CN117343242A - Polyaniline-polyacrylic acid composite material and preparation method and application thereof - Google Patents
Polyaniline-polyacrylic acid composite material and preparation method and application thereof Download PDFInfo
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- CN117343242A CN117343242A CN202311356914.7A CN202311356914A CN117343242A CN 117343242 A CN117343242 A CN 117343242A CN 202311356914 A CN202311356914 A CN 202311356914A CN 117343242 A CN117343242 A CN 117343242A
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- polyaniline
- composite material
- polyacrylic acid
- acid composite
- acrylic
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- 229920002125 Sokalan® Polymers 0.000 title claims abstract description 50
- 239000004584 polyacrylic acid Substances 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229920000767 polyaniline Polymers 0.000 claims abstract description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000839 emulsion Substances 0.000 claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 239000003999 initiator Substances 0.000 claims abstract description 18
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011248 coating agent Substances 0.000 claims abstract description 16
- 238000000576 coating method Methods 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 17
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 238000005260 corrosion Methods 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 claims description 3
- 230000004224 protection Effects 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- 238000012360 testing method Methods 0.000 abstract description 13
- 239000000758 substrate Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 11
- 229920000178 Acrylic resin Polymers 0.000 description 7
- 239000004925 Acrylic resin Substances 0.000 description 7
- 239000002270 dispersing agent Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- 238000011065 in-situ storage Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 239000005543 nano-size silicon particle Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- PIIRYSWVJSPXMW-UHFFFAOYSA-N 1-octyl-4-(4-octylphenoxy)benzene Chemical compound C1=CC(CCCCCCCC)=CC=C1OC1=CC=C(CCCCCCCC)C=C1 PIIRYSWVJSPXMW-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- -1 acrylic ester Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
-
- 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a polyaniline-polyacrylic acid composite material, and a preparation method and application thereof. The preparation method of the composite material comprises the following steps: s1, dissolving modified polyaniline and modified silicon dioxide into an organic solvent to form an organic mixed solution; dissolving an acrylic acid monomer, inorganic acid and an initiator into water to form an acrylic acid emulsion; s2, uniformly mixing the organic mixed solution prepared in the step S1 with the acrylic emulsion, and reacting at 20-40 DEG CAnd (3) obtaining the polyaniline-polyacrylic acid composite material after 2-4 hours. The surface resistance of the polyaniline-polyacrylic acid composite material is 10 8 Omega or less, as low as 6.16X10 6 Omega; the water resistance test can be kept for more than 504 hours; as a coating, the adhesion to the substrate can reach a level of 1.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a polyaniline-polyacrylic acid composite material, and a preparation method and application thereof.
Background
Acrylic resins, including acrylic resin emulsions, aqueous acrylic resin dispersions (also known as aqueous dilute acrylic acid) and aqueous acrylic resin solutions, are widely used in the electrical and electronic fields because of their excellent properties such as environmental friendliness, high insulation, uv resistance, and chemical degradation resistance. However, the conventional acrylic resin has disadvantages such as low film hardness, poor water resistance, poor adhesion, and the like, and at the same time, because of its high insulation, static electricity is easily accumulated on the surface thereof, so that dust is easily adsorbed on the surface of the film, and the accumulated charge also causes bubbles to appear on the surface of the paint, so that it is necessary to modify the acrylic resin to have antistatic ability.
The addition of antistatic agents such as metals (oxides), conductive polymers, etc. is a common effective method for inhibiting the accumulation of static electricity on the surface of acrylic resin, and among antistatic agents, conductive polymers are considered as potential high-efficiency materials, and compared with other materials, they have advantages of long-term stability, flame retardance, thermal stability, etc., and typical conductive polymers are polyaniline, which has the longest application history in various fields of the coating industry, has good corrosion resistance, and has electromagnetic shielding and antistatic properties. At present, polyaniline is mostly dispersed into acrylic emulsion, and the dispersibility of polyaniline in the acrylic emulsion is improved, so that the antistatic performance and the mechanical new performance of the obtained polyaniline-polyacrylate composite material are improved. However, the rigid chain of polyaniline causes poor solubility and difficult processing, and the intrinsic polyaniline has low conductivity, which greatly limits the improvement of antistatic property of polyaniline to acrylic coating.
Therefore, it is desirable to provide a polyaniline-polyacrylic acid composite material that is excellent in mechanical properties and electrical conductivity.
Disclosure of Invention
The invention aims to overcome the defect that the antistatic performance and the coating performance of the existing polyaniline-polyacrylic acid coating are to be further improved, and provides a novel preparation process, wherein polyaniline and modified silicon dioxide are dissolved into an organic solvent to form an organic phase; then, the aqueous phase of the acrylic emulsion containing the initiator and the inorganic acid is dripped into the organic phase for in-situ polymerization reaction, and the polyaniline-polyacrylic acid composite material with excellent mechanical property and conductivity is obtained.
The invention also aims to provide the polyaniline-polyacrylic acid composite material prepared by the preparation process.
Another object of the present invention is to provide the use of the polyaniline-polyacrylic acid composite material in the field of corrosion protection.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of polyaniline-acrylate composite material comprises the following steps:
s1, dissolving polyaniline and modified silicon dioxide into an organic solvent to form an organic mixed solution; dissolving an acrylic acid monomer, inorganic acid and an initiator into water to form an acrylic acid emulsion;
s2, uniformly mixing the organic mixed solution prepared in the step S1 with the acrylic emulsion, and reacting at 20-40 ℃ for 2-4 hours to obtain the polyaniline-polyacrylic acid composite material.
The method takes polyaniline and modified nano silicon dioxide as fillers, firstly mixes the fillers into an organic solvent to form an organic phase, then dropwise adds aqueous phase solution containing acrylic acid monomers into the organic phase, and the acrylic acid monomers can be polymerized in situ in the aqueous phase; polyaniline and modified nano silicon dioxide are uniformly dispersed into a polyacrylic acid matrix along with polymerization of acrylic acid monomers under the action of an organic solvent, aniline can undergo oxidative polymerization reaction at an oil-water interface and is grafted onto a polyacrylic acid matrix chain segment to form a polyaniline-polyacrylic acid composite material, and ideal antistatic performance and mechanical property are achieved under the in-situ synthesis of the interface and the dispersion of the organic solvent, so that the conductive property of the composite material is remarkably improved. Meanwhile, the addition of the modified silicon dioxide can further improve the water resistance and the adhesive force with the base material of the polyaniline-polyacrylic acid coating, so that the modified silicon dioxide can be widely applied to various industries.
Preferably, the modified silica is a silica modified with a surfactant including, but not limited to, a silane coupling agent. In order to further improve the dispersibility of the modified silica in the composite material, nano silica is preferred.
It should be noted that modification of silica may be performed by modification methods commonly known in the art, for example: the nano silicon dioxide can be dispersed in an organic solvent (such as methyl ethyl ketone) and stirred, 3 percent of surfactant is added until the turbidity is stable and uniform, and the modified nano silicon dioxide can be obtained after washing and drying.
Preferably, the polyaniline is prepared by a method comprising the steps of:
dispersing and dissolving aniline and an initiator into water, and stirring and reacting for 24-48 hours at the temperature of 0-10 ℃ to obtain the polyaniline.
Preferably, the average molecular weight of the polyaniline is 300-400 g/mol. The polyaniline in the particle size range can be dispersed into the polyacrylic acid matrix more rapidly and stably. In the present invention, the molecular weight of polyaniline can be measured by gel chromatography.
In order to further improve the dispersibility of polyaniline in polyacrylic acid, the polyaniline is doped and modified by using a modifier, wherein the modifier comprises at least one of dodecylbenzene sulfonic acid and chlorosulfonic acid. The modifier is added in an amount of 38 to 42wt% based on the polyaniline.
In the present invention, the organic solvent for dissolving polyaniline and modified silica is an insoluble good solvent, and the organic solvent includes, but is not limited to, at least one of chloroform, toluene, and acetonitrile, and more preferably chloroform.
Preferably, the organic mixed solution has a solid content of 23 to 27wt%.
Preferably, the solid content in the acrylic emulsion is 18 to 22wt%.
Preferably, the acrylic monomer includes at least one of acrylic acid, acrylic esters, and methacrylic esters. The acrylic ester comprises at least one of methyl acrylate, ethyl acrylate and butyl acrylate; the methacrylates include, but are not limited to, methyl methacrylate.
Preferably, a dispersing agent is further added into the acrylic emulsion, wherein the dispersing agent comprises but is not limited to an ether dispersing agent, and the ether dispersing agent can be polyethylene glycol mono octyl phenyl ether. The dispersant is added in an amount of 0.9 to 1.5wt% based on the acrylic monomer.
Initiators common in the art may be used in the present invention, including but not limited to at least one of peroxide initiators, persulfate initiators, azo-type initiators; the persulfate initiator is preferred and may be, for example, ammonium persulfate. The initiator is added in an amount of 0.9 to 1.5wt% based on the acrylic monomer.
Preferably, the inorganic acid includes at least one of hydrochloric acid, sulfuric acid, and nitric acid.
Preferably, the polyaniline, the modified silicon dioxide and the acrylic monomer have the following weight proportion: polyaniline: modified silica: acrylic monomer = 1: (0.22-0.27): (2.8-3.2).
Preferably, the specific steps of mixing in step S2 are: the acrylic emulsion was added dropwise to the organic mixed solution.
The polyaniline-polyacrylic acid composite material prepared by the preparation method is also in the protection scope of the invention.
The invention also protects the application of the polyaniline-polyacrylic acid composite material as a coating in the field of corrosion prevention.
Compared with the prior art, the invention has the beneficial effects that:
the invention forms an organic phase by dissolving polyaniline and modified silicon dioxide into an organic solvent; then, the aqueous phase of the acrylic emulsion containing the initiator and the inorganic acid is dripped into the organic phase for in-situ polymerization reaction, and the polyaniline-polyacrylic acid composite material with excellent mechanical property and conductivity is obtained.
The surface resistance of the polyaniline-polyacrylic acid composite material is 10 7 Omega or less, can be as low as xΩ; the water resistance test can be kept for more than 504 hours; as a coating, the adhesion to the substrate can reach a level of 1.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples, which are not intended to limit the present invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art. The reagents and materials used in the present invention are commercially available unless otherwise specified.
Example 1
The embodiment provides a polyaniline-polyacrylic acid composite material, which is prepared by the following steps:
s1, dissolving doped polyaniline and modified silicon dioxide into chloroform serving as an organic solvent to form an organic mixed solution with the solid content of 20wt%, wherein the doped polyaniline is prepared by the steps of: the weight ratio of the modified silicon dioxide is 1:0.25;
acrylic acid monomer (methyl methacrylate), hydrochloric acid, initiator ammonium persulfate and dispersant polyethylene glycol mono octyl phenyl ether are dissolved in water to form an acrylic acid emulsion with solid content of 25wt%, wherein the pH value of the acrylic acid emulsion is 7.4; the addition amount of the initiator was 1.2wt% and the addition amount of the dispersant was 1.2wt% based on the acrylic monomer;
s2, uniformly mixing the organic mixed solution prepared in the step S1 with the acrylic emulsion (according to the weight ratio of doped polyaniline to acrylic acid monomer=1:3), and reacting for 2-4 h at 25 ℃ under the stirring condition to obtain the polyaniline-polyacrylic acid composite material.
In this embodiment, the doped polyaniline is prepared according to the following method:
137.12g of dodecylbenzenesulfonic acid is added into 350mL of deionized water, continuously stirred for 30 minutes, fully dispersed and dissolved, and then added into a three-necked flask to obtain an aqueous solution of dodecylbenzenesulfonic acid with the concentration of 1.29 mol/L; 13.97g of aniline was weighed and added to the three-necked flask via a separatory funnel and stirred continuously; 17.1g of initiator ammonium persulfate is weighed and dissolved in 50mL of deionized water, and then dripped into a three-necked flask at a rate of 0.8mL/min by using a peristaltic pump; the mixture was stirred continuously in an ice water bath for 24 hours; after the reaction is completed, the dark green reaction product is soaked in methanol for 5 hours, washed by deionized water, centrifuged for several times until the pH value of the supernatant is close to neutral, and finally dried in a vacuum drying oven for 24 hours, and the dried composite polyaniline solid is ground into 300 mesh powder. The average molecular weight of the doped polyaniline was measured by gel chromatography to be 350g/mol.
In this example, the modified silica was prepared as follows:
the nano-silica (particle size 50nm-100 nm) was dispersed in methyl ethyl ketone and stirred, 3wt% (based on nano-silica) of 3-aminopropyl triethoxysilane was added until turbidity was stable and uniform.
Example 2
This example provides a polyaniline-polyacrylic acid composite material, prepared by the method of example 1, which differs from example 1 in that: in step S1, hydrochloric acid in the acrylic emulsion is replaced with sulfuric acid.
Example 3
This example provides a polyaniline-polyacrylic acid composite material, prepared by the method of example 1, which differs from example 1 in that: in step S1, chloroform is replaced with toluene.
Example 4
This example provides a polyaniline-polyacrylic acid composite material, prepared by the method of example 1, which differs from example 1 in that: in step S1, the solid content of the organic mixed solution was 18wt%.
Example 5
This example provides a polyaniline-polyacrylic acid composite material, prepared by the method of example 1, which differs from example 1 in that: in step S1, the solid content of the acrylic emulsion was 27% by weight.
Example 6
The present example provides a polyaniline-polyacrylic acid composite material, prepared by referring to the method of example 1, which is different from example 1 in that the weight ratio of the doped polyaniline, the modified silica, and the acrylic acid monomer in the preparation process satisfies: doping polyaniline: modified silica: acrylic monomer = 1: (0.27): (2.8).
Example 7
The difference between the polyaniline and the preparation method of the embodiment 1 is that sodium dodecyl sulfate is added into a reaction system after the polymerization reaction of the polyaniline is completed in the preparation process of the polyaniline, and finally the polyaniline-polyacrylic acid composite material is stirred for 10min, namely the modifier sodium dodecyl sulfate and the polyaniline are physically modified and are not doped into the polyaniline polymer.
Example 8
The present example provides a polyaniline-polyacrylic acid composite material, which was prepared by the method of example 1, and the difference from example 1 is that sodium dodecyl sulfate was not added in the preparation process of polyaniline, i.e. no doping modification was performed.
Comparative example 1
This comparative example provides a polyaniline-polyacrylic acid composite material, prepared by the method of example 1, differing from example 1 in that: in step S1, no modified silica is added.
Comparative example 2
This comparative example provides a polyaniline-polyacrylic acid composite material, prepared by the method of example 1, differing from example 1 in that: in step S1, chloroform is replaced with deionized water of equal mass.
Comparative example 3
This comparative example provides a polyaniline-polyacrylic acid composite material, prepared by the method of example 1, differing from example 1 in that: and (2) after the acrylic acid monomer is completely polymerized in the step (S2), adding an organic mixed solution for further reaction.
Performance testing
The properties of the polyaniline-polyacrylic acid composite materials obtained in the above examples and comparative examples were characterized, and specific test items, test methods and results are as follows:
1. conducting performance test: measuring the surface resistance of the coating according to standard ASTM F105-98 in omega;
2. and (3) testing the water resistance of the coating: coating the polyaniline-polyacrylic acid composite material on a base material (tinplate), testing the water resistance of the cured coating according to the method in the standard GB/T1733-93, wherein the test result is expressed by the bubbling resistance time (h);
3. coating adhesion test: the test was carried out according to the cross-hatch test described in standard GB/T9286-1998, the grades being recorded, wherein the higher the number of grades, the worse the adhesion is indicated, the test results are given in Table 1.
Table 1 test results of polyaniline-polyacrylic acid composite materials obtained in examples and comparative examples
From the above results, it can be seen that:
the surface resistance of the polyaniline-polyacrylic acid composite material prepared by the invention is 10 8 Omega or less, as low as 6.16X10 6 Omega; the water resistance test can be kept for more than 504 hours; as a coating, the adhesive force with the base material can reach grade 1 waterFlat.
In comparative example 1, modified silica was not added, in-situ polymerization at the interface was not performed in comparative example 2, and in-situ polymerization was not performed in comparative example 3, the conductivity and adhesion of the obtained coating were remarkably deteriorated.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. A preparation method of polyaniline-polyacrylic acid composite material comprises the following steps:
s1, dissolving modified polyaniline and modified silicon dioxide into an organic solvent to form an organic mixed solution; dissolving an acrylic acid monomer, inorganic acid and an initiator into water to form an acrylic acid emulsion;
s2, uniformly mixing the organic mixed solution prepared in the step S1 with the acrylic emulsion, and reacting at 20-40 ℃ for 2-4 hours to obtain the polyaniline-polyacrylic acid composite material.
2. The method for preparing a polyaniline-polyacrylic acid composite material according to claim 1, wherein the modified silica is obtained by modifying silica with a surfactant, and the surfactant comprises a silane coupling agent.
3. The method for producing a polyaniline-polyacrylic acid composite material according to claim 1, wherein the organic solvent is a water-insoluble organic solvent comprising at least one of chloroform, toluene, and acetonitrile.
4. The method for producing a polyaniline-polyacrylic acid composite material according to claim 1, wherein the inorganic acid comprises at least one of hydrochloric acid, sulfuric acid, and nitric acid.
5. The method for producing a polyaniline-polyacrylic acid composite material according to claim 1, wherein the initiator comprises at least one of a peroxide initiator and an azo initiator.
6. The method for preparing a polyaniline-polyacrylic acid composite material according to claim 1, wherein the polyaniline, the modified silica and the acrylic monomer have the weight ratio: polyaniline: modified silica: acrylic monomer = 1: (0.22-0.27): (2.8-3.2).
7. The method for producing a polyaniline-polyacrylic acid composite material according to claim 1, wherein the average molecular weight of the polyaniline is 300 to 400g/mol.
8. The method for producing a polyaniline-polyacrylic acid composite material according to claim 1, wherein at least one of the following characteristics is satisfied:
(1) The solid content of the acrylic emulsion is 23-27 wt%;
(2) The solid content of the organic mixed solution is 18-22 wt%.
9. A polyaniline-polyacrylic acid composite material, characterized in that it is prepared by the preparation method according to any one of claims 1 to 8.
10. The application of the polyaniline-polyacrylic acid composite material is characterized in that the polyaniline-polyacrylic acid as a coating is applied to the field of corrosion protection.
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