CN111019091A - Bio-based modified epoxy resin, bio-based electrophoretic coating and preparation method thereof - Google Patents
Bio-based modified epoxy resin, bio-based electrophoretic coating and preparation method thereof Download PDFInfo
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- CN111019091A CN111019091A CN201911260534.7A CN201911260534A CN111019091A CN 111019091 A CN111019091 A CN 111019091A CN 201911260534 A CN201911260534 A CN 201911260534A CN 111019091 A CN111019091 A CN 111019091A
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1477—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing nitrogen
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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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/028—Polyamidoamines
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
- C09D5/443—Polyepoxides
- C09D5/4434—Polyepoxides characterised by the nature of the epoxy binder
- C09D5/4442—Binder characterised by functional groups
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
- C09D5/443—Polyepoxides
- C09D5/4457—Polyepoxides containing special additives, e.g. pigments, polymeric particles
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention discloses a bio-based modified epoxy resin, which is modified by a bio-based material, and a cathode electrophoretic coating is modified by structures such as a bio-based oil group, a bio-based alkyl long chain and the like through molecular design, so that the glass transition temperature of the bio-based modified epoxy resin can be effectively reduced, the leveling and appearance of the bio-based modified epoxy resin are improved, and the leveling and toughening effects of the bio-based modified epoxy resin can be more efficiently exerted. The invention also discloses a method for preparing the bio-based electrophoretic coating by adopting the bio-based modified epoxy resin and the bio-based electrophoretic coating, and the prepared bio-based electrophoretic coating can be used for coating in the field of electrophoretic coatings, and has more excellent throwing power, corrosion resistance, low heating decrement, low VOC emission, environmental protection and the like compared with the traditional electrophoretic coating, and particularly has the properties of flexibility, impact resistance and the like. Meanwhile, the bio-based electrophoretic coating system has wide raw material sources and 20% -50% of renewable materials or bio-based internal content.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a bio-based modified epoxy resin, a bio-based electrophoretic coating and a preparation method thereof.
Background
The electrophoretic coating is widely applied to the fields with various special properties such as automobile bodies, automobile parts and the like, and particularly, the electrophoretic coating mainly adopts a cathode electrophoretic coating mode, so that the electrophoretic coating is widely applied. Since the sixties of the last century put into industrial production, the electrophoretic coating industry has developed very rapidly due to the advantages of excellent coating performance, high coating utilization rate and the like of electrophoretic coating. The cathode electrophoretic coating is widely applied to the industries and fields of automobile bodies, automobile and motorcycle accessories, household appliances, furniture accessories, hardware, electromechanics, war industry and the like. However, most of the raw materials of these electrodeposition paints are converted from fossil fuels, such as petroleum and coal, and environmental pollution is seriously aggravated by two problems of shortage of petrochemical resources and environmental pollution caused by excessive exploitation of petroleum and coal production.
Bio-based materials, generally referred to as high molecular materials, are formed by biotransformation of renewable raw materials to give biopolymer materials or monomers, which are then further polymerized. Compared with the traditional petroleum-based material, the bio-based material is mainly derived from plants, the emission of carbon dioxide and the dependence on petroleum are reduced, meanwhile, the production process is more green, the pursuit of people on environmental protection and sustainable development is met, the current bio-based material has rapid industrial development and continuous technical breakthrough, and the variety and the application of the bio-based material are greatly leaped. Therefore, the electrophoretic paint industry needs to modify the electrophoretic paint from a bio-based material, and the electrophoretic paint can be developed more green and sustainable on the premise of ensuring the comprehensive performance of the electrophoretic paint.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a bio-based electrophoretic coating and a preparation method thereof, the bio-based electrophoretic coating modifies epoxy resin through bio-based materials and is used for preparing the bio-based electrophoretic coating, and the prepared bio-based electrophoretic coating has more excellent comprehensive performances such as flexibility, impact resistance and the like compared with the traditional electrophoretic coating.
The technical scheme adopted by the invention is as follows:
a bio-based modified epoxy resin has a structural formula as follows:
b is secondary amine compound, including diethylamine, dibutylamine, methylbutylamine, diethanolamine, dibutanolamine, N-methylethanolamine; a base amine providing a cationic structure to the modified epoxy resin;
r8 is selected from at least one of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac resin and cresol novolac resin; preferably bisphenol a type epoxy resin;
r9 is a bio-based diacid including bio-based succinic acid.
As a further improvement of the above scheme, the bio-based modified epoxy resin is synthesized by: adding 800 parts of 500-plus-one bisphenol A epoxy resin, 50-100 parts of methyl isobutyl ketone, 150 parts of 100-plus-one bio-based succinic acid and 500 parts of 400-plus-one bisphenol A into a reactor in a nitrogen environment, stirring and mixing uniformly, heating to 80-100 ℃, adding 1-2 parts of an alkaline catalyst, preserving heat for 4-6h at the temperature of 150-plus-one 170 ℃, cooling to below 100 ℃, adding 200-plus-one 300 parts of epoxidized soybean oil, 150-plus-one N-methylethanolamine and 200-plus-one 300 parts of polyamide modified ketimine resin, preserving heat for 6-10h at the temperature of 120-plus-one 150 ℃, obtaining the bio-based modified epoxy resin, cooling to 60-80 ℃ for later use.
Wherein the basic catalyst is at least one selected from triethylamine, N-methyldiethylamine, N-dimethylbenzylamine, N-dimethylisopropylamine, N-diethylbutylamine, triethanolamine, tetramethylammonium chloride, triphenylphosphine, a triethanolamine salt, 2-methyl-3 imidazole, N-dimethylethanolamine and 4, 4-diazabicyclo [2,2,2] octane.
According to the bio-based modified epoxy resin, the traditional bio-based epoxy resin of epoxidized soybean oil is introduced, so that the usage amount of petrochemical epoxy resin can be effectively reduced, and meanwhile, soft groups in a system are ensured, so that the synthesized bio-based electrophoretic coating has better thermal stability, light stability, mechanical strength, weather resistance and electric conductivity compared with the traditional electrophoretic coating, and the environmental protection property of the electrophoretic coating is greatly improved.
As a further improvement of the above scheme, the structural formula of the polyamide modified ketimine resin is:
wherein R0 is a bio-based aliphatic amine, including bio-based pentanediamine; r1 is a biobased dimer acid, including dimer fatty acid; r2 is bio-based vegetable oil acid, which is selected from one or two of ricinoleic acid, cotton oil acid, linoleic acid, and rapeseed oil acid; r3 is fatty amine, and the fatty amine is one or two selected from ethylenediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine and polyethylene polyamine; r4 is a ketone in which the number of carbon atoms in the hydrocarbon group is 1 to 8.
As a further improvement of the scheme, the polyamide modified ketimine resin comprises the following components in parts by weight:
the polyamide modified ketimine resin is synthesized by the following method: adding bio-based fatty amine, bio-based dimer acid, bio-based vegetable oleic acid and fatty amine into a reaction kettle filled with nitrogen, stirring and heating, carrying out dehydration reaction, controlling the temperature below 160 ℃, collecting 95-100% of dehydration amount which is the theoretical dehydration amount (calculating the theoretical dehydration amount according to the amount of amine and acid added after the reaction of amine hydrogen and carboxyl), cooling to below 100 ℃, adding ketone, heating to 170-230 ℃, setting the pressure value of a vacuum meter to-0.092 MPa, reducing the pressure for 30min, and cooling to below 100 ℃ after collecting the dehydration amount which is 95-100% of the theoretical dehydration amount (calculating the theoretical dehydration amount according to the reaction of ketone and amine hydrogen and the amount of amine added after the reaction of ketone and ketone).
The bio-based electrophoretic paint comprises a bio-based electrophoretic paint emulsion and a bio-based pigment dispersion color paste, wherein the raw material composition of the bio-based electrophoretic paint emulsion comprises the bio-based modified epoxy resin.
As a further improvement of the scheme, the bio-based electrophoretic coating emulsion comprises the following components in parts by weight:
wherein, the polyurethane curing agent is a self-crosslinking bio-based modified polyurethane curing agent and is prepared by adopting the following method: taking 50-70 parts of 4, 4' -diphenylmethane diisocyanate and 10-30 parts of methyl isobutyl ketone, stirring and mixing uniformly, setting the temperature to be 30-50 ℃, adding 5-10 parts of bio-based ethanol, preserving the heat for 2-4 hours, then dropwise adding 10-15 parts of bio-based propylene glycol at a certain rate, and continuously preserving the heat for 3-5 hours at 30-50 ℃ to obtain the product.
As a further improvement of the above aspect, the bio-based co-solvent is selected from at least one of ethanol, propylene glycol, acetone, hydroxymethyl fiber, and rosin.
As a further improvement of the above aspect, the bio-based neutralizing agent is selected from at least one of formic acid, acetic acid, lactic acid, and trihydroxypropionic acid.
As a further improvement of the scheme, the bio-based pigment dispersion color paste comprises the following raw materials in parts by weight: 0-30 parts of titanium dioxide, 10-20 parts of diatomite, 10-20 parts of cellulose, 0-5 parts of bio-based carbon black, 1-5 parts of mixed solution of acetone and rosin, 30-40 parts of dispersion resin, 0-2 parts of neutralizer and 20-40 parts of water.
Wherein, titanium dioxide, diatomite and cellulose are used as pigment and filler, and the pigment and filler can also comprise titanium dioxide and other colored pigments; kaolin, barium sulfate, talcum powder, silica, aluminum silicate and fillers thereof; zinc phosphate, aluminum phosphate, zinc oxide, aluminum tripolyphosphate, zinc molybdate and rust-inhibiting pigments thereof, preferably fillers for marine shellfish petrochemicals, particularly preferably diatomaceous earth and quartz.
The bio-based carbon black comprises at least one of bio-based bamboo charcoal carbon black and other plant carbon black.
The dispersion resin comprises at least one of dispersion resin containing quaternary ammonium salt groups or sulfonium salt groups and amine modified epoxy resin containing tertiary amine groups, and the dispersion resin containing quaternary ammonium salt groups is preferably AD-3 dispersion resin of Guangdong Kode environmental protection science and technology corporation; the dispersing resin containing sulfonium salt group is preferably AD-4 dispersing resin of Guangdong environmental protection science and technology, and the amine modified epoxy resin of tertiary amine group is preferably ED-1 dispersing resin of Guangdong science and technology.
A preparation method of a bio-based electrophoretic coating comprises the following process steps:
(1) synthesis of bio-based electrophoretic coating emulsion
Weighing the raw materials according to the formula of the bio-based electrophoretic coating emulsion, adding the bio-based modified epoxy resin, the polyurethane curing agent and the bio-based cosolvent into a reaction kettle, uniformly mixing at 70-80 ℃, adding the bio-based neutralizing agent and 25-35 parts of water, stirring at a high speed for 60-120min, adding 150 parts of 100-organic solvent, and adding 200 parts of 100-organic solvent at an interval of 60min in the stirring process to obtain the bio-based electrophoretic coating emulsion;
(2) synthesis of bio-based pigment dispersion color paste
a. Pre-dispersing: weighing the raw materials according to the formula of the biological pigment dispersion color paste, adding the raw materials except the titanium dioxide, the diatomite and the cellulose into a dispersion kettle, and stirring for 30-60min at the speed of 800-1500r/min until the raw materials are uniformly dispersed; adding the pigment and the filler, stirring for 2-4h at the speed of 1500-;
b. grinding: adding the wetted pigment paste into a vertical or horizontal sand mill, adding zirconium or ceramic beads with the particle size of 1.2-1.5mm for grinding, controlling the grinding temperature below 40 ℃, and obtaining uniform bio-based pigment dispersoid color paste after grinding, wherein the grinding fineness is required to be less than or equal to 10 mu m;
c. and (3) filtering and packaging: filtering with bag filter with filter bag mesh of 1 μm;
(3) adding water (the conductivity is controlled to be less than 5 mu s/cm, the temperature is controlled to be below 30 ℃) into a tank body, adding the bio-based electrophoretic coating emulsion, starting a main circulation system and a constant temperature system, adding the bio-based pigment dispersion color paste, and curing for 24-48h at normal temperature to obtain the bio-based electrophoretic coating working solution according to the mass ratio of 1 (1-8) to (2-9).
Wherein the preferred value of the bio-based electrophoretic coating emulsion, the bio-based pigment dispersion color paste and the water is 1:3:4 according to the mass ratio.
The solid content of the bio-based electrophoretic coating emulsion is 30-40%, the particle size is less than or equal to 80nm, the pH value is 5-7, and the conductivity (mu s/cm) is 800-.
The pigment dispersion color paste has the following characteristics: fineness is less than or equal to 10 mu m, solid content: 40-60%, pH: 5.5-8.5, conductivity (. mu.s/cm): 500-1500.
The bio-based electrophoretic coating bath solution has the following characteristics: pH: 5.0-6.5, conductivity (. mu.s/cm): 800-2000, the MEQA value is 25-40(MEQA refers to millimole number of acid needed for titrating the coating containing 100g of solid in the electrophoretic coating, the unit is mmol), the coulombic efficiency is more than 25, the electrophoretic voltage is 80-300V, the electrophoretic temperature is 25-35 ℃, and the electrophoretic time is 3min (30 second soft start); the baking temperature is 160-180 ℃, and the baking time is 20-40 minutes; the prepared paint film has uniform, flat and smooth appearance and adjustable film thickness within 10-40 mu m.
The invention has the beneficial effects that:
(1) the invention provides a bio-based modified epoxy resin, which is modified by a bio-based material, and a cathode electrophoretic coating is modified by structures such as a bio-based oil group, a bio-based alkyl long chain and the like through molecular design, so that the glass transition temperature of the bio-based modified epoxy resin can be effectively reduced, the leveling and appearance of the bio-based modified epoxy resin are improved, and the leveling and toughening effects of the bio-based modified epoxy resin can be more efficiently exerted.
(2) The invention also provides a method for preparing the bio-based electrophoretic coating by adopting the bio-based modified epoxy resin and the bio-based electrophoretic coating, and the prepared bio-based electrophoretic coating can be used for coating in the field of electrophoretic coatings, and has more excellent throwing power, corrosion resistance, low heating decrement, low VOC emission, environmental protection and the like compared with the traditional electrophoretic coating, and particularly has the properties of flexibility, impact resistance and the like. Meanwhile, the bio-based electrophoretic coating system has wide raw material sources, 20% -50% of renewable materials or bio-based internal content, and good compatibility and dispersibility in a water-based electrophoretic coating matrix.
Detailed Description
The present invention is specifically described below with reference to examples in order to facilitate understanding of the present invention by those skilled in the art. It should be particularly noted that the examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as non-essential improvements and modifications to the invention may occur to those skilled in the art, which fall within the scope of the invention as defined by the appended claims. Meanwhile, the raw materials mentioned below are not specified in detail and are all commercial products; the process steps or preparation methods not mentioned in detail are all process steps or preparation methods known to the person skilled in the art.
Example 1
Adding 500 parts of bisphenol A epoxy resin, 50 parts of methyl isobutyl ketone, 100 parts of bio-based succinic acid and 400 parts of bisphenol A into a reactor in a nitrogen environment, stirring and mixing uniformly, heating to 80 ℃, adding 1 part of N, N-dimethylbenzylamine, preserving heat for 4 hours at 150 ℃, cooling to 95 ℃, adding 200 parts of epoxidized soybean oil, 150 parts of N-methylethanolamine and 200 parts of polyamide modified ketimine resin, preserving heat for 6 hours at 120 ℃ to obtain bio-based modified epoxy resin 1, and cooling to 60-80 ℃ for later use.
Example 2
Adding 800 parts of bisphenol A epoxy resin, 100 parts of methyl isobutyl ketone, 150 parts of bio-based succinic acid and 500 parts of bisphenol A into a reactor in a nitrogen environment, stirring and mixing uniformly, heating to 100 ℃, adding 2 parts of N, N-dimethylbenzylamine, preserving heat for 6 hours at 170 ℃, cooling to 95 ℃, adding 300 parts of epoxidized soybean oil, 250 parts of N-methylethanolamine and 300 parts of polyamide modified ketimine resin, preserving heat for 6-10 hours at 150 ℃, obtaining bio-based modified epoxy resin 2, and cooling to 60-80 ℃ for later use.
Example 3
Adding 700 parts of bisphenol A epoxy resin, 80 parts of methyl isobutyl ketone, 130 parts of bio-based succinic acid and 450 parts of bisphenol A into a reactor in a nitrogen environment, stirring and mixing uniformly, heating to 90 ℃, adding 2 parts of N, N-dimethylbenzylamine, preserving heat for 5 hours at 160 ℃, cooling to 95 ℃, adding 250 parts of epoxidized soybean oil, 200 parts of N-methylethanolamine and 250 parts of polyamide modified ketimine resin, preserving heat for 8 hours at 130 ℃ to obtain bio-based modified epoxy resin 3, and cooling to 60-80 ℃ for later use.
The bio-based electrophoretic coating is prepared by respectively taking the bio-based modified epoxy resins 1-3 obtained in the examples 1-3 as raw materials, and the preparation process comprises the following steps:
example 4
The preparation method of the bio-based electrophoretic coating comprises the following steps:
(1) synthesis of bio-based electrophoretic coating emulsion
Weighing raw materials according to a formula, adding 100 parts of bio-based modified epoxy resin 1, 20 parts of polyurethane curing agent and 1 part of bio-based cosolvent into a reaction kettle, uniformly mixing at 70 ℃, adding 4 parts of bio-based neutralizer and 25 parts of water, stirring at a high speed for 60min, adding 100 parts of water, and adding 100 parts of water at an interval of 60min in the stirring process to obtain a bio-based electrophoretic coating emulsion;
(2) synthesis of bio-based pigment dispersion color paste
d. Pre-dispersing: weighing raw materials according to the formula of the bio-based pigment dispersion color paste, adding 1 part of bio-based carbon black, 1 part of mixed solution of acetone and rosin, 30 parts of dispersion resin, 1 part of neutralizer and 20 parts of water into a dispersion kettle, and stirring for 30min at 800r/min until the mixture is uniformly dispersed; then adding 20 parts of titanium dioxide, 10 parts of diatomite and 10 parts of cellulose, stirring for 2 hours at 1500r/min, keeping the temperature below 60 ℃ to obtain uniform pre-dispersed pigment slurry, and standing for more than 48 hours;
e. grinding: adding the mixture into a sand mill, adding zirconium or ceramic beads into the sand mill, grinding at the temperature of below 40 ℃ until the grinding fineness is required to be less than or equal to 10 mu m, and grinding to obtain the bio-based pigment dispersion color paste;
f. filtering and packaging;
(3) adding water into the tank according to the mass ratio of 1:3:4, adding the bio-based electrophoretic coating emulsion, starting the main circulation system and the constant temperature system, adding the bio-based pigment dispersion color paste, and curing at normal temperature for 24 hours to obtain the bio-based electrophoretic coating working solution 1.
Example 5
The preparation method of the bio-based electrophoretic coating comprises the following steps:
(1) synthesis of bio-based electrophoretic coating emulsion
Weighing raw materials according to a formula, adding 200 parts of bio-based modified epoxy resin 2, 50 parts of polyurethane curing agent and 15 parts of bio-based cosolvent into a reaction kettle, uniformly mixing at 80 ℃, adding 10 parts of bio-based neutralizer and 35 parts of water, stirring at a high speed for 120min, adding 150 parts of water, and adding 200 parts of water at an interval of 60min in the stirring process to obtain a bio-based electrophoretic coating emulsion;
(2) synthesis of bio-based pigment dispersion color paste
g. Pre-dispersing: weighing raw materials according to the formula of the bio-based pigment dispersion color paste, adding 5 parts of bio-based carbon black, 5 parts of a mixed solution of acetone and rosin, 40 parts of dispersion resin, 2 parts of a neutralizer and 40 parts of water into a dispersion kettle, and stirring for 60min at 1500r/min until the mixture is uniformly dispersed; then adding 30 parts of titanium dioxide, 20 parts of diatomite and 20 parts of cellulose, stirring for 4 hours at 2000r/min, keeping the temperature below 60 ℃ to obtain uniform pre-dispersed pigment slurry, and standing for more than 24 hours;
h. grinding: adding the mixture into a sand mill, adding zirconium or ceramic beads into the sand mill, grinding at the temperature of below 40 ℃ until the grinding fineness is required to be less than or equal to 10 mu m, and grinding to obtain the bio-based pigment dispersion color paste;
i. filtering and packaging;
(3) adding water into the tank according to the mass ratio of 1:3:4, adding the bio-based electrophoretic coating emulsion, starting the main circulation system and the constant temperature system, adding the bio-based pigment dispersion color paste, and curing at normal temperature for 48 hours to obtain the bio-based electrophoretic coating working solution 2.
Example 6
The preparation method of the bio-based electrophoretic coating comprises the following steps:
(1) synthesis of bio-based electrophoretic coating emulsion
Weighing raw materials according to a formula, adding 150 parts of bio-based modified epoxy resin 3, 35 parts of polyurethane curing agent and 8 parts of bio-based cosolvent into a reaction kettle, uniformly mixing at 75 ℃, adding 7 parts of bio-based neutralizer and 30 parts of water, stirring at a high speed for 90min, adding 120 parts of water, and adding 150 parts of water at an interval of 60min in the stirring process to obtain a bio-based electrophoretic coating emulsion;
(2) synthesis of bio-based pigment dispersion color paste
j. Pre-dispersing: weighing the raw materials according to the formula of the bio-based pigment dispersion color paste, adding 3 parts of bio-based carbon black, 3 parts of mixed solution of acetone and rosin, 35 parts of dispersion resin, 1 part of neutralizer and 30 parts of water into a dispersion kettle, and stirring for 45min at 1200r/min until the mixture is uniformly dispersed; then adding 15 parts of titanium dioxide, 15 parts of diatomite and 15 parts of cellulose, stirring for 3 hours at 1800r/min, keeping the temperature below 60 ℃ to obtain uniform pre-dispersed pigment slurry, and standing for more than 24 hours;
k. grinding: adding the mixture into a sand mill, adding zirconium or ceramic beads into the sand mill, grinding at the temperature of below 40 ℃ until the grinding fineness is required to be less than or equal to 10 mu m, and grinding to obtain the bio-based pigment dispersion color paste;
l, filtering and packaging;
(4) adding water into the tank according to the mass ratio of 1:3:4, adding the bio-based electrophoretic coating emulsion, starting the main circulation system and the constant temperature system, adding the bio-based pigment dispersion color paste, and curing at normal temperature for 36 hours to obtain the bio-based electrophoretic coating working solution 3.
Comparative example 1
The electrophoretic paint working solution is obtained by mixing EED-060M emulsion and EEB-068A color paste which are commercially available from Youli industries, Ltd, according to a proportion, and is marked as comparative example working solution 1.
Example 7
As a result of examination, the working solutions 1 to 3 for bio-based electrodeposition paints obtained in examples 4 to 6 and the working solution 1 for comparative example were evaluated for film properties in terms of appearance, film thickness, gloss, adhesion, cupping, flexibility, water resistance (40 ℃ C.), impact resistance, salt spray resistance, alkali resistance, acid resistance, etc., and the following Table 1 was obtained. The electrophoretic coating in the film coating performance evaluation process is subjected to plate beating test according to the following standards: the bath temperature is set to 25-35 deg.C, the plate is made by conventional method under the voltage of 20 + -2 μm of film thickness, and after electrophoresis, the plate is cleaned and baked at 160 deg.C for 20min for film coating performance test.
TABLE 1 evaluation of coating film Performance of Bio-based electrophoretic coating working fluids 1-3
As can be seen from table 1, the heating loss of the bio-based electrodeposition coating, i.e., VOC emission of the electrodeposition coating, is significantly reduced compared to the conventional electrodeposition coating. As the epoxy main body resin introduces the bio-based oil group and the bio-based long chain through a molecular grafting mode, the bio-based electrophoretic coating has obvious flexibility and impact resistance compared with the traditional electrophoretic coating.
It will be obvious to those skilled in the art that many simple derivations or substitutions can be made without inventive effort without departing from the inventive concept. Therefore, simple modifications to the present invention by those skilled in the art according to the present disclosure should be within the scope of the present invention. The above embodiments are preferred embodiments of the present invention, and all similar processes and equivalent variations to those of the present invention should fall within the scope of the present invention.
Claims (10)
1. The bio-based modified epoxy resin is characterized by having a structural formula as follows:
wherein A is polyamide modified ketimine resin;
b is secondary amine compound, including diethylamine, dibutylamine, methylbutylamine, diethanolamine, dibutanolamine, N-methylethanolamine;
r8 is selected from at least one of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac resin and cresol novolac resin;
r9 is a bio-based diacid including bio-based succinic acid.
2. The bio-based modified epoxy resin as claimed in claim 1, wherein the bio-based modified epoxy resin is synthesized by: adding bisphenol A epoxy resin, methyl isobutyl ketone, bio-based succinic acid and bisphenol A into a reactor in a nitrogen environment, stirring and mixing uniformly, heating to 80-100 ℃, adding an alkaline catalyst, keeping the temperature at 150-170 ℃ for 4-6h, cooling to below 100 ℃, adding epoxidized soybean oil, N-methylethanolamine and polyamide modified ketimine resin, and keeping the temperature at 120-150 ℃ for 6-10h to obtain the bio-based modified epoxy resin.
3. The bio-based modified epoxy resin as claimed in claim 1, wherein the structural formula of the polyamide-modified ketimine resin is:
wherein R0 is a bio-based aliphatic amine, including bio-based pentanediamine; r1 is a biobased dimer acid, including dimer fatty acid; r2 is bio-based vegetable oil acid, which is selected from one or two of ricinoleic acid, cotton oil acid, linoleic acid, and rapeseed oil acid; r3 is fatty amine, and the fatty amine is one or two selected from ethylenediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine and polyethylene polyamine; r4 is a ketone in which the number of carbon atoms in the hydrocarbon group is 1 to 8.
4. The bio-based modified epoxy resin as claimed in claim 3, wherein the polyamide modified ketimine resin comprises the following components in parts by weight:
5. the bio-based electrophoretic paint is characterized by comprising a bio-based electrophoretic paint emulsion and a bio-based pigment dispersion color paste, wherein the raw material composition of the bio-based electrophoretic paint emulsion comprises the bio-based modified epoxy resin as claimed in claim 1 or 2.
6. The bio-based electrophoretic paint as claimed in claim 5, wherein the bio-based electrophoretic paint emulsion comprises the following components in parts by weight:
7. the bio-based electrophoretic paint as claimed in claim 6, wherein the bio-based co-solvent is at least one selected from ethanol, propylene glycol, acetone, hydroxymethyl fiber and rosin.
8. The bio-based electrophoretic coating according to claim 6, wherein the bio-based neutralizing agent is at least one selected from the group consisting of formic acid, acetic acid, lactic acid, and trihydroxypropionic acid.
9. The bio-based electrophoretic paint as claimed in claim 6, wherein the bio-based pigment dispersion color paste comprises the following raw materials in parts by weight: 0-30 parts of titanium dioxide, 10-20 parts of diatomite, 10-20 parts of cellulose, 0-5 parts of bio-based carbon black, 1-5 parts of mixed solution of acetone and rosin, 30-40 parts of dispersion resin, 0-2 parts of neutralizer and 20-40 parts of water.
10. The preparation method of the bio-based electrophoretic coating is characterized by comprising the following steps:
(1) synthesis of bio-based electrophoretic coating emulsion
Weighing raw materials according to the formula of the bio-based electrophoretic paint emulsion of claim 6, adding the bio-based modified epoxy resin, the polyurethane curing agent and the bio-based cosolvent into a reaction kettle, uniformly mixing at 70-80 ℃, adding the bio-based neutralizing agent and water, and stirring at a high speed for 60-120min to obtain the bio-based electrophoretic paint emulsion;
(2) synthesis of bio-based pigment dispersion color paste
a. Pre-dispersing: weighing the raw materials according to the formula of the bio-based pigment dispersion color paste as claimed in claim 9, adding the raw materials except titanium dioxide, diatomite and cellulose into a dispersion kettle, and stirring for 30-60min at 800-; then adding titanium dioxide, diatomite and cellulose, stirring for 2-4h at the temperature of below 60 ℃ at 2000r/min of 1500-;
b. grinding: adding the mixture into a sand mill, adding zirconium or ceramic beads into the sand mill, grinding at the temperature of below 40 ℃ until the grinding fineness is required to be less than or equal to 10 mu m, and grinding to obtain the bio-based pigment dispersion color paste;
c. filtering and packaging;
(3) adding water into a tank according to the mass ratio of 1 (1-8) to (2-9), adding the bio-based electrophoretic coating emulsion, starting a main circulation system and a constant temperature system, adding the bio-based pigment dispersion color paste, and curing at normal temperature for 24-48h to obtain the bio-based electrophoretic coating working solution.
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| CN113980575A (en) * | 2021-09-23 | 2022-01-28 | 枣阳市润图化工有限责任公司 | Water-soluble electrophoretic paint with uniform coating film and strong adhesive force |
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