large amount of phenolic hydroxyl groups in the polyurethane composite coating matrix, the generated B-O bond energy is higher, the energy required by thermal decomposition of the polyurethane composite coating matrix is improved, and the thermal stability of a polyurethane resin material is improved; in addition, the high specific surface area of the graphene oxide nano layer can slow down the escape of polyurethane thermal degradation products, delay oxygen permeation and further enhance the thermal stability of the polyurethane composite coating.
(4) The preparation method of the modified polyurethane coating provided by the invention has the advantages of simple process, simple components, easy operation and higher application value.
Drawings
Fig. 1 is a schematic diagram of a reaction of aminated graphene oxide with boric acid.
Fig. 2 is a schematic diagram of a reaction of boric acid-modified graphene oxide, 4' -dihydroxybiphenyl, and boric acid.
Fig. 3 is a schematic diagram of a reaction of hyperbranched modified graphene oxide and amine-terminated polyurethane.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clearly illustrated, the present invention will be further explained in detail with reference to the accompanying drawings.
It is particularly emphasized that the starting materials or reagents of the present invention are commercially available, unless otherwise specified. Wherein, the amine-terminated polyurethane of the invention is prepared by referring to the prior art.
Example 1
A preparation method of a modified polyurethane coating comprises the following steps:
(1) weighing 1g of graphene oxide and 100g of methyl isobutyl ketone, mixing and then carrying out ultrasonic treatment for 10 min; then adding 0.5g of gamma-aminopropyltriethoxysilane, reacting for 8 hours at 70 ℃ in a nitrogen atmosphere, and cooling to room temperature; adding the reaction mixture into petroleum ether, centrifugally separating precipitates, dispersing the precipitates in acetone, finally precipitating in the petroleum ether again, and centrifugally separating to obtain aminated graphene oxide;
(2) weighing 100g of aminated graphene oxide obtained in the step (1), adding the aminated graphene oxide into 150g of xylene solvent, and uniformly dispersing by ultrasonic; then adding 14g of boric acid, mechanically stirring uniformly, transferring to an oil bath kettle, stirring and reacting for 4 hours at 60 ℃ in a nitrogen atmosphere, and filtering, washing and drying after a product is cooled to obtain boric acid modified graphene oxide;
(3) weighing 100g of boric acid modified graphene oxide obtained in the step (2), adding the boric acid modified graphene oxide into 160mL of N-methyl-2-pyrrolidone, uniformly dispersing by ultrasonic wave, continuously adding 120g of 4,4' -dihydroxybiphenyl and 15g of ferric trichloride, mechanically stirring uniformly, transferring the mixture into an oil bath pot, and reacting for 8 hours at 80 ℃ in a nitrogen atmosphere; continuously adding 180g of boric acid, taking dimethylbenzene as a water-carrying agent, raising the temperature to 150 ℃, reacting for 10 hours, continuously raising the temperature to 200 ℃, reacting for 12 hours, cooling the product, and then settling, washing, purifying and drying to obtain the hyperbranched modified graphene oxide;
(4) adding 3g of copper acetate, 3g of pyridine triethylamine, 2g of hyperbranched modified graphene oxide prepared in the step (3) and 100g of amine-terminated polyurethane into 125mL of dichloromethane solvent, mechanically stirring uniformly, stirring and reacting for 12h at room temperature in a nitrogen atmosphere, and filtering, washing and drying after the product is cooled to obtain a modified polyurethane emulsion;
(5) and (3 g) weighing tributyl phosphate serving as a defoaming agent, 3g polyvinyl alcohol serving as a flatting agent and 100g of the modified polyurethane emulsion prepared in the step (4), adding the weighed modified polyurethane emulsion into a deionized water solvent, adjusting the properties of the emulsion by controlling the amount of deionized water, and then ultrasonically dispersing uniformly to obtain the modified polyurethane coating.
Example 2
A preparation method of a modified polyurethane coating comprises the following steps:
(1) weighing 2g of graphene oxide and 100g of methyl isobutyl ketone, mixing and performing ultrasonic treatment for 20 min; then adding 1g of gamma-aminopropyltriethoxysilane, reacting for 12 hours at 80 ℃ in a nitrogen atmosphere, and cooling to room temperature; adding the reaction mixture into petroleum ether, centrifugally separating precipitates, dispersing the precipitates in acetone, finally precipitating in the petroleum ether again, and centrifugally separating to obtain aminated graphene oxide;
(2) weighing 100g of aminated graphene oxide obtained in the step (1), adding the aminated graphene oxide into 150g of xylene solvent, and uniformly dispersing by ultrasonic; then adding 18g of boric acid, mechanically stirring uniformly, transferring to an oil bath kettle, stirring and reacting for 5 hours at 65 ℃ in a nitrogen atmosphere, and filtering, washing and drying after a product is cooled to obtain boric acid modified graphene oxide;
(3) weighing 100g of boric acid modified graphene oxide obtained in the step (2), adding the boric acid modified graphene oxide into 160mL of N-methyl-2-pyrrolidone, uniformly dispersing by ultrasonic wave, continuously adding 140g of 4,4' -dihydroxybiphenyl and 18g of ferric trichloride, mechanically stirring uniformly, transferring the mixture into an oil bath pot, and reacting for 9 hours at 85 ℃ in a nitrogen atmosphere; continuously adding 200g of boric acid, taking dimethylbenzene as a water-carrying agent, raising the temperature to 155 ℃, reacting for 12 hours, continuously raising the temperature to 205 ℃, reacting for 14 hours, cooling the product, and then settling, washing, purifying and drying to obtain the hyperbranched modified graphene oxide;
(4) adding 3.5g of copper acetate, 3.5g of pyridine triethylamine, 2.5g of hyperbranched modified graphene oxide prepared in the step (3) and 100g of amine-terminated polyurethane into 125mL of dichloromethane solvent, mechanically stirring uniformly, stirring and reacting for 14h at room temperature in a nitrogen atmosphere, filtering, washing and drying after the product is cooled to obtain a modified polyurethane emulsion;
(5) and (3.5 g of defoaming agent tributyl phosphate, 3.5g of flatting agent polyvinyl alcohol and 100g of modified polyurethane emulsion prepared in the step (4) are weighed, added into a deionized water solvent, the properties of the emulsion are adjusted by controlling the amount of deionized water, and then the modified polyurethane coating is obtained by uniformly dispersing through ultrasonic.
Example 3
A preparation method of a modified polyurethane coating comprises the following steps:
(1) weighing 3g of graphene oxide and 100g of methyl isobutyl ketone, mixing and performing ultrasonic treatment for 30 min; then 2g of gamma-aminopropyltriethoxysilane is added, the mixture reacts for 18 hours at 85 ℃ in nitrogen atmosphere, and the mixture is cooled to room temperature; adding the reaction mixture into petroleum ether, centrifugally separating precipitates, dispersing the precipitates in acetone, finally precipitating in the petroleum ether again, and centrifugally separating to obtain aminated graphene oxide;
(2) weighing 100g of aminated graphene oxide obtained in the step (1), adding the aminated graphene oxide into 150g of xylene solvent, and uniformly dispersing by ultrasonic; then adding 25g of boric acid, mechanically stirring uniformly, transferring to an oil bath kettle, stirring and reacting for 8 hours at 70 ℃ in a nitrogen atmosphere, and filtering, washing and drying after a product is cooled to obtain boric acid modified graphene oxide;
(3) weighing 100g of boric acid modified graphene oxide obtained in the step (2), adding the boric acid modified graphene oxide into 160mL of N-methyl-2-pyrrolidone, uniformly dispersing by ultrasonic wave, continuously adding 200g of 4,4' -dihydroxybiphenyl and 25g of ferric trichloride, mechanically stirring uniformly, transferring the mixture into an oil bath pot, and reacting for 13 hours at 90 ℃ in a nitrogen atmosphere; continuously adding 200g of boric acid, taking dimethylbenzene as a water-carrying agent, raising the temperature to 160 ℃, reacting for 16 hours, continuously raising the temperature to 210 ℃, reacting for 18 hours, cooling the product, and then settling, washing, purifying and drying to obtain the hyperbranched modified graphene oxide;
(4) adding 5g of copper acetate, 5g of pyridine triethylamine, 4g of hyperbranched modified graphene oxide prepared in the step (3) and 100g of amine-terminated polyurethane into 125mL of dichloromethane solvent, mechanically stirring uniformly, stirring and reacting for 24 hours at room temperature in a nitrogen atmosphere, and filtering, washing and drying after the product is cooled to obtain a modified polyurethane emulsion;
(5) and (3) weighing 5g of defoaming agent tributyl phosphate, 5g of flatting agent polyvinyl alcohol and 100g of modified polyurethane emulsion prepared in the step (4), adding the weighed materials into a deionized water solvent, adjusting the properties of the emulsion by controlling the amount of deionized water, and then carrying out ultrasonic dispersion uniformly to obtain the modified polyurethane coating.
Example 4
A preparation method of a modified polyurethane coating comprises the following steps:
(1) weighing 4g of graphene oxide and 100g of methyl isobutyl ketone, mixing and performing ultrasonic treatment for 40 min; then adding 2.5g of gamma-aminopropyltriethoxysilane, reacting for 21h at 90 ℃ in a nitrogen atmosphere, and cooling to room temperature; adding the reaction mixture into petroleum ether, centrifugally separating precipitates, dispersing the precipitates in acetone, finally precipitating in the petroleum ether again, and centrifugally separating to obtain aminated graphene oxide;
(2) weighing 100g of aminated graphene oxide obtained in the step (1), adding the aminated graphene oxide into 150g of xylene solvent, and uniformly dispersing by ultrasonic; then adding 31g of boric acid, mechanically stirring uniformly, transferring to an oil bath kettle, stirring and reacting for 9 hours at 75 ℃ in a nitrogen atmosphere, and filtering, washing and drying after a product is cooled to obtain boric acid modified graphene oxide;
(3) weighing 100g of boric acid modified graphene oxide obtained in the step (2), adding the boric acid modified graphene oxide into 160mL of N-methyl-2-pyrrolidone, uniformly dispersing by ultrasonic wave, continuously adding 220g of 4,4' -dihydroxybiphenyl and 30g of ferric trichloride, mechanically stirring uniformly, transferring the mixture into an oil bath pot, and reacting for 15 hours at 95 ℃ in a nitrogen atmosphere; continuously adding 340g of boric acid, taking dimethylbenzene as a water-carrying agent, raising the temperature to 165 ℃ for reacting for 18h, continuously raising the temperature to 215 ℃ for reacting for 22h, cooling the product, and then settling, washing, purifying and drying to obtain the hyperbranched modified graphene oxide;
(4) adding 5.5g of copper acetate, 5.5g of pyridine triethylamine, 4.5g of hyperbranched modified graphene oxide prepared in the step (3) and 100g of amine-terminated polyurethane into 125mL of dichloromethane solvent, mechanically stirring uniformly, stirring and reacting for 30h at room temperature in a nitrogen atmosphere, and filtering, washing and drying after the product is cooled to obtain a modified polyurethane emulsion;
(5) and (3) weighing 5.5g of defoaming agent tributyl phosphate, 5.5g of flatting agent polyvinyl alcohol and 100g of modified polyurethane emulsion prepared in the step (4), adding the weighed materials into a deionized water solvent, adjusting the properties of the emulsion by controlling the amount of deionized water, and then carrying out ultrasonic dispersion uniformly to obtain the modified polyurethane coating.
Example 5
A preparation method of a modified polyurethane coating comprises the following steps:
(1) weighing 5g of graphene oxide and 100g of methyl isobutyl ketone, mixing and performing ultrasonic treatment for 50 min; then adding 3g of gamma-aminopropyltriethoxysilane, reacting for 24 hours at 95 ℃ in a nitrogen atmosphere, and cooling to room temperature; adding the reaction mixture into petroleum ether, centrifugally separating precipitates, dispersing the precipitates in acetone, finally precipitating in the petroleum ether again, and centrifugally separating to obtain aminated graphene oxide;
(2) weighing 100g of aminated graphene oxide obtained in the step (1), adding the aminated graphene oxide into 150g of xylene solvent, and uniformly dispersing by ultrasonic; then adding 35g of boric acid, mechanically stirring uniformly, transferring to an oil bath kettle, stirring and reacting for 10 hours at 80 ℃ in a nitrogen atmosphere, and filtering, washing and drying after a product is cooled to obtain boric acid modified graphene oxide;
(3) weighing 100g of boric acid modified graphene oxide obtained in the step (2), adding the boric acid modified graphene oxide into 160mL of N-methyl-2-pyrrolidone, uniformly dispersing by using ultrasonic waves, continuously adding 250g of 4,4' -dihydroxybiphenyl and 32g of ferric trichloride, mechanically stirring uniformly, transferring the mixture into an oil bath pot, and reacting for 16 hours at 100 ℃ in a nitrogen atmosphere; continuously adding 360g of boric acid, taking dimethylbenzene as a water-carrying agent, raising the temperature to 170 ℃, reacting for 20 hours, continuously raising the temperature to 220 ℃, reacting for 24 hours, cooling the product, and then settling, washing, purifying and drying to obtain the hyperbranched modified graphene oxide;
(4) adding 6g of copper acetate, 6g of pyridine triethylamine, 5g of hyperbranched modified graphene oxide prepared in the step (3) and 100g of amine-terminated polyurethane into 125mL of dichloromethane solvent, mechanically stirring uniformly, stirring and reacting for 30h at room temperature in a nitrogen atmosphere, and filtering, washing and drying after the product is cooled to obtain a modified polyurethane emulsion;
(5) weighing 6g of defoaming agent tributyl phosphate, 6g of flatting agent polyvinyl alcohol and 100g of modified polyurethane emulsion prepared in the step (4), adding the weighed materials into a deionized water solvent, adjusting the properties of the emulsion by controlling the amount of deionized water, and then carrying out ultrasonic dispersion uniformly to obtain the modified polyurethane coating.
Comparative example 1
A preparation method of a modified polyurethane coating comprises the following steps:
(1) weighing 1g of graphene oxide and 100g of methyl isobutyl ketone, mixing and then carrying out ultrasonic treatment for 10 min; then adding 0.5g of gamma-aminopropyltriethoxysilane, reacting for 8 hours at 70 ℃ in a nitrogen atmosphere, and cooling to room temperature; adding the reaction mixture into petroleum ether, centrifugally separating precipitates, dispersing the precipitates in acetone, finally precipitating in the petroleum ether again, and centrifugally separating to obtain aminated graphene oxide;
(2) adding 3g of copper acetate, 3g of pyridine triethylamine, 2g of aminated graphene oxide prepared in the step (1) and 100g of amine-terminated polyurethane into 125mL of dichloromethane solvent, mechanically stirring uniformly, stirring and reacting at room temperature in a nitrogen atmosphere for 12h, and filtering, washing and drying after the product is cooled to obtain the modified polyurethane emulsion;
(3) and (3 g) weighing tributyl phosphate serving as a defoaming agent, 3g polyvinyl alcohol serving as a flatting agent and 100g of the modified polyurethane emulsion prepared in the step (2), adding the weighed modified polyurethane emulsion into a deionized water solvent, adjusting the properties of the emulsion by controlling the amount of deionized water, and then ultrasonically dispersing uniformly to obtain the modified polyurethane coating.
Comparative example 2
A preparation method of a modified polyurethane coating comprises the following steps:
(1) weighing 1g of graphene oxide and 100g of methyl isobutyl ketone, mixing and then carrying out ultrasonic treatment for 10 min; then adding 0.5g of gamma-aminopropyltriethoxysilane, reacting for 8 hours at 70 ℃ in a nitrogen atmosphere, and cooling to room temperature; adding the reaction mixture into petroleum ether, centrifugally separating precipitates, dispersing the precipitates in acetone, finally precipitating in the petroleum ether again, and centrifugally separating to obtain aminated graphene oxide;
(2) weighing 100g of aminated graphene oxide obtained in the step (1), adding the aminated graphene oxide into 150g of xylene solvent, and uniformly dispersing by ultrasonic; then adding 14g of boric acid, mechanically stirring uniformly, transferring to an oil bath kettle, stirring and reacting for 4 hours at 60 ℃ in a nitrogen atmosphere, and filtering, washing and drying after a product is cooled to obtain boric acid modified graphene oxide;
(3) adding 3g of copper acetate, 3g of pyridine triethylamine, 2g of boric acid modified graphene oxide prepared in the step (2) and 100g of amine-terminated polyurethane into 125mL of dichloromethane solvent, mechanically stirring uniformly, stirring and reacting for 12h at room temperature in a nitrogen atmosphere, and filtering, washing and drying after the product is cooled to obtain a modified polyurethane emulsion;
(4) and (3) weighing 3g of defoaming agent tributyl phosphate, 3g of flatting agent polyvinyl alcohol and 100g of modified polyurethane emulsion prepared in the step (3), adding the weighed materials into a deionized water solvent, adjusting the properties of the emulsion by controlling the amount of deionized water, and then carrying out ultrasonic dispersion uniformly to obtain the modified polyurethane coating.
The modified polyurethane coatings obtained in examples 1-5 and comparative examples 1-2 were uniformly coated on tinplate, dried at room temperature and placed in an oven for curing, and then demolded, and the tensile strength of the paint film was tested using a CTM 6005-type universal testing machine.
TABLE 1
The modified polyurethane coatings obtained in examples 1-5 and comparative examples 1-2 were uniformly coated on tin plates, dried at room temperature and placed in an oven for curing, and demolded, and the hardness of the paint film was tested using an HR-150A shore hardness tester.
TABLE 2
| Item | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 |
| Hardness of | 52.5 | 56.1 | 57.9 | 53.2 | 54.1 | 34.3 | 37.0 |
The thermal decomposition temperature of the modified polyurethane coatings obtained in examples 1-5 and comparative examples 1-2 was tested by using a TG-DSC comprehensive thermal analyzer, and the test standard was GB/T13464-.
TABLE 3
As can be seen from tables 1, 2 and 3, the modified polyurethane coatings prepared in examples 1 to 5 of the present application have high tensile strength, high hardness and good mechanical properties compared to comparative examples 1 and 2; meanwhile, the thermal decomposition temperature is higher, and the thermal stability is better.
The above description describes the preferred embodiments of the present invention and should not be taken as limiting the scope of the invention as claimed. Any modification, equivalent replacement and improvement without departing from the principle and spirit of the present invention shall be considered to be within the protection scope of the present claims.
Claims (10)
1. The modified polyurethane coating is characterized by comprising the following preparation raw materials in parts by weight:
2. the modified polyurethane coating of claim 1, wherein the defoamer is tributyl phosphate.
3. The modified polyurethane paint as claimed in claim 1, wherein the leveling agent is polyvinyl alcohol.
4. A preparation method of the modified polyurethane coating described in any one of claims 1 to 3, characterized by comprising the following steps: weighing the defoaming agent, the flatting agent and the modified polyurethane emulsion according to the proportion, adding the weighed materials into deionized water, and performing ultrasonic dispersion uniformly to obtain the modified polyurethane coating.
5. The method according to claim 4, wherein the modified polyurethane emulsion is prepared by the steps of:
(1) preparation of aminated graphene oxide: weighing graphene oxide and methyl isobutyl ketone, ultrasonically mixing uniformly, adding gamma-aminopropyltriethoxysilane, reacting for 8-24 hours at 70-95 ℃ in a nitrogen atmosphere, and after the reaction is finished, performing centrifugal separation and precipitation treatment to obtain aminated graphene oxide;
(2) preparing boric acid modified graphene oxide: adding the aminated graphene oxide prepared in the step (1) into dimethylbenzene, uniformly mixing by ultrasonic, then adding boric acid, uniformly stirring, heating to 60-80 ℃, reacting for 4-10 h in a nitrogen atmosphere, and filtering, washing and drying after the reaction is finished to obtain boric acid modified graphene oxide;
(3) preparing hyperbranched modified graphene oxide: adding the boric acid modified graphene oxide prepared in the step (2) into N-methyl-2-pyrrolidone, ultrasonically mixing uniformly, adding 4,4' -dihydroxybiphenyl and ferric trichloride, stirring uniformly, then reacting for 6-18 h at 70-110 ℃ in a nitrogen atmosphere, adding boric acid after the reaction is finished, starting hyperbranched polymerization reaction by taking dimethylbenzene as a water-carrying agent, and settling, washing, purifying and drying after the reaction is finished to obtain hyperbranched modified graphene oxide;
(4) preparing modified polyurethane emulsion: and (3) adding the hyperbranched modified graphene oxide prepared in the step (3), copper acetate, pyridine triethylamine and amine-terminated polyurethane into dichloromethane, uniformly stirring, then reacting for 12-36 h under the nitrogen atmosphere at room temperature, and filtering, washing and drying after the reaction is finished to obtain the modified polyurethane emulsion.
6. The preparation method according to claim 5, wherein the mass ratio of the gamma-aminopropyltriethoxysilane, the graphene oxide and the methyl isobutyl ketone in the step (1) is 0.5-3: 1-5: 100.
7. the preparation method according to claim 5, wherein the mass ratio of the aminated graphene oxide to the boric acid in the step (2) is 100: 14 to 35.
8. The preparation method according to claim 5, wherein the mass ratio of the boric acid-modified graphene oxide, 4' -dihydroxybiphenyl, ferric trichloride and boric acid in step (3) is 100: 120-250: 15-32: 180-360.
9. The method according to claim 8, wherein the hyperbranched polymerization reaction in step (3) is carried out at 150-170 ℃ for 10-20 hours, and then at 200-220 ℃ for 12-24 hours.
10. The preparation method according to any one of claims 5 to 9, wherein the mass ratio of copper acetate, pyridine triethylamine, boric acid group-terminated hyperbranched polyborate modified graphene oxide to amine-terminated polyurethane in step (4) is 3 to 6: 3-6: 2-5: 100.
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| CN114179543A (en) * | 2021-11-25 | 2022-03-15 | 深圳市深大极光科技有限公司 | Holographic self-repairing graphene liquid crystal modified polyurethane decorative film and preparation method and application thereof |
| CN114179543B (en) * | 2021-11-25 | 2023-12-22 | 深圳市深大极光科技股份有限公司 | Holographic self-repairing graphene liquid crystal modified polyurethane decorative film and preparation method and application thereof |
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