CN113667117A - Preparation method of water-soluble polyaniline, water-soluble polyaniline-containing high-temperature conductive primer for glass fiber reinforced plastics and preparation method of water-soluble polyaniline-containing water-soluble high-temperature conductive primer - Google Patents
Preparation method of water-soluble polyaniline, water-soluble polyaniline-containing high-temperature conductive primer for glass fiber reinforced plastics and preparation method of water-soluble polyaniline-containing water-soluble high-temperature conductive primer Download PDFInfo
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- CN113667117A CN113667117A CN202110899940.9A CN202110899940A CN113667117A CN 113667117 A CN113667117 A CN 113667117A CN 202110899940 A CN202110899940 A CN 202110899940A CN 113667117 A CN113667117 A CN 113667117A
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- 229920000767 polyaniline Polymers 0.000 title claims abstract description 65
- 239000011152 fibreglass Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 81
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 38
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 229920003180 amino resin Polymers 0.000 claims abstract description 22
- 239000000839 emulsion Substances 0.000 claims abstract description 19
- 229920000728 polyester Polymers 0.000 claims abstract description 18
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004645 polyester resin Substances 0.000 claims abstract description 12
- 229920001225 polyester resin Polymers 0.000 claims abstract description 12
- 239000012948 isocyanate Substances 0.000 claims abstract description 11
- BWWHTIHDQBHTHP-UHFFFAOYSA-N 2-nitrobenzoyl chloride Chemical compound [O-][N+](=O)C1=CC=CC=C1C(Cl)=O BWWHTIHDQBHTHP-UHFFFAOYSA-N 0.000 claims abstract description 10
- DDHRZXUHAFEJIO-UHFFFAOYSA-N n-(2-hydroxyethyl)-2-nitrobenzamide Chemical compound OCCNC(=O)C1=CC=CC=C1[N+]([O-])=O DDHRZXUHAFEJIO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 10
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 9
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 8
- TWRJRCKCJRVPKH-UHFFFAOYSA-N 2-amino-n-(2-hydroxyethyl)benzamide Chemical compound NC1=CC=CC=C1C(=O)NCCO TWRJRCKCJRVPKH-UHFFFAOYSA-N 0.000 claims abstract description 7
- VRVRGVPWCUEOGV-UHFFFAOYSA-N 2-aminothiophenol Chemical compound NC1=CC=CC=C1S VRVRGVPWCUEOGV-UHFFFAOYSA-N 0.000 claims abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- 239000002518 antifoaming agent Substances 0.000 claims description 13
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 13
- 239000002318 adhesion promoter Substances 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 239000000080 wetting agent Substances 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- 239000006184 cosolvent Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 239000011258 core-shell material Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000003377 acid catalyst Substances 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 6
- 239000000049 pigment Substances 0.000 claims description 6
- 239000002562 thickening agent Substances 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 238000004440 column chromatography Methods 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 239000013530 defoamer Substances 0.000 claims 6
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 claims 1
- 239000003973 paint Substances 0.000 abstract description 54
- 238000010422 painting Methods 0.000 abstract description 8
- 229910000831 Steel Inorganic materials 0.000 abstract description 6
- 239000011521 glass Substances 0.000 abstract description 6
- 239000010959 steel Substances 0.000 abstract description 6
- 238000007590 electrostatic spraying Methods 0.000 abstract description 5
- 239000002987 primer (paints) Substances 0.000 description 34
- 238000012360 testing method Methods 0.000 description 26
- 238000000576 coating method Methods 0.000 description 20
- 239000011248 coating agent Substances 0.000 description 18
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 229920000877 Melamine resin Polymers 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000004020 conductor Substances 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- -1 imino methylated melamine formaldehyde Chemical class 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000000889 atomisation Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 238000007665 sagging Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- IBLKWZIFZMJLFL-UHFFFAOYSA-N 1-phenoxypropan-2-ol Chemical compound CC(O)COC1=CC=CC=C1 IBLKWZIFZMJLFL-UHFFFAOYSA-N 0.000 description 1
- WMDZKDKPYCNCDZ-UHFFFAOYSA-N 2-(2-butoxypropoxy)propan-1-ol Chemical compound CCCCOC(C)COC(C)CO WMDZKDKPYCNCDZ-UHFFFAOYSA-N 0.000 description 1
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 description 1
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- JABXMSSGPHGCII-UHFFFAOYSA-N acetic acid;propane-1,2-diol Chemical compound CC(O)=O.CC(O)CO JABXMSSGPHGCII-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000009503 electrostatic coating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000005007 epoxy-phenolic resin Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000005002 finish coating Substances 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
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Classifications
-
- 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
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
-
- 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
- C09D5/24—Electrically-conducting paints
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a preparation method of water-soluble polyaniline, a water-soluble high-temperature conductive primer for glass steel containing water-soluble polyaniline and a preparation method of the water-soluble high-temperature conductive primer, and relates to the field of water-soluble high-temperature baking paint. The preparation method of the polyaniline comprises the following steps: preparing N- (2-hydroxyethyl) -2-nitrobenzamide from o-nitrobenzoyl chloride, dichloromethane, ethanolamine and triethylamine; treating N- (2-hydroxyethyl) -2-nitrobenzamide with iron powder, concentrated sulfuric acid and tetrahydrofuran to obtain N- (2-hydroxyethyl) -2-aminobenzamide; then the water-soluble polyaniline is prepared by the reaction of the polyaniline and o-aminothiophenol. The preparation method of the conductive primer comprises the following steps: the conductive primer is prepared by mixing the components of waterborne acrylic modified polyester, waterborne acrylic emulsion, saturated polyester resin, amino resin, blocked isocyanate, water-soluble polyaniline and the like. The method improves the solubility of polyaniline in the water-based conductive primer, reduces the surface resistance of the glass fiber reinforced plastic by the conductive primer, realizes the electrostatic spraying of the finish paint, and improves the painting rate.
Description
Technical Field
The invention relates to the technical field of water-based high-temperature baking paint, in particular to a preparation method of water-soluble polyaniline, a water-based high-temperature conductive primer containing the water-soluble polyaniline for glass steel and a preparation method of the water-based high-temperature conductive primer.
Background
The glass fiber reinforced plastic is also called glass fiber reinforced composite plastic, is a composite material invented in the middle of the last century, and generally refers to a continuous section bar which is formed by using glass fiber reinforcing agent, unsaturated polyester, epoxy resin and phenolic resin adhesive as basic components and by pultrusion through a high-temperature die and special equipment. The glass fiber reinforced plastic has the characteristics of light weight, high strength, corrosion resistance, good electrical insulation performance, good heat insulation performance, high pressure resistance, long service life, excellent designability, excellent construction process performance and the like, so that the glass fiber reinforced plastic is widely applied to the fields of military affairs, chemical engineering (sewage treatment equipment, storage tank storage tanks, pipelines and the like), buildings (cooling towers, decorative plates, doors, windows, storage bins), transportation (automobile shells, train window frames and the like), ships, communication, transportation, home furnishing and the like. According to statistics, the types of the current glass fiber reinforced plastic products reach more than 4 ten thousand.
When the glass fiber reinforced plastic is heated and cured in a mold, a release agent is added into resin for facilitating demolding, and the release agent can be uniformly transferred to the surface of a product after the product is demolded, so that the surface tension of the glass fiber reinforced plastic is low. If the conventional coating is used for spraying on the surface of the glass fiber reinforced plastic, the adhesion is poor, and the surface coating often falls off in the using process, so that the service life and the appearance of the surface coating are seriously influenced.
In order to solve the problem of the falling off of a surface paint layer, the currently commonly used glass fiber reinforced plastic paint with strong adhesive force and high paint film hardness is mainly a solvent type system and a water-based double-component PU system, however, the solvent type paint has the defects of large smell, high VOC content, flammability and the like, while the water-based PU system is a double-component system, the activation period is only 2-3 hours, the construction is very inconvenient, and the water resistance and the high temperature resistance are poor.
In addition, electrostatic spraying is widely popular with customers due to its high painting rate, and because the surface resistance of the glass fiber reinforced plastic substrate is high, electrostatic painting is not facilitated, and a conductive material is required to provide conductivity in a water-based paint. The conductive graphite is widely selected as the conductive material at present, and the defects that the conductivity of the conductive graphite is gradually reduced along with the time, and the conductive graphite is unstable and even separated out after being stored in a water-based system for a long time, so that the water-based paint is coarse and cannot be used.
Polyaniline has good electrical conductivity and is a hotspot field of material science, but the rigidity and interaction of polyaniline chains make the polyaniline insoluble and infusible, and even grinding technology is difficult to grind the polyaniline to a small enough fineness, so that the polyaniline is poor in dispersion and easy to agglomerate in an aqueous coating, and the application of the polyaniline as an electrically conductive material in the aqueous coating is limited. Therefore, there is an urgent need to improve the solubility of polyaniline in water-based paint to obtain a water-based conductive primer coating of glass fiber reinforced plastic with superior conductivity and stable performance, thereby solving the problems of poor adhesion, low painting rate and paint removal of glass fiber reinforced plastic.
Disclosure of Invention
The invention provides a preparation method of water-soluble polyaniline, a water-soluble high-temperature conductive primer for glass steel containing the water-soluble polyaniline and a preparation method thereof, which improve the solubility of the polyaniline in a water-soluble coating so as to improve the phenomena of poor dispersibility and easy agglomeration of the polyaniline in the water-soluble coating.
In order to solve the above technical problem, an embodiment of the present invention provides a method for preparing water-soluble polyaniline, including the following steps:
s01, dissolving o-nitrobenzoyl chloride into dichloromethane with equal mass, stirring, sequentially adding ethanolamine with the mass of 5% of that of the o-nitrobenzoyl chloride and triethylamine with the mass of 10% of that of the o-nitrobenzoyl chloride, reacting at room temperature for 24h-48h, carrying out reduced pressure distillation to obtain a residue, and carrying out column chromatography on the residue to obtain N- (2-hydroxyethyl) -2-nitrobenzamide;
s02, mixing tetrahydrofuran and deionized water A in proportion to obtain a tetrahydrofuran solution for later use, mixing iron powder and concentrated sulfuric acid in proportion to obtain a first reaction solution for later use, and mixing concentrated hydrochloric acid and ammonium persulfate in proportion to obtain a second reaction solution for later use;
s03, dissolving N- (2-hydroxyethyl) -2-nitrobenzamide in tetrahydrofuran solution, stirring, adding into the first reaction solution, reacting at room temperature for 24-48 h, filtering, and washing with anhydrous sodium sulfate or anhydrous calcium oxide to obtain N- (2-hydroxyethyl) -2-aminobenzamide;
s04, dissolving N- (2-hydroxyethyl) -2-aminobenzamide and o-aminothiophenol in deionized water B at the temperature of 35-45 ℃, stirring and adding a second reaction solution, heating to 35-45 ℃, reacting for 24-48 h, precipitating by acetone, filtering and drying to obtain the water-soluble polyaniline.
By adopting the scheme, the polyaniline raw material is modified in the polyaniline preparation process, so that the surface of the polyaniline is attached with hydrophilic groups, the solubility of the polyaniline in the water-based paint is improved, the polyaniline can be stably dispersed in the water-based paint and provides conductivity, the surface resistance of the glass steel substrate can be reduced by utilizing the conductive primer, the electrostatic spraying of the finish paint is realized, the problems of poor adhesion force, paint removal and the like of the glass steel surface are solved, and the painting rate is improved.
Preferably, in S02, the mass ratio of tetrahydrofuran to water in the tetrahydrofuran solution is 1: 1, wherein the mass ratio of iron powder to concentrated sulfuric acid in the first reaction solution is 1: 3, the mass ratio of the concentrated sulfuric acid to the ammonium persulfate in the second reaction solution is 1: 2; in the S03, the weight parts of the components are as follows:
n- (2-hydroxyethyl) -2-nitrobenzamide: 0.5 to 1 portion;
tetrahydrofuran solution: 3-5 parts of:
first reaction solution: 0.05 to 0.1 portion;
in the S04, the weight parts of the components are as follows:
n- (2-hydroxyethyl) -2-aminobenzamide: 0.5 to 1.5 portions;
o-aminothiophenol: 0.5 to 1.5 portions;
deionized water B: 2-4 parts;
second reaction solution: 1-2 parts;
acetone: 2.5 to 7.5 portions.
In order to solve the above technical problems, a second embodiment of the present invention provides a water-based high temperature conductive primer for glass fiber reinforced plastics, which contains water-soluble polyaniline, and comprises the following raw material components:
aqueous acrylic modified polyester: 40-55 wt%;
aqueous acrylic emulsion: 5-10 wt%;
saturated polyester resin: 2-6 wt%;
amino resin: 5-15 wt%;
blocked isocyanate: 2-5 wt%;
an adhesion promoter: 1 wt% -3 wt%;
cosolvent: 2-4 wt%;
color paste: 10 wt% -30 wt%;
water-soluble polyaniline: 3 to 8 weight percent;
functional auxiliary agents: 0.8 wt% -2.5 wt%;
deionized water C: and (4) the balance.
By adopting the scheme, the water-soluble polyaniline is stably dissolved in the system and can provide conductivity, and the resistance can be reduced by coating the conductive primer on the surface of the glass fiber reinforced plastic substrate, so that electrostatic spraying of the finish paint is realized, the construction is convenient and environment-friendly, and the painting rate is improved; because the viscosity of the saturated polyester resin is low, the alkaline water-based acrylic acid modified polyester is used for emulsification in the system, so that the flexibility, the adhesive force, the hardness, the water resistance, the humidity resistance, the heat resistance and the salt spray resistance of a paint film can be improved, the gloss of the paint film is higher, and the leveling property is better; in addition, the chemical bond formed inside the blocked isocyanate is weak and cannot react and crosslink with-OH in the system at normal temperature, but the high-temperature baking during coating causes the ring opening of the blocked isocyanate bond and releases-NCO, which can react with-OH in the system and crosslink into a urethane film, so that the flexibility and the stone-impact resistance of the paint film are improved.
Preferably, the solid content of the waterborne acrylic modified polyester is 30-50%, the pH value is 7-9, and the waterborne acrylic modified polyester contains 0.05-0.15 wt% of blocked acid catalyst.
By adopting the scheme, the waterborne acrylic modified polyester resin is used as the main resin, contains the acid catalyst capable of accelerating the reaction, can accelerate the curing of smearing, ensures that the coating obtained after the resin reaction has high hardness, and has excellent flexibility, water resistance and solvent resistance.
As a preferable scheme, the water-based acrylic emulsion has a core-shell structure, the solid content is 20-35%, the acid value is 2-15 mgKOH/g, and the hydroxyl value is 20-40 mgKOH/g.
By adopting the scheme, the waterborne high-temperature conductive primer has strong pseudoplasticity after being neutralized by resin, the viscosity of the system is increased under the action of static and low shearing force, the anti-settling effect is obvious, but the viscosity is reduced under the action of high shearing force in the coating construction process, the viscosity is increased again when coating particles are attached to the surface of the glass steel substrate, and the waterborne acrylic emulsion is used as the core-shell pseudoplastic acrylic emulsion, so that the atomization and leveling of the system can be ensured, and the sagging phenomenon is avoided in the process of continuous change of the viscosity; in addition, the pseudoplastic water-based acrylic emulsion is sensitive to pH, and the stability of the viscosity of the system can be ensured by controlling the pH within a certain range.
Preferably, the amino resin is prepared from methylated amino resin and butylated amino resin according to the mass ratio of (7-10): 3, the polymerization degree of the methylated amino resin is less than or equal to 2.5, and the solid content is not less than 60 percent.
By adopting the scheme, the methylated amino resin has extremely high reactivity and self-condensation tendency, can improve the hardness, gloss, chemical resistance and outdoor durability of a paint film, has good compatibility, good wettability and high reactivity of the butylated amino resin, and can improve the interlayer adhesion with a finish paint.
Preferably, the cosolvent is one or more of DPM, BCS, PPH, DPNB, TPM, BDGA and PGDA; the adhesion promoter is one or more of polyester adhesion promoter, epoxy phosphate adhesion promoter, epoxy modified acrylic resin and silane coupling agent.
Preferably, the auxiliary agent comprises a defoaming agent B and a wetting agent, wherein the defoaming agent B is one or more of an organic defoaming agent, a polyether defoaming agent and an organic silicon defoaming agent, and the content of the defoaming agent B is 0.5-1.5 wt% of the total amount of the conductive primer; the wetting agent is a modified organic silicon wetting agent, and the content of the wetting agent is 0.3 wt% -1 wt% of the total amount of the conductive primer.
As a preferred scheme, the color paste is prepared by the following steps:
s001, adding deionized water D into a container, stirring and controlling the speed to be 200-800 rpm, and sequentially adding a water-based dispersant, a defoaming agent A and a thickening agent for 10-20 min;
s002, continuously adding the pigment and the filler into the container, and dispersing for 30-60 min to prepare color paste;
s003, grinding the color paste, and controlling the fineness of the color paste to be less than 25 micrometers;
wherein the weight parts of the components are as follows:
pigment and filler: 78 parts of (1);
aqueous dispersant: 2 parts of (1);
defoaming agent A: 0.5 part;
thickening agent: 0.2 part;
deionized water D: and 20 parts.
In order to solve the above technical problems, a third embodiment of the present invention provides a method for preparing a water-based high temperature conductive primer for glass fiber reinforced plastics, the method comprising the following steps:
s1, adding the color paste into a container, stirring and controlling the speed to be 400-900 rpm, then slowly adding the water-based acrylic modified polyester, the water-based acrylic emulsion, the saturated polyester resin, the amino resin, the blocked isocyanate, the adhesion promoter, the cosolvent, the water-soluble polyaniline, the auxiliary agent and the deionized water C, dispersing for 30-60 min, and uniformly mixing to obtain a primary mixed material;
s2, filtering the primary mixed material, wherein the filtering aperture is 50-100 microns, and obtaining the water-based high-temperature conductive primer.
Compared with the prior art, the embodiment of the invention has the following beneficial effects:
1. the polyaniline is modified in the preparation process, so that the surface of the polyaniline is attached with hydrophilic groups, the solubility of the polyaniline in the water-based paint is improved, the polyaniline can be stably dispersed in the water-based paint and provides conductivity, the electrostatic spraying of finish paint is realized, the problems of poor adhesion, paint removal and the like on the surface of glass fiber reinforced plastic are solved, and the painting rate is improved.
2. The saturated polyester resin has low viscosity, the emulsion is carried out by using the alkaline water-based acrylic acid modified polyester, the flexibility, the adhesive force, the hardness, the water resistance, the humidity resistance, the salt spray resistance and the luster of a paint film can be improved, the leveling property is better, and the flexibility and the stone impact resistance of the paint film are improved by using the closed isocyanate.
3. The aqueous acrylic modified polyester resin is used as a main resin, contains an acid catalyst capable of accelerating the reaction, can accelerate the curing of smearing, ensures that a coating film obtained after the resin reaction has high hardness, and has excellent flexibility, water resistance and solvent resistance.
4. The water-based acrylic emulsion is used as the core-shell pseudoplastic acrylic emulsion, so that the atomization and the leveling of the system can be ensured, the sagging phenomenon is avoided in the process of continuously changing the viscosity, and the stability of the viscosity of the system can be ensured by controlling the pH value within a certain range.
5. The methylated amino resin has extremely high reactivity and self-condensation tendency, can improve the hardness, gloss, chemical resistance and outdoor durability of a paint film, has good compatibility, good wettability and high reactivity, and can improve the interlayer adhesion with a finish paint.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The following are the performance indicators of the raw materials, where table 1 is the type and source of the raw materials used in the preparation examples, examples and comparative examples:
TABLE 1 type and manufacturer of raw materials
Wherein the solid content of the waterborne acrylic modified polyester is 30-50%, the pH is 7-9, preferably the pH is 8.4-8.8, and the waterborne acrylic modified polyester contains 0.05-0.15 wt% of a blocked acid catalyst; the water-based acrylic emulsion is core-shell pseudoplastic acrylic emulsion, has a core-shell structure, and has the solid content of 20-35 percent, the acid value of 2-15 mgKOH/g and the hydroxyl value of 20-40 mgKOH/g; the acid value of the saturated polyester is 1-15mgKOH/g, and the hydroxyl value is 80mgKOH/g-300 mgKOH/g; the polymerization degree of the high imino methylated melamine formaldehyde resin is 1.75, and the solid content is not lower than 60%.
Preparation example
Preparation examples 1 to 3
A water-soluble polyaniline is prepared by the following steps:
s01, dissolving o-nitrobenzoyl chloride into dichloromethane with equal mass, stirring and controlling the stirring speed to be shown in table 2, then sequentially adding ethanolamine with the mass of 5% of that of the o-nitrobenzoyl chloride and triethylamine with the mass of 10% of that of the o-nitrobenzoyl chloride, reacting at room temperature for the time shown in table 2, obtaining a residue through reduced pressure distillation, and carrying out column chromatography on the residue to obtain N- (2-hydroxyethyl) -2-nitrobenzamide;
s02, mixing tetrahydrofuran and deionized water A according to a mass ratio of 1: 1 to obtain a tetrahydrofuran solution for later use, and mixing iron powder and concentrated sulfuric acid according to a mass ratio of 1: 3 to obtain a first reaction solution for later use, and mixing concentrated hydrochloric acid and ammonium persulfate according to the mass ratio of 1: 2 to obtain a second reaction solution for later use;
s03, dissolving N- (2-hydroxyethyl) -2-nitrobenzamide in tetrahydrofuran solution, stirring and controlling the stirring speed to be shown in table 2, then adding the first reaction solution, reacting at room temperature for the time shown in table 2, filtering, and washing with the solvent shown in table 2 to obtain N- (2-hydroxyethyl) -2-aminobenzamide;
s04, dissolving N- (2-hydroxyethyl) -2-aminobenzamide and o-aminothiophenol in deionized water B under the temperature condition shown in the table 2, stirring and controlling the stirring speed to be shown in the table 2, then adding a second reaction solution, heating to the temperature shown in the table 2, reacting for the time shown in the table 2, then precipitating by acetone, filtering and drying to obtain the water-soluble polyaniline.
TABLE 2 contents of the components and the process parameters in preparations 1 to 3
Preparation examples 4 to 5
A color paste is prepared by the following steps:
s001, adding deionized water D into a moving tank, starting a dispersion machine to stir, controlling the speed to be shown in table 3, and sequentially adding a water-based dispersing agent, a defoaming agent A and a thickening agent, wherein the dispersion time is shown in table 3;
s002, continuously adding the pigment and the filler into the movable tank, wherein the dispersion time is shown in the table 3, and preparing color paste;
and S003, transferring the color paste in the movable tank to a grinding machine, grinding the color paste for 2-10pass, and controlling the fineness of the color paste to be less than 25 micrometers.
TABLE 3 contents of the components and Process parameters in preparations 4 to 6
| Item | Preparation example 4 | Preparation example 5 |
| Deionized Water D (g) | 20 | 20 |
| Aqueous dispersant (g) | 2 | 2 |
| Defoaming agent A (g) | 0.5 | 0.5 |
| Thickening agent (g) | 0.2 | 0.2 |
| Pigment and filler (g) | 78 | 78 |
| S001 Medium stirring speed (rpm) | 200 | 800 |
| Dispersing time (min) in S001 | 20 | 10 |
| Dispersing time (min) in S002 | 20 | 10 |
Examples
Examples 1 to 4
The water-soluble polyaniline-containing high-temperature conductive primer for glass fiber reinforced plastics is prepared by the following steps:
s1, adding the color paste into a clean moving tank, starting a dispersion machine to stir and controlling the speed to be shown in table 4, then slowly adding the water-based acrylic acid modified polyester, the water-based acrylic acid emulsion, the saturated polyester resin, the amino resin, the blocked isocyanate, the adhesion promoter, the cosolvent, the water-soluble polyaniline, the auxiliary agent and the deionized water C, controlling the dispersion time to be shown in table 4, and uniformly mixing to obtain a primary mixed material;
s2, filtering and filling the primary mixed material by using filter cloth, wherein the filter aperture of the filter cloth is 50-100 microns, and thus obtaining the water-based high-temperature conductive primer;
wherein the amino resin is prepared from methylated amino resin and butylated amino resin according to the mass ratio of (7-10): 3, the methylated amino resin is specifically high-imino methylated melamine formaldehyde resin, and the butylated amino resin is specifically high-imino butylated melamine formaldehyde resin;
wherein, the cosolvent can be but is not limited to one of DPM (dipropylene glycol methyl ether), BCS (ethylene glycol butyl ether), PPH (propylene glycol phenyl ether), DPNB (dipropylene glycol n-butyl ether), TPM (tripropylene glycol methyl ether), BDGA (diethylene glycol butyl ether acetate) and PGDA (propylene glycol acetate);
wherein, the auxiliary agent comprises a defoaming agent B and a wetting agent, and the wetting agent is a modified organic silicon wetting agent.
TABLE 4 Components, amounts, and Process parameters of examples 1-4
Performance test
1. And (3) testing the adhesive force: the adhesion ratings of the conductive primers of examples 1-4 were tested at 25 ℃ according to GB/T9286-1998 test run on a paint and varnish-paint film grid, with grade 0 being the best and grade 5 being the worst, and the test results are shown in Table 5.
2. Flexibility test: the flexibility (mm) of the conductive primers obtained in examples 1 to 4 was measured at 25 ℃ according to GB/T1731-1993 paint flexibility test, and the test results are shown in Table 5.
3. And (3) testing the hardness of the paint film: the paint film hardness grades of the conductive primers obtained in the examples 1-4 are detected under the condition of 25 ℃ according to GB/T6739-2006 paint film hardness determination by a color paint and varnish-pencil method, and the hardness is as follows from low to high: 9B-8B-7B-6B-5B-4B-3B-2B-B-HB-F-H-2H-3H-4H-5H-6H-7H-8H-9H, the test results are shown in Table 5.
4. And (3) impact resistance test: the conductive primers obtained in examples 1 to 4 were tested for their impact resistance (Kg. cm) according to GB/T1732-1993 "paint impact test", and the test results are shown in Table 5.
5. And (3) testing water resistance: the water resistance of the conductive primer obtained in examples 1-4 was examined according to GB/T5209-1985 Water immersion method for measuring Water resistance of colored and clear paints, using deionized water having a conductivity of not more than μ s/cm, controlling the water temperature to 40. + -. 1 ℃ and the results are shown in Table 5.
6. Acid resistance test: the acid resistance of the conductive primers obtained in examples 1 to 4 was tested according to GB/T9274-1998 determination of the resistance of paints and varnishes to liquid media, the test results being shown in Table 5.
7. Alkali resistance test: the conductive primers obtained in examples 1 to 4 were tested for alkali resistance according to GB/T9274-1998 determination of the resistance of paints and varnishes to liquid media, the test results being shown in Table 5.
8. And (3) testing the engine oil resistance: the conductive primers obtained in examples 1 to 4 were tested for gasoline resistance according to GB/T1734-1993 test for gasoline resistance of paint films, the test results are shown in Table 5.
9. Moisture and heat resistance test: the wet heat resistance of the conductive primers obtained in examples 1-4 was measured according to GB/T1740-2007 determination of Wet Heat resistance of paint films, and the results are shown in Table 5.
10. And (3) stone impact resistance test: the electrically conductive primers obtained in examples 1 to 4 were tested for chip resistance according to ISO 20567-1-2005 "determination of chip resistance of pigmented and clearcoat coatings", the test results being shown in Table 5.
11. And (3) testing the surface resistance: the surface resistance (Ω) of the conductive primer obtained in examples 1-4 was measured by a FEITA antistatic tester according to GB/T1410-2006 test method for volume resistivity and surface resistivity of solid insulating material, and the test results are shown in Table 5.
12. And (3) determining the finish coating rate:
1) taking 4 glass fiber reinforced plastic substrates with the same size, respectively, and spraying the conductive primer obtained in the above examples 1 to 4 to the corresponding surface of the glass fiber reinforced plastic substrate by using a rotary cup, wherein the sprayed film thickness (20 to 30 micrometers) is the same, flashing for 15 to 30min, then placing the glass fiber reinforced plastic substrate in an oven at 140 ℃ for baking for 15 to 20min, and testing the weight of the sprayed dry film and the substrate and recording the weight as m 1;
2) spraying the water-based high-temperature white finish paint with the weight recorded as m2 on the upper surface of the conductive primer by using a rotary cup, flashing for 10-15min, and then placing in an oven with the temperature of 140 ℃ for baking for 20-30min, wherein the water-based high-temperature white finish paint is used for testing the total weight of the dry film and the base material and is recorded as m 3;
3) and (3) continuously calculating the finish paint coating rate according to the following formula: the painting rate (%) (m3-m1)/m 2%
TABLE 5 results of Performance test tests of examples 1-5
The polyaniline selected by the invention has the characteristics of simple and convenient synthesis, low price of raw materials, diversified derivative structures and the like, and is used for replacing conductive materials such as conductive carbon black, metal powder and the like. The water-soluble polyaniline is obtained by the preparation steps from the raw materials of the polyaniline, the problems that the polyaniline is poor in dispersibility and easy to agglomerate in the water-based high-temperature conductive primer due to the interaction between the rigidity of chains and the chains are solved, the water-soluble polyaniline can be dispersed in the water-based high-temperature conductive primer only through high-speed stirring, so that the water-based high-temperature conductive primer achieves lower surface resistance and stable conductivity, when the electrostatic coating mode is adopted for coating the finish paint, the paint coating rate of the finish paint is remarkably improved, and the paint stripping phenomenon can be avoided.
The waterborne high-temperature conductive primer obtained by the invention adopts waterborne acrylic modified polyester resin as main resin, contains an acid catalyst capable of accelerating reaction, can accelerate curing of coating, and ensures that a coating obtained after the resin reaction has high hardness. The saturated polyester resin has low viscosity, the alkaline water-based acrylic acid modified polyester is used for emulsification in the system, the flexibility, the adhesive force, the hardness, the water resistance, the humidity resistance, the heat resistance and the salt spray resistance of a paint film can be improved, and the paint film has high gloss and better leveling property. As the viscosity of the system of the water-based high-temperature conductive primer can change in resin and in the coating process, the water-based acrylic emulsion serving as the core-shell pseudoplastic acrylic emulsion can ensure the atomization and leveling of the system and avoid the sagging phenomenon; in addition, the pseudoplastic water-based acrylic emulsion is sensitive to pH, and the stability of the viscosity of the system can be ensured by controlling the pH within a certain range. The polymerization degree of the high imino methylated melamine formaldehyde resin is less than 2.5, the high imino methylated melamine formaldehyde resin has extremely high reaction activity and self-condensation tendency, and the hardness, the gloss, the chemical resistance and the outdoor durability of a paint film can be improved; the high imino butyl etherified melamine formaldehyde resin has good compatibility, good wettability and high reaction activity, and can improve the interlayer adhesion with finish paint. The chemical bond formed in the blocked isocyanate is weaker, and the blocked isocyanate bond can be opened and release-NCO to react with-OH in a system to be crosslinked into a urethane film, so that the flexibility and the stone-impact resistance of the paint film are improved.
The above-mentioned embodiments are provided to further explain the objects, technical solutions and advantages of the present invention in detail, and it should be understood that the above-mentioned embodiments are only examples of the present invention and are not intended to limit the scope of the present invention. It should be understood that any modifications, equivalents, improvements and the like, which come within the spirit and principle of the invention, may occur to those skilled in the art and are intended to be included within the scope of the invention.
Claims (10)
1. A preparation method of water-soluble polyaniline is characterized by comprising the following steps:
s01, dissolving o-nitrobenzoyl chloride into dichloromethane with equal mass, stirring, sequentially adding ethanolamine with the mass of 5% of that of the o-nitrobenzoyl chloride and triethylamine with the mass of 10% of that of the o-nitrobenzoyl chloride, reacting at room temperature for 24h-48h, carrying out reduced pressure distillation to obtain a residue, and carrying out column chromatography on the residue to obtain N- (2-hydroxyethyl) -2-nitrobenzamide;
s02, mixing tetrahydrofuran and deionized water A in proportion to obtain a tetrahydrofuran solution for later use, mixing iron powder and concentrated sulfuric acid in proportion to obtain a first reaction solution for later use, and mixing concentrated hydrochloric acid and ammonium persulfate in proportion to obtain a second reaction solution for later use;
s03, dissolving N- (2-hydroxyethyl) -2-nitrobenzamide in tetrahydrofuran solution, stirring, adding into the first reaction solution, reacting at room temperature for 10-18 h, filtering, and washing with anhydrous sodium sulfate or anhydrous calcium oxide to obtain N- (2-hydroxyethyl) -2-aminobenzamide;
s04, dissolving N- (2-hydroxyethyl) -2-aminobenzamide and o-aminothiophenol in deionized water B at the temperature of 35-45 ℃, stirring and adding a second reaction solution, heating to 35-45 ℃, reacting for 24-48 h, precipitating by acetone, filtering and drying to obtain the water-soluble polyaniline.
2. The method according to claim 1, wherein in S02, the mass ratio of tetrahydrofuran to water in the tetrahydrofuran solution is 1: 1, wherein the mass ratio of iron powder to concentrated sulfuric acid in the first reaction solution is 1: 3, the mass ratio of the concentrated sulfuric acid to the ammonium persulfate in the second reaction solution is 1: 2;
in the S03, the weight parts of the components are as follows:
n- (2-hydroxyethyl) -2-nitrobenzamide: 0.5 to 1 portion;
tetrahydrofuran solution: 3-5 parts of:
first reaction solution: 0.05 to 0.1 portion;
in the S04, the weight parts of the components are as follows:
n- (2-hydroxyethyl) -2-aminobenzamide: 0.5 to 1.5 portions;
o-aminothiophenol: 0.5 to 1.5 portions;
deionized water B: 2-4 parts;
second reaction solution: 1-2 parts;
acetone: 2.5 to 7.5 portions.
3. The water-soluble polyaniline-containing water-soluble high-temperature conductive primer for glass reinforced plastics, which is characterized in that the water-soluble polyaniline obtained by the preparation method of the water-soluble polyaniline in the claim 1 or 2 comprises the following raw material components:
aqueous acrylic modified polyester: 40-55 wt%;
aqueous acrylic emulsion: 5-10 wt%;
saturated polyester resin: 2-6 wt%;
amino resin: 5-15 wt%;
blocked isocyanate: 2-5 wt%;
an adhesion promoter: 1 wt% -3 wt%;
cosolvent: 2-4 wt%;
color paste: 10 wt% -30 wt%;
water-soluble polyaniline: 3 to 8 weight percent;
functional auxiliary agents: 0.8 wt% -2.5 wt%;
deionized water C: and (4) the balance.
4. The waterborne high-temperature conductive primer for glass fiber reinforced plastics containing water-soluble polyaniline according to claim 3, wherein the waterborne acrylic modified polyester has a solid content of 30-50% and a pH of 7-9, and the waterborne acrylic modified polyester contains 0.05-0.15 wt% of blocked acid catalyst.
5. The water-based high-temperature conductive primer for glass fiber reinforced plastics containing water-soluble polyaniline as claimed in claim 3, wherein the water-based acrylic emulsion has a core-shell structure, a solid content of 20% to 35%, an acid value of 2mgKOH/g to 15mgKOH/g, and a hydroxyl value of 20mgKOH/g to 40 mgKOH/g.
6. The water-based high-temperature conductive primer for glass fiber reinforced plastics containing water-soluble polyaniline according to claim 3, wherein the amino resin is prepared from methylated amino resin and butylated amino resin according to a mass ratio of (7-10): 3, the polymerization degree of the methylated amino resin is less than or equal to 2.5, and the solid content is not less than 60 percent.
7. The waterborne high-temperature conductive primer for glass fiber reinforced plastics containing water-soluble polyaniline according to claim 3, wherein the cosolvent is one or more of DPM, BCS, PPH, DPNB, TPM, BDGA and PGDA; the adhesion promoter is one or more of polyester adhesion promoter, epoxy phosphate adhesion promoter, epoxy modified acrylic resin and silane coupling agent.
8. The waterborne high-temperature conductive primer for glass fiber reinforced plastics containing water-soluble polyaniline as claimed in claim 3, wherein the auxiliary agent comprises defoamer B and wetting agent, the defoamer B is one or more of organic defoamer, polyether defoamer and organic silicon defoamer, and the content of the defoamer B is 0.5-1.5 wt% of the total weight of the conductive primer; the wetting agent is a modified organic silicon wetting agent, and the content of the wetting agent is 0.3 wt% -1 wt% of the total amount of the conductive primer.
9. The water-based high-temperature conductive primer for glass fiber reinforced plastics containing water-soluble polyaniline according to claim 3, wherein the color paste is prepared by the following steps:
s001, adding deionized water D into a container, stirring and controlling the speed to be 200-800 rpm, and sequentially adding a water-based dispersant, a defoaming agent A and a thickening agent for 10-20 min;
s002, continuously adding the pigment and the filler into the container, and dispersing for 30-60 min to prepare color paste;
s003, grinding the color paste, and controlling the fineness of the color paste to be less than 25 micrometers;
wherein the weight parts of the components are as follows:
pigment and filler: 78 parts of (1);
aqueous dispersant: 2 parts of (1);
defoaming agent A: 0.5 part;
thickening agent: 0.2 part;
deionized water D: and 20 parts.
10. A preparation method of the water-soluble polyaniline-containing water-soluble high-temperature conductive primer for glass fiber reinforced plastics, which is used for preparing the water-soluble polyaniline-containing water-soluble high-temperature conductive primer for glass fiber reinforced plastics, as claimed in any one of claims 3 to 9, and is characterized by comprising the following steps:
s1, adding the color paste into a container, stirring and controlling the speed to be 400-900 rpm, then slowly adding the water-based acrylic modified polyester, the water-based acrylic emulsion, the saturated polyester resin, the amino resin, the blocked isocyanate, the adhesion promoter, the cosolvent, the water-soluble polyaniline, the auxiliary agent and the deionized water C, dispersing for 30-60 min, and uniformly mixing to obtain a primary mixed material;
s2, filtering the primary mixed material, wherein the filtering aperture is 50-100 microns, and obtaining the water-based high-temperature conductive primer.
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| CN113667117B (en) | 2023-10-31 |
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