CN111040141B - Water-based alkyd resin and application thereof - Google Patents

Water-based alkyd resin and application thereof Download PDF

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CN111040141B
CN111040141B CN201911161935.7A CN201911161935A CN111040141B CN 111040141 B CN111040141 B CN 111040141B CN 201911161935 A CN201911161935 A CN 201911161935A CN 111040141 B CN111040141 B CN 111040141B
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parts
alkyd resin
water
waterborne alkyd
silver paste
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CN111040141A (en
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王庆军
孙光明
孙亮亮
丁晓东
隋振奎
武林华
韩洪太
李丽
段洪东
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Shandong Qilu Paint Industry Ltd
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Shandong Qilu Paint Industry Ltd
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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
    • 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
    • C08G63/78—Preparation processes
    • 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
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
    • 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
    • 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
    • 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
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • 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
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0812—Aluminium

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention relates to the technical field of water-based paint, in particular to water-based alkyd resin and application thereof. The water resistance, stability, color retention and other properties of the water-based alkyd resin are greatly improved mainly by optimizing the components and the proportion; the water-based alcohol acid silver paste finish paint prepared by the paint has good water resistance, good dispersion stability and good storage stability, and avoids the risk that a paint film of the traditional water-based alcohol acid silver paste finish paint is damaged in a rainwater and dew environment. And the preparation method has simple process and mild conditions and is suitable for industrial production.

Description

Water-based alkyd resin and application thereof
Technical Field
The invention relates to the technical field of water-based paint, in particular to water-based alkyd resin and application thereof.
Background
The alkyd resin is the main resin for the coating industry by virtue of the advantages of easily available raw materials and good performance, and the highest market proportion of the alkyd resin reaches over 90 percent once. The use of the water-based alkyd resin greatly reduces the VOC content, improves the construction operation and improves the safety, and particularly meets the increasing requirements of people on environmental protection at present, but the application of the water-based alkyd resin is limited due to a large number of easily hydrolyzed ester bonds in the structure, and the defects of poor water resistance, poor storage stability and the like of the water-based alkyd resin still remain to be solved urgently at present.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a waterborne alkyd silver paste finish and a preparation method thereof, so as to solve the defects, and the specific technical scheme is as follows:
the invention firstly discloses a waterborne alkyd resin, which greatly improves the performances of the waterborne alkyd resin such as water resistance, stability, color retention and the like mainly through optimization of components and proportion.
The water-based alkyd resin comprises the following raw materials in parts by weight: 25-40 parts of vegetable oil fatty acid, 1-5 parts of benzoic acid, 6-19 parts of polyhydric alcohol, 0.005-0.015 part of alcoholysis catalyst, 1-15 parts of trimellitic anhydride, 0.1-0.8 part of initiator, 10-20 parts of cosolvent, 3-10 parts of neutralizer and 20-35 parts of deionized water.
After the anhydride group of the trimellitic anhydride is opened, carboxyl can be introduced into a macromolecular chain, and the water-based resin can be realized through neutralization; the water resistance of the prepared water-based alkyd resin is improved and the dryness and hardness of a film forming substance are improved by introducing benzene ring units of benzoic acid.
Preferably, the water-based alkyd resin comprises the following raw materials in parts by weight: 30-32 parts of vegetable oil fatty acid, 1.5-2 parts of benzoic acid, 9.6-12 parts of polyol, 0.008-0.01 part of alcoholysis catalyst, 10-12 parts of trimellitic anhydride, 0.4-0.6 part of initiator, 15-18 parts of cosolvent, 5-7 parts of neutralizer and 25-30 parts of deionized water.
The vegetable oil fatty acid is one or more of soybean oil, tung oil, linseed oil and dehydrated castor oil; more preferably, the vegetable oil fatty acid is a combination of soybean oil, tung oil, linseed oil and dehydrated castor oil, and the mass ratio of the vegetable oil fatty acid to the dehydrated castor oil is (2-8): (1-4): (2-8): 1, preferably (4-6): 2-3): 4-6): 1.
According to the invention, the mixed vegetable oil fatty acid is adopted, and the specific mass ratio is adopted, so that the prepared water-based alkyd resin has the advantages of dryness fraction, stability and color retention.
The polyalcohol is selected from one or more of pentaerythritol, ethylene glycol and trimethylolpropane;
preferably, the polyalcohol is selected from the combination of pentaerythritol, ethylene glycol and trimethylolpropane, and the mass ratio of the polyalcohol to the polyol is (8-15) to 1:1, preferably (10-12) to 1: 1.
According to the invention, the mixed polyol is adopted, the specific mass ratio is adopted, the ester bond of the polyester can be protected by utilizing the steric hindrance effect of the ethyl group on the trimethylolpropane, so that the prepared waterborne alkyd resin has hydrolytic resistance, oxidation resistance stability, alkali resistance and thermal stability, and the combination of the glycol and the pentaerythritol can adjust the functionality, so that the polymerization is stable, and the gelation is avoided.
Preferably, the alcoholysis catalyst is lithium hydroxide; lithium hydroxide is used as an alcoholysis catalyst, so that alcoholysis balance time can be effectively adjusted.
Preferably, the initiator is selected from one or more of acyl peroxides, dialkyl peroxides, inorganic peroxides and azo initiators; more preferably, the initiator is selected from acyl peroxides, such as lauroyl peroxide.
Preferably, the cosolvent is propylene glycol methyl ether acetate, and compared with the commonly used ethylene glycol butyl ether, the propylene glycol methyl ether acetate adopted by the invention has strong dissolving power on polar and non-polar substances and slow volatility, can improve the leveling property, gloss and fullness of a paint film, and avoids toxicity caused by using the ethylene glycol butyl ether.
Preferably, the neutralizing agent is N, N-dimethylethanolamine, the N, N-dimethylethanolamine adopted by the invention can react with carboxyl on the molecular chain of the alkyd resin to neutralize and form salt, so that the water solubility of the resin is improved, and the pH stability of the coating neutralized by the N, N-dimethylethanolamine is more excellent.
More preferably, the waterborne alkyd resin comprises the following components in parts by weight: 10.909-12 parts of soybean oil, 5.455-6 parts of tung oil, 10.909-12 parts of linseed oil, 1.875-2 parts of dehydrated castor oil, 1.5-2 parts of benzoic acid, 8-12 parts of pentaerythritol, 0.686-1 part of trimethylolpropane, 0.686-1 part of ethylene glycol, 0.008-0.01 part of lithium hydroxide, 10-12 parts of trimellitic anhydride, 0.4-0.6 part of lauroyl peroxide, 15-18 parts of propylene glycol monomethyl ether acetate, 5-7 parts of N, N-dimethylethanolamine and 25-30 parts of deionized water.
The invention further discloses a preferable preparation method of the waterborne alkyd resin, which comprises the following steps:
s1 adding vegetable oil fatty acid (soybean oil, tung oil, linseed oil and dehydrated castor oil) into a reaction kettle, stirring, heating to 80 ℃, adding polyhydric alcohol (pentaerythritol, trimethylolpropane and propylene glycol), heating to 130 ℃, adding alcoholysis catalyst (lithium hydroxide), heating to (240 +/-5) ℃, keeping the temperature, reacting for about 1h until the volume ratio of the reaction mixture to 95% ethanol is 1: 4, obtaining the alcoholysis end point when the mixed solution is clear (25 ℃), and cooling for later use.
S2 cooling the mixture obtained in S1 to below 200 ℃, adding benzoic acid, heating to 160-170 ℃, refluxing and esterifying until the acid value (calculated by KOH) is not more than 4mg/g, and cooling for later use.
S3, cooling the alkyd resin obtained in S2 to below 180 ℃, adding trimellitic anhydride, heating to 160-170 ℃, refluxing until the acid value (calculated by KOH) of the reactant is not more than 50mg/g, cooling to 100 ℃, and adding deionized water, a cosolvent (propylene glycol monomethyl ether acetate), an initiator (lauroyl peroxide) and a neutralizing agent (N, N-dimethylethanolamine). Stirring evenly to obtain the waterborne alkyd resin.
The invention further provides a waterborne alkyd silver paste finish prepared by the waterborne alkyd resin, which comprises the following components in parts by weight: 30-46 parts of water-based alkyd resin, 5-8 parts of propylene glycol methyl ether acetate, 1-2.5 parts of N, N-dimethylethanolamine, 25-55 parts of an auxiliary agent and 40-55 parts of deionized water;
preferably, the waterborne alkyd silver paste finish paint comprises the following components in parts by weight: 39-41 parts of water-based alkyd resin, 6-7 parts of propylene glycol methyl ether acetate, 1.5-1.8 parts of N, N-dimethylethanolamine, 30-40 parts of an auxiliary agent and 45-48 parts of deionized water.
More preferably, the solid content of the waterborne alkyd resin is 50 ± 2%.
More preferably, the auxiliary agent comprises one or more of a drier, a thickening agent, a defoaming agent, a leveling agent and pigment and filler. More preferably, the auxiliary agent comprises 0.2-1 part of drier, 0.05-0.6 part of thickener, 0.05-0.2 part of defoamer, 0.05-0.2 part of leveling agent and 30-38 parts of pigment and filler in parts by weight.
More preferably, the drier is Octa-Soligen Cobalt 7Aqua drier.
More preferably, the thickener is a RW-8W thickener.
More preferably, the defoamer is a Foamex 810 defoamer.
More preferably, the leveling agent is a ZY-9208 leveling agent.
More preferably, the pigment filler is water-based aluminum paste.
The invention further discloses a preparation method of the waterborne alkyd silver paste finish paint, which comprises the following steps:
and uniformly mixing the raw materials to obtain the waterborne alcohol acid silver paste finish paint.
Preferably, the preparation method of the waterborne alkyd silver paste finish paint comprises the following steps:
adding a certain amount of propylene glycol methyl ether acetate and part of deionized water into a dispersion kettle, adding a part of deionized water for dilution while stirring, adjusting the pH to 7-8, and slowly adding a defoaming agent and a drier under the condition of continuous stirring;
slowly adding pigment and filler while keeping stirring, grinding with a sand mill until the fineness is less than or equal to 20 μm, discharging the color paste, washing the sand mill kettle with part of deionized water for 3 times, and keeping the washing water for later use;
mixing the rest propylene glycol methyl ether acetate and N, N-dimethylethanolamine, adding part of deionized water (including obtained washing water), adding water-based alkyd resin under the stirring condition, and adjusting the pH value to 7-8 after dilution;
keeping the stirring state, and slowly adding auxiliary agents such as a flatting agent, a thickening agent and the like and the obtained color paste; adjusting the pH value to 7-8, and adjusting the viscosity by using the residual deionized water; and filtering the mixture by using a 80-120-mesh filter screen to obtain the waterborne alcohol acid silver paste finish paint.
The water-based alcohol acid silver paste finish paint prepared by the invention has good water resistance and good storage stability, and avoids the risk that a paint film of the traditional water-based alcohol acid silver paste finish paint is damaged in a rainwater and dew environment.
The waterborne alkyd silver paste finish paint prepared by the preparation method disclosed by the invention is good in dispersion stability, simple in preparation method process and mild in condition, and is suitable for industrial production.
Detailed Description
The preparation of the waterborne alkyd silver paste topcoat is further described in connection with the following examples.
Example 1
The waterborne alkyd resin disclosed by the embodiment comprises the following components in parts by weight:
11 parts of soybean oil, 5.5 parts of tung oil, 11 parts of linseed oil, 1.9 parts of dehydrated castor oil, 1.8 parts of benzoic acid, 8 parts of pentaerythritol, 0.8 part of trimethylolpropane, 0.8 part of ethylene glycol, 0.008 part of lithium hydroxide, 11 parts of trimellitic anhydride, 0.5 part of lauroyl peroxide, 17 parts of propylene glycol methyl ether acetate, 6 parts of N, N-dimethylethanolamine and 28 parts of deionized water.
The preparation method of the waterborne alkyd resin comprises the following steps:
s1 adding soybean oil, tung oil, linseed oil and dehydrated castor oil into a reaction kettle, stirring, heating to 80 ℃, adding pentaerythritol, trimethylolpropane and propylene glycol, heating to 130 ℃, adding lithium hydroxide, heating to 240 +/-5 ℃, and then keeping the temperature to react for about 1 hour until V (reaction mixture): v (95% ethanol) ═ 1: 4, obtaining the alcoholysis end point when the mixed solution is clear (25 ℃), and cooling for later use.
S2 cooling the mixture obtained in S1 to below 200 ℃, adding benzoic acid, heating to 160-170 ℃, refluxing and esterifying until the acid value (calculated by KOH) is not more than 4mg/g, and cooling for later use.
S3, cooling the alkyd resin obtained in S2 to below 180 ℃, adding trimellitic anhydride, heating to 160-170 ℃, refluxing until the acid value (calculated by KOH) of the reactant is not more than 50mg/g, cooling to 100 ℃, and adding deionized water, propylene glycol monomethyl ether acetate, lauroyl peroxide and N, N-dimethylethanolamine. Stirring evenly to obtain the waterborne alkyd resin.
Example 2
The waterborne alkyd resin disclosed by the embodiment comprises the following components in parts by weight:
11.5 parts of soybean oil, 5.5 parts of tung oil, 11.5 parts of linseed oil, 1.9 parts of dehydrated castor oil, 1.5 parts of benzoic acid, 9 parts of pentaerythritol, 0.8 part of trimethylolpropane, 0.8 part of ethylene glycol, 0.008 part of lithium hydroxide, 11 parts of trimellitic anhydride, 0.5 part of lauroyl peroxide, 17 parts of propylene glycol monomethyl ether acetate, 6 parts of N, N-dimethylethanolamine and 28 parts of deionized water.
The preparation method thereof is as described in example 1.
Example 3
The waterborne alkyd resin of this example consists of the following components in parts by weight:
11 parts of soybean oil, 5.5 parts of tung oil, 11 parts of linseed oil, 1.9 parts of dehydrated castor oil, 1.8 parts of benzoic acid, 8 parts of pentaerythritol, 0.8 part of trimethylolpropane, 0.7 part of ethylene glycol, 0.009 part of lithium hydroxide, 11.5 parts of trimellitic anhydride, 0.4 part of lauroyl peroxide, 16 parts of propylene glycol monomethyl ether acetate, 5 parts of N, N-dimethylethanolamine and 25 parts of deionized water.
The preparation method thereof is as described in example 1.
Example 4
The waterborne alkyd resin of this example consists of the following components in parts by weight:
11.5 parts of soybean oil, 5.5 parts of tung oil, 11.5 parts of linseed oil, 1.9 parts of dehydrated castor oil, 1.5 parts of benzoic acid, 9 parts of pentaerythritol, 0.8 part of trimethylolpropane, 0.7 part of ethylene glycol, 0.009 part of lithium hydroxide, 11.5 parts of trimellitic anhydride, 0.4 part of lauroyl peroxide, 16 parts of propylene glycol methyl ether acetate, 5 parts of N, N-dimethylethanolamine and 25 parts of deionized water.
The preparation method thereof is as described in example 1.
Example 5
The waterborne alkyd resin of this example consists of the following components in parts by weight:
10.909 parts of soybean oil, 5.455 parts of tung oil, 10.909 parts of linseed oil, 1.875 parts of dehydrated castor oil, 1.5 parts of benzoic acid, 8 parts of pentaerythritol, 0.686 part of trimethylolpropane, 0.686 part of ethylene glycol, 0.008 part of lithium hydroxide, 10 parts of trimellitic anhydride, 0.4 part of lauroyl peroxide, 15 parts of propylene glycol monomethyl ether acetate, 5 parts of N, N-dimethylethanolamine and 25 parts of deionized water.
The preparation method thereof is as described in example 1.
Example 6
The waterborne alkyd resin of this example consists of the following components in parts by weight:
12 parts of soybean oil, 6 parts of tung oil, 12 parts of linseed oil, 2 parts of dehydrated castor oil, 2 parts of benzoic acid, 12 parts of pentaerythritol, 1 part of trimethylolpropane, 1 part of ethylene glycol, 0.01 part of lithium hydroxide, 12 parts of trimellitic anhydride, 0.6 part of lauroyl peroxide, 18 parts of propylene glycol monomethyl ether acetate, 7 parts of N, N-dimethylethanolamine and 30 parts of deionized water.
The preparation method thereof is as described in example 1.
Example 7
The waterborne alkyd resin of this example consists of the following components in parts by weight:
10.909 parts of soybean oil, 5.455 parts of tung oil, 10.909 parts of linseed oil, 1.875 parts of dehydrated castor oil, 1.5 parts of benzoic acid, 8 parts of pentaerythritol, 0.686 part of trimethylolpropane, 0.686 part of ethylene glycol, 0.008 part of lithium hydroxide, 11 parts of trimellitic anhydride, 0.5 part of lauroyl peroxide, 17 parts of propylene glycol monomethyl ether acetate, 6 parts of N, N-dimethylethanolamine and 28 parts of deionized water.
The preparation method thereof is as described in example 1.
Example 8
The waterborne alkyd resin of this example consists of the following components in parts by weight:
12 parts of soybean oil, 6 parts of tung oil, 12 parts of linseed oil, 2 parts of dehydrated castor oil, 2 parts of benzoic acid, 12 parts of pentaerythritol, 1 part of trimethylolpropane, 1 part of ethylene glycol, 0.008 part of lithium hydroxide, 11 parts of trimellitic anhydride, 0.5 part of lauroyl peroxide, 17 parts of propylene glycol monomethyl ether acetate, 6 parts of N, N-dimethylethanolamine and 28 parts of deionized water.
The preparation method thereof is as described in example 1.
Example 9
The waterborne alkyd resin of this example consists of the following components in parts by weight:
11 parts of soybean oil, 5.5 parts of tung oil, 11 parts of linseed oil, 1.9 parts of dehydrated castor oil, 1.8 parts of benzoic acid, 8 parts of pentaerythritol, 0.8 part of trimethylolpropane, 0.8 part of ethylene glycol, 0.008 part of lithium hydroxide, 10 parts of trimellitic anhydride, 0.4 part of lauroyl peroxide, 15 parts of propylene glycol methyl ether acetate, 5 parts of N, N-dimethylethanolamine and 25 parts of deionized water.
The preparation method thereof is as described in example 1.
Example 10
The waterborne alkyd resin of this example consists of the following components in parts by weight:
11.5 parts of soybean oil, 5.5 parts of tung oil, 11.5 parts of linseed oil, 1.9 parts of dehydrated castor oil, 1.5 parts of benzoic acid, 9 parts of pentaerythritol, 0.8 part of trimethylolpropane, 0.8 part of ethylene glycol, 0.01 part of lithium hydroxide, 12 parts of trimellitic anhydride, 0.6 part of lauroyl peroxide, 18 parts of propylene glycol monomethyl ether acetate, 7 parts of N, N-dimethylethanolamine and 30 parts of deionized water.
The preparation method thereof is as described in example 1.
Example 11
The waterborne alkyd resin of this example consists of the following components in parts by weight:
12 parts of soybean oil, 6 parts of tung oil, 12 parts of linseed oil, 2 parts of dehydrated castor oil, 2 parts of benzoic acid, 12 parts of pentaerythritol, 1 part of trimethylolpropane, 1 part of ethylene glycol, 0.009 part of lithium hydroxide, 11.6 parts of trimellitic anhydride, 0.5 part of lauroyl peroxide, 16 parts of propylene glycol monomethyl ether acetate, 5 parts of N, N-dimethylethanolamine and 25 parts of deionized water.
The preparation method thereof is as described in example 1.
Example 12
The waterborne alkyd resin of this example consists of the following components in parts by weight:
10.909 parts of soybean oil, 5.455 parts of tung oil, 10.909 parts of linseed oil, 1.875 parts of dehydrated castor oil, 1.5 parts of benzoic acid, 8 parts of pentaerythritol, 0.686 part of trimethylolpropane, 0.686 part of ethylene glycol, 0.01 part of lithium hydroxide, 12 parts of trimellitic anhydride, 0.6 part of lauroyl peroxide, 18 parts of propylene glycol monomethyl ether acetate, 7 parts of N, N-dimethylethanolamine and 30 parts of deionized water.
The preparation method thereof is as described in example 1.
Example 13
The water-based alkyd resins prepared in examples 1 to 12 are respectively used for preparing water-based silver alkyd paste surface 1 to 12 paints, and the dosage of each raw material is as follows:
the water-based alkyd silver paste finish paint 1 comprises the following raw materials: 39-41 parts of the waterborne alkyd resin prepared in the embodiment 1, 6-7 parts of propylene glycol methyl ether acetate, 1.5-1.8 parts of N, N-dimethylethanolamine, 0.2-1 part of drier, 0.05-0.6 part of thickener, 0.05-0.2 part of defoamer, 0.05-0.2 part of flatting agent, 30-38 parts of pigment and filler and 45-48 parts of deionized water.
The raw materials of the waterborne alkyd silver paste finish paint 2 are similar to those of the waterborne alkyd silver paste finish paint 1, and the differences are as follows: the waterborne alkyd resin prepared in example 2 was used in place of the waterborne alkyd resin prepared in example 1.
The raw materials of the waterborne alkyd silver paste finish paint 3 are similar to those of the waterborne alkyd silver paste finish paint 1, and the differences are as follows: the waterborne alkyd resin prepared in example 3 was used in place of the waterborne alkyd resin prepared in example 1.
The raw materials of the waterborne alkyd silver paste finish paint 4 are similar to those of the waterborne alkyd silver paste finish paint 1, and the differences are as follows: the waterborne alkyd resin prepared in example 4 was used in place of the waterborne alkyd resin prepared in example 1.
The raw materials of the waterborne alkyd silver paste finish 5 are similar to those of the waterborne alkyd silver paste finish 1, and the differences are as follows: the waterborne alkyd resin prepared in example 5 was used in place of the waterborne alkyd resin prepared in example 1.
The raw materials of the waterborne alkyd silver paste finish 6 are similar to those of the waterborne alkyd silver paste finish 1, and the differences are as follows: the waterborne alkyd resin prepared in example 6 was used in place of the waterborne alkyd resin prepared in example 1.
The raw materials of the waterborne alkyd silver paste finish paint 7 are similar to those of the waterborne alkyd silver paste finish paint 1, and the differences are as follows: the waterborne alkyd resin prepared in example 7 was used in place of the waterborne alkyd resin prepared in example 1.
The raw materials of the waterborne alkyd silver paste finish paint 8 are similar to those of the waterborne alkyd silver paste finish paint 1, and the differences are as follows: the waterborne alkyd resin prepared in example 8 was used in place of the waterborne alkyd resin prepared in example 1.
The raw materials of the waterborne alkyd silver paste finish paint 9 are similar to those of the waterborne alkyd silver paste finish paint 1, and the differences are as follows: the waterborne alkyd resin prepared in example 9 was used in place of the waterborne alkyd resin prepared in example 1.
The raw materials of the waterborne alkyd silver paste finish paint 10 are similar to those of the waterborne alkyd silver paste finish paint 1, and the differences are as follows: the waterborne alkyd resin prepared in example 10 was used in place of the waterborne alkyd resin prepared in example 1.
The raw materials of the waterborne alkyd silver paste finish paint 11 are similar to those of the waterborne alkyd silver paste finish paint 1, and the differences are as follows: the waterborne alkyd resin prepared in example 11 was used in place of the waterborne alkyd resin prepared in example 1.
The raw materials of the waterborne alkyd silver paste finish paint 12 are similar to those of the waterborne alkyd silver paste finish paint 1, and the differences are as follows: the waterborne alkyd resin prepared in example 12 was used in place of the waterborne alkyd resin prepared in example 1. The preparation method of the waterborne alkyd silver paste finish paint comprises the following steps:
adding part of propylene glycol methyl ether acetate and part of deionized water into a dispersion kettle, adding part of deionized water for dilution while stirring, adjusting the pH to 7-8, and slowly adding a defoaming agent and a drier under the condition of continuous stirring;
slowly adding pigment and filler while keeping stirring, grinding with a sand mill until the fineness is less than or equal to 20 μm, discharging the color paste, washing the sand mill kettle with part of deionized water for 3 times, and keeping the washing water for later use;
mixing the rest propylene glycol methyl ether acetate and N, N-dimethylethanolamine, adding part of deionized water (including obtained washing water), adding water-based alkyd resin under the stirring condition, and adjusting the pH value to 7-8 after dilution;
keeping the stirring state, and slowly adding auxiliary agents such as a flatting agent, a thickening agent and the like and the obtained color paste; adjusting the pH value to 7-8, and adjusting the viscosity by using the residual deionized water; and filtering the mixture by using a 80-120-mesh filter screen to obtain the waterborne alcohol acid silver paste finish paint.
Comparative example 1
Comparative example 1 referring to the waterborne alkyd silver paste topcoat 1 of example 13 and the preparation method thereof, the difference is that 11 parts of soybean oil, 5.5 parts of tung oil, 11 parts of linseed oil, 1.9 parts of dehydrated castor oil, 1.8 parts of benzoic acid, 8 parts of pentaerythritol, 0.008 parts of lithium hydroxide, 11 parts of trimellitic anhydride, 0.5 parts of lauroyl peroxide, 17 parts of propylene glycol methyl ether acetate, 6 parts of N, N-dimethylethanolamine, and 28 parts of deionized water are used as the waterborne alkyd resin raw materials, and the waterborne alkyd silver paste topcoat is prepared according to the preparation method of example 1.
Comparative example 2
Comparative example 2 referring to the waterborne alkyd paste topcoat 1 of example 13 and the preparation method thereof, the difference is that 11 parts of soybean oil, 5.5 parts of tung oil, 11 parts of linseed oil, 1.9 parts of dehydrated castor oil, 1.8 parts of benzoic acid, 8 parts of pentaerythritol, 0.8 part of ethylene glycol, 0.008 part of lithium hydroxide, 11 parts of trimellitic anhydride, 0.5 part of lauroyl peroxide, 17 parts of propylene glycol methyl ether acetate, 6 parts of N, N-dimethylethanolamine, and 28 parts of deionized water are used as the waterborne alkyd resin raw materials not containing trimethylolpropane and ethylene glycol, and the waterborne alkyd resin topcoat is prepared by the preparation method of reference example 1.
Experimental example 1
To illustrate the performance of the waterborne alkyd finishes prepared according to inventive example 12 and comparative example by comparison, the following tests were carried out and the results are shown in Table 1.
Table 1 performance test results of different waterborne alkyd silver paste finishes
Figure BDA0002284669630000071
Figure BDA0002284669630000081
It can be seen from the above examples and comparative examples that the water-based alkyd resin of the present invention greatly improves the water resistance, stability, color retention, etc. of the conventional water-based alkyd resin. The prepared waterborne alkyd silver paste finish paint has good water resistance, good dispersion stability and good storage stability, and avoids the risk that a paint film of the traditional waterborne alkyd silver paste finish paint is damaged in a rainwater and dew environment. And the preparation method has simple process and mild conditions and is suitable for industrial production.

Claims (8)

1. The water-based alkyd resin is characterized by comprising the following raw materials in parts by weight: 25-40 parts of vegetable oil fatty acid, 1-5 parts of benzoic acid, 6-19 parts of polyhydric alcohol, 0.005-0.015 part of alcoholysis catalyst, 1-15 parts of trimellitic anhydride, 0.1-0.8 part of initiator, 10-20 parts of cosolvent, 3-10 parts of neutralizer and 20-35 parts of deionized water;
the alcoholysis catalyst is lithium hydroxide; the initiator is selected from one or more of acyl peroxides, dialkyl peroxides, inorganic peroxides and azo initiators; the cosolvent is propylene glycol methyl ether acetate; the neutralizing agent is N, N-dimethylethanolamine;
the vegetable oil fatty acid is a combination of soybean oil, tung oil, linseed oil and dehydrated castor oil, and the mass ratio of the vegetable oil fatty acid to the dehydrated castor oil is 2-8: 1-4: 2-8: 1; the polyhydric alcohol is selected from the combination of pentaerythritol, ethylene glycol and trimethylolpropane, and the mass ratio of the polyhydric alcohol to the trimethylolpropane is 8-15:1: 1.
2. A process for the preparation of a waterborne alkyd resin according to claim 1, comprising the steps of:
s1, adding vegetable oil fatty acid into a reaction kettle, starting stirring, adding polyol when the temperature is raised to 80 ℃, adding alcoholysis catalyst when the temperature is raised to 130 ℃, heating to 240 +/-5 ℃, and then carrying out heat preservation reaction for 1h until the volume ratio of the reaction mixture to 95% ethanol is 1: 4, clarifying the mixed solution at 25 ℃ to obtain an alcoholysis end point, and cooling for later use;
s2, cooling the mixture obtained in S1 to below 200 ℃, adding benzoic acid, heating to 160-170 ℃, refluxing and esterifying until the acid value is not more than 4mg/g, and cooling for later use;
s3, cooling the alkyd resin obtained in S2 to below 180 ℃, adding trimellitic anhydride, heating to 160-170 ℃, refluxing until the acid value of the reactant is not more than 50mg/g, cooling to 100 ℃, adding deionized water, cosolvent, initiator and neutralizer, and uniformly stirring to obtain the waterborne alkyd resin.
3. The waterborne alkyd silver paste finish paint is characterized by comprising the following components in parts by weight: 30-46 parts of water-based alkyd resin, 5-8 parts of propylene glycol methyl ether acetate, 1-2.5 parts of N, N-dimethylethanolamine, 25-55 parts of an auxiliary agent and 40-55 parts of deionized water; the waterborne alkyd resin of claim 1.
4. The waterborne alkyd silver paste topcoat of claim 3, wherein the waterborne alkyd resin has a solids content of 50 ± 2%.
5. The waterborne alkyd silver paste topcoat of claim 3, wherein the additive comprises one or more of a drier, a thickener, a defoamer, a leveling agent, and a pigment and filler.
6. The waterborne alkyd silver paste finish paint of claim 5, wherein the additive comprises, by weight, 0.2-1 part of a drier, 0.05-0.6 part of a thickener, 0.05-0.2 part of a defoamer, 0.05-0.2 part of a leveling agent, and 30-38 parts of a pigment and filler.
7. The waterborne alkyd silver paste topcoat of claim 5, wherein the drier is an Octa-Soligen Cobalt 7Aqua drier; the thickening agent is RW-8W thickening agent; the antifoaming agent is a Foamex 810 antifoaming agent; the leveling agent is ZY-9208; the pigment and filler is water-based aluminum paste.
8. The method for preparing the waterborne alkyd silver paste topcoat according to any one of claims 5 to 7, comprising the following steps:
adding part of propylene glycol methyl ether acetate and part of deionized water into a dispersion kettle, adding part of deionized water for dilution while stirring, adjusting the pH to 7-8, and slowly adding a defoaming agent and a drier under the condition of continuous stirring;
slowly adding pigment and filler while keeping stirring, grinding with a sand mill until the fineness is less than or equal to 20 μm, discharging the color paste, washing the sand mill kettle with part of deionized water for 3 times, and keeping the washing water for later use;
mixing the rest propylene glycol methyl ether acetate and N, N-dimethylethanolamine, adding flushing water and part of deionized water, adding water-based alkyd resin under the stirring condition, and adjusting the pH value to 7-8 after dilution;
keeping the stirring state, and slowly adding the rest of the auxiliary agent and the obtained color paste; adjusting the pH value to 7-8, and adjusting the viscosity by using the residual deionized water; and filtering the mixture by using a 80-120-mesh filter screen to obtain the waterborne alcohol acid silver paste finish paint.
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