CN113667117B - Preparation method of water-soluble polyaniline, water-soluble high-temperature conductive primer containing water-soluble polyaniline for glass fiber reinforced plastic and preparation method - Google Patents
Preparation method of water-soluble polyaniline, water-soluble high-temperature conductive primer containing water-soluble polyaniline for glass fiber reinforced plastic and preparation method Download PDFInfo
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- CN113667117B CN113667117B CN202110899940.9A CN202110899940A CN113667117B CN 113667117 B CN113667117 B CN 113667117B CN 202110899940 A CN202110899940 A CN 202110899940A CN 113667117 B CN113667117 B CN 113667117B
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- 229920000767 polyaniline Polymers 0.000 title claims abstract description 57
- 239000011152 fibreglass Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 71
- 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
- 229920003180 amino resin Polymers 0.000 claims abstract description 22
- 229920000728 polyester Polymers 0.000 claims abstract description 19
- 239000000839 emulsion Substances 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
- 239000012948 isocyanate Substances 0.000 claims abstract description 14
- 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
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 229920001225 polyester resin Polymers 0.000 claims abstract description 12
- 239000004645 polyester resin Substances 0.000 claims abstract description 12
- 150000002513 isocyanates Chemical class 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
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-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
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 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
- 238000000034 method Methods 0.000 claims description 14
- 239000002518 antifoaming agent Substances 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 12
- 239000002318 adhesion promoter Substances 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
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 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
- 239000006185 dispersion Substances 0.000 claims description 7
- 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
- 239000004593 Epoxy Substances 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 4
- 238000000227 grinding Methods 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
- 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
- IBLKWZIFZMJLFL-UHFFFAOYSA-N 1-phenoxypropan-2-ol Chemical compound CC(O)COC1=CC=CC=C1 IBLKWZIFZMJLFL-UHFFFAOYSA-N 0.000 claims description 2
- WMDZKDKPYCNCDZ-UHFFFAOYSA-N 2-(2-butoxypropoxy)propan-1-ol Chemical compound CCCCOC(C)COC(C)CO WMDZKDKPYCNCDZ-UHFFFAOYSA-N 0.000 claims description 2
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- LATPRGOTJGNZTM-UHFFFAOYSA-N 2-amino-3-phenylbenzenethiol Chemical compound NC1=C(S)C=CC=C1C1=CC=CC=C1 LATPRGOTJGNZTM-UHFFFAOYSA-N 0.000 claims description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
- 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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 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
- JABXMSSGPHGCII-UHFFFAOYSA-N acetic acid;propane-1,2-diol Chemical compound CC(O)=O.CC(O)CO JABXMSSGPHGCII-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000013530 defoamer Substances 0.000 claims 5
- 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 64
- 238000007590 electrostatic spraying Methods 0.000 abstract description 5
- 239000002966 varnish Substances 0.000 abstract description 5
- 238000012360 testing method Methods 0.000 description 25
- 238000000576 coating method Methods 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 7
- 229920000877 Melamine resin Polymers 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- -1 imino methylated melamine formaldehyde Chemical class 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- 238000003556 assay Methods 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000000889 atomisation Methods 0.000 description 3
- 238000009833 condensation Methods 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
- 239000002932 luster Substances 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- 238000007665 sagging Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
- 230000009471 action Effects 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
- 230000003993 interaction Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000006082 mold release agent 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
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000006309 butyl amino group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 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
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical class O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 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
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
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
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- 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 application discloses a preparation method of water-soluble polyaniline, a water-based high-temperature conductive primer for glass fiber reinforced plastic containing the water-soluble polyaniline and a preparation method thereof, and relates to the field of water-based high-temperature baking varnish. The preparation method of polyaniline comprises the following steps: preparing N- (2-hydroxyethyl) -2-nitrobenzamide by adopting 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 water-soluble polyaniline and the o-aminophenylsulfiol. The preparation method of the conductive primer comprises the following steps: the conductive primer is prepared by mixing the components of water-based acrylic modified polyester, water-based acrylic emulsion, saturated polyester resin, amino resin, blocked isocyanate, water-soluble polyaniline and the like. The application improves the solubility of polyaniline in the water-based conductive primer, so that the conductive primer reduces the surface resistance of the glass fiber reinforced plastic, realizes the electrostatic spraying of the finish paint, and improves the paint application rate.
Description
Technical Field
The application relates to the technical field of water-based high-temperature baking paint, in particular to a preparation method of water-soluble polyaniline, water-based high-temperature conductive primer for glass fiber reinforced plastic containing the water-soluble polyaniline and a preparation method.
Background
The application relates to a glass fiber reinforced plastic, which is a composite material invented in the middle of the last century, generally refers to a continuous section bar with a specific section shape which is formed by using a glass fiber reinforcing agent, unsaturated polyester, epoxy resin and phenolic resin adhesive as basic components and adopting special equipment for pultrusion through a high-temperature die, and the used resin varieties are different, so that the composite material is called as polyester glass fiber reinforced plastic, epoxy glass fiber reinforced plastic and phenolic glass fiber reinforced plastic. 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, chemical industry (sewage treatment equipment, storage tank, pipelines and the like), buildings (cooling towers, decorative plates, doors and windows, storage bins), transportation (automobile shells, train window frames and the like), ships, communication, transportation, home furnishings and the like. According to statistics, the types of glass fiber reinforced plastic products at present reach more than 4 ten thousand.
When the glass fiber reinforced plastic is heated and cured in a mold for molding, in order to facilitate demolding, a mold release agent is added into the resin, and the mold release agent is 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 lower. If the conventional paint is used for spraying on the surface of the glass fiber reinforced plastic, the adhesive force is poor, the surface paint often falls off in the use process, and the service life and the appearance of the surface paint are seriously affected.
In order to solve the problem of falling of a surface paint layer, a paint for glass fiber reinforced plastics with strong adhesive force and high paint film hardness is generally used at present, and is mainly a solvent type system and a water-based two-component PU system, however, the solvent type paint has the defects of large smell, high VOC content, flammability and the like, the water-based PU system is a two-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 the higher paint rate, and the glass fiber reinforced plastic substrate has high surface resistance, is unfavorable for electrostatic coating, and needs to adopt conductive materials to provide conductive performance in water paint. The conductive material is widely selected from conductive graphite at present, and has the defects that the conductivity of the conductive graphite gradually decays along with time, and the conductive graphite is unstable and even separated out after long-term storage in an aqueous system, so that the aqueous coating is thickened and cannot be used.
Polyaniline becomes a hot field of material science by good conductivity, but the rigidity and interaction of polyaniline chains make the polyaniline insoluble and infusible, so that the polyaniline is difficult to grind to a sufficiently small fineness even by a grinding technology, is poorly dispersed and easily agglomerated in water-based paint, and limits the application of the polyaniline as a conductive material in water-based paint. Therefore, there is an urgent need to improve the solubility of polyaniline in water paint to obtain glass fiber reinforced plastic water-based conductive primer paint with superior conductivity and stable performance, so as to solve the problems of poor adhesion, low paint application rate and paint removal of glass fiber reinforced plastic.
Disclosure of Invention
The application provides a preparation method of water-soluble polyaniline, a water-soluble high-temperature conductive primer for glass fiber reinforced plastic containing the water-soluble polyaniline and a preparation method thereof.
In order to solve the technical problems, one of the embodiments of the present application provides a method for preparing water-soluble polyaniline, which includes the following steps:
s01, dissolving o-nitrobenzoyl chloride into dichloromethane with equal mass, stirring, sequentially adding ethanolamine with the mass of 5% of the o-nitrobenzoyl chloride and triethylamine with the mass of 10% of the o-nitrobenzoyl chloride, reacting for 24-48 hours at room temperature, distilling under reduced pressure to obtain a residue, and performing column chromatography on the residue to obtain N- (2-hydroxyethyl) -2-nitrobenzamide;
s02, mixing tetrahydrofuran and deionized water A in proportion to obtain tetrahydrofuran solution for standby, mixing iron powder and concentrated sulfuric acid in proportion to obtain first reaction solution for standby, and mixing concentrated hydrochloric acid and ammonium persulfate in proportion to obtain second reaction solution for standby;
s03, dissolving N- (2-hydroxyethyl) -2-nitrobenzamide in tetrahydrofuran solution, stirring and adding the solution into a first reaction solution, reacting for 24-48 hours at room temperature, 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-aminophenylsulfiol in deionized water B at the temperature of 35-45 ℃, stirring, adding a second reaction solution, heating to the temperature of 35-45 ℃ for 24-48 hours, precipitating by acetone, filtering and drying to obtain the water-soluble polyaniline.
By adopting the scheme, the polyaniline is modified in the preparation process of the polyaniline starting from the raw material of the polyaniline, so that hydrophilic groups are attached to the surface of the polyaniline, the solubility of the polyaniline in the water-based paint is improved, the polyaniline can be stably dispersed in the water-based paint and the conductivity is provided, the surface resistance of the glass fiber reinforced plastic substrate can be reduced by utilizing the conductive primer, the electrostatic spraying of the finish paint is realized, the problems of poor surface adhesion, paint removal and the like of the glass fiber reinforced plastic are solved, and the paint application rate is improved.
As a preferable solution, in S02, a mass ratio of tetrahydrofuran to water in the tetrahydrofuran solution is 1:1, the mass ratio of the iron powder to the 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 step S03, the following components in parts by weight are provided:
n- (2-hydroxyethyl) -2-nitrobenzamide: 0.5-1 part;
tetrahydrofuran solution: 3-5 parts of:
first reaction solution: 0.05-0.1 parts;
in the step S04, the following components in parts by weight are adopted:
n- (2-hydroxyethyl) -2-aminobenzamide: 0.5 to 1.5 parts;
o-aminophenylthiophenol: 0.5 to 1.5 parts;
deionized water B: 2-4 parts;
second reaction solution: 1-2 parts;
acetone: 2.5 parts to 7.5 parts.
In order to solve the technical problems, a second embodiment of the present application provides an aqueous high-temperature conductive primer for glass fiber reinforced plastic containing water-soluble polyaniline, which comprises the following raw material components:
aqueous acrylic modified polyester: 40-55 wt%;
aqueous acrylic emulsion: 5wt% to 10wt%;
saturated polyester resin: 2-6 wt%;
amino resin: 5-15 wt%;
blocked isocyanates: 2-5 wt%;
adhesion promoters: 1wt% to 3wt%;
cosolvent: 2-4 wt%;
color paste: 10wt% to 30wt%;
water-soluble polyaniline: 3wt% to 8wt%;
functional auxiliary agent: 0.8wt% to 2.5wt%;
deionized water C: the balance.
By adopting the scheme, the water-soluble polyaniline is stable in dissolution in the system, 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 the electrostatic spraying of the finish paint is realized, the construction is convenient and environment-friendly, and the paint application rate is improved; because the saturated polyester resin has low viscosity, the alkaline aqueous acrylic modified polyester is utilized to emulsify in the system, the flexibility, adhesive force, hardness, water resistance, damp and heat resistance and salt fog resistance of a paint film can be improved, and the paint film has higher gloss and better leveling property; in addition, the chemical bond formed in the blocked isocyanate is weaker, and the blocked isocyanate can not react and crosslink with-OH in a system at normal temperature, but the blocked isocyanate bond is opened and releases-NCO through high-temperature baking in the process of coating, so that the blocked isocyanate can react with-OH in the system and crosslink into a carbamate film, and the flexibility and stone-impact resistance of a paint film are improved.
Preferably, the solid content of the aqueous acrylic acid modified polyester is 30-50%, the pH value is 7-9, and the aqueous acrylic acid modified polyester contains 0.05-0.15% by weight of closed acid catalyst.
By adopting the scheme, the aqueous acrylic modified polyester resin is taken as a main resin, contains an acid catalyst capable of accelerating reaction, can accelerate the curing of painting, and ensures that the coating film obtained after the resin reaction has high hardness and excellent flexibility, water resistance and solvent resistance.
As a preferable scheme, the aqueous acrylic emulsion has a core-shell structure, the solid content is 20% -35%, the acid value is 2mgKOH/g-15mgKOH/g, and the hydroxyl value is 20mgKOH/g-40mgKOH/g.
By adopting the scheme, the aqueous 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 the coating particles are adhered to the surface of the glass fiber reinforced plastic substrate, and the aqueous acrylic emulsion is used as 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 continuously changing the viscosity; in addition, the pseudoplastic aqueous acrylic emulsion is sensitive to pH, and the pH is controlled within a certain range, so that the stability of the viscosity of the system can be ensured.
As a preferable scheme, the amino resin is prepared from methylated amino resin and butylated amino resin according to the mass ratio of (7-10): 3, wherein 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%.
By adopting the scheme, the methylated amino resin has extremely high reactivity and self-condensation tendency, can improve the hardness, luster, chemical resistance and outdoor durability of a paint film, has good compatibility, good wettability and high reactivity, and can improve the interlayer adhesive force with the finishing paint.
Preferably, the cosolvent is one or more of DPM, BCS, PPH, DPNB, TPM, BDGA, PGDA; the adhesion promoter is one or more of polyester adhesion promoter, epoxy phosphate adhesion promoter, epoxy modified acrylic resin and silane coupling agent.
As a preferable scheme, the auxiliary agent comprises an antifoaming agent B and a wetting agent, wherein the antifoaming agent B is one or more of an organic antifoaming agent, a polyether antifoaming agent and an organosilicon antifoaming agent, and the content of the antifoaming 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 0.3-1 wt% of the total amount of the conductive primer.
As a preferable 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 200rpm-800rpm, and sequentially adding an aqueous dispersing agent, a defoaming agent A and a thickening agent, wherein the dispersing time is 10-20 min;
s002, continuously adding pigment and filler into the container, wherein the dispersion time is 30-60 min, and preparing color paste;
s003, grinding the color paste, and controlling the fineness of the color paste to be less than 25 microns;
wherein the weight portions of the components are as follows:
pigment and filler: 78 parts;
aqueous dispersants: 2 parts;
defoaming agent a:0.5 parts;
and (3) a thickening agent: 0.2 parts;
deionized water D:20 parts.
In order to solve the technical problems, a third embodiment of the present application provides a method for preparing an aqueous high-temperature conductive primer for glass fiber reinforced plastic containing water-soluble polyaniline, comprising the following steps:
s1, adding color paste into a container, stirring and controlling the speed to be 400-900 rpm, then slowly adding water-based acrylic modified polyester, water-based acrylic emulsion, saturated polyester resin, amino resin, blocked isocyanate, adhesion promoter, cosolvent, water-soluble polyaniline, auxiliary agent and deionized water C, wherein the dispersing time is 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 thus the water-based high-temperature conductive primer is obtained.
Compared with the prior art, the embodiment of the application has the following beneficial effects:
1. the polyaniline is modified in the preparation process, so that hydrophilic groups are attached to the surface of the polyaniline, the solubility of the polyaniline in the water-based paint is improved, the polyaniline can be stably dispersed in the water-based paint and the conductivity is provided, the electrostatic spraying of the finish paint is realized, the problems of poor adhesion force, paint removal and the like of the glass fiber reinforced plastic surface are solved, and the paint application rate is improved.
2. The saturated polyester resin has low viscosity, and the alkali aqueous acrylic modified polyester is used for emulsification, so that the flexibility, adhesive force, hardness, water resistance, damp and heat resistance and salt spray resistance of a paint film can be improved, the paint film has higher gloss and better leveling property, and the flexibility and stone impact resistance of the paint film are improved by the closed isocyanate.
3. The aqueous acrylic modified polyester resin is used as a main resin, contains an acid catalyst capable of accelerating reaction, can accelerate the curing of painting, and ensures that a coating film obtained after the resin reaction has high hardness and excellent flexibility, water resistance and solvent resistance.
4. The water-based acrylic emulsion is used as the core-shell pseudoplastic acrylic emulsion, so that atomization and leveling of a system can be ensured, sagging phenomenon is avoided in the process of continuously changing 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, luster, 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 adhesive force with a finish paint.
Detailed Description
The technical solutions of the embodiments of the present application will be clearly and completely described below in conjunction with the embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
The following are performance indexes of the raw materials, wherein table 1 is the model and source of the raw materials used in the preparation examples, examples and comparative examples:
TABLE 1 model and manufacturer of raw materials
Wherein the solid content of the aqueous acrylic acid modified polyester is 30-50%, the pH is 7-9, the pH is preferably 8.4-8.8, and the aqueous acrylic acid modified polyester contains 0.05-0.15 wt% of a closed acid catalyst; the aqueous acrylic emulsion is core-shell pseudo-plastic acrylic emulsion and has a core-shell structure, the solid content is 20% -35%, the acid value is 2mgKOH/g-15mgKOH/g, and the hydroxyl value is 20mgKOH/g-40mgKOH/g; the acid value of the saturated polyester is 1-15mgKOH/g, and the hydroxyl value is 80-300 mgKOH/g; the polymerization degree of the high imino methylated melamine formaldehyde resin is 1.75, and the solid content is not less than 60%.
Preparation example
Preparation examples 1 to 3
The 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 a table 2, sequentially adding ethanolamine with 5% of the mass of the o-nitrobenzoyl chloride and triethylamine with 10% of the mass of the o-nitrobenzoyl chloride, reacting at room temperature for a period of time shown in the table 2, distilling under reduced pressure to obtain a residue, and performing column chromatography on the residue to obtain N- (2-hydroxyethyl) -2-nitrobenzamide;
s02, tetrahydrofuran and deionized water A are mixed according to the mass ratio of 1:1 to obtain tetrahydrofuran solution for standby, and mixing iron powder and concentrated sulfuric acid according to the mass ratio of 1:3, obtaining a first reaction solution for standby, and mixing concentrated hydrochloric acid and ammonium persulfate according to the mass ratio of 1:2, obtaining a second reaction solution for standby;
s03, dissolving N- (2-hydroxyethyl) -2-nitrobenzamide in tetrahydrofuran solution, stirring, controlling the stirring speed to be shown in table 2, then adding a first reaction solution, reacting at room temperature for a period of time shown in table 2, filtering, and washing with a solvent shown in table 2 to obtain N- (2-hydroxyethyl) -2-aminobenzamide;
s04, dissolving N- (2-hydroxyethyl) -2-aminobenzamide and o-aminophenylsulfiol in deionized water B under the temperature condition shown in table 2, stirring and controlling the stirring speed to be shown in table 2, then adding a second reaction solution, heating to the temperature shown in table 2, reacting for the time shown in table 2, precipitating by acetone, filtering and drying to obtain the water-soluble polyaniline.
TABLE 2 contents of the components and process parameters in preparation examples 1 to 3
PREPARATION EXAMPLES 4 to 5
The color paste is prepared by the following steps:
s001, adding deionized water D into a movable tank, starting a dispersing machine to stir and control the speed to be shown in a table 3, and sequentially adding a water-based dispersing agent, a defoaming agent A and a thickening agent, wherein the dispersing time is shown in the table 3;
s002, continuously adding pigment and filler into the movable tank, wherein the dispersion time is shown in the table 3, and preparing color paste;
s003, transferring the color paste of the movable tank into a grinder, grinding the color paste for 2-10pass, and controlling the fineness of the color paste to be less than 25 microns.
TABLE 3 content of the components and process parameters in preparation examples 4 to 6
| Project | Preparation example 4 | Preparation example 5 |
| Deionized water D (g) | 20 | 20 |
| Water-based 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 |
| Stirring speed (rpm) in S001 | 200 | 800 |
| Dispersion time (min) in S001 | 20 | 10 |
| Dispersion time (min) in S002 | 20 | 10 |
Examples
Examples 1 to 4
The water-soluble polyaniline-containing water-based high-temperature conductive primer for glass fiber reinforced plastic is prepared by the following steps:
s1, adding color paste into a cleaned movable tank, starting a dispersion machine to stir and controlling the speed to be shown in a table 4, then slowly adding water-based acrylic modified polyester, water-based acrylic emulsion, saturated polyester resin, amino resin, blocked isocyanate, adhesion promoter, cosolvent, water-soluble polyaniline, auxiliary agent and deionized water C, controlling the dispersion time to be shown in the 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 filtering pore diameter of the filter cloth is 50-100 microns, and thus the water-based high-temperature conductive primer is obtained;
wherein the amino resin is prepared from methylated amino resin and butyl etherified amino resin according to the mass ratio of (7-10): 3, wherein the methylated amino resin is specifically high imino methyl melamine formaldehyde resin, and the butyl amino resin is specifically high imino butyl melamine formaldehyde resin;
the cosolvent can be 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 organosilicon wetting agent.
TABLE 4 Components, contents and process parameters in examples 1-4
Performance test
1. Adhesion test: the adhesion rating of the conductive primers of examples 1 to 4 was measured at 25℃according to GB/T9286-1998 Cross-cut test of color paint and varnish-paint film, with a rating of 0 being optimal and a rating of 5 being worst, and the test results are shown in Table 5.
2. Flexibility test: the conductive primers obtained in examples 1 to 4 were tested for flexibility (mm) at 25℃according to GB/T1731-1993 paint film flexibility assay, and the test results are shown in Table 5.
3. Paint film hardness test: the hardness of the paint film of the conductive primer obtained in examples 1 to 4 was measured at 25℃according to GB/T6739-2006 "measurement of paint film hardness by the paint and varnish-pencil method", and the hardness was: 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. Impact resistance test: the conductive primers obtained in examples 1 to 4 were tested for impact resistance (Kg. Cm) according to GB/T1732-1993 paint film impact resistance assay, and the test results are shown in Table 5.
5. And (3) water resistance test: the water resistance of the conductive primers obtained in examples 1 to 4 was measured according to GB/T5209-1985 "determination of water resistance of paint and varnish immersion method", the conductivity of deionized water used was less than or equal to μs/cm, the water temperature was controlled to 40.+ -. 1 ℃, and the test results are shown in Table 5.
6. Acid resistance test: the acid resistance of the conductive primers obtained in examples 1 to 4 was measured according to GB/T9274-1998 determination of liquid medium resistance of paints and varnishes, and the test results are shown in Table 5.
7. Alkali resistance test: the alkali resistance of the conductive primers obtained in examples 1 to 4 was measured according to GB/T9274-1998 determination of liquid medium resistance of paints and varnishes, and the test results are shown in Table 5.
8. Oil resistance test: the gasoline resistance of the conductive primers obtained in examples 1 to 4 was measured according to GB/T1734-1993 paint film gasoline resistance assay, and the test results are shown in Table 5.
9. Wet heat resistance test: the conductive primers obtained in examples 1 to 4 were tested for wet heat resistance according to GB/T1740-2007 "film Wet heat resistance assay", and the test results are shown in Table 5.
10. Stone chip resistance test: the conductive primers obtained in examples 1 to 4 were tested for stone-chip resistance according to ISO 20567-1-2005 determination of stone-chip resistance of colored paint and varnish coatings, and the test results are shown in Table 5.
11. Surface resistance test: the surface resistance (Ω) of the conductive primers obtained in examples 1 to 4 was measured by a FEITA antistatic tester according to GB/T1410-2006 test method for volume resistivity and surface resistivity of solid insulation materials, and the test results are shown in Table 5.
12. And (3) measuring the paint application rate of the surface paint:
1) Taking 4 glass fiber reinforced plastic substrates with the same size, respectively spraying the conductive primer obtained in the examples 1-4 onto the surfaces of the corresponding glass fiber reinforced plastic substrates by adopting a rotary cup, wherein the sprayed film thickness (20-30 μm) is the same, flashing for 15-30min, then placing in a 140-DEG oven for baking for 15-20min, and testing the weight of the sprayed dry film and the substrate and recording as m1;
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, then placing in a 140-DEG C oven for baking for 20-30min, and testing the total weight of the dry film and the base material and recording as m3;
3) The paint application rate of the finish paint is continuously calculated according to the following formula: paint application rate (%) = (m 3-m 1)/m 2 × 100%
TABLE 5 Performance test results for examples 1-5
The polyaniline selected by the application has the characteristics of simple synthesis, low raw material price, diversified derivative structures and the like, and is used for replacing conductive materials such as conductive carbon black, metal powder and the like. Starting from the raw material of polyaniline, the preparation steps are adopted to obtain the water-soluble polyaniline, so that the problems of poor dispersibility and easy agglomeration of the polyaniline in the water-based high-temperature conductive primer due to the interaction between chains are solved.
The aqueous high-temperature conductive primer uses the aqueous acrylic modified polyester resin as main resin, contains an acid catalyst capable of accelerating reaction, can accelerate the curing of painting, and ensures that the coating obtained after the resin reaction has high hardness. The saturated polyester resin has low viscosity, and the alkaline aqueous acrylic modified polyester is used for emulsification in a system, so that the flexibility, adhesive force, hardness, water resistance, damp heat resistance and salt fog resistance of a paint film can be improved, and the paint film has higher gloss and better leveling property. Because the viscosity of the system of the water-based high-temperature conductive primer can change in the resin neutralization coating process, the water-based 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 can be avoided; in addition, the pseudoplastic aqueous acrylic emulsion is sensitive to pH, and the pH is controlled within a certain range, so that the stability of the viscosity of the system can be ensured. The polymerization degree of the high imino methyl melamine formaldehyde resin is less than 2.5, the high imino methyl melamine formaldehyde resin has extremely high reactivity and self-condensation tendency, and the hardness, the luster, the chemical resistance and the outdoor durability of a paint film can be improved; the high-iminobutylated melamine formaldehyde resin has good compatibility, good wettability and high reactivity, and can improve interlayer adhesion with finishing paint. The chemical bond formed in the blocked isocyanate is weaker, the blocked isocyanate bond can be opened and released to react with-OH in the system, and the blocked isocyanate bond is crosslinked into a carbamate film, so that the flexibility and stone-impact resistance of the paint film are improved.
The foregoing embodiments have been provided for the purpose of illustrating the general principles of the present application, and are not to be construed as limiting the scope of the application. It should be noted that any modifications, equivalent substitutions, improvements, etc. made by those skilled in the art without departing from the spirit and principles of the present application are intended to be included in the scope of the present application.
Claims (6)
1. The water-based high-temperature conductive primer for glass fiber reinforced plastic containing water-soluble polyaniline is characterized by comprising the following raw material components:
aqueous acrylic modified polyester: 40-55 wt%;
aqueous acrylic emulsion: 5wt% to 10wt%;
saturated polyester resin: 2-6 wt%;
amino resin: 5-15 wt%;
blocked isocyanates: 2-5 wt%;
adhesion promoters: 1wt% to 3wt%;
cosolvent: 2-4 wt%;
color paste: 10wt% to 30wt%;
water-soluble polyaniline: 3wt% to 8wt%;
functional auxiliary agent: 0.8wt% to 2.5wt%;
deionized water C: the balance;
the solid content of the aqueous acrylic modified polyester is 30-50%, the pH value is 7-9, and the aqueous acrylic modified polyester contains 0.05-0.15 wt% of a closed acid catalyst;
the aqueous acrylic emulsion has a core-shell structure, the solid content is 20% -35%, the acid value is 2mgKOH/g-15mgKOH/g, and the hydroxyl value is 20mgKOH/g-40mgKOH/g;
the amino resin is prepared from methylated amino resin and butyl etherified amino resin according to the mass ratio of (7-10): 3, wherein 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%;
the preparation method of the water-soluble polyaniline comprises the following steps:
s01, dissolving o-nitrobenzoyl chloride into dichloromethane with equal mass, stirring, sequentially adding ethanolamine with the mass of 5% of the o-nitrobenzoyl chloride and triethylamine with the mass of 10% of the o-nitrobenzoyl chloride, reacting for 24-48 hours at room temperature, distilling under reduced pressure to obtain a residue, and performing column chromatography on the residue to obtain N- (2-hydroxyethyl) -2-nitrobenzamide;
s02, mixing tetrahydrofuran and deionized water A in proportion to obtain tetrahydrofuran solution for standby, mixing iron powder and concentrated sulfuric acid in proportion to obtain first reaction solution for standby, and mixing concentrated hydrochloric acid and ammonium persulfate in proportion to obtain second reaction solution for standby;
s03, dissolving N- (2-hydroxyethyl) -2-nitrobenzamide in tetrahydrofuran solution, stirring and adding the solution into a first reaction solution, reacting for 10-18 hours at room temperature, 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-aminophenylsulfiol in deionized water B at the temperature of 35-45 ℃, stirring, adding a second reaction solution, heating to the temperature of 35-45 ℃ for 24-48 hours, precipitating by acetone, filtering and drying to obtain the water-soluble polyaniline.
2. The aqueous high-temperature conductive primer for glass fiber reinforced plastic containing water-soluble polyaniline according to claim 1, wherein in S02, the mass ratio of tetrahydrofuran and water in the tetrahydrofuran solution is 1:1, the mass ratio of the iron powder to the concentrated sulfuric acid in the first reaction solution is 1:3, the mass ratio of the concentrated hydrochloric acid to the ammonium persulfate in the second reaction solution is 1:2;
in the step S03, the following components in parts by weight are provided:
n- (2-hydroxyethyl) -2-nitrobenzamide: 0.5-1 part;
tetrahydrofuran solution: 3-5 parts of:
first reaction solution: 0.05-0.1 parts;
in the step S04, the following components in parts by weight are adopted:
n- (2-hydroxyethyl) -2-aminobenzamide: 0.5 to 1.5 parts;
o-aminophenylthiophenol: 0.5 to 1.5 parts;
deionized water B: 2-4 parts;
second reaction solution: 1-2 parts;
acetone: 2.5 parts to 7.5 parts.
3. The water-based high-temperature conductive primer for glass fiber reinforced plastic containing water-soluble polyaniline according to claim 1, wherein the cosolvent is one or more of dipropylene glycol methyl ether DPM, ethylene glycol butyl ether BCS, propylene glycol phenyl ether PPH, dipropylene glycol n-butyl ether DPNB, tripropylene glycol methyl ether TPM, diethylene glycol butyl ether acetate BDGA, and propylene glycol acetate PGDA; the adhesion promoter is one or more of polyester adhesion promoter, epoxy phosphate adhesion promoter, epoxy modified acrylic resin and silane coupling agent.
4. The aqueous high-temperature conductive primer for glass fiber reinforced plastic containing water-soluble polyaniline according to claim 1, wherein the functional auxiliary agent comprises a defoamer B and a wetting agent, wherein the defoamer B is one or more of a polyether defoamer and an organosilicon defoamer, and the content of the defoamer 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 0.3-1 wt% of the total amount of the conductive primer.
5. The aqueous high-temperature conductive primer for glass fiber reinforced plastic containing water-soluble polyaniline according to claim 1, 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 200rpm-800rpm, and sequentially adding an aqueous dispersing agent, a defoaming agent A and a thickening agent, wherein the dispersing time is 10-20 min;
s002, continuously adding pigment and filler into the container, wherein the dispersion time is 30-60 min, and preparing color paste;
s003, grinding the color paste, and controlling the fineness of the color paste to be less than 25 microns;
wherein the weight portions of the components are as follows:
pigment and filler: 78 parts;
aqueous dispersants: 2 parts;
defoaming agent a:0.5 parts;
and (3) a thickening agent: 0.2 parts;
deionized water D:20 parts.
6. A method for preparing a water-soluble polyaniline-containing water-based high-temperature conductive primer for glass fiber reinforced plastics, which is used for preparing the water-soluble polyaniline-containing water-based high-temperature conductive primer for glass fiber reinforced plastics according to any one of claims 1 to 5, and is characterized by comprising the following steps:
s1, adding color paste into a container, stirring and controlling the speed to be 400-900 rpm, then slowly adding water-based acrylic modified polyester, water-based acrylic emulsion, saturated polyester resin, amino resin, blocked isocyanate, adhesion promoter, cosolvent, water-soluble polyaniline, functional auxiliary agent and deionized water C, wherein the dispersing time is 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 thus the water-based high-temperature conductive primer is obtained.
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