CN103642422B - A kind of prosthetic conductive resin and preparation method thereof - Google Patents
A kind of prosthetic conductive resin and preparation method thereof Download PDFInfo
- Publication number
- CN103642422B CN103642422B CN201310666741.9A CN201310666741A CN103642422B CN 103642422 B CN103642422 B CN 103642422B CN 201310666741 A CN201310666741 A CN 201310666741A CN 103642422 B CN103642422 B CN 103642422B
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- composition epoxy
- silica particles
- parts
- agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Conductive Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The present invention relates to a kind of prosthetic conductive resin, it calculates by its parts by weight, composed as follows: epoxy resin I100 part, flake silver powder 250 ~ 900 parts, solidifying agent I10 ~ 50 part, epoxide diluent I10 ~ 40 part, coupling agent 3 ~ 20 parts and composite mesopore particle 8 ~ 60 parts; Wherein, the solidification value of the composition epoxy resin I of solidifying agent I, epoxy resin I and epoxide diluent I composition is 60 ~ 80 DEG C; Composite mesopore particle has the mesoporous silicon oxide of nanometer silver for carrier with load, carrier outer surface has wall capsule material layer, mesoporous in containing composition epoxy resin II, solidification value >=150 DEG C of described composition epoxy resin II, epoxide diluent II in composition epoxy resin II is insoluble to or is insoluble in water, and boiling point is at >=150 DEG C.The invention still further relates to this can the preparation method of repairing type conductive resin.This conductive resin remediation efficiency is high, and the cracks after repairing can be avoided to produce stress concentration.
Description
Technical field
The present invention relates to conductive resin, be specifically related to a kind of prosthetic conductive resin and preparation method thereof.
Background technology
The development trend of conductive resin as conductive resin can be repaired, due to the Application Areas that it can improve the reliability of conduction and work-ing life, expansion conductive resin, be significant.
Conductive resin can be repaired at present mainly by adding microscapsule powder in conductive resin, the repair mechanisms of this conductive silver glue are: conductive resin is when cured subject to External Force Acting or produces after tiny crack in inside due to fatigue, fill up to solidify bonding crackle in crackle containing releases such as nanometer silver, latent curing agent, epoxy resin in microscapsule powder, reach the dual reparation of crackle and conductive network.Its main drawback is that repair rate is low.It is that liquid in microcapsule produces volumetric shrinkage after hardening that its reason mainly contains two: one, therefore there is stress concentration after crack forming mechanism; Two is microcapsule preparation difficulties, and epoxy resin encapsulation ratio is low.In addition, microcapsule poorly conductive, is unfavorable for the electrical property of conductive resin.
Summary of the invention
The technical issues that need to address of the present invention are to provide a kind of prosthetic conductive resin, and its remediation efficiency can up to 73 ~ 87%.
The technical issues that need to address of the present invention are also the preparation method providing above-mentioned prosthetic conductive resin.
The present invention needs first technical problem solved to be achieved through the following technical solutions: a kind of prosthetic conductive resin, and it calculates by its parts by weight, composed as follows:
Wherein, the solidification value of the composition epoxy resin I be made up of solidifying agent I, epoxy resin I and epoxide diluent I is 60 ~ 80 DEG C; Described composite mesopore particle has the mesoporous silicon oxide of nanometer silver for carrier with load, carrier outer surface has wall capsule material layer, mesoporous in containing composition epoxy resin II, composite mesopore particle calculates by its parts by weight, composed as follows:
Wherein, solidification value >=150 DEG C of described composition epoxy resin II, composition epoxy resin II calculates by its parts by weight, composed as follows:
Epoxy resin II100 part
Solidifying agent II10 ~ 20 part
Epoxide diluent II35 ~ 80 part;
And described epoxide diluent II is the epoxide diluent being insoluble to or being insoluble in water, and boiling point >=150 DEG C.
Here, described composite mesopore particle can be prepared by following steps:
S1. prepare load and have the mesoporous silica particles of nanometer silver: mesoporous silicon oxide is dispersed in the mixed solution of deionized water and ethanol, drip the silver nitrate solution of 0.01 ~ 2mol/L, control temperature 25 ~ 45 DEG C, after ultrasonic 3 ~ 30min, in oven for drying after dipping 12 ~ 48h, then in the nitrogen and atmosphere of hydrogen of 300 ~ 500 DEG C of temperature, decompose Silver Nitrate, obtain the mesoporous silica particles that load has nanometer silver;
S2. absorption is flooded: the load obtained by step S1 has the mesoporous silica particles of nanometer silver to flood in above-mentioned composition epoxy resin II, centrifugal after dipping 0.5 ~ 24h, use deionized water wash again, subsequently at 50 ~ 60 DEG C of more than vacuum-drying 3h, have the mesoporous silica particles of nanometer silver in obtaining containing composition epoxy resin II, load, wherein the weight ratio of composition epoxy resin II and mesoporous silicon oxide is 10 ~ 60:100;
S3. composite mesopore particle is prepared: the mesoporous silica particles dispersion containing composition epoxy resin II in being obtained by step S2 in deionized water, add the pre-polymerization liquid of wall capsule material, or the monomer of wall capsule material, emulsifying agent, dispersion agent and initiator, heating also stirring reaction 1 ~ 24h in 50 ~ 80 DEG C of water-baths, stir subsequently and be cooled to room temperature, centrifugal, with deionized water wash, subsequently at 50 ~ 60 DEG C of more than vacuum-drying 3h, obtain outside surface and have wall capsule material layer, interior containing composition epoxy resin II, load has the mesoporous silica particles of nanometer silver, the weight ratio of its mesospore capsule material and mesoporous silicon oxide is 5 ~ 30:100.
Here, described epoxide diluent II can be propylene oxide phenyl ether or epoxy propane butyl ether; Described solidifying agent II is 70# acid anhydrides, 647# acid anhydrides or trimellitic anhydride.The boiling point of propylene oxide phenyl ether and epoxy propane butyl ether is respectively 245 DEG C and 164 DEG C, and neither water-soluble, ensure that the drying phase under vacuum of composite mesopore particle when it is prepared is non-volatile, the washing stage is water insoluble and keep good mobility in conductive resin LOTES process.Described epoxide diluent II is preferably propylene oxide phenyl ether, because propylene oxide phenyl ether boiling point is higher.70# acid anhydrides is synthesized by divinyl and MALEIC ANHYDRIDE, and 647# acid anhydrides is synthesized by dicyclopentadiene and MALEIC ANHYDRIDE.They and trimellitic anhydride are all commercially available epoxy curing agents, their solidification values respectively needed for cured epoxy resin are 150 ~ 160 DEG C, and the solidification value of composition epoxy resin I is 60 ~ 80 DEG C, therefore in composite mesopore particulate production vacuum-drying and conductive resin solidification process in, mesoporous in composition epoxy resin II can not solidify, keep good mobility.
Described coupling agent can be organo silane coupling agent; Described solidifying agent I can be Dyhard RU 100 or modified amine curing agent; Described epoxide diluent I is epoxy propane butyl ether or polypropylene glycol diglycidyl ether.This solidifying agent I and epoxide diluent I with the use of, its solidification value is 60 ~ 80 DEG C, therefore the solidification of composition epoxy resin II in composite mesopore particle can not be caused, thus make mesoporous interior composition epoxy resin II keep good mobility, and then discharge when repairing, play repair.
Described wall capsule material can be the one in urethane, polyester, polyureas, polymeric amide, polystyrene, poly(urea formaldehyde), polyacrylic ester or its modifier.Wall capsule material layer can continue polyreaction by performed polymer and obtain, and also can be obtained by monomer direct polymerization.Preferably, described wall capsule material is polymethylmethacrylate.Here, the polymethyl methacrylate layers of meso-porous titanium dioxide silicon face can be formed by the letex polymerization of methacrylic acid monomer.
In technique scheme, preferably, the particle diameter of described mesoporous silica particles is 25 ~ 800 nanometers.Because mesoporous silicon oxide load has nanometer silver, nanometer silver improves the electroconductibility of mesoporous silicon oxide, even if therefore select the mesoporous silicon oxide of greater particle size also can not the electroconductibility of deteriorated conductive resin.Based on same reason, the addition of composite mesopore particle in conductive resin to a certain degree can also be improved and the electroconductibility of deteriorated conductive resin.
Preferably, the median size of described flake silver powder is 5 ~ 10 μm, tap density>=4.0g/cm
3, specific surface area>=0.5m
2/ g.
The present invention needs second technical problem solved to be achieved through the following technical solutions: a kind of preparation method of prosthetic conductive resin, and it comprises the following steps:
S1. prepare load and have the mesoporous silica particles of nanometer silver: mesoporous silicon oxide is dispersed in the mixed solution of deionized water and ethanol, drip the silver nitrate solution of 0.01 ~ 2mol/L, control temperature 25 ~ 45 DEG C, after ultrasonic 3 ~ 30min, in oven for drying after dipping 12 ~ 48h, then in the nitrogen and atmosphere of hydrogen of 300 ~ 500 DEG C of temperature, decompose Silver Nitrate, obtain the mesoporous silica particles that load has nanometer silver;
S2. absorption is flooded: the load obtained by step S1 has the mesoporous silica particles of nanometer silver to flood in composition epoxy resin II, composition epoxy resin II calculates by its parts by weight and comprises epoxy resin II100 part, solidifying agent II10 ~ 20 part, epoxide diluent II35 ~ 80 part, and described epoxide diluent II is the epoxide diluent being insoluble to or being insoluble in water, and boiling point >=150 DEG C; Centrifugal after dipping 0.5 ~ 24h, use deionized water wash again, subsequently at 50 ~ 60 DEG C of more than vacuum-drying 3h, have the mesoporous silica particles of nanometer silver in obtaining containing composition epoxy resin II, load, wherein the weight ratio of composition epoxy resin II and mesoporous silicon oxide is 10 ~ 60:100;
S3. composite mesopore particle is prepared: the mesoporous silica particles dispersion containing composition epoxy resin II in being obtained by step S2 in deionized water, add the pre-polymerization liquid of wall capsule material, or the monomer of wall capsule material, emulsifying agent, dispersion agent and initiator, heating also stirring reaction 1 ~ 24h in 50 ~ 80 DEG C of water-baths, stir subsequently and be cooled to room temperature, centrifugal, with deionized water wash, subsequently at 50 ~ 60 DEG C of more than vacuum-drying 3h, obtain outside surface and have wall capsule material layer, interior containing composition epoxy resin II, load has the mesoporous silica particles of nanometer silver, i.e. composite mesopore particle, the weight ratio of its mesospore capsule material and mesoporous silicon oxide is 5 ~ 30:100,
S4. conductive resin is modulated: weigh each component according to the parts by weight of epoxy resin I100 part, flake silver powder 250 ~ 900 parts, solidifying agent I10 ~ 50 part, epoxide diluent I10 ~ 40 part, coupling agent 3 ~ 20 parts, composite mesopore particle 8 ~ 60 parts, each component is at room temperature mixed, obtains prosthetic conductive resin.
In the above-mentioned methods, preferably, described epoxide diluent II is propylene oxide phenyl ether or epoxy propane butyl ether; Described solidifying agent II is 70# acid anhydrides, 647# acid anhydrides or trimellitic anhydride; Described coupling agent is organo silane coupling agent; Described solidifying agent I is Dyhard RU 100 or modified amine curing agent; Described epoxide diluent I is epoxy propane butyl ether or polypropylene glycol diglycidyl ether; Described wall capsule material is the one in urethane, polyester, polyureas, polymeric amide, polystyrene, poly(urea formaldehyde), polyacrylic ester or its modifier; The particle diameter of described mesoporous silica particles is 25 ~ 800 nanometers; The median size of described flake silver powder is 5 ~ 10 μm, tap density>=4.0g/cm
3, specific surface area>=0.5m
2/ g.
In the above-mentioned methods, preferably, in described step S3, the weight ratio of deionized water, emulsifying agent, dispersion agent, initiator and monomer is 600 ~ 1800:8 ~ 12:0.5 ~ 1.5:0.1 ~ 0.3:100, emulsifying agent is OP-10 and the Sodium dodecylbenzene sulfonate mixture by weight 1:1, dispersion agent is polyvinyl alcohol, and initiator is ammonium persulphate, and monomer is methyl methacrylate.The described wall capsule material obtained is polymethylmethacrylate.
Compared with prior art, advantage of the present invention and beneficial effect are:
Can be repaired after crackle appears in this conductive resin, long service life: after in use cracking, crackle is diffused into cyst material layer place, carries out local heating or heating and pressurizing to cracks, mesoporous interior composition epoxy resin II flowing can be made to discharge, repaired crackle;
Because this conductive resin is added with mesoporous silicon oxide, it is mesoporous has good adsorptivity, in the process of the coated cyst material layer of mesoporous silicon oxide, not easily discharged by the composition epoxy resin II of mesoporous absorption, ensure composition epoxy resin be stored in mesoporous in, thus repair time improve remediation efficiency;
Mesoporous silicon oxide has the volumetric shrinkage that hole can offset the generation of cracks liquid curing, avoids the cracks after being repaired and produces stress concentration, improve the mechanical strength after repairing;
Mesoporous silicon oxide load has nanometer silver, which raises the electroconductibility of mesoporous silicon oxide, and then can improve the electrical efficiency of conductive resin; Because load has nanometer silver, the addition of the mesoporous silicon oxide in conductive resin can also be increased, thus further increase the remediation efficiency of conductive resin.
Polymethylmethacrylate can be selected to be wall capsule material layer, in repair process, can to heat and make that wall capsule material is softening, melting, thus can make mesoporous in composition epoxy resin II discharge more fully;
Provide and a kind ofly prepare the new way can repairing conductive resin, this conductive resin technique is simple, parameter is easily controlled.
Embodiment
Below in conjunction with embodiment, the specific embodiment of the present invention is described further.Following examples only for technical scheme of the present invention is clearly described, and can not limit the scope of the invention with this.
Embodiment 1 ~ 6
The present invention is a kind of prosthetic conductive resin, and its composition comprises: epoxy resin I, flake silver powder, solidifying agent I, epoxide diluent I, coupling agent and composite mesopore particle, each parts by weight are as shown in table 1.Wherein, the solidification value of the composition epoxy resin I be made up of solidifying agent I, epoxy resin I and epoxide diluent I is 60 ~ 80 DEG C.Coupling agent can be organo silane coupling agent; Solidifying agent I can be Dyhard RU 100 or modified amine curing agent; Epoxide diluent I can be epoxy propane butyl ether or polypropylene glycol diglycidyl ether.Certainly, solidify as long as the selection of solidifying agent I, epoxide diluent I meets the composition I realizing epoxy resin 60 ~ 80 DEG C of temperature ranges.
Table 1: each feed composition of prosthetic conductive resin containing scale
Wherein, composite mesopore particle has the mesoporous silicon oxide of nanometer silver for carrier with load, carrier outer surface has wall capsule material layer, mesoporous in containing composition epoxy resin II, the particle diameter of mesoporous silica particles is 25 ~ 800 nanometers.Described wall capsule material can be the one in urethane, polyester, polyureas, polymeric amide, polystyrene, poly(urea formaldehyde), polyacrylic ester or its modifier, as polymethylmethacrylate.In embodiment 1 ~ 6, the composition of composite mesopore particle is in table 2.
Table 2: composite mesopore grain fraction containing scale
Table 2 epoxy resin composition I I comprises by composition: epoxy resin II, solidifying agent II and epoxide diluent II, and the parts by weight of embodiment 1 ~ 6 epoxy resin composition I I are as shown in table 3.Here, solidification value >=150 DEG C of described composition epoxy resin II.For this reason, solidifying agent II can select 70# acid anhydrides, 647# acid anhydrides or trimellitic anhydride, and their solidification values needed for cured epoxy resin II are 150 ~ 160 DEG C.Here epoxide diluent II select be insoluble to or be insoluble in water and boiling point at the epoxide diluent of >=150 DEG C, such as propylene oxide phenyl ether or epoxy propane butyl ether.
Table 3: composition epoxy resin II component containing scale
The preparation method of above-mentioned prosthetic conductive resin comprises the following steps:
S1. prepare load and have the mesoporous silica particles of nanometer silver: mesoporous silicon oxide is dispersed in the mixed solution of deionized water and ethanol, drip the silver nitrate solution of 0.01 ~ 2mol/L, control temperature 25 ~ 45 DEG C, after ultrasonic 3 ~ 30min, in oven for drying after dipping 12 ~ 48h, then in the nitrogen and atmosphere of hydrogen of 300 ~ 500 DEG C of temperature, decompose Silver Nitrate, obtain the mesoporous silica particles that load has 1 ~ 20% (weight percentage) nanometer silver; The charge capacity of concrete silver, namely relative to nanometer silver relative to the content of mesoporous silicon oxide in table 2.
S2. absorption is flooded: flood in the composition epoxy resin II that the load obtained by step S1 has the mesoporous silica particles of nanometer silver described in table 3, centrifugal after dipping 0.5 ~ 24h, use deionized water wash mesoporous silica particles again, subsequently at 50 ~ 60 DEG C of more than vacuum-drying 3h, the mesoporous silica particles containing composition epoxy resin II in obtaining; Wherein, composition epoxy resin II relative to the addition of mesoporous silicon oxide in table 2.
S3. composite mesopore particle is prepared: the mesoporous silica particles dispersion containing composition epoxy resin II in being obtained by step S2 in deionized water, add the pre-polymerization liquid of wall capsule material, or the monomer of wall capsule material, emulsifying agent, dispersion agent and initiator, heating also stirring reaction 1 ~ 24h in 50 ~ 80 DEG C of water-baths, stir subsequently and be cooled to room temperature, centrifugal, with deionized water wash, subsequently at 50 ~ 60 DEG C of more than vacuum-drying 3h, obtain outside surface and have wall capsule material layer, interior containing composition epoxy resin II, load has the mesoporous silica particles of nanometer silver, wherein, wall capsule material relative to the addition of mesoporous silicon oxide in table 2.
S4. conductive resin is modulated: the composite mesopore particle, epoxy resin I, flake silver powder, solidifying agent, epoxide diluent I and the coupling agent that obtain according to the parts by weight weighing step S3 described in table 1, at room temperature mix it, obtain prosthetic conductive resin.
In embodiment 1, what add in step S3 is by trimeric cyanamide, the formaldehyde of 37% and the pre-polymerization liquid of the trimeric cyanamide that obtains of deionized water 1:1.5:1.6 ratio and copolyoxymethylenes.In embodiment 2, what add in step S3 is the pre-polymerization liquid of poly(urea formaldehyde) resin that obtains of formaldehyde solution 1:1.5 ratio by urea and 37%.In embodiment 3 ~ 6, what add in step S3 is methacrylic acid monomer, polyvinyl alcohol dispersion agent, ammonium persulfate initiator, compound emulsifying agent (OP-10 and Sodium dodecylbenzene sulfonate are by weight the mixture of 1:1), and the weight ratio of deionized water, emulsifying agent, dispersion agent, initiator and monomer is 600 ~ 1800:8 ~ 12:0.5 ~ 1.5:0.1 ~ 0.3:100.Wherein, the selection of the concrete technology parameter in S1 ~ S3 step is in table 4.
Table 4: concrete technology parameter list
Prosthetic conductive resin embodiment 1 ~ 6 obtained solidifies 6 hours at 60 ~ 80 DEG C, obtains solidifying rear product.Tested respectively by four-point probe method and calculate conductive resin original volume resistivity, adopting ASTMD5045-99 standard testing initial breaking strength.By the batten alignment after test, at 150 DEG C, solidify 2h.Then continuation four-point probe method calculates the volume specific resistance after conductive resin reparation, and breaking tenacity after adopting ASTMD5045-99 standard test reparation.Volume specific resistance after reparation and the ratio of initial electrical resistivity, and after repairing, the ratio of breaking tenacity and initial breaking strength is all listed in table 5.
Table 5: performance table
As can be seen from Table 5, after prosthetic conductive resin of the present invention reparation, breaking tenacity can reach 73 ~ 87% of initial breaking strength, and repair after volume specific resistance also suitable with initial volume specific resistance.
Comparative example 1
Prepare a kind of prosthetic conductive resin in comparative example, it is the same with the composition of the conductive resin in embodiment 4, and except composite mesopore particle is without loading nano silvery process, according to S2 ~ S4 step preparation in embodiment 4, concrete preparation method is:
(1) dipping absorption: by centrifugal after dipping in the composition epoxy resin II of the mesoporous silica particles without any process described in table 3, then in obtaining with deionized water wash, vacuum-drying, contain the mesoporous silica particles of composition epoxy resin II; Wherein, processing parameter is identical with corresponding parameter value in step S2 in embodiment 4.
(2) composite mesopore particle is prepared: the interior mesoporous silica particles dispersion containing composition epoxy resin II step (1) obtained in deionized water, add methyl methacrylate monomer, deionized water, emulsifying agent, dispersion agent, initiator, heating also stirring reaction in a water bath, stir subsequently and be cooled to room temperature, centrifugal, with deionized water wash, vacuum-drying subsequently, obtain outside surface and have wall capsule material layer, the interior mesoporous silica particles containing composition epoxy resin II, i.e. composite mesopore particle; Concrete technology parameter is identical with corresponding parameter value in step S3 in embodiment 4.
Conductive resin is prepared according to S4 step in embodiment 4 by after the composite mesopore particle obtained as stated above, and solidify in the condition identical with embodiment 4, the original volume resistivity of conductive resin after the solidification that test and comparison example 1 and embodiment 4 obtain, finds that the original volume resistivity of conductive resin in comparative example 1 is 0.89 ~ 0.94 times of the original volume resistivity of conductive resin in embodiment 4.Visible, after mesoporous silicon oxide area load has nanometer silver, be conducive to the electric conductivity improving conductive resin.
Above-mentioned each embodiment is further illustrating of making foregoing of the present invention, but the scope that should not be construed as the above-mentioned theme of the present invention is only limitted to above-described embodiment.It should be pointed out that for those skilled in the art, under the prerequisite not departing from the technology of the present invention principle, can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (9)
1. a prosthetic conductive resin, is characterized in that, calculates by its parts by weight, composed as follows:
Epoxy resin I100 part
Flake silver powder 250 ~ 900 parts
Solidifying agent I10 ~ 50 part
Epoxide diluent I10 ~ 40 part
Coupling agent 3 ~ 20 parts
Composite mesopore particle 8 ~ 60 parts;
Wherein, the solidification value of the composition epoxy resin I be made up of solidifying agent I, epoxy resin I and epoxide diluent I is 60 ~ 80 DEG C; Described composite mesopore particle has the mesoporous silicon oxide of nanometer silver for carrier with load, carrier outer surface has wall capsule material layer, mesoporous in containing composition epoxy resin II, composite mesopore particle calculates by its parts by weight, composed as follows:
Mesoporous silica particles 100 parts
Nanometer silver 1 ~ 20 part
Composition epoxy resin II10 ~ 60 part
Wall capsule material 5 ~ 30 parts;
Wherein, solidification value >=150 DEG C of described composition epoxy resin II, composition epoxy resin II calculates by its parts by weight, composed as follows:
Epoxy resin II100 part
Solidifying agent II10 ~ 20 part
Epoxide diluent II35 ~ 80 part;
And described epoxide diluent II is the epoxide diluent being insoluble to or being insoluble in water, and boiling point >=150 DEG C; Described composite mesopore particle is prepared by following steps:
S1. prepare load and have the mesoporous silica particles of nanometer silver: mesoporous silicon oxide is dispersed in the mixed solution of deionized water and ethanol, drip the silver nitrate solution of 0.01 ~ 2mol/L, control temperature 25 ~ 45 DEG C, after ultrasonic 3 ~ 30min, in oven for drying after dipping 12 ~ 48h, then in the nitrogen and atmosphere of hydrogen of 300 ~ 500 DEG C of temperature, decompose Silver Nitrate, obtain the mesoporous silica particles that load has nanometer silver;
S2. absorption is flooded: the load obtained by step S1 has the mesoporous silica particles of nanometer silver to flood in described composition epoxy resin II, centrifugal after dipping 0.5 ~ 24h, use deionized water wash again, subsequently at 50 ~ 60 DEG C of more than vacuum-drying 3h, have the mesoporous silica particles of nanometer silver in obtaining containing composition epoxy resin II, load, wherein the weight ratio of composition epoxy resin II and mesoporous silicon oxide is 10 ~ 60:100;
S3. composite mesopore particle is prepared: the mesoporous silica particles dispersion containing composition epoxy resin II in being obtained by step S2 in deionized water, add the pre-polymerization liquid of wall capsule material, or the monomer of wall capsule material, emulsifying agent, dispersion agent and initiator, heating also stirring reaction 1 ~ 24h in 50 ~ 80 DEG C of water-baths, stir subsequently and be cooled to room temperature, centrifugal, with deionized water wash, subsequently at 50 ~ 60 DEG C of more than vacuum-drying 3h, obtain outside surface and have wall capsule material layer, interior containing composition epoxy resin II, load has the mesoporous silica particles of nanometer silver, i.e. composite mesopore particle, the weight ratio of its mesospore capsule material and mesoporous silicon oxide is 5 ~ 30:100.
2. prosthetic conductive resin according to claim 1, is characterized in that: described epoxide diluent II is propylene oxide phenyl ether or epoxy propane butyl ether; Described solidifying agent II is 70# acid anhydrides, 647# acid anhydrides or trimellitic anhydride.
3. prosthetic conductive resin according to claim 1, is characterized in that: described coupling agent is organo silane coupling agent; Described solidifying agent I is Dyhard RU 100 or modified amine curing agent; Described epoxide diluent I is epoxy propane butyl ether or polypropylene glycol diglycidyl ether; Described wall capsule material is the one in urethane, polyester, polyureas, polymeric amide, polystyrene, poly(urea formaldehyde), polyacrylic ester or its modifier.
4. prosthetic conductive resin according to claim 3, is characterized in that: described wall capsule material is polymethylmethacrylate.
5. the prosthetic conductive resin according to Claims 1-4 any one, is characterized in that: the particle diameter of described mesoporous silica particles is 25 ~ 800 nanometers.
6. prosthetic conductive resin according to claim 5, is characterized in that: the median size of described flake silver powder is 5 ~ 10 μm, tap density>=4.0g/cm
3, specific surface area>=0.5m
2/ g.
7. a preparation method for prosthetic conductive resin, is characterized in that, comprises the following steps:
S1. prepare load and have the mesoporous silica particles of nanometer silver: mesoporous silicon oxide is dispersed in the mixed solution of deionized water and ethanol, drip the silver nitrate solution of 0.01 ~ 2mol/L, control temperature 25 ~ 45 DEG C, after ultrasonic 3 ~ 30min, in oven for drying after dipping 12 ~ 48h, then in the nitrogen and atmosphere of hydrogen of 300 ~ 500 DEG C of temperature, decompose Silver Nitrate, obtain the mesoporous silica particles that load has nanometer silver;
S2. absorption is flooded: the load obtained by step S1 has the mesoporous silica particles of nanometer silver to flood in composition epoxy resin II, composition epoxy resin II calculates by its parts by weight and comprises epoxy resin II100 part, solidifying agent II10 ~ 20 part, epoxide diluent II35 ~ 80 part, and described epoxide diluent II is the epoxide diluent being insoluble to or being insoluble in water, and boiling point >=150 DEG C; Centrifugal after dipping 0.5 ~ 24h, use deionized water wash again, subsequently at 50 ~ 60 DEG C of more than vacuum-drying 3h, have the mesoporous silica particles of nanometer silver in obtaining containing composition epoxy resin II, load, wherein the weight ratio of composition epoxy resin II and mesoporous silicon oxide is 10 ~ 60:100;
S3. composite mesopore particle is prepared: the mesoporous silica particles dispersion containing composition epoxy resin II in being obtained by step S2 in deionized water, add the pre-polymerization liquid of wall capsule material, or the monomer of wall capsule material, emulsifying agent, dispersion agent and initiator, heating also stirring reaction 1 ~ 24h in 50 ~ 80 DEG C of water-baths, stir subsequently and be cooled to room temperature, centrifugal, with deionized water wash, subsequently at 50 ~ 60 DEG C of more than vacuum-drying 3h, obtain outside surface and have wall capsule material layer, interior containing composition epoxy resin II, load has the mesoporous silica particles of nanometer silver, i.e. composite mesopore particle, the weight ratio of its mesospore capsule material and mesoporous silicon oxide is 5 ~ 30:100,
S4. conductive resin is modulated: weigh each component according to the parts by weight of epoxy resin I100 part, flake silver powder 250 ~ 900 parts, solidifying agent I10 ~ 50 part, epoxide diluent I10 ~ 40 part, coupling agent 3 ~ 20 parts, composite mesopore particle 8 ~ 60 parts, each component is at room temperature mixed, obtains prosthetic conductive resin.
8. the preparation method of prosthetic conductive resin according to claim 7, is characterized in that: described epoxide diluent II is propylene oxide phenyl ether or epoxy propane butyl ether; Described solidifying agent II is 70# acid anhydrides, 647# acid anhydrides or trimellitic anhydride; Described coupling agent is organo silane coupling agent; Described solidifying agent I is Dyhard RU 100 or modified amine curing agent; Described epoxide diluent I is epoxy propane butyl ether or polypropylene glycol diglycidyl ether; Described wall capsule material is the one in urethane, polyester, polyureas, polymeric amide, polystyrene, poly(urea formaldehyde), polyacrylic ester or its modifier; The particle diameter of described mesoporous silica particles is 25 ~ 800 nanometers; The median size of described flake silver powder is 5 ~ 10 μm, tap density>=4.0g/cm
3, specific surface area>=0.5m
2/ g.
9. the preparation method of prosthetic conductive resin according to claim 7, it is characterized in that: in described step S3, the weight ratio of deionized water, emulsifying agent, dispersion agent, initiator and monomer is 600 ~ 1800:8 ~ 12:0.5 ~ 1.5:0.1 ~ 0.3:100, emulsifying agent is OP-10 and the Sodium dodecylbenzene sulfonate mixture by weight 1:1, dispersion agent is polyvinyl alcohol, initiator is ammonium persulphate, and monomer is methyl methacrylate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310666741.9A CN103642422B (en) | 2013-12-10 | 2013-12-10 | A kind of prosthetic conductive resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310666741.9A CN103642422B (en) | 2013-12-10 | 2013-12-10 | A kind of prosthetic conductive resin and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103642422A CN103642422A (en) | 2014-03-19 |
| CN103642422B true CN103642422B (en) | 2016-01-20 |
Family
ID=50247713
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310666741.9A Active CN103642422B (en) | 2013-12-10 | 2013-12-10 | A kind of prosthetic conductive resin and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103642422B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104460063B (en) * | 2014-12-15 | 2017-05-03 | 京东方科技集团股份有限公司 | display module and manufacturing method thereof |
| CN104845548B (en) * | 2015-04-24 | 2017-05-03 | 京东方科技集团股份有限公司 | Conductive adhesive composition and preparation method thereof, seal agent and display panel |
| CN105182623A (en) * | 2015-09-09 | 2015-12-23 | 京东方科技集团股份有限公司 | Frame sealing glue, method for preparing frame sealing glue and display device |
| CN106971791A (en) * | 2017-03-31 | 2017-07-21 | 合肥悦兰信息技术有限公司 | The method that Conductive inorganic thing is prepared by additive of nano silicon |
| CN112574533A (en) * | 2020-12-22 | 2021-03-30 | 江苏中海华核环保有限公司 | High-temperature-resistant borosilicate resin neutron shielding material and preparation process thereof |
| CN113582693B (en) * | 2021-08-04 | 2022-07-12 | 湖南省美程陶瓷科技有限公司 | Ceramic atomized sheet material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508823A (en) * | 2009-03-12 | 2009-08-19 | 中山大学 | Quick self-repair type polymer composite material at room temperature |
| CN102086364A (en) * | 2010-12-16 | 2011-06-08 | 广东风华高新科技股份有限公司 | Conductive silver paste for microelectronic packaging and preparation method thereof |
| CN103194164A (en) * | 2013-04-26 | 2013-07-10 | 中国电子科技集团公司第三十八研究所 | High temperature self-repairing conductive silver adhesive and preparation method thereof |
-
2013
- 2013-12-10 CN CN201310666741.9A patent/CN103642422B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508823A (en) * | 2009-03-12 | 2009-08-19 | 中山大学 | Quick self-repair type polymer composite material at room temperature |
| CN102086364A (en) * | 2010-12-16 | 2011-06-08 | 广东风华高新科技股份有限公司 | Conductive silver paste for microelectronic packaging and preparation method thereof |
| CN103194164A (en) * | 2013-04-26 | 2013-07-10 | 中国电子科技集团公司第三十八研究所 | High temperature self-repairing conductive silver adhesive and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103642422A (en) | 2014-03-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103642422B (en) | A kind of prosthetic conductive resin and preparation method thereof | |
| US8658120B2 (en) | Non-thermofusible phenol resin powder, method for producing the same, thermosetting resin composition, sealing material for semiconductor, and adhesive for semiconductor | |
| CN103194164B (en) | High temperature self-repairing conductive silver adhesive and preparation method thereof | |
| CN104774573B (en) | A kind of high-performance conductive silver paste of containing graphene and preparation method thereof | |
| CN104830031B (en) | A kind of epoxy resin composite material and preparation method thereof having both heat conduction and antistatic property | |
| CN112538307B (en) | Polypyrrole corrosion-resistant anticorrosive paint, preparation method and use method thereof, and composite material | |
| CN104910625A (en) | Preparation method of heat conduction silicone rubber interface material containing graphene | |
| CN101914264B (en) | Electric-insulation heat-conduction epoxy resin composite material and preparation method thereof | |
| CN105176081A (en) | Preparation method for flame-retardant heat-resistant antenna radome base material | |
| CN102719211A (en) | Silver nanowire-filled self-repairing conducting resin and preparation method thereof | |
| Agrawal et al. | An experimental investigation of epoxy‐based hybrid composites with hexagonal boron nitride and short sisal fiber as reinforcement for high performance microelectronic applications | |
| Pittala et al. | Self‐healing performance assessment of epoxy resin and amine hardener encapsulated polymethyl methacrylate microcapsules reinforced epoxy composite | |
| CN101597436B (en) | Silicon tiny powder surface treating and modifying method, epoxy resin combination and preparation method thereof | |
| CN103740309B (en) | Repairable conductive adhesive and preparation method thereof | |
| CN103642423B (en) | A kind of high repair rate conductive resin and preparation method thereof | |
| CN103666317B (en) | A kind of two microcapsule-component conductive adhesive | |
| CN102421814A (en) | (meth)acrylate polymer, resin composition, and molded article | |
| CN103666318B (en) | A kind of Self-repair conductive adhesive and preparation method thereof | |
| CN103725238B (en) | Reparable conducting resin and preparation method thereof | |
| CN103666316A (en) | High-temperature-repairable conductive adhesive and preparation method thereof | |
| Li et al. | Incorporating paraffin@ SiO 2 nanocapsules with abundant surface hydroxyl groups into polydimethylsiloxane to develop composites with enhanced interfacial heat conductance for chip heat dissipation | |
| Pu et al. | Carbon fiber in situ grown ZIF‐67 nanocrystals with excellent electrochemical and interfacial property | |
| CN103725237B (en) | Conductive adhesive and preparation method thereof | |
| Liao et al. | Regulating surface energy and establishing covalent bonds to enhance interface interaction between m‐BN and polyphenylene oxide for 5G applications | |
| Song et al. | Rationally Tunable Phase Change Material Thermal Properties Enabled by Three‐Dimensionally Printed Structural Materials and Carbon‐Based Functional Additives |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |