CN113861700A - Hybrid material flame retardant, flame-retardant epoxy resin and preparation methods of hybrid material flame retardant and flame-retardant epoxy resin - Google Patents
Hybrid material flame retardant, flame-retardant epoxy resin and preparation methods of hybrid material flame retardant and flame-retardant epoxy resin Download PDFInfo
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- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 9
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- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a hybrid material flame retardant, flame-retardant epoxy resin and preparation methods of the hybrid material flame retardant and the flame-retardant epoxy resin. The hybrid material flame retardant is a hybrid material flame retardant of an ionic liquid modified Graphene Oxide (GO) loaded molybdenum-based metal-organic framework material (Mo-MOF), and can be applied to EP flame retardance. The hybrid material flame retardant is prepared by the following method: firstly, graphene oxide is prepared through a Hummer's method, then Mo-MOF grows on the surface of GO through a hydrothermal method, and finally, the preparation of the ionic liquid modified graphene oxide loaded Mo-MOF is completed through a solid grinding method. The invention adopts a simpler method to combine the ionic liquid and the Mo-MOF and obtains good flame retardant effect, thereby providing a new idea for the development of novel MOF materials.
Description
Technical Field
The invention relates to a flame retardant, in particular to a hybrid material flame retardant, flame-retardant epoxy resin and preparation methods thereof.
Background
Epoxy resin (EP) is a thermosetting resin having various excellent properties such as mechanical properties, adhesion, and chemical resistance. Therefore, epoxy resins are widely used in the fields of electronic and electric appliances, coatings, adhesives and the like. However, the flammability of epoxy resins and the large amount of smoke released during combustion limit their use in construction, aerospace, and other applications. Therefore, the fire-proof performance of the epoxy resin is improved, and the fire risk is reduced, so that the epoxy resin has important practical significance.
The flame retardant is added into EP, which is one of the main ways for improving the flame retardant property of EP, and the flame retardant mainly comprises compounds containing P, N, Si and other elements, and the flame retardant can endow EP with certain flame retardant property and reduce the fire risk of EP. However, the additive flame retardant is often low in flame retardant efficiency, especially promotes the generation of smoke during the combustion of EP to a certain extent, and in addition, the compatibility of the substances with the matrix is poor, so that the mechanical and processing properties of the material are deteriorated to different extents. Therefore, the development of an efficient flame-retardant smoke suppressor for EP and the construction of a flame-retardant system with excellent compatibility are still the focus of flame-retardant research for EP.
Disclosure of Invention
The invention aims to provide a hybrid material flame retardant, flame-retardant epoxy resin and preparation methods of the flame retardant and the flame-retardant epoxy resin, so as to improve the flame retardant property of the epoxy resin.
The invention is realized by the following steps: the hybrid material flame retardant provided by the invention is a hybrid material flame retardant of Graphene Oxide (GO) loaded Mo-MOF (molybdenum-Organic framework) by Ionic Liquid (IL, such as [ BMIM ] BF4), and is prepared by the following method: firstly, graphene oxide is prepared through a Hummer's method, then Mo-MOF grows on the surface of GO through a hydrothermal method, and finally, the preparation of the ionic liquid modified graphene oxide loaded Mo-MOF is completed through a simple solid-phase grinding method.
The specific preparation method of the hybrid material flame retardant comprises the following steps:
(a) graphene Oxide (GO) was prepared by Hummer's method. The process is as follows: weighing 1 part of graphite powder and 2.5 parts of sodium nitrate in a beaker, slowly adding concentrated sulfuric acid under the ice bath condition, stirring and dissolving for 1 hour until the mixture is brown yellow, and then slowly adding 4 parts of potassium permanganate. The solution was warmed to 30 ℃ and stirred for 2h before deionized water was added. Heating the solution to 92 ℃, stirring for 1h, then cooling to 30 ℃, adding 10mL hydrogen peroxide, stirring for 2h under the condition of constant speed, then washing for several times by deionized water and 5% hydrochloric acid until BaCl2No white precipitate was detected. And finally, centrifugally washing the graphene oxide to be neutral by using deionized water, and carrying out vacuum drying for 24 hours to obtain graphene oxide which is recorded as GO for later use.
(b) Preparing 0.00012g/mL GO aqueous solution in a three-neck flask, carrying out ultrasonic treatment for 20 minutes until the GO is uniformly dispersed, and then adding MoO3And imidazole were added to the above solution at a mass ratio of 2.168:1, stirred at room temperature for ten minutes until dispersed uniformly, then the flask was transferred to a 75 ℃ oil bath, stirred at 400rpm/min and condensed back overnight. Finally, the collected sample was washed five times with deionized water and dried in an oven at 50 ℃ for 12h, and was designated as GM.
(c) And (3) completing the preparation of the ionic liquid modified graphene oxide loaded Mo-MOF by using a simple solid-phase grinding method. Firstly, weighing the graphene oxide loaded Mo-MOF and the ionic liquid with the mass ratio of 1:0.15, grinding the mixture in an agate mortar in the same direction for twenty minutes until the mixture is fine and uniform, and finally drying the mixture at 60 ℃ for 6 hours, and marking the mixture as GMB for later use.
The ionic liquid modified graphene oxide loaded Mo-MOF hybrid material flame retardant disclosed by the invention can be applied to preparation of flame retardant materials. The flame retardant material may be, for example, a flame retardant epoxy resin.
When the hybrid material flame retardant is adopted to prepare the flame-retardant epoxy resin, the preparation method comprises the following steps: adding a hybrid material flame retardant into epoxy resin; and adding m-phenylenediamine after uniformly stirring, heating and curing after uniformly stirring, and cooling to obtain the flame-retardant epoxy resin. Specifically, 100 parts (by weight, the same below) of epoxy resin is placed in a filter flask, heated and stirred for 20min at the temperature of 60 ℃ and the rotating speed of 180rpm, then the hybrid material flame retardant is added, the mass ratio of the hybrid material flame retardant to the epoxy resin is 1-4: 100, the mixture is stirred for 20min, 10-14 parts of m-phenylenediamine is added, and the mixture is stirred for 20 min; taking out, pouring into a mold, standing at 60 deg.C for 20min in an oven with vacuum degree of 0.05MPa, transferring into an oven with 80 deg.C, heating for 120min, adjusting temperature to 150 deg.C, and heating and curing for 220 min; and cooling to room temperature, and taking out from the mold to obtain the flame-retardant epoxy resin.
The ionic liquid modified graphene oxide loaded Mo-MOF hybrid material flame retardant prepared by the invention can be used as a flame retardant which can be independently used to be added into a material needing to improve the flame retardant performance to prepare a corresponding flame retardant material, and when the flame retardant material is added into epoxy resin, the flame retardant effect of the obtained flame retardant epoxy resin is greatly improved, so that the flame retardant material has a wide industrial application prospect.
Drawings
FIG. 1 is a Thermogravimetric (TG) plot of Mo-MOF, GM and GMB prepared in example 1.
FIG. 2 is SEM and TEM images of a sample, where (a) is a TEM image of GO; (b) is an SEM image of Mo-MOF; (c) SEM picture of GM; (d) is a TEM image of GMB.
FIG. 3 is a graph of the Heat Release Rate (HRR) in cone calorimetry for the epoxy resin prepared in comparative example 1.
FIG. 4 is a graph of the Heat Release Rate (HRR) in cone calorimetry for the epoxy composite prepared in example 2.
FIG. 5 is a graph of the Heat Release Rate (HRR) in cone calorimetry for the epoxy composite prepared in example 3.
FIG. 6 is a graph of the Heat Release Rate (HRR) in cone calorimetry for the epoxy composite prepared in example 4.
Detailed Description
The invention is further illustrated by the following examples, which are given by way of illustration only and are not intended to limit the scope of the invention in any way.
The procedures and methods not described in detail in the examples of the present invention are conventional methods well known in the art, and the reagents used in the examples are all analytically or chemically pure and are either commercially available or prepared by methods well known to those of ordinary skill in the art. The following examples all achieve the objects of the present invention.
Example 1:
(a) graphene Oxide (GO) was prepared by Hummer's method. The process is as follows: weighing 1 part of graphite powder and 2.5 parts of sodium nitrate in a beaker, slowly adding concentrated sulfuric acid under the ice bath condition, stirring and dissolving for 1 hour until the mixture is brown yellow, and then slowly adding 4 parts of potassium permanganate. The solution was warmed to 30 ℃ and stirred for 2h before deionized water was added. Heating the solution to 92 ℃, stirring for 1h, then cooling to 30 ℃, adding 10mL hydrogen peroxide, stirring for 2h under the condition of constant speed, then washing for several times by deionized water and 5% hydrochloric acid until BaCl2No white precipitate was detected. And finally, centrifugally washing the graphene oxide to be neutral by using deionized water, and carrying out vacuum drying for 24 hours to obtain graphene oxide which is recorded as GO for later use.
(b) Preparing 0.00012g/mL GO aqueous solution in a three-neck flask, carrying out ultrasonic treatment for 20 minutes until the GO is uniformly dispersed, and then adding MoO3And imidazole were added to the above aqueous GO solution in a mass ratio of 2.168:1, stirred at room temperature for ten minutes until well dispersed, then the flask was transferred to a 75 ℃ oil bath, stirred at 400rpm/min and condensed back to reflux overnight. Finally, the collected sample was washed five times with deionized water and dried in an oven at 50 ℃ for 12h, and was designated as GM.
A similar procedure produces pure Mo-MOF without the addition of GO.
(c) The preparation of the ionic liquid ([ BMIM ] BF4) modified graphene oxide loaded Mo-MOF is completed by using a simple solid phase grinding method. Firstly, weighing the graphene oxide loaded Mo-MOF and the ionic liquid with the mass ratio of 1:0.15, grinding the mixture in an agate mortar in the same direction for twenty minutes until the mixture is fine and uniform, and finally drying the mixture at 60 ℃ for 6 hours, and marking the mixture as GMB for later use.
Mo-MOF, GM and GMB were measured by using STA449C model thermogravimetry, T is5％The results are shown in fig. 1 and table 1, which are temperatures corresponding to 5% weight loss of the sample.
Table 1: comparison of the thermal stability of the products of the invention
As can be seen from Table 1, the initial decomposition temperature of the hybrid material is 238.6 ℃ and the hybrid material can be used as a flame retardant in EP.
The test was carried out using electron scanning electron microscopy (SEM, JSM, JEOL Ltd., Japan) and transmission electron microscopy analysis (TEM-EDX, FEI Tecnai G2F 20 Corporation, USA). The resulting correlation data are shown in fig. 2.
From the transmission electron microscope image of GO in fig. 2, it can be seen that GO is lamellar and has a wrinkle phenomenon, which indicates that GO has been successfully exfoliated. FIG. 2 (b) is an SEM image of Mo-MOF, which has a rod-like morphology, a length of about 10 μm, a width of about 1 μm, and a smooth surface. FIG. 2 (c) is an SEM image of GO-supported Mo-MOF, from which it can be seen that rod-like Mo-MOF grows on the surface and in the folds of GO and interweaves with each other, which shows that GO provides a platform for the growth of MOF, and Mo-MOF is successfully supported. FIG. 2 (d) is a TEM image of the GMB, from which it can be seen that rod-like Mo-MOF materials are grown on the GO sheet and both surfaces are coated with ionic liquid, and the GMB has a staggered overlap phenomenon due to the adhesion of the ionic liquid itself, which causes the MOF particles to stick together.
Comparative example 1:
weighing 120g of epoxy resin, placing the epoxy resin in a clean filter flask, heating and stirring the epoxy resin for 20min at 60 ℃ and 180rpm, then adding 13.2g of curing agent m-phenylenediamine, and stirring the epoxy resin for 20min to ensure that the m-phenylenediamine is uniformly dispersed; pouring the mold, placing in an oven with a vacuum degree of 0.05MPa at 60 deg.C for 20min, transferring into an oven with a temperature of 80 deg.C, heating for 120min, adjusting temperature to 150 deg.C, and heating and curing for 220 min. After cooling to room temperature, the specimens were removed to give EP material.
Example 2:
weighing 120g of epoxy resin, placing the epoxy resin in a clean filter flask, heating and stirring the epoxy resin for 20min at 60 ℃ and 180rpm, then adding 3.6g of the Mo-MOF flame retardant prepared in the example 1, then adding 13.2g of m-phenylenediamine, and stirring the epoxy resin for 20min to ensure that the m-phenylenediamine serving as a curing agent is uniformly dispersed; pouring into a mold, standing at 60 deg.C for 20min in an oven with vacuum degree of 0.05MPa, transferring into an oven with temperature of 80 deg.C, heating for 120min, adjusting temperature to 150 deg.C, and heating and curing for 220 min. And cooling to room temperature, and taking out the sample strip from the mold to obtain the flame-retardant EP material.
Example 3:
corresponding flame retardant EP materials were prepared by adding 3.6g of the GM flame retardant prepared in example 1, respectively, to an epoxy resin (instead of the Mo-MOF flame retardant in example 2) according to the process conditions of example 2.
Example 4:
corresponding flame-retardant EP materials were prepared by adding 3.6g of the GMB flame retardant prepared in example 1, respectively, to an epoxy resin (instead of the Mo-MOF flame retardant in example 2) according to the process conditions of example 2.
The experimental method comprises the following steps:
limiting Oxygen Index (LOI): the minimum oxygen percentage required to maintain combustion of the sample material in the nitrogen-oxygen mixture is used to characterize the flame retardant effect of the flame retardant. The sample size was 140mm by 6mm by 3mm as measured by ASTM D2863-2000 using HC-2 oxygen index apparatus (Nanjing Jiangning Analyzer Co.).
CONE Calorimetry (CONE): the cone calorimetric test was carried out using an icone plus (FTT Co., UK) with a sample size of 100mm X3 mm and an irradiation power of 50Kw/m2。
The detection results are as follows:
table 2: effect of the inventive products on the flame retardancy of flame-retardant EP
As can be seen from Table 2, the limiting oxygen index of the pure epoxy resin is 23.4%, and it is a flammable product. The oxygen index increased to 26.4%, 26.7% and 27.6% respectively after addition of the Mo-MOF, GM and GMB flame retardants to the epoxy resin.
As can be seen from the graphs of Heat Release Rate (HRR) in cone calorimetry of the epoxy resin composites prepared in comparative example 1 and examples 2, 3 and 4 shown in FIGS. 3 to 6, the heat release rate of the epoxy resin is shown inThe peak value of the heat release rate (PHRR) reaches 1207.2Kw/m2Higher heat release rate; from FIGS. 4, 5 and 6, it is evident that PHRR of the flame retardant epoxy resin prepared by the examples with Mo-MOF, GM and GMB flame retardant is reduced to 1030.1, 677.2 and 578.3Kw/m respectively2The reduction is 14.67%, 43.90% and 52.09% respectively compared with that of epoxy resin.
Claims (10)
1. A hybrid material flame retardant is characterized in that the flame retardant is formed by modifying graphene oxide loaded Mo-MOF by ionic liquid.
2. The preparation method of the hybrid material flame retardant is characterized by comprising the following steps: firstly, graphene oxide is prepared through a Hummer's method, then Mo-MOF grows on the surface of the graphene oxide through a hydrothermal method, and finally the preparation of the ionic liquid modified graphene oxide loaded Mo-MOF is completed through a solid-phase grinding method.
3. The preparation method of the hybrid material flame retardant according to claim 2, which is characterized by comprising the following steps:
(a) graphene oxide was prepared by Hummer's method as follows: weighing 1 part of graphite powder and 2.5 parts of sodium nitrate in a beaker, slowly adding concentrated sulfuric acid under the ice bath condition, stirring and dissolving for 1 hour until the mixture is brown yellow, and then slowly adding 4 parts of potassium permanganate; heating the solution to 30 ℃, stirring for 2 hours, and then adding deionized water; heating the solution to 92 ℃, stirring for 1h, then cooling to 30 ℃, adding 10mL hydrogen peroxide, stirring for 2h under the condition of constant speed, then washing for several times by deionized water and 5% hydrochloric acid until BaCl2Detecting that no white precipitate is generated; finally, centrifugally washing the graphene oxide to be neutral by using deionized water, and carrying out vacuum drying for 24 hours to obtain graphene oxide;
(b) preparing 0.00012g/mL graphene oxide aqueous solution in a three-neck flask, carrying out ultrasonic treatment for 20 minutes until the graphene oxide aqueous solution is uniformly dispersed, and then carrying out MoO treatment3And imidazole were added to the above graphene oxide aqueous solution at a mass ratio of 2.168:1, stirred at room temperature for 10 minutes until dispersed uniformly, then the flask was transferred to a 75 ℃ oil bath,stirring at 400rpm/min and reflux condensing overnight; finally, collecting a sample, washing the sample for five times by using deionized water, and drying the sample in a 50 ℃ oven for 12 hours;
(c) the preparation of the ionic liquid modified graphene oxide loaded Mo-MOF is completed by using a solid phase grinding method, and the process is as follows: firstly, weighing the graphene oxide loaded Mo-MOF and the ionic liquid with the mass ratio of 1:0.15, grinding the mixture in an agate mortar in the same direction for 20 minutes until the mixture is fine and uniform, and finally drying the mixture at 60 ℃ for 6 hours to obtain the hybrid material flame retardant.
4. Use of a hybrid material flame retardant according to any one of claims 1 to 3 for the preparation of flame retardant materials.
5. The use of the hybrid material flame retardant according to claim 4 in the preparation of flame retardant materials, wherein the flame retardant materials are flame retardant epoxy resins.
6. A flame-retardant epoxy resin, characterized in that the hybrid material flame retardant of any one of claims 1 to 3 is added to an epoxy resin.
7. The flame-retardant epoxy resin as claimed in claim 6, wherein the mass ratio of the hybrid material flame retardant to the epoxy resin is 1-4: 100.
8. The preparation method of the flame-retardant epoxy resin is characterized by comprising the following steps of:
(a) heating and stirring the epoxy resin, then adding the hybrid material flame retardant of any one of claims 1-3, and uniformly stirring; the mass ratio of the hybrid material flame retardant to the epoxy resin is 1-4: 100;
(b) and adding m-phenylenediamine, wherein the mass ratio of the m-phenylenediamine to the epoxy resin is 10-14: 100, uniformly stirring, heating for curing, and cooling to obtain the flame-retardant epoxy resin.
9. The method for preparing the flame-retardant epoxy resin according to claim 8, wherein the step a is specifically as follows: placing the epoxy resin into a filter flask, heating and stirring for 20min under the conditions that the temperature is 60 ℃ and the rotating speed is 180rpm, then adding 3 wt% of the hybrid material flame retardant, and stirring for 20 min.
10. The method for preparing the flame-retardant epoxy resin according to claim 8, wherein the step b is specifically as follows: adding 10-14 parts of m-phenylenediamine, and stirring for 20 min; taking out, pouring into a mold, standing at 60 deg.C for 20min in an oven with vacuum degree of 0.05MPa, transferring into an oven with 80 deg.C, heating for 120min, adjusting temperature to 150 deg.C, and heating and curing for 220 min; and cooling to room temperature, and taking out from the mold to obtain the flame-retardant epoxy resin.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116041719A (en) * | 2022-12-23 | 2023-05-02 | 北京航天新立科技有限公司 | Halogen-free flame retardant, flame-retardant modified epoxy resin and preparation methods thereof |
| WO2023178453A1 (en) * | 2022-03-25 | 2023-09-28 | Zentek Ltd. | Hybridized graphene family/metallic organic frameworks nanocomposite composition, and use as additive for intumescent coatings |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104448822A (en) * | 2015-01-04 | 2015-03-25 | 苏州大学 | Modified cyanate ester resin and preparation method thereof |
| CN104910447A (en) * | 2015-05-28 | 2015-09-16 | 沈阳化工大学 | Flame-retardant rubber |
| US20150274927A1 (en) * | 2014-02-20 | 2015-10-01 | Rutgers, The State University Of New Jersey | Inorganic Ionomers Made From Minerals |
| CN112430429A (en) * | 2020-11-23 | 2021-03-02 | 广东电网有限责任公司电力科学研究院 | Metal organic framework material, preparation method thereof and coating |
| CN112592492A (en) * | 2020-12-31 | 2021-04-02 | 河北大学 | Flame retardant, flame-retardant epoxy resin and preparation methods of flame retardant and flame-retardant epoxy resin |
-
2021
- 2021-09-10 CN CN202111060901.6A patent/CN113861700A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150274927A1 (en) * | 2014-02-20 | 2015-10-01 | Rutgers, The State University Of New Jersey | Inorganic Ionomers Made From Minerals |
| CN104448822A (en) * | 2015-01-04 | 2015-03-25 | 苏州大学 | Modified cyanate ester resin and preparation method thereof |
| CN104910447A (en) * | 2015-05-28 | 2015-09-16 | 沈阳化工大学 | Flame-retardant rubber |
| CN112430429A (en) * | 2020-11-23 | 2021-03-02 | 广东电网有限责任公司电力科学研究院 | Metal organic framework material, preparation method thereof and coating |
| CN112592492A (en) * | 2020-12-31 | 2021-04-02 | 河北大学 | Flame retardant, flame-retardant epoxy resin and preparation methods of flame retardant and flame-retardant epoxy resin |
Non-Patent Citations (4)
| Title |
|---|
| XU, BAOLING等: ""Zeolitic imidazolate frameworks-8 modified graphene as a green flame retardant for reducing the fire risk of epoxy resin"", 《POLYMERS FOR ADVANCED TECHNOLOGIES》 * |
| ZHANG, FENG等: ""A Mo-based metal-organic framework toward improving flame retardancy and smoke suppression of epoxy resin"", 《POLYMERS FOR ADVANCED TECHNOLOGIES》 * |
| 张凯伦等: ""石墨烯负载离子液体的制备及其与六苯氧基环三磷腈协效阻燃环氧树脂的性能研究"", 《中国科学:化学》 * |
| 罗春华等: "《普通高等教育规划教材 材料制备与性能 测试实验》", 31 July 2019, 机械工业出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023178453A1 (en) * | 2022-03-25 | 2023-09-28 | Zentek Ltd. | Hybridized graphene family/metallic organic frameworks nanocomposite composition, and use as additive for intumescent coatings |
| CN116041719A (en) * | 2022-12-23 | 2023-05-02 | 北京航天新立科技有限公司 | Halogen-free flame retardant, flame-retardant modified epoxy resin and preparation methods thereof |
| CN116041719B (en) * | 2022-12-23 | 2024-04-30 | 北京航天新立科技有限公司 | Halogen-free flame retardant, flame-retardant modified epoxy resin and preparation methods thereof |
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