CN117363130A - Water-based heat-insulating weather-resistant waterproof coating and preparation method thereof - Google Patents
Water-based heat-insulating weather-resistant waterproof coating and preparation method thereof Download PDFInfo
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- CN117363130A CN117363130A CN202311343508.7A CN202311343508A CN117363130A CN 117363130 A CN117363130 A CN 117363130A CN 202311343508 A CN202311343508 A CN 202311343508A CN 117363130 A CN117363130 A CN 117363130A
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- resistant waterproof
- based heat
- epoxy emulsion
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000000576 coating method Methods 0.000 title claims abstract description 60
- 239000011248 coating agent Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000839 emulsion Substances 0.000 claims abstract description 63
- 239000004593 Epoxy Substances 0.000 claims abstract description 59
- 125000000129 anionic group Chemical group 0.000 claims abstract description 55
- 239000003822 epoxy resin Substances 0.000 claims abstract description 37
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 37
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 32
- 239000011737 fluorine Substances 0.000 claims abstract description 32
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- KQOIBXZRCYFZSO-UHFFFAOYSA-N 3,5-difluoroaniline Chemical compound NC1=CC(F)=CC(F)=C1 KQOIBXZRCYFZSO-UHFFFAOYSA-N 0.000 claims abstract description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 40
- 239000003973 paint Substances 0.000 claims description 38
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 34
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000003960 organic solvent Substances 0.000 claims description 21
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 claims description 19
- 238000004321 preservation Methods 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 18
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 12
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 11
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 9
- 239000012528 membrane Substances 0.000 claims description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000006260 foam Substances 0.000 claims description 7
- 239000003517 fume Substances 0.000 claims description 7
- 239000012948 isocyanate Substances 0.000 claims description 7
- 150000002513 isocyanates Chemical class 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000009775 high-speed stirring Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 12
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract description 10
- 238000009413 insulation Methods 0.000 abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical class C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 abstract 2
- YNGRGHODNDCZCC-UHFFFAOYSA-N nitro hydrogen sulfate Chemical compound OS(=O)(=O)O[N+]([O-])=O YNGRGHODNDCZCC-UHFFFAOYSA-N 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 24
- 238000012360 testing method Methods 0.000 description 23
- 230000000694 effects Effects 0.000 description 18
- 238000001914 filtration Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000005465 channeling Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a water-based heat-insulating weather-resistant waterproof coating and a preparation method thereof. The preparation method of the water-based heat-insulating weather-resistant waterproof coating comprises the following steps of (1) preparing anionic water-based epoxy emulsion by using epoxy resin as a basic raw material; step (2) taking 3, 5-difluoroaniline as a raw material, and synthesizing a fluorine-containing polynitroazobenzene derivative under a nitrosulfuric acid mixed system; and (3) adding the obtained fluorine-containing polynitroazobenzene derivative into the anionic water-based epoxy emulsion after photoinitiation, and adding a curing agent to obtain the water-based heat-insulating weather-resistant waterproof coating. The invention firstly prepares the anionic aqueous epoxy emulsion with certain stability and wear resistance, but as the anionic aqueous epoxy emulsion has hydrophilic groups, the azobenzene derivative containing fluorine atoms and nitro groups is prepared, and after the anionic aqueous epoxy emulsion and the azobenzene derivative are combined, hydroxyl groups are substituted, so that the coating with heat insulation, weather resistance, hydrophobicity and certain stability and wear resistance is obtained.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a water-based heat-insulating weather-resistant waterproof coating and a preparation method thereof.
Background
Along with the development of modern economy, the coating is widely applied in daily life, epoxy resin serving as one of raw materials is widely applied due to good thermal stability and mechanical strength, but due to the solvent characteristic, the coating is easy to generate shrinkage cavity and other defects, meanwhile, after water is evaporated, tiny pores are left on the surface of the coating, so that water molecules and other corrosive media in the air can invade the surface of a substrate along with the tiny gaps to corrode the substrate, and the coating does not have the characteristics of heat insulation and weather resistance, so that the application range of the coating is limited, and people focus on modifying the coating taking the epoxy resin as the raw material to improve the heat insulation, weather resistance and water resistance of the coating.
Patent CN 103254752A proposes a preparation method of a water-based polyurethane weather-resistant elastic waterproof coating, which takes PU resin as a raw material of a water-based polyurethane prepolymer, and takes 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate as a film forming auxiliary agent to prepare the water-based polyurethane weather-resistant elastic waterproof coating without coal tar and toluene solvent, thereby solving the problems of complicated use process, low elasticity, poor crack resistance and poor ultraviolet radiation resistance of the coating; patent CN 114958049A proposes a weather-resistant roof waterproof paint with heat insulation and preservation functions, and the formula of the paint is as follows: 20-40 parts of pure acrylic emulsion, 40-80 parts of butyl emulsion, 300-500 parts of white cement, 600-800 parts of calcium sand, 40-80 parts of vitrified micro bubble, 20-60 parts of infrared ceramic powder, 100-200 parts of heavy calcium powder, 50-100 parts of talcum powder, and dispersing agent, multifunctional auxiliary agent, dry powder defoamer and water reducer. The paint only needs to be coated on the surface of the roof cement protective layer, has light dead weight and no load influence, has flexibility of organic materials, has rigidity, water-foaming resistance and corrosion resistance of inorganic materials, and has heat insulation and heat preservation functions. The two coatings cannot have heat insulation, weather resistance and water resistance at the same time, and therefore, the components and the preparation method of the coatings need to be improved.
Disclosure of Invention
The invention aims to provide a preparation method of an environment-friendly flame-retardant modified composite plastic product, which is used for solving the technical problems of heat insulation, weather resistance and water resistance in the prior art.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention provides a preparation method of an environment-friendly flame-retardant modified composite plastic product, which comprises the following steps:
step (1) adding epoxy resin into a three-neck flask provided with a constant-pressure dropping funnel and a condenser pipe, then adding an organic solvent, heating the three-neck flask and rapidly stirring to uniformly mix the epoxy resin and the organic solvent; placing alpha-methacrylic acid, butyl acrylate, styrene and benzoyl peroxide into a beaker, stirring and mixing uniformly, transferring into a constant-pressure dropping funnel, heating the three-neck flask, dropwise adding the mixture into the mixture of the epoxy resin and the organic solvent, controlling the dropwise adding time, and carrying out heat preservation reaction after the dropwise adding is finished; cooling after the heat preservation reaction is finished to obtain anionic epoxy emulsion, then dropwise adding an aqueous solution of N, N-dimethylethanolamine under high-speed stirring, and continuously stirring after the dropwise adding is finished to obtain anionic aqueous epoxy emulsion;
in the process, the anionic aqueous epoxy emulsion is prepared by taking epoxy resin, alpha-methacrylic acid, butyl acrylate and styrene as raw materials through a free radical polymerization method, and the mechanism is shown as the following formula:
the solvent formed by the anionic aqueous epoxy emulsion is water, so that the environment-friendly aqueous epoxy emulsion has the advantages that the dispersion system is favorable for improving the stability of the epoxy resin, so that the epoxy resin is more stable in the storage and construction process, the particle size of the aqueous epoxy emulsion is smaller, and the wear resistance and the permeation resistance of the coating can be improved; the negative charge in the anionic water-based epoxy emulsion is beneficial to reducing the static charge on the surface of the paint, reducing the attractive force between the paints, further improving the stability of the paint, and in addition, the negative charge in the anionic water-based epoxy emulsion can neutralize the positive charge on the surface of the paint, reduce the adsorbed moisture on the surface of the paint and improve the water resistance of the paint.
Dropwise adding a nitric acid solution into a cooled three-neck flask containing a sulfuric acid solution, controlling the temperature of a system in the dropwise adding process, adding 3, 5-difluoroaniline in batches after the dropwise adding is finished, then carrying out gradient heating, carrying out heat preservation reaction when orange foam and yellow solid are generated in the three-neck flask, then naturally cooling, pouring the reacted mixed solution into crushed ice, precipitating the yellow solid, carrying out suction filtration, washing to neutrality, and drying to obtain the fluorine-containing polynitroazobenzene derivative;
in the above process, the mechanism of the fluorine-containing polynitroazobenzene derivative is shown as the following formula:
and (3) dissolving the obtained fluorine-containing polynitroazobenzene derivative in an organic solvent, exposing the fluorine-containing polynitroazobenzene derivative to ultraviolet light, then placing the exposed substance in a fume hood, completely adding the residual substance into an anionic aqueous epoxy emulsion after the organic solvent is completely volatilized, performing ultrasonic dispersion to uniformly disperse the residual substance in the anionic aqueous epoxy emulsion, then adding a curing agent, uniformly mixing, and aging to obtain the water-based heat-insulating weather-resistant waterproof coating.
In the process, the fluorine-containing polynitroazobenzene derivative is firstly exposed under the ultraviolet light condition, the light energy excites chemical bonds in fluorine-containing polynitroazobenzene derivative molecules to enable the fluorine-containing polynitroazobenzene derivative molecules to transit to an excited state, then the excited state fluorine-containing polynitroazobenzene derivative molecules transit to an excited triplet state through intersystem channeling, then free radicals are generated through a thermodynamic way, the generation of the free radicals can react with hydroxyl groups and carbonyl groups in the anionic aqueous epoxy emulsion, and therefore fluorine atoms and nitro groups are led into the anionic aqueous epoxy emulsion.
The fluorine atoms have strong electronegativity and can form stable chemical bonds with hydrogen atoms, so that overflow of hydrogen is reduced, and the weather resistance of the coating is improved; the introduction of fluorine atoms and nitro groups can improve the thermal stability of the coating, and the heat absorption effect of the fluorine atoms and the nitro groups reduces the glass transition temperature of the epoxy emulsion, so that the coating can still keep good fluidity at high temperature; the introduction of fluorine atoms and nitro groups can also increase the density of the coating and reduce the heat conduction performance of the coating; in addition, the introduction of fluorine atoms and nitro groups increases the complexity of the structure, creating a steric hindrance effect that impedes the interaction between water molecules and hydrophobic groups, thereby increasing the hydrophobicity of the coating.
Preferably, in the step (1), the epoxy resin is epoxy resin E-44, the molecular weight is 1000-3000, the organic solvent is n-butanol, the purity is 99%, the volume ratio of the epoxy resin to the organic solvent is 1:3-4, the heating temperature is 60-80 ℃, and the rapid stirring time is 10-18min.
Preferably, in the step (1), the ratio of the epoxy resin, the α -methacrylic acid, the butyl acrylate, the styrene and the benzoyl peroxide is 1L: (0.2-0.3) L: (0.08-0.12) L: (0.06-0.08) L: (0.07-0.09) g, the purity of alpha-methacrylic acid was 99%, the purity of butyl acrylate was 96%, the purity of styrene was 98%, and the purity of benzoyl peroxide was 95%.
Preferably, in the step (1), the three-neck flask is heated to a temperature of 110-120 ℃, the dripping time is 0.5-1h, and the heat preservation reaction time is 5-6h.
Preferably, in the step (1), the temperature is reduced by 50-60 ℃, the high-speed stirring speed is 200-300rpm, and the volume ratio of the anionic epoxy emulsion to the aqueous solution of N, N-dimethylethanolamine is 20: the concentration of the aqueous solution of the 1, N-dimethylethanolamine is 83vt percent, and the continuous stirring time is 25-35min.
Preferably, in the step (2), the concentration of the sulfuric acid solution is 98vt%, the cooling temperature is 8-12 ℃, the concentration of the nitric acid solution is 95vt%, and the volume ratio of sulfuric acid to nitric acid is 1:0.06-0.075, and controlling the temperature of the system to be lower than 20 ℃.
Preferably, in the step (2), the mass ratio of 3, 5-difluoroaniline to sulfuric acid is 1:80-90, wherein the gradient heating rate is 5 ℃/min, the final temperature is 80-85 ℃, the reaction time is 3-5h, the cooling temperature is 25-30 ℃, the crushed ice mass is 200-400g, and the suction filtration conditions are as follows: the pore diameter of the filter membrane is 0.45 mu m, the suction filtration speed is 10mL/min, the filter membrane is washed by deionized water, the drying temperature is 25-30 ℃, and the drying time is 12-15h.
Preferably, in the step (3), the organic solvent is acetone with the purity of 99%, the wavelength range of ultraviolet light is 200-400nm, the exposure time is 60-120s, and the ratio of the fluorine-containing polynitroazobenzene derivative to the anionic aqueous epoxy emulsion is 0.1kg: (1.0-1.3) L, the ultrasonic dispersion time is 30-50s, the curing agent is commercially available N3300 isocyanate curing agent, and the aging time is 30-45min.
The water-based heat-insulating weather-resistant waterproof coating prepared by the preparation method of the water-based heat-insulating weather-resistant waterproof coating.
In summary, due to the adoption of the technical scheme, the beneficial effects of the invention are as follows:
1. according to the invention, epoxy resin E-44 is used as a raw material, and is reacted with alpha-methacrylic acid, butyl acrylate and styrene to generate anionic aqueous epoxy emulsion with certain stability and wear resistance.
2. According to the invention, the anionic aqueous epoxy emulsion is prepared by using the epoxy resin E-44, alpha-methacrylic acid, butyl acrylate and styrene through a free radical polymerization method, the solvent formed by the emulsion is water, the emulsion has environmental protection, the particle size of the formed anionic aqueous epoxy emulsion is smaller, the paint has good wear resistance and permeation resistance, and negative charge in the anionic aqueous epoxy emulsion is beneficial to reducing the electrostatic charge on the surface of the paint, reducing the attractive force between the paints and increasing the stability of the paint.
3. The fluorine-containing multi-nitro azobenzene derivative with fluorine atoms and nitro groups is selected to modify the anionic water-based epoxy emulsion, the fluorine atoms have strong electronegativity, stable chemical bonds can be formed with hydrogen atoms, overflow of hydrogen is reduced, and weather resistance of the coating can be improved; the glass transition temperature of the epoxy emulsion is reduced due to the endothermic effect of fluorine atoms and nitro groups, so that the thermal stability of the coating is improved; the introduction of fluorine atoms and nitro groups can also increase the density of the coating and reduce the heat conduction performance of the coating; the introduction of fluorine atoms and nitro groups increases the complexity of the structure, creating a steric hindrance effect that impedes the interaction between water molecules and hydrophobic groups, thereby enhancing the hydrophobicity of the coating.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a preparation method of the water-based heat-insulating weather-resistant waterproof coating.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described 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.
Example 1
Referring to fig. 1, the embodiment discloses a preparation method of a water-based heat-insulating weather-resistant waterproof coating, which comprises the following steps:
step (1), adding 1L of epoxy resin E-44 (with the molecular weight of 1000-3000) into a three-neck flask with a constant pressure dropping funnel and a condenser, then adding 3L of n-butanol with the purity of 99%, heating the three-neck flask to 60 ℃ and rapidly stirring for 15min, so that the epoxy resin E-44 and the n-butanol are uniformly mixed; taking 0.25L of alpha-methacrylic acid with the purity of 99%, 0.1L of butyl acrylate with the purity of 96%, 0.07L of styrene with the purity of 98% and 0.08g of benzoyl peroxide with the purity of 95%, placing the materials into a beaker, stirring and mixing the materials uniformly, transferring the materials into a constant-pressure dropping funnel, heating the three-neck flask to the temperature of 110 ℃, dropwise adding the mixture into a mixture of epoxy resin E-44 and n-butanol, controlling the dropwise adding time to be 0.5h, and carrying out heat preservation reaction for 5h after the dropwise adding is finished; after the heat preservation reaction is finished, cooling to 55 ℃ to obtain anionic epoxy emulsion, then dropwise adding 0.05L of an aqueous solution of N, N-dimethylethanolamine with the concentration of 83vt percent at the rotation speed of 300rpm, and continuously stirring for 30min after the dropwise adding is finished to obtain anionic aqueous epoxy emulsion;
dropwise adding 4.2mL of 95vt percent nitric acid solution into a three-neck flask containing 60mL of 98vt percent sulfuric acid solution and cooled to 10 ℃, controlling the temperature of a system to be lower than 20 ℃ in the dropping process, adding 1.29g of 3, 5-difluoroaniline in batches after the dropping is finished, then heating to 85 ℃ in a gradient way at a temperature of 5 ℃/min, keeping the temperature for reaction for 3 hours when orange foam and yellow solid are generated in the three-neck flask, naturally cooling to 25 ℃, pouring the reacted mixed solution into crushed ice to separate out yellow solid, filtering (the aperture of a filter membrane is 0.45 mu m, the filtering speed is 10 mL/min), washing to be neutral by deionized water, and drying at 30 ℃ for 15 hours to obtain the fluorine-containing polynitroazobenzene derivative;
and (3) dissolving the obtained fluorine-containing polynitroazobenzene derivative in acetone with the purity of 99%, exposing the acetone to ultraviolet light with the wavelength range of 200-400nm for 120s, then placing the exposed substance in a fume hood, completely adding 0.1kg of residual substance into 1.1L of anionic aqueous epoxy emulsion after the organic solvent is completely volatilized, performing ultrasonic dispersion for 50s to uniformly disperse the residual substance in the anionic aqueous epoxy emulsion, then adding a commercially available N3300 isocyanate curing agent, uniformly mixing, and aging for 30min to obtain the water-based heat-insulating weather-resistant waterproof paint.
Example 2
Referring to fig. 1, the embodiment discloses a preparation method of an environment-friendly flame-retardant modified composite plastic product, which comprises the following steps:
step (1), adding 1L of epoxy resin E-44 (with the molecular weight of 1000-3000) into a three-neck flask with a constant pressure dropping funnel and a condenser, then adding 4L of n-butanol with the purity of 99%, heating the three-neck flask to 60 ℃ and rapidly stirring for 15min, so that the epoxy resin E-44 and the n-butanol are uniformly mixed; taking 0.3L of alpha-methacrylic acid with the purity of 99%, 0.12L of butyl acrylate with the purity of 96%, 0.08L of styrene with the purity of 98% and 0.09g of benzoyl peroxide with the purity of 95%, placing the mixture into a beaker, stirring and uniformly mixing the mixture, transferring the mixture into a constant-pressure dropping funnel, heating the three-neck flask to the temperature of 110 ℃, dropwise adding the mixture into a mixture of epoxy resin E-44 and n-butanol, controlling the dropwise adding time to be 0.5h, and carrying out heat preservation reaction for 5h after the dropwise adding is finished; after the heat preservation reaction is finished, cooling to 55 ℃ to obtain anionic epoxy emulsion, then dropwise adding 0.05L of an aqueous solution of N, N-dimethylethanolamine with the concentration of 83vt percent at the rotation speed of 300rpm, and continuously stirring for 30min after the dropwise adding is finished to obtain anionic aqueous epoxy emulsion;
dropwise adding 4.5mL of 95vt percent nitric acid solution into a three-neck flask containing 60mL of 98vt percent sulfuric acid solution and cooled to 10 ℃, controlling the temperature of a system to be lower than 20 ℃ in the dropping process, adding 1.29g of 3, 5-difluoroaniline in batches after the dropping is finished, then heating to 85 ℃ in a gradient way at a temperature of 5 ℃/min, keeping the temperature for reaction for 3 hours when orange foam and yellow solid are generated in the three-neck flask, naturally cooling to 25 ℃, pouring the reacted mixed solution into crushed ice to separate out yellow solid, filtering (the aperture of a filter membrane is 0.45 mu m, the filtering speed is 10 mL/min), washing to be neutral by deionized water, and drying at 30 ℃ for 15 hours to obtain the fluorine-containing polynitroazobenzene derivative;
and (3) dissolving the obtained fluorine-containing polynitroazobenzene derivative in acetone with the purity of 99%, exposing the acetone to ultraviolet light with the wavelength range of 200-400nm for 120s, then placing the exposed substance in a fume hood, completely adding 0.1kg of residual substance into 1.3L of anionic aqueous epoxy emulsion after the organic solvent is completely volatilized, performing ultrasonic dispersion for 50s to uniformly disperse the residual substance in the anionic aqueous epoxy emulsion, then adding a commercially available N3300 isocyanate curing agent, uniformly mixing, and aging for 30min to obtain the water-based heat-insulating weather-resistant waterproof paint.
Example 3
Referring to fig. 1, the embodiment discloses a preparation method of an environment-friendly flame-retardant modified composite plastic product, which comprises the following steps:
step (1), adding 1L of epoxy resin E-44 (with the molecular weight of 1000-3000) into a three-neck flask with a constant pressure dropping funnel and a condenser, then adding 3.5L of n-butanol with the purity of 99%, heating the three-neck flask to 60 ℃ and rapidly stirring for 15min, so that the epoxy resin E-44 and the n-butanol are uniformly mixed; taking 0.2L of alpha-methacrylic acid with the purity of 99%, 0.08L of butyl acrylate with the purity of 96%, 0.06L of styrene with the purity of 98% and 0.07g of benzoyl peroxide with the purity of 95%, placing the materials into a beaker, stirring and mixing the materials uniformly, transferring the materials into a constant-pressure dropping funnel, heating the three-neck flask to the temperature of 110 ℃, dropwise adding the mixture into a mixture of epoxy resin E-44 and n-butanol, controlling the dropwise adding time to be 0.5h, and carrying out heat preservation reaction for 5h after the dropwise adding is finished; after the heat preservation reaction is finished, cooling to 55 ℃ to obtain anionic epoxy emulsion, then dropwise adding 0.05L of an aqueous solution of N, N-dimethylethanolamine with the concentration of 83vt percent at the rotation speed of 300rpm, and continuously stirring for 30min after the dropwise adding is finished to obtain anionic aqueous epoxy emulsion;
dropwise adding 3.6mL of 95vt percent nitric acid solution into a three-neck flask containing 60mL of 98vt percent sulfuric acid solution and cooled to 10 ℃, controlling the temperature of a system to be lower than 20 ℃ in the dropwise adding process, adding 1.29g of 3, 5-difluoroaniline in batches after the dropwise adding, then heating to 85 ℃ in a gradient way at a temperature of 5 ℃/min, keeping the temperature for reaction for 3 hours when orange foam and yellow solid are generated in the three-neck flask, naturally cooling to 25 ℃, pouring the reacted mixed solution into crushed ice to separate out yellow solid, filtering (the aperture of a filter membrane is 0.45 mu m, the filtering speed is 10 mL/min), washing to be neutral by deionized water, and drying at 30 ℃ for 15 hours to obtain the fluorine-containing polynitroazobenzene derivative;
and (3) dissolving the obtained fluorine-containing polynitroazobenzene derivative in acetone with the purity of 99%, exposing the acetone to ultraviolet light with the wavelength range of 200-400nm for 120s, then placing the exposed substance in a fume hood, completely adding 0.1kg of residual substance into 1.0L of anionic aqueous epoxy emulsion after the organic solvent is completely volatilized, performing ultrasonic dispersion for 50s to uniformly disperse the residual substance in the anionic aqueous epoxy emulsion, then adding a commercially available N3300 isocyanate curing agent, uniformly mixing, and aging for 30min to obtain the water-based heat-insulating weather-resistant waterproof paint.
Example 4
Referring to fig. 1, the embodiment discloses a preparation method of an environment-friendly flame-retardant modified composite plastic product, which comprises the following steps:
step (1), adding 1L of epoxy resin E-44 (with the molecular weight of 1000-3000) into a three-neck flask with a constant pressure dropping funnel and a condenser, then adding 3.7L of n-butanol with the purity of 99%, heating the three-neck flask to 60 ℃ and rapidly stirring for 15min, so that the epoxy resin E-44 and the n-butanol are uniformly mixed; taking 0.28L of alpha-methacrylic acid with the purity of 99%, 0.11L of butyl acrylate with the purity of 96%, 0.065L of styrene with the purity of 98% and 0.078g of benzoyl peroxide with the purity of 95%, placing the mixture into a beaker, stirring and mixing the mixture uniformly, transferring the mixture into a constant pressure dropping funnel, heating the three-neck flask to the temperature of 110 ℃, dropwise adding the mixture into a mixture of epoxy resin E-44 and n-butanol, controlling the dropwise adding time to be 0.5h, and carrying out heat preservation reaction for 5h after the dropwise adding is finished; after the heat preservation reaction is finished, cooling to 55 ℃ to obtain anionic epoxy emulsion, then dropwise adding 0.05L of an aqueous solution of N, N-dimethylethanolamine with the concentration of 83vt percent at the rotation speed of 300rpm, and continuously stirring for 30min after the dropwise adding is finished to obtain anionic aqueous epoxy emulsion;
dropwise adding 4.2mL of 95vt percent nitric acid solution into a three-neck flask containing 60mL of 98vt percent sulfuric acid solution and cooled to 10 ℃, controlling the temperature of a system to be lower than 20 ℃ in the dropping process, adding 1.29g of 3, 5-difluoroaniline in batches after the dropping is finished, then heating to 85 ℃ in a gradient way at a temperature of 5 ℃/min, keeping the temperature for reaction for 3 hours when orange foam and yellow solid are generated in the three-neck flask, naturally cooling to 25 ℃, pouring the reacted mixed solution into crushed ice to separate out yellow solid, filtering (the aperture of a filter membrane is 0.45 mu m, the filtering speed is 10 mL/min), washing to be neutral by deionized water, and drying at 30 ℃ for 15 hours to obtain the fluorine-containing polynitroazobenzene derivative;
and (3) dissolving the obtained fluorine-containing polynitroazobenzene derivative in acetone with the purity of 99%, exposing the acetone to ultraviolet light with the wavelength range of 200-400nm for 120s, then placing the exposed substance in a fume hood, completely adding 0.1kg of residual substance into 1.2L of anionic aqueous epoxy emulsion after the organic solvent is completely volatilized, performing ultrasonic dispersion for 50s to uniformly disperse the residual substance in the anionic aqueous epoxy emulsion, then adding a commercially available N3300 isocyanate curing agent, uniformly mixing, and aging for 30min to obtain the water-based heat-insulating weather-resistant waterproof paint.
Example 5
Referring to fig. 1, the embodiment discloses a preparation method of an environment-friendly flame-retardant modified composite plastic product, which comprises the following steps:
step (1), adding 1L of epoxy resin E-44 (with the molecular weight of 1000-3000) into a three-neck flask with a constant pressure dropping funnel and a condenser, then adding 3.6L of n-butanol with the purity of 99%, heating the three-neck flask to 60 ℃ and rapidly stirring for 15min, so that the epoxy resin E-44 and the n-butanol are uniformly mixed; taking 0.22L of alpha-methacrylic acid with the purity of 99%, 0.084L of butyl acrylate with the purity of 96%, 0.067L of styrene with the purity of 98% and 0.088g of benzoyl peroxide with the purity of 95%, placing the materials into a beaker, stirring and mixing the materials uniformly, transferring the materials into a constant-pressure dropping funnel, heating the three-neck flask to the temperature of 110 ℃, dropwise adding the mixture into a mixture of epoxy resin E-44 and n-butanol, controlling the dropwise adding time to be 0.5h, and carrying out heat preservation reaction for 5h after the dropwise adding is finished; after the heat preservation reaction is finished, cooling to 55 ℃ to obtain anionic epoxy emulsion, then dropwise adding 0.05L of an aqueous solution of N, N-dimethylethanolamine with the concentration of 83vt percent at the rotation speed of 300rpm, and continuously stirring for 30min after the dropwise adding is finished to obtain anionic aqueous epoxy emulsion;
dropwise adding 4.12mL of 95vt percent nitric acid solution into a three-neck flask containing 60mL of 98vt percent sulfuric acid solution and cooled to 10 ℃, controlling the temperature of a system to be lower than 20 ℃ in the dropping process, adding 1.29g of 3, 5-difluoroaniline in batches after the dropping is finished, then heating to 85 ℃ in a gradient way at a temperature of 5 ℃/min, keeping the temperature for reaction for 3 hours when orange foam and yellow solid are generated in the three-neck flask, naturally cooling to 25 ℃, pouring the reacted mixed solution into crushed ice to separate out yellow solid, filtering (the aperture of a filter membrane is 0.45 mu m, the filtering speed is 10 mL/min), washing to be neutral by deionized water, and drying at 30 ℃ for 15 hours to obtain the fluorine-containing polynitroazobenzene derivative;
and (3) dissolving the obtained fluorine-containing polynitroazobenzene derivative in acetone with the purity of 99%, exposing the acetone to ultraviolet light with the wavelength range of 200-400nm for 120s, then placing the exposed substance in a fume hood, completely adding 0.1kg of residual substance into 1.15L of anionic aqueous epoxy emulsion after the organic solvent is completely volatilized, performing ultrasonic dispersion for 50s to uniformly disperse the residual substance in the anionic aqueous epoxy emulsion, then adding a commercially available N3300 isocyanate curing agent, uniformly mixing, and aging for 30min to obtain the water-based heat-insulating weather-resistant waterproof paint.
Comparative example 1
Comparative example 1 in comparison with example 1, comparative example 1 was prepared without adding alpha-methacrylic acid during the preparation of the anionic aqueous epoxy emulsion, and the other conditions were unchanged.
Comparative example 2
Comparative example 2 in comparison with example 1, the prepared fluorine-containing polynitroazobenzene derivative was directly reacted with an anionic aqueous epoxy emulsion without photoinitiation to prepare a coating, and the other conditions were unchanged.
Experimental example
The properties of the aqueous heat-insulating weather-resistant waterproof coatings prepared in examples 1 to 5 and comparative examples 1 to 2 were tested.
1. Test of thermal insulation effect
The obtained water-based heat-insulating weather-proof waterproof paint is uniformly coated on a standard test board, after standing for 24 hours at room temperature, a probe of a heat conductivity coefficient tester (DZDR-S, nanjing Dazhu detection instrument Co., ltd.) is placed on the surface of the coating, and the heat conductivity coefficient of the paint is measured by applying a certain temperature gradient to the probe, and the test result is shown in the following table:
TABLE 1
As can be seen from the test results in Table 1, the coatings prepared in examples 1 to 5 of the present invention have excellent heat insulating effect. As is clear from comparison of comparative example 1 and examples 1 to 5, the absence of added α -methacrylic acid as a raw material of the anionic aqueous epoxy emulsion reduces the heat insulating effect of the coating; as is evident from a comparison of comparative example 2 and examples 1-5, the fluorine-containing polynitroazobenzene derivatives without photoinitiation reduced the heat insulating effect of the coating.
2. Weather resistance test
The obtained water-based heat-insulating weather-proof waterproof paint is uniformly coated on a standard test board, the test board is exposed to ultraviolet irradiation after standing for 24 hours at room temperature, the integrity change of the coating within three weeks is observed, and the test results are shown in the following table:
TABLE 2
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 | |
| Coating integrity/% | 98.4 | 98.1 | 98.0 | 97.6 | 97.7 | 93.3 | 93.1 |
As can be seen from the test results in Table 2, the coatings prepared in examples 1 to 5 of the present invention have excellent weather-resistant effects. From comparison of comparative example 1 and examples 1 to 5, it is known that the absence of the addition of α -methacrylic acid as a raw material of the anionic aqueous epoxy emulsion reduces the weather-resistant effect of the paint; as is evident from the comparison of comparative example 2 and examples 1 to 5, the fluorine-containing polynitroazobenzene derivative without photoinitiation reduces the weather-resistant effect of the coating.
3. Waterproof effect test
Uniformly coating the obtained water-based heat-insulating weather-proof waterproof paint on a standard test board, standing for 24 hours at room temperature, placing the test board under a water spraying device, and observing whether water drops or water stains appear on the surface of the coating by applying a certain pressure and a certain distance of water column to the test board, wherein the test results are shown in the following table:
TABLE 3 Table 3
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 | |
| Whether or not water drops or water stains appear | Whether or not | Whether or not | Whether or not | Whether or not | Whether or not | Is that | Is that |
As can be seen from the test results in Table 3, the coatings prepared in examples 1 to 5 of the present invention have excellent waterproof effects. As is clear from comparison of comparative example 1 and examples 1 to 5, the absence of added α -methacrylic acid as a raw material of the anionic aqueous epoxy emulsion reduces the water-repellent effect of the paint; as is evident from the comparison of comparative example 2 and examples 1 to 5, the fluorine-containing polynitroazobenzene derivative without photoinitiation reduces the water-repellent effect of the paint.
4. Stabilization effect test
After the obtained water-based heat-insulating weather-proof waterproof paint is kept at 85 ℃ for 2 hours, whether the paint layer is precipitated or not is observed, and the test result is shown in the following table:
TABLE 4 Table 4
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 | |
| Whether or not precipitation occurs | Whether or not | Whether or not | Whether or not | Whether or not | Whether or not | Is that | Is that |
As can be seen from the test results in Table 4, the coatings prepared in examples 1 to 5 of the present invention have excellent stabilizing effect. From comparison of comparative example 1 and examples 1 to 5, it is known that the absence of the addition of α -methacrylic acid as a raw material of the anionic aqueous epoxy emulsion reduces the stabilizing effect of the paint; as is evident from the comparison of comparative example 2 and examples 1 to 5, the fluorine-containing polynitroazobenzene derivative without photoinitiation reduces the stabilizing effect of the paint.
5. Wear resistance effect test
Uniformly coating the obtained water-based heat-insulating weather-proof waterproof paint on a standard test board, standing for 24 hours at room temperature, rubbing the surface of the coating by using a grinding wheel with certain pressure and abrasive particles, observing the abrasion degree of the coating after 6 hours, and testing the abrasion degree of the coating, wherein the test results are shown in the following table:
TABLE 5
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 | |
| Wear rate/% | 1.1 | 1.4 | 1.6 | 1.6 | 1.8 | 3.7 | 4.1 |
As can be seen from the test results in Table 5, the coatings prepared in examples 1 to 5 of the present invention have excellent abrasion resistance. From comparison of comparative example 1 and examples 1 to 5, it is known that the absence of the addition of α -methacrylic acid as a raw material of the anionic aqueous epoxy emulsion reduces the abrasion resistance effect of the coating; as is evident from the comparison of comparative example 2 and examples 1-5, the fluorine-containing polynitroazobenzene derivatives without photoinitiation reduce the abrasion resistance of the coating.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (9)
1. The preparation method of the water-based heat-insulating weather-resistant waterproof coating is characterized by comprising the following steps of:
step (1) adding epoxy resin into a three-neck flask provided with a constant-pressure dropping funnel and a condenser pipe, then adding an organic solvent, heating the three-neck flask and rapidly stirring to uniformly mix the epoxy resin and the organic solvent; placing alpha-methacrylic acid, butyl acrylate, styrene and benzoyl peroxide into a beaker, stirring and mixing uniformly, transferring into a constant-pressure dropping funnel, heating the three-neck flask, dropwise adding the mixture into the mixture of the epoxy resin and the organic solvent, controlling the dropwise adding time, and carrying out heat preservation reaction after the dropwise adding is finished; cooling after the heat preservation reaction is finished to obtain anionic epoxy emulsion, then dropwise adding an aqueous solution of N, N-dimethylethanolamine under high-speed stirring, and continuously stirring after the dropwise adding is finished to obtain anionic aqueous epoxy emulsion;
dropwise adding a nitric acid solution into a cooled three-neck flask containing a sulfuric acid solution, controlling the temperature of a system in the dropwise adding process, adding 3, 5-difluoroaniline in batches after the dropwise adding is finished, then carrying out gradient heating, carrying out heat preservation reaction when orange foam and yellow solid are generated in the three-neck flask, then naturally cooling, pouring the reacted mixed solution into crushed ice, precipitating the yellow solid, carrying out suction filtration, washing to neutrality, and drying to obtain the fluorine-containing polynitroazobenzene derivative;
and (3) dissolving the obtained fluorine-containing polynitroazobenzene derivative in an organic solvent, exposing the fluorine-containing polynitroazobenzene derivative to ultraviolet light, then placing the exposed substance in a fume hood, completely adding the residual substance into an anionic aqueous epoxy emulsion after the organic solvent is completely volatilized, performing ultrasonic dispersion to uniformly disperse the residual substance in the anionic aqueous epoxy emulsion, then adding a curing agent, uniformly mixing, and aging to obtain the water-based heat-insulating weather-resistant waterproof coating.
2. The method for preparing the water-based heat-insulating weather-resistant waterproof paint according to claim 1, wherein in the step (1), the epoxy resin is epoxy resin E-44, the molecular weight is 1000-3000, the organic solvent is n-butanol, the purity is 99%, the volume ratio of the epoxy resin to the organic solvent is 1:3-4, the heating temperature is 60-80 ℃, and the rapid stirring time is 10-18min.
3. The method for preparing the water-based heat-insulating weather-resistant waterproof paint according to claim 1, wherein in the step (1), the ratio of epoxy resin, alpha-methacrylic acid, butyl acrylate, styrene and benzoyl peroxide is 1L: (0.2-0.3) L: (0.08-0.12) L: (0.06-0.08) L: (0.07-0.09) g, the purity of alpha-methacrylic acid was 99%, the purity of butyl acrylate was 96%, the purity of styrene was 98%, and the purity of benzoyl peroxide was 95%.
4. The method for preparing the water-based heat-insulating weather-resistant waterproof paint according to claim 1, wherein in the step (1), a three-neck flask is heated to a temperature of 110-120 ℃, dripping time is 0.5-1h, and heat-insulating reaction time is 5-6h.
5. The method for preparing the water-based heat-insulating weather-resistant waterproof paint according to claim 1, wherein in the step (1), the temperature is reduced to 50-60 ℃, the high-speed stirring speed is 200-300rpm, and the volume ratio of the anionic epoxy emulsion to the aqueous solution of N, N-dimethylethanolamine is 20: the concentration of the aqueous solution of the 1, N-dimethylethanolamine is 83vt percent, and the continuous stirring time is 25-35min.
6. The method for preparing the water-based heat-insulating weather-resistant waterproof paint according to claim 1, wherein in the step (2), the concentration of the sulfuric acid solution is 98vt%, the cooling temperature is 8-12 ℃, the concentration of the nitric acid solution is 95vt%, and the volume ratio of sulfuric acid to nitric acid is 1:0.06-0.075, and controlling the temperature of the system to be lower than 20 ℃.
7. The method for preparing the water-based heat-insulating weather-resistant waterproof paint according to claim 1, wherein in the step (2), the mass ratio of 3, 5-difluoroaniline to sulfuric acid is 1:80-90, wherein the gradient heating rate is 5 ℃/min, the final temperature is 80-85 ℃, the reaction time is 3-5h, the cooling temperature is 25-30 ℃, and the suction filtration conditions are as follows: the pore diameter of the filter membrane is 0.45 mu m, the suction filtration speed is 10mL/min, the filter membrane is washed by deionized water, the drying temperature is 25-30 ℃, and the drying time is 12-15h.
8. The method for preparing the water-based heat-insulating weather-resistant waterproof paint according to claim 1, wherein in the step (3), the organic solvent is acetone with the purity of 99%, the wavelength range of ultraviolet light is 200-400nm, the exposure time is 60-120s, and the ratio of the fluorine-containing polynitroazobenzene derivative to the anionic water-based epoxy emulsion is 0.1kg: (1.0-1.3) L, the ultrasonic dispersion time is 30-50s, the curing agent is commercially available N3300 isocyanate curing agent, and the aging time is 30-45min.
9. The water-based heat-insulating weather-resistant waterproof paint prepared by the method according to any one of claims 1 to 8.
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