CN110862736A - Durable waterproof engineering coating and preparation method thereof - Google Patents
Durable waterproof engineering coating and preparation method thereof Download PDFInfo
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
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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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- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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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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- C09D7/65—Additives macromolecular
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention discloses a durable waterproof engineering coating which is characterized by being prepared from the following raw materials in parts by weight: 25-30 parts of allyl thiourea/3-amino-3- (2-pyridine) acrylonitrile/1-vinyl-1, 2, 4-triazole/titanium triisopropoxide methacrylate copolymer, 2-4 parts of epoxy modified 2,4, 6-triphenylborohexaalkane, 20-30 parts of amino-terminated polyurethane, 1-4 parts of asphalt, 2-5 parts of vinyl-terminated fluorosilicone oil, 0.5-1.5 parts of photoinitiator, 15-20 parts of filler, 1-3 parts of defoaming agent, 1-3 parts of dispersing agent, 1-3 parts of emulsifier and 20-30 parts of organic solvent. The invention also provides a preparation method of the durable waterproof engineering coating. The durable waterproof engineering coating disclosed by the invention has the advantages of remarkable waterproof effect, good comprehensive performance, and excellent weather resistance, mechanical property, heat resistance and wear resistance.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a durable waterproof engineering coating and a preparation method thereof.
Background
In recent years, the Chinese speed represented by high-speed rails brings convenient and agreeable life experiences to many people, and the increasing passenger transport demands are greatly met from four vertical lines and four horizontal lines to eight vertical lines and eight horizontal lines. The north and south China are no longer far away, the wonderful world is at hand, the travel plans of common people are suddenly increased, and the places where high-speed railways go are the first choice for travel. The high-speed rail not only accelerates the welfare of the people, but also promotes the development of local economy. With the vigorous development of railway construction, especially high-speed rail industry, railway system technology is also continuously developed, wherein one of the most important technologies, namely railway system waterproof technology, is mainly realized by a waterproof coating special for high-speed rails. Therefore, the development of a durable waterproof engineering coating which has excellent comprehensive properties and can be used for high-speed rails is imperative.
At present, common high-iron waterproof coatings comprise four types of coatings of polyurethane, spray polyurea, epoxy resin and polymethyl methacrylate, wherein the polymethyl methacrylate is free of solvent VOC (volatile organic Compounds), does not contain heavy metal, has excellent optical performance, tensile property, elastic modulus, impact strength, weather resistance and arc resistance, but has poor thermal performance, narrow applicable temperature range, poor chemical resistance, certain brittleness, cracking under high impact energy, insufficient surface hardness and easy scratching by hard objects. The polyurethane waterproof coating can form a stronger waterproof membrane, but the polyurethane waterproof coating has lower solid content, longer drying time and poorer low-temperature flexibility, and can not meet the requirement of the durability quality standard of a bridge structure, so the using effect of a waterproof layer of a structure is influenced. The epoxy resin has excellent mechanical properties and high adhesive strength, but the toughness and heat resistance are required to be further improved, and the epoxy resin is easy to yellow and affects the appearance. Polyurea spray coatings are expensive and require high spray techniques.
The invention Chinese patent CN102108234A discloses a colorful environment-friendly synthetic polymer waterproof paint, which comprises, by weight, 3-7 parts of petroleum resin, 5-15 parts of SEBS, 5-15 parts of SBS, 510 parts of thermoplastic polyurethane elastomer TPU, 4-8 parts of terpene resin, 4-8 parts of poly α -methylstyrene, 2-5 parts of tung oil, 10-15 parts of mica powder, 0.2-0.5 part of anti-aging agent D, 0.26-0.5 part of antioxidant 2640.2, 0.2-0.5 part of defoamer, 0.3-0.5 part of ultraviolet absorbent, 35-45 parts of 120# solvent, 5-15 parts of butyl acetate and 1-3 parts of color paste.
Therefore, the durable waterproof engineering coating with good comprehensive performance, obvious waterproof effect, excellent weather resistance, mechanical property and heat resistance is developed to meet the market demand, has wide market value and application prospect, and has very important significance for development of waterproof coatings and high-speed rail industry.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a durable waterproof engineering coating which has the advantages of remarkable waterproof effect, good comprehensive performance, excellent weather resistance, mechanical property, heat resistance and wear resistance; meanwhile, the invention also provides a preparation method of the durable waterproof engineering coating, and the preparation method is simple and easy to implement, convenient to construct, good in environmental protection property, high in preparation efficiency and suitable for large-scale industrial production.
In order to achieve the aim, the invention adopts the technical scheme that the durable waterproof engineering coating is characterized by being prepared from the following raw materials in parts by weight: 25-30 parts of allyl thiourea/3-amino-3- (2-pyridine) acrylonitrile/1-vinyl-1, 2, 4-triazole/titanium triisopropoxide methacrylate copolymer, 2-4 parts of epoxy modified 2,4, 6-triphenylborohexaalkane, 20-30 parts of amino-terminated polyurethane, 1-4 parts of asphalt, 2-5 parts of vinyl-terminated fluorosilicone oil, 0.5-1.5 parts of photoinitiator, 15-20 parts of filler, 1-3 parts of defoaming agent, 1-3 parts of dispersing agent, 1-3 parts of emulsifier and 20-30 parts of organic solvent.
Further, the photoinitiator is at least one of benzoin dimethyl ether, benzoin ethyl ether and 2, 4-dihydroxy benzophenone; the filler is at least one of talcum powder, pumice powder, bentonite, montmorillonite and attapulgite; the defoaming agent is one or more of tributyl phosphate, a defoaming agent Demodex 3100 and a defoaming agent BYK 088; the dispersing agent is sodium hexametaphosphate and/or sodium polycarboxylate.
Further, the organic solvent is one of isopropanol, pentaerythritol, cyclohexanone and ethylene glycol monoethyl ether acetate; the emulsifier is at least one of sodium dodecyl sulfate, polyoxyethylene fatty acid ester and ammonium alkylphenol polyethoxy ether sulfate; the asphalt is at least one of petroleum asphalt and natural asphalt.
Preferably, the amino-terminated polyurethane has an average molecular weight of 1836, and for the prior preparation, the preparation method refers to: example 1 of chinese invention patent CN 201110382645.2; the number average molecular weight of the vinyl-terminated fluorosilicone oil is 3.6 ten thousand.
Further, the preparation method of the epoxy-modified 2,4, 6-triphenylborazonexadecane comprises the following steps: adding 2,4, 6-triphenylboron nitrogen hexaalkane, epoxy chloropropane and an alkaline catalyst into a high-boiling-point solvent, stirring and reacting for 5-8 hours at 40-60 ℃, filtering to remove the alkaline catalyst, and then removing the solvent and unreacted epoxy chloropropane by rotary evaporation to obtain the epoxy group modified 2,4, 6-triphenylboron nitrogen hexaalkane.
Preferably, the mass ratio of the 2,4, 6-triphenylboron nitrogen hexaalkane to the epoxy chloropropane to the basic catalyst to the high-boiling-point solvent is 3.34:1 (0.5-0.8) to (15-22).
Preferably, the alkaline catalyst is at least one of sodium hydroxide, sodium carbonate, potassium hydroxide and potassium carbonate; the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
Further, the preparation method of the allylthiourea/3-amino-3- (2-pyridine) acrylonitrile/1-vinyl-1, 2, 4-triazole/titanium triisopropoxide methacrylate copolymer comprises the following steps: adding allylthiourea, 3-amino-3- (2-pyridine) acrylonitrile, 1-vinyl-1, 2, 4-triazole, titanium triisopropoxide methacrylate and an initiator into N-methylpyrrolidone, stirring and reacting for 3-5 hours at 70-80 ℃ in a nitrogen or inert gas atmosphere, then precipitating in water, and drying the precipitated polymer at 80-90 ℃ in a vacuum drying box to constant weight to obtain the copolymer of allylthiourea/3-amino-3- (2-pyridine) acrylonitrile/1-vinyl-1, 2, 4-triazole/titanium triisopropoxide methacrylate.
Preferably, the mass ratio of the allylthiourea to the 3-amino-3- (2-pyridine) acrylonitrile to the 1-vinyl-1, 2, 4-triazole to the triisopropanolate titanium methacrylate to the initiator to the N-methylpyrrolidone is 2:1:0.3:0.5 (0.03-0.04) to (13-20).
Preferably, the initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile; the inert gas is one of helium, neon and argon.
Another object of the present invention is to provide a method for preparing the durable waterproof engineering paint, which comprises the following steps: mixing the raw materials according to the proportion, keeping the rotation speed at 1000-1200r/min, stirring for 1-2h, then keeping the rotation speed at 2200-2400r/min, stirring for 0.8-1.5h, then grinding by a grinder until the fineness is 20-50 μm, dispersing for 15-20 min at the rotation speed of 800-1000 r/min, post-curing for 1-3 days, sampling and inspecting, sieving and packaging after passing, and obtaining the finished durable waterproof engineering coating.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:
(1) the durable waterproof engineering coating provided by the invention is simple and easy to operate in a preparation method, rich in preparation raw material source, low in price, convenient to construct, good in environmental protection property, high in preparation efficiency and suitable for large-scale industrial production.
(2) The durable waterproof engineering coating overcomes the defects that the traditional waterproof coating is poor in thermal performance, narrow in applicable temperature range, poor in chemical resistance, certain in brittleness, capable of being broken under high impact energy, insufficient in surface hardness and easy to scratch by hard objects, and the like; the solid content is low, the drying time is long, the low-temperature flexibility is poor, and the requirement of the durability quality standard of the bridge structure cannot be met; the toughness and the weather resistance need to be further improved, and the paint is easy to yellow and affects the appearance; the paint has the defects of high price and high requirement on a spraying technology, and has the advantages of remarkable waterproof effect, good comprehensive performance, and excellent weather resistance, mechanical property, heat resistance and wear resistance.
(3) The invention provides a durable waterproof engineering coating, which adopts the synergistic effect of allyl thiourea/3-amino-3- (2-pyridine) acrylonitrile/1-vinyl-1, 2, 4-triazole/titanium triisopropoxide methacrylate copolymer, amino-terminated polyurethane and vinyl-terminated fluorosilicone oil as a film-forming polymer; epoxy modified 2,4, 6-triphenylboron nitrogen hexaalkane is adopted for curing; vinyl-terminated fluorosilicone oil and an allylthiourea/3-amino-3- (2-pyridine) acrylonitrile/1-vinyl-1, 2, 4-triazole/methacrylic acid triisopropanolate titanium copolymer are subjected to a grafting reaction under the initiation action of a photoinitiator, and epoxy groups on epoxy group modified 2,4, 6-triphenylcycloborazine and allylthiourea/3-amino-3- (2-pyridine) acrylonitrile/1-vinyl-1, 2, 4-triazole/methacrylic acid triisopropanolate titanium copolymer and amino groups on amino-terminated polyurethane are subjected to a chemical reaction in a curing stage, so that all components form a three-dimensional waterproof network structure in a chemical bond form, the comprehensive performance of the coating is effectively improved, and the coating is enabled to be water repellent, The weather resistance and the heat resistance are better; the film forming material in the coating combines the advantages of urea, polyurethane and organosilicon waterproof materials, so that the waterproof performance of the coating is better; and more amino and titanate structures are arranged on the molecular chain, so that the bonding strength of the coating and the base material is effectively enhanced; the introduction of the triazole structure and the synergism of the nitrile group effectively improve the weather resistance and the ageing resistance of the coating and also improve the fire resistance and the flame retardance of the coating; the introduction of the thiourea structure can improve the bonding property and further improve the comprehensive performance of the coating.
(4) According to the durable waterproof engineering coating provided by the invention, the epoxy group modified 2,4, 6-triphenylboron nitrogen hexaalkane is used as a curing agent, and a 2,4, 6-triphenylboron nitrogen hexaalkane structure is introduced, so that the obtained coating has higher hardness, better wear resistance, better flame retardance, weather resistance, mechanical property and waterproof property; the synergistic effect of the amino-terminated polyurethane and the vinyl-terminated fluorosilicone oil can also improve the lubricity and toughness; the addition of bitumen further improves the water and corrosion resistance properties.
Detailed Description
In order to make the technical solutions of the present invention better understood and make the above features, objects, and advantages of the present invention more comprehensible, the present invention is further described with reference to the following examples. The examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.
The average molecular weight of the amino-terminated polyurethane described in the following examples of the present invention is 1836, for preparation in advance, reference is made to the preparation method: example 1 of chinese invention patent CN 201110382645.2; the number average molecular weight of the vinyl-terminated fluorosilicone oil is 3.6 ten thousand, and the preparation method is self-made and is referred to as follows: zhangguan et al, preparation and performance research of vinyl-terminated fluorosilicone rubber, university of Hangzhou teachers and universities academic newspaper (Nature science edition), 11 months in 2008, No. 7, No. 6; other raw materials were all purchased commercially.
Example 1
The durable waterproof engineering coating is characterized by being prepared from the following raw materials in parts by weight: 25 parts of allyl thiourea/3-amino-3- (2-pyridine) acrylonitrile/1-vinyl-1, 2, 4-triazole/titanium triisopropoxide methacrylate copolymer, 2 parts of epoxy modified 2,4, 6-triphenylboroxine, 20 parts of amino-terminated polyurethane, 1 part of petroleum asphalt, 2 parts of vinyl-terminated fluorosilicone oil, 0.5 part of benzoin dimethyl ether, 15 parts of talcum powder, 1 part of tributyl phosphate, 1 part of sodium hexametaphosphate, 1 part of sodium dodecyl sulfate and 20 parts of isopropanol.
The preparation method of the epoxy group modified 2,4, 6-triphenylboron nitrogen hexaalkane comprises the following steps: adding 33.4g of 2,4, 6-triphenylboron nitrogen hexaalkane, 10g of epoxy chloropropane and 5g of sodium hydroxide into 150g of dimethyl sulfoxide, stirring and reacting for 5 hours at 40 ℃, filtering to remove the sodium hydroxide, and then removing the solvent and unreacted epoxy chloropropane by rotary evaporation to obtain the epoxy group modified 2,4, 6-triphenylboron nitrogen hexaalkane.
The preparation method of the allyl thiourea/3-amino-3- (2-pyridine) acrylonitrile/1-vinyl-1, 2, 4-triazole/titanium triisopropoxide methacrylate copolymer comprises the following steps: 20g of allylthiourea, 10g of 3-amino-3- (2-pyridine) acrylonitrile, 3g of 1-vinyl-1, 2, 4-triazole, 5g of titanium triisopropoxide methacrylate and 0.3g of azobisisobutyronitrile are added to 130g of N-methylpyrrolidone, stirred and reacted at 70 ℃ for 3 hours under a nitrogen atmosphere, and then precipitated in water, and the precipitated polymer is dried to constant weight at 80 ℃ in a vacuum drying oven to obtain the allylthiourea/3-amino-3- (2-pyridine) acrylonitrile/1-vinyl-1, 2, 4-triazole/titanium triisopropoxide methacrylate copolymer.
The preparation method of the durable waterproof engineering coating is characterized by comprising the following steps: mixing the raw materials according to the proportion, keeping the rotation speed at 1000r/min, stirring for 1h, keeping the rotation speed at 2200r/min, stirring for 0.8h, grinding to the fineness of 20 mu m by a grinder, dispersing for 15 min at the rotation speed of 800 r/min, post-curing for 1 day, sampling, inspecting, sieving and packaging after passing, thus obtaining the finished durable waterproof engineering coating.
Example 2
The durable waterproof engineering coating is characterized by being prepared from the following raw materials in parts by weight: 26 parts of allyl thiourea/3-amino-3- (2-pyridine) acrylonitrile/1-vinyl-1, 2, 4-triazole/titanium triisopropoxide methacrylate copolymer, 2.5 parts of epoxy modified 2,4, 6-triphenylborazine hexaalkane, 22 parts of amino-terminated polyurethane, 2 parts of asphalt, 3 parts of vinyl-terminated fluorosilicone oil, 0.7 part of benzoin ethyl ether, 17 parts of pumice powder, 31001.5 parts of defoaming agent, 1.5 parts of polycarboxylic acid sodium salt, 1.5 parts of fatty acid polyoxyethylene ester and 23 parts of pentaerythritol.
The preparation method of the epoxy group modified 2,4, 6-triphenylboron nitrogen hexaalkane comprises the following steps: adding 33.4g of 2,4, 6-triphenylboron nitrogen hexaalkane, 10g of epoxy chloropropane and 6g of sodium carbonate into 170g of N, N-dimethylformamide, stirring and reacting for 6 hours at 45 ℃, filtering to remove the sodium carbonate, and then removing the solvent and unreacted epoxy chloropropane by rotary evaporation to obtain the epoxy group modified 2,4, 6-triphenylboron nitrogen hexaalkane.
The preparation method of the allyl thiourea/3-amino-3- (2-pyridine) acrylonitrile/1-vinyl-1, 2, 4-triazole/titanium triisopropoxide methacrylate copolymer comprises the following steps: 20g of allylthiourea, 10g of 3-amino-3- (2-pyridine) acrylonitrile, 3g of 1-vinyl-1, 2, 4-triazole, 5g of triisopropanolato titanium methacrylate and 0.33g of azobisisoheptonitrile were added to 150g of N-methylpyrrolidone, and the mixture was stirred and reacted at 73 ℃ for 3.5 hours under a helium atmosphere, and then precipitated in water, and the precipitated polymer was dried to a constant weight at 82 ℃ in a vacuum drying oven to obtain an allylthiourea/3-amino-3- (2-pyridine) acrylonitrile/1-vinyl-1, 2, 4-triazole/triisopropanolato titanium methacrylate copolymer.
The preparation method of the durable waterproof engineering coating is characterized by comprising the following steps: mixing the raw materials according to the proportion, keeping the rotation speed at 1050r/min, stirring for 1.2h, keeping the rotation speed at 2250r/min, stirring for 0.9h, grinding to the fineness of 30 mu m by a grinder, dispersing for 16 min at the rotation speed of 850 r/min, post-curing for 1.5 days, sampling, inspecting, sieving and packaging after qualification to obtain the finished product of the durable waterproof engineering coating.
Example 3
The durable waterproof engineering coating is characterized by being prepared from the following raw materials in parts by weight: 28 parts of allyl thiourea/3-amino-3- (2-pyridine) acrylonitrile/1-vinyl-1, 2, 4-triazole/titanium triisopropoxide methacrylate copolymer, 3 parts of epoxy modified 2,4, 6-triphenylboroxine, 25 parts of amino-terminated polyurethane, 2.5 parts of natural asphalt, 3.5 parts of vinyl-terminated fluorosilicone oil, 1 part of 2, 4-dihydroxy benzophenone, 17 parts of bentonite, BYK0882 parts of defoaming agent, 2 parts of sodium hexametaphosphate, 2 parts of ammonium alkylphenol polyethoxy ether sulfate and 25 parts of cyclohexanone.
The preparation method of the epoxy group modified 2,4, 6-triphenylboron nitrogen hexaalkane comprises the following steps: adding 33.4g of 2,4, 6-triphenylboron nitrogen hexaalkane, 10g of epoxy chloropropane and 6.5g of potassium hydroxide into 190g of N, N-dimethylacetamide, stirring and reacting at 50 ℃ for 6.5 hours, filtering to remove potassium hydroxide, and performing rotary evaporation to remove the solvent and unreacted epoxy chloropropane to obtain the epoxy group modified 2,4, 6-triphenylboron nitrogen hexaalkane.
The preparation method of the allyl thiourea/3-amino-3- (2-pyridine) acrylonitrile/1-vinyl-1, 2, 4-triazole/titanium triisopropoxide methacrylate copolymer comprises the following steps: 20g of allylthiourea, 10g of 3-amino-3- (2-pyridine) acrylonitrile, 3g of 1-vinyl-1, 2, 4-triazole, 5g of triisopropanolato titanium methacrylate and 0.35g of azobisisoheptonitrile were added to 160g of N-methylpyrrolidone, and the mixture was stirred and reacted at 75 ℃ for 4 hours in a neon atmosphere, and then precipitated in water, and the precipitated polymer was dried at 85 ℃ in a vacuum drying oven to a constant weight to obtain a copolymer of allylthiourea/3-amino-3- (2-pyridine) acrylonitrile/1-vinyl-1, 2, 4-triazole/triisopropanolato titanium methacrylate.
The preparation method of the durable waterproof engineering coating is characterized by comprising the following steps: mixing the raw materials according to the proportion, keeping the rotation speed at 1100r/min, stirring for 1.5h, keeping the rotation speed at 2300r/min, stirring for 1.2h, grinding to the fineness of 35 mu m by a grinder, dispersing for 17.5 min at the rotation speed of 900 r/min, post-curing for 2 days, sampling, inspecting, sieving and packaging after qualification to obtain the finished product of the durable waterproof engineering coating.
Example 4
The durable waterproof engineering coating is characterized by being prepared from the following raw materials in parts by weight: 29 parts of allyl thiourea/3-amino-3- (2-pyridine) acrylonitrile/1-vinyl-1, 2, 4-triazole/titanium triisopropoxide methacrylate copolymer, 3.5 parts of epoxy modified 2,4, 6-triphenylboroxine, 28 parts of amino-terminated polyurethane, 3 parts of asphalt, 4 parts of vinyl-terminated fluorosilicone oil, 1.4 parts of photoinitiator, 19 parts of filler, 2.7 parts of defoaming agent, 2.8 parts of dispersing agent, 2.5 parts of emulsifier and 28 parts of ethylene glycol ether acetate.
The photoinitiator is prepared by mixing benzoin dimethyl ether, benzoin ethyl ether and 2, 4-dihydroxy benzophenone in a mass ratio of 1:2: 3; the filler is formed by mixing talcum powder, pumice powder, bentonite, montmorillonite and attapulgite according to the mass ratio of 1:1:2:1: 2; the defoaming agent is formed by mixing tributyl phosphate, a defoaming agent Demodex 3100 and a defoaming agent BYK088 according to the mass ratio of 1:2: 4; the dispersing agent is formed by mixing sodium hexametaphosphate and sodium polycarboxylate according to the mass ratio of 3: 5; the emulsifier is formed by mixing sodium dodecyl sulfate, polyoxyethylene fatty acid ester and ammonium alkylphenol polyethenoxy ether sulfate according to the mass ratio of 1:3: 5; the asphalt is formed by mixing petroleum asphalt and natural asphalt according to the mass ratio of 2: 3.
The preparation method of the epoxy group modified 2,4, 6-triphenylboron nitrogen hexaalkane comprises the following steps: adding 33.4g of 2,4, 6-triphenylborazonhexaalkane, 10g of epoxy chloropropane and 7.5g of basic catalyst into 200g of high-boiling-point solvent, stirring and reacting for 6.5 hours at 50 ℃, filtering to remove the basic catalyst, and then performing rotary evaporation to remove the solvent and unreacted epoxy chloropropane to obtain epoxy group modified 2,4, 6-triphenylborazonhexaalkane; the alkaline catalyst is prepared by mixing sodium hydroxide, sodium carbonate, potassium hydroxide and potassium carbonate according to the mass ratio of 1:2:4: 2; the high boiling point solvent is formed by mixing dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone according to a mass ratio of 1:2:4: 2.
The preparation method of the allyl thiourea/3-amino-3- (2-pyridine) acrylonitrile/1-vinyl-1, 2, 4-triazole/titanium triisopropoxide methacrylate copolymer comprises the following steps: adding 20g of allylthiourea, 10g of 3-amino-3- (2-pyridine) acrylonitrile, 3g of 1-vinyl-1, 2, 4-triazole, 5g of titanium triisopropoxide methacrylate and 0.38g of an initiator into 180g of N-methylpyrrolidone, stirring and reacting at 78 ℃ for 4.8 hours under an argon atmosphere, precipitating in water, and drying the precipitated polymer at 88 ℃ in a vacuum drying box to constant weight to obtain the allylthiourea/3-amino-3- (2-pyridine) acrylonitrile/1-vinyl-1, 2, 4-triazole/titanium triisopropoxide methacrylate copolymer; the initiator is formed by mixing azodiisobutyronitrile and azodiisoheptonitrile according to the mass ratio of 3: 5.
The preparation method of the durable waterproof engineering coating is characterized by comprising the following steps: mixing the raw materials according to the proportion, keeping the rotation speed at 1150r/min, stirring for 1.8h, keeping the rotation speed at 2350r/min, stirring for 1.4h, grinding to the fineness of 45 mu m by a grinder, dispersing for 19 min at the rotation speed of 970 rpm, post-curing for 2.5 days, sampling, inspecting, sieving and packaging after being qualified, and obtaining the finished product of the durable waterproof engineering coating.
Example 5
The durable waterproof engineering coating is characterized by being prepared from the following raw materials in parts by weight: 30 parts of allyl thiourea/3-amino-3- (2-pyridine) acrylonitrile/1-vinyl-1, 2, 4-triazole/titanium triisopropoxide methacrylate copolymer, 4 parts of epoxy modified 2,4, 6-triphenylborazine hexaalkane, 30 parts of amino-terminated polyurethane, 4 parts of petroleum asphalt, 5 parts of vinyl-terminated fluorosilicone oil, 1.5 parts of benzoin ethyl ether, 20 parts of montmorillonite, 31003 parts of defoaming agent, 3 parts of polycarboxylic acid sodium salt, 3 parts of fatty acid polyoxyethylene ester and 30 parts of ethylene glycol ethyl ether acetate.
The preparation method of the epoxy group modified 2,4, 6-triphenylboron nitrogen hexaalkane comprises the following steps: adding 33.4g of 2,4, 6-triphenylboron nitrogen hexaalkane, 10g of epoxy chloropropane and 8g of potassium carbonate into 220g of N-methylpyrrolidone, stirring and reacting for 8 hours at 60 ℃, filtering to remove the potassium carbonate, and then removing the solvent and unreacted epoxy chloropropane by rotary evaporation to obtain the epoxy group modified 2,4, 6-triphenylboron nitrogen hexaalkane.
The preparation method of the allyl thiourea/3-amino-3- (2-pyridine) acrylonitrile/1-vinyl-1, 2, 4-triazole/titanium triisopropoxide methacrylate copolymer comprises the following steps: 20g of allylthiourea, 10g of 3-amino-3- (2-pyridine) acrylonitrile, 3g of 1-vinyl-1, 2, 4-triazole, 5g of titanium triisopropoxide methacrylate and 0.4g of azobisisobutyronitrile are added to 200g of N-methylpyrrolidone, stirred and reacted for 5 hours at 80 ℃ in a nitrogen atmosphere, and then precipitated in water, and the precipitated polymer is dried to constant weight at 90 ℃ in a vacuum drying oven to obtain the allylthiourea/3-amino-3- (2-pyridine) acrylonitrile/1-vinyl-1, 2, 4-triazole/titanium triisopropoxide methacrylate copolymer.
The preparation method of the durable waterproof engineering coating is characterized by comprising the following steps: mixing the raw materials according to the proportion, keeping the rotation speed at 1200r/min, stirring for 2h, keeping the rotation speed at 2400r/min, stirring for 1.5h, grinding to the fineness of 50 microns by a grinder, dispersing for 20 min at the rotation speed of 1000r/min, post-curing for 3 days, sampling, inspecting, sieving and packaging after passing, thus obtaining the finished durable waterproof engineering coating.
Comparative example 1
A durable, water-repellent engineering coating having substantially the same formulation as in example 1, except that the allylthiourea/3-amino-3- (2-pyridine) acrylonitrile/1-vinyl-1, 2, 4-triazole/titanium triisopropoxide methacrylate copolymer was not added.
Comparative example 2
A durable waterproof engineering paint was prepared in substantially the same manner and formulation as in example 1, except that no amino-terminated polyurethane was added.
Comparative example 3
A durable waterproof engineering paint is prepared in the same way and formula as in example 1, except that no vinyl-terminated fluorosilicone oil is added.
Comparative example 4
A durable waterproof engineering coating is prepared by the method which is basically the same as the formula of the durable waterproof engineering coating in the embodiment 1, except that epoxy group is not added to modify 2,4, 6-triphenylboron nitrogen hexaalkane.
To further illustrate the advantageous technical effects of the examples of the present invention, performance tests were performed on each of the waterproof coatings of examples 1 to 5 of the present invention and comparative examples 1 to 3, and the test methods and test results are shown in table 1.
TABLE 1
| Item | Adhesion force | Limit of fire resistance | Flexibility | Water resistance after 60 days of soaking | Water permeability |
| Unit of | Stage | min | Stage | — | ml |
| Test standard | GB/T5210 | GB14907-2002 | GB/T1731 | GB/T1733-1993 | GB/T9755-2014 |
| Example 1 | 1 | 51.5 | 1 | No abnormality | 0.20 |
| Example 2 | 1 | 52.9 | 1 | No abnormality | 0.17 |
| Example 3 | 0 | 53.5 | 1 | No abnormality | 0.13 |
| Example 4 | 0 | 54.6 | 1 | No abnormality | 0.10 |
| Example 5 | 0 | 55.5 | 1 | No abnormality | 0.08 |
| Comparative example 1 | 3 | 30.2 | 2 | No abnormality | 0.42 |
| Comparative example 2 | 2 | 31.3 | 3 | No abnormality | 0.39 |
| Comparative example 3 | 3 | 31.0 | 3 | No abnormality | 0.33 |
| Comparative example 4 | 2 | 30.4 | 2 | No abnormality | 0.30 |
As can be seen from Table 1, the durable waterproof engineering coating disclosed by the embodiment of the invention has more excellent fire resistance and flexibility, higher adhesion and more excellent water resistance and impermeability; this is a result of the synergistic effect of the individual starting components.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The durable waterproof engineering coating is characterized by being prepared from the following raw materials in parts by weight: 25-30 parts of allyl thiourea/3-amino-3- (2-pyridine) acrylonitrile/1-vinyl-1, 2, 4-triazole/titanium triisopropoxide methacrylate copolymer, 2-4 parts of epoxy modified 2,4, 6-triphenylborohexaalkane, 20-30 parts of amino-terminated polyurethane, 1-4 parts of asphalt, 2-5 parts of vinyl-terminated fluorosilicone oil, 0.5-1.5 parts of photoinitiator, 15-20 parts of filler, 1-3 parts of defoaming agent, 1-3 parts of dispersing agent, 1-3 parts of emulsifier and 20-30 parts of organic solvent.
2. The durable waterproof engineering paint of claim 1, wherein the photoinitiator is at least one of benzoin dimethyl ether, benzoin ethyl ether, and 2, 4-dihydroxy benzophenone; the filler is at least one of talcum powder, pumice powder, bentonite, montmorillonite and attapulgite; the defoaming agent is one or more of tributyl phosphate, a defoaming agent Demodex 3100 and a defoaming agent BYK 088; the dispersing agent is sodium hexametaphosphate and/or sodium polycarboxylate.
3. The durable waterproof engineering paint of claim 1, wherein the organic solvent is one of isopropyl alcohol, pentaerythritol, cyclohexanone, ethylene glycol monoethyl ether acetate; the emulsifier is at least one of sodium dodecyl sulfate, polyoxyethylene fatty acid ester and ammonium alkylphenol polyethoxy ether sulfate; the asphalt is at least one of petroleum asphalt and natural asphalt.
4. The durable waterproof engineered coating of claim 1, wherein said amino-terminated polyurethane has an average molecular weight of 1836; the number average molecular weight of the vinyl-terminated fluorosilicone oil is 3.6 ten thousand.
5. The durable waterproof engineering coating of claim 1, wherein the preparation method of the epoxy-modified 2,4, 6-triphenylboroazahexaalkane comprises the following steps: adding 2,4, 6-triphenylboron nitrogen hexaalkane, epoxy chloropropane and an alkaline catalyst into a high-boiling-point solvent, stirring and reacting for 5-8 hours at 40-60 ℃, filtering to remove the alkaline catalyst, and then removing the solvent and unreacted epoxy chloropropane by rotary evaporation to obtain the epoxy group modified 2,4, 6-triphenylboron nitrogen hexaalkane.
6. The durable waterproof engineering paint according to claim 5, wherein the mass ratio of the 2,4, 6-triphenylboroazahexaalkane, the epichlorohydrin, the basic catalyst and the high-boiling-point solvent is 3.34:1 (0.5-0.8) to (15-22).
7. The durable waterproof engineering paint of claim 5, wherein the basic catalyst is at least one of sodium hydroxide, sodium carbonate, potassium hydroxide and potassium carbonate; the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
8. The durable waterproof engineering paint of claim 1, wherein the preparation method of the copolymer of allylthiourea/3-amino-3- (2-pyridine) acrylonitrile/1-vinyl-1, 2, 4-triazole/titanium triisopropoxide methacrylate comprises the following steps: adding allylthiourea, 3-amino-3- (2-pyridine) acrylonitrile, 1-vinyl-1, 2, 4-triazole, titanium triisopropoxide methacrylate and an initiator into N-methylpyrrolidone, stirring and reacting for 3-5 hours at 70-80 ℃ in a nitrogen or inert gas atmosphere, then precipitating in water, and drying the precipitated polymer at 80-90 ℃ in a vacuum drying box to constant weight to obtain the copolymer of allylthiourea/3-amino-3- (2-pyridine) acrylonitrile/1-vinyl-1, 2, 4-triazole/titanium triisopropoxide methacrylate.
9. The durable waterproof engineering paint according to claim 8, wherein the mass ratio of the allylthiourea, the 3-amino-3- (2-pyridine) acrylonitrile, the 1-vinyl-1, 2, 4-triazole, the titanium triisopropoxide methacrylate to the initiator to the N-methylpyrrolidone is 2:1:0.3:0.5 (0.03-0.04) to (13-20); the initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile; the inert gas is one of helium, neon and argon.
10. A durable water-repellent engineering paint according to any one of claims 1 to 9, characterized in that the process for the preparation of said durable water-repellent engineering paint comprises the following steps: mixing the raw materials according to the proportion, keeping the rotation speed at 1000-1200r/min, stirring for 1-2h, then keeping the rotation speed at 2200-2400r/min, stirring for 0.8-1.5h, then grinding by a grinder until the fineness is 20-50 μm, dispersing for 15-20 min at the rotation speed of 800-1000 r/min, post-curing for 1-3 days, sampling and inspecting, sieving and packaging after passing, and obtaining the finished durable waterproof engineering coating.
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