CN113214733B - Environment-friendly wood paint and preparation method thereof - Google Patents
Environment-friendly wood paint and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
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- C08G18/348—Hydroxycarboxylic acids
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
- C08G18/3882—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having phosphorus bound to oxygen only
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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Abstract
The invention discloses an environment-friendly wood lacquer and a preparation method thereof, belonging to the technical field of water-based lacquer production and comprising the following raw materials in parts by weight: 70-90 parts of film-forming resin, 1-2 parts of hexanediol butyl ether acetate, 2-3 parts of dipropylene glycol monomethyl ether, 0.4-0.6 part of defoaming agent, 0.1-0.3 part of flatting agent and 10 parts of deionized water; dissolving metered hexanediol butyl ether acetate and dipropylene glycol monomethyl ether in deionized water, adding the dissolved hexanediol butyl ether acetate and dipropylene glycol monomethyl ether into low-speed stirring film-forming resin, stirring and mixing, adding a defoaming agent and a leveling agent, and stirring for 1-1.5 h to obtain the wood lacquer. In the preparation process of the film-forming resin, a crosslinking chain extender with larger crosslinking reaction space is adopted, and the problems of difficult crosslinking and low crosslinking density caused by the fact that the existing crosslinking chain extender has closer crosslinking central atom to the space position of reaction hydroxyl and larger steric hindrance are solved.
Description
Technical Field
The invention belongs to the technical field of water-based paint production, and particularly relates to environment-friendly wood paint and a preparation method thereof.
Background
The waterborne polyurethane is an environment-friendly coating, has the advantages of low VOC, environmental friendliness, capability of reducing the production cost by using water as a diluent, more sanitation, convenience in cleaning and the like, and the adhesive film has quite high mechanical strength, abrasion resistance and excellent toughness. However, the aqueous polyurethane has many hydrophilic groups in its side chains, which makes it inferior in water resistance itself.
The polycarbonate diol has a regular structure and a narrow molecular weight distribution, and the molecular chain of the polycarbonate diol contains a carbonate-based repeating group (-OROCO-), so that the intermolecular cohesion is strong, and compared with most common polyurethanes, the waterborne polyurethane synthesized by the polycarbonate diol has excellent water resistance.
The woodware is flammable, the existing environment-friendly woodware paint taking the polycarbonate type polyurethane as a main component has poor flame retardant property, so that the existing woodware paint taking the polycarbonate type polyurethane as a main component needs to be subjected to flame retardant treatment, when the polycarbonate type waterborne polyurethane coating is subjected to flame retardant treatment, a flame retardant is usually added, the flame retardant and the material are mixed together by adopting a physical blending method, the using amount is large, and meanwhile, the emulsion is unstable due to the addition of the flame retardant in the polycarbonate type waterborne polyurethane material, so that the use of the polycarbonate type waterborne polyurethane is influenced; and the existing crosslinking chain extender has the problems of difficult crosslinking and low crosslinking density because the crosslinking central atom is closer to the spatial position of the reaction hydroxyl and the steric hindrance is larger.
Disclosure of Invention
The invention aims to provide environment-friendly wood lacquer and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
the environment-friendly wood lacquer comprises the following raw materials in parts by weight: 70-90 parts of film-forming resin, 1-2 parts of hexanediol butyl ether acetate, 2-3 parts of dipropylene glycol monomethyl ether, 0.4-0.6 part of defoaming agent, 0.1-0.3 part of flatting agent and 10 parts of deionized water;
the film-forming resin is prepared by the following steps:
step S11, heating polycarbonate diol to 60 ℃ in a state of introducing cooling water for condensation and reflux, slowly dropwise adding isophorone diisocyanate while stirring, heating the solution to 80 ℃ after dropwise adding is completed, preserving heat for 2 hours to obtain an intermediate 1, cooling to 70 ℃, adding dimethylolpropionic acid, preserving heat for 4 hours, slightly heating to remove redundant dimethylolpropionic acid, and preparing an intermediate 2;
the reaction process is shown as the following formula:
step S12, after the temperature is reduced to 50 ℃, adding phosphorus-containing diol and stannous oxide into the intermediate 2, adjusting the viscosity by using acetone, keeping the temperature for 2 hours, then adding polyol crosslinking chain extender, heating to 60 ℃, detecting the real-time value of NCO according to the method of HG/T3409-92, measuring the content of NCO for many times in the reaction process, when the isocyanate index is 7, cooling to 20 ℃, adding acetone, stirring and diluting to prepare prepolymer emulsion, wherein the isocyanate index is the equivalent ratio of isocyanate and polyol;
and step S13, adding a small amount of triethylamine into the prepolymer emulsion for multiple times to neutralize, reacting for 10min, then adding a mixture of isophorone diamine and water, stirring and emulsifying for 30min at the stirring speed of 700rpm, and vacuumizing to remove acetone to obtain the film-forming resin.
Further, the amount ratio of the polycarbonate diol, isophorone diisocyanate, and dimethylolpropionic acid in step S11 was 45g:50g:8 g; the using amount ratio of the intermediate 2, the phosphorus-containing diol, the stannous oxide and the polyol crosslinking chain extender in the step S12 is 78g to 24g to 0.2g to 13 g; the total amount of acetone used in step S12 was 124mL, and the ratio of the amount of isophoronediamine used to the amount of water used in step S13 was 5.5g:332 mL.
Further, the phosphorus-containing diol is prepared by the following steps:
step S21, adding 1, 4-diene-3-pentanol into a dried flask under the protection of nitrogen, adding benzene to dissolve, cooling to 0 ℃, sequentially adding phosphorus oxychloride and triethylamine into the flask, reacting at constant temperature of 0 ℃ for 30min, slowly dropwise adding a sodium bicarbonate solution into a reaction system after the reaction is finished under the condition of ice water bath, then adding benzene to separate liquid, and concentrating on a rotary evaporator to obtain an intermediate 3;
the reaction process is shown as the following formula:
step S22, dissolving the intermediate 3 in dichloromethane, adding m-chloroperoxybenzoic acid, stirring for 12h, and performing post-treatment after the reaction is finished, wherein the post-treatment process comprises the steps of adding a saturated sodium carbonate solution into the reacted solution for quenching, then adding dichloromethane for liquid separation and washing, concentrating on a rotary evaporator, and performing purification and separation through column chromatography to obtain an intermediate 4;
the reaction process is shown as the following formula:
and step S23, dissolving the intermediate 4 in tetrahydrofuran under the protection of nitrogen, adding a phosphoric acid solution, reacting for 6 hours at 40 ℃, performing post-treatment after the reaction is finished, wherein the post-treatment process comprises the steps of adding a saturated sodium carbonate solution to neutralize excessive phosphoric acid, adding dichloromethane to perform liquid separation, washing the obtained organic phase with saturated saline solution, concentrating by using a rotary evaporator, and purifying after the concentration is finished to obtain the phosphorus-containing diol.
The reaction process is shown as the following formula:
further, 1, 4-diene-3-pentanol, benzene, phosphorus oxychloride and triethylamine in step S21 are used in a ratio of 0.2mol:2000mL:0.3mol:0.5 mol; the dosage ratio of the intermediate 3, the dichloromethane and the m-chloroperoxybenzoic acid in the step S22 is 0.6mol, 800mL and 0.9 mol; the phosphoric acid solution in step S23 had a mass fraction concentration of 2%, and the amount ratio of the intermediate 4, tetrahydrofuran and phosphoric acid solution in step S23 was 0.54mol:2L:200 mL.
Further, the preparation of the polyol crosslinking chain extender comprises the following steps:
s31, dissolving dimethyl malonate and citronellal in dichloromethane at normal temperature, adding piperidine acetate, stirring for 24h, and carrying out post-treatment after the reaction is finished, wherein the post-treatment process comprises washing the reaction solution for multiple times by using saturated saline solution, then concentrating the reaction solution on a rotary evaporator, and purifying by adopting a column chromatography manner to obtain an intermediate 5;
the reaction process is shown as the following formula:
s32, dissolving the intermediate 5 in dichloromethane to obtain a solution A, adding ferric chloride, aluminum trichloride and dichloromethane into a flask, cooling to-78 ℃ in an anhydrous and oxygen-free environment, slowly adding the solution A into the flask, naturally heating to room temperature, and performing post-treatment after the reaction is finished, wherein the post-treatment process comprises the steps of adding a saturated ammonium chloride solution into a reaction solution, washing an organic phase, concentrating the organic phase, and recrystallizing to obtain an intermediate 6;
the reaction process is shown as the following formula:
s33, dissolving the intermediate 6 in dichloromethane, adding m-chloroperoxybenzoic acid, stirring for reaction for 3 hours, carrying out aftertreatment after the reaction is finished to obtain an intermediate 7, dissolving the intermediate 7 in tetrahydrofuran, heating to 70 ℃, slowly dropwise adding a phosphoric acid solution under the condition of condensation reflux, stirring for reaction for 12 hours, and carrying out aftertreatment after the reaction is finished, wherein the aftertreatment comprises adding a saturated solution of sodium thiosulfate, then carrying out reduced pressure concentration, and carrying out separation in a column chromatography manner to obtain the polyol crosslinking chain extender.
The reaction process is shown as the following formula:
further, the amount ratio of dimethyl malonate, citronellal, piperidine acetate and dichloromethane in step S31 was 1mol:0.7mol:0.01mol:2000mL, and the concentration of solution A in step S32 was 0.4 mol/L; the dosage ratio of the solution A, the ferric chloride, the aluminum trichloride and the dichloromethane in the step S32 is 120mL to 15.6g to 14.8g to 300 mL; the phosphoric acid solution in step S33 had a mass fraction concentration of 12%, and the amount ratio of the intermediate 6, methylene chloride, m-chloroperoxybenzoic acid, tetrahydrofuran and phosphoric acid solution in step S33 was 0.2mol:1200mL:0.32mol:800mL:60 mL.
The preparation method of the environment-friendly wood lacquer comprises the following steps: dissolving metered hexanediol butyl ether acetate and dipropylene glycol monomethyl ether in deionized water, adding the dissolved hexanediol butyl ether acetate and dipropylene glycol monomethyl ether into the film-forming resin stirred at a low speed, stirring and mixing, adding the defoaming agent and the leveling agent, and stirring for 1-1.5 h to obtain the wood lacquer.
The invention has the beneficial effects that:
the main component of the wood lacquer prepared by the invention is polycarbonate type polyurethane, water can be used as a solvent, the emission of VOC is reduced, and the requirement of environmental protection is met, the invention obtains the polyol crosslinking chain extender containing phosphate groups by an epoxy ring-opening mode, phosphorus elements in the phosphate groups generate phosphorus oxides harmless to human bodies and the environment after combustion, the polyol crosslinking chain extender is an environment-friendly flame retardant mode, the crosslinking center of the existing polyol crosslinking chain extender has a distance of only 1-2 atoms from a reaction site, the polyol crosslinking chain extender takes the phosphorus atoms as the crosslinking center, the hydroxyl group as the reaction site has a longer spatial distance from the crosslinking center, the steric hindrance is reduced, thus an intermediate 2 with higher molecular weight is easier to react with the polyol crosslinking chain extender, the crosslinking density of the polycarbonate type waterborne polyurethane is improved, so that the formed film layer has better water-resistant effect; meanwhile, special phosphorus-containing diol containing phosphorus atoms is further prepared in a phosphoric acid nucleophilic substitution mode, the phosphorus-containing diol is embedded between chain segments of the intermediate 2 in an isocyanate addition mode under the catalysis of stannous oxide, the storage stability of the prepolymer emulsion is guaranteed while the content of phosphoric acid groups in the prepolymer emulsion is increased, the phosphoric acid groups combined in the film-forming resin are firstly broken with a main molecular chain after contacting high temperature, and then the phosphoric acid films are formed on the surface of the film formed by the film-forming resin.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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 case of the example 1, the following examples are given,
the film-forming resin is prepared by the following steps:
step S11, heating polycarbonate diol to 60 ℃ in a state of introducing cooling water for condensation and reflux, slowly dropwise adding isophorone diisocyanate while stirring, heating the solution to 80 ℃ after dropwise adding is completed, preserving heat for 2 hours to obtain an intermediate 1, cooling to 70 ℃, adding dimethylolpropionic acid, preserving heat for 4 hours, slightly heating to remove redundant dimethylolpropionic acid, and preparing an intermediate 2;
step S12, after the temperature is reduced to 50 ℃, adding phosphorus-containing diol and stannous oxide into the intermediate 2, adjusting the viscosity by using acetone, keeping the temperature for 2 hours, then adding polyol crosslinking chain extender, heating to 60 ℃, detecting the real-time value of NCO according to the method of HG/T3409-92, measuring the content of NCO for many times in the reaction process, when the isocyanate index is 7, cooling to 20 ℃, adding acetone, stirring and diluting to prepare prepolymer emulsion, wherein the isocyanate index is the equivalent ratio of isocyanate and polyol;
and step S13, adding a small amount of triethylamine into the prepolymer emulsion for multiple times to neutralize, reacting for 10min, then adding a mixture of isophorone diamine and water, stirring and emulsifying for 30min at the stirring speed of 700rpm, and vacuumizing to remove acetone to obtain the film-forming resin.
The using amount ratio of the polycarbonate diol, the isophorone diisocyanate and the dimethylolpropionic acid in the step S11 is 45g:50g:8 g; the using amount ratio of the intermediate 2, the phosphorus-containing diol, the stannous oxide and the polyol crosslinking chain extender in the step S12 is 78g to 24g to 0.2g to 13 g; the total amount of acetone used in step S12 was 124mL, and the ratio of the amount of isophoronediamine used to the amount of water used in step S13 was 5.5g:332 mL.
Example 2
Preparing the phosphorus-containing diol:
step S21, adding 1, 4-diene-3-pentanol into a dried flask under the protection of nitrogen, adding benzene to dissolve, cooling to 0 ℃, sequentially adding phosphorus oxychloride and triethylamine into the flask, reacting at constant temperature of 0 ℃ for 30min, slowly dropwise adding a sodium bicarbonate solution into a reaction system after the reaction is finished under the condition of ice water bath, then adding benzene to separate liquid, and concentrating on a rotary evaporator to obtain an intermediate 3;
step S22, dissolving the intermediate 3 in dichloromethane, adding m-chloroperoxybenzoic acid, stirring for 12h, and performing post-treatment after the reaction is finished, wherein the post-treatment process comprises the steps of adding a saturated sodium carbonate solution into the reacted solution for quenching, then adding dichloromethane for liquid separation and washing, concentrating on a rotary evaporator, and performing purification and separation through column chromatography to obtain an intermediate 4;
and step S23, dissolving the intermediate 4 in tetrahydrofuran under the protection of nitrogen, adding a phosphoric acid solution, reacting for 6 hours at 40 ℃, performing post-treatment after the reaction is finished, wherein the post-treatment process comprises the steps of adding a saturated sodium carbonate solution to neutralize excessive phosphoric acid, adding dichloromethane to perform liquid separation, washing the obtained organic phase with saturated saline solution, concentrating by using a rotary evaporator, and purifying after the concentration is finished to obtain the phosphorus-containing diol.
Wherein the amount ratio of 1, 4-diene-3-pentanol, benzene, phosphorus oxychloride and triethylamine in step S21 is 0.2mol:2000mL:0.3mol:0.5 mol; the dosage ratio of the intermediate 3, the dichloromethane and the m-chloroperoxybenzoic acid in the step S22 is 0.6mol, 800mL and 0.9 mol; the phosphoric acid solution in step S23 had a mass fraction concentration of 2%, and the amount ratio of the intermediate 4, tetrahydrofuran and phosphoric acid solution in step S23 was 0.54mol:2L:200 mL.
Example 3
Preparing a polyol crosslinking chain extender:
s31, dissolving dimethyl malonate and citronellal in dichloromethane at normal temperature, adding piperidine acetate, stirring for 24h, and carrying out post-treatment after the reaction is finished, wherein the post-treatment process comprises washing the reaction solution for multiple times by using saturated saline solution, then concentrating the reaction solution on a rotary evaporator, and purifying by adopting a column chromatography manner to obtain an intermediate 5;
s32, dissolving the intermediate 5 in dichloromethane to obtain a solution A, adding ferric chloride, aluminum trichloride and dichloromethane into a flask, cooling to-78 ℃ in an anhydrous and oxygen-free environment, slowly adding the solution A into the flask, naturally heating to room temperature, and performing post-treatment after the reaction is finished, wherein the post-treatment process comprises the steps of adding a saturated ammonium chloride solution into a reaction solution, washing an organic phase, concentrating the organic phase, and recrystallizing to obtain an intermediate 6;
s33, dissolving the intermediate 6 in dichloromethane, adding m-chloroperoxybenzoic acid, stirring for reaction for 3 hours, carrying out aftertreatment after the reaction is finished to obtain an intermediate 7, dissolving the intermediate 7 in tetrahydrofuran, heating to 70 ℃, slowly dropwise adding a phosphoric acid solution under the condition of condensation reflux, stirring for reaction for 12 hours, and carrying out aftertreatment after the reaction is finished, wherein the aftertreatment comprises adding a saturated solution of sodium thiosulfate, then carrying out reduced pressure concentration, and carrying out separation in a column chromatography manner to obtain the polyol crosslinking chain extender.
Wherein the dosage ratio of the dimethyl malonate, the citronellal, the piperidine acetate and the dichloromethane in the step S31 is 1mol:0.7mol:0.01mol:2000mL, and the concentration of the solution A in the step S32 is 0.4 mol/L; the dosage ratio of the solution A, the ferric chloride, the aluminum trichloride and the dichloromethane in the step S32 is 120mL to 15.6g to 14.8g to 300 mL; the phosphoric acid solution in step S33 had a mass fraction concentration of 12%, and the amount ratio of the intermediate 6, methylene chloride, m-chloroperoxybenzoic acid, tetrahydrofuran and phosphoric acid solution in step S33 was 0.2mol:1200mL:0.32mol:800mL:60 mL.
Example 4
The preparation method of the environment-friendly wood lacquer comprises the following steps: weighing the following raw materials in parts by weight: 90 parts of film-forming resin, 2 parts of hexanediol butyl ether acetate, 3 parts of dipropylene glycol monomethyl ether, 0.6 part of defoaming agent, 0.3 part of flatting agent and 10 parts of deionized water; dissolving metered hexanediol butyl ether acetate and dipropylene glycol monomethyl ether in deionized water, adding the dissolved hexanediol butyl ether acetate and dipropylene glycol monomethyl ether into film-forming resin which is stirred at a low speed, stirring and mixing, adding a defoaming agent and a leveling agent, wherein the defoaming agent is BYK022, and the leveling agent is BYK331, and stirring for 1-1.5 h to obtain the wood lacquer.
Example 5
The preparation method of the environment-friendly wood lacquer comprises the following steps: weighing the following raw materials in parts by weight: 82 parts of film-forming resin, 1.3 parts of hexanediol butyl ether acetate, 2.4 parts of dipropylene glycol monomethyl ether, 0.48 part of defoaming agent, 0.22 part of flatting agent and 10 parts of deionized water; dissolving metered hexanediol butyl ether acetate and dipropylene glycol monomethyl ether in deionized water, adding the dissolved hexanediol butyl ether acetate and dipropylene glycol monomethyl ether into low-speed stirring film-forming resin, stirring and mixing, adding a defoaming agent and a leveling agent, wherein the defoaming agent is TECO810, and the leveling agent is BYK331, and stirring for 1-1.5 h to obtain the wood lacquer.
Example 6
The preparation method of the environment-friendly wood lacquer comprises the following steps: weighing the following raw materials in parts by weight: 90 parts of film-forming resin, 2 parts of hexanediol butyl ether acetate, 3 parts of dipropylene glycol monomethyl ether, 0.6 part of defoaming agent, 0.3 part of flatting agent and 10 parts of deionized water; dissolving metered hexanediol butyl ether acetate and dipropylene glycol monomethyl ether in deionized water, adding the dissolved hexanediol butyl ether acetate and dipropylene glycol monomethyl ether into low-speed stirring film-forming resin, stirring and mixing, adding a defoaming agent and a leveling agent, wherein the defoaming agent is TECO810, and the leveling agent is BYK331, and stirring for 1-1.5 h to obtain the wood lacquer.
Comparative example 1
Conventional polycarbonate polyurethane emulsions were blended with the phosphorous flame retardant tris (2, 3-dibromopropyl) phosphate.
Comparative example 2
The polyhydric alcohol crosslinking chain extender is replaced by trimethylolpropane, and the other raw materials and the preparation process are kept unchanged.
The samples prepared in the examples 4-6 and the comparative examples 1-2 are tested, 2mL of the sample is placed in a centrifuge tube, the sample is centrifuged by a centrifuge for 30min, and the rotation speed of the centrifuge is 4500 rpm; observing the appearance of the sample; taking 50mL of sample, storing for 10 days at 80 ℃, and observing the appearance of the sample to judge the thermal stability of the sample; the water resistance of the sample was judged by coating the sample on a glass plate to prepare a film, and then dissolving the film in water for 12 hours and observing the water solubility of the film.
The results of the tests are shown in the following table,
the result shows that the unit containing phosphate group is embedded into the polymer chain in a copolymerization mode, the interface between two phases is eliminated, the unit with flame retardant effect is more uniformly dispersed between polymer chain segments, emulsion with more stable storage is obtained, and simultaneously, with the use of the polyol crosslinking chain extender, the crosslinking degree of the polycarbonate polyurethane is higher, so that better water resistance is obtained.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely exemplary and illustrative of the present invention and various modifications, additions and substitutions may be made by those skilled in the art to the specific embodiments described without departing from the scope of the invention as defined in the accompanying claims.
Claims (3)
1. The environment-friendly wood lacquer is characterized by comprising the following raw materials in parts by weight: 70-90 parts of film-forming resin, 1-2 parts of hexanediol butyl ether acetate, 2-3 parts of dipropylene glycol monomethyl ether, 0.4-0.6 part of defoaming agent, 0.1-0.3 part of flatting agent and 10 parts of deionized water;
the film-forming resin is prepared by the following steps:
step S11, heating polycarbonate diol to 60 ℃ in a condensation reflux state, slowly dropwise adding isophorone diisocyanate while stirring, heating the solution to 80 ℃ after dropwise adding, preserving heat for 2 hours to obtain an intermediate 1, cooling to 70 ℃, adding dimethylolpropionic acid, and preserving heat for 4 hours to obtain an intermediate 2;
step S12, after the temperature is reduced to 50 ℃, adding phosphorus-containing diol and stannous oxide into the intermediate 2, adjusting the viscosity by using acetone, preserving the temperature for 2 hours, then adding polyol cross-linking chain extender, heating to 60 ℃, measuring the content of NCO, when the isocyanate index is 7, reducing the temperature to 20 ℃, and adding acetone for dilution to prepare prepolymer emulsion;
step S13, adding triethylamine into the prepolymer emulsion for neutralization, reacting for 10min, then adding a mixture of isophorone diamine and water, stirring and emulsifying, vacuumizing to remove acetone, and obtaining film-forming resin;
the phosphorus-containing diol is prepared by the following steps:
step S21, adding 1, 4-diene-3-pentanol into the dried flask under the protection of nitrogen, adding benzene for dissolving, cooling to 0 ℃, sequentially adding phosphorus oxychloride and triethylamine into the flask, reacting at constant temperature of 0 ℃ for 30min, and performing post-treatment after the reaction is finished to obtain an intermediate 3;
step S22, dissolving the intermediate 3 in dichloromethane, adding m-chloroperoxybenzoic acid into the dichloromethane, stirring for 12 hours, and carrying out post-treatment after the reaction is finished to obtain an intermediate 4;
step S23, under the protection of nitrogen, dissolving the intermediate 4 in tetrahydrofuran, then adding a phosphoric acid solution into the tetrahydrofuran, reacting for 6 hours at 40 ℃, and performing post-treatment after the reaction is finished to obtain phosphorus-containing diol;
the amount ratio of 1, 4-diene-3-pentanol, benzene, phosphorus oxychloride and triethylamine in step S21 is 0.2mol:2000mL:0.3mol:0.5 mol; the dosage ratio of the intermediate 3, the dichloromethane and the m-chloroperoxybenzoic acid in the step S22 is 0.6mol, 800mL and 0.9 mol; the mass fraction concentration of the phosphoric acid solution in the step S23 is 2%, and the dosage ratio of the intermediate 4, the tetrahydrofuran and the phosphoric acid solution in the step S23 is 0.54mol:2L:200 mL;
the polyol crosslinking chain extender is prepared by the following steps:
s31, dissolving dimethyl malonate and citronellal in dichloromethane at normal temperature, adding piperidine acetate into the dichloromethane, stirring for 24 hours, and carrying out post-treatment after the reaction is finished to obtain an intermediate 5;
s32, dissolving the intermediate 5 in dichloromethane to obtain a solution A, adding ferric chloride, aluminum trichloride and dichloromethane into a flask, cooling to-78 ℃ in an anhydrous and oxygen-free environment, slowly adding the solution A into the flask, naturally heating to room temperature, and performing post-treatment after the reaction is finished to obtain an intermediate 6;
s33, dissolving the intermediate 6 in dichloromethane, adding m-chloroperoxybenzoic acid into the dichloromethane, stirring for reaction for 3 hours, carrying out aftertreatment after the reaction is finished to obtain an intermediate 7, dissolving the intermediate 7 in tetrahydrofuran, heating to 70 ℃, slowly dropwise adding a phosphoric acid solution under the condition of condensation reflux, stirring for reaction for 12 hours, and carrying out aftertreatment after the reaction is finished to obtain a polyol crosslinking chain extender;
the dosage ratio of the dimethyl malonate, the citronellal, the piperidine acetate and the dichloromethane in the step S31 is 1mol:0.7mol:0.01mol:2000mL, and the concentration of the solution A in the step S32 is 0.4 mol/L; the dosage ratio of the solution A, the ferric chloride, the aluminum trichloride and the dichloromethane in the step S32 is 120mL to 15.6g to 14.8g to 300 mL; the phosphoric acid solution in step S33 had a mass fraction concentration of 12%, and the amount ratio of the intermediate 6, methylene chloride, m-chloroperoxybenzoic acid, tetrahydrofuran and phosphoric acid solution in step S33 was 0.2mol:1200mL:0.32mol:800mL:60 mL.
2. The environment-friendly wood lacquer according to claim 1, wherein the amount ratio of the polycarbonate diol, the isophorone diisocyanate and the dimethylolpropionic acid in the step S11 is 45g:50g:8 g; the using amount ratio of the intermediate 2, the phosphorus-containing diol, the stannous oxide and the polyol crosslinking chain extender in the step S12 is 78g to 24g to 0.2g to 13 g; the total amount of acetone used in step S12 was 124mL, and the ratio of the amount of isophoronediamine used to the amount of water used in step S13 was 5.5g:332 mL.
3. The preparation method of the environment-friendly wood lacquer as claimed in claim 1, characterized by comprising the following steps: dissolving metered hexanediol butyl ether acetate and dipropylene glycol monomethyl ether in deionized water, adding the dissolved hexanediol butyl ether acetate and dipropylene glycol monomethyl ether into the film-forming resin stirred at a low speed, stirring and mixing, adding the defoaming agent and the leveling agent, and stirring for 1-1.5 h to obtain the wood lacquer.
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| CN1749291A (en) * | 2005-09-29 | 2006-03-22 | 上海申真企业发展有限公司 | Flame-retardant polyurethane water dispersion and its preparing method |
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| CN103140555A (en) * | 2010-09-28 | 2013-06-05 | Adeka株式会社 | Aqueous polyurethane resin composition for flame retardant coated materials and coated products obtained by applying said composition |
| EP3150646A1 (en) * | 2015-09-29 | 2017-04-05 | SYNTHOPOL CHEMIE Dr. rer. pol. Koch GmbH & CO. KG | Aqueous dispersions of pre-polymers containing isocyanate-terminated phosphorus and coatings made from same and use |
| CN110724451A (en) * | 2019-11-12 | 2020-01-24 | 杭州美多乐环保新材料有限公司 | Self-flame-retardant waterborne polyurethane industrial wood paint |
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| CN1749291A (en) * | 2005-09-29 | 2006-03-22 | 上海申真企业发展有限公司 | Flame-retardant polyurethane water dispersion and its preparing method |
| CN101148457A (en) * | 2007-11-02 | 2008-03-26 | 湖南大学 | Phosphorus-containing tri-functional group liquid alicyclic epoxy compound and preparation method thereof |
| CN103140555A (en) * | 2010-09-28 | 2013-06-05 | Adeka株式会社 | Aqueous polyurethane resin composition for flame retardant coated materials and coated products obtained by applying said composition |
| EP3150646A1 (en) * | 2015-09-29 | 2017-04-05 | SYNTHOPOL CHEMIE Dr. rer. pol. Koch GmbH & CO. KG | Aqueous dispersions of pre-polymers containing isocyanate-terminated phosphorus and coatings made from same and use |
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