CN111286071A - Graphene oxide reinforced modified phenolic foam plastic and preparation method thereof - Google Patents
Graphene oxide reinforced modified phenolic foam plastic and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of foam plastic preparation, and particularly relates to graphene oxide reinforced modified phenolic foam plastic and a preparation method thereof, wherein an isocyanate group-terminated polyurethane prepolymer is prepared by reacting isophorone diisocyanate and polyethylene glycol, and then graphene oxide dispersion liquid is added for mixing, so that an oxygen-containing functional group in graphene oxide reacts with an isocyanate group in the prepolymer; and (2) stirring and mixing the graphene oxide covalently-bonded polyurethane prepolymer with resol phenolic resin, a surfactant, a foaming agent, a curing agent and the like at a high speed, pouring the mixture into a mold, closing the mold to foam, curing the mixture at a certain temperature to obtain the graphene oxide reinforced modified phenolic foam plastic.
Description
Technical Field
The invention belongs to the technical field of plastic preparation, and particularly relates to graphene oxide reinforced modified phenolic foam plastic and a preparation method thereof.
Background
The phenolic foam plastic is a novel foam plastic developed in recent years, has unique performances of flame retardance, low smoke, self-extinguishing, stable size, no harmful gas release after thermal decomposition in case of fire and the like, has fireproof performance far superior to that of other various foam plastics, and has excellent performance which is highly valued by countries in the world.
The traditional phenolic resin raw materials for foaming are fossil resources of phenol and formaldehyde, and due to the fact that the phenolic resin raw materials are large in molecular crosslinking density, too short in intramolecular network chain and containing a large number of rigid benzene rings, the prepared foam has the problems of low elongation, high hardness, poor impact resistance, powder falling and the like, and application and rapid development of phenolic foam plastic are limited.
The graphene material can obviously improve the mechanical strength of the foam plastic, but because the graphene or graphene oxide has small particle size, the original graphene has unique lamellar structure, high specific surface area and strong hydrophobicity, the graphene is easy to agglomerate and difficult to disperse in a resin system, and the mechanical strength of the foam is influenced instead of being directly added for enhancing modification, so that the development of the graphene for enhancing the foam plastic field is limited.
Chinese patent application No. 201510357134.3 discloses a preparation method of lignin-based polyurethane prepolymer modified phenolic foam plastic, wherein, polyol and lignin are mixed uniformly, heated and reacted in the presence of a catalyst, and vacuum dehydration is carried out to prepare lignin-based polyol; then dripping isocyanate under nitrogen atmosphere to obtain lignin-based polyurethane prepolymer; adding the lignin-based polyurethane prepolymer into the resol, stirring, adding the surfactant, the foaming agent and the curing agent, uniformly stirring, pouring into a mold, heating, curing and forming to obtain the lignin-based polyurethane prepolymer modified phenolic foam. The mechanical property of the prepared phenolic foam heat-insulating material is obviously improved, and meanwhile, a benzene ring structure is introduced into the polyurethane prepolymer, so that the problem of reduced foam heat stability caused by introducing carbamate into phenolic foam is solved. Provides a new way for the high-value utilization of lignin and lays theoretical and technical foundation for the development of new performance of the phenolic foam thermal insulation material.
Chinese patent application No. 201310032938.7 discloses a preparation method of phenolic foam plastic, which comprises the following steps: mixing 90-100 parts by weight of expandable resol, based on the weight percentage of the expandable resol, 3-5% of a foam stabilizer, 5-30% of a curing agent, 10-20% of a foaming agent, 3-20% of a modifier and 5-20% of an inorganic flame retardant, and reacting to obtain a mixed product; and carrying out post-treatment on the mixed product under the conditions of constant temperature and constant humidity to obtain the phenolic foam plastic. The phenolic foam plastic provided by the invention has the advantages that as the curing agent is introduced, the phenolic foam plastic not only has the catalytic curing effect, but also participates in a foam structure, so that the toughness of the phenolic foam plastic is improved, the brittleness is reduced, and the strength of a phenolic foam plastic plate is improved; the method makes up the defect of low curing degree of the organic curing agent by a constant-temperature and constant-humidity post-treatment mode, so that the phenolic resin foam can reach higher strength in a short time.
Chinese patent application No. 201410310392.1 discloses a preparation method of polyurethane prepolymer toughened and modified phenolic foam plastic, firstly, polyol is vacuumized to remove moisture, then the polyol is dripped into isocyanate in nitrogen atmosphere for reaction, and a chain extender is added for reaction; adjusting alkaline resol by using acid, and then adding a toughening agent polyurethane prepolymer, a surfactant, 1 a foaming agent and a curing agent into the resin to obtain a foaming system; and (3) uniformly stirring the foaming system at room temperature, and then heating, curing and molding to obtain the polyurethane prepolymer modified flame-retardant phenolic foam thermal insulation material. The prepared phenolic foam has the advantages of less slag falling, high toughness and the like, and meanwhile, the phenolic resin adopted by the invention has low viscosity, good compatibility with the polyurethane prepolymer and easy and uniform mixing.
Chinese patent application No. 201210120826.2 discloses a flame-retardant toughened phenolic foamed plastic which is prepared from the following components in parts by weight: 100 parts of expandable phenolic resin, 5-20 parts of toughening agent, 5-10 parts of surfactant, 10-20 parts of foaming agent, 8-20 parts of curing agent and 5-10 parts of flame retardant. The invention also discloses a preparation method of the flame-retardant toughened phenolic foamed plastic. According to the invention, the toughness of the phenolic foam material is improved by using a small amount of polyurethane prepolymer, the fire resistance of the foam is improved by adding the composite fire retardant, the slag falling rate of the phenolic foam is reduced by adopting a new composite curing agent, and the original excellent performance of the phenolic foam material is maintained.
Disclosure of Invention
Aiming at the defect that graphene oxide is difficult to disperse in a phenolic foam system as a reinforcing component at present, the invention provides the phenolic foam plastic containing the graphene oxide reinforced and modified and the preparation method thereof, which not only solve the defect that the graphene oxide is difficult to disperse in the phenolic foam system, but also obviously improve the mechanical property of the phenolic foam material, increase the stability in the foaming process and improve the foaming quality.
In order to solve the problems, the invention adopts the following technical scheme:
a preparation method of graphene oxide reinforced modified phenolic foam plastic comprises the steps of preparing an isocyanate group-terminated polyurethane prepolymer by reacting isophorone diisocyanate with polyethylene glycol, adding graphene oxide dispersion liquid, and mixing to enable oxygen-containing functional groups in graphene oxide to react with isocyanate groups in the prepolymer; stirring and mixing the graphene oxide covalently-bonded polyurethane prepolymer with resol phenolic resin, a surfactant, a foaming agent, a curing agent and the like at a high speed, pouring the mixture into a mold, closing the mold for foaming, curing the mixture at a certain temperature to obtain graphene oxide reinforced modified phenolic foam plastic; the method specifically comprises the following steps:
s1, mixing isophorone diisocyanate and polyethylene glycol, adding a solvent and a catalyst, heating to 60-80 ℃, and reacting to obtain an isocyanate group-terminated polyurethane prepolymer;
s2, mixing the isocyanate group-terminated polyurethane prepolymer obtained in the step S1 with the graphene oxide dispersion liquid, and reacting oxygen-containing functional groups in the graphene oxide with isocyanate groups in the prepolymer to obtain a graphene oxide covalently-bonded polyurethane prepolymer;
and S3, stirring and mixing the graphene oxide covalently-bonded polyurethane prepolymer obtained in the step S2 with resol, a surfactant, a foaming agent and a curing agent, pouring the mixture into a mold, closing the mold to foam, curing and curing to obtain the graphene oxide reinforced and modified phenolic foam plastic.
Further, the preparation method of the graphene oxide reinforced and modified phenolic foam plastic comprises the step of S1, wherein the mass ratio of the isophorone diisocyanate, the polyethylene glycol, the solvent and the catalyst is 1-3:3-5:1-2:0.05, and the catalyst is at least one of dibutyltin dilaurate and triphenylbismuth.
Preferably, the mass ratio of the isocyanate group-terminated polyurethane prepolymer to the graphene oxide dispersion in the S2 step is 1: 3.
Further, in the preparation method of the graphene oxide reinforced and modified phenolic foam plastic, in the step S3, the curing agent is an organic acid; the organic acid is at least one of p-toluenesulfonic acid, phenolsulfonic acid, benzenesulfonic acid and xylenesulfonic acid.
Further, in the preparation method of the graphene oxide reinforced and modified phenolic foam plastic, the surfactant in the step S3 is polyethylene glycol.
Further, in the preparation method of the graphene oxide reinforced and modified phenolic foam, the foaming agent in the step S3 is at least one of n-pentane, isopentane, n-hexane, cyclopentane, petroleum ether, isopropyl chloride and chlorodifluoroethane.
Further, the preparation method of the graphene oxide reinforced and modified phenolic foam plastic comprises the step of S3, wherein the mass ratio of the polyurethane prepolymer, the resol, the surfactant, the foaming agent and the curing agent is 15-40: 20-30: 10-15: 5-15: 6-12.
Further, the preparation method of the graphene oxide reinforced and modified phenolic foam plastic comprises the step of S3, wherein the curing temperature is 100-180 ℃.
The invention also provides the graphene oxide reinforced modified phenolic foam plastic prepared by the preparation method. The phenolic foam plastic is a novel flame-retardant, fireproof and low-smoke heat-insulating material, and is closed-cell rigid foam plastic prepared by adding a flame retardant, a smoke inhibitor, a foaming agent, a curing agent or other auxiliaries into phenolic resin. Its outstanding features are flame-retarding, low smoke and high-temp. It can be cast and foamed in situ, and can be moulded, also can be machined, and can be made into plate material, pipe shell and various special-shaped products. The foam plastic type heat-insulating material overcomes the defects of inflammability, smoke and deformation when heated of the original foam plastic type heat-insulating material, and keeps the characteristics of light weight, convenient construction and the like of the original foam plastic type heat-insulating material. The phenolic foam plastic has the advantages of rich raw material sources, low price, simple production and processing and wide product application. It is suitable for large cold storage, storage tank, ship, various heat insulating pipes and building industry. If the flame retardant is used for factories, mines and mechanical equipment with strict fire protection requirements, the characteristics of flame resistance, low smoke and high temperature resistant bifurcation can be highlighted. Such as: the heat preservation of steamships, warships, trains and armored vehicles, the papermaking, the chemical industry, the pharmacy and the like.
According to the graphene oxide reinforced and modified phenolic foam plastic, the isocyanate group-containing polyurethane prepolymer and the graphene oxide are covalently combined to serve as a reinforcing agent of phenolic foam, so that the good compatibility of the polyurethane prepolymer and a phenolic foam system is fully utilized, the graphene oxide is prevented from agglomerating, the defect that the graphene oxide is difficult to disperse in the phenolic foam system is overcome, the mechanical property of a phenolic foam material is remarkably improved, the stability in the foaming process is improved, and the foaming quality is improved.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
A preparation method of graphene oxide reinforced modified phenolic foam plastic comprises the following steps:
s1, mixing isophorone diisocyanate, polyethylene glycol, a solvent and a catalyst according to a mass ratio of 1:3:1:0.05, heating to 70 ℃, and reacting to obtain an isocyanate group-terminated polyurethane prepolymer; the solvent is acetone, and the catalyst is triphenyl bismuth;
s2, mixing the isocyanate group-terminated polyurethane prepolymer obtained in the step S1 with the graphene oxide dispersion liquid, and reacting oxygen-containing functional groups in the graphene oxide with isocyanate groups in the prepolymer to obtain a graphene oxide covalently-bonded polyurethane prepolymer; the mass ratio of the isocyanate-terminated polyurethane prepolymer to the graphene oxide dispersion liquid is 1: 3;
s3, stirring and mixing the graphene oxide covalently-bonded polyurethane prepolymer obtained in the step S2 with resol, a surfactant, a foaming agent and a curing agent, pouring the mixture into a mold, closing the mold to foam, curing and curing to obtain graphene oxide reinforced modified phenolic foam plastic; the curing agent is organic acid; the organic acid is p-toluenesulfonic acid; the surfactant is polyethylene glycol; the foaming agent is n-pentane; the mass ratio of the polyurethane prepolymer to the resol resin to the surfactant to the foaming agent to the curing agent is 20:25:11:10: 8; the curing temperature is 160 ℃.
Example 2
A preparation method of graphene oxide reinforced modified phenolic foam plastic comprises the following steps:
s1, mixing isophorone diisocyanate, polyethylene glycol, a solvent and a catalyst according to a mass ratio of 2:3:1:0.05, heating to 60 ℃, and reacting to obtain an isocyanate group-terminated polyurethane prepolymer; the solvent is acetone, and the catalyst is dibutyltin dilaurate;
s2, mixing the isocyanate group-terminated polyurethane prepolymer obtained in the step S1 with the graphene oxide dispersion liquid, and reacting oxygen-containing functional groups in the graphene oxide with isocyanate groups in the prepolymer to obtain a graphene oxide covalently-bonded polyurethane prepolymer; the mass ratio of the isocyanate-terminated polyurethane prepolymer to the graphene oxide dispersion liquid is 1: 3;
s3, stirring and mixing the graphene oxide covalently-bonded polyurethane prepolymer obtained in the step S2 with resol, a surfactant, a foaming agent and a curing agent, pouring the mixture into a mold, closing the mold to foam, curing and curing to obtain graphene oxide reinforced modified phenolic foam plastic; the curing agent is organic acid; the organic acid is benzenesulfonic acid; the surfactant is polyethylene glycol; the foaming agent is petroleum ether; the mass ratio of the polyurethane prepolymer to the resol resin to the surfactant to the foaming agent to the curing agent is 30:27:13:11: 9; the curing temperature is 140 ℃.
Example 3
A preparation method of graphene oxide reinforced modified phenolic foam plastic comprises the following steps:
s1, mixing isophorone diisocyanate, polyethylene glycol, a solvent and a catalyst according to a mass ratio of 3:5:2:0.05, heating to 75 ℃, and reacting to obtain an isocyanate group-terminated polyurethane prepolymer; the solvent is acetone, and the catalyst is dibutyltin dilaurate;
s2, mixing the isocyanate group-terminated polyurethane prepolymer obtained in the step S1 with the graphene oxide dispersion liquid, and reacting oxygen-containing functional groups in the graphene oxide with isocyanate groups in the prepolymer to obtain a graphene oxide covalently-bonded polyurethane prepolymer; the mass ratio of the isocyanate-terminated polyurethane prepolymer to the graphene oxide dispersion liquid is 1: 3;
s3, stirring and mixing the graphene oxide covalently-bonded polyurethane prepolymer obtained in the step S2 with resol, a surfactant, a foaming agent and a curing agent, pouring the mixture into a mold, closing the mold to foam, curing and curing to obtain graphene oxide reinforced modified phenolic foam plastic; the curing agent is organic acid; the organic acid is p-phenolsulfonic acid; the surfactant is polyethylene glycol; the foaming agent is isopentane; the mass ratio of the polyurethane prepolymer to the resol resin to the surfactant to the foaming agent to the curing agent is 30:28:13:10: 10; the curing temperature is 150 ℃.
Example 4
A preparation method of graphene oxide reinforced modified phenolic foam plastic comprises the following steps:
s1, mixing isophorone diisocyanate, polyethylene glycol, a solvent and a catalyst according to a mass ratio of 1:3:2:0.05, heating to 80 ℃, and reacting to obtain an isocyanate group-terminated polyurethane prepolymer; the solvent is acetone, and the catalyst is triphenyl bismuth;
s2, mixing the isocyanate group-terminated polyurethane prepolymer obtained in the step S1 with the graphene oxide dispersion liquid, and reacting oxygen-containing functional groups in the graphene oxide with isocyanate groups in the prepolymer to obtain a graphene oxide covalently-bonded polyurethane prepolymer; the mass ratio of the isocyanate-terminated polyurethane prepolymer to the graphene oxide dispersion liquid is 1: 3;
s3, stirring and mixing the graphene oxide covalently-bonded polyurethane prepolymer obtained in the step S2 with resol, a surfactant, a foaming agent and a curing agent, pouring the mixture into a mold, closing the mold to foam, curing and curing to obtain graphene oxide reinforced modified phenolic foam plastic; the curing agent is organic acid; the organic acid is xylene sulfonic acid; the surfactant is polyethylene glycol; the foaming agent is isopropyl chloride; the mass ratio of the polyurethane prepolymer to the resol resin to the surfactant to the foaming agent to the curing agent is 35:26:13:12: 10; the curing temperature is 160 ℃.
Example 5
A preparation method of graphene oxide reinforced modified phenolic foam plastic comprises the following steps:
s1, mixing isophorone diisocyanate, polyethylene glycol, a solvent and a catalyst according to a mass ratio of 3:3:1:0.05, heating to 77 ℃, and reacting to obtain an isocyanate group-terminated polyurethane prepolymer; the solvent is acetone, and the catalyst is dibutyltin dilaurate;
s2, mixing the isocyanate group-terminated polyurethane prepolymer obtained in the step S1 with the graphene oxide dispersion liquid, and reacting oxygen-containing functional groups in the graphene oxide with isocyanate groups in the prepolymer to obtain a graphene oxide covalently-bonded polyurethane prepolymer; the mass ratio of the isocyanate-terminated polyurethane prepolymer to the graphene oxide dispersion liquid is 1: 3;
s3, stirring and mixing the graphene oxide covalently-bonded polyurethane prepolymer obtained in the step S2 with resol, a surfactant, a foaming agent and a curing agent, pouring the mixture into a mold, closing the mold to foam, curing and curing to obtain graphene oxide reinforced modified phenolic foam plastic; the curing agent is organic acid; the organic acid is phenolsulfonic acid; the surfactant is polyethylene glycol; the foaming agent is chlorodifluoroethane; the mass ratio of the polyurethane prepolymer to the resol resin to the surfactant to the foaming agent to the curing agent is 30:25:12:10: 8; the curing temperature is 160 ℃.
Example 6
A preparation method of graphene oxide reinforced modified phenolic foam plastic comprises the following steps:
s1, mixing isophorone diisocyanate, polyethylene glycol, a solvent and a catalyst according to a mass ratio of 1:5:1:0.05, heating to 60-80 ℃, and reacting to obtain an isocyanate-terminated polyurethane prepolymer; the solvent is acetone, and the catalyst is dibutyltin dilaurate;
s2, mixing the isocyanate group-terminated polyurethane prepolymer obtained in the step S1 with the graphene oxide dispersion liquid, and reacting oxygen-containing functional groups in the graphene oxide with isocyanate groups in the prepolymer to obtain a graphene oxide covalently-bonded polyurethane prepolymer; the mass ratio of the isocyanate-terminated polyurethane prepolymer to the graphene oxide dispersion liquid is 1: 3;
s3, stirring and mixing the graphene oxide covalently-bonded polyurethane prepolymer obtained in the step S2 with resol, a surfactant, a foaming agent and a curing agent, pouring the mixture into a mold, closing the mold to foam, curing and curing to obtain graphene oxide reinforced modified phenolic foam plastic; the curing agent is organic acid; the organic acid is p-toluenesulfonic acid; the surfactant is polyethylene glycol; the foaming agent is cyclopentane; the mass ratio of the polyurethane prepolymer to the resol resin to the surfactant to the foaming agent to the curing agent is 24:24:12:9: 11; the curing temperature is 140 ℃.
Comparative example 1
A preparation method of graphene oxide reinforced modified phenolic foam plastic comprises the following steps:
mixing graphene oxide with resol, a surfactant, a foaming agent and a curing agent, stirring, pouring into a mold, closing the mold, foaming, curing and curing to obtain graphene oxide reinforced modified phenolic foam plastic; the curing agent is organic acid; the organic acid is p-toluenesulfonic acid; the surfactant is polyethylene glycol; the foaming agent is cyclopentane; the mass ratio of the graphene oxide to the resol resin to the surfactant to the foaming agent to the curing agent is 24:24:12:9: 11; the curing temperature is 140 ℃.
Comparative example 2
Stirring and mixing the step A phenolic resin, the surfactant, the foaming agent and the curing agent, pouring the mixture into a mold, closing the mold, foaming, curing and curing to obtain the graphene oxide reinforced modified phenolic foamed plastic; the curing agent is organic acid; the organic acid is p-toluenesulfonic acid; the surfactant is polyethylene glycol; the foaming agent is cyclopentane; the mass ratio of the resol to the surfactant to the foaming agent to the curing agent is 24:12:9: 11; the curing temperature is 140 ℃.
The performance of the phenolic foam prepared in the above examples and comparative examples was tested as follows:
TABLE 1 results of performance test of phenolic foam prepared in examples of the present invention and comparative examples
Claims (9)
1. The preparation method of the graphene oxide reinforced and modified phenolic foam plastic is characterized by comprising the following steps:
s1, mixing isophorone diisocyanate and polyethylene glycol, adding a solvent and a catalyst, heating to 60-80 ℃, and reacting to obtain an isocyanate group-terminated polyurethane prepolymer;
s2, mixing the isocyanate group-terminated polyurethane prepolymer obtained in the step S1 with the graphene oxide dispersion liquid, and reacting oxygen-containing functional groups in the graphene oxide with isocyanate groups in the prepolymer to obtain a graphene oxide covalently-bonded polyurethane prepolymer;
and S3, stirring and mixing the graphene oxide covalently-bonded polyurethane prepolymer obtained in the step S2 with resol, a surfactant, a foaming agent and a curing agent, pouring the mixture into a mold, closing the mold to foam, curing and curing to obtain the graphene oxide reinforced and modified phenolic foam plastic.
2. The method for preparing graphene oxide reinforced and modified phenolic foam plastic according to claim 1, wherein in the step S1, the mass ratio of isophorone diisocyanate, polyethylene glycol, solvent and catalyst is 1-3:3-5:1-2:0.05, the solvent is acetone, and the catalyst is at least one of dibutyltin dilaurate and triphenylbismuth.
3. The method for preparing graphene oxide reinforced and modified phenolic foam plastic according to claim 2, wherein the mass ratio of the isocyanate group-terminated polyurethane prepolymer to the graphene oxide dispersion liquid in the step S2 is 1: 3.
4. The method for preparing graphene oxide reinforced and modified phenolic foam plastic according to claim 1, wherein the curing agent in the step S3 is an organic acid; the organic acid is at least one of p-toluenesulfonic acid, phenolsulfonic acid, benzenesulfonic acid and xylenesulfonic acid.
5. The method for preparing graphene oxide reinforced and modified phenolic foam plastic according to claim 1, wherein the surfactant in the step S3 is polyethylene glycol.
6. The method for preparing graphene oxide reinforced and modified phenolic foam plastic according to claim 1, wherein the foaming agent in the step S3 is at least one of n-pentane, isopentane, n-hexane, cyclopentane, petroleum ether, isopropyl chloride and chlorodifluoroethane.
7. The preparation method of the graphene oxide reinforced and modified phenolic foam plastic as claimed in claim 1, wherein the mass ratio of the polyurethane prepolymer, the resol, the surfactant, the foaming agent and the curing agent in the step S3 is 15-40: 20-30: 10-15: 5-15: 6-12.
8. The method for preparing the graphene oxide reinforced and modified phenolic foam plastic according to claim 1, wherein the curing temperature in the step S3 is 100-180 ℃.
9. The graphene oxide reinforced and modified phenolic foam plastic prepared by the preparation method according to any one of claims 1 to 8.
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| CN201810842244.2A Withdrawn CN111286071A (en) | 2018-07-27 | 2018-07-27 | Graphene oxide reinforced modified phenolic foam plastic and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112223861A (en) * | 2020-10-12 | 2021-01-15 | 广东华瑞环保材料有限公司 | Energy-saving silicon phenol fireproof insulation board |
| CN112297321A (en) * | 2020-10-12 | 2021-02-02 | 广东华瑞环保材料有限公司 | Insulation board foaming equipment, insulation board production line and production process |
| CN114752180A (en) * | 2022-05-13 | 2022-07-15 | 哈尔滨工业大学 | Shape memory phenolic foam and preparation method thereof |
| CN115772328A (en) * | 2022-12-09 | 2023-03-10 | 陕西科技大学 | High-dielectric heat-conducting composite material, and preparation method and application thereof |
-
2018
- 2018-07-27 CN CN201810842244.2A patent/CN111286071A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112223861A (en) * | 2020-10-12 | 2021-01-15 | 广东华瑞环保材料有限公司 | Energy-saving silicon phenol fireproof insulation board |
| CN112297321A (en) * | 2020-10-12 | 2021-02-02 | 广东华瑞环保材料有限公司 | Insulation board foaming equipment, insulation board production line and production process |
| CN112223861B (en) * | 2020-10-12 | 2021-06-22 | 广东华瑞环保材料有限公司 | Energy-saving silicon phenol fireproof insulation board |
| CN114752180A (en) * | 2022-05-13 | 2022-07-15 | 哈尔滨工业大学 | Shape memory phenolic foam and preparation method thereof |
| CN115772328A (en) * | 2022-12-09 | 2023-03-10 | 陕西科技大学 | High-dielectric heat-conducting composite material, and preparation method and application thereof |
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Application publication date: 20200616 |