CN111269536A - Nano cellulose/copper composite material modified resin and preparation method thereof - Google Patents
Nano cellulose/copper composite material modified resin and preparation method thereof Download PDFInfo
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- CN111269536A CN111269536A CN202010298421.2A CN202010298421A CN111269536A CN 111269536 A CN111269536 A CN 111269536A CN 202010298421 A CN202010298421 A CN 202010298421A CN 111269536 A CN111269536 A CN 111269536A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/085—Copper
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention provides a nano-cellulose modified nano-copper, a nano-cellulose/copper-epoxy resin composite material and a preparation method thereof, and aims to provide a modified nano-copper with excellent dielectric property, stability and dispersibility, in particular to the nano-cellulose modified nano-copper, and also provides a nano-cellulose/copper-epoxy resin composite material and a preparation method thereof, wherein the nano-cellulose modified nano-copper has good electrical conductivity, heat conductivity and weather resistance.
Description
Technical Field
The invention relates to a high dielectric composite material, in particular to nano-cellulose modified nano-copper and a nano-cellulose/copper composite-epoxy resin composite material, and also relates to a preparation method of the nano-cellulose/copper composite-epoxy resin composite material, belonging to the technical field of materials.
Background
In order to improve the performance of the material, the material is usually modified, chinese patent 201310363280.8 epoxy resin/nano copper/carbon nanotube thermal interface composite material and the preparation method thereof, the scheme is that the epoxy resin/nano copper/carbon nanotube thermal interface composite material is characterized in that the composition by weight portion is: 100 parts of epoxy resin, 1-20 parts of curing agent, 1-10 parts of epoxypropane butyl ether diluent, 50-235 parts of nano copper particles and 0.5-25 parts of carboxylated carbon nano tubes, wherein the curing agent is polyamide resin. The composite material aims to realize good dispersion of the carbon nano tubes in the epoxy resin and simultaneously uniformly mix the carbon nano tubes with the nano copper particles, thereby obviously improving the thermal conductivity of the epoxy resin composite material. The surface of the carbon nano tube is firstly carboxylated, and then the carbon nano tube and nano copper particles are co-dissolved in an epoxy resin base material under a certain condition and can be uniformly dispersed.
As a novel green nano material, nanocellulose has received wide attention in the field of energy storage in recent years. Besides the natural advantages of abundant reserves and reproducible circulation, the nanocellulose also has the advantages of fine nano-structure, good mechanical strength, lower thermal expansion coefficient and the like. Under the dehydration state, the nano-cellulose can spontaneously form a self-assembled film under the action of non-valence bond forces such as hydrogen bond, van der waals force or electrostatic force, and the novel film material has the performance advantages of fast ion diffusion, high temperature resistance and the like, and has wide application prospect in the fields of diaphragms and electrode materials for energy storage devices such as metal ion batteries, super capacitors and the like. In addition, the nanocellulose can also form a three-dimensional network porous structure through gelation, and can be compounded with inorganic nanoparticles, metal ions and oxides thereof, carbon materials, conductive polymers and other photoelectric materials to form a multifunctional composite material with conductive and energy storage effects. The thermal conductivity to nanocellulose is insufficient, and therefore, the thermal conductivity is not fully utilized.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the nano-cellulose/copper composite material modified resin and the preparation method thereof, the method is simple, and can provide the nano-cellulose modified nano-copper with excellent dielectric property, stability and dispersibility, so as to provide the nano-cellulose/copper composite material-epoxy resin composite material with low dielectric loss, controllable percolation threshold and good weather resistance.
Therefore, the technical scheme provided by the invention comprises the following steps:
(1) under the protection of inert gas, dispersing graphene, nano-cellulose and nano-copper in different proportions in 100 parts of sodium hydroxide solution, performing 800w ultrasonic treatment, then washing with water to neutrality, evaporating by using an evaporation-induced self-assembly method, and controlling the temperature at 25 ℃ to obtain the nano-cellulose/copper composite material.
(2) Uniformly mixing 1-10 parts of dried and refined composite material, 80-90 parts of epoxy resin, 0.2-0.35 part of antioxidant, 0.2-0.4 part of coupling agent and 10-20 parts of dispersing agent in a low-speed mixer, and then extruding and granulating by a single screw at 180-240 ℃.
The size of the copper nanoparticles in the step (1) is 10-40nm, the surface of the copper nanoparticles is coated with silicon dioxide, and the thickness of the copper nanoparticles is 40-400 nm.
The mass concentration of the sodium hydroxide solution in the step (1) is 10-16%; the ultrasonic treatment time is 20-30 min.
The antioxidant in the step (2) is selected from pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], and the phosphite antioxidant is one of tris [2, 4-di-tert-butylphenyl ] phosphite, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester (anti-1076).
The coupling agent in the step (2) is selected from silane coupling agents, and specifically is one of gamma-aminopropyltriethoxysilane, vinyl-tri-tert-butyl-peroxide silane and diethylamino-methyl-triethoxy silane.
The dispersant in the step (2) is selected from acrylic acid, methacrylic acid, maleic acid, fumaric acid, phosphonic acid, citric acid, tartaric acid and mixtures thereof.
And (3) the rotating speed of the low-speed mixer in the step (2) is 300-350 r/min.
Compared with the prior art, the modified nano-copper has excellent stability and dispersibility;
the nano copper-epoxy resin composite material overcomes the defects of poor oxidation resistance and the like of the traditional composite material, and has good conductivity, heat transfer property and weather resistance.
Detailed Description
In order to make the objects, technical solutions and advantageous technical effects of the present invention clearer, the present invention is further described in detail with reference to the following embodiments. It should be understood that the embodiments described in this specification are only for the purpose of illustrating the invention and are not to be construed as limiting the invention, and the parameters, proportions and the like of the embodiments may be suitably selected without materially affecting the results.
Example 1
(1) Under the protection of inert gas, dispersing graphene, nano-cellulose and nano-copper (the size is 350nm, and the size of copper nanoparticles is 25nm) in a mass ratio of 10:10:50 in 100 parts of 10% sodium hydroxide solution, performing ultrasonic treatment for 20min at 800w, washing with water to be neutral, evaporating to dryness by using an evaporation-induced self-assembly method, and controlling the temperature to be 25 ℃ to obtain the nano-cellulose/copper composite material.
(2) 9 parts of the dried and refined composite material, 89 parts of epoxy resin, 0.2 part of tris [2, 4-di-tert-butylphenyl ] phosphite, 0.4 part of gamma-aminopropyltriethoxysilane and 20 parts of methacrylic acid are uniformly mixed in a mixer with the rotating speed of 300r/min, and then are extruded and granulated by a single screw at 180 ℃.
The heat conductivity of the composite material is 1570 W.m-1·K-1。
Example 2
(1) Under the protection of inert gas, dispersing graphene, nano-cellulose and nano-copper (with the size of 200nm and the size of copper nanoparticles of 10nm) in a mass ratio of 20:10:70 in 100 parts of 15% sodium hydroxide solution, performing ultrasonic treatment for 30min at 800w, washing with water to be neutral, evaporating to dryness by using an evaporation-induced self-assembly method, and controlling the temperature to be 25 ℃ to obtain the nano-cellulose/copper composite material.
(2) Mixing 10 parts of the dried and refined composite material, 80 parts of epoxy resin, 0.25 part of N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylene diamine, 0.35 part of vinyl tri-tert-butyl peroxide silane and 15 parts of maleic acid uniformly in a mixer with the rotating speed of 350r/min, and extruding and granulating by a single screw at 200 ℃.
The heat conductivity of the composite material is 2013 W.m-1·K-1。
Example 3
(1) Under the protection of inert gas, dispersing graphene, nano-cellulose and nano-copper (the size is 400nm, and the size of copper nanoparticles is 20nm) in a mass ratio of 10:20:40 in 100 parts of 15% sodium hydroxide solution, performing ultrasonic treatment for 20min at 800w, washing with water to be neutral, evaporating to dryness by using an evaporation-induced self-assembly method, and controlling the temperature to be 25 ℃ to obtain the nano-cellulose/copper composite material.
(2) 5 parts of the dried and refined composite material, 85 parts of epoxy resin, 0.2 part of β - (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, 0.3 part of diethylamino methyl triethoxysilane and 20 parts of fumaric acid are uniformly mixed in a mixer with the rotating speed of 350r/min, and then are extruded and granulated by a single screw at the temperature of 200 ℃.
The heat conductivity of the composite material is 761 W.m-1·K-1。
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (7)
1. The nano-cellulose/copper composite modified resin and the preparation method thereof are characterized by sequentially comprising the following steps:
(1) under the protection of inert gas, dispersing graphene, nano-cellulose and nano-copper in different proportions in 100 parts of sodium hydroxide solution, performing 800w ultrasonic treatment, then washing with water to neutrality, evaporating by using an evaporation-induced self-assembly method, and controlling the temperature at 25 ℃ to obtain the nano-cellulose/copper composite material.
(2) Uniformly mixing 1-10 parts of dried and refined composite material, 80-90 parts of epoxy resin, 0.2-0.35 part of antioxidant, 0.2-0.4 part of coupling agent and 10-20 parts of dispersing agent in a low-speed mixer, and then extruding and granulating by a single screw at 180-240 ℃.
2. The nano-cellulose/copper composite modified resin and the preparation method thereof according to claim 1, wherein the nano-copper in the step (1) has a size of 10-40nm, is coated with silicon dioxide on the surface, and has a thickness of 4-400 nm.
3. The nano-cellulose/copper composite modified resin and the preparation method thereof according to claim 1, wherein the mass concentration of the sodium hydroxide solution in the step (1) is 10-16%; the ultrasonic treatment time is 20-30 h.
4. The nano-cellulose/copper composite modified resin and the preparation method thereof as claimed in claim 1, wherein the antioxidant in step (2) is selected from pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and the phosphite antioxidant is one of tris [2, 4-di-tert-butylphenyl ] phosphite, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, and octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (anti-1076).
5. The nano-cellulose/copper composite modified resin and the preparation method thereof as claimed in claim 1, wherein the coupling agent in step (2) is selected from silane coupling agents, specifically one of γ -aminopropyltriethoxysilane, vinyltri-tert-butylperoxide, diethylamino-methyl-triethoxy silane.
6. The nano-cellulose/copper composite modified resin and the preparation method thereof according to claim 1, wherein the dispersant in the step (2) is selected from acrylic acid, methacrylic acid, maleic acid, fumaric acid, phosphonic acid, citric acid, tartaric acid and mixtures thereof.
7. The nano-cellulose/copper composite modified resin and the preparation method thereof according to claim 1, wherein the rotation speed of the low-speed mixer in the step (2) is 300-350 r/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202010298421.2A CN111269536A (en) | 2020-04-16 | 2020-04-16 | Nano cellulose/copper composite material modified resin and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010298421.2A CN111269536A (en) | 2020-04-16 | 2020-04-16 | Nano cellulose/copper composite material modified resin and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104530653A (en) * | 2014-12-26 | 2015-04-22 | 黑龙江大学 | Preparation method of epoxy resin/graphene/nano copper composite material |
| CN107936295A (en) * | 2017-11-24 | 2018-04-20 | 广东聚航新材料研究院有限公司 | A kind of modified Nano copper and Nanometer Copper epoxy resin composite material and preparation method thereof |
| CN108250677A (en) * | 2016-12-29 | 2018-07-06 | 中国科学院深圳先进技术研究院 | A kind of polymer matrix composite comprising filler grain three-dimensional network and preparation method thereof |
| WO2019216700A1 (en) * | 2018-05-11 | 2019-11-14 | 주식회사 삼양사 | Solid dispersion, preparation method therefor, chain-extended polyurethane using same, and epoxy resin composition comprising same |
-
2020
- 2020-04-16 CN CN202010298421.2A patent/CN111269536A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104530653A (en) * | 2014-12-26 | 2015-04-22 | 黑龙江大学 | Preparation method of epoxy resin/graphene/nano copper composite material |
| CN108250677A (en) * | 2016-12-29 | 2018-07-06 | 中国科学院深圳先进技术研究院 | A kind of polymer matrix composite comprising filler grain three-dimensional network and preparation method thereof |
| CN107936295A (en) * | 2017-11-24 | 2018-04-20 | 广东聚航新材料研究院有限公司 | A kind of modified Nano copper and Nanometer Copper epoxy resin composite material and preparation method thereof |
| WO2019216700A1 (en) * | 2018-05-11 | 2019-11-14 | 주식회사 삼양사 | Solid dispersion, preparation method therefor, chain-extended polyurethane using same, and epoxy resin composition comprising same |
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