CN112759748A - Nano titanium dioxide modified alkyd resin and preparation method and application thereof - Google Patents
Nano titanium dioxide modified alkyd resin and preparation method and application thereof Download PDFInfo
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- CN112759748A CN112759748A CN202011613443.XA CN202011613443A CN112759748A CN 112759748 A CN112759748 A CN 112759748A CN 202011613443 A CN202011613443 A CN 202011613443A CN 112759748 A CN112759748 A CN 112759748A
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- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/46—Polyesters chemically modified by esterification
- C08G63/48—Polyesters chemically modified by esterification by unsaturated higher fatty oils or their acids; by resin acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention provides a nano titanium dioxide modified alkyd resin and a preparation method and application thereof. The nano titanium dioxide modified alkyd resin comprises the following raw material components in parts by weight: 110-120 parts of castor oil, 40-50 parts of polyol, 80-90 parts of polybasic acid and/or anhydride and 5-15 parts of modified nano titanium dioxide; the modifier for modifying the nano titanium dioxide comprises a composition of castor oil and an alcohol compound. The preparation method comprises the following steps: (1) performing alcoholysis reaction on castor oil and polyhydric alcohol to obtain a precursor; (2) and (2) carrying out esterification reaction on the precursor obtained in the step (1), polybasic acid and modified nano titanium dioxide to obtain the nano titanium dioxide modified alkyd resin. The nano titanium dioxide modified alkyd resin provided by the invention has the advantages of good adhesive force, good impact resistance, good hardness, good storage stability and low production cost, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of alkyd resin coatings, and particularly relates to a nano titanium dioxide modified alkyd resin and a preparation method and application thereof.
Background
Alkyd resin is a functional polymer material widely used in the paint industry. The alkyd resin has various synthetic formulas, and a paint film prepared from the alkyd resin is bright, has good adhesive force and excellent flexibility and fullness, but the alkyd resin coating has poor drying property, hardness and water resistance, so that the application of the alkyd resin in some fields is limited. Therefore, the modification of the alkyd resin is needed to further expand the application range of the alkyd resin.
With the development of nanotechnology, researches on adding inorganic nanoparticles to organic materials to improve the performance of the organic materials are increasing. Wherein, TiO2Is a white inorganic pigment, has the advantages of no toxicity, opacity, excellent whiteness and brightness and the like, is considered to be one of the white pigments with the best performance in the world nowadays, and the nano-particles can improve the wear resistance of the coating and have the effects of ultraviolet resistance and aging resistance, so the nano TiO2The method is widely applied to the modification of the coating. However, the nano titanium dioxide has high surface energy and is easy to agglomerate, so that the nano titanium dioxide is uniformly and stably dispersed in the coating.
The surface of the nano titanium dioxide has strong hydrophilicity, so that the nano titanium dioxide is uniformly dispersed in the alkyd resin with good lipophilicity, and the surface of the nano titanium dioxide needs to be modified firstly, so that the hydrophilicity of the nano titanium dioxide is changed into lipophilicity. Due to TiO2The polarity of the middle Ti-O bond is larger, and water adsorbed on the surface can be dissociated to form hydroxyl which is TiO due to polarization2The surface modification of (2) provides convenience. At present, the modification of titanium dioxide nano particles is divided into inorganic modification and organic modification, and the organic modification mode comprises surfactant modification, coupling agent modification, polymer coating modification and the like; the inorganic modification modes comprise inorganic coating modification, ion surface doping, gas phase surface treatment, strong acid modification and the like.
For example, CN104926999A discloses a PIA/nano titanium dioxide modified alkyd resin and a preparation method thereof, wherein the raw materials of the PIA/nano titanium dioxide modified alkyd resin comprise: acrylic acid, methacrylic acid, methyl methacrylate, vinyl triethoxysilane, nano titanium dioxide, epoxy resin, castor oil, trimethylolpropane, 2, 4-trimethyl-1, 3-pentanediol, tetrachlorophthalic anhydride, PIA waste, trimellitic anhydride, triethylamine, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, lauric acid, a catalytic assistant, benzoyl peroxide, xylene and water. According to the technical scheme, the nano titanium dioxide is modified by using the vinyltriethoxysilane so as to improve the compatibility of the titanium dioxide in the alkyd resin, but the modification cost is high, and the industrial production of the alkyd resin is not facilitated.
CN107722805A discloses a water-soluble alkyd resin paint for metals. The water-soluble alkyd resin paint is prepared from the following raw materials in parts by weight: 200-300 parts of dehydrated castor oil fatty acid, 5-15 parts of preservative, 1-10 parts of dispersant, 100-150 parts of polyoxyethylene bisphenol A, 40-60 parts of ethylene glycol monobutyl ether, 220-260 parts of trimethylolpropane, 300-320 parts of isophthalic acid, 1-10 parts of triethylamine, 50-100 parts of titanium dioxide, 100-160 parts of melamine resin and 10-80 parts of water.
CN106381025A discloses a waterproof and anti-aging alkyd resin coating. The waterproof and ageing-resistant alkyd resin coating comprises the following raw material components in parts by weight: 25-45 parts of acrylic acid modified alkyd resin, 10-20 parts of organic silicon modified alkyd resin, 30-35 parts of drying oil alkyd resin, 2-4 parts of urea-formaldehyde resin, 3-5 parts of melamine formaldehyde resin, 8-16 parts of modified methyl cellulose, 1-2 parts of sodium dodecyl benzene sulfonate, 1.5-2.5 parts of dimethyldichlorosilane, 3-6 parts of nano titanium dioxide, 5-10 parts of fly ash, 8-12 parts of heavy calcium carbonate, 15-20 parts of mica powder, 2-3 parts of lauryl phenylacetate, 1-2 parts of ethylene glycol ether, 1-2 parts of wetting agent and 30-80 parts of water. In the technical scheme, titanium dioxide is easy to agglomerate and precipitate, and the dispersibility is poor, so that the prepared waterproof aging-resistant alkyd resin coating is poor in storage stability.
Therefore, how to provide a nano titanium dioxide modified alkyd resin which has better storage stability, better compatibility between the modified nano titanium dioxide and the alkyd resin, and lower cost and is suitable for industrial production becomes a technical problem to be solved at present.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a nano titanium dioxide modified alkyd resin and a preparation method and application thereof. The modified nanometer titanium dioxide alkyd resin prepared by modifying the modified nanometer titanium dioxide with the castor oil and the alcohol compound has the advantages of good adhesive force, good impact resistance, high hardness, good storage stability, low production cost and suitability for industrial production.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a nano titanium dioxide modified alkyd resin, which comprises the following raw material components in parts by weight:
the modifier for modifying the nano titanium dioxide comprises a composition of castor oil and an alcohol compound.
In the invention, the nano titanium dioxide modified alkyd resin prepared by adopting the modified nano titanium dioxide has good adhesive force, good impact resistance, high hardness, good storage stability and low production cost, and is suitable for industrial production.
In the invention, the composition of castor oil and alcohol compounds is further used as a modifier to modify the nano titanium dioxide, so that the obtained modified nano titanium dioxide has better compatibility with the raw material components of the alkyd resin, is not easy to precipitate, and further improves the storage stability of the nano titanium dioxide modified alkyd resin.
In the invention, the weight parts of the castor oil can be 110 parts, 111 parts, 112 parts, 113 parts, 114 parts, 115 parts, 116 parts, 117 parts, 118 parts, 119 parts or 120 parts and the like.
The weight parts of the polyol may be 40 parts, 41 parts, 42 parts, 43 parts, 44 parts, 45 parts, 46 parts, 47 parts, 48 parts, 49 parts, 50 parts, or the like.
The parts by weight of the polyacid and/or anhydride may be 80 parts, 81 parts, 82 parts, 83 parts, 84 parts, 85 parts, 86 parts, 87 parts, 88 parts, 89 parts, 90 parts, or the like.
The modified nano titanium dioxide can be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts or 15 parts by weight.
The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the object and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.
As a preferred embodiment of the present invention, the polyhydric alcohol is any one or a combination of at least two selected from glycerol, pentaerythritol, ethylene glycol, neopentyl glycol, and trimethylolpropane.
Preferably, the polybasic acid is isophthalic acid.
Preferably, the acid anhydride is selected from any one of phthalic anhydride, maleic anhydride or trimellitic anhydride or a combination of at least two thereof.
As a preferred technical scheme of the invention, the modified nano titanium dioxide is prepared by adopting the following method, wherein the method comprises the following steps:
and carrying out modification reaction on nano titanium dioxide, castor oil and alcohol compounds to obtain the modified nano titanium dioxide.
Preferably, the alcohol compound is selected from any one of glycerol, pentaerythritol or trimethylolpropane or a combination of at least two thereof.
Preferably, the total mass percent of the castor oil and the alcohol compound is 4-10% based on 100% of the nano titanium dioxide, and may be 4%, 5%, 6%, 7%, 8%, 9%, 10%, or the like, for example.
Preferably, the molar ratio of the castor oil to the alcohol compound is 1 (2-2.5), and may be, for example, 1:2, 1:2.05, 1:2.1, 1:2.15, 1:2.2, 1:2.25, 1:2.3, 1:2.35, 1:2.4, 1:2.45, or 1: 2.5.
According to the invention, the molar ratio of the castor oil to the alcohol compound in the modifier is further controlled within a specific proportion range of 1 (2-2.5), so that the prepared modified nano titanium dioxide has good compatibility with other raw material components, and the prepared nano titanium dioxide modified alkyd resin has good storage stability and good impact resistance. If the molar ratio of the castor oil to the alcohol compound is relatively small, the storage stability of the prepared alkyd resin is poor; if the molar ratio of the castor oil to the alcohol compound is relatively large, the prepared modified nano titanium dioxide is easy to separate out in the preparation process of the alkyd resin, so that the storage stability and the impact resistance of the alkyd resin are poor.
In a preferred embodiment of the present invention, the modification reaction is carried out in the presence of a solvent.
Preferably, the solvent is an alcohol solvent and water.
Preferably, the alcoholic solvent is selected from any one of ethanol, propanol or isopropanol or a combination of at least two thereof.
The volume ratio of the alcohol solvent to water is preferably 1 (2-4), and may be, for example, 1:2, 1:2.2, 1:2.4, 1:2.6, 1:2.8, 1:3, 1:3.2, 1:3.4, 1:3.6, 1:3.8, or 1: 4.
Preferably, the temperature of the modification reaction is 90 to 120 ℃, for example, 90 ℃, 92 ℃, 95 ℃, 98 ℃, 100 ℃, 103 ℃, 105 ℃, 107 ℃, 110 ℃, 112 ℃, 115 ℃, 118 ℃ or 120 ℃ and the like.
Preferably, the time of the modification reaction is 3 to 5 hours, for example, 3 hours, 3.2 hours, 3.4 hours, 3.6 hours, 3.8 hours, 4 hours, 4.2 hours, 4.4 hours, 4.6 hours, 4.8 hours, or 5 hours.
Preferably, the modification reaction is carried out at a pH of 8 to 10, for example, 8, 8.2, 8.4, 8.6, 8.8, 9, 9.2, 9.4, 9.6, 9.8, or 10.
Preferably, the modification reaction also comprises a pretreatment step before.
Preferably, the pretreatment method comprises the following steps: mixing the nano titanium dioxide with a solvent.
Preferably, after the modification reaction is completed, a post-treatment step is further included.
Preferably, the method of post-processing comprises: washing, drying and grinding.
Preferably, the drying temperature is 35-55 deg.C, such as 35 deg.C, 37 deg.C, 40 deg.C, 42 deg.C, 44 deg.C, 46 deg.C, 48 deg.C, 50 deg.C, 52 deg.C or 55 deg.C.
Preferably, the drying time is 20-25 h, for example, 20h, 20.5h, 21h, 21.5h, 22h, 22.5h, 23h, 23.5h, 24h, 24.5h or 25 h.
As a preferable technical scheme of the invention, the acid value of the nano titanium dioxide modified alkyd resin is 5-25 mg KOH/g, and can be, for example, 5mg KOH/g, 8mg KOH/g, 10mg KOH/g, 12mg KOH/g, 15mg KOH/g, 18mg KOH/g, 20mg KOH/g, 22mg KOH/g or 25mg KOH/g, and the like.
The viscosity of the nano-titania-modified alkyd resin is preferably 225 to 600 mPas, and may be, for example, 225 mPas, 250 mPas, 300 mPas, 350 mPas, 400 mPas, 450 mPas, 500 mPas, 550 mPas, 600 mPas, or the like.
In a second aspect, the present invention provides a method for preparing the nano titanium dioxide modified alkyd resin according to the first aspect, comprising the following steps:
(1) performing alcoholysis reaction on castor oil and polyhydric alcohol to obtain a precursor;
(2) and (2) carrying out esterification reaction on the precursor obtained in the step (1), polybasic acid and modified nano titanium dioxide to obtain the nano titanium dioxide modified alkyd resin.
As a preferred embodiment of the present invention, the alcoholysis reaction in step (1) is carried out in the presence of a catalyst.
Preferably, the catalyst is selected from any one of lithium hydroxide, sodium hydroxide or potassium hydroxide or a combination of at least two thereof.
Preferably, the weight part of the catalyst in the raw material components of the nano titanium dioxide modified alkyd resin is 0.02-0.05, such as 0.02 part, 0.022 part, 0.025 part, 0.028 part, 0.03 part, 0.033 part, 0.035 part, 0.037 part, 0.04 part, 0.042 part, 0.046 part or 0.05 part.
Preferably, the alcoholysis reaction of step (1) is carried out in the presence of an inert gas.
Preferably, the inert gas is selected from nitrogen and/or argon.
Preferably, the temperature of the alcoholysis reaction in step (1) is 100-120 ℃, and may be, for example, 100 ℃, 102 ℃, 104 ℃, 106 ℃, 108 ℃, 110 ℃, 112 ℃, 114 ℃, 116 ℃, 118 ℃ or 120 ℃.
Preferably, the alcoholysis reaction time in the step (1) is 2-3 h, such as 2h, 2.1h, 2.2h, 2.3h, 2.4h, 2.5h, 2.6h, 2.7h, 2.8h, 2.9h or 3 h.
As a preferred embodiment of the present invention, the esterification reaction in the step (2) is carried out in the presence of a solvent.
Preferably, the solvent for the esterification reaction in step (2) is xylene.
Preferably, the esterification solvent in the step (2) is 10 to 20 parts by weight, for example, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, or the like, in the raw material components of the nano titanium dioxide modified alkyd resin.
Preferably, the esterification reaction of step (2) is carried out in the presence of an inert gas.
Preferably, the inert gas is selected from nitrogen and/or argon.
Preferably, the esterification reaction in step (2) is carried out at a temperature of 200 to 220 ℃, for example, 200 ℃, 202 ℃, 204 ℃, 206 ℃, 208 ℃, 210 ℃, 212 ℃, 214 ℃, 216 ℃, 218 ℃ or 220 ℃.
Preferably, the esterification reaction time in the step (2) is 1.5-2.5 h, for example, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h, 2h, 2.1h, 2.2h, 2.3h, 2.4h or 2.5h, etc.
Preferably, after the esterification reaction in the step (2) is completed, a post-treatment step is further included.
Preferably, the method of post-treatment comprises dilution.
Preferably, the diluted organic solvent is selected from any one of xylene, methylcyclohexane, dimethylcyclohexane or toluene or a combination of at least two thereof.
Preferably, the weight part of the diluted organic solvent in the raw material components of the nano titanium dioxide modified alkyd resin is 150-200 parts, such as 150 parts, 155 parts, 160 parts, 165 parts, 170 parts, 175 parts, 180 parts, 185 parts, 190 parts, 195 parts or 200 parts.
As a preferred technical scheme of the invention, the preparation method specifically comprises the following steps:
(1) carrying out alcoholysis reaction on castor oil, polyol and a catalyst for 2-3 h at 100-120 ℃ in the presence of an inert gas to obtain a precursor;
(2) and (2) in the presence of inert gas, carrying out esterification reaction on the precursor obtained in the step (1), polybasic acid, modified nano titanium dioxide and an optional solvent at 200-220 ℃ for 1.5-2.5 h, and then adding an optional organic solvent for dilution to obtain the nano titanium dioxide modified alkyd resin.
In a third aspect, the present invention provides the use of a titanium dioxide modified alkyd resin according to the first aspect in a coating.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the combination of castor oil and alcohol compounds is used as a modifier of the nano titanium dioxide, and the molar ratio of the castor oil to the alcohol compounds is further controlled within a specific proportion range of 1 (2-2.5), so that the prepared modified nano titanium dioxide has good compatibility with other raw material components of alkyd resin, and the prepared nano titanium dioxide modified alkyd resin has good storage stability, can be stored for more than 30 days, has low production cost, and is suitable for industrial production.
(2) The paint film prepared from the nano titanium dioxide modified alkyd resin provided by the invention has higher hardness which can reach 2H; the adhesive force is high and can reach level 2; meanwhile, the material has high impact resistance, and can realize 50-53 cm.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Some of the component sources in the examples and comparative examples are as follows:
castor oil: laddin, C110662;
nano titanium dioxide: santong dongjia group, SR 236.
Example 1
The embodiment provides a nanometer titanium dioxide modified alkyd resin (with the viscosity of 370mPa · s and the acid value of 18mg KOH/g) and a preparation method thereof, and the nanometer titanium dioxide modified alkyd resin comprises the following raw material components in parts by weight:
the modifier of the modified nano titanium dioxide is a composition of castor oil and glycerol.
The preparation method of the modified nano titanium dioxide comprises the following steps:
uniformly dispersing nano titanium dioxide in a mixed solution of ethanol and water, adding sodium hydroxide to enable the pH value to be 8, adding castor oil and glycerol, reacting for 4 hours at 90 ℃, washing for 3 times by using a mixed solution of ethanol and water (the volume ratio of ethanol to water is 1:2), drying for 24 hours at 40 ℃, and grinding to obtain the modified nano titanium dioxide; the volume ratio of ethanol to water in the mixed solution is 1:2, the sum of the mass percentages of the castor oil and the glycerol is 6.5% according to 100% of the nano titanium dioxide, and the molar ratio of the castor oil to the glycerol is 1: 2.3.
The preparation method of the nano titanium dioxide modified alkyd resin comprises the following steps:
(1) carrying out alcoholysis reaction on castor oil, glycerol and lithium hydroxide at 100 ℃ for 3h under the protection of nitrogen to obtain a precursor;
(2) and (2) under the protection of nitrogen, carrying out esterification reaction on the precursor obtained in the step (1), phthalic anhydride, modified nano titanium dioxide and xylene at 200 ℃ for 2h, and then adding toluene for dilution to obtain the nano titanium dioxide modified alkyd resin.
Example 2
The embodiment provides a nanometer titanium dioxide modified alkyd resin (with the viscosity of 400mPa · s and the acid value of 18mg KOH/g) and a preparation method thereof, and the nanometer titanium dioxide modified alkyd resin comprises the following raw material components in parts by weight:
the modifier of the modified nano titanium dioxide is a composition of castor oil and pentaerythritol, and the organic solvent is composed of xylene and toluene according to a mass ratio of 1: 4.
The preparation method of the modified nano titanium dioxide comprises the following steps:
uniformly dispersing nano titanium dioxide in a mixed solution of propanol and water, adding sodium hydroxide to enable the pH value of the mixed solution to be 8, adding castor oil and pentaerythritol, reacting for 3 hours at 120 ℃, washing for 3 times by using a mixed solution of ethanol and water (the volume ratio of the ethanol to the water is 1:2), drying for 22 hours at 50 ℃, and grinding to obtain the modified nano titanium dioxide; the volume ratio of the propylene alcohol to the water in the mixed solution is 1:3, the sum of the mass percentages of the castor oil and the pentaerythritol is 7% according to 100% of the nano titanium dioxide, and the molar ratio of the castor oil to the pentaerythritol is 1:2.
The preparation method of the nano titanium dioxide modified alkyd resin comprises the following steps:
(1) carrying out alcoholysis reaction on castor oil, pentaerythritol and potassium hydroxide at 120 ℃ for 2h under the protection of argon gas to obtain a precursor;
(2) and (2) under the protection of argon, carrying out esterification reaction on the precursor obtained in the step (1), isophthalic acid, modified nano titanium dioxide and xylene at 220 ℃ for 1.5h, and adding an organic solvent for dilution to obtain the nano titanium dioxide modified alkyd resin.
Example 3
The embodiment provides a nanometer titanium dioxide modified alkyd resin (with the viscosity of 400mPa · s and the acid value of 22mg KOH/g) and a preparation method thereof, and the nanometer titanium dioxide modified alkyd resin comprises the following raw material components in parts by weight:
the modifier of the modified nano titanium dioxide is a composition of castor oil and trimethylolpropane.
The preparation method of the modified nano titanium dioxide comprises the following steps:
uniformly dispersing nano titanium dioxide in a mixed solution of isopropanol and water, adding sodium hydroxide to enable the pH value of the mixed solution to be 9, adding castor oil and trimethylolpropane, reacting for 3.5 hours at 110 ℃, washing for 3 times by using a mixed solution of ethanol and water (the volume ratio of the ethanol to the water is 1:2), drying for 20 hours at 55 ℃, and grinding to obtain the modified nano titanium dioxide; the volume ratio of isopropanol to water in the mixed solution is 1:4, the sum of the mass percentages of the castor oil and the trimethylolpropane is 4% according to 100% of the nano titanium dioxide, and the molar ratio of the castor oil to the trimethylolpropane is 1: 2.2.
The preparation method of the nano titanium dioxide modified alkyd resin comprises the following steps:
(1) carrying out alcoholysis reaction on castor oil, neopentyl glycol and potassium hydroxide for 2.5h at 115 ℃ under the protection of nitrogen to obtain a precursor;
(2) and (2) under the protection of nitrogen, carrying out esterification reaction on the precursor obtained in the step (1), maleic anhydride, modified nano titanium dioxide and xylene at 205 ℃ for 2.5h, and adding methylcyclohexane for dilution to obtain the nano titanium dioxide modified alkyd resin.
Example 4
The embodiment provides a nanometer titanium dioxide modified alkyd resin (with viscosity of 600mPa · s and acid value of 24mg KOH/g) and a preparation method thereof, and the nanometer titanium dioxide modified alkyd resin comprises the following raw material components in parts by weight:
the modifier of the modified nano titanium dioxide is a composition of castor oil and glycerol.
The preparation method of the modified nano titanium dioxide comprises the following steps:
uniformly dispersing nano titanium dioxide in a mixed solution of ethanol and water, adding sodium hydroxide to enable the pH value to be 10, adding castor oil and glycerol, reacting for 5 hours at 90 ℃, washing for 3 times by using a mixed solution of ethanol and water (the volume ratio of ethanol to water is 1:2), drying for 21 hours at 45 ℃, and grinding to obtain the modified nano titanium dioxide; the volume ratio of ethanol to water in the mixed solution is 1:2.5, the sum of the mass percentages of the castor oil and the glycerol is 10% according to 100% of the nano titanium dioxide, and the molar ratio of the castor oil to the glycerol is 1: 2.5.
The preparation method of the nano titanium dioxide modified alkyd resin comprises the following steps:
(1) carrying out alcoholysis reaction on castor oil, ethylene glycol and potassium hydroxide for 3h at 110 ℃ under the protection of nitrogen to obtain a precursor;
(2) and (2) under the protection of nitrogen, carrying out esterification reaction on the precursor obtained in the step (1), trimellitic anhydride, modified nano titanium dioxide and xylene at 210 ℃ for 2.4h, and adding dimethyl cyclohexane for dilution to obtain the nano titanium dioxide modified alkyd resin.
Example 5
The embodiment provides a nanometer titanium dioxide modified alkyd resin (with the viscosity of 300mPa · s and the acid value of 20mg KOH/g) and a preparation method thereof, and the nanometer titanium dioxide modified alkyd resin comprises the following raw material components in parts by weight:
the modifier for modifying the nano titanium dioxide comprises a combination of castor oil and pentaerythritol, and the organic solvent consists of xylene and toluene according to a mass ratio of 1: 7.
The preparation method of the modified nano titanium dioxide comprises the following steps:
uniformly dispersing nano titanium dioxide in a mixed solution of ethanol and water, adding sodium hydroxide to enable the pH value of the mixed solution to be 8, adding castor oil and pentaerythritol, reacting for 4 hours at 120 ℃, washing for 3 times by using a mixed solution of ethanol and water (the volume ratio of the ethanol to the water is 1:2), drying for 25 hours at 30 ℃, and grinding to obtain the modified nano titanium dioxide; the volume ratio of ethanol to water in the mixed solution is 1:3, the sum of the mass percentages of the castor oil and the pentaerythritol is 8% according to 100% of the nano titanium dioxide, and the molar ratio of the castor oil to the pentaerythritol is 1: 2.4.
The preparation method of the nano titanium dioxide modified alkyd resin comprises the following steps:
(1) carrying out alcoholysis reaction on castor oil, trimethylolpropane and sodium hydroxide for 3h at 100 ℃ under the protection of nitrogen to obtain a precursor;
(2) and (2) under the protection of nitrogen, carrying out esterification reaction on the precursor obtained in the step (1), maleic anhydride, modified nano titanium dioxide and xylene at 215 ℃ for 1.8h, and adding an organic solvent for dilution to obtain the nano titanium dioxide modified alkyd resin.
Example 6
This example provides a nano titanium dioxide modified alkyd resin (viscosity 340 mPas, acid number 18mg KOH/g) and its preparation method, which is different from example 1 only in that the molar ratio of castor oil and glycerol in the modifier of the modified nano titanium dioxide is 1:2, and other conditions are the same as example 1.
Example 7
This example provides a nano titanium dioxide modified alkyd resin (viscosity 340 mPas, acid number 18mg KOH/g) and its preparation method, which is different from example 1 only in that the molar ratio of castor oil and glycerol in the modifier of the modified nano titanium dioxide is 1:2.5, and the other conditions are the same as example 1.
Example 8
This example provides a nano titanium dioxide modified alkyd resin (viscosity 320 mPas, acid number 18mg KOH/g) and its preparation method, which differs from example 1 only in that the molar ratio of castor oil and glycerol in the modifier of the modified nano titanium dioxide is 1:1.7, and the other conditions are the same as example 1.
Example 9
This example provides a nano titanium dioxide modified alkyd resin (viscosity of 225mPa · s, acid value of 18mg KOH/g) and its preparation method, which differs from example 1 only in that the molar ratio of castor oil and glycerol in the modifier of the modified nano titanium dioxide is 1:2.8, and the other conditions are the same as example 1.
Comparative example 1
This comparative example provides a nano-titania modified alkyd resin (viscosity of 275 mPa-s, acid value of 18mg KOH/g) and a method for preparing the same, differing from example 1 only in that the modifier of the modified nano-titania is castor oil, and the other conditions are the same as example 1.
Comparative example 2
This comparative example provides a nano-titania modified alkyd resin (viscosity of 300mPa · s, acid value of 18mg KOH/g) and a method for preparing the same, differing from example 1 only in that the modifier of the modified nano-titania is glycerin, and other conditions are the same as example 1.
Comparative example 3
This comparative example provides a nano-titania-modified alkyd resin (viscosity of 300mPa · s, acid value of 18mg KOH/g) and a method for preparing the same, differing from example 1 only in that the modified nano-titania is replaced with nano-titania, and the other conditions are the same as example 1.
Comparative example 4
This comparative example provides a nano titanium dioxide modified alkyd resin (viscosity of 370mPa · s, acid value of 18mg KOH/g) and a method for preparing the same, differing from example 1 only in that the modifier of the nano titanium dioxide is vinyltriethoxysilane, and other conditions are the same as example 1.
Application examples 1 to 9
Application examples 1 to 9 provide a paint film and a preparation method thereof, wherein the preparation method comprises the following steps:
the nano titanium dioxide modified alkyd resin provided by examples 1-9 was coated on a tinplate according to the GB/T1731-79 standard and dried in an oven at 50 ℃ for 72h to obtain the paint film.
Application of comparative examples 1 to 4
Application comparative examples 1-4 provide a paint film and a method for preparing the same, the method comprising:
the nano titanium dioxide modified alkyd resin provided by comparative examples 1-4 is coated on a tinplate according to the standard of GB/T1927-92, and dried in an oven at 50 ℃ for 72 hours to obtain the paint film.
The nano titanium dioxide modified alkyd resins provided in the above examples and comparative examples and the paint films provided in the application examples and comparative application examples were tested, and the test standards were as follows:
storage stability: GB 6753.3-86;
hardness: GB 6739-86;
adhesion force: GB/T1720-1979;
impact resistance: GB/T1732 + 1993.
The storage stability of the nano titanium dioxide modified alkyd resin provided by the above examples and comparative examples is shown in the following table 1 after testing:
TABLE 1
The performances of the paint films provided by the application examples and the application comparative examples are shown in the following table 2 after the tests:
TABLE 2
As can be seen from Table 1, the combination of castor oil and alcohol compounds is used as the modifier of the nano titanium dioxide, and the molar ratio of the castor oil to the alcohol compounds is further controlled within a specific proportion range of 1 (2-2.5), so that the obtained modified nano titanium dioxide has good compatibility with other raw material components of the alkyd resin, and the prepared nano titanium dioxide modified alkyd resin has good storage stability and can be stored for more than 30 days.
As shown in Table 2, the combination of castor oil and alcohol compounds is used as a modifier of the nano titanium dioxide, and the molar ratio of the castor oil to the alcohol compounds is controlled within a specific proportion range of 1 (2-2.5), so that the prepared paint film has high hardness of 2H; the adhesive force is high and is 2 grade; meanwhile, the material has high impact resistance of 50-53 cm.
Compared with the example 1, if the molar ratio of the castor oil and the alcohol compound in the modifier for modifying the nano titanium dioxide is larger (example 8), the storage stability of the prepared nano titanium dioxide modified alkyd resin is poorer, and is 15 days; if the mole ratio of castor oil and alcohol compound in the modifier for modifying the nano titanium dioxide is small (example 9), the storage stability of the prepared nano titanium dioxide modified alkyd resin is poor, 17 days, and the hardness of the paint film prepared by the method is low, namely H. Therefore, when the molar ratio of the castor oil to the alcohol compound in the modifier for modifying the nano titanium dioxide is not in a specific range, the storage stability of the prepared nano titanium dioxide modified alkyd resin is poor.
Compared with example 1, if the modifier for modifying the nano titanium dioxide is castor oil (comparative example 1), the storage stability of the prepared nano titanium dioxide modified alkyd resin is poor, namely 20 days; if the modifier of the modified nano titanium dioxide is castor oil (comparative example 2), the storage stability of the prepared nano titanium dioxide modified alkyd resin is poor, namely 10 days, and the hardness of the prepared paint film is low, namely H. Therefore, the castor oil and the alcohol compound have a synergistic interaction effect, and the combination of the castor oil and the alcohol compound is selected as the modifier of the nano titanium dioxide, so that the prepared nano titanium dioxide modified alkyd resin has good storage stability, can be stored for more than 30 days, and has no obvious change.
Compared with the example 1, if the modified nano titanium dioxide is replaced by the nano titanium dioxide (comparative example 3), the prepared nano titanium dioxide modified alkyd resin has poor storage stability and can be stored for only 4 days, and the hardness of a paint film prepared from the nano titanium dioxide modified alkyd resin is lower and is H; if the modifier of the modified nano titanium dioxide is a silane coupling agent (comparative example 4), the storage stability of the prepared nano titanium dioxide modified alkyd resin is 25 days, and the hardness of the prepared paint film is lower and is H. Therefore, if unmodified nano titanium dioxide or a silane coupling agent is used as a modifier of the nano titanium dioxide, the prepared nano titanium dioxide modified alkyd resin has poor storage stability and low hardness.
In conclusion, the combination of the castor oil and the alcohol compound is adopted as the modifier of the nano titanium dioxide, and the molar ratio of the castor oil to the alcohol compound is further controlled within a specific proportion range, so that the prepared nano titanium dioxide modified alkyd resin has good storage stability, and the prepared paint film has high hardness, adhesion and impact resistance, and is low in production cost and suitable for industrial production.
The applicant states that the present invention is illustrated by the detailed process flow of the present invention through the above examples, but the present invention is not limited to the above detailed process flow, that is, it does not mean that the present invention must rely on the above detailed process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The nano titanium dioxide modified alkyd resin is characterized by comprising the following raw material components in parts by weight:
the modifier for modifying the nano titanium dioxide comprises a composition of castor oil and an alcohol compound.
2. The nanotitania-modified alkyd resin according to claim 1, wherein said polyol is selected from any one or a combination of at least two of glycerol, pentaerythritol, ethylene glycol, neopentyl glycol or trimethylolpropane;
preferably, the polybasic acid is isophthalic acid;
preferably, the acid anhydride is selected from any one of phthalic anhydride, maleic anhydride or trimellitic anhydride or a combination of at least two thereof.
3. The nano titanium dioxide-modified alkyd resin of claim 1 or 2, wherein the modified nano titanium dioxide is prepared by a method comprising:
carrying out modification reaction on nano titanium dioxide, castor oil and an alcohol compound to obtain modified nano titanium dioxide;
preferably, the alcohol compound is selected from any one of glycerol, pentaerythritol or trimethylolpropane or a combination of at least two thereof;
preferably, the total mass percent of the castor oil and the alcohol compound is 4-10% based on 100% of the nano titanium dioxide;
preferably, the molar ratio of the castor oil to the alcohol compound is 1 (2-2.5).
4. The nano titanium dioxide-modified alkyd resin of claim 3, wherein the modification reaction is carried out in the presence of a solvent;
preferably, the solvent is an alcohol solvent and water;
preferably, the alcohol solvent is selected from any one of ethanol, propanol or isopropanol or a combination of at least two thereof;
preferably, the volume ratio of the alcohol solvent to the water is 1 (2-4);
preferably, the temperature of the modification reaction is 90-120 ℃;
preferably, the time of the modification reaction is 3-5 h;
preferably, the modification reaction is carried out under the condition that the pH value is 8-10;
preferably, the modification reaction also comprises a pretreatment step before;
preferably, the pretreatment method comprises the following steps: mixing the nano titanium dioxide with a solvent;
preferably, after the modification reaction is finished, a post-treatment step is further included;
preferably, the method of post-processing comprises: washing, drying and grinding;
preferably, the drying temperature is 35-55 ℃;
preferably, the drying time is 20-25 h.
5. The nano titanium dioxide modified alkyd resin of any one of claims 1 to 4, wherein the acid value of the nano titanium dioxide modified alkyd resin is 5 to 25mg KOH/g;
preferably, the viscosity of the nano titanium dioxide modified alkyd resin is 225-600 mPa & s.
6. A process for preparing the nano titania modified alkyd resin of any of claims 1-5, comprising the steps of:
(1) performing alcoholysis reaction on castor oil and polyhydric alcohol to obtain a precursor;
(2) and (2) carrying out esterification reaction on the precursor obtained in the step (1), polybasic acid and modified nano titanium dioxide to obtain the nano titanium dioxide modified alkyd resin.
7. The method according to claim 6, wherein the alcoholysis reaction of step (1) is carried out in the presence of a catalyst;
preferably, the catalyst is selected from any one or a combination of at least two of lithium hydroxide, sodium hydroxide or potassium hydroxide;
preferably, the weight part of the catalyst in the raw material components of the nano titanium dioxide modified alkyd resin is 0.02-0.05;
preferably, the alcoholysis reaction of step (1) is carried out in the presence of an inert gas;
preferably, the inert gas is selected from nitrogen and/or argon;
preferably, the temperature of the alcoholysis reaction in the step (1) is 100-120 ℃;
preferably, the alcoholysis reaction time in the step (1) is 2-3 h.
8. The production method according to claim 6 or 7, wherein the esterification reaction of step (2) is carried out in the presence of a solvent;
preferably, the solvent for the esterification reaction in step (2) is xylene;
preferably, the esterification solvent in the step (2) accounts for 10-20 parts by weight of the raw material components of the nano titanium dioxide modified alkyd resin;
preferably, the esterification reaction of step (2) is carried out in the presence of an inert gas;
preferably, the inert gas is selected from nitrogen and/or argon;
preferably, the temperature of the esterification reaction in the step (2) is 200-220 ℃;
preferably, the esterification reaction time in the step (2) is 1.5-2.5 h;
preferably, after the esterification reaction in the step (2) is completed, a post-treatment step is further included;
preferably, the method of post-treatment comprises dilution;
preferably, the diluted organic solvent is selected from any one or a combination of at least two of xylene, methylcyclohexane, dimethylcyclohexane or toluene;
preferably, the weight part of the diluted organic solvent in the raw material components of the nano titanium dioxide modified alkyd resin is 150-200 parts.
9. The method according to any one of claims 6 to 8, comprising in particular the steps of:
(1) carrying out alcoholysis reaction on castor oil, polyol and a catalyst for 2-3 h at 100-120 ℃ in the presence of an inert gas to obtain a precursor;
(2) and (2) in the presence of inert gas, carrying out esterification reaction on the precursor obtained in the step (1), polybasic acid, modified nano titanium dioxide and an optional solvent at 200-220 ℃ for 1.5-2.5 h, and then adding an optional organic solvent for dilution to obtain the nano titanium dioxide modified alkyd resin.
10. Use of a nano-titania modified alkyd resin according to any of claims 1-5 in a coating.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114605598A (en) * | 2022-03-31 | 2022-06-10 | 长兴化学（天津）有限公司 | Bio-based dispersant, preparation method and application thereof |
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| CN107118593A (en) * | 2017-05-15 | 2017-09-01 | 柳州博泽科技有限公司 | The surface treatment method of nano titanium oxide |
| CN108359361A (en) * | 2018-01-30 | 2018-08-03 | 华南理工大学 | Sorbic acid/nanometer particle-modified aqueous alkide resin and preparation method and application |
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| GB991028A (en) * | 1961-02-16 | 1965-05-05 | Soto Chemical Coatings Inc De | Coating compositions |
| GB966621A (en) * | 1962-01-17 | 1964-08-12 | Ici Ltd | Modifying alkyd resins |
| CN104926999A (en) * | 2015-05-20 | 2015-09-23 | 安徽省金盾涂料有限责任公司 | PIA (meta-phthalic acid)/nanometer titania modified alkyd resin and preparation method thereof |
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| CN108359361A (en) * | 2018-01-30 | 2018-08-03 | 华南理工大学 | Sorbic acid/nanometer particle-modified aqueous alkide resin and preparation method and application |
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| CN114605598A (en) * | 2022-03-31 | 2022-06-10 | 长兴化学（天津）有限公司 | Bio-based dispersant, preparation method and application thereof |
| CN114605598B (en) * | 2022-03-31 | 2024-03-01 | 长兴化学（天津）有限公司 | Bio-based dispersing agent and preparation method and application thereof |
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