CN110408014B - Preparation method of environment-friendly high-performance water-based alkyd resin - Google Patents
Preparation method of environment-friendly high-performance water-based alkyd resin Download PDFInfo
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Abstract
A preparation method of environment-friendly high-performance water-based alkyd resin relates to the field of paint, and comprises the following preparation steps: 1) mixing vegetable oil fatty acid, epoxy resin and a catalyst, stirring and reacting; 2) vegetable oil fatty acid, organic acid anhydride, polyalcohol, esterification catalyst and dimethylbenzene are mixed and stirred for reaction; 3) mixing and stirring epoxy ester, alkyd resin, an esterification catalyst and xylene for reaction, and 4) adding aminated nano cellulose aerogel particles into epoxy ester modified alkyd resin, and mixing and stirring for reaction; 5) the preparation method comprises the steps of distilling the aerogel modified alkyd resin under reduced pressure, adding organic acid anhydride, adding a cosolvent and a neutralizing agent, uniformly stirring, and finally adding water for dispersion to prepare the environment-friendly high-performance water-based alkyd resin.
Description
Technical Field
The invention relates to the field of coatings, and in particular relates to a preparation method of an environment-friendly high-performance water-based alkyd resin.
Background
Alkyd resins, one of the most widely used resin coatings in the coating field today, are prepared by esterification reaction using polybasic acid, polyhydric alcohol, and vegetable oil fatty acid as main raw materials, and are classified into long-oil alkyd resins, medium-oil alkyd resins, and short-oil alkyd resins according to the content of the vegetable oil fatty acid, wherein the long-oil alkyd resins are often used as coating coatings because of their relatively long fatty acid chain segments and thus relatively weak polarity and good solubility, while the short-oil alkyd resins are often used as baking paints because of their relatively short fatty acid chain segments and thus relatively strong polarity and poor solubility.
The water-soluble alkyd resin is prepared by grafting a certain amount of hydrophilic groups such as hydroxyl, amino, carboxyl and the like on a molecular chain of oily alkyd resin, so that the hydrophilicity of the molecular chain of the alkyd resin is greatly improved, and the molecular weight and acid value of the alkyd resin are controlled. Compared with oily alkyd resin, the water-based alkyd resin reduces the usage amount of organic solvent, greatly reduces the emission amount of volatile organic compounds in the using process, not only reduces the production cost, but also reduces the harm to the environment and constructors, so that the water-based alkyd resin is the main development direction in the alkyd resin along with the enhancement of health and environmental awareness of the country and people.
With the advancement of science and technology, the market has higher requirements on coatings, and as the water-based alkyd resin is often used for indoor and outdoor coating, the market has higher requirements on the hardness and flame retardancy of the water-based alkyd resin, while most of the water-based alkyd resins in the market at present have poor flame retardancy, and a flame retardant is added in a blending manner, so that the performance of the water-based alkyd resin is easily reduced, the flame retardancy is not obviously improved, and secondary pollution to the environment is easily caused.
For example, a "high performance water-based alkyd resin coating" disclosed in chinese patent literature, whose publication number CN105086791A, discloses a high performance water-based alkyd resin coating, which comprises the following raw materials in parts by weight: 20-50 parts of waterborne alkyd resin, 10-30 parts of fluorine-containing acrylate emulsion, 2-10 parts of epoxy resin, 1-5 parts of acrylate prepolymer, 1-3 parts of talcum powder, 5-10 parts of titanium dioxide, 0.1-0.8 part of graphene oxide, 3-12 parts of nano titanium dioxide, 0.1-0.5 part of benzoyl peroxide, 0.3-2 parts of dibutyl tin dilaurate, 5-20 parts of ethylene glycol butyl ether, 2-10 parts of cyclohexanone, 1-5 parts of dimethylbenzene, 1-3.5 parts of N, N-diethyl ethylamine, 2-5 parts of N, N-dimethyl ethanolamine, 0.5-1.5 parts of ammonia water, 40-50 parts of water, 10-15 parts of flame retardant, 3-7 parts of auxiliary agent and 1-5 parts of silane coupling agent, the invention adopts a blending and adding mode to add filler and flame retardant, the performance of the waterborne alkyd resin is easily reduced, the flame retardance is not obviously improved, and secondary pollution to the environment is easily caused.
Disclosure of Invention
The invention provides a preparation method of environment-friendly high-performance water-based alkyd resin, aiming at solving the problems that the performance of the water-based alkyd resin is easily reduced, the flame retardance is not obviously improved, the secondary pollution to the environment is easily caused and the like because the filler and the flame retardant are added in a blending manner in the existing water-based alkyd resin.
In order to achieve the purpose, the invention adopts the following technical scheme: a preparation method of environment-friendly high-performance water-based alkyd resin comprises the following preparation steps:
1) mixing vegetable oil fatty acid, epoxy resin and a catalyst, stirring and reacting to obtain epoxy ester;
2) mixing vegetable oil fatty acid, organic acid anhydride, polyalcohol, esterification catalyst and dimethylbenzene, stirring and carrying out esterification reaction to obtain alkyd resin;
3) mixing and stirring epoxy ester, alkyd resin, an esterification catalyst and xylene for reaction to obtain epoxy ester modified alkyd resin;
4) adding aminated nano cellulose aerogel particles into epoxy ester modified alkyd resin, and mixing, stirring and reacting to obtain aerogel modified alkyd resin;
5) and distilling the aerogel modified alkyd resin under reduced pressure to remove xylene, then adding organic acid anhydride, adding a cosolvent and a neutralizing agent after reaction, uniformly stirring, and finally adding water for dispersion to prepare the environment-friendly high-performance water-based alkyd resin.
Firstly, vegetable oil fatty acid and epoxy resin react in the presence of a catalyst to obtain epoxy ester, wherein the epoxy resin contains epoxy groups and can easily generate ring-opening reaction of the epoxy groups with carboxyl groups in the vegetable oil fatty acid to prepare the epoxy ester containing hydroxyl groups; and then, vegetable oil fatty acid, organic acid anhydride, polyalcohol, an esterification catalyst and a solvent xylene are used for carrying out esterification reaction to prepare basic alkyd resin, after the basic alkyd resin is mixed with epoxy ester, the epoxy ester can carry out esterification reaction with the residual vegetable oil fatty acid in the basic alkyd resin, epoxy groups can be introduced into the molecular chain end of the alkyd resin after the epoxy ester obtained from the epoxy resin is modified, and the performances of the alkyd resin such as hardness, dryness, adhesion and the like can be correspondingly improved. Then, amino groups on the surface of the aminated nano-cellulose aerogel particles can react with epoxy groups to firmly coat the aminated nano-cellulose aerogel particles in a molecular chain of alkyd resin, so that the alkyd resin is endowed with excellent flame retardant capability and higher hardness, then, in the water-based process of alkyd resin, organic acid anhydride is introduced, carboxyl groups on the organic acid anhydride are easy to perform esterification reaction with hydroxyl groups on the molecular chain of the alkyd resin, carboxyl groups in the organic acid anhydride are successfully introduced into a macromolecular chain of the alkyd resin, and finally, the carboxyl groups on the molecular chain are neutralized by adding a proper amount of neutralizing agent, so that the alkyd resin has better water solubility, and then, water is added for dispersion to prepare the environment-friendly high-performance water-based alkyd resin.
Preferably, nitrogen is adopted for protection during mixing and stirring in the step 1), the temperature is 110-150 ℃, and the temperature is kept for 0.5-2 h; the weight parts of the components are as follows: 20-50 parts of vegetable oil fatty acid, 25-55 parts of epoxy resin and 0.1-1 part of catalyst.
The epoxy resin has certain improvement capacity on the performances of the waterborne alkyd resin such as hardness, dryness, adhesive force and the like, the content of the epoxy resin is increased, the introduced rigid groups such as benzene rings and the like can increase the hardness of the waterborne alkyd resin, and the introduced polar groups such as side chain hydroxyl and the like can increase the adhesive force of the waterborne alkyd resin, but the molecular weight of the alkyd resin is too large due to the excessive content of the epoxy resin, and the molecular chain structure is more compact, so that the neutralization reaction is not easy to occur, and the water solubility of the alkyd resin is poor.
Preferably, the temperature is raised to 150-180 ℃ for heat preservation for 1-2h during the esterification reaction in the step 2), then the temperature is raised to 220-240 ℃ for heat preservation for 1-3h until the acid value is lower than 20 mgKOH/g; the weight parts of the components are as follows: 30-60 parts of vegetable oil fatty acid, 10-40 parts of organic acid anhydride, 20-50 parts of polyhydric alcohol, 0.1-0.5 part of esterification catalyst and 10-15 parts of dimethylbenzene.
In the preparation process, the using amount of the polyhydric alcohol plays a crucial role in the dryness and water solubility of the water-based alkyd resin, when the using amount of the polyhydric alcohol is too small, the hydroxyl in the molecular chain of the alkyd resin is too little, the water solubility is reduced, and when the using amount of the polyhydric alcohol is too much, the drying speed of the alkyd resin is slowed down due to the fact that the hydroxyl in the molecular chain of the alkyd resin is too much and the hydrophilicity is good; and the method comprises the steps of carrying out esterification reaction at a lower temperature, raising the temperature after the small molecular chain segment is synthesized into the middle chain segment, and synthesizing the large molecular chain segment, so that the prepared alkyd resin has more uniform molecular chain segments.
Preferably, the mixing and stirring reaction temperature in the step 3) is 150-170 ℃, and the temperature is kept for 0.5-1.5h until the acid value is lower than 10 mgKOH/g; the weight parts of the components are as follows: 20-30 parts of epoxy ester, 100-130 parts of alkyd resin, 1-3 parts of esterification catalyst and 10-25 parts of dimethylbenzene.
The reaction is carried out until the acid value is lower than 10mgKOH/g, the esterification degree of the reaction is ensured, and the performance reduction of the alkyd resin caused by too low esterification degree and too low molecular weight is prevented.
Preferably, the mixing and stirring reaction time in the step 4) is 0.5-1h, and the mass ratio of the epoxy ester modified alkyd resin to the aminated nano cellulose aerogel particles is 10-15: 1.
The amino on the surface of the aminated nano-cellulose aerogel particles reacts with an epoxy group on the chain end of the epoxy ester modified alkyd resin, so that the aminated nano-cellulose aerogel particles can be firmly coated in the chain segment of the alkyd resin, and the aminated nano-cellulose aerogel particles are endowed with excellent flame retardant capability and higher hardness.
Preferably, the preparation steps of the aminated nano cellulose aerogel particles are as follows:
a) placing the nano cellulose fiber in deionized water to obtain a nano cellulose fiber suspension, and stirring for 1-3h for later use; placing montmorillonite in deionized water to obtain montmorillonite suspension, and stirring for 1-3 h;
b) mixing the nano cellulose fiber suspension, the montmorillonite suspension and the etherified hexamethylol melamine resin to obtain a mixed solution, then adding phosphoric acid to adjust the pH value to 3.5-4.5, freeze-drying, and placing in an oven with the temperature of 100-130 ℃ for heat preservation for 5-10 hours to obtain the composite modified aerogel;
c) soaking the composite modified aerogel into propanol to obtain propanol wet gel, and then immersing the propanol wet gel into an amino modified solution to react for 12-24h at 20-40 ℃; and taking out the solution after the reaction is finished, washing the solution by using ethanol and water in sequence for replacement, and then carrying out freeze drying and grinding to obtain the aminated nano cellulose aerogel particles.
According to the invention, the montmorillonite, the etherified hexamethylol melamine resin and the nanocellulose fiber are mixed to prepare the composite modified aerogel, and both the montmorillonite and the etherified hexamethylol melamine resin have excellent flame retardant property, so that the composite modified aerogel is endowed with excellent flame retardant property, and a montmorillonite sheet layer can form a hydrogen bond with hydroxyl on the nanocellulose, and the etherified hexamethylol melamine resin can also be chemically cross-linked with the hydroxyl on the surface of the nanocellulose fiber, so that the mechanical property of the composite modified aerogel can be improved, the structural integrity of the composite modified aerogel is enhanced, and the montmorillonite sheet layer and the etherified hexamethylol melamine resin can be firmly fixed on the composite modified aerogel, thereby preventing secondary pollution of the environment-friendly high-performance waterborne alkyd resin. And then, soaking the composite modified aerogel into propanol to obtain propanol wet gel, carrying out amino modification, and carrying out freeze drying and grinding to obtain the aminated nano cellulose aerogel particles.
Preferably, the N-aminoethyl-3-aminopropyl methyl dimethoxysilane aqueous solution comprises the following components in parts by weight: 2-3 parts of nano cellulose fiber, 1-2 parts of montmorillonite, 0.5-1.5 parts of etherified hexamethylol melamine resin and 150 parts of water.
Preferably, the amino group modification solution is 3 to 10 wt% of an aqueous solution of N-aminoethyl-3-aminopropylmethyldimethoxysilane.
N-aminoethyl-3-aminopropylmethyldimethoxysilane is easy to hydrolyze and condense with hydroxyl, and the composite modified aerogel is soaked in propanol to obtain propanol wet gel, so that the propanol wet gel has extremely strong hygroscopicity and can absorb moisture into the propanol wet gel, and therefore, the N-aminoethyl-3-aminopropylmethyldimethoxysilane is also easy to hydrolyze in the propanol wet gel and condense with the hydroxyl on the nanocellulose, and is grafted on the surface of the propanol wet gel.
Preferably, in the step 5), after removing xylene by reduced pressure distillation, cooling to 110-130 ℃, adding organic acid anhydride, raising the temperature to 150-170 ℃, reacting at constant temperature until the acid value is 20-40mgKOH/g, then cooling to 50-70 ℃, adding cosolvent and neutralizer, stirring, adjusting the pH value to 7-8.5, adding water for dispersion, and obtaining the environment-friendly high-performance waterborne alkyd resin; the weight parts of the components are as follows: 200 parts of aerogel modified alkyd resin and 250 parts of aerogel modified alkyd resin; 10-15 parts of organic acid anhydride; 30-50 parts of a cosolvent; 10-15 parts of a neutralizer; 400 portions of water and 500 portions of water.
After organic acid anhydride is used, the carboxyl is grafted to a macromolecular chain of the alkyd resin, finally, the carboxyl on the molecular chain is neutralized by adding a proper amount of neutralizing agent, so that the alkyd resin has better water solubility, and finally, water is added for dispersion, so that the environment-friendly high-performance water-based alkyd resin is prepared.
Preferably, the vegetable oil fatty acid is one or more of soya oil acid, ricinoleic acid, linoleic acid and eleostearic acid; the epoxy resin is one or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin and glycidyl ester type epoxy resin, the catalyst is triphenyl phosphorus, and the organic acid anhydride is: one or more of phthalic anhydride, isophthalic anhydride, maleic anhydride and trimellitic anhydride; the polyol is: one of trimethylolpropane, ethylene glycol, glycerol and pentaerythritol; the esterification catalyst is: an organotin catalyst; the cosolvent is: one or more of n-butyl alcohol, ethylene glycol butyl ether, propylene glycol methyl ether, ethylene glycol propylene glycol butyl ether and diethylene glycol butyl ether; the neutralizing agent is as follows: one or more of ammonia water, triethylamine, dimethylethanolamine, triethanolamine and diethylenetriamine.
Therefore, the invention has the following beneficial effects: the invention endows the composite modified aerogel with excellent flame retardant property and mechanical property by adding the montmorillonite and the etherified hexamethylol melamine resin into the nano-cellulose, and then, the amino-modified nano-cellulose aerogel particles are prepared by amino modification and grinding, and the amino is utilized to react with an epoxy group on the molecular chain end of the epoxy ester-modified alkyd resin, so that the aminated nano cellulose aerogel particles can be firmly coated in the molecular chain of the alkyd resin and are combined with the alkyd resin more firmly, therefore, the prepared environment-friendly high-performance water-based alkyd resin has excellent flame retardance, hardness and dryness, and simultaneously effectively prevents secondary pollution caused by blending and adding a flame retardant, and the polar groups on the surface of the aminated nano cellulose aerogel particles can further increase the adhesive force of the alkyd resin.
Detailed Description
The invention is further described with reference to specific embodiments.
Example 1: a preparation method of environment-friendly high-performance water-based alkyd resin comprises the following preparation steps:
1) mixing 20 parts of soya-bean oil acid, 40 parts of epoxy resin and 0.1 part of triphenyl phosphine, stirring and reacting for 2 hours at 110 ℃ under the protection of nitrogen to obtain epoxy ester;
2) mixing 30 parts of soya-bean oil acid, 12 parts of m-phthalic anhydride, 13 parts of maleic anhydride, 20 parts of trimethylolpropane, 0.1 part of dibutyltin dilaurate and 15 parts of dimethylbenzene, stirring and reacting at 180 ℃, keeping the temperature for 1 hour, then heating to 240 ℃, and keeping the temperature for esterification for 1 hour until the acid value is lower than 20mgKOH/g to obtain alkyd resin;
3) mixing 30 parts of epoxy ester, 100 parts of alkyd resin, 2 parts of dibutyltin dilaurate and 10 parts of dimethylbenzene, stirring and reacting at 150 ℃, and keeping the temperature for 1.5 hours until the acid value is lower than 10mgKOH/g to obtain epoxy ester modified alkyd resin;
4) adding aminated nano cellulose aerogel particles into epoxy ester modified alkyd resin, mixing and stirring for 0.7h to react to obtain aerogel modified alkyd resin, wherein the mass ratio of the epoxy ester modified alkyd resin to the aminated nano cellulose aerogel particles is 12: 1;
5) distilling 200 parts of aerogel modified alkyd resin under reduced pressure to remove xylene, then cooling to 110 ℃, adding 10 parts of trimellitic anhydride, raising the temperature to 150 ℃, reacting at a constant temperature until the acid value is 20mgKOH/g, then cooling to 60 ℃, adding 30 parts of n-butanol and 13 parts of triethylamine, stirring, adjusting the pH value to 8, and adding 400 parts of water for dispersion to obtain the environment-friendly high-performance water-based alkyd resin.
Wherein the preparation steps of the aminated nano cellulose aerogel particles are as follows:
placing the nano cellulose fiber in deionized water to obtain a nano cellulose fiber suspension, stirring for 2 hours for later use, placing montmorillonite in the deionized water to obtain a montmorillonite suspension, stirring for 2 hours for later use, and then mixing the nano cellulose fiber suspension, the montmorillonite suspension and etherified hexamethylol melamine resin to obtain a mixed solution, wherein the mixed solution comprises the following components in parts by weight: 3 parts of nano cellulose fiber, 1.5 parts of montmorillonite, 1 part of etherified hexamethylol melamine resin and 150 parts of water; then adding phosphoric acid to adjust the pH value to 3.5, freeze-drying, and then placing in an oven at 130 ℃ for heat preservation for 5 hours to obtain the composite modified aerogel; soaking the composite modified aerogel into propanol to obtain propanol wet gel, and then immersing the propanol wet gel into 3 wt% of N-aminoethyl-3-aminopropyl methyl dimethoxy silane aqueous solution to react for 24 hours at 40 ℃; and taking out the solution after the reaction is finished, washing the solution by using ethanol and water in sequence for replacement, and then carrying out freeze drying and grinding to obtain the aminated nano cellulose aerogel particles.
Example 2: a preparation method of environment-friendly high-performance water-based alkyd resin comprises the following preparation steps:
1) mixing 50 parts of ricinoleic acid, 25 parts of epoxy resin and 0.5 part of triphenyl phosphine, stirring and reacting for 1.2 hours at 130 ℃ under the protection of nitrogen to obtain epoxy ester;
2) mixing 60 parts of ricinoleic acid, 4 parts of phthalic anhydride, 6 parts of isophthalic anhydride, 35 parts of pentaerythritol, 0.3 part of dibutyltin dilaurate and 13 parts of dimethylbenzene, stirring for reaction at 150 ℃, keeping the temperature for 2 hours, then heating to 230 ℃, and keeping the temperature for esterification for 2 hours until the acid value is lower than 20mgKOH/g to obtain alkyd resin;
3) mixing 20 parts of epoxy ester, 120 parts of alkyd resin, 1 part of dibutyltin dilaurate and 20 parts of xylene, stirring and reacting at 160 ℃, and keeping the temperature for 1 hour until the acid value is lower than 10mgKOH/g to obtain epoxy ester modified alkyd resin;
4) adding aminated nano cellulose aerogel particles into epoxy ester modified alkyd resin, mixing and stirring for 0.5h to react to obtain aerogel modified alkyd resin, wherein the mass ratio of the epoxy ester modified alkyd resin to the aminated nano cellulose aerogel particles is 10: 1;
5) and (2) distilling 250 parts of aerogel modified alkyd resin under reduced pressure to remove xylene, then cooling to 120 ℃, adding 15 parts of trimellitic anhydride, raising the temperature to 170 ℃, reacting at a constant temperature until the acid value is 40mgKOH/g, then cooling to 70 ℃, adding 40 parts of butyl cellosolve and 15 parts of dimethylethanolamine, stirring, adjusting the pH value to 7, and adding 450 parts of water for dispersion to obtain the environment-friendly high-performance waterborne alkyd resin.
Wherein the preparation steps of the aminated nano cellulose aerogel particles are as follows:
placing the nano cellulose fiber in deionized water to obtain a nano cellulose fiber suspension, stirring for 1h for later use, placing montmorillonite in the deionized water to obtain a montmorillonite suspension, stirring for 1h for later use, and then mixing the nano cellulose fiber suspension, the montmorillonite suspension and etherified hexamethylol melamine resin to obtain a mixed solution, wherein the mixed solution comprises the following components in parts by weight: 2 parts of nano cellulose fiber, 1 part of montmorillonite, 1.5 parts of etherified hexamethylol melamine resin and 100 parts of water; then adding phosphoric acid to adjust the pH value to 4.5, freeze-drying, and then placing in a drying oven at 100 ℃ for heat preservation for 10 hours to obtain the composite modified aerogel; soaking the composite modified aerogel into propanol to obtain propanol wet gel, and then immersing the propanol wet gel into 6 wt% of N-aminoethyl-3-aminopropylmethyldimethoxysilane aqueous solution to react for 18h at 30 ℃; and taking out the solution after the reaction is finished, washing the solution by using ethanol and water in sequence for replacement, and then carrying out freeze drying and grinding to obtain the aminated nano cellulose aerogel particles.
Example 3: a preparation method of environment-friendly high-performance water-based alkyd resin comprises the following preparation steps:
1) mixing 35 parts of linoleic acid, 55 parts of epoxy resin and 1 part of triphenyl phosphine, stirring and reacting for 0.5h at 150 ℃ under the protection of nitrogen to obtain epoxy ester;
2) mixing 45 parts of linoleic acid, 18 parts of phthalic anhydride, 22 parts of maleic anhydride, 50 parts of ethylene glycol, 0.5 part of dibutyltin dilaurate and 10 parts of dimethylbenzene, stirring for reaction at 165 ℃, keeping the temperature for 1.5h, then heating to 220 ℃, and keeping the temperature for esterification for 3h until the acid value is lower than 20mgKOH/g to obtain alkyd resin;
3) mixing 25 parts of epoxy ester, 130 parts of alkyd resin, 3 parts of dibutyltin dilaurate and 25 parts of xylene, stirring and reacting at 170 ℃, and keeping the temperature for 0.5h until the acid value is lower than 10mgKOH/g to obtain epoxy ester modified alkyd resin;
4) adding aminated nano-cellulose aerogel particles into epoxy ester modified alkyd resin, mixing and stirring for 1h to react to obtain aerogel modified alkyd resin, wherein the mass ratio of the epoxy ester modified alkyd resin to the aminated nano-cellulose aerogel particles is 15: 1;
5) distilling 220 parts of aerogel modified alkyd resin under reduced pressure to remove xylene, then cooling to 130 ℃, adding 13 parts of trimellitic anhydride, raising the temperature to 160 ℃, reacting at a constant temperature until the acid value is 30mgKOH/g, then cooling to 50 ℃, adding 50 parts of propylene glycol methyl ether and 10 parts of triethanolamine, stirring, adjusting the pH value to 8.5, and adding 500 parts of water for dispersion to obtain the environment-friendly high-performance waterborne alkyd resin.
Wherein the preparation steps of the aminated nano cellulose aerogel particles are as follows:
placing the nano cellulose fiber in deionized water to obtain a nano cellulose fiber suspension, stirring for 3 hours for later use, placing montmorillonite in the deionized water to obtain a montmorillonite suspension, stirring for 3 hours for later use, and then mixing the nano cellulose fiber suspension, the montmorillonite suspension and etherified hexamethylol melamine resin to obtain a mixed solution, wherein the mixed solution comprises the following components in parts by weight: 2.5 parts of nano cellulose fiber, 2 parts of montmorillonite, 0.5 part of etherified hexamethylol melamine resin and 130 parts of water; then adding phosphoric acid to adjust the pH value to 4, freeze-drying, and then placing in a drying oven at 120 ℃ for heat preservation for 7h to obtain the composite modified aerogel; soaking the composite modified aerogel into propanol to obtain propanol wet gel, and then immersing the propanol wet gel into 10 wt% of N-aminoethyl-3-aminopropylmethyldimethoxysilane aqueous solution to react for 12 hours at 20 ℃; and taking out the solution after the reaction is finished, washing the solution by using ethanol and water in sequence for replacement, and then carrying out freeze drying and grinding to obtain the aminated nano cellulose aerogel particles.
Comparative example 1: the difference from example 1 is that step 4) is eliminated and no aminated nanocellulose aerogel particles are added during preparation.
Comparative example 2: the difference from example 1 is that step 4) is eliminated, and the non-aminated nano cellulose aerogel particles are prepared without amino modification in the preparation of the aerogel particles, and are used for preparing the water-based alkyd resin.
Comparative example 3: the difference from example 1 is that 1.5 parts of montmorillonite and 1 part of etherified hexamethylol melamine resin added in the preparation of the aminated nano-cellulose aerogel particle are modified to be 2.5 parts of montmorillonite.
Comparative example 4: the difference from example 1 is that 1.5 parts of montmorillonite and 1 part of etherified hexamethylolmelamine resin added in the preparation of the aminated nanocellulose aerogel particles is modified to add 2.5 parts of etherified hexamethylolmelamine resin.
The alkyd resins prepared in the examples and comparative examples were subjected to a performance test in which the hardness of the paint film was determined in accordance with GB/T6739-2006; the water resistance of the paint film was determined according to GB/T1733-one 1993; the adhesion of the paint film was determined according to GB/T9216-1998; the film flame retardance was measured in accordance with American flame retardant Standard ANSI/UL-94-1985.
The comparison shows that the hardness of a paint film can be increased after the aminated nano-cellulose aerogel particles are used, and when the non-aminated nano-cellulose aerogel particles are used, the non-aminated nano-cellulose aerogel particles cannot be cross-linked by utilizing the reaction of amino groups and alkyd resin molecular chains, so that the aerogel particles cannot be firmly coated in the alkyd resin molecular chains, and the hardness is relatively low; the etherified hexamethylol melamine resin has certain improvement capability on the mechanical strength of the aerogel particles, while the etherified hexamethylol melamine resin is not added in comparative example 3, so the hardness is relatively low. After the aminated nano cellulose aerogel particles are added, the adhesive force of a paint film can be increased due to the existence of hydroxyl on the surfaces of the aminated nano cellulose aerogel particles. The results of the measurement of flame retardancy indicate that the examples have excellent flame retardancy, comparative example 1 has no added aminated nano-cellulose aerogel particles, and thus has no flame retardancy, comparative example 2 has slightly reduced flame retardancy because the aerogel particles cannot be firmly coated in the molecular chain of the alkyd resin, and comparative examples 3 and 4 have slightly reduced flame retardancy compared with the examples even though the etherified hexamethylol melamine resin or montmorillonite which is the same as the examples in total parts is used, which indicates that there is a certain synergistic effect between the etherified hexamethylol melamine resin and the montmorillonite, and the flame retardancy is higher when the etherified hexamethylol melamine resin and the montmorillonite are used in combination compared with the single flame retardant of the same parts.
Claims (7)
1. The preparation method of the environment-friendly high-performance water-based alkyd resin is characterized by comprising the following preparation steps of:
1) mixing vegetable oil fatty acid, epoxy resin and a catalyst, stirring and reacting to obtain epoxy ester;
2) mixing vegetable oil fatty acid, organic acid anhydride, polyalcohol, esterification catalyst and dimethylbenzene, stirring and carrying out esterification reaction to obtain alkyd resin;
3) mixing and stirring epoxy ester, alkyd resin, an esterification catalyst and xylene for reaction to obtain epoxy ester modified alkyd resin;
4) adding aminated nano cellulose aerogel particles into epoxy ester modified alkyd resin, and mixing, stirring and reacting to obtain aerogel modified alkyd resin;
5) carrying out reduced pressure distillation on aerogel modified alkyd resin to remove xylene, then adding organic acid anhydride, adding a cosolvent and a neutralizing agent after reaction, stirring uniformly, and finally adding water for dispersion to prepare the environment-friendly high-performance waterborne alkyd resin;
the preparation steps of the aminated nano cellulose aerogel particles are as follows:
a) placing the nano cellulose fiber in deionized water to obtain a nano cellulose fiber suspension, and stirring for 1-3h for later use; placing montmorillonite in deionized water to obtain montmorillonite suspension, and stirring for 1-3 h;
b) mixing a nano cellulose fiber suspension, a montmorillonite suspension and etherified hexamethylol melamine resin to obtain a mixed solution, wherein the mixed solution comprises the following components in parts by weight: 2-3 parts of nano cellulose fiber, 1-2 parts of montmorillonite, 0.5-1.5 parts of etherified hexamethylol melamine resin and 150 parts of water; then adding phosphoric acid to adjust the pH value to 3.5-4.5, freeze-drying, and then placing in an oven at 100-130 ℃ for heat preservation for 5-10h to obtain the composite modified aerogel;
c) soaking the composite modified aerogel into propanol to obtain propanol wet gel, and then immersing the propanol wet gel into an amino modified solution to react for 12-24h at 20-40 ℃, wherein the amino modified solution is 3-10 wt% of N-aminoethyl-3-aminopropyl methyl dimethoxysilane aqueous solution; taking out the solution after the reaction is finished, sequentially washing the solution with ethanol and water for replacement, and then freeze-drying and grinding the solution to obtain aminated nano cellulose aerogel particles;
and 4) the mass ratio of the epoxy ester modified alkyd resin to the aminated nano cellulose aerogel particles is 10-15: 1.
2. The method for preparing the environment-friendly high-performance water-based alkyd resin as claimed in claim 1, wherein the mixing and stirring in step 1) are carried out under the protection of nitrogen at the temperature of 110-; the weight parts of the components are as follows: 20-50 parts of vegetable oil fatty acid, 25-55 parts of epoxy resin and 0.1-1 part of catalyst.
3. The method as claimed in claim 1, wherein the temperature during the esterification reaction in step 2) is raised to 150-; the weight parts of the components are as follows: 30-60 parts of vegetable oil fatty acid, 10-40 parts of organic acid anhydride, 20-50 parts of polyhydric alcohol, 0.1-0.5 part of esterification catalyst and 10-15 parts of dimethylbenzene.
4. The method as claimed in claim 1, wherein the mixing and stirring reaction temperature in step 3) is 150 ℃ and 170 ℃, and the temperature is maintained for 0.5-1.5h until the acid value is lower than 10 mgKOH/g; the weight parts of the components are as follows: 20-30 parts of epoxy ester, 100-130 parts of alkyd resin, 1-3 parts of esterification catalyst and 10-25 parts of dimethylbenzene.
5. The method for preparing the environment-friendly high-performance water-based alkyd resin according to claim 1, wherein the mixing and stirring reaction time in the step 4) is 0.5-1 h.
6. The method as claimed in claim 1, wherein in step 5), after removing xylene by reduced pressure distillation, the temperature is reduced to 110-130 ℃, after adding organic acid anhydride, the temperature is increased to 150-170 ℃, the reaction is carried out at constant temperature until the acid value is 20-40mgKOH/g, then the temperature is reduced to 50-70 ℃, cosolvent and neutralizer are added, the pH is adjusted to 7-8.5, and water is added for dispersion, so as to obtain the environment-friendly high-performance waterborne alkyd resin; the weight parts of the components are as follows: 200 parts of aerogel modified alkyd resin and 250 parts of aerogel modified alkyd resin; 10-15 parts of organic acid anhydride; 30-50 parts of a cosolvent; 10-15 parts of a neutralizer; 400 portions of water and 500 portions of water.
7. The preparation method of the environment-friendly high-performance water-based alkyd resin according to claim 1, wherein the vegetable oil fatty acid is one or more of soya oil acid, ricinoleic acid, linoleic acid, linolenic acid and eleostearic acid; the epoxy resin is one or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin and glycidyl ester type epoxy resin, the catalyst is triphenyl phosphorus, and the organic acid anhydride is: one or more of phthalic anhydride, isophthalic anhydride, maleic anhydride and trimellitic anhydride; the polyol is: one of trimethylolpropane, ethylene glycol, glycerol and pentaerythritol; the esterification catalyst is: an organotin catalyst; the cosolvent is: one or more of n-butyl alcohol, ethylene glycol butyl ether, propylene glycol methyl ether, ethylene glycol propylene glycol butyl ether and diethylene glycol butyl ether; the neutralizing agent is as follows: one or more of ammonia water, triethylamine, dimethylethanolamine, triethanolamine and diethylenetriamine.
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| CN111171299B (en) * | 2020-01-20 | 2021-12-14 | 湖南省林业科学院 | Preparation method of modified water-based alkyd resin, soybean-based adhesive and application of soybean-based adhesive in bamboo and wood particle boards |
| CN112724809B (en) * | 2020-09-18 | 2022-01-04 | 杭州左工建材有限公司 | Preparation method of alkyd resin plate moisture-proof agent |
| CN114133546A (en) * | 2021-08-17 | 2022-03-04 | 南京杰腾新材料科技有限公司 | High-performance water-based resin and preparation method thereof |
| CN113858376A (en) * | 2021-09-27 | 2021-12-31 | 湖南九富家居材料有限公司 | Preparation method of high-strength environment-friendly ecological plate |
| CN114835883B (en) * | 2022-04-01 | 2023-04-04 | 佛山市国化新材料科技有限公司 | Carboxylic acid micro-nano cellulose-based alkyd resin and preparation method thereof |
| CN115477398B (en) * | 2022-08-26 | 2024-01-09 | 南京佳和日化有限公司 | Low-temperature storage-resistant phosphorus-free green environment-friendly grey water dispersing agent |
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