CN114605910B - Semi-inorganic silicon steel sheet paint - Google Patents

Semi-inorganic silicon steel sheet paint Download PDF

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CN114605910B
CN114605910B CN202210229033.8A CN202210229033A CN114605910B CN 114605910 B CN114605910 B CN 114605910B CN 202210229033 A CN202210229033 A CN 202210229033A CN 114605910 B CN114605910 B CN 114605910B
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silicon steel
semi
polyoxyethylene ether
paint
inorganic silicon
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CN114605910A (en
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沈超
张春琪
吴斌
顾健峰
潘德忠
周林江
井丰喜
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Suzhou Taihu Electric Advanced Material Co ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D179/00Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular 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
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/02Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/09Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
    • C08J3/091Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
    • C08J3/095Oxygen containing compounds
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/61Additives non-macromolecular inorganic
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
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    • C09DCOATING 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
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C09D7/65Additives macromolecular
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2237Oxides; Hydroxides of metals of titanium
    • C08K2003/2241Titanium dioxide
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/30Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045Sulfates

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Abstract

The invention discloses a silicon steel sheet paint which is prepared by adopting a specific polyamide-imide emulsion, trimellitic anhydride is reacted with a double-end amino compound in a combined form, triethylamine is added to further improve the reaction degree and endow the whole system with better flexibility and toughness, tributyl phosphate can further improve the toughness of the system through physical modification, all organic solvents are evaporated out, a certain amount of water-soluble organic solvent is added, then an activating agent in a combined form is added, mixing is carried out, water is dripped to form stable emulsion, and finally residual active groups of bismaleimide end capping are added.

Description

Semi-inorganic silicon steel sheet paint
The invention is a divisional application of Chinese patent application with the application date of 22.12.2020 and 22.2020115287067 and the name of 'semi-inorganic silicon steel sheet paint and a preparation method and application thereof'.
Technical Field
The invention belongs to the technical field of insulating paint, and particularly relates to semi-inorganic silicon steel sheet paint.
Background
The silicon steel sheet varnish is covering varnish which plays a role in insulation protection on the surface of a silicon steel sheet. The paint for silicon steel sheets is coated on the surface of the processed and formed silicon steel sheets, is used for reducing eddy current loss after lamination and enhancing the antirust and corrosion resistant capabilities, and has the requirements of thinness, strong adhesion, hardness, smoothness, uniformity, oil resistance, moisture resistance and excellent electrical performance.
With the increasing demand of the country for environmental protection, the semi-inorganic silicon steel sheet paint with the properties of low VOC, little smell, convenient application and the like receives wide attention. For the paint for silicon steel sheets, the electrical property, the bonding strength and the temperature resistance index of the paint are the most core properties of the paint, and the resistance and the construction performance of the paint to various environments are very important because the paint is coated on the silicon steel sheets. However, the current semi-inorganic silicon steel sheet varnish, especially the semi-inorganic silicon steel sheet varnish capable of being stably dispersed in water, generally cannot simultaneously take into consideration the most critical performances.
Therefore, the preparation of the semi-inorganic silicon steel sheet paint which has high temperature resistance, high bonding strength, strong electrical property, good environmental resistance and construction performance and good water dispersibility is of great significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the improved semi-inorganic silicon steel sheet paint which not only can adopt water as a main solvent and improve the environment protection, but also has the advantages of high temperature resistance, high bonding strength, strong electrical performance and the like and has good environmental resistance and construction performance.
In order to solve the technical problems, the invention adopts the following technical scheme:
the semi-inorganic silicon steel sheet paint comprises the following components: the resin emulsion is polyamide-imide clear emulsion, the inorganic filler is composed of titanium dioxide, silicon dioxide and barium sulfate, and the curing agent is amino resin;
wherein the polyamide-imide emulsion is prepared by the following method:
(1) Under the protection of protective gas, under the reflux state, enabling trimellitic anhydride and a double-end amino compound to perform a first reaction in a first organic solvent to obtain a first mixed solution, adding tributyl phosphate and triethylamine into the obtained first mixed solution, and performing a second reaction to obtain a second mixed solution; the amino-terminated compound consists of 4,4 '-diaminodiphenyl ether, 4' -diaminodiphenylmethane and 1, 6-diaminohexane;
(2) Under the protection of protective gas, the first organic solvent contained in the second mixed solution is evaporated outwards to obtain a third mixed solution;
(3) And adding a second organic solvent into the third mixed solution, adding linear alkyl benzene sodium sulfonate, fatty alcohol-polyoxyethylene ether sodium sulfate and fatty alcohol-polyoxyethylene ether, mixing, dripping water under the stirring condition, and adding bismaleimide for end capping after dripping to obtain the polyamide-imide emulsion.
According to some preferred aspects of the present invention, in step (1), the first reaction is carried out at 140 to 170 ℃.
According to some preferred aspects of the present invention, in the step (1), the molar ratio of the trimellitic anhydride to the double-terminal amino compound is fed in a range of 1: 1.02 to 1.50.
According to some preferred aspects of the present invention, in step (1), the 4,4 '-diaminodiphenyl ether, the 4,4' -diaminodiphenylmethane and the 1, 6-diaminohexane are fed in a molar ratio of 1: 0.8-1.3: 0.3-0.9.
According to some preferred aspects of the invention, in step (1), the second reaction is carried out at 185-205 ℃.
According to some preferred aspects of the present invention, in step (1), the molar ratio of the fed triethylamine to the fed trimellitic anhydride is in the range of 0.1-0.2: 1.
According to some preferred aspects of the present invention, in the step (3), the temperature of the third mixed solution is controlled to be 60 to 80 ℃, and then the linear alkylbenzene sodium sulfonate, the fatty alcohol-polyoxyethylene ether sodium sulfate and the fatty alcohol-polyoxyethylene ether are added.
According to some preferred aspects of the invention, in step (3), the capping is performed at 15 to 35 ℃; and/or in the step (3), the feeding mass ratio of the linear alkyl benzene sodium sulfonate, the fatty alcohol-polyoxyethylene ether sodium sulfate and the fatty alcohol-polyoxyethylene ether is 2-4: 0.5-4: 1.
According to some preferred aspects of the present invention, the mass ratio of the total charge of the sodium linear alkylbenzene sulfonate, the sodium fatty alcohol-polyoxyethylene ether sulfate and the fatty alcohol-polyoxyethylene ether to the charge of the trimellitic anhydride is 0.06-0.18: 1.
According to some preferred aspects of the present invention, in step (3), the linear alkyl benzene sulfonic acid sodium salt is sodium dodecyl benzene sulfonate, the fatty alcohol-polyoxyethylene ether sodium sulfate is one or more selected from the group consisting of sodium lauryl alcohol polyoxyethylene ether sulfate, sodium tridecanol polyoxyethylene ether sulfate, sodium tetradecanol polyoxyethylene ether sulfate and sodium pentadecanol polyoxyethylene ether sulfate, and the fatty alcohol-polyoxyethylene ether is lauryl alcohol polyoxyethylene ether and/or tridecanol polyoxyethylene ether.
According to some preferred aspects of the present invention, in step (3), the charged molar ratio of the bismaleimide to the trimellitic anhydride is 0.2-0.3: 1.
According to some preferred aspects of the present invention, in the step (3), the bismaleimide is diphenylmethane bismaleimide, N' -m-phenylene bismaleimide.
According to some preferred aspects of the present invention, in step (1) or step (2), the protective gas is nitrogen and/or argon.
According to some preferred aspects of the present invention, in the step (2), the evaporation is performed at 210 to 230 ℃.
According to some preferred aspects of the present invention, the first organic solvent in step (1) is dimethylacetamide and the second organic solvent in step (3) is diethylene glycol monobutyl ether.
According to some preferred aspects of the invention, the amino resin is cyanite 325 amino resin.
According to some preferred aspects of the present invention, the silica is a modified silica, which is produced by reacting silica with a silane coupling agent; the feeding mass ratio of the titanium dioxide, the modified silicon dioxide and the barium sulfate is 1: 0.8-1.2.
According to the invention, the three fillers are added simultaneously, so that the dispersibility of the fillers under the same addition amount is improved, and the performance of the paint is improved.
According to some preferred aspects of the invention, the semi-inorganic silicon steel sheet paint comprises, by mass, 500-600 parts of polyamideimide clear emulsion, 90-150 parts of inorganic filler, 30-50 parts of curing agent, and optionally 10-30 parts of suspension stabilizer, wherein the suspension stabilizer is lithium bentonite, and the solid content of the polyamideimide clear emulsion is 55-65%.
The invention also provides a technical scheme: the preparation method of the semi-inorganic silicon steel sheet varnish comprises the following steps: the semi-inorganic silicon steel sheet varnish is prepared by mixing the components and then carrying out ultrasonic dispersion.
The invention also provides a technical scheme: the utility model provides a silicon steel sheet, includes the silicon steel sheet body and covers and establish the covering paint on silicon steel sheet body surface, the covering paint include above-mentioned semi-inorganic silicon steel sheet lacquer.
The invention innovatively provides a specific polyamide-imide emulsion, in the process of preparing polyamide-imide, an activator combination (linear alkylbenzene sulfonate, fatty alcohol-polyoxyethylene ether sodium sulfate and fatty alcohol-polyoxyethylene ether) is introduced, specifically, trimellitic anhydride reacts with a combined double-end amino compound, triethylamine is added to further improve the reaction degree and endow the whole with better flexibility and toughness, tributyl phosphate can further improve the toughness of the system through physical modification, all organic solvents are evaporated, a certain amount of water-soluble organic solvent is added, then a combined activator is added, mixing is carried out, water is dripped to form stable emulsion, and finally the residual active group of bismaleimide end capping is added to further ensure the stable performance of the emulsion in all aspects.
Due to the implementation of the technical scheme, compared with the prior art, the invention has the following advantages:
according to the invention, the semi-inorganic silicon steel sheet paint is prepared by mixing the specific polyamide-imide clear emulsion, the specific inorganic filler and the amino resin, and the paint not only can adopt water as a main solvent, thereby improving the environmental protection, but also has the advantages of high temperature resistance, high bonding strength, strong electrical performance and the like, and has good environmental resistance and construction performance.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It is to be understood that these examples are for the purpose of illustrating the general principles, essential features and advantages of the present invention, and the present invention is not limited by the following examples. The implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not indicated are generally the conditions in routine experiments. The raw materials used in the examples are all commercially available commercial products.
In the following examples, all starting materials are essentially commercially available or prepared by conventional methods in the art, unless otherwise specified. Sodium linear alkylbenzene sulfonate was purchased from linyi, lvsen chemical ltd, brand LAS-30; sodium fatty alcohol polyoxyethylene ether sulfate is available from commercial Limited of Hongxin of Jinen, jinan, under the trade designation HXY-ethoxylated alkyl sodium sulfate (series); the fatty alcohol-polyoxyethylene ether is purchased from Heian petrochemical plants in Jiangsu province under the trade name AEO-3; bismaleimides purchased from the reuleaux group under the brand number DDM-BMI; lithium bentonite is available from Xiangyang Baishi mountain clay GmbH, no. 7342080.
In the following implementation, the modified nano-silica used is prepared by the following method: 10 parts of nano SiO 2 Adding 500 parts of N-methylpyrrolidone, performing ultrasonic dispersion for 1 hour, adding 0.3 part of KH550 coupling agent, stirring for 3 hours at room temperature, performing suction filtration, repeatedly cleaning with ethanol, and drying the product at 140 ℃ for 5 hours to obtain the product.
Example 1
The embodiment provides a semi-inorganic silicon steel sheet paint which comprises the following components: polyamideimide emulsion, titanium dioxide (TiO) 2 ) Modified silica (modified SiO) 2 ) Barium sulfate (BaSO) 4 ) Lithium bentonite and cyanot 325 amino resin.
The preparation method of the semi-inorganic silicon steel sheet varnish comprises the following steps:
(1) Preparation of polyamideimide emulsion: adding 100 parts of trimellitic anhydride, 50 parts of 4,4' -diaminodiphenyl ether, 50 parts of 4,4' -diaminodiphenylmethane, 15 parts of 1,6' -diaminohexane and 150 parts of dimethylacetamide into a reaction vessel, and introducing N 2 Heating to 155 +/-2 ℃, stirring and keeping the temperature for 2.5 hours; adding 2.5 parts of tributyl phosphate and 8 parts of triethylamine, heating to 200 +/-2 ℃, and increasing N 2 Heating to 220 deg.c for gas amount to evaporate off dimethyl acetamide completely; cooling to 100 ℃, adding 20 parts of diethylene glycol monobutyl ether, cooling to 70 ℃, adding 4 parts of linear alkyl benzene sodium sulfonate, 1 part of fatty alcohol-polyoxyethylene ether sodium sulfate and 2 parts of fatty alcohol-polyoxyethylene ether as activators, accelerating the stirring speed, dripping 250 parts of water, cooling to room temperature, adding 50 parts of bismaleimide for end capping after dripping is finished, and preparing the polyamide imide emulsion;
(2) Adding 40 parts of cyanamide 325 amino resin and 40 parts of TiO into the polyamide-imide emulsion prepared in the step (1) 2 40 portions of modified SiO 2 40 parts of BaSO 4 And 20 parts of lithium bentonite, mixing, and performing ultrasonic oscillation for 1 hour to prepare the semi-inorganic silicon steel sheet paint.
Example 2
The embodiment provides a semi-inorganic silicon steel sheet paint which comprises the following components: polyamideimide emulsion, titanium dioxide (TiO) 2 ) Modified silica (modified SiO) 2 ) Barium sulfate (BaSO) 4 ) Lithium bentonite and cyanot 325 amino resin.
The preparation method of the semi-inorganic silicon steel sheet varnish comprises the following steps:
(1) Preparation of polyamideimide emulsion: adding 100 parts of trimellitic anhydride, 50 parts of 4,4' -diaminodiphenyl ether, 40 parts of 4,4' -diaminodiphenylmethane, 12 parts of 1,6' -diaminohexane and 150 parts of dimethylacetamide into a reaction vessel, and introducing N 2 Heating to 155 +/-2 ℃, opening and stirring, and keeping the temperature for 2.5 hours; adding 2.5 parts of tributyl phosphate and 6 parts of triethylamine, heating to 200 +/-2 ℃, and increasing N 2 Heating the gas quantity to 220 ℃, and completely evaporating the dimethylacetamide; cooling to 100 ℃, adding 20 parts of diethylene glycol monobutyl ether, cooling to 70 ℃, adding 4 parts of linear alkyl benzene sodium sulfonate, 1 part of fatty alcohol-polyoxyethylene ether sodium sulfate and 1 part of fatty alcohol-polyoxyethylene ether as activators, accelerating the stirring speed, dripping 250 parts of water, cooling to room temperature, adding 60 parts of bismaleimide end capping, and preparing the polyamideimide emulsion;
(2) Adding 40 parts of cyanamide 325 amino resin and 30 parts of TiO into the polyamide-imide emulsion prepared in the step (1) 2 24 portions of modified SiO 2 36 parts of BaSO 4 And 20 parts of lithium bentonite, mixing, and performing ultrasonic oscillation for 1 hour to prepare the semi-inorganic silicon steel sheet paint.
Example 3
The embodiment provides a semi-inorganic silicon steel sheet paint which comprises the following components: polyamideimide emulsion, titanium dioxide (TiO) 2 ) Modified silica (modified SiO) 2 ) Barium sulfate (BaSO) 4 ) Lithium bentonite and cyanot 325 amino resin.
The preparation method of the semi-inorganic silicon steel sheet varnish comprises the following steps:
(1) Preparation of polyamideimide emulsion: adding 100 parts of trimellitic anhydride, 50 parts of 4,4' -diaminodiphenyl ether, 60 parts of 4,4' -diaminodiphenylmethane, 25 parts of 1,6' -diaminohexane and 150 parts of dimethylacetamide into a reaction vessel, and introducing N 2 Heating to 155 +/-2 ℃, stirring and keeping the temperature for 2.5 hours; adding 2.5 parts of tributyl phosphate and 12 parts of triethylamine, heating to 200 +/-2 ℃, and increasing N 2 The gas quantity is increased to 220 ℃,completely distilling the dimethylacetamide; cooling to 100 ℃, adding 20 parts of diethylene glycol monobutyl ether, cooling to 70 ℃, adding 8 parts of linear alkyl benzene sodium sulfonate, 8 parts of fatty alcohol-polyoxyethylene ether sodium sulfate and 2 parts of fatty alcohol-polyoxyethylene ether as activators, accelerating the stirring speed, dripping 250 parts of water, cooling to room temperature, adding 40 parts of bismaleimide end capping, and preparing the polyamide imide emulsion;
(2) Adding 40 parts of cyanamide 325 amino resin and 50 parts of TiO into the polyamide-imide emulsion prepared in the step (1) 2 60 parts of modified SiO 2 40 parts of BaSO 4 And 20 parts of lithium bentonite, mixing, and performing ultrasonic oscillation for 1 hour to prepare the semi-inorganic silicon steel sheet paint.
Comparative example 1
Basically, the method is the same as the method of the embodiment 1, and the method only differs from the method in that: only 140 parts of 4,4 '-diaminodiphenyl ether equivalent in molar amount to "50 parts of 4,4' -diaminodiphenyl ether, 50 parts of 4,4 '-diaminodiphenylmethane, and 15 parts of 1,6' -diaminohexane" were added to the terminal amino group-containing compound.
Comparative example 2
Basically, the method is the same as the method of the embodiment 1, and the method only differs from the method in that: the amino-terminated compound was adjusted to 100 parts of 4,4 '-diaminodiphenylmethane without adding 4,4' -diaminodiphenyl ether.
Comparative example 3
Basically, the method is the same as the embodiment 1, and the differences are that: no fatty alcohol polyoxyethylene ether sodium sulfate is added, and 5 parts of linear alkyl benzene sodium sulfonate is correspondingly adjusted.
Comparative example 4
Basically, the method is the same as the embodiment 1, and the differences are that: only 7 parts of sodium fatty alcohol-polyoxyethylene ether sulfate is added, and linear alkyl benzene sulfonate and fatty alcohol-polyoxyethylene ether are not added.
Performance test
The semi-inorganic silicon steel sheet paints obtained in the above examples 1 to 3 and comparative examples 1 to 4 were cured at 120 c/1 hour, 180 c/1 hour, and 200 c/2 hour, and the following performance tests were performed, referring to table 1.
TABLE 1
Figure GDA0003894134310000061
Figure GDA0003894134310000071
The above-mentioned embodiments are provided only for illustrating the technical idea and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and to implement the present invention, and not to limit the protection scope of the present invention by this, and all equivalent changes or modifications made according to the spirit of the present invention should be covered in the protection scope of the present invention.

Claims (10)

1. The semi-inorganic silicon steel sheet paint is characterized in that raw materials of the semi-inorganic silicon steel sheet paint comprise polyamide-imide emulsion, inorganic filler, curing agent and suspension stabilizer, wherein the inorganic filler is composed of titanium dioxide, modified silicon dioxide and barium sulfate, the feeding mass ratio of the titanium dioxide, the modified silicon dioxide and the barium sulfate is 1: 0.8-1.2, the modified silicon dioxide is prepared by reacting the silicon dioxide with silane coupling agent, and the curing agent is amino resin;
the semi-inorganic silicon steel sheet varnish is prepared by mixing the components contained in the semi-inorganic silicon steel sheet varnish and then performing ultrasonic dispersion;
wherein the polyamide-imide emulsion is prepared by the following method:
under the protection of protective gas, under the reflux state, enabling trimellitic anhydride and a double-end amino compound to perform a first reaction in a first organic solvent to obtain a first mixed solution, adding tributyl phosphate and triethylamine into the obtained first mixed solution, and performing a second reaction to obtain a second mixed solution; the double-amino-terminal compound is composed of 4,4 '-diaminodiphenyl ether, 4' -diaminodiphenylmethane and 1, 6-diaminohexane;
the feeding molar ratio of the trimellitic anhydride to the double-end amino compound is 1: 1.02-1.50, and the feeding molar ratio of the 4,4 '-diaminodiphenyl ether, the 4,4' -diaminodiphenylmethane and the 1, 6-diaminohexane is 1: 0.8-1.3: 0.3-0.9;
(ii) under the protection of protective gas, evaporating the first organic solvent contained in the second mixed solution outwards to obtain a third mixed solution;
(iii) adding a second organic solvent into the third mixed solution, adding linear alkyl benzene sodium sulfonate, fatty alcohol-polyoxyethylene ether sodium sulfate and fatty alcohol-polyoxyethylene ether, mixing, dropwise adding water under the stirring condition, adding bismaleimide for end capping after dropwise adding is finished, and obtaining a polyamide imide emulsion, wherein the feeding molar ratio of the bismaleimide to the trimellitic anhydride is 0.2-0.3: 1, and the bismaleimide is diphenylmethane bismaleimide and/or N, N' -m-phenylene bismaleimide.
2. The paint for semi-inorganic silicon steel sheets according to claim 1, wherein in the step (i), the protective gas is nitrogen and/or argon.
3. The paint for semi-inorganic silicon steel sheets according to claim 1, wherein the first reaction is performed at 140-170 ℃ and the second reaction is performed at 185-205 ℃ in step (i), and the first organic solvent is dimethylacetamide.
4. The semi-inorganic silicon steel sheet varnish according to claim 1, wherein in step (i), the input molar ratio of the triethylamine to the trimellitic anhydride is 0.1-0.2: 1.
5. The paint for semi-inorganic silicon steel sheets as claimed in claim 1, wherein in the step (ii), the steaming is performed at 210 to 230 ℃.
6. The paint for semiinorganic silicon steel sheets according to claim 1, wherein in the step (iii), the second organic solvent is diethylene glycol monobutyl ether, and the end-capping is performed at 15 to 35 ℃.
7. The paint for semi-inorganic silicon steel sheets as claimed in claim 1, wherein in step (iii), the temperature of the third mixed solution is controlled to be 60-80 ℃, the linear alkylbenzene sulfonic acid sodium, the fatty alcohol-polyoxyethylene ether sodium sulfate and the fatty alcohol-polyoxyethylene ether are added, the mass ratio of the total feeding amount of the linear alkylbenzene sulfonic acid sodium, the fatty alcohol-polyoxyethylene ether sodium sulfate and the fatty alcohol-polyoxyethylene ether to the feeding amount of the trimellitic anhydride is 0.06-0.18: 1, and the mass ratio of the feeding amount of the linear alkylbenzene sulfonic acid sodium, the feeding amount of the fatty alcohol-polyoxyethylene ether sodium sulfate and the feeding amount of the fatty alcohol-polyoxyethylene ether is 2-4: 0.5-4: 1.
8. The paint for semi-inorganic silicon steel sheets as claimed in claim 1 or 7, wherein in step (iii), the linear alkyl benzene sulfonic acid sodium is sodium dodecyl benzene sulfonate, the fatty alcohol-polyoxyethylene ether sodium sulfate is one or more selected from the group consisting of sodium lauryl polyoxyethylene ether sulfate, sodium trideceth sulfate, sodium tetradeceth sulfate and sodium pentadecyl polyoxyethylene ether sulfate, and the fatty alcohol-polyoxyethylene ether is lauryl polyoxyethylene ether and/or trideceth.
9. The semi-inorganic silicon steel sheet varnish according to claim 1, wherein the semi-inorganic silicon steel sheet varnish comprises, by mass, 500-600 parts of polyamideimide emulsion, 90-150 parts of inorganic filler, 30-50 parts of curing agent and 10-30 parts of suspension stabilizer, and the polyamideimide emulsion has a solid content of 55-65%.
10. The paint for semi-inorganic silicon steel sheets as claimed in claim 9, wherein the amino resin is cyante 325 amino resin and the suspension stabilizer is lithium bentonite.
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