CN107987468A - A kind of production technology of the compound melamine resin of high dielectric property graphene oxide - Google Patents
A kind of production technology of the compound melamine resin of high dielectric property graphene oxide Download PDFInfo
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- CN107987468A CN107987468A CN201711383673.XA CN201711383673A CN107987468A CN 107987468 A CN107987468 A CN 107987468A CN 201711383673 A CN201711383673 A CN 201711383673A CN 107987468 A CN107987468 A CN 107987468A
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- graphene oxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/40—Chemically modified polycondensates
- C08G12/42—Chemically modified polycondensates by etherifying
- C08G12/424—Chemically modified polycondensates by etherifying of polycondensates based on heterocyclic compounds
- C08G12/425—Chemically modified polycondensates by etherifying of polycondensates based on heterocyclic compounds based on triazines
- C08G12/427—Melamine
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
- C08G12/32—Melamines
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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
- C08K3/04—Carbon
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
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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 discloses a kind of production technology of the compound melamine resin of high dielectric property graphene oxide, include the following steps：(1) preparation of modified graphene oxide, the preparation of (2) melamine resin reaction solution, the preparation of the melamine resin performed polymer of (3) containing graphene oxide, the preparation of (4) graphene oxide/melamine resin composite material.Resin of the present invention with the addition of graphene oxide so that resin thermal conductivity factor improves 42% compared with the resin for being not added with graphene oxide so that melamine resin structure is more stablized, and heat endurance improves a lot；By adding barium titanate, the dielectric properties of resin are improved；Production technology of the present invention can improve the dispersing uniformity of graphene oxide, improve bond strength, improve the toughness and anti-bending strength of melamine resin.
Description
Technical field
The present invention relates to melamine resin Material Field, more particularly to a kind of compound melamine resin of high dielectric property graphene oxide
Production technology.
Background technology
Graphene be by single layer of carbon atom it is tightly packed into the carbonaceous material with two dimensional surface honeycomb crystal lattice structure,
Its unique nanostructured determines that it is up to 2600 ㎡/g with a series of excellent performances, theoretical specific surface area；Thermal conductivity factor
Up to 5000W/ (m.K), is 5 times of diamond, and intensity is highest in known materials, is more than 100 times of steel up to 130GPa,
At present, graphene is considered having extensively in functional composite material, nano-device, energy storage material and catalyst carrier etc.
General application space.
Using the excellent properties of graphene, graphene/polymer composites are prepared, solution graphene is first had to and is polymerizeing
In thing the problem of stable dispersion, surface of graphene oxide carries many oxygen-containing functional groups, although oxidation is destroyed to a certain degree
The lattice structure of graphene, but these functional groups can form strong interaction with polymer, so as to improve composite wood
The performance of material.The method for preparing graphene oxide/polymer composites mainly has solution blended process, melt-blending process, original position
It polymerize graft process.
Melamine resin, that is, melamine formaldehyde resin, is a kind of widely used thermosetting plastics.By using oxidation
Graphene carries out polymeric modification, can improve the heat endurance of resin, electric conductivity, thermal conductivity.But single graphene oxide
It is limited to the performance improvement of resin, it is also necessary to the performance of resin is further improved, can by improve technique and component come
Improve the performance of resin；Such as need to improve intensity, water-resistant capacity, heat endurance, wearability, hardness, chemicals supported
The performances such as anti-ability, poor toughness are easily rupturable, Storage period is short so that the resin is more broadly useful for the side such as furniture, vehicle, building
Face.
The content of the invention
, should the present invention seeks to aim to provide a kind of production technology of the compound melamine resin of high dielectric property graphene oxide
Resin structure stability and dielectric properties prepared by method is good.
To realize above-mentioned technical purpose, the technical solution adopted by the present invention is as follows：
A kind of production technology of the compound melamine resin of high dielectric property graphene oxide, includes the following steps,
(1) preparation of modified graphene oxide
Polyacrylonitrile is dissolved in dimethylformamide, is configured to the solution of 4wt%；Polyethylene glycol oxide is dissolved in dimethyl
Formamide/methylene chloride volume ratio is 1:In 1 double solvents, the solution of 4wt% is configured to, then above two solution is mixed
It is even, barium titanate, graphene oxide are added, is stirred evenly, is added trifluoroethyl methacrylate, tert-butyl hydroperoxide, add
Heat is to 60-70 DEG C, and stirring 1-2 hour of reaction, filtering, filter cake is cleaned 2-3 times with ethanol, obtains modified graphite oxide
Alkene；
Wherein, come in parts by weight, the barium titanate is 0.5-0.9 parts, and graphene oxide is 2.2-2.5 parts, methyl-prop
Olefin(e) acid trifluoro ethyl ester is 0.5-0.7 parts, and tert-butyl hydroperoxide is 0.3-0.5 parts, 0.7-0.9 parts of polyacrylonitrile, polyoxyethylene
0.3-0.5 parts of alkene；
(2) preparation of compound melamine resin
A, formalin, melamine, hexa are added reaction kettle to be reacted under agitation, three
The molar ratio of poly cyanamid and 37% formalin prepolymerization reaction, melamine and formaldehyde is 1:2-3, control ph 8-8.5, control
85-105 DEG C of pre-polymerization temperature processed, pre-polymerization time are 70-120min, and the quality of hexa is the 4- of melamine quality
12%；
B, add polyethylene glycol and carry out polycondensation reaction, control ph 5-6, the quality of polyethylene glycol is melamine quality
40-60%, the wherein molecular weight of polyethylene glycol is 800-1500；45-55 DEG C of condensation temperature is controlled, the polycondensation time is 80-
100min, obtains compound melamine resin；
(3) preparation of the melamine resin performed polymer containing graphene oxide
Obtained graphene oxide in step (1) is added in the compound melamine resin in step (2), is stirred
Mix 10-20 minutes, add alkaline pH adjuster, adjusting pH value is 8-9, when reaction 3-4 is small, is obtained containing the close of graphene oxide
Polyimide resin performed polymer；
(4) preparation of graphene oxide/melamine resin composite material
Performed polymer is placed in 30 DEG C of vacuum drying ovens, adjusting pH value is 5-6 after removing water, and it is small to cure 8-9 in 50 DEG C of baking ovens
When be molded, obtain graphene oxide/melamine resin composite material.
Further limit, the rate of charge of modified graphene oxide and compound melamine resin is 1:1.6-1:
2.8。
Further limit, the pH adjusting agent in step (3) is sodium hydroxide.
Beneficial effects of the present invention：
Resin of the present invention with the addition of graphene oxide so that resin thermal conductivity factor is carried compared with the resin for being not added with graphene oxide
It is high by 42% so that melamine resin structure is more stablized, and heat endurance improves a lot；By adding barium titanate, improve
The dielectric properties of resin；Production technology of the present invention can improve the dispersing uniformity of graphene oxide, improve bond strength, carry
The high toughness and anti-bending strength of melamine resin.
Embodiment
In order to make those skilled in the art that the present invention may be better understood, with reference to embodiment to the technology of the present invention
Scheme further illustrates.
A kind of production technology of the compound melamine resin of high dielectric property graphene oxide, includes the following steps,
(1) preparation of modified graphene oxide
Polyacrylonitrile is dissolved in dimethylformamide, is configured to the solution of 4wt%；Polyethylene glycol oxide is dissolved in dimethyl
Formamide/methylene chloride volume ratio is 1:In 1 double solvents, the solution of 4wt% is configured to, then above two solution is mixed
It is even, barium titanate, graphene oxide are added, is stirred evenly, is added trifluoroethyl methacrylate, tert-butyl hydroperoxide, add
Heat is to 60-70 DEG C, and stirring 1-2 hour of reaction, filtering, filter cake is cleaned 2-3 times with ethanol, obtains modified graphite oxide
Alkene；
Wherein, come in parts by weight, the barium titanate is 0.5-0.9 parts, and graphene oxide is 2.2-2.5 parts, methyl-prop
Olefin(e) acid trifluoro ethyl ester is 0.5-0.7 parts, and tert-butyl hydroperoxide is 0.3-0.5 parts, 0.7-0.9 parts of polyacrylonitrile, polyoxyethylene
0.3-0.5 parts of alkene；
(2) preparation of compound melamine resin
A, formalin, melamine, hexa are added reaction kettle to be reacted under agitation, three
The molar ratio of poly cyanamid and 37% formalin prepolymerization reaction, melamine and formaldehyde is 1:2-3, control ph 8-8.5, control
85-105 DEG C of pre-polymerization temperature processed, pre-polymerization time are 70-120min, and the quality of hexa is the 4- of melamine quality
12%；
B, add polyethylene glycol and carry out polycondensation reaction, control ph 5-6, the quality of polyethylene glycol is melamine quality
40-60%, the wherein molecular weight of polyethylene glycol is 800-1500；45-55 DEG C of condensation temperature is controlled, the polycondensation time is 80-
100min, obtains compound melamine resin；
(3) preparation of the melamine resin performed polymer containing graphene oxide
Obtained graphene oxide in step (1) is added in the compound melamine resin in step (2), is stirred
Mix 10-20 minutes, add alkaline pH adjuster, adjusting pH value is 8-9, when reaction 3-4 is small, is obtained containing the close of graphene oxide
Polyimide resin performed polymer；
(4) preparation of graphene oxide/melamine resin composite material
Performed polymer is placed in 30 DEG C of vacuum drying ovens, adjusting pH value is 5-6 after removing water, and it is small to cure 8-9 in 50 DEG C of baking ovens
When be molded, obtain graphene oxide/melamine resin composite material.
In preferred embodiment, the rate of charge of modified graphene oxide and compound melamine resin is 1:1.6-
1:2.8。
In preferred embodiment, the pH adjusting agent in step (3) is sodium hydroxide.
Graphene oxide made from the present embodiment/melamine resin composite material is made into performance test, obtains following data：Lead
Hot coefficient：0.35W/ (m.K), bending strength 105MPa, water absorption rate ＜ 0.1%.
A kind of production technology of the compound melamine resin of high dielectric property graphene oxide provided by the invention is carried out above
It is discussed in detail.The explanation of specific embodiment is only intended to help the method and its core concept for understanding the present invention.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
Claims (3)
- A kind of 1. production technology of the compound melamine resin of high dielectric property graphene oxide, it is characterised in that：Include the following steps,(1) preparation of modified graphene oxidePolyacrylonitrile is dissolved in dimethylformamide, is configured to the solution of 4wt%；Polyethylene glycol oxide is dissolved in dimethyl formyl Amine/methylene chloride volume ratio is 1:In 1 double solvents, the solution of 4wt% is configured to, then above two solution is uniformly mixed, Barium titanate, graphene oxide are added, is stirred evenly, is added trifluoroethyl methacrylate, tert-butyl hydroperoxide, be heated to 60-70 DEG C, stirring 1-2 hour of reaction, filtering, filter cake is cleaned 2-3 times with ethanol, obtains modified graphene oxide；Wherein, come in parts by weight, the barium titanate is 0.5-0.9 parts, and graphene oxide is 2.2-2.5 parts, methacrylic acid Trifluoro ethyl ester is 0.5-0.7 parts, and tert-butyl hydroperoxide is 0.3-0.5 parts, 0.7-0.9 parts of polyacrylonitrile, polyethylene glycol oxide 0.3-0.5 parts；(2) preparation of compound melamine resinA, formalin, melamine, hexa are added reaction kettle to be reacted under agitation, melamine The molar ratio of amine and 37% formalin prepolymerization reaction, melamine and formaldehyde is 1:2-3, control ph 8-8.5, control are pre- Poly- 85-105 DEG C of temperature, pre-polymerization time are 70-120min, and the quality of hexa is the 4-12% of melamine quality；B, add polyethylene glycol and carry out polycondensation reaction, control ph 5-6, the quality of polyethylene glycol is melamine quality The molecular weight of 40-60%, wherein polyethylene glycol are 800-1500；45-55 DEG C of condensation temperature is controlled, the polycondensation time is 80- 100min, obtains compound melamine resin；(3) preparation of the melamine resin performed polymer containing graphene oxideObtained graphene oxide in step (1) is added in the compound melamine resin in step (2), is stirred 10-20 minutes, alkaline pH adjuster is added, adjusting pH value is 8-9, when reaction 3-4 is small, obtains the melamine containing graphene oxide Resin prepolymer；(4) preparation of graphene oxide/melamine resin composite materialPerformed polymer is placed in 30 DEG C of vacuum drying ovens, it be 5-6 to remove and adjust pH value after water, when curing 8-9 is small in 50 DEG C of baking ovens into Type, obtains graphene oxide/melamine resin composite material.
- 2. a kind of production technology of compound melamine resin of high dielectric property graphene oxide according to claim 1, its feature It is：The rate of charge of modified graphene oxide and compound melamine resin is 1:1.6-1:2.8.
- 3. a kind of production technology of compound melamine resin of high dielectric property graphene oxide according to claim 2, its feature It is：PH adjusting agent in step (3) is sodium hydroxide.
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| CN201711383673.XA CN107987468A (en) | 2017-12-20 | 2017-12-20 | A kind of production technology of the compound melamine resin of high dielectric property graphene oxide |
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| CN201711383673.XA CN107987468A (en) | 2017-12-20 | 2017-12-20 | A kind of production technology of the compound melamine resin of high dielectric property graphene oxide |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109913178A (en) * | 2019-03-19 | 2019-06-21 | 北京服装学院 | A kind of preparation method of the modified phase-change microcapsule material of graphene |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104910583A (en) * | 2015-05-04 | 2015-09-16 | 芜湖市宝艺游乐科技设备有限公司 | High-dielectric graphene oxide melamine resin and preparation method thereof |
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- 2017-12-20 CN CN201711383673.XA patent/CN107987468A/en not_active Withdrawn
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104910583A (en) * | 2015-05-04 | 2015-09-16 | 芜湖市宝艺游乐科技设备有限公司 | High-dielectric graphene oxide melamine resin and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109913178A (en) * | 2019-03-19 | 2019-06-21 | 北京服装学院 | A kind of preparation method of the modified phase-change microcapsule material of graphene |
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