CN112391096A - Flame-retardant waterproof exterior wall paint - Google Patents
Flame-retardant waterproof exterior wall paint Download PDFInfo
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- CN112391096A CN112391096A CN201910728997.5A CN201910728997A CN112391096A CN 112391096 A CN112391096 A CN 112391096A CN 201910728997 A CN201910728997 A CN 201910728997A CN 112391096 A CN112391096 A CN 112391096A
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- flame
- retardant
- waterproof
- exterior wall
- phosphorus
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- 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 title claims abstract description 76
- 239000003063 flame retardant Substances 0.000 title claims abstract description 76
- 239000003973 paint Substances 0.000 title claims abstract description 50
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 57
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 49
- 239000011574 phosphorus Substances 0.000 claims abstract description 49
- 239000003822 epoxy resin Substances 0.000 claims abstract description 42
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 42
- 238000000576 coating method Methods 0.000 claims abstract description 39
- 239000011248 coating agent Substances 0.000 claims abstract description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 13
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 13
- 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 claims abstract description 13
- 239000000839 emulsion Substances 0.000 claims abstract description 13
- 239000012188 paraffin wax Substances 0.000 claims abstract description 13
- 229920000570 polyether Polymers 0.000 claims abstract description 13
- 229920005862 polyol Polymers 0.000 claims abstract description 13
- 150000003077 polyols Chemical class 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 31
- 238000001816 cooling Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 8
- 229920013822 aminosilicone Polymers 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 238000007711 solidification Methods 0.000 claims description 5
- 230000008023 solidification Effects 0.000 claims description 5
- 238000004078 waterproofing Methods 0.000 claims description 5
- 238000007792 addition Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 3
- VJLOFJZWUDZJBX-UHFFFAOYSA-N bis(2-hydroxyethyl)azanium;chloride Chemical compound [Cl-].OCC[NH2+]CCO VJLOFJZWUDZJBX-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- TXFOLHZMICYNRM-UHFFFAOYSA-N dichlorophosphoryloxybenzene Chemical compound ClP(Cl)(=O)OC1=CC=CC=C1 TXFOLHZMICYNRM-UHFFFAOYSA-N 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 6
- 230000003628 erosive effect Effects 0.000 abstract description 5
- 230000002035 prolonged effect Effects 0.000 abstract description 4
- 230000032683 aging Effects 0.000 abstract description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000011414 polymer cement Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 229910001294 Reinforcing steel Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/54—Amino amides>
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a flame-retardant waterproof exterior wall paint which comprises the following raw materials in percentage by weight: 55-75% of epoxy resin, 5-8% of propyl benzene emulsion, 3-6% of phosphorus-containing waterproof agent, 5-10% of talcum powder, 0.5-1.5% of chlorinated paraffin, 2-5% of polyether polyol, 4-9% of vinyl acetate, 0.3-0.8% of defoaming agent and 5-10% of ethanol; the phosphorus-containing waterproof agent with waterproof and flame-retardant performances is prepared, the phosphorus-containing waterproof agent is connected into the epoxy resin, the phosphorus-containing waterproof agent and the epoxy resin are firmly connected together through chemical bonds through ring-opening polymerization, the condition that the waterproof agent or the flame retardant is not uniformly mixed in the preparation of the exterior wall paint coating is avoided, the condition that the waterproof and flame-retardant performances are not uniform in the process of preparing a coating is prevented, meanwhile, when the coating is subjected to sunlight erosion by rainwater, the waterproof and flame-retardant components cannot break, the aging of the exterior wall paint is effectively prevented, and the service life of the exterior wall paint is prolonged.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a flame-retardant waterproof exterior wall paint coating.
Background
The exterior wall paint is mainly applied to buildings and has two functions: firstly, the building is protected from being influenced by external environment or the influence of the external environment is minimized, the exterior wall paint can form a continuous coating on the surface of the building after being coated on the building, the coating has the effects of corrosion resistance, pollution resistance, ultraviolet irradiation resistance and bacterial erosion resistance, the reinforcing steel bars are protected from being corroded easily, and the concrete is protected from being carbonized and chlorinated easily, so that the service life of the building is prolonged; and secondly, the building is decorated and beautified, and the exterior wall paint can form coating films with different colors, different gloss and different textures after being coated on the surface of the building, so that the effect of beautifying the environment is achieved. However, the currently used exterior wall paint only plays a role in decorating and protecting the wall from the external environment, and often does not have flame retardant property, or has poor flame retardant property, some waterproof exterior wall paints are not uniformly mixed, so that the waterproof property of the exterior wall coating is different in level, and moreover, due to long-time rainwater solarization and erosion, the exterior wall paint is easy to age, so that the waterproof property of a local wall is poor, the rainy wall surface is mottled, and the appearance is influenced.
Disclosure of Invention
The invention aims to provide a flame-retardant waterproof exterior wall paint, which is characterized in that a phosphorus-containing waterproof agent with waterproof and flame-retardant properties is prepared, the phosphorus-containing waterproof agent is connected into epoxy resin, the phosphorus-containing waterproof agent and the epoxy resin are subjected to ring-opening polymerization and are firmly connected together by chemical bonds, the condition of nonuniform mixing of the waterproof agent or a flame retardant does not exist in the preparation of the exterior wall paint, the condition of nonuniform waterproof and flame-retardant properties is prevented when a coating is prepared, meanwhile, the waterproof and flame-retardant components of the coating cannot be broken when the coating is subjected to sunlight erosion by rainwater, the aging of the exterior wall paint is effectively prevented, and the service life of the exterior wall paint is prolonged.
The purpose of the invention can be realized by the following technical scheme:
the flame-retardant waterproof exterior wall paint comprises the following raw materials in percentage by weight: 55-75% of epoxy resin, 5-8% of propyl benzene emulsion, 3-6% of phosphorus-containing waterproof agent, 5-10% of talcum powder, 0.5-1.5% of chlorinated paraffin, 2-5% of polyether polyol, 4-9% of vinyl acetate, 0.3-0.8% of defoaming agent and 5-10% of ethanol.
Further, the preparation method of the phosphorus-containing waterproof agent comprises the following steps:
s1 preparation of flame-retardant component
Adding 38.0g of p-hydroxybenzaldehyde, 150mL of dry acetonitrile and 35.0g of diethanolamine into a reaction bottle in sequence, stirring at room temperature, dropwise adding 29.3g of phenylphosphoryl dichloride into a reaction system within 60min, and heating to reflux reaction for 24h after dropwise addition; filtering to remove diethanolamine hydrochloride, concentrating the filtrate by a rotary evaporator to remove part of the solvent, pouring into deionized water, precipitating white solid, filtering, washing the obtained product with cold tetrahydrofuran and distilled water for 3 times respectively, and vacuum drying at 50 deg.C for 48h to obtain flame retardant component intermediate 1;
the reaction formula is as follows:
adding the flame-retardant component intermediate 1 into a reaction bottle, adding a 10% sodium carbonate aqueous solution, starting stirring, heating to 66-68 ℃, slowly dropwise adding a 40% hydrogen peroxide solution, continuously reacting for 2 hours after dropwise adding is completed within 20min, cooling the reaction solution to room temperature, transferring the reaction solution into a separating funnel, extracting with 10mL ethyl acetate, acidifying the water phase with 1:1 hydrochloric acid until the pH value is 2-3, cooling in an ice water bath, filtering under reduced pressure, washing the filter cake with 5mL x 2 ice water, then washing with 5mL petroleum ether, and drying to obtain a flame-retardant component 2;
s2 preparation of phosphorus-containing waterproofing agent
Adding the flame-retardant component 2 and amino silicone resin into a reaction bottle, adding a solvent DMSO, starting stirring, heating and stirring for reaction, after the reaction is finished, precipitating a product by using a 50% ethanol aqueous solution, drying in vacuum, recrystallizing in DMF, rinsing in acetone, and filtering to obtain a phosphorus-containing waterproof agent 3;
the reaction formula is as follows:
further, the molar ratio of the flame retardant component 2 and the amino silicone resin in step S2 is 1: 4.
Further, the temperature rise temperature in step S2 is 45 ℃.
Further, the stirring reaction time in step S2 is 5 hours.
Because the activity of the reactant is higher and the reaction time is long at high temperature, the synthesized phosphorus-containing waterproof agent 3 is easy to continue to react with the flame-retardant component 2 to form oligomer, so that the single product 3 can be synthesized by controlling the proportion, the reaction temperature and the reaction time of the flame-retardant component 2 and the amino silicone resin, and the generation of the oligomer is prevented.
Further, the preparation method of the flame-retardant waterproof exterior wall paint coating specifically comprises the following steps:
(1) curing modification of epoxy resins
Heating the epoxy resin to 110 ℃ for melting, adding the phosphorus-containing waterproof agent for 3 times, adding 50% of the phosphorus-containing waterproof agent for the first time, 30% of the phosphorus-containing waterproof agent for the second time, 10% of the phosphorus-containing waterproof agent for the third time, uniformly stirring, and carrying out heat preservation and solidification reaction for 2 hours to obtain the solidified and modified epoxy resin, wherein the structure of the solidified and modified epoxy resin is shown as a structural formula 4;
wherein,
(2) cooling to 45-50 ℃, adding propyl benzene emulsion, talcum powder, chlorinated paraffin, polyether polyol, vinyl acetate and ethanol, mixing and stirring for 1h, adding a defoaming agent, continuously stirring for 30min, standing for 1-2h, and naturally cooling to room temperature to obtain the flame-retardant waterproof exterior wall paint.
The invention has the beneficial effects that:
(1) the flame-retardant waterproof exterior wall paint comprises phosphorus-containing waterproof agents, the existing waterproof agents only have waterproof performance, P-O groups with flame-retardant components are connected into the organic silicon waterproof agents in a chemical bond mode, and the prepared waterproof agents have the waterproof function and the flame-retardant performance;
(2) the prepared phosphorus-containing waterproof agent contains-NH at two ends2Group, therefore, the epoxy resin is easily subjected to ring-openingThe introduced silicone grease groups form hydrophobic films on the surface of the concrete and the inner walls of the capillary holes in a polymerization reaction, so that the capillary absorption of the capillary holes to water is prevented, the waterproof effect is fully exerted, the water immersion is effectively prevented, and the purposes of preventing water and improving the durability of the concrete are achieved; in addition, a hydrolysis-resistant P-C bond and a rigid hydrophobic aryl structure are introduced into the organophosphorus waterproof agent structure, so that the water resistance of the epoxy resin is further improved; in addition, a hydrolysis-resistant P-C bond and a rigid hydrophobic aryl structure are introduced into the organophosphorus waterproof agent structure, so that the water resistance of the epoxy resin is further improved;
(3) the flame-retardant components are introduced into the epoxy resin, and are decomposed to generate substances such as phosphoric acid and polyphosphoric acid at the initial stage of heating, so that the degradation of the epoxy resin is catalyzed, the thermal stability of the epoxy resin is reduced to a certain extent, the char formation reaction of the material is advanced, the formed carbon layer can well isolate oxygen and heat in a combustion area from entering the material inside, and can well inhibit the escape of combustible gas, so that the degradation of the internal material is protected, the incomplete degradation of the internal material can reduce the generation of the combustible gas and increase the residual carbon content of the material, the residual carbon content of the cured flame-retardant epoxy resin at 700 ℃ is increased from 14.3% to 28.7%, and the flame-retardant performance of the material is improved due to the increase of the residual carbon content;
(4) the waterproof organic silicon group and the flame-retardant P-O group are connected by chemical bonds to form the phosphorus-containing waterproof agent, the phosphorus-containing waterproof agent and the epoxy resin are firmly connected by the chemical bonds through ring-opening polymerization, the condition that the waterproof agent or the flame retardant is not uniformly mixed in the preparation of the exterior wall paint coating is avoided, the condition that the waterproof and flame-retardant performances are not uniform in the coating is prevented when the coating is prepared, and meanwhile, when the coating is subjected to sunlight erosion by rainwater, the waterproof and flame-retardant components cannot be broken, the aging of the exterior wall paint is effectively prevented, and the service life of the exterior wall paint is prolonged.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following examples, the preparation of the phosphorus-containing waterproofing agent was as follows:
s1 preparation of flame-retardant component
Adding 38.0g of p-hydroxybenzaldehyde, 150mL of dry acetonitrile and 35.0g of diethanolamine into a reaction bottle in sequence, stirring at room temperature, dropwise adding 29.3g of phenylphosphoryl dichloride into a reaction system within 60min, and heating to reflux reaction for 24h after dropwise addition; filtering to remove diethanolamine hydrochloride, concentrating the filtrate by a rotary evaporator to remove part of the solvent, pouring into deionized water, precipitating white solid, filtering, washing the obtained product with cold tetrahydrofuran and distilled water for 3 times respectively, and vacuum drying at 50 deg.C for 48h to obtain flame retardant component intermediate 1;
the reaction formula is as follows:
adding the flame-retardant component intermediate 1 into a reaction bottle, adding a 10% sodium carbonate aqueous solution, starting stirring, heating to 66-68 ℃, slowly dropwise adding a 40% hydrogen peroxide solution, continuously reacting for 2 hours after dropwise adding is completed within 20min, cooling the reaction solution to room temperature, transferring the reaction solution into a separating funnel, extracting with 10mL ethyl acetate, acidifying the water phase to pH 2-3 with 1:1 hydrochloric acid, cooling in an ice water bath, filtering under reduced pressure, washing the filter cake with 5mL x 2 ice water, then washing with 5mL petroleum ether, and drying to obtain a flame-retardant component 2; the mass spectrum result of the obtained flame retardant component 2 is: HRMS m/z (ESI)+)calcd for C20H15O7P([M]+),398.30,found 398.0686；
S2 preparation of phosphorus-containing waterproofing agent
Adding the flame-retardant component 2 and amino silicone resin into a reaction bottle, adding a solvent DMSO, starting stirring, heating to 45 ℃, stirring for reaction for 5 hours, precipitating a product by using a 50% ethanol aqueous solution after the reaction is finished, drying in vacuum, recrystallizing in DMF, rinsing in acetone, and filtering to obtain a phosphorus-containing waterproof agent 3; the molar ratio of the flame-retardant component 2 to the amino silicone resin is 1: 4;
the reaction formula is as follows:
(ii) a Infrared characterization of phosphorus-containing waterproofing agent 3: IR (KBr):
3399.45(-NH2) 3265.12(-CONH-),3034.22 (stretching vibration of benzene ring), 1685.45(-CONH-),1590.71(-CONH-),1376.25,1106.74 (Si-O-Si).
Example 1
The flame-retardant waterproof exterior wall paint comprises the following raw materials in percentage by weight: 60% of epoxy resin, 8% of propyl benzene emulsion, 5% of phosphorus-containing waterproof agent, 10% of talcum powder, 1% of chlorinated paraffin, 4% of polyether polyol, 6.5% of vinyl acetate, 0.5% of defoaming agent and 5% of ethanol;
the preparation method of the flame-retardant waterproof exterior wall paint coating specifically comprises the following steps:
(1) curing modification of epoxy resins
Heating the epoxy resin to 110 ℃ for melting, adding the phosphorus-containing waterproof agent for 3 times, adding 50% of the phosphorus-containing waterproof agent for the first time, 30% of the phosphorus-containing waterproof agent for the second time, 10% of the phosphorus-containing waterproof agent for the third time, uniformly stirring, and carrying out heat preservation and solidification reaction for 2 hours to obtain the solidified and modified epoxy resin, wherein the structure of the solidified and modified epoxy resin is shown as a structural formula 4;
wherein,
(2) cooling to 45 ℃, adding propyl benzene emulsion, talcum powder, chlorinated paraffin, polyether polyol, vinyl acetate and ethanol, mixing and stirring for 1h, adding a defoaming agent, continuously stirring for 30min, standing for 1h, and naturally cooling to room temperature to obtain the flame-retardant waterproof exterior wall paint coating.
Example 2
The flame-retardant waterproof exterior wall paint comprises the following raw materials in percentage by weight: 70% of epoxy resin, 5% of propyl benzene emulsion, 3% of phosphorus-containing waterproof agent, 5% of talcum powder, 0.7% of chlorinated paraffin, 2% of polyether polyol, 4% of vinyl acetate, 0.3% of defoaming agent and 10% of ethanol;
the preparation method of the flame-retardant waterproof exterior wall paint coating specifically comprises the following steps:
(1) curing modification of epoxy resins
Heating epoxy resin to 110 ℃ for melting, adding a phosphorus-containing waterproof agent for 3 times, adding 50% of the phosphorus-containing waterproof agent for the first time, 30% of the phosphorus-containing waterproof agent for the second time, and 10% of the phosphorus-containing waterproof agent for the third time, uniformly stirring, and carrying out heat preservation and solidification reaction for 2 hours to obtain the solidified and modified epoxy resin;
(2) cooling to 50 ℃, adding propyl benzene emulsion, talcum powder, chlorinated paraffin, polyether polyol, vinyl acetate and ethanol, mixing and stirring for 1h, adding a defoaming agent, continuously stirring for 30min, standing for 2h, and naturally cooling to room temperature to obtain the flame-retardant waterproof exterior wall paint coating.
Example 3
The flame-retardant waterproof exterior wall paint comprises the following raw materials in percentage by weight: 64% of epoxy resin, 6% of propyl benzene emulsion, 6% of phosphorus-containing waterproof agent, 7% of talcum powder, 1.5% of chlorinated paraffin, 4% of polyether polyol, 5% of vinyl acetate, 0.8% of defoaming agent and 5.7% of ethanol;
the preparation method of the flame-retardant waterproof exterior wall paint coating specifically comprises the following steps:
(1) curing modification of epoxy resins
Heating epoxy resin to 110 ℃ for melting, adding a phosphorus-containing waterproof agent for 3 times, adding 50% of the phosphorus-containing waterproof agent for the first time, 30% of the phosphorus-containing waterproof agent for the second time, and 10% of the phosphorus-containing waterproof agent for the third time, uniformly stirring, and carrying out heat preservation and solidification reaction for 2 hours to obtain the solidified and modified epoxy resin;
(2) cooling to 47 ℃, adding propyl benzene emulsion, talcum powder, chlorinated paraffin, polyether polyol, vinyl acetate and ethanol, mixing and stirring for 1h, adding a defoaming agent, continuously stirring for 30min, standing for 1.5h, and naturally cooling to room temperature to obtain the flame-retardant waterproof exterior wall paint coating.
Comparative example 1
The flame-retardant waterproof exterior wall paint comprises the following raw materials in percentage by weight: 64 percent of epoxy resin, 6 percent of propyl benzene emulsion, 2 percent of phosphorus-containing waterproof agent, 7 percent of talcum powder, 1.5 percent of chlorinated paraffin, 4 percent of polyether polyol, 5 percent of vinyl acetate, 0.8 percent of defoaming agent and 9.7 percent of ethanol; the preparation of the exterior wall paint coating was the same as in example 3.
Comparative example 2
The flame-retardant waterproof exterior wall paint comprises the following raw materials in percentage by weight in example 3;
the preparation method of the flame-retardant waterproof exterior wall paint coating specifically comprises the following steps:
mixing and stirring epoxy resin, propyl benzene emulsion, a phosphorus-containing waterproof agent, talcum powder, chlorinated paraffin, polyether polyol, vinyl acetate and ethanol at 45 ℃ for 1h, adding a defoaming agent, continuously stirring for 30min, standing for 1.5h, and naturally cooling to room temperature to obtain the flame-retardant waterproof exterior wall paint.
Flame retardant property test experiment of cured modified epoxy resin:
(1) vertical burning test of cured modified epoxy resin:
TABLE I vertical burn test results for cure modified epoxy resins
| LOI％ | Vertical combustion class | |
| Example 1 | 34.4 | V-0 |
| Example 2 | 33.6 | V-0 |
| Example 3 | 34.9 | V-0 |
| Comparative example 1 | 27.3 | V-1 |
| Pure epoxy resins | 19.6 | Failing to meet the specification |
(2) Thermogravimetric analysis experiment of cured modified epoxy resin
TABLE II thermogravimetric analysis data of cured modified epoxy resins
And (3) testing the performance of the flame-retardant waterproof exterior wall paint coating:
the prepared coating is prepared into a coating film according to the requirements in GB/T23445-2009 Polymer Cement waterproof coating, and is subjected to physical and mechanical property tests, wherein the detection results are shown in the third table:
third, performance of flame-retardant waterproof exterior wall paint coating
The mechanical properties of the flame-retardant waterproof exterior wall paint coating, such as tensile strength, impermeability and the like, are far higher than the requirements of GB/T23445-2009 Polymer Cement waterproof coating, and the flame-retardant waterproof exterior wall paint coating has good flame-retardant waterproof property, has the characteristics of environmental friendliness, no pollution and the like, and meets good development prospects.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (6)
1. The flame-retardant waterproof exterior wall paint is characterized in that: the weight percentage of each raw material is as follows: 55-75% of epoxy resin, 5-8% of propyl benzene emulsion, 3-6% of phosphorus-containing waterproof agent, 5-10% of talcum powder, 0.5-1.5% of chlorinated paraffin, 2-5% of polyether polyol, 4-9% of vinyl acetate, 0.3-0.8% of defoaming agent and 5-10% of ethanol.
2. The flame-retardant waterproof exterior wall paint coating of claim 1, wherein: the preparation method of the phosphorus-containing waterproof agent comprises the following steps:
s1 preparation of flame-retardant component
Adding 38.0g of p-hydroxybenzaldehyde, 150mL of dry acetonitrile and 35.0g of diethanolamine into a reaction bottle in sequence, stirring at room temperature, dropwise adding 29.3g of phenylphosphoryl dichloride into a reaction system within 60min, and heating to reflux reaction for 24h after dropwise addition; filtering to remove diethanolamine hydrochloride, concentrating the filtrate by a rotary evaporator to remove part of the solvent, pouring into deionized water, precipitating white solid, filtering, washing the obtained product with cold tetrahydrofuran and distilled water for 3 times respectively, and vacuum drying at 50 deg.C for 48h to obtain flame retardant component intermediate 1;
the reaction formula is as follows:
adding the flame-retardant component intermediate 1 into a reaction bottle, adding a 10% sodium carbonate aqueous solution, starting stirring, heating to 66-68 ℃, slowly dropwise adding a 40% hydrogen peroxide solution, continuously reacting for 2 hours after dropwise adding within 20min, cooling the reaction solution to room temperature, transferring the reaction solution into a separating funnel, extracting with 10mL ethyl acetate, acidifying the water phase with 1:1 hydrochloric acid until the pH value is 2-3, cooling in an ice water bath, filtering under reduced pressure, washing the filter cake with 5mL x 2 ice water, then washing with 5mL petroleum ether, and drying to obtain a flame-retardant component 2;
s2 preparation of phosphorus-containing waterproofing agent
Adding the flame-retardant component 2 and amino silicone resin into a reaction bottle, adding a solvent DMSO, starting stirring, heating and stirring for reaction, after the reaction is finished, precipitating a product by using a 50% ethanol aqueous solution, drying in vacuum, recrystallizing in DMF, rinsing in acetone, and filtering to obtain a phosphorus-containing waterproof agent 3;
the reaction formula is as follows:
3. the flame-retardant waterproof exterior wall paint coating of claim 2, wherein: the molar ratio of the flame-retardant component 2 and the amino silicone resin in the step S2 is 1: 4.
4. The flame-retardant waterproof exterior wall paint coating of claim 2, wherein: the temperature rise temperature in step S2 is 45 ℃.
5. The flame-retardant waterproof exterior wall paint coating of claim 2, wherein: the stirring reaction time of the step S2 is 5 h.
6. The flame-retardant waterproof exterior wall paint coating of claim 1, wherein: the preparation method of the flame-retardant waterproof exterior wall paint coating specifically comprises the following steps:
(1) curing modification of epoxy resins
Heating the epoxy resin to 110 ℃ for melting, adding the phosphorus-containing waterproof agent for 3 times, adding 50% of the phosphorus-containing waterproof agent for the first time, 30% of the phosphorus-containing waterproof agent for the second time, 10% of the phosphorus-containing waterproof agent for the third time, uniformly stirring, and carrying out heat preservation and solidification reaction for 2 hours to obtain the solidified and modified epoxy resin, wherein the structure of the solidified and modified epoxy resin is shown as a structural formula 4;
wherein,
(2) cooling to 45-50 ℃, adding propyl benzene emulsion, talcum powder, chlorinated paraffin, polyether polyol, vinyl acetate and ethanol, mixing and stirring for 1h, adding a defoaming agent, continuously stirring for 30min, standing for 1-2h, and naturally cooling to room temperature to obtain the flame-retardant waterproof exterior wall paint.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116218195A (en) * | 2023-03-20 | 2023-06-06 | 固达电线电缆(集团)有限公司 | High-flame-retardance modified polyurethane cable material and preparation method thereof |
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| IL30131A (en) * | 1967-06-16 | 1972-08-30 | Stauffer Chemical Co | Oximinophenyl phosphates,phosphonates and phosphinates and their use for pest control |
| CN109337079A (en) * | 2018-09-11 | 2019-02-15 | 南京理工大学 | Aggretion type phosphorus nitrogen silicon fire retardant, synthetic method and its application |
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2019
- 2019-08-13 CN CN201910728997.5A patent/CN112391096A/en not_active Withdrawn
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL30131A (en) * | 1967-06-16 | 1972-08-30 | Stauffer Chemical Co | Oximinophenyl phosphates,phosphonates and phosphinates and their use for pest control |
| CN109337079A (en) * | 2018-09-11 | 2019-02-15 | 南京理工大学 | Aggretion type phosphorus nitrogen silicon fire retardant, synthetic method and its application |
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| 管学茂: "《现代材料分析测试技术》", 30 April 2018 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116218195A (en) * | 2023-03-20 | 2023-06-06 | 固达电线电缆(集团)有限公司 | High-flame-retardance modified polyurethane cable material and preparation method thereof |
| CN116218195B (en) * | 2023-03-20 | 2023-07-25 | 固达电线电缆(集团)有限公司 | High-flame-retardance modified polyurethane cable material and preparation method thereof |
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