CN116200086A - Preparation method of water-based amino baking varnish - Google Patents
Preparation method of water-based amino baking varnish Download PDFInfo
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- CN116200086A CN116200086A CN202310376633.1A CN202310376633A CN116200086A CN 116200086 A CN116200086 A CN 116200086A CN 202310376633 A CN202310376633 A CN 202310376633A CN 116200086 A CN116200086 A CN 116200086A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002966 varnish Substances 0.000 title claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 110
- 239000004005 microsphere Substances 0.000 claims abstract description 77
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 69
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 68
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000003756 stirring Methods 0.000 claims abstract description 35
- 229920003180 amino resin Polymers 0.000 claims abstract description 34
- -1 amino carbon Chemical compound 0.000 claims abstract description 19
- 239000003973 paint Substances 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 230000008719 thickening Effects 0.000 claims abstract description 6
- 238000003825 pressing Methods 0.000 claims description 75
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 60
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 239000012065 filter cake Substances 0.000 claims description 35
- 239000008367 deionised water Substances 0.000 claims description 33
- 229910021641 deionized water Inorganic materials 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 30
- 239000011268 mixed slurry Substances 0.000 claims description 26
- 238000000967 suction filtration Methods 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000009210 therapy by ultrasound Methods 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 239000008098 formaldehyde solution Substances 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 22
- 239000000706 filtrate Substances 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 19
- 229920001225 polyester resin Polymers 0.000 claims description 18
- 239000004645 polyester resin Substances 0.000 claims description 18
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 16
- 238000005086 pumping Methods 0.000 claims description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000002518 antifoaming agent Substances 0.000 claims description 13
- 238000002955 isolation Methods 0.000 claims description 13
- 239000004925 Acrylic resin Substances 0.000 claims description 12
- 229920000178 Acrylic resin Polymers 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
- 239000006184 cosolvent Substances 0.000 claims description 12
- 239000002270 dispersing agent Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims description 12
- 230000005855 radiation Effects 0.000 claims description 12
- 239000007853 buffer solution Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000002562 thickening agent Substances 0.000 claims description 10
- 150000001721 carbon Chemical class 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims description 8
- 229920000877 Melamine resin Polymers 0.000 claims description 7
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- 238000000265 homogenisation Methods 0.000 claims description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- 229920002866 paraformaldehyde Polymers 0.000 claims description 7
- 239000004408 titanium dioxide Substances 0.000 claims description 7
- 230000021523 carboxylation Effects 0.000 claims description 6
- 238000006473 carboxylation reaction Methods 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 230000001678 irradiating effect Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 239000001038 titanium pigment Substances 0.000 claims description 5
- 239000013530 defoamer Substances 0.000 claims description 4
- 238000007790 scraping Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 2
- 238000011085 pressure filtration Methods 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 abstract description 4
- 239000002253 acid Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 238000005576 amination reaction Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C—CHEMISTRY; METALLURGY
- 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
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
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- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides a preparation method of a water-based amino baking varnish. The preparation method of the water-based amino baking varnish comprises the following steps: selecting raw materials, carboxylating, pretreating, preparing amino carbon microspheres/graphene, modifying amino resin by amino carbon microspheres/graphene, stirring, dispersing, homogenizing under high pressure, and thickening. According to the preparation method, the amino groups are introduced into the carbon microspheres/graphene through the preparation of the amino carbon microspheres/graphene, and the amino carbon microspheres/graphene are used for modifying amino resin through the amino carbon microspheres/graphene, so that the amino carbon microspheres/graphene can react with free formaldehyde in the amino resin, the free formaldehyde content in the finally prepared water-based amino baking paint is reduced, and the use safety of the water-based amino baking paint is improved.
Description
Technical Field
The invention belongs to the technical field of water-based paint, and particularly relates to a preparation method of water-based amino baking paint.
Background
The water-based paint takes water as a solvent or a dispersion medium, basically does not contain volatile organic matters, has excellent environmental protection, is prepared from amino resin serving as one of raw materials, and the amino resin is prepared by polycondensating an amino-containing compound and formaldehyde into a resin, wherein free formaldehyde is always contained, so that the water-based amino-based paint can continuously release formaldehyde when in use, serious damage is caused to human health, and the use safety of the water-based amino-based paint is reduced.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a preparation method of water-based amino baking paint.
A preparation method of water-based amino baking varnish comprises the following steps:
s1: selecting raw materials
Respectively selecting 15-45 parts of aqueous polyester resin, 40-50 parts of aqueous acrylic resin, 7-15 parts of modified amino resin, 20-40 parts of deionized water, 1.5-2.5 parts of pH regulator, 8-20 parts of titanium dioxide, 0.3-0.5 part of flatting agent, 0.2-0.8 part of defoamer, 0.3-1 part of dispersing agent, 2-7 parts of cosolvent and 0.3-0.8 part of thickener as raw materials for standby;
s2: pretreatment of
Carrying out carboxylation pretreatment on the carbon microspheres and the graphene by using a mixed solution of concentrated nitric acid and concentrated sulfuric acid to obtain carboxylated carbon microspheres/graphene;
s3: preparation of aminated carbon microsphere/graphene
Adding the carboxylated carbon microspheres/graphene into deionized water, performing ultrasonic treatment, adding hexamethylenediamine and ammonia water for reaction, performing microwave radiation, performing suction filtration, washing, and drying to obtain the aminated carbon microspheres/graphene;
s4: amino carbon microsphere/graphene modified amino resin
Preparing formaldehyde solution from paraformaldehyde and deionized water, adding the amino carbon microspheres/graphene, and then adding melamine for reaction to obtain modified amino resin;
s5: stirring dispersion and high-pressure homogenization
Stirring and dispersing the aqueous polyester resin, the aqueous acrylic resin, deionized water, the pH regulator, the dispersing agent, the titanium pigment and the cosolvent to obtain mixed slurry I, homogenizing the mixed slurry I under high pressure, and adding the modified amino resin, the leveling agent and the defoamer to uniformly mix to obtain mixed slurry II;
s6: thickening
And (3) adding a thickener into the mixed slurry II to thicken, thus obtaining the water-based amino baking paint.
Further, the carboxylated carbon microsphere in the step S2 specifically includes the following steps:
s2.1: regulating the flow of concentrated sulfuric acid
Adding concentrated nitric acid into a stirrer with an anticorrosive coating on the inner wall, opening a flow regulating valve on the inner wall of the stirrer, enabling concentrated sulfuric acid to enter the stirrer, starting stirring by the stirrer, detecting that the temperature rises too fast by a temperature detector in the stirrer, reducing the flow of the flow regulating valve until the ratio of the added concentrated sulfuric acid to the concentrated nitric acid is 1-1.5:3, closing the flow regulating valve, and stopping adding the concentrated sulfuric acid;
s2.2: ultrasonic treatment
Adding carbon microspheres into a stirrer, heating a heating plate at the outer side of the stirrer to 70-80 ℃ to obtain buffer solution, simultaneously carrying out ultrasonic treatment on the buffer solution by an ultrasonic generator in the stirrer, then adding graphene, carrying out ultrasonic treatment again, cooling to room temperature to obtain mixed solution, pressing the mixed solution into a filter pressing box from a filter pressing pipe by a hydraulic pump, passing through a filter pressing net, enabling filtrate to fall into the lower layer of the filter pressing box, and closing an isolation valve above the filtrate to obtain a filter cake A;
s2.3: washing and pressure filtration
And closing a filter pressing valve at the lower side of the filter pressing net, adding deionized water into a filter pressing box to obtain washing liquid, opening the filter pressing valve, pumping air into the upper layer of the filter pressing box by an air pump to pressurize the air, performing filter pressing, dropping filtrate onto an isolation valve, repeating the above actions until the pH detector detects that the pH of the washing liquid is neutral, opening the filter pressing valve, removing the filtrate to obtain a filter cake B, and scraping the filter cake B by a scraper to obtain carboxylated carbon microspheres/graphene.
Further, the amino grafted carbon microsphere/graphene in the step S3 specifically includes the following steps:
s3.1: microwave assisted reaction
Placing the carboxylated carbon microspheres/graphene into a reactor, adding deionized water to prepare carboxylated carbon microspheres/graphene solution, performing ultrasonic treatment on the carboxylated carbon microspheres/graphene solution in the reactor by an ultrasonic generator in the reactor, adding hexamethylenediamine and ammonia water, uniformly stirring, performing microwave radiation by a microwave generator in the reactor, and keeping the temperature of an outer heat-insulating plate of the reactor at 70-95 ℃ for 10-12 hours to obtain a precursor;
s3.2: suction filtration and washing
The method comprises the steps that a suction filtration valve at the lower side of a suction filtration screen in the middle of a reactor is opened, a gas pump continuously pumps out gas at the lower layer of the reactor, suction filtration is carried out, filtrate is discharged, a filter cake C is obtained, the suction filtration valve is closed, deionized water is added into the reactor, an ultrasonic generator carries out ultrasonic treatment again, then the suction filtration valve is opened, suction filtration is carried out, filtrate is discharged, and the suction filtration valve is closed, so that a filter cake D is obtained;
s3.3: infrared ray drying
And irradiating the filter cake D by an infrared lamp in the reactor, drying, and scraping off the dried filter cake D to obtain the amino carbon microsphere/graphene.
Further, the step S4 of the carbon microsphere amide/graphene modified amino resin specifically includes the following steps:
s4.1: adding paraformaldehyde and deionized water into a reaction kettle to prepare 30-40% formaldehyde solution, heating to 75-85 ℃, opening a micro valve at the upper side inside the reaction kettle, dripping NaOH solution in a liquid reservoir into the formaldehyde solution until the formaldehyde solution becomes transparent, closing the micro valve, and stopping dripping the NaOH solution into the reaction kettle;
s4.2: cooling formaldehyde solution to 25-30 ℃, adding the aminated carbon microspheres/graphene into a reaction kettle to obtain a mixed solution, opening a micro valve, dripping NaOH solution into the reaction kettle, closing the micro valve when a pH detector detects that the pH value of the mixed solution is 8.5-9, stopping dripping the NaOH solution into the reaction kettle, adding melamine, preserving heat for 0.5-1h at 85-90 ℃, and then dehydrating in vacuum to obtain the modified amino resin.
Further, before the air pump in the step S2.2 pumps air into the upper layer of the filter pressing box, an air suction valve in a guide pipe connected between the filter pressing box and the reactor in the step S3.2 is opened, then the air pump in the guide pipe pumps air in the lower layer of the reactor into the upper layer of the filter pressing box, the upper layer of the filter pressing box is pressurized for filter pressing, in the step S3.2, the air pump pumps air in the lower layer of the reactor into the filter pressing box continuously, the lower layer of the reactor is depressurized until the suction filtration is completed, the air pump stops pumping, the air suction valve is kept in an open state, and the air pressure is balanced.
Further, the high-speed dispersion and high-pressure homogenization in the step S5 specifically includes the following steps:
adding the aqueous polyester resin, the aqueous acrylic resin, deionized water, a pH regulator, a defoaming agent and a dispersing agent into a stirring and dispersing machine, stirring and dispersing at the speed of 800-900r/min, adding titanium dioxide and a cosolvent, increasing the stirring speed to 1100-1300r/min, stirring to obtain mixed slurry I, putting the mixed slurry I into a high-pressure homogenizer, circularly homogenizing, adding the modified amino resin, a flatting agent and the defoaming agent, and uniformly mixing to obtain mixed slurry II.
Further, the leveling agent selected in the step S1 is a phosphate modified acrylic leveling agent.
Further, in the step S3, the microwave temperature in the microwave radiation is 80-90 ℃, the microwave power is 850-1000W, and the microwave time is 3-5min.
Compared with the prior art, the invention has the advantages that:
1. according to the preparation method, the amino groups are introduced into the carbon microspheres/graphene through the preparation of the amino carbon microspheres/graphene, and the amino groups of the amino carbon microspheres/graphene can react with free formaldehyde in the amino resin through the amino carbon microspheres/graphene modified amino resin, so that the free formaldehyde content in the finally prepared water-based amino baking paint is reduced, and the use safety of the water-based amino baking paint is improved.
2. According to the invention, through the microwave-assisted reaction, the carboxylated carbon microspheres/graphene and hexamethylenediamine can be catalyzed to react with ammonia water, and more amino groups can be introduced into the carboxylated carbon microspheres/graphene, so that the subsequent preparation of modified amino resin is facilitated.
Drawings
FIG. 1 is a flow chart of a method for preparing an aqueous amino baking varnish according to an embodiment of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
A preparation method of the water-based amino baking varnish, as shown in figure 1, comprises the following steps:
s1: selecting raw materials
Respectively selecting 30 parts of aqueous polyester resin, 44 parts of aqueous acrylic resin, 8 parts of modified amino resin, 35 parts of deionized water, 1.5 parts of pH regulator, 12 parts of titanium pigment, 0.4 part of flatting agent, 0.7 part of defoaming agent, 0.6 part of dispersing agent, 4 parts of cosolvent and 0.5 part of thickening agent as raw materials for standby, wherein the aqueous polyester resin is water-soluble acrylic modified polyester resin 799 produced by Jiangyin Ke chemical company, and the flatting agent is phosphate modified acrylic flatting agent;
s2: carboxylation pretreatment
Adding concentrated nitric acid into a stirrer, coating anticorrosive paint on the inner wall of the stirrer, installing a flow control valve on the inner wall of the stirrer, connecting the flow control valve with an acid accumulator, opening the flow control valve, slowly introducing concentrated sulfuric acid in the acid accumulator into the stirrer along the inner wall of the stirrer while stirring the stirrer, installing a temperature detector in the stirrer, detecting that the temperature rises too fast, reducing the flow of the flow control valve until the ratio of the added concentrated sulfuric acid to the concentrated nitric acid is 1:3, closing the flow control valve, stopping adding concentrated sulfuric acid, adding carbon microspheres into the stirrer, installing a heating plate outside the stirrer, heating the heating plate to 75 ℃ to obtain a buffer solution, installing an ultrasonic probe in the stirrer, performing ultrasonic treatment on the buffer solution for 1h, then adding graphene, performing ultrasonic treatment again for 1h, stopping heating the heating plate, naturally cooling to room temperature, obtaining a mixed solution, connecting the stirrer through a filter pressing pipe and a filter pressing box, installing a temperature detector in the filter pressing pipe, introducing the mixed solution into the filter pressing box, passing through a filter pressing net, dropping the filtrate into a filter pressing box, installing an isolation valve at the lower layer of the filter pressing box, closing the isolation valve at the lower layer of the filter pressing box, opening the pressure filter pressing valve, pumping down the isolation valve, and closing the pressure filter box, washing the pressure filter, and opening the pressure filter pressing the pressure filter, washing the pressure filter, and the pressure filter is performed by opening the pressure filter, and the pressure filter is opened, and the pressure-pressing to obtain a pressure filter, and washing the pressure filter, and repeatedly washing for 3 times, wherein the pH detector detects that the pH of the washing liquid is neutral, a filter pressing valve is opened, filtrate is discharged to obtain a filter cake B, the air pump stops pumping air, the air pumping valve is closed, and the filter cake B is scraped by a scraper to obtain carboxylated carbon microspheres/graphene.
S3: preparation of aminated carbon microsphere/graphene
Placing the carboxylated carbon microspheres/graphene into a reactor, adding deionized water to prepare carboxylated carbon microspheres/graphene solution, arranging an ultrasonic generator, a microwave generator and an infrared lamp in the reactor, performing ultrasonic treatment on the carboxylated carbon microspheres/graphene solution in the reactor by the ultrasonic generator, adding hexamethylenediamine and ammonia water, performing microwave radiation by the microwave generator for 5min, performing microwave temperature of 90 ℃, performing microwave power of 900W, arranging a heat-insulating plate outside the reactor, keeping the temperature at 90 ℃, keeping the temperature for 11h to obtain a precursor, arranging a suction filter screen in the middle of the reactor, arranging a suction filter valve on the lower side of the suction filter screen, opening the suction filter valve and the suction valve, sucking lower-layer gas of the reactor into the upper layer of a filter pressing box by the air pump, performing suction filtration, discharging filtrate to obtain a filter cake C, closing the suction filter valve, adding deionized water into the reactor, performing ultrasonic treatment again by the ultrasonic generator, opening the suction filter valve, performing suction filtration, closing the filter valve to obtain a filter cake D, stopping the air pump, keeping the suction valve in a state, keeping the suction filter cake at a temperature of 90 ℃, balancing the suction filter cake, and drying the filter cake by irradiating the carbon microspheres D by infrared radiation, and performing the drying of the carbon microspheres;
s4: amino carbon microsphere/graphene modified amino resin
Adding paraformaldehyde and deionized water into a reaction kettle to prepare 37% formaldehyde solution, heating to 80 ℃, installing a micro valve on the upper side of the inside of the reaction kettle, opening the micro valve, slowly dripping NaOH solution in a liquid reservoir into the formaldehyde solution until the formaldehyde solution becomes transparent, closing the micro valve, stopping dripping the NaOH solution into the reaction kettle, cooling the formaldehyde solution to 30 ℃, adding the carbon amination microspheres/graphene into the reaction kettle to obtain a mixed solution, opening the micro valve, dripping the NaOH solution into the reaction kettle, detecting the pH value of the mixed solution to be 9 by a pH detector, closing the micro valve, stopping dripping the NaOH solution into the reaction kettle, adding melamine, preserving the heat for 1h at 85 ℃, and vacuum dehydrating to obtain modified amino resin;
s5: stirring dispersion and high-pressure homogenization
Adding aqueous polyester resin, aqueous acrylic resin, deionized water, a pH regulator, a defoaming agent and a dispersing agent into a stirring and dispersing machine, stirring and dispersing at the speed of 900r/min, adding titanium dioxide and a cosolvent, increasing the stirring speed to 1200r/min, stirring to obtain mixed slurry I, putting the mixed slurry I into a high-pressure homogenizer, circularly homogenizing, and then adding the modified amino resin, a leveling agent and the defoaming agent, and uniformly mixing to obtain mixed slurry II;
s6: thickening
And (3) adding a thickener into the mixed slurry II to thicken, thus obtaining the water-based amino baking paint.
Example 2
A preparation method of the water-based amino baking varnish, as shown in figure 1, comprises the following steps:
s1: selecting raw materials
Respectively selecting 30 parts of aqueous polyester resin, 44 parts of aqueous acrylic resin, 12 parts of modified amino resin, 35 parts of deionized water, 1.5 parts of pH regulator, 12 parts of titanium pigment, 0.4 part of flatting agent, 0.7 part of defoaming agent, 0.6 part of dispersing agent, 4 parts of cosolvent and 0.5 part of thickening agent as raw materials for standby, wherein the aqueous polyester resin is water-soluble acrylic modified polyester resin 799 produced by Jiangyin Ke chemical company, and the flatting agent is phosphate modified acrylic flatting agent;
s2: carboxylation pretreatment
Adding concentrated nitric acid into a stirrer, coating anticorrosive paint on the inner wall of the stirrer, installing a flow control valve on the inner wall of the stirrer, connecting the flow control valve with an acid accumulator, opening the flow control valve, slowly introducing concentrated sulfuric acid in the acid accumulator into the stirrer along the inner wall of the stirrer while stirring the stirrer, installing a temperature detector in the stirrer, detecting that the temperature rises too fast, reducing the flow of the flow control valve until the ratio of the added concentrated sulfuric acid to the concentrated nitric acid is 1:3, closing the flow control valve, stopping adding concentrated sulfuric acid, adding carbon microspheres into the stirrer, installing a heating plate outside the stirrer, heating the heating plate to 75 ℃ to obtain a buffer solution, installing an ultrasonic probe in the stirrer, performing ultrasonic treatment on the buffer solution for 1h, then adding graphene, performing ultrasonic treatment again for 1h, stopping heating the heating plate, naturally cooling to room temperature, obtaining a mixed solution, connecting the stirrer through a filter pressing pipe and a filter pressing box, installing a temperature detector in the filter pressing pipe, introducing the mixed solution into the filter pressing box, passing through a filter pressing net, dropping the filtrate into a filter pressing box, installing an isolation valve at the lower layer of the filter pressing box, closing the isolation valve at the lower layer of the filter pressing box, opening the pressure filter pressing valve, pumping down the isolation valve, and closing the pressure filter box, washing the pressure filter, and opening the pressure filter pressing the pressure filter, washing the pressure filter, and the pressure filter is performed by opening the pressure filter, and the pressure filter is opened, and the pressure-pressing to obtain a pressure filter, and washing the pressure filter, and repeatedly washing for 3 times, wherein the pH detector detects that the pH of the washing liquid is neutral, a filter pressing valve is opened, filtrate is discharged to obtain a filter cake B, the air pump stops pumping air, the air pumping valve is closed, and the filter cake B is scraped by a scraper to obtain carboxylated carbon microspheres/graphene.
S3: preparation of aminated carbon microsphere/graphene
Placing the carboxylated carbon microspheres/graphene into a reactor, adding deionized water to prepare carboxylated carbon microspheres/graphene solution, arranging an ultrasonic generator, a microwave generator and an infrared lamp in the reactor, performing ultrasonic treatment on the carboxylated carbon microspheres/graphene solution in the reactor by the ultrasonic generator, adding hexamethylenediamine and ammonia water, performing microwave radiation by the microwave generator for 5min, performing microwave temperature of 90 ℃, performing microwave power of 900W, arranging a heat-insulating plate outside the reactor, keeping the temperature at 90 ℃, keeping the temperature for 11h to obtain a precursor, arranging a suction filter screen in the middle of the reactor, arranging a suction filter valve on the lower side of the suction filter screen, opening the suction filter valve and the suction valve, sucking lower-layer gas of the reactor into the upper layer of a filter pressing box by the air pump, performing suction filtration, discharging filtrate to obtain a filter cake C, closing the suction filter valve, adding deionized water into the reactor, performing ultrasonic treatment again by the ultrasonic generator, opening the suction filter valve, performing suction filtration, closing the filter valve to obtain a filter cake D, stopping the air pump, keeping the suction valve in a state, keeping the suction filter cake at a temperature of 90 ℃, balancing the suction filter cake, and drying the filter cake by irradiating the carbon microspheres D by infrared radiation, and performing the drying of the carbon microspheres;
s4: amino carbon microsphere/graphene modified amino resin
Adding paraformaldehyde and deionized water into a reaction kettle to prepare 37% formaldehyde solution, heating to 80 ℃, installing a micro valve on the upper side of the inside of the reaction kettle, opening the micro valve, slowly dripping NaOH solution in a liquid reservoir into the formaldehyde solution until the formaldehyde solution becomes transparent, closing the micro valve, stopping dripping the NaOH solution into the reaction kettle, cooling the formaldehyde solution to 30 ℃, adding the carbon amination microspheres/graphene into the reaction kettle to obtain a mixed solution, opening the micro valve, dripping the NaOH solution into the reaction kettle, detecting the pH value of the mixed solution to be 9 by a pH detector, closing the micro valve, stopping dripping the NaOH solution into the reaction kettle, adding melamine, preserving the heat for 1h at 85 ℃, and vacuum dehydrating to obtain modified amino resin;
s5: stirring dispersion and high-pressure homogenization
Adding aqueous polyester resin, aqueous acrylic resin, deionized water, a pH regulator, a defoaming agent and a dispersing agent into a stirring and dispersing machine, stirring and dispersing at the speed of 900r/min, adding titanium dioxide and a cosolvent, increasing the stirring speed to 1200r/min, stirring to obtain mixed slurry I, putting the mixed slurry I into a high-pressure homogenizer, circularly homogenizing, and then adding the modified amino resin, a leveling agent and the defoaming agent, and uniformly mixing to obtain mixed slurry II;
s6: thickening
And (3) adding a thickener into the mixed slurry II to thicken, thus obtaining the water-based amino baking paint.
Example 3
A preparation method of the water-based amino baking varnish, as shown in figure 1, comprises the following steps:
s1: selecting raw materials
Respectively selecting 30 parts of aqueous polyester resin, 44 parts of aqueous acrylic resin, 8 parts of modified amino resin, 35 parts of deionized water, 1.5 parts of pH regulator, 12 parts of titanium pigment, 0.4 part of flatting agent, 0.7 part of defoaming agent, 0.6 part of dispersing agent, 4 parts of cosolvent and 0.5 part of thickening agent as raw materials for standby, wherein the aqueous polyester resin is water-soluble acrylic modified polyester resin 799 produced by Jiangyin Ke chemical company, and the flatting agent is phosphate modified acrylic flatting agent;
s2: carboxylation pretreatment
Adding concentrated nitric acid into a stirrer, coating anticorrosive paint on the inner wall of the stirrer, installing a flow control valve on the inner wall of the stirrer, connecting the flow control valve with an acid accumulator, opening the flow control valve, slowly introducing concentrated sulfuric acid in the acid accumulator into the stirrer along the inner wall of the stirrer while stirring the stirrer, installing a temperature detector in the stirrer, detecting that the temperature rises too fast, reducing the flow of the flow control valve until the ratio of the added concentrated sulfuric acid to the concentrated nitric acid is 1:3, closing the flow control valve, stopping adding concentrated sulfuric acid, adding carbon microspheres into the stirrer, installing a heating plate outside the stirrer, heating the heating plate to 75 ℃ to obtain a buffer solution, installing an ultrasonic probe in the stirrer, performing ultrasonic treatment on the buffer solution for 1h, then adding graphene, performing ultrasonic treatment again for 1h, stopping heating the heating plate, naturally cooling to room temperature, obtaining a mixed solution, connecting the stirrer through a filter pressing pipe and a filter pressing box, installing a temperature detector in the filter pressing pipe, introducing the mixed solution into the filter pressing box, passing through a filter pressing net, dropping the filtrate into a filter pressing box, installing an isolation valve at the lower layer of the filter pressing box, closing the isolation valve at the lower layer of the filter pressing box, opening the pressure filter pressing valve, pumping down the isolation valve, and closing the pressure filter box, washing the pressure filter, and opening the pressure filter pressing the pressure filter, washing the pressure filter, and the pressure filter is performed by opening the pressure filter, and the pressure filter is opened, and the pressure-pressing to obtain a pressure filter, and washing the pressure filter, and repeatedly washing for 3 times, wherein the pH detector detects that the pH of the washing liquid is neutral, a filter pressing valve is opened, filtrate is discharged to obtain a filter cake B, the air pump stops pumping air, the air pumping valve is closed, and the filter cake B is scraped by a scraper to obtain carboxylated carbon microspheres/graphene.
S3: preparation of aminated carbon microsphere/graphene
Placing the carboxylated carbon microspheres/graphene into a reactor, adding deionized water to prepare carboxylated carbon microspheres/graphene solution, arranging an ultrasonic generator, a microwave generator and an infrared lamp in the reactor, performing ultrasonic treatment on the carboxylated carbon microspheres/graphene solution in the reactor by the ultrasonic generator, adding hexamethylenediamine and ammonia water, performing microwave radiation by the microwave generator for 5min, performing microwave temperature of 90 ℃, performing microwave power of 900W, arranging a heat-insulating plate outside the reactor, keeping the temperature at 90 ℃, keeping the temperature for 11h to obtain a precursor, arranging a suction filter screen in the middle of the reactor, arranging a suction filter valve on the lower side of the suction filter screen, opening the suction filter valve and the suction valve, sucking lower-layer gas of the reactor into the upper layer of a filter pressing box by the air pump, performing suction filtration, discharging filtrate to obtain a filter cake C, closing the suction filter valve, adding deionized water into the reactor, performing ultrasonic treatment again by the ultrasonic generator, opening the suction filter valve, performing suction filtration, closing the filter valve to obtain a filter cake D, stopping the air pump, keeping the suction valve in a state, keeping the suction filter cake at a temperature of 90 ℃, balancing the suction filter cake, and drying the filter cake by irradiating the carbon microspheres D by infrared radiation, and performing the drying of the carbon microspheres;
s4: amino carbon microsphere/graphene modified amino resin
Adding paraformaldehyde and deionized water into a reaction kettle to prepare 37% formaldehyde solution, heating to 80 ℃, installing a micro valve on the upper side of the inside of the reaction kettle, opening the micro valve, slowly dripping NaOH solution in a liquid reservoir into the formaldehyde solution until the formaldehyde solution becomes transparent, closing the micro valve, stopping dripping the NaOH solution into the reaction kettle, cooling the formaldehyde solution to 30 ℃, adding the carbon amination microspheres/graphene into the reaction kettle to obtain a mixed solution, opening the micro valve, dripping the NaOH solution into the reaction kettle, detecting the pH value of the mixed solution to be 9 by a pH detector, closing the micro valve, stopping dripping the NaOH solution into the reaction kettle, adding melamine, preserving the heat for 1h at 85 ℃, and vacuum dehydrating to obtain modified amino resin;
s5: stirring dispersion and high-pressure homogenization
Adding aqueous polyester resin, aqueous acrylic resin, deionized water, a pH regulator, a defoaming agent and a dispersing agent into a stirring and dispersing machine, stirring and dispersing at the speed of 900r/min, adding titanium dioxide and a cosolvent, increasing the stirring speed to 1200r/min, stirring to obtain mixed slurry I, putting the mixed slurry I into a high-pressure homogenizer, circularly homogenizing, and then adding the modified amino resin, a leveling agent and the defoaming agent, and uniformly mixing to obtain mixed slurry II;
s6: thickening
And (3) adding a thickener into the mixed slurry II to thicken, thus obtaining the water-based amino baking paint.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (8)
1. The preparation method of the water-based amino baking varnish is characterized by comprising the following steps of:
s1: selecting raw materials
Respectively selecting 15-45 parts of aqueous polyester resin, 40-50 parts of aqueous acrylic resin, 7-15 parts of modified amino resin, 20-40 parts of deionized water, 1.5-2.5 parts of pH regulator, 8-20 parts of titanium dioxide, 0.3-0.5 part of flatting agent, 0.2-0.8 part of defoamer, 0.3-1 part of dispersing agent, 2-7 parts of cosolvent and 0.3-0.8 part of thickener as raw materials for standby;
s2: carboxylation pretreatment
Carrying out carboxylation pretreatment on the carbon microspheres and the graphene by using a mixed solution of concentrated nitric acid and concentrated sulfuric acid to obtain carboxylated carbon microspheres/graphene;
s3: preparation of aminated carbon microsphere/graphene
Adding the carboxylated carbon microspheres/graphene into deionized water, performing ultrasonic treatment, adding hexamethylenediamine and ammonia water for reaction, performing microwave radiation, performing suction filtration, washing, and drying to obtain the aminated carbon microspheres/graphene;
s4: amino carbon microsphere/graphene modified amino resin
Preparing formaldehyde solution from paraformaldehyde and deionized water, adding the amino carbon microspheres/graphene, and then adding melamine for reaction to obtain modified amino resin;
s5: stirring dispersion and high-pressure homogenization
Stirring and dispersing the aqueous polyester resin, the aqueous acrylic resin, deionized water, the pH regulator, the dispersing agent, the titanium pigment and the cosolvent to obtain mixed slurry I, homogenizing the mixed slurry I under high pressure, and adding the modified amino resin, the leveling agent and the defoamer to uniformly mix to obtain mixed slurry II;
s6: thickening
And (3) adding a thickener into the mixed slurry II to thicken, thus obtaining the water-based amino baking paint.
2. The method for preparing an aqueous amino baking varnish according to claim 1, wherein the carboxylated carbon microspheres in the step S2 specifically comprise the following steps:
s2.1: regulating the flow of concentrated sulfuric acid
Adding concentrated nitric acid into a stirrer with an anticorrosive coating on the inner wall, opening a flow regulating valve on the inner wall of the stirrer, enabling concentrated sulfuric acid to enter the stirrer, starting stirring by the stirrer, detecting that the temperature rises too fast by a temperature detector in the stirrer, reducing the flow of the flow regulating valve until the ratio of the added concentrated sulfuric acid to the concentrated nitric acid is 1-1.5:3, closing the flow regulating valve, and stopping adding the concentrated sulfuric acid;
s2.2: ultrasonic treatment
Adding carbon microspheres into a stirrer, heating a heating plate at the outer side of the stirrer to 70-80 ℃ to obtain buffer solution, simultaneously carrying out ultrasonic treatment on the buffer solution by an ultrasonic generator in the stirrer, then adding graphene, carrying out ultrasonic treatment again, cooling to room temperature to obtain mixed solution, pressing the mixed solution into a filter pressing box from a filter pressing pipe by a hydraulic pump, passing through a filter pressing net, enabling filtrate to fall into the lower layer of the filter pressing box, and closing an isolation valve above the filtrate to obtain a filter cake A;
s2.3: washing and pressure filtration
And closing a filter pressing valve at the lower side of the filter pressing net, adding deionized water into a filter pressing box to obtain washing liquid, opening the filter pressing valve, pumping air into the upper layer of the filter pressing box by an air pump to pressurize the air, performing filter pressing, dropping filtrate onto an isolation valve, repeating the above actions until the pH detector detects that the pH of the washing liquid is neutral, opening the filter pressing valve, removing the filtrate to obtain a filter cake B, and scraping the filter cake B by a scraper to obtain carboxylated carbon microspheres/graphene.
3. The method for preparing the aqueous amino baking varnish according to claim 2, wherein the amino grafted carbon microsphere/graphene in the step S3 specifically comprises the following steps:
s3.1: microwave assisted reaction
Placing the carboxylated carbon microspheres/graphene into a reactor, adding deionized water to prepare carboxylated carbon microspheres/graphene solution, performing ultrasonic treatment on the carboxylated carbon microspheres/graphene solution in the reactor by an ultrasonic generator in the reactor, adding hexamethylenediamine and ammonia water, uniformly stirring, performing microwave radiation by a microwave generator in the reactor, and keeping the temperature of an outer heat-insulating plate of the reactor at 70-95 ℃ for 10-12 hours to obtain a precursor;
s3.2: suction filtration and washing
The method comprises the steps that a suction filtration valve at the lower side of a suction filtration screen in the middle of a reactor is opened, a gas pump continuously pumps out gas at the lower layer of the reactor, suction filtration is carried out, filtrate is discharged, a filter cake C is obtained, the suction filtration valve is closed, deionized water is added into the reactor, an ultrasonic generator carries out ultrasonic treatment again, then the suction filtration valve is opened, suction filtration is carried out, filtrate is discharged, and the suction filtration valve is closed, so that a filter cake D is obtained;
s3.3: infrared ray drying
And irradiating the filter cake D by an infrared lamp in the reactor, drying, and scraping off the dried filter cake D to obtain the amino carbon microsphere/graphene.
4. The method for preparing the aqueous amino baking varnish according to claim 1, wherein the step S4 of preparing the amino carbon microsphere/graphene modified amino resin comprises the following steps:
s4.1: adding paraformaldehyde and deionized water into a reaction kettle to prepare 30-40% formaldehyde solution, heating to 75-85 ℃, opening a micro valve at the upper side inside the reaction kettle, dripping NaOH solution in a liquid reservoir into the formaldehyde solution until the formaldehyde solution becomes transparent, closing the micro valve, and stopping dripping the NaOH solution into the reaction kettle;
s4.2: cooling formaldehyde solution to 25-30 ℃, adding the aminated carbon microspheres/graphene into a reaction kettle to obtain a mixed solution, opening a micro valve, dripping NaOH solution into the reaction kettle, closing the micro valve when a pH detector detects that the pH value of the mixed solution is 8.5-9, stopping dripping the NaOH solution into the reaction kettle, adding melamine, preserving heat for 0.5-1h at 85-90 ℃, and then dehydrating in vacuum to obtain the modified amino resin.
5. The method for preparing the aqueous amino baking varnish according to claim 3, wherein before the air pump in the step S2.2 pumps air into the upper layer of the filter pressing box, an air pumping valve in a conduit connected between the filter pressing box and the reactor in the step S3.2 is opened, then the air pump in the conduit pumps air in the lower layer of the reactor into the upper layer of the filter pressing box, pressurizes the upper layer of the filter pressing box, performs filter pressing, and in the step S3.2, the air pump pumps air in the lower layer of the reactor into the filter pressing box continuously, decompresses the lower layer of the reactor until the suction filtration is completed, and the air pump stops pumping, and the air pumping valve keeps an open state, and balances air pressure.
6. The method for preparing an aqueous amino baking varnish according to claim 1, wherein the high-speed dispersion and high-pressure homogenization in step S5 comprises the following steps:
adding the aqueous polyester resin, the aqueous acrylic resin, deionized water, a pH regulator, a defoaming agent and a dispersing agent into a stirring and dispersing machine, stirring and dispersing at the speed of 800-900r/min, adding titanium dioxide and a cosolvent, increasing the stirring speed to 1100-1300r/min, stirring to obtain mixed slurry I, putting the mixed slurry I into a high-pressure homogenizer, circularly homogenizing, adding the modified amino resin, a flatting agent and the defoaming agent, and uniformly mixing to obtain mixed slurry II.
7. The method for preparing an aqueous amino baking varnish according to claim 1, wherein the leveling agent selected in the step S1 is a phosphate modified acrylic leveling agent.
8. The method for preparing an aqueous amino baking varnish according to claim 3, wherein the microwave temperature in the microwave radiation in the step S3.1 is 80-90 ℃, the microwave power is 850-1000W, and the microwave time is 3-5min.
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| CN110358035A (en) * | 2019-07-31 | 2019-10-22 | 西安工业大学 | The method that amination graphene modified urea-formaldehyde resin prepares environmental-protection type adhesive |
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| CN110358035A (en) * | 2019-07-31 | 2019-10-22 | 西安工业大学 | The method that amination graphene modified urea-formaldehyde resin prepares environmental-protection type adhesive |
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