CN112608436A - Polyurethane modified graphene microchip and preparation method thereof - Google Patents
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Abstract
The invention discloses a polyurethane modified graphene microchip and a preparation method thereof, wherein the preparation method specifically comprises the following steps: adding graphene oxide and polyol into a three-neck flask according to the proportion, stirring and mixing, and simultaneously carrying out high-temperature vacuum dehydration; then continuing mixing and stirring after the high-temperature vacuum dehydration is finished, stopping heating, controlling the reaction temperature to cool to room temperature, gradually adding isocyanate, monitoring the reaction temperature, adjusting the adding rate according to the reaction temperature, and controlling the reaction temperature to be kept below T ℃; and finally, after the isocyanate is added and reacts for 10-30 min, heating by adopting an oil bath to control the reaction temperature within the range of 75-85 ℃, stirring and reacting for 1.5-3h, and filtering and packaging by adopting a filter screen to complete the preparation of the polyurethane modified graphene microchip. When the polyurethane modified graphene microchip prepared by the invention is used in epoxy resin coating, graphene can be uniformly and directionally distributed in a coating layer, and the corrosion resistance of the coating layer is greatly improved.
Description
Technical Field
The invention belongs to the field of coatings, relates to an epoxy coating modification technology, and particularly relates to a polyurethane modified graphene microchip and a preparation method thereof.
Background
With the stricter environmental protection policy in China, the application requirements of the environment-friendly long-life protective coating in the industries of ocean engineering equipment, ships, petrochemical industry, bridges, heavy equipment and the like are urgent increasingly. The common solvent anticorrosive paint is gradually eliminated by the market, and the application of the solvent-free paint is more and more extensive, wherein the solvent-free epoxy paint is one of the varieties with the largest application amount. The solvent-free epoxy coating has the advantages of strong adhesive force, good corrosion resistance, long service life and the like. But the coating has the defects of larger viscosity, short mixed working life, low-temperature curing speed, large brittleness, poor interlayer adhesion, unobvious labyrinth shielding effect and the like of the coating, and has a larger gap compared with the use requirement of long-acting anticorrosion protection of a steel structure in a severe environment. Graphene (Gr) is a flaky two-dimensional structure formed by carbon atoms, has the characteristics of high strength, strong physical barrier property, good thermal stability and the like, can be added into a solvent-free epoxy coating to improve the anti-precipitation performance of the coating under an ideal state, and can remarkably improve the flexibility, corrosion resistance and high and low temperature resistance of the coating, but due to the defects of large surface polarity, easy agglomeration and stacking and the like, the actual use effect of graphene micro-sheets in the coating is greatly reduced, and due to the fact that the graphene micro-sheets have conductivity, conductive channels are formed in a closed coating in a lap joint mode to further accelerate the electrochemical corrosion of a metal substrate, so that the key for popularization and application of the graphene modified coating is to solve the long-term dispersion stability of graphene and the compatibility of the graphene with organic resin.
The invention patent with publication number CN110128943A discloses a graphene high-performance anticorrosive paint and a preparation method and a product thereof, the graphene high-performance anticorrosive paint prepared by using solvent type epoxy resin, antirust pigment, organic solvent, curing agent and other raw materials enhances the long-acting property of anticorrosion protection to a certain extent by utilizing the characteristics of graphene, but the preparation method uses more solvents and catalysts for dispersion reaction, and is not high in environmental protection property.
Disclosure of Invention
The invention aims to provide a polyurethane modified graphene microchip and a preparation method thereof. The polyurethane modified graphene nanoplatelets prepared by the invention are used for modifying epoxy resin, and the polyurethane prepolymer modified graphene oxide nanoplatelets and hydroxyl groups on an epoxy molecular chain are subjected to addition polymerization to form a graphene block polymer, so that the chemical bonding of the graphene nanoplatelets and a resin matrix is realized, the graphene nanoplatelets are completely directionally arranged in the resin matrix to form a labyrinth effect, the shielding performance of the graphene nanoplatelets is fully exerted, and the corrosion protection performance of a coating is greatly improved.
The purpose of the invention is realized by the following technical scheme:
the invention also provides a preparation method of the polyurethane modified graphene nanoplatelets, which comprises the following steps:
adding graphene oxide and polyol into a three-neck flask according to a ratio, stirring and mixing, and simultaneously performing high-temperature vacuum dehydration;
continuously mixing and stirring after the high-temperature vacuum dehydration is finished, stopping heating, controlling the reaction temperature to be cooled to room temperature, gradually adding isocyanate, monitoring the reaction temperature, adjusting the adding rate according to the reaction temperature, and controlling the reaction temperature to be kept below T ℃;
and (3) after the isocyanate is added and reacts for 10-30 min, heating by adopting an oil bath to control the reaction temperature within the range of 75-85 ℃, stirring and reacting for 1.5-3h, filtering and packaging by adopting a filter screen, cooling to room temperature after packaging, and completing the preparation of the polyurethane modified graphene microchip.
Preferably, the ratio of the polyol to the isocyanate to the graphene oxide is as follows by mass:
60-100% of polyol
80-150 parts of isocyanate
1-10% of graphene oxide.
Preferably, in the step (1), the high-temperature vacuum dehydration is specifically performed by heating in an oil bath to control the temperature within the range of 105-120 ℃, and performing vacuum dehydration for 1.5-3 hours by using a vacuum pump.
Preferably, in the step (3), the mesh number of the filter screen is 150-.
Preferably, the polyol is any one or more of PTMG1000, PTMG650, PCDL1000, diethanolamine and triethanolamine.
Preferably, the isocyanate is any one or more of HDI (1, 6-hexamethylene diisocyanate), MDI (diphenylmethane diisocyanate), IPDI (isophorone diisocyanate), HMDI (4,4' -dicyclohexylmethane diisocyanate), TDI (toluene diisocyanate) and LDI (L-lysine diisocyanate).
Preferably, said T in step (2) ranges from 70 to 80 ℃.
The invention also provides a polyurethane modified graphene microchip prepared by any one of the preparation methods.
The invention also provides application of the polyurethane modified graphene nanoplatelets in modification of solvent-free epoxy coatings. The polyurethane modified graphene nanoplatelets prepared by the invention are used for modifying the solvent-free epoxy coating, and the specific method comprises the following steps:
adding polyurethane modified graphene nanoplatelets into solvent-free epoxy resin according to a formula ratio, and stirring for 20-60 min at the temperature of 60-80 ℃ to prepare matrix resin of the coating;
step (2) adding the wetting dispersant, the antirust pigment and the thickening agent into the matrix resin at one time according to a ratio, and grinding for 2-5 hours at normal temperature by using a sand mill, wherein the rotating speed is controlled to be 1000-2500 r/min;
adding the defoaming agent in batches in the grinding process in the step (3), controlling the using amount not to exceed 5% of the total amount of the formula, grinding until the fineness reaches below 50 mu m, and filtering and packaging by using a filter screen to obtain a coating base material;
stirring and curing the coating base material for 30-40 min before coating in the step (4), and then mixing the coating base material with a curing agent according to the proportion to obtain the long-acting anticorrosion graphene modified solvent-free epoxy coating capable of being coated.
Preferably, the components of the formula proportion are as follows by mass:
preferably, the polyurethane modified graphene microchip is prepared by mainly using polyol, isocyanate and graphene oxide as raw materials through dehydration, addition polymerization and purification processes.
Preferably, the solvent-free epoxy resin is any one or more of low molecular weight modified bisphenol A epoxy, low molecular weight modified bisphenol F epoxy, low molecular weight alicyclic epoxy and low molecular weight phenolic aldehyde modified epoxy resin.
Preferably, the wetting dispersant is a solvent-free associative polyurethane and/or a solvent-free acrylic dispersant.
Preferably, the antirust pigment is any one or more of zinc phosphate, aluminum tripolyphosphate, glass flakes, iron oxide red and zinc powder.
Preferably, the defoaming agent is a hydrophobic ion-containing silicone defoaming agent.
Preferably, the thickener is any one of an organic soil, fumed silica and a polyamide thickener.
Preferably, the curing agent is any one or more of DETA (diethylenetriamine), TETA (triethylenetetramine), DEPA (triethylaminopropylamine), TEPA (tetraethylenepentamine), MDA (menthanediamine), IPDA (isophoronediamine), DDS (diaminodiphenyl sulfone) and DDM (diaminodiphenyl methane).
Preferably, the filter screen used in step (3) is 150-250 meshes, and most preferably 200 meshes.
The invention also provides a long-acting anticorrosion graphene modified solvent-free epoxy coating, which is characterized in that: is prepared by any one of the preparation methods.
The invention has the following beneficial effects:
according to the invention, graphene is grafted onto an epoxy molecular chain in a chemical grafting manner, and graphene nanoplatelets are subjected to limiting dispersion through chemical bonds, so that the problem that the graphene nanoplatelets are easy to agglomerate and stack is solved, and long-term stable dispersion of the graphene nanoplatelets in the coating is realized. In addition, the graphene oxide micro-sheets are chemically grafted to an epoxy molecular chain by utilizing a polyurethane structure, a compact three-dimensional network structure is formed by ring-opening polymerization of epoxy groups and amino groups in a curing agent, the graphene micro-sheets are thoroughly spread out in a chemical bonding mode, and the directional arrangement of the graphene micro-sheets in a coating can be realized, so that the characteristics of ultrahigh specific surface area, super-hydrophobicity and high shielding property of graphene are fully embodied, a favorable guarantee is provided for the long-acting corrosion resistance of the coating, and the corrosion resistance of the coating can be further improved by combining with the traditional antirust pigment.
Drawings
FIG. 1 is a low multiple fracture morphology plot of a pure epoxy resin in an example of the present invention.
FIG. 2 is a high multiple fracture morphology plot of pure epoxy in an example of the present invention.
Fig. 3 shows a low-fold fracture morphology of the graphene-modified epoxy resin in the embodiment of the invention.
Fig. 4 shows a high-fold fracture morphology of the graphene-modified epoxy resin in the embodiment of the invention.
FIG. 5 mechanical properties of modified and unmodified epoxy resins.
Fig. 6 is a macro morphology diagram of a graphene modified solvent-free epoxy coating in a salt spray test, in which fig. 6(a) is an original morphology of the coating before the salt spray test, and fig. 6(b) is a corrosion morphology of the coating after the salt spray test.
FIG. 7 is a salt spray test macro-topography of a comparative solvent-free epoxy coating, wherein FIG. 7(a) is an original topography of the coating before the salt spray test and FIG. 7(b) is a corrosion topography of the coating after the salt spray test.
Detailed Description
The embodiments of the present invention will be described in further detail with reference to the drawings and examples. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The preparation method of the polyurethane modified graphene nanoplatelets comprises the following steps:
example 1:
adding 1g of graphene oxide and 60g of polyhydric alcohol into a three-neck flask, stirring and mixing, heating by adopting an oil bath to control the temperature within a range of 105-120 ℃, and performing vacuum dehydration for 1.5-3h by using a vacuum pump;
continuously mixing and stirring after the high-temperature vacuum dehydration is finished, stopping heating, controlling the reaction temperature to be cooled to room temperature, gradually adding 80g of isocyanate, monitoring the reaction temperature, adjusting the addition rate according to the reaction temperature, and controlling the reaction temperature to be kept below T ℃;
and (3) after the isocyanate is added and reacts for 10-30 min, heating by adopting an oil bath to control the reaction temperature within the range of 75-85 ℃, stirring and reacting for 1.5-3h, and filtering and packaging by adopting a 200-mesh filter screen to complete the preparation of the polyurethane modified graphene nanoplatelets.
Example 2:
adding 5g of graphene oxide and 70g of polyol into a three-neck flask, stirring and mixing, heating by adopting an oil bath to control the temperature within a range of 105-120 ℃, and performing vacuum dehydration for 1.5-3h by using a vacuum pump;
continuously mixing and stirring after the high-temperature vacuum dehydration is finished, stopping heating, controlling the reaction temperature to be cooled to room temperature, gradually adding 100g of isocyanate, monitoring the reaction temperature, adjusting the addition rate according to the reaction temperature, and controlling the reaction temperature to be kept below T ℃;
and (3) after the isocyanate is added and reacts for 10-30 min, heating by adopting an oil bath to control the reaction temperature within the range of 75-85 ℃, stirring and reacting for 1.5-3h, and filtering and packaging by adopting a 200-mesh filter screen to complete the preparation of the polyurethane modified graphene nanoplatelets.
Example 3:
adding 8g of graphene oxide and 80g of polyol into a three-neck flask, stirring and mixing, heating by adopting an oil bath to control the temperature within a range of 105-120 ℃, and performing vacuum dehydration for 1.5-3h by using a vacuum pump;
continuously mixing and stirring after the high-temperature vacuum dehydration is finished, stopping heating, controlling the reaction temperature to be cooled to room temperature, gradually adding 130g of isocyanate, monitoring the reaction temperature, adjusting the addition rate according to the reaction temperature, and controlling the reaction temperature to be kept below T ℃;
and (3) after the isocyanate is added and reacts for 10-30 min, heating by adopting an oil bath to control the reaction temperature within the range of 75-85 ℃, stirring and reacting for 1.5-3h, and filtering and packaging by adopting a 200-mesh filter screen to complete the preparation of the polyurethane modified graphene nanoplatelets.
Example 4:
adding 10g of graphene oxide and 100g of polyol into a three-neck flask, stirring and mixing, heating by adopting an oil bath to control the temperature within a range of 105-120 ℃, and performing vacuum dehydration for 1.5-3h by using a vacuum pump;
continuously mixing and stirring after the high-temperature vacuum dehydration is finished, stopping heating, controlling the reaction temperature to be cooled to room temperature, gradually adding 140g of isocyanate, monitoring the reaction temperature, adjusting the addition rate according to the reaction temperature, and controlling the reaction temperature to be kept below T ℃;
and (3) after the isocyanate is added and reacts for 10-30 min, heating by adopting an oil bath to control the reaction temperature within the range of 75-85 ℃, stirring and reacting for 1.5-3h, and filtering and packaging by adopting a 200-mesh filter screen to complete the preparation of the polyurethane modified graphene nanoplatelets.
The examples of the polyurethane modified graphene nanoplatelets prepared above for use in the modified solvent-free epoxy coating are as follows:
example 5: adding 1g of polyurethane modified graphene nanoplatelets into 20g of solvent-free epoxy resin, and stirring for 20-60 min at the temperature of 60-80 ℃ to prepare matrix resin of the coating;
step (2) adding 1g of wetting dispersant, 1g of antirust pigment and 1g of thickener into matrix resin at one time, and grinding for 2-5 hours at normal temperature by using a sand mill, wherein the rotating speed is controlled to be 1000-2500 r/min;
adding 1g of defoaming agent in batches in the grinding process in the step (3), controlling the using amount not to exceed 5% of the total amount of the formula, grinding until the fineness reaches below 50 mu m, and filtering and packaging by adopting a 200-mesh filter screen to prepare a coating base material;
stirring and curing the coating base material for 30-40 min before coating in the step (4), and then mixing the coating base material with 10g of curing agent according to the proportion to obtain the long-acting anticorrosive graphene modified solvent-free epoxy coating capable of being coated.
Example 6: adding 2g of polyurethane modified graphene nanoplatelets into 25g of solvent-free epoxy resin, and stirring for 20-60 min at the temperature of 60-80 ℃ to prepare matrix resin of the coating;
step (2) adding 2g of wetting dispersant, 1g of antirust pigment and 2g of thickener into matrix resin at one time, and grinding for 2-5 h at normal temperature by using a sand mill, wherein the rotating speed is controlled to be 1000-2500 r/min;
adding 1g of defoaming agent in batches in the grinding process in the step (3), controlling the using amount not to exceed 5% of the total amount of the formula, grinding until the fineness reaches below 50 mu m, and filtering and packaging by adopting a 200-mesh filter screen to prepare a coating base material;
stirring and curing the coating base material for 30-40 min before coating in the step (4), and then mixing the coating base material with 10g of curing agent according to the proportion to obtain the long-acting anticorrosive graphene modified solvent-free epoxy coating capable of being coated.
Example 7: adding 10g of polyurethane modified graphene nanoplatelets into 25g of solvent-free epoxy resin, and stirring for 20-60 min at the temperature of 60-80 ℃ to prepare matrix resin of the coating;
step (2) adding 3g of antirust pigment and 2g of thickening agent into matrix resin at one time, and grinding for 2-5 h at normal temperature by using a sand mill, wherein the rotating speed is controlled to be 1000-2500 r/min;
adding 2g of defoaming agent in batches in the grinding process in the step (3), controlling the using amount not to exceed 5% of the total amount of the formula, grinding until the fineness reaches below 50 mu m, and filtering and packaging by adopting a 200-mesh filter screen to prepare a coating base material;
stirring and curing the coating base material for 30-40 min before coating in the step (4), and then mixing the coating base material with 10g of curing agent according to the proportion to obtain the long-acting anticorrosive graphene modified solvent-free epoxy coating capable of being coated.
Example 8: adding 15g of polyurethane modified graphene nanoplatelets into 50g of solvent-free epoxy resin, and stirring for 20-60 min at the temperature of 60-80 ℃ to prepare matrix resin of the coating;
step (2) adding 3g of antirust pigment and 3g of thickening agent into matrix resin at one time, and grinding for 2-5 h at normal temperature by using a sand mill, wherein the rotating speed is controlled to be 1000-2500 r/min;
adding 4g of defoaming agent in batches in the grinding process in the step (3), controlling the using amount not to exceed 5% of the total amount of the formula, grinding until the fineness reaches below 50 mu m, and filtering and packaging by adopting a 200-mesh filter screen to prepare a coating base material;
stirring and curing the coating base material for 30-40 min before coating in the step (4), and then mixing the coating base material with 10g of curing agent according to the proportion to obtain the long-acting anticorrosive graphene modified solvent-free epoxy coating capable of being coated.
Example 9: adding 20g of polyurethane modified graphene nanoplatelets into 70g of solvent-free epoxy resin, and stirring for 20-60 min at the temperature of 60-80 ℃ to prepare matrix resin of the coating;
adding 4g of antirust pigment and 5g of thickening agent into matrix resin at one time, and grinding for 2-5 hours at normal temperature by using a sand mill, wherein the rotating speed is controlled to be 1000-2500 r/min;
adding 4g of defoaming agent in batches in the grinding process in the step (3), controlling the using amount not to exceed 5% of the total amount of the formula, grinding until the fineness reaches below 50 mu m, and filtering and packaging by adopting a 200-mesh filter screen to prepare a coating base material;
stirring and curing the coating base material for 30-40 min before coating in the step (4), and then mixing the coating base material with 10g of curing agent according to the proportion to obtain the long-acting anticorrosive graphene modified solvent-free epoxy coating capable of being coated.
The polyurethane modified graphene microchip modified solvent-free epoxy coating and the pure solvent-free epoxy coating prepared in the embodiment 5 of the invention are scanned by an electron microscope to obtain structures as shown in fig. 1 to 4, and as can be seen from fig. 1 to 4, fracture morphology of pure epoxy resin is smooth and flat, and has no ductile fracture characteristics such as diffusion cracks, steps and the like, and belongs to obvious brittle fracture, the fracture morphology of the resin is cured after graphene oxide microchip is chemically grafted to an epoxy molecular chain by utilizing a polyurethane structure, and a large number of structural characteristics such as vortexes, channels, steps and the like appear, which shows that the material is subjected to resistance in different directions when being damaged by stress, and the stress damage direction is randomly diffused, so that the obvious ductile fracture characteristic is shown, because the directionally arranged graphene microchip has a large specific surface area and excellent mechanical properties, and plays an obvious reinforcing role in the epoxy resin, the toughness of the epoxy resin is improved, and the defect of brittleness of the epoxy resin is overcome.
Reference standard GBT 228.1-2010 "metallic material tensile test part 1: the tensile property and the bending property of the pure epoxy resin material and the graphene modified epoxy resin material prepared in example 5 were tested by a room temperature test method and a standard GB/T232-.
Referring to a standard GB/T10125-.
The above embodiments are merely illustrative of the present invention and are not to be construed as limiting the invention. Although the present invention has been described in detail with reference to the embodiments, it should be understood by those skilled in the art that various combinations, modifications or equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention, and the technical solution of the present invention is covered by the claims of the present invention.
Claims (8)
1. A preparation method of a polyurethane modified graphene microchip is characterized by comprising the following steps:
adding graphene oxide and polyol into a three-neck flask according to a ratio, stirring and mixing, and simultaneously performing high-temperature vacuum dehydration;
continuously mixing and stirring after the high-temperature vacuum dehydration is finished, stopping heating, controlling the reaction temperature to be cooled to room temperature, gradually adding isocyanate, monitoring the reaction temperature, adjusting the adding rate according to the reaction temperature, and controlling the reaction temperature to be kept below T ℃;
and (3) after the isocyanate is added and reacts for 10-30 min, controlling the reaction temperature within the range of 75-85 ℃ by adopting oil bath heating, stirring and reacting for 1.5-3h, and filtering and packaging by adopting a filter screen to complete the preparation of the polyurethane modified graphene microchip.
2. The method for preparing the polyurethane modified graphene nanoplatelets of claim 1, wherein: the ratio of the polyol to the isocyanate to the graphene oxide is as follows by mass:
60-100% of polyol
80-150 parts of isocyanate
1-10% of graphene oxide.
3. The method for preparing the polyurethane modified graphene nanoplatelets of claim 1, wherein: in the step (1), the specific method for high-temperature vacuum dehydration is to control the temperature within the range of 105-120 ℃ by adopting oil bath heating, and carry out vacuum dehydration for 1.5-3h by using a vacuum pump.
4. The method for preparing the polyurethane modified graphene nanoplatelets of claim 1, wherein: in step (3), the mesh number of the filter screen is 150-.
5. The method for preparing the polyurethane modified graphene nanoplatelets of claim 1, wherein: the polyalcohol is any one or more of PTMG1000, PTMG650, PCDL1000, diethanolamine and triethanolamine.
6. The method for preparing the polyurethane modified graphene nanoplatelets of claim 1, wherein: the isocyanate is any one or more of HDI, MDI, IPDI, HMDI, TDI and LDI.
7. The method for preparing the polyurethane modified graphene nanoplatelets of claim 1, wherein: the range of T in the step (2) is 70-80 ℃.
8. A polyurethane modified graphene microchip is characterized in that: prepared by the preparation method of any one of claims 1 to 7.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011476438.9A CN112608436A (en) | 2020-12-14 | 2020-12-14 | Polyurethane modified graphene microchip and preparation method thereof |
| PCT/CN2021/137546 WO2022127745A1 (en) | 2020-12-14 | 2021-12-13 | Polyurethane modified graphene microsheet and preparation method therefor |
| AU2021402785A AU2021402785A1 (en) | 2020-12-14 | 2021-12-13 | Polyurethane modified graphene microsheet and preparation method therefor |
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| WO2022127745A1 (en) * | 2020-12-14 | 2022-06-23 | 武汉材料保护研究所有限公司 | Polyurethane modified graphene microsheet and preparation method therefor |
| CN115449248A (en) * | 2022-10-14 | 2022-12-09 | 山东京博装备制造安装有限公司 | Graphene heavy-duty anticorrosive paint for outer wall of earthing storage tank |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116284655B (en) * | 2023-01-10 | 2024-01-09 | 中威北化科技有限公司 | Preparation method of graphene-organosilicon synergistically-reinforced polyurethane grafted modified epoxy resin |
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| AU2021402785A1 (en) | 2023-06-22 |
| WO2022127745A1 (en) | 2022-06-23 |
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