CN116640499B - Polyurea waterproof composition and preparation method thereof - Google Patents

Polyurea waterproof composition and preparation method thereof Download PDF

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CN116640499B
CN116640499B CN202310686815.9A CN202310686815A CN116640499B CN 116640499 B CN116640499 B CN 116640499B CN 202310686815 A CN202310686815 A CN 202310686815A CN 116640499 B CN116640499 B CN 116640499B
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graphene oxide
carbon nano
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CN116640499A (en
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李洪剑
李强
王晓刚
李春花
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Dongying Hairuibao New Material Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/02—Polyureas
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C09D7/61—Additives non-macromolecular inorganic
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract

The invention provides a polyurea waterproof composition and a preparation method thereof, and belongs to the technical field of waterproof compositions. Coating a layer of wrinkled graphene oxide on the surface of the carbon nano tube subjected to acid treatment, and depositing Al on the surface 2 O 3 /SiO 2 And (3) reducing graphene oxide, modifying the surface by polydopamine to obtain a modifier, uniformly mixing the modifier with a flame retardant prepared from resorcinol bis (diphenyl phosphate) and triphenyl phosphate to obtain a modified material, mixing the modified material with polyaspartic acid ester F524 and polyaspartic acid ester D2925 to obtain a component A, mixing an isocyanate composition and polyether polyol, heating for reaction to obtain a component B, uniformly mixing the dispersed component A and component B, and spraying a coating film to obtain the polyurea waterproof composition. The polyurea waterproof composition prepared by the invention has good mechanical properties, is not easy to crack, is ageing-resistant, has long service life, excellent high temperature resistance, low temperature flexibility and good durability, and has wide application prospect.

Description

Polyurea waterproof composition and preparation method thereof
Technical Field
The invention relates to the technical field of waterproof compositions, in particular to a polyurea waterproof composition and a preparation method thereof.
Background
With the increase of urban construction pace, the utilization rate of underground space is also increased. Since underground buildings are often in a vibration interference environment, the waterproof coating film is broken and peeled off, and thus the waterproof effect is lost. In addition, since the underground construction is a reinforced concrete structure buried under the ground, and is subjected to the pressure of the groundwater and the erosion of corrosive media, mold and the like in the soil and the groundwater for a long period of time, the waterproof coating material used in the underground construction is required to have excellent weather resistance.
The double-component polyurea waterproof coating has the advantages of high tensile strength, high elongation at break, acid and alkali resistance, salt resistance and the like, and becomes the first-choice coating for protecting the surface of an underground building. However, the construction process is complex, the construction performance of the construction process has a great relation with temperature and humidity, and the construction process is not easy to lift needle eyes, lift drums and separate. In addition, the cost of the two-component polyurea waterproof coating is more than twice that of the common waterproof coating, so that the two-component polyurea waterproof coating is difficult to popularize in a large area.
The single-component semi-polyurea waterproof coating has similar performance to the double-component polyurea waterproof coating, is firmly bonded with a cement base layer, has lower cost and wider adaptability. However, the existing semi-polyurea waterproof coating still has the problems of pinholes and foaming of a coating film caused by the influence of construction environment, and the phenomena of bulging, water channeling and the like of the coating film at the later stage are easy to occur under the condition of soaking, so that the use requirements of underground high-humidity or water-soaking environments cannot be met.
In addition, in the prior art, although the waterproof compositions have greatly improved waterproof effect, the flame retardant effect is not ideal, the mechanical property is poor, and the use safety of the waterproof compositions is affected; the durability is poor, and the service life is greatly reduced. Therefore, there is a need for technical improvements that result in better overall performance.
Disclosure of Invention
The invention aims to provide a polyurea waterproof composition and a preparation method thereof, wherein the composition is continuous and compact, has no seam, has strong bonding force with a base layer and has high waterproof reliability; is not easy to crack; aging resistance and long service life; compared with the traditional waterproof material, the polyurea has better waterproof performance, excellent high temperature resistance, low temperature flexibility, long-time inherent property maintenance and good durability. The spray polyurea waterproof composition has the advantages of high tensile strength, high elongation at break, high tearing strength, high adhesive force and the like, has excellent waterproof performance, also shows good tolerance in corrosive media such as seawater acid-base salt and the like, and has good adhesive force on substrates such as steel-aluminum concrete and the like.
The technical scheme of the invention is realized as follows:
The invention provides a preparation method of a polyurea waterproof composition, which comprises the steps of coating a layer of wrinkled graphene oxide on the surface of a carbon nano tube subjected to acid treatment, and depositing Al on the surface 2 O 3 /SiO 2 The layer, the graphene oxide is reduced, then the surface is modified by polydopamine to obtain a modifier, the modifier is uniformly mixed with a flame retardant prepared from resorcinol bis (diphenyl phosphate) and triphenyl phosphate to obtain a modified material, and the modified material is mixed with polyaspartic acid ester F524 and polyaspartic acid esterAnd (3) mixing the aspartic acid ester D2925 to obtain a component A, mixing the isocyanate composition and the polyether polyol, heating for reaction to obtain a component B, uniformly mixing the dispersed component A and component B, and spraying a coating film to obtain the polyurea waterproof composition.
As a further improvement of the invention, the method comprises the following steps:
s1, pretreatment of carbon nanotubes: adding the carbon nano tube into dilute nitric acid, heating, stirring, reacting, centrifuging, washing, and drying to obtain a pretreated carbon nano tube;
s2, wrapping and fixing the pleated graphene oxide: dissolving graphene oxide in water, adding the pretreated carbon nanotubes prepared in the step S1, stirring and dispersing uniformly, and spray drying to obtain the wrinkled graphene oxide coated carbon nanotubes;
S3.Al 2 O 3 /SiO 2 is deposited by: dissolving alkyl orthosilicate and aluminum isopropoxide in ethanol, adding the coated carbon nanotube of the pleated graphene oxide prepared in the step S2, dropwise adding ammonia water solution, stirring for reaction, centrifuging, washing and calcining to obtain Al 2 O 3 /SiO 2 Depositing the wrinkled graphene oxide coated carbon nano tube;
s4, reduction of graphene oxide: al prepared in the step S3 2 O 3 /SiO 2 Adding the deposited wrinkled graphene oxide coated carbon nano tube into water, adding hydrazine hydrate and ammonia water, heating, stirring for reaction, centrifuging, washing and drying to obtain Al 2 O 3 /SiO 2 Depositing the wrinkled graphene-coated carbon nano tube;
s5, modifying polydopamine: al prepared in the step S4 2 O 3 /SiO 2 Adding the deposited wrinkled graphene coated carbon nano tube into water, adding dopamine hydrochloride and a catalyst, heating, stirring, reacting, centrifuging, washing and drying to obtain a modifier;
s6, combination of flame retardants: resorcinol bis (diphenyl phosphate) and triphenyl phosphate are uniformly mixed to prepare a flame retardant;
s7, preparing a modified material: uniformly mixing the modifier prepared in the step S5 and the flame retardant prepared in the step S6 to prepare a modified material;
s8, preparation of a component A: uniformly mixing the polyaspartic acid ester F524, the polyaspartic acid ester D2925 and the modified material prepared in the step S7 to obtain a component A;
s9. Preparation of the component B: mixing the isocyanate composition and polyether polyol, and heating for reaction to obtain a component B;
s10, preparing a polyurea waterproof composition: uniformly mixing the dispersed component A and component B, and spraying a coating film to obtain the polyurea waterproof composition.
As a further improvement of the invention, the concentration of the dilute nitric acid in the step S1 is 1-2mol/L, the temperature of the heating and stirring reaction is 40-50 ℃ and the time is 20-30min; in the step S2, the mass ratio of the graphene oxide to the pretreated carbon nano tube is 10-12:7-10, the spray drying condition is that the air inlet temperature is 85-100 ℃, the air outlet temperature is 50-70 ℃, and the evaporation water amount is 1700-2000mL/h.
As a further improvement of the invention, in the step S3, the mass ratio of the alkyl orthosilicate, the aluminum isopropoxide and the wrinkled graphene oxide coated carbon nano tube to the ammonia water solution is 5-7:7-10:15-20:20-30, the concentration of the ammonia water is 12-15wt%, the temperature of the stirring reaction is 40-45 ℃, the time is 2-3h, the temperature of the calcination is 300-500 ℃, and the time is 2-3h; al described in step S4 2 O 3 /SiO 2 The mass ratio of the deposited wrinkled graphene oxide coated carbon nano tube to the hydrazine hydrate to the ammonia water is 10-12:3-5:2-3, the concentration of the ammonia water is 20-22wt%, the temperature of the heating and stirring reaction is 40-45 ℃, and the time is 2-3h.
As a further improvement of the present invention, the Al is as described in step S5 2 O 3 /SiO 2 Depositing a pleated graphene-coated carbon nano tube, wherein the mass ratio of the dopamine hydrochloride to the catalyst is 10-12:15-17:1-2, the catalyst is Tris-HCl solution with pH value of 8.5-9, the temperature of the heating and stirring reaction is 40-50 ℃, and the time is 2-4 hours; the mass ratio of resorcinol bis (diphenyl phosphate) to triphenyl phosphate in the step S6 is 5-7:2-3.
As a further improvement of the invention, the mass ratio of the modifier to the flame retardant in the step S7 is 10-12:3-5; the mass ratio of the polyaspartic acid ester F524 to the polyaspartic acid ester D2925 to the modified material in the step S8 is 20-30:70-80:12-15.
As a further improvement of the present invention, the mass ratio of the isocyanate composition and the polyether polyol in the step S9 is that the polyether polyol is PPG1000, the isocyanate composition is at least one selected from diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, tetramethyl-m-xylylene diisocyanate, dicyclohexylmethane-4, 4 '-diisocyanate and toluene diisocyanate, preferably is a mixture of dicyclohexylmethane-4, 4' -diisocyanate and hexamethylene diisocyanate, the mass ratio is 7-10:2-3, the heating reaction temperature is 60-70 ℃, and the reaction can be completed after the system-NCO content is 10-12%; the addition amount of the component A and the component B in the step S10 is that the equivalent ratio of-NCO to-NH is 1:1, and the thickness of the spray coating film is 0.5-0.7mm.
As a further improvement of the invention, the method specifically comprises the following steps:
S1, pretreatment of carbon nanotubes: adding 10 parts by weight of carbon nano tubes into 100 parts by weight of 1-2mol/L dilute nitric acid, heating to 40-50 ℃, stirring and reacting for 20-30min, centrifuging, washing and drying to obtain pretreated carbon nano tubes;
s2, wrapping and fixing the pleated graphene oxide: dissolving 10-12 parts by weight of graphene oxide in 100 parts by weight of water, adding 7-10 parts by weight of the pretreated carbon nanotube prepared in the step S1, stirring and dispersing uniformly, and spray-drying to obtain the wrinkled graphene oxide coated carbon nanotube;
the spray drying condition is that the air inlet temperature is 85-100 ℃, the air outlet temperature is 50-70 ℃ and the evaporation water quantity is 1700-2000mL/h;
S3.Al 2 O 3 /SiO 2 is deposited by: dissolving 5-7 parts by weight of alkyl orthosilicate and 7-10 parts by weight of aluminum isopropoxide in 70 parts by weight of ethanol, adding 15-20 parts by weight of the coated carbon nanotube of the pleated graphene oxide prepared in the step S2, dropwise adding 20-30 parts by weight of 12-15wt% ammonia water solution, and stirring to 40-45 DEG CReacting for 2-3h, centrifuging, washing, calcining at 300-500 ℃ for 2-3h to obtain Al 2 O 3 /SiO 2 Depositing the wrinkled graphene oxide coated carbon nano tube;
s4, reduction of graphene oxide: 10-12 parts by weight of Al prepared in the step S3 2 O 3 /SiO 2 Adding the deposited pleated graphene oxide coated carbon nano tube into 100 parts by weight of water, adding 3-5 parts by weight of hydrazine hydrate and 2-3 parts by weight of 20-22wt% ammonia water, heating to 40-45 ℃, stirring and reacting for 2-3 hours, centrifuging, washing and drying to obtain Al 2 O 3 /SiO 2 Depositing the wrinkled graphene-coated carbon nano tube;
s5, modifying polydopamine: 10 to 12 parts by weight of Al prepared in the step S4 2 O 3 /SiO 2 Adding the deposited pleated graphene coated carbon nano tube into 100 parts by weight of water, adding 15-17 parts by weight of dopamine hydrochloride and 1-2 parts by weight of catalyst, heating to 40-50 ℃, stirring and reacting for 2-4 hours, centrifuging, washing and drying to obtain a modifier;
the catalyst is Tris-HCl solution with pH=8.5-9;
s6, combination of flame retardants: uniformly mixing 5-7 parts by weight of resorcinol bis (diphenyl phosphate) and 2-3 parts by weight of triphenyl phosphate to prepare a flame retardant;
s7, preparing a modified material: uniformly mixing 10-12 parts by weight of the modifier prepared in the step S5 and 3-5 parts by weight of the flame retardant prepared in the step S6 to prepare a modified material;
s8, preparation of a component A: uniformly mixing 20-30 parts by weight of polyaspartic acid ester F524, 70-80 parts by weight of polyaspartic acid ester D2925 and 12-15 parts by weight of the modified material prepared in the step S7 to obtain a component A;
s9. Preparation of the component B: mixing the isocyanate composition and polyether polyol PPG1000, heating to 60-70 ℃, and reacting until the system-NCO content is 10-12%, and cooling to finish the reaction to obtain a component B;
the isocyanate composition is a mixture of dicyclohexylmethane-4, 4' -diisocyanate and hexamethylene diisocyanate, and the mass ratio is 7-10:2-3;
S10, preparing a polyurea waterproof composition: and uniformly mixing the dispersed A component and B component, wherein the addition amount of the A component and the B component is that the equivalent ratio of-NCO to-NH is 1:1, and spraying a coating film to obtain the polyurea waterproof composition with the thickness of 0.5-0.7 mm.
The invention further provides the polyurea waterproof composition prepared by the preparation method.
The invention further provides application of the polyurea waterproof composition in building material waterproofing.
The invention has the following beneficial effects:
the preparation method comprises the steps of firstly treating the surface of a carbon nano tube by dilute nitric acid, performing functionalization to form a large number of hydroxyl groups, facilitating hydrogen bond formation with the hydroxyl groups on the surface of graphene oxide, enabling the graphene oxide to be stably wrapped on the surface of the carbon nano tube, simultaneously, adopting a spray drying method, enabling the graphene oxide to pass through a nozzle under the action of air pressure and be smashed into small liquid drops, enabling the small liquid drops and heated nitrogen to enter a cyclone separator, enabling a solvent to quickly evaporate, enabling the volume of the liquid drops to shrink, performing cyclone separation to obtain the wrinkled graphene oxide wrapped carbon nano tube, enabling the surface to pass through sol-gel reaction, and then calcining under the hydrolysis action of aluminum isopropoxide and alkyl orthosilicate to form a layer of Al on the surface 2 O 3 /SiO 2 The layer is then subjected to hydrazine hydrate reduction and oxidation of graphene to obtain Al 2 O 3 /SiO 2 Depositing the wrinkled graphene-coated carbon nano tube; and further depositing a polydopamine layer on the surface to obtain the modifier.
The surface of the modifier obtained by the invention is provided with a polydopamine layer which contains abundant hydroxyl, amino, carboxyl and other active groups and can well form hydrogen bonds with a matrix polyurea material, so that the modifier is connected into a polyurea resin system, and graphene, carbon nano tubes and SiO are utilized 2 The high strength and modulus of (a) improves the tear and tensile strength of the material when subjected to high-speed impact. At the same time Al 2 O 3 The incorporation of the poly-N element can also obviously improve the flame retardant, heat preservation and high temperature resistance of the material, and the flame retardant property of the material is further improved. In addition, the fold structure of the modifier can effectively reduce the stacking of the modifier in the polymer matrix and avoid the modifierAgglomeration caused by ordered stacking among the tiny particles is uniformly dispersed, so that the excellent performance of the modifier is fully exerted, and the mechanical property, antistatic property, flame retardant property, heat preservation property, high temperature resistance and barrier property of the polyurea resin are obviously improved. Meanwhile, the structure of the folds can increase the blocking and shielding effects of the coating, and the coating is similar to fish scales, blocks the invasion of media layer by layer and serves as aggregate to increase the wear resistance of the coating.
The resorcinol bis (diphenyl phosphate) and triphenyl phosphate as flame retardants have good flame retardant effect on the polyurea waterproof composition, and meanwhile, the mechanical property of the composition is not affected, and the flame retardant has good synergistic effect.
The component A of the invention comprises polyaspartic acid ester D2925 and polyaspartic acid ester F524, wherein the polyaspartic acid ester D2925 is prepared by pre-reacting alicyclic isocyanate and polyaspartic acid ester, and has the characteristics of large molecular weight, small functionality, small reaction activity, excellent mechanical property and the like, and the polyaspartic acid ester F524 has the advantages of low cost and the like. The pot life, the surface drying time and the actual drying time of the polyaspartic acid ester polyurea waterproof coating prepared by the prepared component A are prolonged; meanwhile, with the introduction of alicyclic isocyanate, the hardness and flexibility of the system are further increased. In the invention, the dosage of the polyaspartic acid ester D2925 is higher than that of the polyaspartic acid ester F524 in a large proportion, and the tensile strength and the tearing strength of the prepared polyurea composition are increased.
In the component B, the isocyanate such as diphenylmethane diisocyanate, xylylene diisocyanate, tetramethyl-m-xylylene diisocyanate, toluene diisocyanate and the like is provided with phenyl and is an aromatic compound, the prepared polyurea waterproof composition has high hardness, is relatively brittle and has low tensile strength, and the dicyclohexylmethane-4, 4' -diisocyanate and the hexamethylene diisocyanate added in the invention are alicyclic and aliphatic isocyanates, so that the prepared polyurea waterproof composition has high hardness, good flexibility and obviously improved tensile strength.
The polyurea waterproof composition prepared by the invention is continuous and compact, has no seam, and has strong adhesion with a base layer and high waterproof reliability; is not easy to crack; aging resistance and long service life; compared with the traditional waterproof material, the polyurea has better waterproof performance, excellent high temperature resistance, low temperature flexibility, long-time inherent property maintenance and good durability. The spray polyurea waterproof composition has the advantages of high tensile strength, high elongation at break, high tearing strength, high adhesive force and the like, has excellent waterproof performance, also shows good tolerance in corrosive media such as seawater acid-base salt and the like, and has good adhesive force on substrates such as steel-aluminum concrete and the like.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Carbon nanotubes, multiwall carbon nanotubes, XFM04, diameter 5-15nm, length 0.5-2 microns, purity >95%, purchased from Jiangsu Xianfeng nanomaterial technologies Co.
Graphene oxide, industrial grade graphene oxide powder, XFSG01, with a thickness of <5nm, purchased from Jiangsu xianfeng nanomaterial technologies, inc.
Polyaspartic acid ester F524, with a solids content of >95%, was purchased from the company Limited of the Style chemical industry.
Polyaspartic acid ester D2925, with a solid content of >60%, was purchased from Zhuhai Fei chemical Co.
Example 1
The embodiment provides a preparation method of a polyurea waterproof composition, which specifically comprises the following steps:
s1, pretreatment of carbon nanotubes: adding 10 parts by weight of carbon nano tubes into 100 parts by weight of 1mol/L dilute nitric acid, heating to 40 ℃, stirring and reacting for 20min, centrifuging for 15min 5000r/min, washing with deionized water, and drying for 2h at 105 ℃ to obtain pretreated carbon nano tubes;
s2, wrapping and fixing the pleated graphene oxide: dissolving 10 parts by weight of graphene oxide in 100 parts by weight of water, adding 7 parts by weight of the pretreated carbon nanotubes prepared in the step S1, stirring and dispersing for 20min, and spray-drying to obtain the wrinkled graphene oxide-coated carbon nanotubes;
the spray drying condition is that the air inlet temperature is 85 ℃, the air outlet temperature is 50 ℃ and the evaporation water quantity is 1700mL/h;
S3.Al 2 O 3 /SiO 2 is deposited by: dissolving 5 parts by weight of methyl orthosilicate and 7 parts by weight of aluminum isopropoxide in 70 parts by weight of ethanol, adding 15 parts by weight of the carbon nanotube coated with the pleated graphene oxide prepared in the step S2, dropwise adding 20 parts by weight of 12wt% ammonia water solution, stirring to 40 ℃, reacting for 2h, centrifuging for 15min at 5000r/min, washing with deionized water, calcining for 2h at 300 ℃ to prepare Al 2 O 3 /SiO 2 Depositing the wrinkled graphene oxide coated carbon nano tube;
s4, reduction of graphene oxide: 10 parts by weight of Al obtained in step S3 2 O 3 /SiO 2 Adding the deposited pleated graphene oxide coated carbon nano tube into 100 parts by weight of water, adding 3 parts by weight of hydrazine hydrate and 2 parts by weight of 20wt% ammonia water, heating to 40 ℃, stirring and reacting for 2 hours, centrifuging for 15 minutes at 5000r/min, washing with deionized water, and drying at 105 ℃ for 2 hours to obtain Al 2 O 3 /SiO 2 Depositing the wrinkled graphene-coated carbon nano tube;
s5, modifying polydopamine: 10 parts by weight of Al obtained in step S4 2 O 3 /SiO 2 Adding the deposited pleated graphene coated carbon nano tube into 100 parts by weight of water, adding 15 parts by weight of dopamine hydrochloride and 1 part by weight of catalyst, heating to 40 ℃, stirring and reacting for 2 hours, centrifuging for 15 minutes at 5000r/min, washing with deionized water, and drying for 2 hours at 105 ℃ to obtain a modifier;
the catalyst is Tris-HCl solution with pH=8.5;
s6, combination of flame retardants: uniformly mixing 5 parts by weight of resorcinol bis (diphenyl phosphate) and 2 parts by weight of triphenyl phosphate to prepare a flame retardant;
s7, preparing a modified material: stirring and mixing 10 parts by weight of the modifier prepared in the step S5 and 3 parts by weight of the flame retardant prepared in the step S6 for 10 minutes to prepare a modified material;
s8, preparation of a component A: mixing 20 parts by weight of polyaspartic acid ester F524, 70 parts by weight of polyaspartic acid ester D2925 and 12 parts by weight of the modified material prepared in the step S7 for 20 minutes to obtain a component A;
S9. Preparation of the component B: mixing the isocyanate composition and polyether polyol PPG1000, heating to 60 ℃, and cooling to finish the reaction until the-NCO content of the system is 10%, thereby obtaining a component B;
the isocyanate composition is a mixture of dicyclohexylmethane-4, 4' -diisocyanate and hexamethylene diisocyanate, and the mass ratio is 7:2;
s10, preparing a polyurea waterproof composition: and (3) uniformly mixing the dispersed A component and B component, wherein the addition amount of the A component and the B component is that the equivalent ratio of-NCO to-NH is 1:1, spraying a coating film, and the spraying pressure is 10MPa, so as to obtain the polyurea waterproof composition with the thickness of 0.6 mm.
Example 2
The embodiment provides a preparation method of a polyurea waterproof composition, which specifically comprises the following steps:
s1, pretreatment of carbon nanotubes: adding 10 parts by weight of carbon nano tubes into 100 parts by weight of 2mol/L dilute nitric acid, heating to 50 ℃, stirring and reacting for 30min, centrifuging for 15min at 5000r/min, washing with deionized water, and drying for 2h at 105 ℃ to obtain pretreated carbon nano tubes;
s2, wrapping and fixing the pleated graphene oxide: dissolving 12 parts by weight of graphene oxide in 100 parts by weight of water, adding 10 parts by weight of the pretreated carbon nanotubes prepared in the step S1, stirring and dispersing for 20min, and spray-drying to obtain the wrinkled graphene oxide-coated carbon nanotubes;
The spray drying condition is that the air inlet temperature is 100 ℃, the air outlet temperature is 70 ℃ and the evaporation water quantity is 2000mL/h;
S3.Al 2 O 3 /SiO 2 is deposited by: dissolving 7 parts by weight of tetraethoxysilane and 10 parts by weight of aluminum isopropoxide in 70 parts by weight of ethanol, adding 20 parts by weight of the coated carbon nanotube of the pleated graphene oxide prepared in the step S2, dropwise adding 30 parts by weight of 15wt% ammonia water solution, stirring to 45 ℃, reacting for 3h, and separating 5000r/minWashing with deionized water for 15min, and calcining at 500deg.C for 3 hr to obtain Al 2 O 3 /SiO 2 Depositing the wrinkled graphene oxide coated carbon nano tube;
s4, reduction of graphene oxide: 12 parts by weight of Al prepared in step S3 2 O 3 /SiO 2 Adding the deposited pleated graphene oxide coated carbon nano tube into 100 parts by weight of water, adding 5 parts by weight of hydrazine hydrate and 3 parts by weight of 22wt% ammonia water, heating to 45 ℃, stirring and reacting for 3 hours, centrifuging for 15 minutes at 5000r/min, washing with deionized water, and drying for 2 hours at 105 ℃ to obtain Al 2 O 3 /SiO 2 Depositing the wrinkled graphene-coated carbon nano tube;
s5, modifying polydopamine: 12 parts by weight of Al prepared in step S4 2 O 3 /SiO 2 Adding 100 parts by weight of water into the deposited pleated graphene coated carbon nano tube, adding 17 parts by weight of dopamine hydrochloride and 2 parts by weight of catalyst, heating to 50 ℃, stirring and reacting for 4 hours, centrifuging for 15 minutes at 5000r/min, washing with deionized water, and drying at 105 ℃ for 2 hours to obtain a modifier;
The catalyst is Tris-HCl solution with pH=9;
s6, combination of flame retardants: uniformly mixing 7 parts by weight of resorcinol bis (diphenyl phosphate) and 3 parts by weight of triphenyl phosphate to prepare a flame retardant;
s7, preparing a modified material: stirring and mixing 12 parts by weight of the modifier prepared in the step S5 and 5 parts by weight of the flame retardant prepared in the step S6 for 10 minutes to prepare a modified material;
s8, preparation of a component A: mixing 30 parts by weight of polyaspartic acid ester F524, 80 parts by weight of polyaspartic acid ester D2925 and 15 parts by weight of the modified material prepared in the step S7 for 20 minutes to obtain a component A;
s9. Preparation of the component B: mixing the isocyanate composition and polyether polyol PPG1000, heating to 70 ℃, and reacting until the system-NCO content is 12%, so as to cool down and finish the reaction, thereby obtaining a component B;
the isocyanate composition is a mixture of dicyclohexylmethane-4, 4' -diisocyanate and hexamethylene diisocyanate, and the mass ratio is 10:3;
s10, preparing a polyurea waterproof composition: and (3) uniformly mixing the dispersed A component and B component, wherein the addition amount of the A component and the B component is that the equivalent ratio of-NCO to-NH is 1:1, spraying a coating film, and the spraying pressure is 10MPa, so as to obtain the polyurea waterproof composition with the thickness of 0.6 mm.
Example 3
The embodiment provides a preparation method of a polyurea waterproof composition, which specifically comprises the following steps:
s1, pretreatment of carbon nanotubes: adding 10 parts by weight of carbon nano tubes into 100 parts by weight of 1.5mol/L dilute nitric acid, heating to 45 ℃, stirring and reacting for 25min, centrifuging for 15min at 5000r/min, washing with deionized water, and drying for 2h at 105 ℃ to obtain pretreated carbon nano tubes;
s2, wrapping and fixing the pleated graphene oxide: dissolving 11 parts by weight of graphene oxide in 100 parts by weight of water, adding 8.5 parts by weight of the pretreated carbon nanotubes prepared in the step S1, stirring and dispersing for 20min, and spray-drying to obtain the wrinkled graphene oxide coated carbon nanotubes;
the spray drying condition is that the air inlet temperature is 95 ℃, the air outlet temperature is 60 ℃, and the evaporation water quantity is 1850mL/h;
S3.Al 2 O 3 /SiO 2 is deposited by: dissolving 6 parts by weight of tetraethoxysilane and 8.5 parts by weight of aluminum isopropoxide in 70 parts by weight of ethanol, adding 17 parts by weight of the coated carbon nanotube of the pleated graphene oxide prepared in the step S2, dropwise adding 25 parts by weight of 13.5wt% ammonia water solution, stirring to 42 ℃, reacting for 2.5 hours, centrifuging for 15 minutes 5000r/min, washing with deionized water, calcining for 2.5 hours at 400 ℃ to prepare Al 2 O 3 /SiO 2 Depositing the wrinkled graphene oxide coated carbon nano tube;
S4, reduction of graphene oxide: 11 parts by weight of Al obtained in step S3 2 O 3 /SiO 2 Adding the deposited pleated graphene oxide coated carbon nano tube into 100 parts by weight of water, adding 4 parts by weight of hydrazine hydrate and 2.5 parts by weight of 21wt% ammonia water, heating to 42 ℃, stirring and reacting for 2.5h, centrifuging for 15min at 5000r/min, washing with deionized water, and drying at 105 ℃ for 2h to obtain Al 2 O 3 /SiO 2 Depositing the wrinkled graphene-coated carbon nano tube;
s5, gatheringModification of dopamine: 11 parts by weight of Al obtained in step S4 2 O 3 /SiO 2 Adding 100 parts by weight of water into the deposited pleated graphene coated carbon nano tube, adding 16 parts by weight of dopamine hydrochloride and 1.5 parts by weight of catalyst, heating to 45 ℃, stirring and reacting for 3 hours, centrifuging for 15 minutes at 5000r/min, washing with deionized water, and drying for 2 hours at 105 ℃ to obtain a modifier;
the catalyst is Tris-HCl solution with pH=8.7;
s6, combination of flame retardants: uniformly mixing 6 parts by weight of resorcinol bis (diphenyl phosphate) and 2.5 parts by weight of triphenyl phosphate to prepare a flame retardant;
s7, preparing a modified material: stirring and mixing 11 parts by weight of the modifier prepared in the step S5 and 4 parts by weight of the flame retardant prepared in the step S6 for 10 minutes to prepare a modified material;
s8, preparation of a component A: mixing 25 parts by weight of polyaspartic acid ester F524, 75 parts by weight of polyaspartic acid ester D2925 and 13.5 parts by weight of the modified material prepared in the step S7 for 20 minutes to obtain a component A;
S9. Preparation of the component B: mixing the isocyanate composition and polyether polyol PPG1000, heating to 65 ℃, and reacting until the system-NCO content is 11%, so as to cool down and finish the reaction, thereby obtaining a component B;
the isocyanate composition is a mixture of dicyclohexylmethane-4, 4' -diisocyanate and hexamethylene diisocyanate, and the mass ratio is 8.5:2.5;
s10, preparing a polyurea waterproof composition: and (3) uniformly mixing the dispersed A component and B component, wherein the addition amount of the A component and the B component is that the equivalent ratio of-NCO to-NH is 1:1, spraying a coating film, and the spraying pressure is 10MPa, so as to obtain the polyurea waterproof composition with the thickness of 0.6 mm.
Comparative example 1
In comparison with example 3, the difference is that step S1 is not performed.
The method comprises the following steps:
s1, wrapping and fixing the pleated graphene oxide: dissolving 11 parts by weight of graphene oxide in 100 parts by weight of water, adding 8.5 parts by weight of carbon nanotubes, stirring and dispersing for 20min, and spray drying to obtain the wrinkled graphene oxide coated carbon nanotubes;
the spray drying condition is that the air inlet temperature is 95 ℃, the air outlet temperature is 60 ℃, and the evaporation water quantity is 1850mL/h;
S2.Al 2 O 3 /SiO 2 is deposited by: dissolving 6 parts by weight of tetraethoxysilane and 8.5 parts by weight of aluminum isopropoxide in 70 parts by weight of ethanol, adding 17 parts by weight of the coated carbon nanotube of the pleated graphene oxide prepared in the step S1, dropwise adding 25 parts by weight of 13.5wt% ammonia water solution, stirring to 42 ℃, reacting for 2.5 hours, centrifuging for 15 minutes 5000r/min, washing with deionized water, calcining for 2.5 hours at 400 ℃ to prepare Al 2 O 3 /SiO 2 Depositing the wrinkled graphene oxide coated carbon nano tube;
s3, reduction of graphene oxide: 11 parts by weight of Al prepared in step S2 2 O 3 /SiO 2 Adding the deposited pleated graphene oxide coated carbon nano tube into 100 parts by weight of water, adding 4 parts by weight of hydrazine hydrate and 2.5 parts by weight of 21wt% ammonia water, heating to 42 ℃, stirring and reacting for 2.5h, centrifuging for 15min at 5000r/min, washing with deionized water, and drying at 105 ℃ for 2h to obtain Al 2 O 3 /SiO 2 Depositing the wrinkled graphene-coated carbon nano tube;
s4, modifying polydopamine: 11 parts by weight of Al obtained in step S3 2 O 3 /SiO 2 Adding 100 parts by weight of water into the deposited pleated graphene coated carbon nano tube, adding 16 parts by weight of dopamine hydrochloride and 1.5 parts by weight of catalyst, heating to 45 ℃, stirring and reacting for 3 hours, centrifuging for 15 minutes at 5000r/min, washing with deionized water, and drying for 2 hours at 105 ℃ to obtain a modifier;
the catalyst is Tris-HCl solution with pH=8.7;
s5, combination of flame retardants: uniformly mixing 6 parts by weight of resorcinol bis (diphenyl phosphate) and 2.5 parts by weight of triphenyl phosphate to prepare a flame retardant;
s6, preparing a modified material: stirring and mixing 11 parts by weight of the modifier prepared in the step S4 and 4 parts by weight of the flame retardant prepared in the step S5 for 10 minutes to prepare a modified material;
s7, preparation of a component A: mixing 25 parts by weight of polyaspartic acid ester F524, 75 parts by weight of polyaspartic acid ester D2925 and 13.5 parts by weight of the modified material prepared in the step S6 for 20 minutes to obtain a component A;
S8, preparation of a component B: mixing the isocyanate composition and polyether polyol PPG1000, heating to 65 ℃, and reacting until the system-NCO content is 11%, so as to cool down and finish the reaction, thereby obtaining a component B;
the isocyanate composition is a mixture of dicyclohexylmethane-4, 4' -diisocyanate and hexamethylene diisocyanate, and the mass ratio is 8.5:2.5;
s9, preparing a polyurea waterproof composition: and (3) uniformly mixing the dispersed A component and B component, wherein the addition amount of the A component and the B component is that the equivalent ratio of-NCO to-NH is 1:1, spraying a coating film, and the spraying pressure is 10MPa, so as to obtain the polyurea waterproof composition with the thickness of 0.6 mm.
Comparative example 2
In comparison with example 3, the difference is that step S2 and step S4 are not performed.
The method comprises the following steps:
s1, pretreatment of carbon nanotubes: adding 10 parts by weight of carbon nano tubes into 100 parts by weight of 1.5mol/L dilute nitric acid, heating to 45 ℃, stirring and reacting for 25min, centrifuging for 15min at 5000r/min, washing with deionized water, and drying for 2h at 105 ℃ to obtain pretreated carbon nano tubes;
S2.Al 2 O 3 /SiO 2 is deposited by: dissolving 6 parts by weight of tetraethoxysilane and 8.5 parts by weight of aluminum isopropoxide in 70 parts by weight of ethanol, adding 17 parts by weight of the pretreated carbon nanotube prepared in the step S1, dropwise adding 25 parts by weight of 13.5wt% ammonia water solution, stirring to 42 ℃, reacting for 2.5h, centrifuging for 15min at 5000r/min, washing with deionized water, calcining for 2.5h at 400 ℃ to prepare Al 2 O 3 /SiO 2 Depositing carbon nanotubes;
s3, modifying polydopamine: 11 parts by weight of Al prepared in step S2 2 O 3 /SiO 2 Adding deposited carbon nano tubes into 100 parts by weight of water, adding 16 parts by weight of dopamine hydrochloride and 1.5 parts by weight of catalyst, heating to 45 ℃, stirring and reacting for 3 hours, centrifuging for 15 minutes 5000r/min, washing with deionized water, and drying at 105 ℃ for 2 hours to obtain a modifier;
the catalyst is Tris-HCl solution with pH=8.7;
s4, combination of flame retardants: uniformly mixing 6 parts by weight of resorcinol bis (diphenyl phosphate) and 2.5 parts by weight of triphenyl phosphate to prepare a flame retardant;
s5, preparing a modified material: stirring and mixing 11 parts by weight of the modifier prepared in the step S3 and 4 parts by weight of the flame retardant prepared in the step S4 for 10 minutes to prepare a modified material;
s6, preparation of a component A: mixing 25 parts by weight of polyaspartic acid ester F524, 75 parts by weight of polyaspartic acid ester D2925 and 13.5 parts by weight of the modified material prepared in the step S5 for 20 minutes to obtain a component A;
s7, preparation of a component B: mixing the isocyanate composition and polyether polyol PPG1000, heating to 65 ℃, and reacting until the system-NCO content is 11%, so as to cool down and finish the reaction, thereby obtaining a component B;
the isocyanate composition is a mixture of dicyclohexylmethane-4, 4' -diisocyanate and hexamethylene diisocyanate, and the mass ratio is 8.5:2.5;
S8, preparing a polyurea waterproof composition: and (3) uniformly mixing the dispersed A component and B component, wherein the addition amount of the A component and the B component is that the equivalent ratio of-NCO to-NH is 1:1, spraying a coating film, and the spraying pressure is 10MPa, so as to obtain the polyurea waterproof composition with the thickness of 0.6 mm.
Comparative example 3
In comparison with example 3, the difference is that no ethyl orthosilicate was added in step S3.
The method comprises the following steps:
S3.Al 2 O 3 is deposited by: dissolving 14.5 parts by weight of aluminum isopropoxide in 70 parts by weight of ethanol, adding 17 parts by weight of the carbon nanotube coated with the pleated graphene oxide prepared in the step S2, dropwise adding 25 parts by weight of 13.5wt% ammonia water solution, stirring to 42 ℃, reacting for 2.5h, centrifuging for 15min at 5000r/min, washing with deionized water, calcining for 2.5h at 400 ℃, and preparing the Al 2 O 3 And depositing the wrinkled graphene oxide coated carbon nano tube.
Comparative example 4
In comparison with example 3, the difference is that aluminum isopropoxide is not added in step S3.
The method comprises the following steps:
S3.SiO 2 is deposited by: dissolving 14.5 parts by weight of ethyl orthosilicate in 70 parts by weight of ethanol, adding 17 parts by weight of the coated carbon nanotube of the pleated graphene oxide prepared in the step S2, dropwise adding 25 parts by weight of 13.5wt% ammonia water solution, stirring to 42 ℃, reacting for 2.5h, centrifuging for 15min at 5000r/min, washing with deionized water, calcining for 2.5h at 400 ℃, and obtaining SiO 2 And depositing the wrinkled graphene oxide coated carbon nano tube.
Comparative example 5
In comparison with example 3, the difference is that step S3 is not performed.
The method comprises the following steps:
s1, pretreatment of carbon nanotubes: adding 10 parts by weight of carbon nano tubes into 100 parts by weight of 1.5mol/L dilute nitric acid, heating to 45 ℃, stirring and reacting for 25min, centrifuging for 15min at 5000r/min, washing with deionized water, and drying for 2h at 105 ℃ to obtain pretreated carbon nano tubes;
s2, wrapping and fixing the pleated graphene oxide: dissolving 11 parts by weight of graphene oxide in 100 parts by weight of water, adding 8.5 parts by weight of the pretreated carbon nanotubes prepared in the step S1, stirring and dispersing for 20min, and spray-drying to obtain the wrinkled graphene oxide coated carbon nanotubes;
the spray drying condition is that the air inlet temperature is 95 ℃, the air outlet temperature is 60 ℃, and the evaporation water quantity is 1850mL/h;
s3, reduction of graphene oxide: adding 11 parts by weight of the pleated graphene oxide coated carbon nanotube prepared in the step S2 into 100 parts by weight of water, adding 4 parts by weight of hydrazine hydrate and 2.5 parts by weight of 21wt% ammonia water, heating to 42 ℃, stirring and reacting for 2.5h, centrifuging for 15min at 5000r/min, washing with deionized water, and drying at 105 ℃ for 2h to prepare the pleated graphene coated carbon nanotube;
S4, modifying polydopamine: adding 11 parts by weight of the wrinkled graphene-coated carbon nano tube prepared in the step S3 into 100 parts by weight of water, adding 16 parts by weight of dopamine hydrochloride and 1.5 parts by weight of catalyst, heating to 45 ℃, stirring and reacting for 3h, centrifuging for 15min at 5000r/min, washing with deionized water, and drying for 2h at 105 ℃ to prepare a modifier;
the catalyst is Tris-HCl solution with pH=8.7;
s5, combination of flame retardants: uniformly mixing 6 parts by weight of resorcinol bis (diphenyl phosphate) and 2.5 parts by weight of triphenyl phosphate to prepare a flame retardant;
s6, preparing a modified material: stirring and mixing 11 parts by weight of the modifier prepared in the step S4 and 4 parts by weight of the flame retardant prepared in the step S5 for 10 minutes to prepare a modified material;
s7, preparation of a component A: mixing 25 parts by weight of polyaspartic acid ester F524, 75 parts by weight of polyaspartic acid ester D2925 and 13.5 parts by weight of the modified material prepared in the step S6 for 20 minutes to obtain a component A;
s8, preparation of a component B: mixing the isocyanate composition and polyether polyol PPG1000, heating to 65 ℃, and reacting until the system-NCO content is 11%, so as to cool down and finish the reaction, thereby obtaining a component B;
the isocyanate composition is a mixture of dicyclohexylmethane-4, 4' -diisocyanate and hexamethylene diisocyanate, and the mass ratio is 8.5:2.5;
S9, preparing a polyurea waterproof composition: and (3) uniformly mixing the dispersed A component and B component, wherein the addition amount of the A component and the B component is that the equivalent ratio of-NCO to-NH is 1:1, spraying a coating film, and the spraying pressure is 10MPa, so as to obtain the polyurea waterproof composition with the thickness of 0.6 mm.
Comparative example 6
In comparison with example 3, the difference is that step S4 is not performed.
The method comprises the following steps:
s1, pretreatment of carbon nanotubes: adding 10 parts by weight of carbon nano tubes into 100 parts by weight of 1.5mol/L dilute nitric acid, heating to 45 ℃, stirring and reacting for 25min, centrifuging for 15min at 5000r/min, washing with deionized water, and drying for 2h at 105 ℃ to obtain pretreated carbon nano tubes;
s2, wrapping and fixing the pleated graphene oxide: dissolving 11 parts by weight of graphene oxide in 100 parts by weight of water, adding 8.5 parts by weight of the pretreated carbon nanotubes prepared in the step S1, stirring and dispersing for 20min, and spray-drying to obtain the wrinkled graphene oxide coated carbon nanotubes;
the spray drying condition is that the air inlet temperature is 95 ℃, the air outlet temperature is 60 ℃, and the evaporation water quantity is 1850mL/h;
S3.Al 2 O 3 /SiO 2 is deposited by: dissolving 6 parts by weight of tetraethoxysilane and 8.5 parts by weight of aluminum isopropoxide in 70 parts by weight of ethanol, adding 17 parts by weight of the coated carbon nanotube of the pleated graphene oxide prepared in the step S2, dropwise adding 25 parts by weight of 13.5wt% ammonia water solution, stirring to 42 ℃, reacting for 2.5 hours, centrifuging for 15 minutes 5000r/min, washing with deionized water, calcining for 2.5 hours at 400 ℃ to prepare Al 2 O 3 /SiO 2 Depositing the wrinkled graphene oxide coated carbon nano tube;
s4, modifying polydopamine: 11 parts by weight of Al obtained in step S3 2 O 3 /SiO 2 Adding the deposited pleated graphene oxide coated carbon nano tube into 100 parts by weight of water, adding 16 parts by weight of dopamine hydrochloride and 1.5 parts by weight of catalyst, heating to 45 ℃, stirring and reacting for 3 hours, centrifuging for 15 minutes at 5000r/min, washing with deionized water, and drying for 2 hours at 105 ℃ to obtain a modifier;
the catalyst is Tris-HCl solution with pH=8.7;
s5, combination of flame retardants: uniformly mixing 6 parts by weight of resorcinol bis (diphenyl phosphate) and 2.5 parts by weight of triphenyl phosphate to prepare a flame retardant;
s6, preparing a modified material: stirring and mixing 11 parts by weight of the modifier prepared in the step S4 and 4 parts by weight of the flame retardant prepared in the step S5 for 10 minutes to prepare a modified material;
s7, preparation of a component A: mixing 25 parts by weight of polyaspartic acid ester F524, 75 parts by weight of polyaspartic acid ester D2925 and 13.5 parts by weight of the modified material prepared in the step S6 for 20 minutes to obtain a component A;
s8, preparation of a component B: mixing the isocyanate composition and polyether polyol PPG1000, heating to 65 ℃, and reacting until the system-NCO content is 11%, so as to cool down and finish the reaction, thereby obtaining a component B;
The isocyanate composition is a mixture of dicyclohexylmethane-4, 4' -diisocyanate and hexamethylene diisocyanate, and the mass ratio is 8.5:2.5;
s9, preparing a polyurea waterproof composition: and (3) uniformly mixing the dispersed A component and B component, wherein the addition amount of the A component and the B component is that the equivalent ratio of-NCO to-NH is 1:1, spraying a coating film, and the spraying pressure is 10MPa, so as to obtain the polyurea waterproof composition with the thickness of 0.6 mm.
Comparative example 7
In comparison with example 3, the difference is that step S5 is not performed.
The method comprises the following steps:
s1, pretreatment of carbon nanotubes: adding 10 parts by weight of carbon nano tubes into 100 parts by weight of 1.5mol/L dilute nitric acid, heating to 45 ℃, stirring and reacting for 25min, centrifuging for 15min at 5000r/min, washing with deionized water, and drying for 2h at 105 ℃ to obtain pretreated carbon nano tubes;
s2, wrapping and fixing the pleated graphene oxide: dissolving 11 parts by weight of graphene oxide in 100 parts by weight of water, adding 8.5 parts by weight of the pretreated carbon nanotubes prepared in the step S1, stirring and dispersing for 20min, and spray-drying to obtain the wrinkled graphene oxide coated carbon nanotubes;
the spray drying condition is that the air inlet temperature is 95 ℃, the air outlet temperature is 60 ℃, and the evaporation water quantity is 1850mL/h;
S3.Al 2 O 3 /SiO 2 Is deposited by: dissolving 6 parts by weight of tetraethoxysilane and 8.5 parts by weight of aluminum isopropoxide in 70 parts by weight of ethanol, adding 17 parts by weight of the coated carbon nanotube of the pleated graphene oxide prepared in the step S2, dropwise adding 25 parts by weight of 13.5wt% ammonia water solution, stirring to 42 ℃, reacting for 2.5 hours, centrifuging for 15 minutes 5000r/min, washing with deionized water, calcining for 2.5 hours at 400 ℃ to prepare Al 2 O 3 /SiO 2 Depositing the wrinkled graphene oxide coated carbon nano tube;
s4, reduction of graphene oxide: 11 parts by weight of Al obtained in step S3 2 O 3 /SiO 2 Adding the deposited pleated graphene oxide coated carbon nano tube into 100 parts by weight of water, adding 4 parts by weight of hydrazine hydrate and 2.5 parts by weight of 21wt% ammonia water, heating to 42 ℃, stirring and reacting for 2.5h, centrifuging for 15min at 5000r/min, washing with deionized water, and drying at 105 ℃ for 2h to obtain Al 2 O 3 /SiO 2 Deposited pleatsThe wrinkled graphene is used for coating the carbon nano tube, namely the modifier;
s5, combination of flame retardants: uniformly mixing 6 parts by weight of resorcinol bis (diphenyl phosphate) and 2.5 parts by weight of triphenyl phosphate to prepare a flame retardant;
s6, preparing a modified material: stirring and mixing 11 parts by weight of the modifier prepared in the step S4 and 4 parts by weight of the flame retardant prepared in the step S5 for 10 minutes to prepare a modified material;
s7, preparation of a component A: mixing 25 parts by weight of polyaspartic acid ester F524, 75 parts by weight of polyaspartic acid ester D2925 and 13.5 parts by weight of the modified material prepared in the step S6 for 20 minutes to obtain a component A;
S8, preparation of a component B: mixing the isocyanate composition and polyether polyol PPG1000, heating to 65 ℃, and reacting until the system-NCO content is 11%, so as to cool down and finish the reaction, thereby obtaining a component B;
the isocyanate composition is a mixture of dicyclohexylmethane-4, 4' -diisocyanate and hexamethylene diisocyanate, and the mass ratio is 8.5:2.5;
s9, preparing a polyurea waterproof composition: and (3) uniformly mixing the dispersed A component and B component, wherein the addition amount of the A component and the B component is that the equivalent ratio of-NCO to-NH is 1:1, spraying a coating film, and the spraying pressure is 10MPa, so as to obtain the polyurea waterproof composition with the thickness of 0.6 mm.
Comparative example 8
The difference compared to example 3 is that only a single resorcinol bis (diphenyl phosphate) is included in step S6.
The method comprises the following steps:
s6, combination of flame retardants: resorcinol bis (diphenyl phosphate) was used as a flame retardant.
Comparative example 9
The difference compared to example 3 is that only a single triphenyl phosphate is included in step S6.
The method comprises the following steps:
s6, combination of flame retardants: triphenyl phosphate was used as a flame retardant.
Comparative example 10
The difference compared to example 3 is that no flame retardant is added in step S7.
The method comprises the following steps:
s7, preparing a modified material: and using a modifier as a modifying material.
Comparative example 11
The difference from example 3 is that only a single polyaspartic acid ester F524 is included in step S8.
The method comprises the following steps:
s8, preparation of a component A: 100 parts by weight of polyaspartic acid ester F524 and 13.5 parts by weight of the modified material prepared in the step S7 are stirred and mixed for 20 minutes to obtain a component A.
Comparative example 12
In comparison with example 3, the difference is that the isocyanate composition in step S9 is replaced with diphenylmethane diisocyanate.
The method comprises the following steps:
s9. Preparation of the component B: and mixing diphenylmethane diisocyanate and polyether polyol PPG1000, heating to 65 ℃, and reacting until the system-NCO content is 11%, so that the temperature reduction is finished, and the component B is obtained.
Test example 1
The polyurea waterproofing compositions prepared in examples 1 to 3 and comparative examples 1 to 12 of the present invention were subjected to performance test.
Reference standard:
GB/T23446-2009 spray polyurea Water-repellent Material;
GB/T19250-2013 polyurethane waterproof paint.
The results are shown in tables 1 to 3.
TABLE 1
TABLE 2
TABLE 3 Table 3
As can be seen from the above table, the polyurea waterproof compositions prepared in examples 1 to 3 of the present invention have good comprehensive properties.
Test example 2
The polyurea waterproof compositions prepared in examples 1 to 3 and comparative examples 1 to 12 of the present invention were further spray-coated to prepare a sample standard size, and flame retardant property experiments were performed.
The results are shown in Table 4.
Vertical burn tests were performed according to standard ASTM 3801 with sample sizes of 125mm by 13mm by 3mm.
Limiting oxygen index was carried out according to standard ASTM D2863, sample sizes 80mm 10mm 4mm.
TABLE 4 Table 4
As is clear from the above table, the polyurea waterproofing compositions prepared in examples 1 to 3 of the present invention have excellent flame retardant properties.
Comparative example 1 compared to example 3, step S1 was not performed. The mechanical property is reduced, the high temperature resistance is reduced, and the flame retardant property is reduced. According to the invention, the surface of the carbon nano tube is treated by dilute nitric acid, and then a large number of hydroxyl groups are formed by functionalization, so that hydrogen bonds are formed between the surface of the carbon nano tube and the hydroxyl groups on the surface of the graphene oxide, and the graphene oxide is stably coated on the surface of the carbon nano tube, so that subsequent modification is facilitated.
Comparative example 2 compared to example 3, steps S2 and S4 were not performed. Comparative example 6 compared to example 3, step S4 was not performed. The mechanical property is reduced, the low-temperature property is reduced, the high-temperature resistance is reduced, and the flame retardant property is reduced. The fold structure of the modifier can effectively reduce the stacking of the modifier in a polymer matrix, avoid aggregation caused by ordered stacking among tiny modifiers, realize uniform dispersion, fully exert the excellent performance of the modifier, and obviously improve the mechanical property, antistatic property, flame retardant property, heat preservation property, high temperature resistance and barrier property of the polyurea resin by blending graphene.
In comparative examples 3 and 4, in comparison with example 3, no ethyl orthosilicate or aluminum isopropoxide was added in step S3. Comparative example 5 compared to example 3, step S3 was not performed. The mechanical property is reduced, the high temperature resistance is reduced, and the flame retardant property is reduced. SiO of the invention 2 The addition of (3) can improve the tearing strength and the tensile strength of the material when the material is impacted at high speed. At the same time Al 2 O 3 The mixing of the material can also obviously improve the flame retardance, heat preservation and high temperature resistance of the material.
Comparative example 7 compared to example 3, step S5 was not performed. The mechanical property is reduced, and the flame retardant property is reduced. The surface of the modifier obtained by the invention is provided with a polydopamine layer which contains abundant hydroxyl, amino, carboxyl and other active groups and can well form hydrogen bonds with a matrix polyurea material, so that the modifier is connected into a polyurea resin system, and graphene, carbon nano tubes and SiO are utilized 2 The high strength and modulus of (a) improves the tear and tensile strength of the material when subjected to high-speed impact. At the same time Al 2 O 3 The incorporation of the poly-N element can also obviously improve the flame retardant, heat preservation and high temperature resistance of the material, and the flame retardant property of the material is further improved.
Comparative examples 8, 9 include only a single resorcinol bis (diphenyl phosphate) or triphenyl phosphate in step S6, as compared to example 3. In comparative example 10, in comparison with example 3, no flame retardant was added in step S7. The high temperature resistance and the flame retardance are reduced. The resorcinol bis (diphenyl phosphate) and triphenyl phosphate as flame retardants have good flame retardant effect on the polyurea waterproof composition, and meanwhile, the mechanical property of the composition is not affected, and the flame retardant has good synergistic effect. The triphenyl phosphate can be hydrolyzed to generate triphenoxyphosphate, and resorcinol bis (diphenyl phosphate) can be hydrolyzed to generate p-hydroxyphenol to participate in chain termination reaction, so that flame retardant effect is realized at a microscopic level. Meanwhile, the organic flame retardant can decompose to generate gas during combustion, and a carbonized layer is formed on the surface of the polymer to block contact and heat transfer between the polymer and air. This carbonized layer will help slow down the burning rate and protect the interior material from flame and heat radiation.
Comparative example 11 includes only a single polyaspartic acid ester F524 in step S8, as compared with example 3. The mechanical property is reduced, and the low-temperature property is reduced. The polyaspartic acid ester D2925 is prepared by pre-reacting alicyclic isocyanate and polyaspartic acid ester, and has the characteristics of large molecular weight, small functionality, small reactivity, excellent mechanical property and the like, and the tensile strength and the tearing strength of the prepared polyurea composition are increased.
Comparative example 12 in comparison with example 3, the isocyanate composition in step S9 was replaced with diphenylmethane diisocyanate. The mechanical property is reduced, the low-temperature property is reduced and the high-temperature resistance is reduced. The diphenyl methane diisocyanate is an aromatic compound, the prepared polyurea waterproof composition has high hardness, is brittle and has low tensile strength, the dicyclohexylmethane-4, 4' -diisocyanate and the hexamethylene diisocyanate added in the invention are alicyclic and aliphatic isocyanates, and the prepared polyurea waterproof composition has high hardness, good flexibility and obviously improved tensile strength.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.

Claims (9)

1. A method for preparing a polyurea waterproofing composition, comprising the steps of:
s1, pretreatment of carbon nanotubes: adding the carbon nano tube into dilute nitric acid, heating, stirring, reacting, centrifuging, washing, and drying to obtain a pretreated carbon nano tube;
s2, wrapping and fixing the pleated graphene oxide: dissolving graphene oxide in water, adding the pretreated carbon nanotubes prepared in the step S1, stirring and dispersing uniformly, and spray drying to obtain the wrinkled graphene oxide coated carbon nanotubes;
S3.Al 2 O 3 /SiO 2 is deposited by: dissolving alkyl orthosilicate and aluminum isopropoxide in ethanol, and adding the mixture into the step S2, dropwise adding ammonia water solution into the prepared wrinkled graphene oxide coated carbon nano tube, stirring for reaction, centrifuging, washing, calcining to obtain Al 2 O 3 /SiO 2 Depositing the wrinkled graphene oxide coated carbon nano tube;
s4, reduction of graphene oxide: al prepared in the step S3 2 O 3 /SiO 2 Adding the deposited wrinkled graphene oxide coated carbon nano tube into water, adding hydrazine hydrate and ammonia water, heating, stirring for reaction, centrifuging, washing and drying to obtain Al 2 O 3 /SiO 2 Depositing the wrinkled graphene-coated carbon nano tube;
s5, modifying polydopamine: al prepared in the step S4 2 O 3 /SiO 2 Adding the deposited wrinkled graphene coated carbon nano tube into water, adding dopamine hydrochloride and a catalyst, heating, stirring, reacting, centrifuging, washing and drying to obtain a modifier;
S6, combination of flame retardants: resorcinol bis (diphenyl phosphate) and triphenyl phosphate are uniformly mixed to prepare a flame retardant;
s7, preparing a modified material: uniformly mixing the modifier prepared in the step S5 and the flame retardant prepared in the step S6 to prepare a modified material;
s8, preparation of a component A: uniformly mixing the polyaspartic acid ester F524, the polyaspartic acid ester D2925 and the modified material prepared in the step S7 to obtain a component A;
s9. Preparation of the component B: mixing the isocyanate composition and polyether polyol, and heating for reaction to obtain a component B; the isocyanate composition is a mixture of dicyclohexylmethane-4, 4' -diisocyanate and hexamethylene diisocyanate, and the mass ratio is 7-10:2-3;
s10, preparing a polyurea waterproof composition: uniformly mixing the dispersed component A and component B, and spraying a coating film to obtain the polyurea waterproof composition.
2. The preparation method according to claim 1, wherein the concentration of the dilute nitric acid in the step S1 is 1-2mol/L, the temperature of the heating and stirring reaction is 40-50 ℃ and the time is 20-30min; in the step S2, the mass ratio of the graphene oxide to the pretreated carbon nano tube is 10-12:7-10, the spray drying condition is that the air inlet temperature is 85-100 ℃, the air outlet temperature is 50-70 ℃, and the evaporation water amount is 1700-2000mL/h.
3. The preparation method of claim 1, wherein in the step S3, the mass ratio of the alkyl orthosilicate, the aluminum isopropoxide, the wrinkled graphene oxide coated carbon nano tube and the ammonia solution is 5-7:7-10:15-20:20-30, the concentration of the ammonia is 12-15wt%, the temperature of the stirring reaction is 40-45 ℃, the time is 2-3h, the temperature of the calcination is 300-500 ℃, and the time is 2-3h; al described in step S4 2 O 3 /SiO 2 The mass ratio of the deposited wrinkled graphene oxide coated carbon nano tube to the hydrazine hydrate to the ammonia water is 10-12:3-5:2-3, the concentration of the ammonia water is 20-22wt%, the temperature of the heating and stirring reaction is 40-45 ℃, and the time is 2-3h.
4. The method according to claim 1, wherein the Al is in step S5 2 O 3 /SiO 2 Depositing a pleated graphene-coated carbon nano tube, wherein the mass ratio of the dopamine hydrochloride to the catalyst is 10-12:15-17:1-2, the catalyst is Tris-HCl solution with pH value of 8.5-9, the temperature of the heating and stirring reaction is 40-50 ℃, and the time is 2-4 hours; the mass ratio of resorcinol bis (diphenyl phosphate) to triphenyl phosphate in the step S6 is 5-7:2-3.
5. The preparation method according to claim 1, wherein the mass ratio of the modifier to the flame retardant in the step S7 is 10-12:3-5; the mass ratio of the polyaspartic acid ester F524 to the polyaspartic acid ester D2925 to the modified material in the step S8 is 20-30:70-80:12-15.
6. The preparation method according to claim 1, wherein the polyether polyol in the step S9 is PPG1000, the temperature of the heating reaction is 60-70 ℃, and the reaction can be completed after the temperature is reduced until the system-NCO content is 10-12%; the addition amount of the component A and the component B in the step S10 is that the equivalent ratio of-NCO to-NH is 1:1, and the thickness of the spray coating film is 0.5-0.7mm.
7. The preparation method according to claim 1, characterized by comprising the following steps:
s1, pretreatment of carbon nanotubes: adding 10 parts by weight of carbon nano tubes into 100 parts by weight of 1-2mol/L dilute nitric acid, heating to 40-50 ℃, stirring and reacting for 20-30min, centrifuging, washing and drying to obtain pretreated carbon nano tubes;
s2, wrapping and fixing the pleated graphene oxide: dissolving 10-12 parts by weight of graphene oxide in 100 parts by weight of water, adding 7-10 parts by weight of the pretreated carbon nanotube prepared in the step S1, stirring and dispersing uniformly, and spray-drying to obtain the wrinkled graphene oxide coated carbon nanotube;
the spray drying condition is that the air inlet temperature is 85-100 ℃, the air outlet temperature is 50-70 ℃ and the evaporation water quantity is 1700-2000mL/h;
S3.Al 2 O 3 /SiO 2 is deposited by: dissolving 5-7 parts by weight of alkyl orthosilicate and 7-10 parts by weight of aluminum isopropoxide in 70 parts by weight of ethanol, adding 15-20 parts by weight of the wrinkled graphene oxide coated carbon nano tube prepared in the step S2, dropwise adding 20-30 parts by weight of 12-15wt% ammonia water solution, stirring to 40-45 ℃, reacting for 2-3h, centrifuging, washing, and calcining at 300-500 ℃ for 2-3h to prepare Al 2 O 3 /SiO 2 Depositing the wrinkled graphene oxide coated carbon nano tube;
s4, reduction of graphene oxide: 10-12 parts by weight of Al prepared in the step S3 2 O 3 /SiO 2 Adding the deposited pleated graphene oxide coated carbon nano tube into 100 parts by weight of water, adding 3-5 parts by weight of hydrazine hydrate and 2-3 parts by weight of 20-22wt% ammonia water, heating to 40-45 ℃, stirring and reacting for 2-3 hours, centrifuging, washing and drying to obtain Al 2 O 3 /SiO 2 Depositing the wrinkled graphene-coated carbon nano tube;
s5, modifying polydopamine: 10 to 12 parts by weight of Al prepared in the step S4 2 O 3 /SiO 2 Adding the deposited wrinkled graphene-coated carbon nano tube into 100 parts by weight of water, and adding 15-17 parts by weight of waterHeating 1-2 parts by weight of catalyst and 1-50 parts by weight of dopamine hydrochloride to 40-50 ℃, stirring and reacting for 2-4 hours, centrifuging, washing and drying to obtain a modifier;
the catalyst is Tris-HCl solution with pH=8.5-9;
s6, combination of flame retardants: uniformly mixing 5-7 parts by weight of resorcinol bis (diphenyl phosphate) and 2-3 parts by weight of triphenyl phosphate to prepare a flame retardant;
s7, preparing a modified material: uniformly mixing 10-12 parts by weight of the modifier prepared in the step S5 and 3-5 parts by weight of the flame retardant prepared in the step S6 to prepare a modified material;
s8, preparation of a component A: uniformly mixing 20-30 parts by weight of polyaspartic acid ester F524, 70-80 parts by weight of polyaspartic acid ester D2925 and 12-15 parts by weight of the modified material prepared in the step S7 to obtain a component A;
S9. Preparation of the component B: mixing the isocyanate composition and polyether polyol PPG1000, heating to 60-70 ℃, and reacting until the system-NCO content is 10-12%, and cooling to finish the reaction to obtain a component B;
the isocyanate composition is a mixture of dicyclohexylmethane-4, 4' -diisocyanate and hexamethylene diisocyanate, and the mass ratio is 7-10:2-3;
s10, preparing a polyurea waterproof composition: and uniformly mixing the dispersed A component and B component, wherein the addition amount of the A component and the B component is that the equivalent ratio of-NCO to-NH is 1:1, and spraying a coating film to obtain the polyurea waterproof composition with the thickness of 0.5-0.7 mm.
8. A polyurea waterproofing composition produced by the production process according to any one of claims 1 to 7.
9. Use of the polyurea waterproofing composition according to claim 8 for waterproofing construction materials.
CN202310686815.9A 2023-06-12 2023-06-12 Polyurea waterproof composition and preparation method thereof Active CN116640499B (en)

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