CN108250332B - Preparation method and application of organic metal polymer - Google Patents
Preparation method and application of organic metal polymer Download PDFInfo
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- CN108250332B CN108250332B CN201810086814.XA CN201810086814A CN108250332B CN 108250332 B CN108250332 B CN 108250332B CN 201810086814 A CN201810086814 A CN 201810086814A CN 108250332 B CN108250332 B CN 108250332B
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 25
- 239000002184 metal Substances 0.000 title claims abstract description 25
- 229920000642 polymer Polymers 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000003822 epoxy resin Substances 0.000 claims abstract description 41
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 41
- 239000000853 adhesive Substances 0.000 claims abstract description 40
- 230000001070 adhesive effect Effects 0.000 claims abstract description 40
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000012745 toughening agent Substances 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 72
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 25
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 239000004793 Polystyrene Substances 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 229920001795 coordination polymer Polymers 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- 229920002223 polystyrene Polymers 0.000 claims description 15
- YOCIJWAHRAJQFT-UHFFFAOYSA-N 2-bromo-2-methylpropanoyl bromide Chemical compound CC(C)(Br)C(Br)=O YOCIJWAHRAJQFT-UHFFFAOYSA-N 0.000 claims description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 10
- 239000012295 chemical reaction liquid Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 150000004698 iron complex Chemical class 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- 230000001376 precipitating effect Effects 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 5
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 4
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 4
- 150000008064 anhydrides Chemical group 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011231 conductive filler Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004154 testing of material 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
-
- 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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- 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
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Epoxy Resins (AREA)
Abstract
The invention belongs to the technical field of epoxy resin adhesives, and particularly relates to a preparation method of an organic metal polymer and an application thereof, wherein the preparation method of the organic metal polymer is simple to operate, the prepared organic metal polymer is high in yield and purity, and the epoxy resin thermosetting conductive adhesive prepared by using the organic metal polymer comprises the following raw materials: epoxy resin, toughening agent, curing agent and organic metal polymer, and the adhesive has the advantages of easy dispersion, good storage stability and good conductivity.
Description
Technical Field
The invention belongs to the technical field of epoxy resin adhesives, and particularly relates to a preparation method and application of an organic metal polymer.
Background
With the rapid development of the semiconductor integrated circuit packaging industry, the semiconductor integrated circuit packaging industry has occupied the dominant position of the domestic integrated circuit industry, and the problem of how to select electronic packaging materials is more important. The data show that most integrated circuits and various electronic devices require a wide variety of bonding materials. The conductive adhesive is a special adhesive with certain conductive performance, is mainly obtained by adding a curing agent, a conductive filler, other additives and the like into an organic polymer matrix for curing, and has the conductive performance similar to that of metal.
The conductive paste can be classified into metal-based conductive pastes and carbon-based conductive pastes according to the kind of conductive particles in the conductive paste. The metal conductive adhesive has good conductivity, but has the defects of high cost, easy layering of conductive metal and resin, short working life and the like; the carbon-based conductive adhesive has low cost and absolute price advantage, but has the defects of difficult dispersion of conductive filler, low conductivity and the like.
Disclosure of Invention
In order to overcome the disadvantages and shortcomings of the prior art, the present invention aims to provide a method for preparing an organometallic polymer, which is simple to operate, and the prepared organometallic polymer has high yield and pure purity; the invention also aims to provide the epoxy resin thermosetting conductive adhesive and the preparation method thereof, the adhesive has good dispersibility, stable storage and good conductivity, and the preparation method is simple and easy to operate.
The purpose of the invention is realized by the following technical scheme: a method for preparing an organometallic polymer, comprising the steps of:
a. mixing 1-5mmol of polystyrene and 50-250mL of toluene, vacuumizing, stirring at 90 ℃ for 30-60min, adding 1-10mL of triethylamine and 1-25mL of 2-bromo-2-methylpropanoyl bromide after the solution is clarified, continuing stirring for 30-60min, continuing reacting for 10-24 h after the solution becomes black, cooling to room temperature to obtain a reaction solution C, adding methanol into the reaction solution C, precipitating, filtering, washing and drying to obtain polystyrene with a terminal group containing bromine;
b. mixing anhydrous methanol solution dissolved with 4-dimethylamino pyridine with Na2NH4[Fe(CN)5dmap]Mixing, evacuating, and adding N2Heating to 40 ℃ under protection, reacting for 10-24 hours, cooling to room temperature to obtain reaction liquid D, performing rotary evaporation on the reaction liquid D, precipitating with a mixed solvent of dichloromethane and n-hexane, filtering, and drying to obtain a blue iron complex, wherein 4-dimethylaminopyridine and Na are used as the raw materials2NH4[Fe(CN)5dmap]Equal mass;
c. dissolving the polystyrene with the end group containing bromine in the step a and the blue iron complex in the step b by using a mixed solution of methanol and toluene, stirring and refluxing for 72h at 80 ℃, filtering after the reaction is finished to obtain a light blue solid, washing by using methanol until the filtrate is colorless, and drying in vacuum for 24h at 40 ℃ to obtain the organometallic polymer with the end group containing iron.
The preparation method of the organic metal polymer is simple, easy to operate and high in yield.
Wherein, the 2-bromo-2-methylpropanoyl bromide is added dropwise when being added in the step a.
In the invention, the 2-bromo-2-methylpropanoyl bromide is added dropwise in the step a, so that the reaction is more sufficient and the team phenomenon does not occur.
Wherein the volume ratio of the methanol to the toluene in the step c is 1: 1-3.
The application of organic metal polymer in preparing thermosetting epoxy resin adhesive is disclosed.
An epoxy resin thermosetting conductive adhesive comprises the following raw materials in parts by weight:
in the invention, the organic metal polymer is added into the thermosetting conductive adhesive, so that the metal has good dispersibility in the adhesive, and the conductivity of the adhesive is effectively improved.
The epoxy resin thermosetting conductive adhesive comprises the following raw materials in parts by weight:
wherein, the epoxy resin is one or two of E44 or bisphenol F epoxy resin.
E44 or bisphenol F epoxy resin has low softening point, good processing formability, better adhesive bonding property and high cost performance.
Wherein the curing agent is an anhydride curing agent.
Wherein the curing agent is one or two of trimellitic anhydride or phthalic anhydride.
A preparation method of an epoxy resin thermosetting conductive adhesive comprises the following steps:
(1) mixing the epoxy resin, the toughening agent, the organic metal polymer and the curing agent in parts by weight, heating to 60-70 ℃ at the speed of 20-25 ℃/min, and stirring for 60-120min to obtain a reactant A;
(2) and dispersing the reactant A by ultrasonic waves for 60-120min, and defoaming for 20-60min in a vacuum environment to obtain the epoxy resin thermosetting conductive adhesive.
The method for preparing the epoxy resin thermosetting conductive adhesive is simple and easy to operate, and the prepared adhesive has high yield.
The invention has the beneficial effects that: the preparation method of the organic metal polymer has the advantages of simple operation, high yield and purity of the prepared organic metal polymer, easy dispersion of the prepared epoxy resin thermosetting conductive adhesive, good storage stability and good conductivity.
Detailed Description
The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.
In the case of the example 1, the following examples are given,
a method of preparing an organometallic polymer comprising the steps of:
a. mixing 1mmol of polystyrene and 50mL of toluene, vacuumizing, stirring for 30min at 90 ℃, adding 1mL of triethylamine and 1mL of 2-bromo-2-methylpropanoyl bromide after the solution is clarified, continuing to stir for 30min, continuing to react for 10 h after the solution becomes black, cooling to room temperature to obtain a reaction solution C, adding methanol into the reaction solution C, and precipitating, filtering, washing and drying to obtain polystyrene with a terminal group containing bromine;
b. mixing anhydrous methanol solution dissolved with 4-dimethylamino pyridine with Na2NH4[Fe(CN)5dmap]Mixing, evacuating, and adding N2Heating to 40 ℃ under protection, reacting for 10 hours, cooling to room temperature to obtain reaction liquid D, performing rotary evaporation on the reaction liquid D, precipitating with a mixed solvent of dichloromethane and n-hexane, filtering, and drying to obtain a blue iron complex, wherein 4-dimethylaminopyridine and Na are2NH4[Fe(CN)5dmap]Equal mass;
c. dissolving the polystyrene with the end group containing bromine in the step a and the blue iron complex in the step b by using a mixed solution of methanol and toluene, stirring and refluxing for 72h at 80 ℃, filtering after the reaction is finished to obtain a light blue solid, washing by using methanol until the filtrate is colorless, and drying in vacuum for 24h at 40 ℃ to obtain the organometallic polymer with the end group containing iron.
Further, the 2-bromo-2-methylpropanoyl bromide is added dropwise in the step a.
Further, the volume ratio of the methanol to the toluene in the step c is 1: 1.
The application of organic metal polymer in preparing thermosetting epoxy resin adhesive is disclosed.
An epoxy resin thermosetting conductive adhesive comprises the following raw materials in parts by weight:
further, the weight ratio of the epoxy resin E44 to the bisphenol F epoxy resin is 1: 1.
Further, the curing agent is trimellitic anhydride.
A preparation method of an epoxy resin thermosetting conductive adhesive comprises the following steps:
(1) mixing the epoxy resin, the toughening agent, the organic metal polymer and the curing agent in parts by weight, heating to 60 ℃ at the speed of 20 ℃/min, and stirring for 60min to obtain a reactant A;
(2) and dispersing the reactant A by ultrasonic waves for 60min, and defoaming for 20min in a vacuum environment to obtain the epoxy resin thermosetting conductive adhesive.
In the case of the example 2, the following examples are given,
example 2 differs from example 1 in that: the preparation method of the organic metal polymer comprises the following steps:
a. mixing 5mmol of polystyrene and 250mL of toluene, vacuumizing, stirring for 60min at 90 ℃, adding 10mL of triethylamine and 25mL of 2-bromo-2-methylpropanoyl bromide after the solution is clarified, continuing to stir for 60min, continuing to react for 24h after the solution becomes black, cooling to room temperature to obtain a reaction solution C, adding methanol into the reaction solution C, and precipitating, filtering, washing and drying to obtain polystyrene with a terminal group containing bromine;
b. mixing anhydrous methanol solution dissolved with 4-dimethylamino pyridine with Na2NH4[Fe(CN)5dmap]Mixing, evacuating, and adding N2Heating to 40 ℃ under protection, reacting for 24 hours, cooling to room temperature to obtain reaction liquid D, performing rotary evaporation on the reaction liquid D, precipitating with a mixed solvent of dichloromethane and n-hexane, filtering, and drying to obtain a blue iron complex, wherein 4-dimethylaminopyridine and Na are2NH4[Fe(CN)5dmap]Equal mass;
c. dissolving the polystyrene with the end group containing bromine in the step a and the blue iron complex in the step b by using a mixed solution of methanol and toluene, stirring and refluxing for 72h at 80 ℃, filtering after the reaction is finished to obtain a light blue solid, washing by using methanol until the filtrate is colorless, and drying in vacuum for 24h at 40 ℃ to obtain the organometallic polymer with the end group containing iron.
In the case of the example 3, the following examples are given,
example 3 differs from example 1 in that: a method of preparing an organometallic polymer comprising the steps of:
a. mixing 3mmol of polystyrene and 150mL of toluene, vacuumizing, stirring for 30-60min at 90 ℃, adding 5mL of triethylamine and 15mL of 2-bromo-2-methylpropanoyl bromide after the solution is clarified, continuing to stir for 45min, continuing to react for 15 h after the solution becomes black, cooling to room temperature to obtain a reaction solution C, adding methanol into the reaction solution C, and precipitating, filtering, washing and drying to obtain polystyrene with a terminal group containing bromine;
b. mixing anhydrous methanol solution dissolved with 4-dimethylamino pyridine with Na2NH4[Fe(CN)5dmap]Mixing, evacuating, and adding N2Heating to 40 ℃ under protection, reacting for 15 hours, cooling to room temperature to obtain reaction liquid D, performing rotary evaporation on the reaction liquid D, precipitating with a mixed solvent of dichloromethane and n-hexane, filtering, and drying to obtain a blue iron complex, wherein 4-dimethylaminopyridine and Na are2NH4[Fe(CN)5dmap]Equal mass;
c. dissolving the polystyrene with the end group containing bromine in the step a and the blue iron complex in the step b by using a mixed solution of methanol and toluene, stirring and refluxing for 72h at 80 ℃, filtering after the reaction is finished to obtain a light blue solid, washing by using methanol until the filtrate is colorless, and drying in vacuum for 24h at 40 ℃ to obtain the organometallic polymer with the end group containing iron.
Further, the 2-bromo-2-methylpropanoyl bromide is added dropwise in the step a.
Further, the volume ratio of the methanol to the toluene in the step c is 1: 3.
Example 4
Example 4 differs from example 1 in that: an epoxy resin thermosetting conductive adhesive comprises the following raw materials in parts by weight:
example 5
Example 5 differs from example 1 in that: an epoxy resin thermosetting conductive adhesive comprises the following raw materials in parts by weight:
example 6
Example 6 differs from example 1 in that: an epoxy resin thermosetting conductive adhesive comprises the following raw materials in parts by weight:
example 6
Example 6 differs from example 1 in that: the curing agent is phthalic anhydride.
Example 7
Example 7 differs from example 1 in that: the curing agent is a mixture of trimellitic anhydride and phthalic anhydride in a weight ratio of 1: 1.
Example 8
Example 8 differs from example 1 in that: the epoxy resin is a mixture of E44 and bisphenol F epoxy resin in a weight ratio of 1: 1.
Example 9
Example 9 differs from example 1 in that: a preparation method of an epoxy resin thermosetting conductive adhesive comprises the following steps:
(1) mixing the epoxy resin, the toughening agent, the organic metal polymer and the curing agent in parts by weight, heating to 0 ℃ at the speed of 5 ℃/min, and stirring for 120min to obtain a reactant A;
(2) and ultrasonically dispersing the reactant A for 20min, and defoaming for 60min in a vacuum environment to obtain the epoxy resin thermosetting conductive adhesive.
Comparative example 1
An epoxy resin thermosetting conductive adhesive comprises the following raw materials in parts by weight:
further, the weight ratio of the epoxy resin E44 to the bisphenol F epoxy resin is 1: 1.
Further, the curing agent is trimellitic anhydride.
A preparation method of an epoxy resin thermosetting conductive adhesive comprises the following steps:
(1) mixing the epoxy resin, the toughening agent, the organic metal polymer and the curing agent in parts by weight, heating to 60 ℃ at the speed of 20 ℃/min, and stirring for 60min to obtain a reactant A;
(2) and dispersing the reactant A by ultrasonic waves for 60min, and defoaming for 20min in a vacuum environment to obtain the epoxy resin thermosetting conductive adhesive.
Comparative example 2
The difference between the comparative example 2 and the comparative example 1 is that the epoxy resin thermosetting conductive adhesive comprises the following raw materials in parts by weight:
the highly conductive epoxy adhesives prepared in the above examples and comparative examples were tested and the test data are shown in table 1:
instrumentation and equipment
An RGT-30 type microcomputer controlled electronic universal material testing machine, Shenzhen Ruigure Limited company; ZC36 high-impedance meter, Shanghai precision instruments and meters Co. Test index Electrical Properties
Test index
Electrical Properties
The volume resistivity of the resin cast body sample was tested with reference to national standards.
Mechanical properties
The resin composite was tested for flexural performance and compressive strength, aluminum/aluminum bond strength, according to relevant national standards.
Investigation of normal-temperature storage stability of glue
The uncured epoxy resin composition was stored in a closed environment at 25 ℃ for one week, and then observed for the presence of delamination or precipitation.
TABLE 1
As can be seen from Table 1, the adhesive prepared by the invention has good dispersibility and good conductivity.
The above examples are preferred embodiments of the present invention, but the present invention is not limited to the above detailed raw material ratios and specific operation methods, and any obvious substitutions are within the protection scope of the present invention without departing from the concept of the present invention.
Claims (10)
1. A method for preparing an organometallic polymer, comprising the steps of:
a. mixing 1-5mmol of polystyrene and 50-250mL of toluene, vacuumizing, stirring at 90 ℃ for 30-60min, adding 1-10mL of triethylamine and 1-25mL of 2-bromo-2-methylpropanoyl bromide after the solution is clarified, continuing stirring for 30-60min, continuing reacting for 10-24 h after the solution becomes black, cooling to room temperature to obtain a reaction solution C, adding methanol into the reaction solution C, precipitating, filtering, washing and drying to obtain polystyrene with a terminal group containing bromine;
b. mixing anhydrous methanol solution dissolved with 4-dimethylamino pyridine with Na2NH4[Fe(CN)5dmap]Mixing, evacuating, and adding N2Heating to 40 ℃ under protection, reacting for 10-24 hours, cooling to room temperature to obtain reaction liquid D, performing rotary evaporation on the reaction liquid D, precipitating with a mixed solvent of dichloromethane and n-hexane, filtering, and drying to obtain a blue iron complex, wherein 4-dimethylaminopyridine and Na are used as the raw materials2NH4[Fe(CN)5dmap]Equal mass;
c. dissolving the polystyrene with the end group containing bromine in the step a and the blue iron complex in the step b by using a mixed solution of methanol and toluene, stirring and refluxing for 72h at 80 ℃, filtering after the reaction is finished to obtain a light blue solid, washing by using methanol until the filtrate is colorless, and drying in vacuum for 24h at 40 ℃ to obtain the organometallic polymer with the end group containing iron.
2. The process for producing an organometallic polymer according to claim 1, wherein: the 2-bromo-2-methylpropanoyl bromide is added dropwise in the step a.
3. The process for producing an organometallic polymer according to claim 1, wherein: the volume ratio of the methanol to the toluene in the step c is 1: 1-3.
4. Use of an organometallic polymer prepared by the preparation method according to any one of claims 1 to 3, wherein an epoxy resin thermosetting conductive adhesive is prepared by using the organometallic polymer.
5. The application of claim 4, wherein the epoxy resin thermosetting conductive adhesive comprises the following raw materials in parts by weight:
6. the application of claim 5, wherein the epoxy resin thermosetting conductive adhesive comprises the following raw materials in parts by weight:
7. use according to any of claims 5 or 6, wherein the epoxy resin is one or both of E44 or bisphenol F epoxy resin.
8. Use according to any one of claims 5 or 6, wherein the curing agent is an anhydride-based curing agent.
9. The use according to any one of claims 5 or 6, wherein the curing agent is one or both of trimellitic anhydride or phthalic anhydride.
10. Use according to any one of claims 5 or 6, wherein the preparation of the epoxy resin thermosetting conductive adhesive comprises the following steps:
(1) mixing the epoxy resin, the toughening agent, the organic metal polymer and the curing agent in parts by weight, heating to 60-70 ℃ at the speed of 20-25 ℃/min, and stirring for 60-120min to obtain a reactant A;
(2) and dispersing the reactant A by ultrasonic waves for 60-120min, and defoaming for 20-60min in a vacuum environment to obtain the epoxy resin thermosetting conductive adhesive.
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2018
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|---|---|---|---|---|
| US4005248A (en) * | 1975-06-10 | 1977-01-25 | The Firestone Tire & Rubber Company | Smoke-inhibited polymer compositions |
| CN1616523A (en) * | 2003-09-29 | 2005-05-18 | 三洋电机株式会社 | Organometallic polymer material and process for preparing the same |
| CN102199407A (en) * | 2011-03-18 | 2011-09-28 | 中科院广州化学有限公司 | High-dispersing nanometer silver and high-performance conductive adhesive |
| CN103819904A (en) * | 2012-11-16 | 2014-05-28 | 陶氏环球技术有限责任公司 | Organometallic polymer composition, method for preparing it, and organic light-emitting diode made therefrom |
| CN103865220A (en) * | 2012-11-16 | 2014-06-18 | 陶氏环球技术有限责任公司 | Organometallic polymer composition, method for preparing it, and organic light-emitting diode made therefrom |
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