CN104086732B - A kind of preparation method of high-k Lauxite - Google Patents
A kind of preparation method of high-k Lauxite Download PDFInfo
- Publication number
- CN104086732B CN104086732B CN201410313906.9A CN201410313906A CN104086732B CN 104086732 B CN104086732 B CN 104086732B CN 201410313906 A CN201410313906 A CN 201410313906A CN 104086732 B CN104086732 B CN 104086732B
- Authority
- CN
- China
- Prior art keywords
- graphite oxide
- preparation
- added
- solution
- lauxite
- 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
- Compositions Of Macromolecular Compounds (AREA)
- Conductive Materials (AREA)
Abstract
The present invention provides a kind of preparation method of high-k Lauxite, including preparing graphite oxide, by graphite oxide and N, N dimethylformamides carry out ultrasonic agitation dispersion, adjust pH value to neutrality after urea, resorcinol dissolving is added, tetrachloro-ethylene solution is added to react with formalin, is eventually adding barium titanate, butanone solution cures to obtain high-k electricity Lauxite.Since graphite oxide carries a large amount of active group, it is easily polarized, while barium titanate itself has high dielectric, low-loss so that the urea-formaldehyde materials of preparation have very high dielectric constant, it is suitable as the basis material of Electronic Packaging, and this preparation method is at low cost, easy processing.
Description
Technical field
The invention belongs to resin modified technologies, and in particular to a kind of preparation method of high-k Lauxite.
Background technology
Lauxite can cure at ambient temperature since its material price is cheap, and viscosity itself is big, and adhesive force is good,
It is a kind of widely used thermosetting plastics.It is usually used in electric equipment products, such as wiring board, switch, machine handle, meter case
Position, but since the dielectric properties of its material are bad, it is less to be used for precise electronic component.With the development of electronic technology, electronics
Product increasingly minimizes and multifunction, develops high-k, the composite material of low-dielectric loss is to realize electronic product
The key of miniaturization.
Often high dielectric ceramic, electrically conductive particles are added in polymeric matrix at present, high-k composite wood can be obtained
Material, but high dielectric ceramic, the addition need of electrically conductive particles are very big in the method, and the mechanical performance of composite material is made to drop significantly
It is low.
Invention content
The object of the present invention is to provide a kind of preparation methods of high-k Lauxite, make the urea-formaldehyde resin of preparation
There are high-k, low-dielectric loss performance, adapts to precise electronic products application.
A kind of preparation method of high-k Lauxite, includes the following steps：
（1）Prepare graphite oxide：
Sodium nitrate is added in 1 gram of crystalline flake graphite to be stirred with concentrated sulfuric acid solution, 0.3-1g potassium permanganate is added and stirs
After mixing 1-3 hours, it is slowly added to 10-40mL distilled water, and be warming up to 90-100 DEG C；Then 10-50mL hydrogen peroxide is added to continue
Stirring 10-20 minutes；Be finally cooled to product is centrifuged after room temperature, dry after graphite oxide；
（2）It will（1）Middle graphite oxide, which is stirred by ultrasonic with N,N-dimethylformamide to graphite oxide, to be dispersed in
Until in N,N-dimethylformamide；
（3）To（2）Middle addition urea, resorcinol simultaneously make them be completely dissolved, then adjust solution ph to neutrality；
（4）It is heated to 40-60 DEG C and tetrachloro-ethylene solution and formalin, isothermal reaction 5-24 hours is added；
（5）After addition 15-30g barium titanates are stirred by ultrasonic with 10-30mL butanone solutions, then it is warming up to 120-180 DEG C
Solidification is carried out 2-5 hours to get high-k electricity Lauxite.
Further, the step（1）Middle stirring is magnetic agitation, and the temperature of the drying is 60-80 DEG C.
The step（1）The addition of middle sodium nitrate and concentrated sulfuric acid solution is respectively 0.2-0.8g, 15-30mL；It is described dense
The mass percent of sulfuric acid solution is 90-99.5%.
The step（2）The mass volume ratio of middle graphite oxide and N,N-dimethylformamide is 5g/（5-20）mL.
The step（3）The mass ratio of middle urea and resorcinol is 2.5/（0.1-0.5）.
The step（3）It is middle adjust pH value be with mass percent be 20-30% sodium hydroxide solution and mass percent
It is adjusted for the hydrochloric acid solution of 8-15%.
The step（4）The mass concentration of middle tetrachloro-ethylene solution is 3.15g/L, its addition is 10-20mL；The first
The mass percent of aldehyde solution is 30-50%, addition 10-20mL.
So the invention has the advantages that：
1, the present invention uses graphene oxide and barium titanate as conductive filler, and graphene oxide carries a large amount of active group
Group, is easily polarized, and barium titanate, which is also itself, has high dielectric property, so lower additive amount can be such that composite material has
Higher dielectric constant.
2, the present invention is using high-k Lauxite made from graphene oxide/barium titanate, in graphene oxide/titanium
When the additive amount of sour barium is 2wt%, under 20 DEG C, 1 kHz, the dielectric constant of material can reach 23, be far above conventional composite material
Material.
Specific implementation mode
Embodiment 1
（1）Prepare graphite oxide：
1 gram of crystalline flake graphite is added in the 20mL concentrated sulfuric acid solutions that 0.5g sodium nitrate is 95% with mass percent and carries out magnetic
Power stirs, and after adding the stirring of 0.5g potassium permanganate 2 hours, is slowly added to 25mL distilled water, and be warming up to 95 DEG C；Then it is added
30mL hydrogen peroxide continues stirring 15 minutes；Product is centrifuged after being finally cooled to room temperature and is obtained after dry in 70 DEG C
Graphite oxide；
（2）5g graphite oxides are stirred by ultrasonic with 10mL N,N-dimethylformamides evenly dispersed to graphite oxide
Until in N,N-dimethylformamide；
（3）To（2）Middle addition 2.5g urea, 0.4g resorcinols simultaneously make them be completely dissolved, and are 25% with mass percent
Sodium hydroxide solution and mass percent be 12% hydrochloric acid solution solution ph is adjusted to 7；
（4）It is heated to 50 DEG C and is added that mass concentrations are 3.15g/L tetrachloro-ethylene solution 15mL and mass percent is 40% first
Aldehyde solution 15mL, isothermal reaction 10 hours；
（5）It is added after 20g barium titanates and 20mL butanone solutions be stirred by ultrasonic, then is warming up to 150 DEG C to carry out solidification 3 small
When to get high-k electricity Lauxite.
Embodiment 2
（1）Prepare graphite oxide：
1 gram of crystalline flake graphite is added in the 15mL concentrated sulfuric acid solutions that 0.2g sodium nitrate is 99.5% with mass percent and is carried out
Magnetic agitation is slowly added to 10mL distilled water, and be warming up to 90 DEG C after adding the stirring of 0.3g potassium permanganate 1 hour；Then plus
Enter 10mL hydrogen peroxide and continues stirring 10 minutes；It is finally cooled to that product is centrifuged after room temperature, obtained after 60 DEG C of dryings
Graphite oxide；
（2）By 5g graphite oxides and 5mLN, dinethylformamide is stirred by ultrasonic to graphite oxide and is dispersed in
Until in N,N-dimethylformamide；
（3）To（2）Middle addition 2.5g urea, 0.1g resorcinols simultaneously make them be completely dissolved, and are 20% with mass percent
Sodium hydroxide solution and mass percent be 15% hydrochloric acid solution solution ph is adjusted to neutrality；
（4）It is heated to 40 DEG C and is added that mass concentrations are 3.15g/L tetrachloro-ethylene solution 10mL and mass percent is 30% first
Aldehyde solution 10mL, isothermal reaction 5 hours；
（5）It is added after 15g barium titanates and 10mL butanone solutions be stirred by ultrasonic, then is warming up to 120 DEG C to carry out solidification 2 small
When to get high-k electricity Lauxite.
Embodiment 3
（1）Prepare graphite oxide：
1 gram of crystalline flake graphite is added in the 18mL concentrated sulfuric acid solutions that 0.4g sodium nitrate is 99.5% with mass percent and is carried out
Magnetic agitation is slowly added to 30mL distilled water, and be warming up to 98 DEG C after adding the stirring of 0.8g potassium permanganate 2 hours；Then plus
Enter 35mL hydrogen peroxide and continues stirring 15 minutes；It is finally cooled to that product is centrifuged after room temperature, obtained after 60 DEG C of dryings
Graphite oxide；
（2）By 5g graphite oxides and 15mLN, dinethylformamide is stirred by ultrasonic to graphite oxide and is dispersed in
Until in N,N-dimethylformamide；
（3）To（2）Middle addition 2.5g urea, 0.3g resorcinols simultaneously make them be completely dissolved, and are 20% with mass percent
Sodium hydroxide solution and mass percent be 12% hydrochloric acid solution solution ph is adjusted to neutrality；
（4）It is heated to 40 DEG C and is added that mass concentrations are 3.15g/L tetrachloro-ethylene solution 10mL and mass percent is 30% first
Aldehyde solution 10mL, isothermal reaction 20 hours；
（5）It is added after 20g barium titanates and 25mL butanone solutions be stirred by ultrasonic, then is warming up to 140 DEG C to carry out solidification 4 small
When to get high-k electricity Lauxite.
Embodiment 4
（1）Prepare graphite oxide：
1 gram of crystalline flake graphite is added in the 30mL concentrated sulfuric acid solutions that 0.8g sodium nitrate is 90% with mass percent and carries out magnetic
Power stirs, and after adding the stirring of 1g potassium permanganate 3 hours, is slowly added to 40mL distilled water, and be warming up to 100 DEG C；Then it is added
50mL hydrogen peroxide continues stirring 15 minutes；It is finally cooled to that product is centrifuged after room temperature, obtains oxygen after 80 DEG C of dryings
Graphite；
（2）By 5g graphite oxides and 20mLN, dinethylformamide is stirred by ultrasonic to graphite oxide and is dispersed in
Until in N,N-dimethylformamide；
（3）To（2）Middle addition 2.5g urea, 0.5g resorcinols simultaneously make them be completely dissolved, and are 30% with mass percent
Sodium hydroxide solution and mass percent be 15% hydrochloric acid solution solution ph is adjusted to neutrality；
（4）It is heated to 60 DEG C and is added that mass concentrations are 3.15g/L tetrachloro-ethylene solution 20mL and mass percent is 50% first
Aldehyde solution 20mL, isothermal reaction 24 hours；
（5）It is added after 30g barium titanates and 30mL butanone solutions be stirred by ultrasonic, then is warming up to 180 DEG C to carry out solidification 5 small
When to get high-k electricity Lauxite.
Embodiment 5
（1）Prepare graphite oxide：
1 gram of crystalline flake graphite is added in the 15mL concentrated sulfuric acid solutions that 0.2g sodium nitrate is 93% with mass percent and carries out magnetic
Power stirs, and after adding the stirring of 0.6g potassium permanganate 1.5 hours, is slowly added to 15mL distilled water, and be warming up to 92 DEG C；Then plus
Enter 15mL hydrogen peroxide and continues stirring 15 minutes；It is finally cooled to that product is centrifuged after room temperature, obtained after 65 DEG C of dryings
Graphite oxide；
（2）By 5g graphite oxides and 8mLN, dinethylformamide is stirred by ultrasonic to graphite oxide and is dispersed in
Until in N,N-dimethylformamide；
（3）To（2）Middle addition 2.5g urea, 0.25g resorcinols simultaneously make them be completely dissolved, and are with mass percent
Solution ph is adjusted to neutrality in the hydrochloric acid solution that 22% sodium hydroxide solution and mass percent is 10%；
（4）It is heated to 45 DEG C and is added that mass concentrations are 3.15g/L tetrachloro-ethylene solution 12mL and mass percent is 35% first
Aldehyde solution 16mL, isothermal reaction 10 hours；
（5）20g barium titanates are added to carry out after being stirred by ultrasonic 2 hours with 15mL butanone solutions, then is warming up to 130 DEG C and is consolidated
Change 3 hours to get high-k electricity Lauxite.
Lauxite prepared by above-described embodiment 1-3 and conductivity ceramics in the prior art/poly(urea formaldehyde) resin compounded material
Material and nickel/poly(urea formaldehyde) resin composite materials, respectively condition be 20 DEG C, under 1kHz according to the dielectric of standard GB/T15662 detections
The dielectric constant of constant detection is as shown in the table：
| Material | Dielectric constant |
| Embodiment 1 | 35 |
| Embodiment 2 | 36 |
| Embodiment 3 | 32 |
| Conductivity ceramics/poly(urea formaldehyde) resin composite materials | 16 |
| Nickel/poly(urea formaldehyde) resin composite materials | 16.4 |
It can be seen that from upper table, the dielectric constant of urea-formaldehyde materials produced by the present invention is 32-36, and significantly larger than tradition is used
The dielectric constant of conductivity ceramics and nickel modified urea-formaldehyde resin composite material.
Claims (5)
1. a kind of preparation method of high-k Lauxite, it is characterised in that：Include the following steps：
（1）Prepare graphite oxide：
Sodium nitrate is added in 1 gram of crystalline flake graphite to be stirred with concentrated sulfuric acid solution, adds 0.3-1g potassium permanganate stirring 1-3
After hour, it is slowly added to 10-40mL distilled water, and be warming up to 90-100 DEG C；Then 10-50mL hydrogen peroxide is added to continue to stir
10-20 minutes；Be finally cooled to product is centrifuged after room temperature, dry after graphite oxide；
（2）It will（1）Middle graphite oxide, which is stirred by ultrasonic with N,N-dimethylformamide to graphite oxide, is dispersed in N, N-
Until in dimethylformamide；
（3）To（2）Middle addition urea, resorcinol simultaneously make them be completely dissolved, then adjust solution ph to neutrality；
（4）It is heated to 40-60 DEG C and tetrachloro-ethylene solution and formalin, isothermal reaction 5-24 hours is added；
（5）After addition 15-30g barium titanates are stirred by ultrasonic with 10-30mL butanone solutions, then it is warming up to 120-180 DEG C of progress
Cure 2-5 hours to get high-k electricity Lauxite；
The step（3）The mass ratio of middle urea and resorcinol is 2.5/（0.1-0.5）；Step（4）Middle tetrachloro-ethylene solution
Mass concentration be 3.15g/L, its addition is 10-20mL；The mass percent of the formalin is 30-50%, addition
For 10-20mL.
2. preparation method according to claim 1, it is characterised in that：The step（1）Middle stirring is magnetic agitation, described
Dry temperature is 60-80 DEG C.
3. preparation method according to claim 1, it is characterised in that：The step（1）Middle sodium nitrate and concentrated sulfuric acid solution
Addition be respectively 0.2-0.8g, 15-30mL；The mass percent of the concentrated sulfuric acid solution is 90-99.5%.
4. preparation method according to claim 1, it is characterised in that：The step（2）Middle graphite oxide and N, N- diformazans
The mass volume ratio of base formamide is 5g/（5-20）mL.
5. preparation method according to claim 1, it is characterised in that：The step（3）Middle adjusting pH value is to use quality hundred
The sodium hydroxide solution that ratio is 20-30% and the hydrochloric acid solution that mass percent is 8-15% is divided to be adjusted.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410313906.9A CN104086732B (en) | 2014-07-03 | 2014-07-03 | A kind of preparation method of high-k Lauxite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410313906.9A CN104086732B (en) | 2014-07-03 | 2014-07-03 | A kind of preparation method of high-k Lauxite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104086732A CN104086732A (en) | 2014-10-08 |
| CN104086732B true CN104086732B (en) | 2018-08-17 |
Family
ID=51634512
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410313906.9A Active CN104086732B (en) | 2014-07-03 | 2014-07-03 | A kind of preparation method of high-k Lauxite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104086732B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105647098B (en) * | 2016-03-02 | 2018-11-30 | 广东石油化工学院 | A kind of high dielectric constant SBS elastic composite and preparation method thereof |
| CN105859992B (en) * | 2016-04-01 | 2018-01-12 | 中南林业科技大学 | A kind of preparation method of the graphene oxide adsorption microspheres based on Lauxite |
| CN105860432B (en) * | 2016-04-01 | 2018-01-12 | 中南林业科技大学 | The preparation method of tartaric acid modified graphene oxide/Lauxite composite |
| CN110752092B (en) * | 2018-10-18 | 2021-03-30 | 嘉兴学院 | Preparation method of capacitor composite dielectric material |
| CN113121770A (en) * | 2019-12-31 | 2021-07-16 | 都江堰市天兴硅业有限责任公司 | Polyamide 1.1, preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102161826A (en) * | 2010-02-24 | 2011-08-24 | 东丽纤维研究所（中国）有限公司 | Polyimide resin based ternary hybrid material and preparation method thereof |
| CN103275488A (en) * | 2013-06-08 | 2013-09-04 | 华东理工大学 | Polyimide high dielectric composite material and preparation method thereof |
-
2014
- 2014-07-03 CN CN201410313906.9A patent/CN104086732B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102161826A (en) * | 2010-02-24 | 2011-08-24 | 东丽纤维研究所（中国）有限公司 | Polyimide resin based ternary hybrid material and preparation method thereof |
| CN103275488A (en) * | 2013-06-08 | 2013-09-04 | 华东理工大学 | Polyimide high dielectric composite material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Synthesis and characterization of polyamide-6/graphite oxide nanocomposites;Yan Liu et al;《J. Mater. Sci.》;20100825;第46卷;882-888 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104086732A (en) | 2014-10-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104086732B (en) | A kind of preparation method of high-k Lauxite | |
| CN102604275B (en) | Polyvinylidene fluoride/graphene composite and preparation method thereof | |
| CN105001601A (en) | Spinning conductive masterbatch containing graphene and preparation method thereof | |
| CN105385106A (en) | Preparation method for high-conductivity insulating composite material | |
| CN106587019B (en) | A kind of preparation method of lignin-base biological carbon/graphene composite nano material | |
| CN106751254A (en) | A kind of high-k covers Copper Foil microwave-medium plate and preparation method thereof | |
| CN103525014B (en) | Three-phase composite high-dielectric-property material, manufacturing method and processing method | |
| CN103219090B (en) | A kind of preparation method of Nano Silver coated high molecular microsphere composite conductive silver slurry | |
| CN104403275A (en) | Modified grapheme/thermosetting resin composite material and preparation method thereof | |
| CN105385100A (en) | Graphene-modified phenolic molding material and preparation method thereof | |
| CN105057690B (en) | A kind of preparation method of polymolecularity superfine spherical silver powder | |
| CN103214844B (en) | Graphene/nylon 66 conductive nano composite material and preparation method thereof | |
| CN102745994B (en) | Silicon carbide-carbon composite material and preparation method thereof | |
| CN103433502A (en) | High-dispersing silver powder and preparation method thereof | |
| CN104177925A (en) | Low-resistivity high-stability conductive ink and preparation method thereof | |
| CN103467986A (en) | Nano titanium carbide/polyimide composite material modified by small organic molecules | |
| CN108003520B (en) | Preparation method of polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property | |
| CN101955620A (en) | High dielectric composite material for filling organic metal modified carbon tube and preparation method thereof | |
| CN104629304A (en) | ABS modified polycarbonate alloy plastic | |
| CN109265880A (en) | A kind of core-shell structured powder and dielectric composite material as made from it | |
| CN102199341B (en) | Preparation method of microwave absorbing material | |
| CN109096660A (en) | Graphite oxide/polyvinylidene fluoride composite material preparation method | |
| US10189973B2 (en) | LCP derivative/soft magnetic ferrite composite material and preparation method therefor | |
| CN103122200A (en) | Expoxy self-adhesion paint with heat dissipation function and preparation method thereof | |
| CN105038228A (en) | Polyimide high-dielectric composite film mixed with nano-boron carbide-loaded graphene and used for capacitor and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |