CN114634791B - Poly-o-epoxy-N-methylaniline conductive adhesive resin, preparation method thereof, conductive organic thermosetting material and application - Google Patents
Poly-o-epoxy-N-methylaniline conductive adhesive resin, preparation method thereof, conductive organic thermosetting material and application Download PDFInfo
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
- C09J179/02—Polyamines
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- 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
- C08G73/0206—Polyalkylene(poly)amines
- C08G73/0213—Preparatory process
- C08G73/022—Preparatory process from polyamines and epihalohydrins
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- 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
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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Abstract
The invention discloses a poly-o-epoxy-N-methylaniline conductive adhesive resin, a preparation method thereof, a conductive organic thermosetting material and application thereof, wherein the structural monomers of the adhesive resin are as follows. The preparation method comprises the following steps: polymerizing N-methylaniline and persulfate under inert atmosphere to obtain N-methylaniline polymer; washing, drying and then treating with ammonia water to obtain an eigenstate N-methylaniline polymer; dissolving the epoxy resin in a good solvent, and adding halogenated epoxide and a catalyst to obtain an o-epoxy-N-methylaniline bonding resin solution; filtering to remove catalyst and solvent to obtain the final product. The conductive organic thermosetting material is prepared by mixing the bonding resin, a polybiphenyl amine curing agent and a doping agent and then crosslinking and curing. The adhesive resin has excellent conductivity and dissolution capacity; the organic thermosetting material has excellent thermal oxidation resistance, ultraviolet resistance and film forming property.
Description
Technical Field
The invention relates to a bonding resin and a preparation method, an organic carrier and a preparation method, a conductive organic thermosetting material and application, conductive slurry and a preparation method, in particular to a poly-o-epoxy-N-methylaniline conductive bonding resin and a preparation method, a conductive organic thermosetting material and application, a poly-o-epoxy-N-methylaniline conductive organic carrier and a preparation method, a high-conductivity slurry with low conductive phase filling quantity and a preparation method thereof.
Background
The resistivity of the conductive polymer is generally 10 -1 ～10 -2 Omega cm, of which conjugated polymers having aromatic heterocyclic rings as basic structural units, such as polyaniline, polypyrrole, polythiophene, and the like, are typical. Especially, polyaniline has simple synthesis process, no toxicity and low raw material cost, and has wide application and research in the aspects of electrocatalysis, electroanalytical chemistry, functional electronic devices and the like, but the action of intermolecular hydrogen bonds between aromatic rings, amino groups and imino groups of polyaniline leads the polyaniline to be almost insoluble in any solvent, and the dissolubility and rheological property are both unfavorable for processing and forming.
Structural modification and modification of polyaniline is one of the effective ways to address polymer dissolution processability. The introduction of substituent groups can reduce coplanarity of the molecular chains, reduce rigidity of a main chain of the macromolecule, and weaken acting force among the macromolecular chains by the dilution effect of the groups, so that solubility is improved. The macromolecular proton acid is adopted for doping, the compatibility between the polymer and the solvent is improved by the soluble long-chain end group and the like, the currently reported modified polyaniline mainly takes a linear structure as a main part, and the prepared conductive layer has poor mechanical strength and bonding strength with a base material, so that the application of the modified polyaniline in a plurality of fields such as electronic circuits, solar photovoltaic panels, electromagnetic shielding, electronic devices and the like is limited.
The conductive paste is the basis for developing electronic components and is usually printed on a printing stock to enable the printing stock to have the capability of conducting current, and consists of a conductive phase and an organic carrier, wherein the conductive phase is mainly silver powder, and the organic carrier is mainly composed of a binder, a viscosity reducing solvent and an auxiliary agent. The trend in the electronic information industry toward high speed transmission and miniaturization and intellectualization requires that the conductive paste used in the components have higher conductivity and higher printing resolution and uniformity.
The binder is a film-forming substance in the conductive paste, and is usually a resin-based organic compound, and its kind, content, molecular weight, and the like have a great influence on properties such as bending resistance, hardness, adhesion, printability, and the like of the paste.
At present, insulating polymer materials such as epoxy resin, phenolic resin, acrylic resin and the like are often adopted as binders in the conductive paste on the market, and the conductive paste of the system has high hardness of a printing film layer, large brittleness and high resistance (generally volume resistivity is 10) -4 ～10 -5 Omega cm), and the like. The binder of the insulating polymer material is insulated and nonconductive, the cured resin can be coated on the surface of the conductive phase particles, even plays a role in blocking the transmission of electrons, and conductive paste with higher reliability can not be obtained by continuously using the insulating resin as the binder for use in miniaturized and intelligent elements.
Disclosure of Invention
The invention aims to: the invention aims to provide a poly-o-epoxy-N-methylaniline bonding resin with strong dissolving capacity;
a second object of the present invention is to provide a method for preparing the above-mentioned poly-o-epoxy-N-methylaniline binding resin;
the third object of the invention is to provide a poly-o-epoxy-N-methylaniline conductive organic thermosetting material with high mechanical strength and high bonding strength;
a fourth object of the present invention is to provide the use of the above-described poly-o-epoxy-N-methylaniline conductive organic thermosetting material in a conductive film;
the fifth object of the invention is to provide a poly-o-epoxy-N-methylaniline conductive organic carrier with good conductivity and strong adhesion;
a sixth object of the present invention is to provide a method for preparing the above-mentioned poly-o-epoxy-N-methylaniline conductive organic carrier;
the seventh object of the present invention is to provide a high-conductivity paste with good conductivity and strong adhesion, which has a low conductive phase loading;
an eighth object of the present invention is to provide a method for producing the above-mentioned high-conductivity paste with a low conductive phase loading.
The technical scheme is as follows: the structural monomers of the poly-o-epoxy-N-methylaniline conductive adhesive resin disclosed by the invention are as follows:
wherein x is a positive integer from 10 to 200.
The preparation method of the poly-o-epoxy-N-methylaniline conductive adhesive resin comprises the following steps:
(1) Placing N-methylaniline and persulfate in a hydrochloric acid aqueous solution for polymerization reaction under inert atmosphere to obtain a planned N-methylaniline polymer; washing, drying and then treating with ammonia water to obtain an eigenstate N-methylaniline polymer;
(2) Dissolving eigenstate N-methylaniline polymer in a good solvent, adding halogenated epoxide, and coupling epoxy groups on aromatic rings of the N-methylaniline polymer under the action of a catalyst to obtain o-epoxy-N-methylaniline bonding resin solution; filtering to remove catalyst and solvent to obtain the final product.
The synthesis route of the o-epoxy-N-methylaniline bonding resin is as follows:
wherein in the step (1), the polymerization time is 3-10 h, and the polymerization temperature is 40-80 ℃.
Wherein in the step (2), the ratio of the epoxy group to the aromatic ring is 1:2-10; the catalyst is anhydrous AlCl with the concentration of 0.05-0.1 g/mL 3 The method comprises the steps of carrying out a first treatment on the surface of the The concentration of the eigenstate N-methylaniline polymer is 0.05-0.5 g/mL, and the concentration of the halogenated epoxide is 0.02-0.1 g/mL; the good solvent is at least one of acetone, butanone, DMF, DMSO, pyridine or N-methylpyrrolidone.
The poly-o-epoxy-N-methylaniline conductive organic thermosetting material is prepared by mixing the o-epoxy-N-methylaniline bonding resin, a polybiphenyl amine curing agent and a doping agent and then crosslinking and curing.
Wherein the doping agent is organic macromolecular protonic acid; the organic macromolecule proton acid is dodecylbenzene sulfonic acid and/or dodecylsulfonic acid.
Wherein, the mass ratio of the o-epoxy-N-methylaniline bonding resin to the polybiphenyl amine curing agent to the doping agent is 100:1 to 5:5 to 20.
Wherein the polymerization degree of the polybiphenyl amine curing agent is 3-5.
The application of the poly-o-epoxy-N-methylaniline conductive organic thermosetting material in a conductive film; specifically, a poly-o-epoxy-N-methylaniline conductive organic thermosetting material is coated on the surface of a matrix material, and after a solvent volatilizes, the film is cured at a certain temperature to obtain a poly-o-epoxy-N-methylaniline thermosetting conductive film; the temperature of the solidified film is preferably 120-150 ℃; more preferably 140℃to 150 ℃.
The polybiphenyl amine curing agent not only can be crosslinked and cured with epoxy groups on the o-epoxy-N-methylaniline bonding resin, but also can be secondarily coupled with the end groups of the o-epoxy-N-methylaniline bonding resin to form polyaniline with a bulk structure, and meanwhile, after being doped by a doping agent, carriers are introduced to form a three-dimensional network conductive path.
The poly-o-epoxy-N-methylaniline conductive organic carrier comprises the following components in percentage by mass: 20-25% of the poly-o-epoxy-N-methylaniline conductive adhesive resin, 1-3% of a polybiphenyl amine curing agent, 70-75% of a solvent and 1-2% of an auxiliary agent.
Wherein the solvent is at least one of isophorone, butyl carbitol acetate or butyl carbitol; the auxiliary is preferably a thixotropic agent, which is preferably an organogel as in patent CN 109473197.
The method for preparing the poly-o-epoxy-N-methylaniline conductive organic vehicle comprises the following steps of:
the adhesive is prepared by mixing, grinding, defoaming and defoaming the poly-o-epoxy-N-methylaniline adhesive resin, the polybiphenyl amine curing agent, the organic macromolecular protonic acid, the solvent and the auxiliary agent according to mass percent.
Wherein, after mixing, the temperature is raised to 70-100 ℃, and the mixture is stirred for 2-4 hours at constant temperature.
The high-conductivity slurry with low conductive phase filling quantity comprises 30-40% of the poly-o-epoxy-N-methylaniline conductive organic carrier and 60-70% of silver powder in percentage by mass; the poly-o-epoxy-N-methylaniline conductive organic carrier comprises the following components in percentage by mass: 20-25% of poly-o-epoxy-N-methylaniline conductive adhesive resin, 1-3% of polybiphenyl amine curing agent, 70-75% of solvent and 1-2% of auxiliary agent.
The preparation method of the high-conductivity slurry with low conductive phase filling amount comprises the following steps:
mixing the poly-o-epoxy-N-methylaniline bonding resin, the polybiphenyl amine curing agent, the solvent and the auxiliary agent according to the mass ratio, defoaming, and mixing with silver powder after defoaming.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable effects:
(1) The o-epoxy-N-methylaniline bonding resin has excellent conductivity, dissolution capacity and film forming property. (2) The poly-o-epoxy-N-methylaniline conductive organic thermosetting material has excellent thermal oxidation resistance and ultraviolet resistance; (3) The poly-o-epoxy-N-methylaniline conductive organic thermosetting material has good conductivity. (4) The poly-o-epoxy-N-methylaniline conductive organic thermosetting material has excellent film forming property and bonding property. (5) In the conductive organic carrier, the polybiphenyl amine is mixed with the bonding resin, the amine N-H on the polybiphenyl amine reacts with the epoxy group on the bonding resin to realize solidification, and meanwhile, the polybiphenyl amine and the bonding resin are subjected to coupling reaction to form an integral conductive network structure, and the conductive organic carrier formed by mixing the polybiphenyl amine with the solvent and the auxiliary agent has high conductivity and also has stronger bonding performance; (6) The conductive organic carrier and silver powder are compounded to form high-conductivity slurry, the conductive organic carrier plays a role in bonding in the slurry and assists the silver powder to form a conductive network, and the purpose of realizing high conductivity by low conductive phase filling quantity can be realized; in addition, the slurry provided by the invention has the low-temperature curing performance of the conductive organic carrier, the conductivity, the low-temperature curing film forming performance and the ageing resistance of the slurry are obviously improved, and the reliability of the high-conductivity slurry application product can be improved.
Detailed Description
The present invention is described in further detail below.
Example 1
A preparation method of a poly-o-epoxy-N-methylaniline conductive adhesive resin comprises the following steps:
(1) Under inert atmosphere, N-methylaniline and (NH) 4 ) 2 S 2 O 2 Placing the mixture in a hydrochloric acid aqueous solution for polymerization reaction, and controlling the polymerization time to be 4 hours to obtain an N-methylaniline polymer with an average polymerization degree of 50;
(2) Washing the obtained N-methylaniline polymer precipitate with deionized water, drying at 80 ℃ for 12 hours, and then treating with ammonia water to obtain eigenstate N-methylaniline polymer;
(3) Preparation of the eigenstate N-methylaniline Polymer with solubility of 0.1g/mL dissolved in DMF, addition of 0.05g/mL epichlorohydrin, 0.05g/mL anhydrous AlCl 3 At the polymerization temperature of 60 ℃, the coupling reaction is carried out for 8 hours, and then the anhydrous AlCl is removed by filtration 3 And (3) removing the solvent from the catalyst to obtain the poly-o-epoxy-N-methylaniline bonding resin with the ratio of the epoxy group to the aromatic ring of about 1:4.
The resistivity test shows that the conductivity and yield of the N-methylaniline polymer increase with the increase of the concentration of the oxidant, and when the concentration of the oxidant is more than 1.0M, the yield and the yield decrease. Infrared spectra of N-methylaniline multimers, the N-methylaniline multimers were found to be 1, 4-linked head-to-tail structures, wherein the quinoid structure (1590 cm -1 ) Strength relative to benzene type structure (1500 cm) -1 ) It is shown that the concentration of the oxidizing agent increases with the increase of the concentration of the oxidizing agent, i.e., the increase of the concentration of the oxidizing agent increases the quinoid structure ratio, which is advantageous for the increase of the electrical conductivity.
In addition, N-methylaniline multimers in both the intrinsic and doped states were soluble in solvents such as DMF, DMSO, pyridine and N-methylpyrrolidone by solubility analysis.
According to the thermal weight loss diagram of the N-methylaniline polymer in the air, the N-methylaniline polymer starts to decompose at about 320 ℃, which shows that the N-methylaniline polymer has good thermal stability.
The N-methylaniline polymer in the doped state has certain environmental stability, and the conductivity of the N-methylaniline polymer in the air for half a year is 8 multiplied by 10 -3 S/cm becomes 1.0X10 -2 S/cm。
The N-methylaniline polymer in a doped state is dissolved in chloroform solution, and shows good film forming property. Epoxy group substitution is carried out on the benzene ring of the N-methylaniline polymer, so that the adhesion and the solubility in various solvents such as DMF, acetone and the like are improved on the basis of keeping the excellent conductivity.
Example 2
A preparation method of a poly-o-epoxy-N-methylaniline conductive adhesive resin comprises the following steps:
(1) Under inert atmosphere, N-methylaniline and (NH) 4 ) 2 S 2 O 2 Placing the mixture in a hydrochloric acid aqueous solution for polymerization reaction, and controlling the polymerization time to be 6 hours to obtain an N-methylaniline polymer with the average polymerization degree of 100;
(2) Washing the obtained N-methylaniline polymer precipitate with deionized water, drying at 80 ℃ for 12 hours, and then treating with ammonia water to obtain eigenstate N-methylaniline polymer;
(3) Preparation of an eigenstate N-methylaniline Polymer with a solubility of 0.4g/mL in acetone, adding 0.1g/mL epichlorohydrin and 0.05g/mL anhydrous AlCl 3 At a polymerization temperature of 40 ℃, through a coupling reaction for 5 hours, and then filtering to remove anhydrous AlCl 3 And (3) removing the solvent from the catalyst to obtain the poly-o-epoxy-N-methylaniline bonding resin with the ratio of the epoxy group to the aromatic ring of about 1:8.
Example 3
On the basis of example 1, the differences from example 1 are: in the step (3), the solubility of the eigenstate N-methylaniline polymer is 0.05g/mL, the epoxy chloropropane is 0.02g/mL, and the anhydrous AlCl is used 3 1g/mL, ratio of epoxy groups to aromatic rings of about 1:2.
example 4
On the basis of example 1, the differences from example 1 are: in step (3), the solubility of the eigenstate N-methylaniline polymer is 0.5g/mL, and the ratio of epoxy groups to aromatic rings is about 1:10.
example 5
Dissolving the poly-o-epoxy-N-methylaniline prepolymer in acetone, adding 5% of dodecylsulfonic acid relative to the mass of the poly-o-epoxy-N-methylaniline prepolymer, adding 5% of polybiphenyl amine curing agent with the polymerization degree of 5 relative to the mass of the poly-o-epoxy-N-methylaniline prepolymer, uniformly mixing, coating on the surface of a base material, and curing to form a film at 150 ℃ after the solvent volatilizes, thereby obtaining the poly-o-epoxy-N-methylaniline thermosetting conductive film with the volume resistivity of 10+/-2 omega cm.
Example 6
Dissolving the poly-o-epoxy-N-methylaniline prepolymer of the example 2 in acetone, adding dodecylsulfonic acid which is 3 percent of the mass of the poly-o-epoxy-N-methylaniline prepolymer, adding a polybiphenyl amine curing agent which is 10 percent of the mass of the poly-o-epoxy-N-methylaniline prepolymer and has a polymerization degree of 3, uniformly mixing, coating the mixture on the surface of a base material, curing the mixture to form a film at 140 ℃ after the solvent volatilizes, and obtaining the polymer with a volume resistivity of 10 2 A polyortho epoxy-N-methylaniline thermosetting conductive film of ± 10 Ω·cm.
Example 7
Dissolving the poly-o-epoxy-N-methylaniline prepolymer of the example 1 in acetone, adding dodecylsulfonic acid accounting for 2% of the mass of the poly-o-epoxy-N-methylaniline prepolymer, adding a polybiphenyl amine curing agent accounting for 15% of the mass of the poly-o-epoxy-N-methylaniline prepolymer and having a polymerization degree of 3, uniformly mixing, coating the mixture on the surface of a base material, curing the mixture to form a film at 140 ℃ after the solvent volatilizes, and obtaining the polymer with a volume resistivity of 10 3 A polyortho epoxy-N-methylaniline thermosetting conductive film of ± 50 Ω·cm.
Example 8
Dissolving the poly-o-epoxy-N-methylaniline prepolymer of example 1 in acetone, adding dodecylsulfonic acid in an amount of 1% by mass relative to the poly-o-epoxy-N-methylaniline prepolymer, and adding a polymer having a degree of polymerization of 20% by mass relative to the poly-o-epoxy-N-methylaniline prepolymer of3, uniformly mixing the polybiphenyl amine curing agent, coating the mixture on the surface of a matrix material, and curing the mixture to form a film at 140 ℃ after the solvent volatilizes to obtain the product with the volume resistivity of 10 4 A polyortho epoxy-N-methylaniline thermosetting conductive film of 500 Ω·cm.
Example 9
Mixing the poly-o-epoxy-N-methylaniline bonding resin of the example 3 with a polybiphenyl amine curing agent, a solvent and an auxiliary agent according to the mass ratio, heating to 70 ℃, stirring at constant temperature for 4 hours, discharging, cooling and detecting to prepare a pasty mixture; then defoaming and obtaining the poly-o-epoxy-N-methylaniline conductive organic carrier. Wherein, the solvent is isophorone, butyl carbitol acetate and butyl carbitol, and the auxiliary agent is organogel in patent CN 109473197. The specific ratios of the components are shown in Table 1.
Example 10
Mixing the poly-o-epoxy-N-methylaniline bonding resin of the example 4 with a polybiphenyl amine curing agent, a solvent and an auxiliary agent according to the mass ratio, heating to 85 ℃, stirring at constant temperature for 3 hours, discharging, cooling and detecting to prepare a pasty mixture; then defoaming and obtaining the poly-o-epoxy-N-methylaniline conductive organic carrier. Wherein, the solvent is isophorone, butyl carbitol acetate and butyl carbitol, and the auxiliary agent is organogel in patent CN 109473197. The specific ratios of the components are shown in Table 1.
Example 11
Mixing the poly-o-epoxy-N-methylaniline bonding resin of the example 1 with a polybiphenyl amine curing agent, a solvent and an auxiliary agent according to the mass ratio, heating to 100 ℃, stirring at constant temperature for 2 hours, discharging, cooling and detecting to prepare a pasty mixture; then defoaming and obtaining the poly-o-epoxy-N-methylaniline conductive organic carrier. Wherein, the solvent is isophorone, butyl carbitol acetate and butyl carbitol, and the auxiliary agent is organogel in patent CN 109473197. The specific ratios of the components are shown in Table 1.
Example 12
A low conductive phase loading high conductivity paste comprising the poly o-epoxy-N-methylaniline conductive organic vehicle of example 9 in mass percent: 30%, silver powder: 70%.
The silver powder of the embodiment has the particle diameter of 0.8-1.2 mu m and the tap density of 3.2-3.8g/ml.
The preparation method of the high-conductivity slurry with low conductive phase filling quantity comprises the following steps: the poly-o-epoxy-N-methylaniline conductive organic carrier of example 9 was mixed with silver powder according to the mass ratio and ground with a three-roll mill to obtain a highly conductive paste having a fineness of less than 5. Mu.m.
Example 13
A low conductive phase loading high conductivity paste comprising the poly o-epoxy-N-methylaniline conductive organic vehicle of example 9 in mass percent: 35%, silver powder: 65%.
The silver powder of the embodiment has the particle diameter of 0.8-1.2 mu m and the tap density of 3.2-3.8g/ml.
The preparation method of the high-conductivity slurry with low conductive phase filling quantity comprises the following steps: the poly-o-epoxy-N-methylaniline conductive organic carrier of example 9 was mixed with silver powder according to the mass ratio and ground with a three-roll mill to obtain a highly conductive paste having a fineness of less than 5. Mu.m.
Example 14
A low conductive phase loading high conductivity paste comprising the poly o-epoxy-N-methylaniline conductive organic vehicle of example 9 in mass percent: 40%, silver powder: 60%.
The silver powder of the embodiment has the particle diameter of 0.8-1.2 mu m and the tap density of 3.2-3.8g/ml.
The preparation method of the high-conductivity slurry with low conductive phase filling quantity comprises the following steps: the poly-o-epoxy-N-methylaniline conductive organic carrier of example 9 was mixed with silver powder according to the mass ratio and ground with a three-roll mill to obtain a highly conductive paste having a fineness of less than 5. Mu.m.
The results of the above-described slurry properties of examples 12 to 14 are shown in Table 2 below.
Table 1 formulations of the Poly-o-epoxy-N-methylaniline conductive organic Carriers of examples 9-11
TABLE 2 results of measurements of slurry properties for examples 12-14
| Numbering device | Volume resistivity (Ω cm) | Bending resistance/resistivity change rate | Weather resistance |
| Example 12 | 6.7*10 -6 | No abnormality/.ltoreq.10% | No discoloration and no peeling |
| Example 13 | 5.3*10 -6 | No abnormality/.ltoreq.10% | No discoloration and no peeling |
| Example 14 | 4.7*10 -6 | No abnormality/.ltoreq.10% | No discoloration and no peeling |
As can be seen from the data in table 2, the paste using the conductive organic vehicle has lower volume resistivity, high conductivity, and good printability while reducing the amount of silver powder used.
In table 2, the bending resistance test method is: the diameter of the cylindrical mandrel was 1mm, and the cracks and the rate of change of the electrical resistance were confirmed. The weather resistance testing method comprises the following steps: using a weathering test apparatus, the black panel temperature was 85+/-1℃and 85% +/-1% humidity for 1000 hours, and the presence or absence of discoloration and peeling was observed.
Claims (7)
1. The preparation method of the poly-o-epoxy-N-methylaniline conductive adhesive resin is characterized by comprising the following steps of:
(1) Placing N-methylaniline and persulfate in a hydrochloric acid aqueous solution for polymerization reaction under inert atmosphere to obtain a planned N-methylaniline polymer; washing, drying and then treating with ammonia water to obtain an eigenstate N-methylaniline polymer; the polymerization time is 3-10 h, and the polymerization temperature is 40-80 ℃;
(2) Dissolving eigenstate N-methylaniline polymer in a good solvent, adding halogenated epoxide, and coupling epoxy groups on aromatic rings of the N-methylaniline polymer under the action of a catalyst to obtain o-epoxy-N-methylaniline bonding resin solution; filtering to remove catalyst and solvent to obtain the final product;
the ratio of the epoxy group to the aromatic ring is 1:2-10.
2. The method for preparing the poly-o-epoxy-N-methylaniline conductive adhesive resin according to claim 1, wherein in the step (2), the catalyst is anhydrous AlCl of 0.05-0.1 g/mL 3 。
3. The method for preparing a poly (o-epoxy) -N-methylaniline conductive adhesive resin according to claim 1, wherein in the step (2), the concentration of the eigen state N-methylaniline polymer is 0.05-0.5 g/mL, and the concentration of the halogenated epoxide is 0.02-0.1 g/mL.
4. The conductive organic thermosetting material of poly-o-epoxy-N-methylaniline is characterized in that the conductive adhesive resin of poly-o-epoxy-N-methylaniline prepared by the method of claim 1 is mixed with a polybiphenyl amine curing agent and a doping agent and then crosslinked and cured.
5. The poly-o-epoxy-N-methylaniline conductive organic thermoset of claim 4 wherein the dopant is an organic macromolecular protonic acid.
6. The poly-o-epoxy-N-methylaniline conductive organic thermosetting material of claim 4 wherein the mass ratio of the poly-o-epoxy-N-methylaniline conductive adhesive resin, the polybiphenyl amine curing agent and the dopant is 100: 1-5: 5-20.
7. Use of the poly-o-epoxy-N-methylaniline conductive organic thermoset material of claim 4 in a conductive film.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210246607.2A CN114605959B (en) | 2022-03-09 | 2022-03-09 | Poly-o-epoxy-N-methylaniline conductive organic carrier and preparation method thereof |
| CN202210231552.8A CN114634791B (en) | 2022-03-09 | 2022-03-09 | Poly-o-epoxy-N-methylaniline conductive adhesive resin, preparation method thereof, conductive organic thermosetting material and application |
| CN202210246877.3A CN114613528A (en) | 2022-03-09 | 2022-03-09 | High-conductivity slurry with low conductive phase filling amount and preparation method thereof |
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| CN202210246877.3A Pending CN114613528A (en) | 2022-03-09 | 2022-03-09 | High-conductivity slurry with low conductive phase filling amount and preparation method thereof |
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| GB810348A (en) * | 1956-09-04 | 1959-03-11 | Gen Mills Inc | Condensates of epoxy fatty acids or esters with polyamines |
| US4195138A (en) * | 1978-06-26 | 1980-03-25 | The Dow Chemical Company | Chelate resins prepared from the cured reaction product of a polyalkylenepolyamine and epoxide |
| EP0279407A2 (en) * | 1987-02-16 | 1988-08-24 | Mitsui Mining Company, Limited | Electroconductive polymer film and method for producing the same |
| EP0345693A1 (en) * | 1988-06-07 | 1989-12-13 | Simon Fraser University | Soluble conducting polymers of poly-o-methoxyaniline |
| CN112980356A (en) * | 2021-02-25 | 2021-06-18 | 深圳市南科康达科技有限公司 | Conductive adhesive, flexible circuit, flexible printed circuit board and flexible electronic element |
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| AU2002314492A1 (en) * | 2001-06-20 | 2003-01-02 | M.S. Tech Ltd | Method and device for the detection of trace amounts of a substance,using a piezoelectric crystal element |
| US8080177B2 (en) * | 2008-08-19 | 2011-12-20 | The Boeing Company | Low RF loss static dissipative adhesive |
| TWI484017B (en) * | 2012-12-11 | 2015-05-11 | Nat Univ Tsing Hua | Method for preparing a conductive paste |
| KR102024975B1 (en) * | 2013-02-15 | 2019-09-24 | 신에츠 폴리머 가부시키가이샤 | Conductive composition, conductive compostion production method, anti-static resin composition and antistatic resin film |
| CN103980798A (en) * | 2014-05-14 | 2014-08-13 | 天津大学 | Doped-state polyaniline epoxy paint and preparation method thereof |
| CN105741904B (en) * | 2014-12-09 | 2018-07-03 | 湖南利德电子浆料股份有限公司 | A kind of touch screen silver paste for mixing polyaniline |
| CN109473197B (en) * | 2018-11-14 | 2020-11-03 | 轻工业部南京电光源材料科学研究所 | High-resolution conductive silver paste containing silver-supermolecule organogel and preparation method thereof |
-
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- 2022-03-09 CN CN202210231552.8A patent/CN114634791B/en active Active
- 2022-03-09 CN CN202210246877.3A patent/CN114613528A/en active Pending
- 2022-03-09 CN CN202210246607.2A patent/CN114605959B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB810348A (en) * | 1956-09-04 | 1959-03-11 | Gen Mills Inc | Condensates of epoxy fatty acids or esters with polyamines |
| US4195138A (en) * | 1978-06-26 | 1980-03-25 | The Dow Chemical Company | Chelate resins prepared from the cured reaction product of a polyalkylenepolyamine and epoxide |
| EP0279407A2 (en) * | 1987-02-16 | 1988-08-24 | Mitsui Mining Company, Limited | Electroconductive polymer film and method for producing the same |
| EP0345693A1 (en) * | 1988-06-07 | 1989-12-13 | Simon Fraser University | Soluble conducting polymers of poly-o-methoxyaniline |
| CN112980356A (en) * | 2021-02-25 | 2021-06-18 | 深圳市南科康达科技有限公司 | Conductive adhesive, flexible circuit, flexible printed circuit board and flexible electronic element |
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| Publication number | Publication date |
|---|---|
| CN114605959B (en) | 2023-10-24 |
| CN114605959A (en) | 2022-06-10 |
| CN114613528A (en) | 2022-06-10 |
| CN114634791A (en) | 2022-06-17 |
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