CN116179061A - Fluorine-containing single-component polyurea coating and preparation method thereof - Google Patents
Fluorine-containing single-component polyurea coating and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of polyurea coatings, in particular to a fluorine-containing single-component polyurea coating and a preparation method thereof; the dispersion stability of the aqueous polyurea emulsion prepared by the invention and the water resistance of the material are optimal; the emulsion has good performance in stability detection projects such as dilution, heat storage, freeze thawing and the like, and the state has no abnormal change; according to the invention, the sulfonated graphene is added, so that the sulfonated graphene has more excellent compatibility and dispersibility in aqueous polyurea, can be kept stable for more than 28 days without layering, and the waterproof performance of the coating is obviously improved; the sulfonated graphene prevents penetration of corrosive media and effectively prolongs the penetration path, and because the sulfonated graphene is uniformly dispersed in the aqueous polyurea, a corrosion protection barrier is formed, and corrosion of moisture is effectively blocked, so that the aqueous polyurea coating has the most excellent corrosion resistance.
Description
Technical Field
The invention relates to the field of polyurea coatings, in particular to a fluorine-containing single-component polyurea coating and a preparation method thereof.
Background
As a novel aqueous polymer, the aqueous polyurea is a hot spot direction of polyurea coating research in recent years, and the development of the product is mainly based on two points: firstly, compared with the traditional reactive double-component polyurea, the aqueous polyurea has the advantages of simple construction operation, no need of special spraying equipment, low cost, more practicability and the like; and secondly, water is used as a dispersion medium, so that the requirements of environmental protection regulations are met. The presence of the hydrophilic structure gives the aqueous polymer a better stability in water, but also inevitably brings about the problems of poor water resistance and corrosion resistance of the coating.
Cn20110433252. X: an anti-sticking wear-resistant polyurea coating and a preparation method thereof are provided, wherein the coating is prepared by mixing A, B components; the component A is synthesized by the following raw materials in parts by weight: 90-120 parts of isocyanate, 40-60 parts of polyether alcohol and 20-30 parts of fluorocarbon diol; the component B is prepared from the following raw materials in parts by weight: 500-800 parts of polyether amine, 400-600 parts of organosilicon diamine, 300-400 parts of high-activity polyether alcohol, 400-550 parts of amino chain extender, 80-100 parts of amino cross-linking agent, 100-150 parts of high-boiling point diluent, 5-10 parts of composite catalyst, 400-600 parts of composite nano metal oxide surface active material, 600-800 parts of filler and 40-60 parts of pigment. The invention also comprises a preparation method of the anti-sticking wear-resistant polyurea coating. The anti-sticking wear-resistant polyurea coating provided by the invention has the advantages of strong adhesive force, good anti-sticking property, wear resistance, corrosion resistance and impact resistance, and is particularly suitable for being sprayed on the surface of a lining of a heavy-duty transport dump truck.
CN201210312247.8: belongs to the field of metal corrosion and protection, and relates to a preparation method of a polyurea anticorrosive coating. The invention comprises the working procedures of preprocessing a metal structural part, degreasing, sand blasting, metal surface treatment, drying, spraying a bottom-layer polyurea coating and spraying a surface-layer polyurea coating; the method is characterized in that inositol phosphate solution is adopted for metal surface treatment, and a layer of inositol phosphate chemical conversion film is formed on the surface of a metal structure substrate; the bottom polyurea coating is an aromatic polyurea coating, and the surface polyurea coating is an aliphatic polyurea coating; metals include steel, aluminum alloys, and galvanized steel structures; the total thickness of the coating is 500-1500 mu m, the bottom layer is 300-1200 mu m, the surface layer is 200-400 mu m, and the bonding strength of the coating is more than 10MPa; the invention has simple process and convenient operation, and is free from priming paint.
CN201310333086.5: relates to a polyurea coating formula and a polyurea coating prepared by the same. A polyurea coating formula comprises a component A and a component B, wherein the component A is aliphatic polyurea resin with an active group of R-NH-R', and the component B is isocyanate prepolymer with an active group of-NCO; the molar ratio of the component A to the component B is-NCO/-NH- =1.0-1.2:1.0. Compared with the prior art, the invention has the following advantages: 1) The polyurea coating of the invention can be brushed, rolled or constructed by using common spraying equipment like the traditional polyurethane two-component coating without special spraying equipment and transitional coating. 2) Because the coating has high crosslinking density, the film forming material does not contain unsaturated double bonds, benzene rings and ether bonds which are easy to damage by ultraviolet rays, contains abundant hydrogenated six-membered rings, urea bonds, urethane bonds and hydrogen bonds, ensures that the coating has excellent adhesive force when forming a film, and has hardness of more than 3H and good impact toughness. 3) The coating material of the invention is suitable for being coated on the base materials such as tinplate, stainless steel plate, metal water pipe, glass, PVC, ABS, polyester, concrete and the like.
The polyurea coating prepared by the patent and the prior art is popular with consumers because of excellent heat resistance, corrosion resistance and mechanical properties. However, the defects are also slowly and prominently manifested, and the construction of the double-component polyurea has the advantages of high reaction activity, high equipment price, high requirements on operation technology and inapplicability to popularization and use in a large range because the double-component polyurea has high reaction activity. The polyurea has an excessively high curing reaction rate, so that the adhesion between the coating and the substrate is poor, and the coating is easy to crack or fall off.
Disclosure of Invention
The invention aims to provide a fluorine-containing single-component polyurea coating and a preparation method thereof, which are used for solving the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
in one aspect, the invention discloses a fluorine-containing single-component polyurea coating and a preparation method thereof:
and uniformly ultrasonically dispersing 0.1-0.7 part of sulfonated graphene in 85-100 parts of aqueous polyurea emulsion according to parts by mass to obtain the modified aqueous polyurea coating.
On the other hand, the invention discloses a preparation method of aqueous polyurea, which comprises the following steps:
s1: adding 15-20 parts by mass of isophorone diisocyanate, 4-8 parts by mass of ethylene glycol acrylate compound, 0.05-0.2 part by mass of dibutyltin dilaurate and 10-15 parts by mass of organic solvent into a reaction kettle, heating under the protection of nitrogen, and reacting;
s2: continuously adding 0.001-0.03 part of 1-aminopropyl-3-methylimidazole tetrafluoroborate, 2-5 parts of triethylamine, stirring for 20-55 minutes at 40-60 ℃, adding 0.05-0.5 part of aminopropyl heptyl-cage polysilsesquioxane, and stirring for 50-90 minutes at a constant temperature;
s3: continuously adding 30-45 parts of polyether amine D2000, stirring for 30-50min at room temperature, slowly adding a mixture of 3-5 parts of polyether amine D230 and 10-15 parts of acetone, and continuously stirring for 30-50min at room temperature;
s4: adding 1-3 parts of triethylamine for neutralization reaction for 20-40min; and (3) placing the reaction product into 100-150 parts of deionized water, stirring by using a high-speed dispersing machine, standing for defoaming, and removing acetone by low-pressure distillation of a rotary evaporator to obtain the aqueous polyurea emulsion.
Further, the reaction temperature of the S1 is 40-60 ℃ and the reaction time is 2-5h.
Further, the organic solvent is DMF.
Further, the stirring speed of the high-speed dispersing machine is 1200-1500rpm, and the stirring time is 20-40min.
Further, the ethylene glycol acrylate compound is selected from the group consisting of ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, decaethylene glycol dimethacrylate and triethylene glycol dimethacrylate.
Further, the amino propyl heptyl-cage polysilsesquioxane has CAS ratio of 444315-15-5.
In yet another aspect, the invention discloses a method for preparing Sulfonated Graphene (SG) comprising:
s1: according to the mass parts, under ice water bath, 4-7 parts of sodium nitrite, 12-15 parts of sulfanilic acid and 85-100 parts of hydrochloric acid solution are stirred to obtain aryl diazonium salt solution;
s2: slowly dripping the aryl diazonium salt solution into 15-25 parts of graphene oxide aqueous solution, stirring in an ice bath for reaction, and then dialyzing and purifying in distilled water to obtain sulfonated graphene oxide dispersoids;
s3: and (3) reacting the sulfonated graphene oxide with 20-30 parts of hydrazine hydrate, removing part of oxygen-containing groups, and repeatedly centrifuging and washing with deionized water to obtain the sulfonated graphene.
Further, the mass concentration of the hydrochloric acid solution is 10-20%.
Further, the reaction time of S2 is 1-3h.
Further, the reaction temperature of the S3 is 70-90 ℃ and the reaction time is 8-12h.
Reaction mechanism:
the isophorone diisocyanate reacts with ethylene glycol acrylate compound, the acrylate functional group of the isophorone diisocyanate further reacts with trace 1-aminopropyl-3-methylimidazole tetrafluoroborate and aminopropyl heptyl-cage polysilsesquioxane to obtain a mixture, and the mixture further reacts with polyetheramine to obtain the aqueous polyurea emulsion.
The technical effects are as follows:
compared with the prior art, the fluorine-containing single-component polyurea coating and the preparation method thereof have the following remarkable effects:
1. the invention synthesizes aqueous polyurea through isophorone diisocyanate, polyether amine and anionic hydrophilic monomer-dimethylolpropionic acid; the addition of the imidazole tetrafluoroborate and the silsesquioxane functional groups improves the dispersion stability and the water resistance of the water-based polyurea emulsion prepared by the invention; by analytical detection: the emulsion has the solid content of 37.0wt%, the viscosity of 74.0KU, the minimum film forming temperature of 12.6 ℃, and the emulsion has good performance in stability detection projects such as dilution, heat storage, freeze thawing and the like, and the state has no abnormal change;
2. according to the invention, the sulfonated graphene is added, so that the sulfonated graphene has more excellent compatibility and dispersibility in aqueous polyurea, can be kept stable for more than 28 days without layering, and the waterproof performance of the coating is obviously improved;
3. the sulfonated graphene prevents penetration of corrosive media and effectively prolongs the penetration path, and because the sulfonated graphene is uniformly dispersed in the aqueous polyurea, a corrosion protection barrier is formed, and corrosion of moisture is effectively blocked, so that the aqueous polyurea coating has the most excellent corrosion resistance.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, based on the embodiments of the invention, which are apparent to those of ordinary skill in the art without undue burden are within the scope of the invention
The following description of the embodiments of the present invention will be presented in further detail with reference to the examples, which should be understood as being merely illustrative of the present invention and not limiting.
Example 1
A fluorine-containing single-component polyurea coating and a preparation method thereof are provided, wherein the operation steps are as follows:
uniformly and ultrasonically dispersing 0.1g of sulfonated graphene in 85g of aqueous polyurea emulsion to obtain the modified aqueous polyurea coating.
The preparation method of the aqueous polyurea comprises the following steps:
s1: 15g of isophorone diisocyanate, 4g of ethylene glycol acrylate compound, 0.05g of dibutyltin dilaurate and 10g of DMF are added into a reaction kettle, and the temperature is raised under the protection of nitrogen, and the reaction is carried out;
s2: continuously adding 0.001g of 1-aminopropyl-3-methylimidazole tetrafluoroborate, 2g of triethylamine, stirring for 20 minutes at 40 ℃, adding 0.05g of aminopropyl heptyl-cage-shaped polysilsesquioxane, and stirring for 50 minutes at a constant temperature;
s3: continuously adding 30g of polyetheramine D2000, stirring for 30min at room temperature, slowly adding a mixture of 3g of polyetheramine D230 and 10g of acetone, and continuously stirring for 30min at room temperature;
s4: adding 1g of triethylamine to perform neutralization reaction for 20min; the reaction product was placed in 100g of deionized water, stirred using a high-speed disperser, left to stand for defoaming, and then acetone was distilled off under low pressure by a rotary evaporator to obtain an aqueous polyurea emulsion.
The reaction temperature of S1 is 40 ℃ and the reaction time is 2h.
The stirring speed of the high-speed dispersing machine is 1200rpm, and the time is 20min.
The ethylene glycol acrylate compound is ethylene glycol dimethacrylate.
The amino propyl heptyl-cage polysilsesquioxane has the CAS of 444315-15-5.
The preparation method of the Sulfonated Graphene (SG) comprises the following steps:
s1: under ice water bath, 4g of sodium nitrite, 12g of sulfanilic acid and 85g of hydrochloric acid solution are stirred to obtain aryl diazonium salt solution;
s2: slowly dripping the aryl diazonium salt solution into 15g of graphene oxide aqueous solution, stirring in an ice bath for reaction, and dialyzing and purifying in distilled water to obtain sulfonated graphene oxide dispersoids;
s3: and (3) reacting the sulfonated graphene oxide with 20g of hydrazine hydrate, removing part of oxygen-containing groups, and repeatedly centrifuging and washing with deionized water to obtain the sulfonated graphene.
The mass concentration of the hydrochloric acid solution is 10%.
The reaction time of S2 is 1h.
The reaction temperature of S3 is 70 ℃ and the reaction time is 8h.
Example 2
A fluorine-containing single-component polyurea coating and a preparation method thereof are provided, wherein the operation steps are as follows:
uniformly and ultrasonically dispersing 0.2g of sulfonated graphene in 90g of aqueous polyurea emulsion to obtain the modified aqueous polyurea coating.
The preparation method of the aqueous polyurea comprises the following steps:
s1: 16g of isophorone diisocyanate, 5g of ethylene glycol acrylate compound, 0.1g of dibutyltin dilaurate and 12g of DMF are added into a reaction kettle, and the temperature is raised under the protection of nitrogen, and the reaction is carried out;
s2: continuously adding 0.01g of 1-aminopropyl-3-methylimidazole tetrafluoroborate, 3g of triethylamine, stirring at 45 ℃ for 30 minutes, adding 0.2g of aminopropyl heptyl-cage-shaped polysilsesquioxane, and stirring for 60 minutes under heat preservation;
s3: continuously adding 35g of polyether amine D2000, stirring at room temperature for 35min, slowly adding a mixture of 4g of polyether amine D230 and 12g of acetone, and continuously stirring at room temperature for 35min;
s4: adding 2g of triethylamine to perform neutralization reaction for 25min; the reaction product was placed in 110g of deionized water, stirred using a high-speed disperser, left to stand for defoaming, and then acetone was distilled off under low pressure by a rotary evaporator to obtain an aqueous polyurea emulsion.
The reaction temperature of S1 is 45 ℃ and the reaction time is 3h.
The stirring speed of the high-speed dispersing machine is 1300rpm, and the time is 25min.
The ethylene glycol acrylate compound is tetraethylene glycol dimethacrylate.
The amino propyl heptyl-cage polysilsesquioxane has the CAS of 444315-15-5.
The preparation method of the Sulfonated Graphene (SG) comprises the following steps:
s1: under ice water bath, 5g of sodium nitrite, 13g of sulfanilic acid and 90g of hydrochloric acid solution are stirred to obtain aryl diazonium salt solution;
s2: slowly dripping the aryl diazonium salt solution into 18g of graphene oxide aqueous solution, stirring in an ice bath for reaction, and dialyzing and purifying in distilled water to obtain sulfonated graphene oxide dispersoids;
s3: and (3) reacting the sulfonated graphene oxide with 24g of hydrazine hydrate, removing part of oxygen-containing groups, and repeatedly centrifuging and washing with deionized water to obtain the sulfonated graphene.
The mass concentration of the hydrochloric acid solution is 15%.
The reaction time of S2 is 2h.
The reaction temperature of S3 is 75 ℃ and the reaction time is 9h.
Example 3
A fluorine-containing single-component polyurea coating and a preparation method thereof are provided, wherein the operation steps are as follows:
uniformly and ultrasonically dispersing 0.6g of sulfonated graphene in 90g of aqueous polyurea emulsion to obtain the modified aqueous polyurea coating.
The preparation method of the aqueous polyurea comprises the following steps:
s1: 19g of isophorone diisocyanate, 7g of ethylene glycol acrylate compound, 0.15g of dibutyltin dilaurate and 14g of DMF are added into a reaction kettle, and the temperature is raised under the protection of nitrogen, and the reaction is carried out;
s2: continuously adding 0.02g of 1-aminopropyl-3-methylimidazole tetrafluoroborate, 4g of triethylamine, stirring at 45 ℃ for 50 minutes, adding 0.4g of aminopropyl heptyl-cage-shaped polysilsesquioxane, and stirring for 80 minutes under heat preservation;
s3: continuously adding 40g of polyether amine D2000, stirring at room temperature for 45min, slowly adding a mixture of 4g of polyether amine D230 and 14g of acetone, and continuously stirring at room temperature for 45min;
s4: adding 2g of triethylamine to perform neutralization reaction for 35min; the reaction product was placed in 140g of deionized water, stirred using a high-speed disperser, left to stand for defoaming, and then acetone was distilled off under low pressure by a rotary evaporator to obtain an aqueous polyurea emulsion.
The reaction temperature of S1 is 55 ℃ and the reaction time is 4h.
The stirring speed of the high-speed dispersing machine is 1400rpm, and the time is 35min.
The ethylene glycol acrylate compound is decaethylene glycol dimethacrylate.
The amino propyl heptyl-cage polysilsesquioxane has the CAS of 444315-15-5.
The preparation method of the Sulfonated Graphene (SG) comprises the following steps:
s1: under ice water bath, stirring 6g of sodium nitrite, 14g of sulfanilic acid and 95g of hydrochloric acid solution to obtain aryl diazonium salt solution;
s2: slowly dripping the aryl diazonium salt solution into 22g of graphene oxide aqueous solution, stirring in an ice bath for reaction, and dialyzing and purifying in distilled water to obtain sulfonated graphene oxide dispersoids;
s3: and (3) reacting the sulfonated graphene oxide with 28g of hydrazine hydrate, removing part of oxygen-containing groups, and repeatedly centrifuging and washing with deionized water to obtain the sulfonated graphene.
The mass concentration of the hydrochloric acid solution is 15%.
The reaction time of S2 is 2h.
The reaction temperature of S3 is 85 ℃ and the reaction time is 11h.
Example 4
A fluorine-containing single-component polyurea coating and a preparation method thereof are provided, wherein the operation steps are as follows:
uniformly and ultrasonically dispersing 0.7g of sulfonated graphene in 100g of aqueous polyurea emulsion to obtain the modified aqueous polyurea coating.
The preparation method of the aqueous polyurea comprises the following steps:
s1: 20g of isophorone diisocyanate, 8g of ethylene glycol acrylate compound, 0.2g of dibutyltin dilaurate and 15g of DMF are added into a reaction kettle, and the temperature is raised under the protection of nitrogen, and the reaction is carried out;
s2: continuously adding 0.03g of 1-aminopropyl-3-methylimidazole tetrafluoroborate, 5g of triethylamine, stirring at 60 ℃ for 55 minutes, adding 0.5g of aminopropyl heptyl-cage-shaped polysilsesquioxane, and stirring for 90 minutes under heat preservation;
s3: 45g of polyetheramine D2000 was added and stirred at room temperature for 50min, a mixture of 5g of polyetheramine D230 and 15g of acetone was added slowly and stirred at room temperature for 50min;
s4: adding 3g of triethylamine to perform neutralization reaction for 40min; the reaction product was placed in 150g of deionized water, stirred using a high-speed disperser, left to stand for defoaming, and then acetone was distilled off under low pressure by a rotary evaporator to obtain an aqueous polyurea emulsion.
The reaction temperature of S1 is 60 ℃ and the reaction time is 5h.
The stirring speed of the high-speed dispersing machine is 1500rpm, and the time is 40min.
The ethylene glycol acrylate compound is triethylene glycol dimethacrylate.
The amino propyl heptyl-cage polysilsesquioxane has the CAS of 444315-15-5.
The preparation method of the Sulfonated Graphene (SG) comprises the following steps:
s1: under ice water bath, 7g of sodium nitrite, 15g of sulfanilic acid and 100g of hydrochloric acid solution are stirred to obtain aryl diazonium salt solution;
s2: slowly dripping the aryl diazonium salt solution into 25g of graphene oxide aqueous solution, stirring in an ice bath for reaction, and dialyzing and purifying in distilled water to obtain sulfonated graphene oxide dispersoids;
s3: and (3) reacting the sulfonated graphene oxide with 30g of hydrazine hydrate, removing part of oxygen-containing groups, and repeatedly centrifuging and washing with deionized water to obtain the sulfonated graphene.
The mass concentration of the hydrochloric acid solution is 20%.
The reaction time of S2 is 3h.
The reaction temperature of S3 is 90 ℃ and the reaction time is 12h.
Comparative example 1
A fluorine-containing single-component polyurea coating and a preparation method thereof are provided, wherein the operation steps are as follows:
uniformly and ultrasonically dispersing 0.1g of sulfonated graphene in 85g of aqueous polyurea emulsion to obtain the modified aqueous polyurea coating.
The preparation method of the aqueous polyurea comprises the following steps:
s1: 15g of isophorone diisocyanate, 0.05g of dibutyltin dilaurate and 10g of DMF are added into a reaction kettle, and the temperature is raised under the protection of nitrogen, and the reaction is carried out;
s2: continuously adding 0.001g of 1-aminopropyl-3-methylimidazole tetrafluoroborate, 2g of triethylamine, stirring for 20 minutes at 40 ℃, adding 0.05g of aminopropyl heptyl-cage-shaped polysilsesquioxane, and stirring for 50 minutes at a constant temperature;
s3: continuously adding 30g of polyetheramine D2000, stirring for 30min at room temperature, slowly adding a mixture of 3g of polyetheramine D230 and 10g of acetone, and continuously stirring for 30min at room temperature;
s4: adding 1g of triethylamine to perform neutralization reaction for 20min; the reaction product was placed in 100g of deionized water, stirred using a high-speed disperser, left to stand for defoaming, and then acetone was distilled off under low pressure by a rotary evaporator to obtain an aqueous polyurea emulsion.
The reaction temperature of S1 is 40 ℃ and the reaction time is 2h.
The stirring speed of the high-speed dispersing machine is 1200rpm, and the time is 20min.
The amino propyl heptyl-cage polysilsesquioxane has the CAS of 444315-15-5.
The preparation method of the Sulfonated Graphene (SG) comprises the following steps:
s1: under ice water bath, 4g of sodium nitrite, 12g of sulfanilic acid and 85g of hydrochloric acid solution are stirred to obtain aryl diazonium salt solution;
s2: slowly dripping the aryl diazonium salt solution into 15g of graphene oxide aqueous solution, stirring in an ice bath for reaction, and dialyzing and purifying in distilled water to obtain sulfonated graphene oxide dispersoids;
s3: and (3) reacting the sulfonated graphene oxide with 20g of hydrazine hydrate, removing part of oxygen-containing groups, and repeatedly centrifuging and washing with deionized water to obtain the sulfonated graphene.
The mass concentration of the hydrochloric acid solution is 10%.
The reaction time of S2 is 1h.
The reaction temperature of S3 is 70 ℃ and the reaction time is 8h.
Comparative example 2
A fluorine-containing single-component polyurea coating and a preparation method thereof are provided, wherein the operation steps are as follows:
uniformly and ultrasonically dispersing 0.1g of sulfonated graphene in 85g of aqueous polyurea emulsion to obtain the modified aqueous polyurea coating.
The preparation method of the aqueous polyurea comprises the following steps:
s1: 15g of isophorone diisocyanate, 4g of ethylene glycol acrylate compound, 0.05g of dibutyltin dilaurate and 10g of DMF are added into a reaction kettle, and the temperature is raised under the protection of nitrogen, and the reaction is carried out;
s2: continuously adding 0.001g of 1-aminopropyl-3-methylimidazole tetrafluoroborate, 2g of triethylamine, and stirring at 40 ℃ for 20 minutes;
s3: continuously adding 30g of polyetheramine D2000, stirring for 30min at room temperature, slowly adding a mixture of 3g of polyetheramine D230 and 10g of acetone, and continuously stirring for 30min at room temperature;
s4: adding 1g of triethylamine to perform neutralization reaction for 20min; the reaction product was placed in 100g of deionized water, stirred using a high-speed disperser, left to stand for defoaming, and then acetone was distilled off under low pressure by a rotary evaporator to obtain an aqueous polyurea emulsion.
The reaction temperature of S1 is 40 ℃ and the reaction time is 2h.
The stirring speed of the high-speed dispersing machine is 1200rpm, and the time is 20min.
The ethylene glycol acrylate compound is ethylene glycol dimethacrylate.
The preparation method of the Sulfonated Graphene (SG) comprises the following steps:
s1: under ice water bath, 4g of sodium nitrite, 12g of sulfanilic acid and 85g of hydrochloric acid solution are stirred to obtain aryl diazonium salt solution;
s2: slowly dripping the aryl diazonium salt solution into 15g of graphene oxide aqueous solution, stirring in an ice bath for reaction, and dialyzing and purifying in distilled water to obtain sulfonated graphene oxide dispersoids;
s3: and (3) reacting the sulfonated graphene oxide with 20g of hydrazine hydrate, removing part of oxygen-containing groups, and repeatedly centrifuging and washing with deionized water to obtain the sulfonated graphene.
The mass concentration of the hydrochloric acid solution is 10%.
The reaction time of S2 is 1h.
The reaction temperature of S3 is 70 ℃ and the reaction time is 8h.
Comparative example 3
A fluorine-containing single-component polyurea coating and a preparation method thereof are provided, wherein the operation steps are as follows:
uniformly and ultrasonically dispersing 0.1g of sulfonated graphene in 85g of aqueous polyurea emulsion to obtain the modified aqueous polyurea coating.
The preparation method of the aqueous polyurea comprises the following steps:
s1: 15g of isophorone diisocyanate, 4g of ethylene glycol acrylate compound and 10g of DMF are added into a reaction kettle, and the temperature is raised under the protection of nitrogen, and the reaction is carried out;
s2: continuously adding 0.001g of 1-aminopropyl-3-methylimidazole tetrafluoroborate, 2g of triethylamine, stirring for 20 minutes at 40 ℃, adding 0.05g of aminopropyl heptyl-cage-shaped polysilsesquioxane, and stirring for 50 minutes at a constant temperature;
s3: continuously adding 30g of polyetheramine D2000, stirring for 30min at room temperature, slowly adding a mixture of 3g of polyetheramine D230 and 10g of acetone, and continuously stirring for 30min at room temperature;
s4: adding 1g of triethylamine to perform neutralization reaction for 20min; the reaction product was placed in 100g of deionized water, stirred using a high-speed disperser, left to stand for defoaming, and then acetone was distilled off under low pressure by a rotary evaporator to obtain an aqueous polyurea emulsion.
The reaction temperature of S1 is 40 ℃ and the reaction time is 2h.
The stirring speed of the high-speed dispersing machine is 1200rpm, and the time is 20min.
The ethylene glycol acrylate compound is ethylene glycol dimethacrylate.
The amino propyl heptyl-cage polysilsesquioxane has the CAS of 444315-15-5.
The preparation method of the Sulfonated Graphene (SG) comprises the following steps:
s1: under ice water bath, 4g of sodium nitrite, 12g of sulfanilic acid and 85g of hydrochloric acid solution are stirred to obtain aryl diazonium salt solution;
s2: slowly dripping the aryl diazonium salt solution into 15g of graphene oxide aqueous solution, stirring in an ice bath for reaction, and dialyzing and purifying in distilled water to obtain sulfonated graphene oxide dispersoids;
s3: and (3) reacting the sulfonated graphene oxide with 20g of hydrazine hydrate, removing part of oxygen-containing groups, and repeatedly centrifuging and washing with deionized water to obtain the sulfonated graphene.
The mass concentration of the hydrochloric acid solution is 10%.
The reaction time of S2 is 1h.
The reaction temperature of S3 is 70 ℃ and the reaction time is 8h.
Example evaluation:
the coatings prepared in the above examples and comparative examples were tested by:
1. water absorption test
The WPUA, SG/WPUA and WPUA film materials respectively containing RP, UP, KUP filler are placed in deionized water to be soaked for 24 hours, and the weight of the WPUA film materials before and after soaking is measured.
2. Hardness test
WPUA coatings coated with WPUA, SG/WPUA and WPUA containing RP, UP, KUP filler respectively were tested using a hand propelled pencil durometer, the dry coating was scratched with a Chinese pencil at a constant speed of 1mm/s according to ASTM D3363-2005, pencil scratch hardness test was done on the pencil leads from soft to hard (5B-HB-5H), and the hardness of the coating was marked with the hardest pencil lead.
WPUA films containing RP, UP, KUP filler were tested using a Shore A hardness tester at 2mm film thickness and averaged over 5 positions.
3. Adhesion test
The adhesion of WPUA coatings containing RP, UP, KUP filler was evaluated using a pullout adhesion tester. The testing method comprises the steps of firstly bonding the round spindle with the surface of the coating to be tested through an adhesive, curing for 24 hours at normal temperature, and then testing according to the standard of ASTMD 4541. At least 5 pullout tests were repeated on each set of panels and the recorded data averaged.
4. Tensile testing
The elongation at break and tensile strength of WPUA film materials each containing RP, UP, KUP filler were tested using a tensile tester. The tensile test sample bars were used with a dumbbell type strain induction calculated as gauge elongation (gauge distance 25 mm) at a tensile rate of 100mm/min.
The test results of the specific embodiments are shown in the following table:
| water absorption/% | Hardness of pencil | adhesion/MPa | Tensile Strength/MPa | |
| Example 1 | 3.2 | 2H | 4.1 | 10.87 |
| Example 2 | 3.1 | 3H | 4.2 | 11.19 |
| Example 3 | 2.7 | 4H | 4.3 | 11.53 |
| Example 4 | 2.9 | 3H | 4.2 | 11.42 |
| Comparative example 1 | 11.4 | 4B | 2.4 | 6.23 |
| Comparative example 2 | 7.2 | 3B | 2.9 | 7.86 |
| Comparative example 3 | 6.6 | 2B | 3.4 | 8.11 |
The foregoing description is only exemplary embodiments of the present invention and is not intended to limit the scope of the invention, but rather, the equivalent structural changes made by the present invention in the light of the inventive concept, or the direct/indirect application in other related technical fields are included in the scope of the present invention.
Claims (10)
1. A fluorine-containing single-component polyurea coating and a preparation method thereof are provided, wherein the operation steps are as follows:
and uniformly ultrasonically dispersing 0.1-0.7 part of sulfonated graphene in 85-100 parts of aqueous polyurea emulsion according to parts by mass to obtain the modified aqueous polyurea coating.
2. The fluorine-containing single-component polyurea coating and the preparation method thereof according to claim 1, wherein the fluorine-containing single-component polyurea coating is characterized in that: the preparation method of the aqueous polyurea comprises the following steps:
s1: adding 15-20 parts by mass of isophorone diisocyanate, 4-8 parts by mass of ethylene glycol acrylate compound, 0.05-0.2 part by mass of dibutyltin dilaurate and 10-15 parts by mass of organic solvent into a reaction kettle, heating under the protection of nitrogen, and reacting;
s2: continuously adding 0.001-0.03 part of 1-aminopropyl-3-methylimidazole tetrafluoroborate, 2-5 parts of triethylamine, stirring for 20-55 minutes at 40-60 ℃, adding 0.05-0.5 part of aminopropyl heptyl-cage polysilsesquioxane, and stirring for 50-90 minutes at a constant temperature;
s3: continuously adding 30-45 parts of polyether amine D2000, stirring for 30-50min at room temperature, slowly adding a mixture of 3-5 parts of polyether amine D230 and 10-15 parts of acetone, and continuously stirring for 30-50min at room temperature;
s4: adding 1-3 parts of triethylamine for neutralization reaction for 20-40min; and (3) placing the reaction product into 100-150 parts of deionized water, stirring by using a high-speed dispersing machine, standing for defoaming, and removing acetone by low-pressure distillation of a rotary evaporator to obtain the aqueous polyurea emulsion.
3. The fluorine-containing single-component polyurea coating and the preparation method thereof according to claim 2, wherein the fluorine-containing single-component polyurea coating is characterized in that: the reaction temperature of the S1 is 40-60 ℃ and the reaction time is 2-5h.
4. The fluorine-containing single-component polyurea coating and the preparation method thereof according to claim 2, wherein the fluorine-containing single-component polyurea coating is characterized in that: the organic solvent is DMF.
5. The fluorine-containing single-component polyurea coating and the preparation method thereof according to claim 2, wherein the fluorine-containing single-component polyurea coating is characterized in that: the stirring speed of the high-speed dispersing machine is 1200-1500rpm, and the stirring time is 20-40min.
6. The fluorine-containing single-component polyurea coating and the preparation method thereof according to claim 2, wherein the fluorine-containing single-component polyurea coating is characterized in that: the ethylene glycol acrylate compound is selected from ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, decaethylene glycol dimethacrylate and triethylene glycol dimethacrylate.
7. The fluorine-containing single-component polyurea coating and the preparation method thereof according to claim 1, wherein the fluorine-containing single-component polyurea coating is characterized in that: the preparation method of the Sulfonated Graphene (SG) comprises the following steps:
s1: according to the mass parts, under ice water bath, 4-7 parts of sodium nitrite, 12-15 parts of sulfanilic acid and 85-100 parts of hydrochloric acid solution are stirred to obtain aryl diazonium salt solution;
s2: slowly dripping the aryl diazonium salt solution into 15-25 parts of graphene oxide aqueous solution, stirring in an ice bath for reaction, and then dialyzing and purifying in distilled water to obtain sulfonated graphene oxide dispersoids;
s3: and (3) reacting the sulfonated graphene oxide with 20-30 parts of hydrazine hydrate, removing part of oxygen-containing groups, and repeatedly centrifuging and washing with deionized water to obtain the sulfonated graphene.
8. The fluorine-containing single-component polyurea coating and the preparation method thereof according to claim 7, wherein: the mass concentration of the hydrochloric acid solution of S2 is 10-20%.
9. The fluorine-containing single-component polyurea coating and the preparation method thereof according to claim 7, wherein: the reaction time of the S2 is 1-3h.
10. The fluorine-containing single-component polyurea coating and the preparation method thereof according to claim 7, wherein: the reaction temperature of the S3 is 70-90 ℃ and the reaction time is 8-12h.
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