CN113336920A - Intrinsic flame-retardant epoxy resin and preparation method thereof - Google Patents
Intrinsic flame-retardant epoxy resin and preparation method thereof Download PDFInfo
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- CN113336920A CN113336920A CN202110703387.7A CN202110703387A CN113336920A CN 113336920 A CN113336920 A CN 113336920A CN 202110703387 A CN202110703387 A CN 202110703387A CN 113336920 A CN113336920 A CN 113336920A
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1488—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing phosphorus
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5033—Amines aromatic
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- Polymers & Plastics (AREA)
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- General Chemical & Material Sciences (AREA)
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Abstract
The invention discloses an intrinsic flame-retardant epoxy resin and a preparation method thereof. The preparation method comprises the steps of reacting epoxy resin with a reactive flame retardant for a period of time at a certain temperature; then adding a hardening agent, and stirring to obtain a uniform solution; then vacuumizing the epoxy solution to remove bubbles, and pouring the epoxy solution into a preheated mold for thermosetting; and naturally cooling to room temperature after curing is finished to obtain the intrinsic flame-retardant epoxy resin material. The intrinsic flame-retardant epoxy resin prepared by the method has excellent flame-retardant property: when the addition amount of the reactive flame retardant in the epoxy resin is 2.5%, the oxygen index can reach 31.6%, and the vertical combustion grade can pass UL-94V-0 grade when the addition amount is 5%, so that the flame retardant property is obviously improved compared with that of pure epoxy resin.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to an intrinsic flame-retardant epoxy resin and a preparation method thereof.
Background
Epoxy resin (EP) is widely used in daily life, has a small shrinkage rate in a curing reaction process, has the characteristics of good electrical insulation, heat resistance, corrosion resistance and the like, is widely used in high and new fields of aerospace, transportation and the like, becomes one of important thermosetting polymer materials and industrially indispensable materials, but belongs to a flammable material, is rapidly combusted after being ignited, releases a large amount of heat, and has great threat to the safety of life and property of people, so that the application and development of the epoxy resin are greatly limited, and the improvement of the flame retardant property of the epoxy resin is very necessary.
At present, the flame retardants for improving the flame retardant performance of epoxy resins can be classified into several categories, including halogen compounds, intumescent compounds, inorganic and nano compounds, synergistic compounds, and the like. The most studied flame retardant with the synergistic compound is the flame retardant with the synergy of phosphorus and nitrogen, which mainly means that a compound system is formed by a nitrogen-containing flame retardant and a phosphorus-containing flame retardant, the synergistic effect is exerted, the flame retardant effect of the flame retardant is generally better than that of the flame retardant with the nitrogen-containing flame retardant or the phosphorus-containing flame retardant which is singly used, because the phosphorus-containing flame retardant mainly exerts a condensed phase flame retardant mechanism in epoxy resin, and is promoted to form carbon by acid catalysis, a carbon layer is formed on the surface, so that the heat insulation and oxygen insulation effects are realized, but most of the phosphorus-containing flame retardant is easy to volatilize in the form of phosphorus-containing oxide in the pyrolysis process, the flame retardant effect is greatly reduced, after the nitrogen-containing flame retardant is added, the stability of the phosphorus-containing flame retardant and the phosphorylation rate of a polymer can be improved, and the nitrogen-containing compound can release inert gases such as nitrogen or ammonia gas and the like in the combustion process, so that the concentration of combustible gases generated in the combustion process can be diluted, thereby exerting a gas-phase flame-retardant mechanism. Based on the method, the phosphorus-containing triazole intrinsic flame retardant is synthesized by using the diphenylphosphinic chloride and the 3-amino-1, 2, 4-triazole as raw materials, is applied to the epoxy resin, and effectively improves the flame retardant property of the epoxy resin.
Disclosure of Invention
The invention aims to solve the problem of flammability of epoxy resin and provides an intrinsic flame-retardant epoxy resin and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of intrinsic flame-retardant epoxy resin comprises the following steps: reacting epoxy resin and a reactive flame retardant at a certain temperature for a period of time; then adding a hardening agent, and stirring until a uniform epoxy solution is obtained; vacuumizing the epoxy solution to remove bubbles, and pouring the epoxy solution into a preheated mold for thermosetting; and naturally cooling to room temperature after curing, and demolding to obtain the intrinsic flame-retardant epoxy resin material.
The reaction type flame retardant in the above steps is a phosphorous triazole compound, and the chemical structural formula of the reaction type flame retardant is as follows:
the epoxy resin is bisphenol A type epoxy resin.
The hardener is 4, 4' -diaminodiphenylmethane.
The weight part ratio of the reactive flame retardant to the epoxy resin is 2.5-10: 100.
the weight part ratio of the hardening agent to the epoxy resin is 20-25: 100.
the reaction temperature of the epoxy resin and the reactive flame retardant is 100-140 ℃, and the reaction time is 10-20 minutes.
When the addition amount of the reactive flame retardant is 2.5%, the oxygen index of the intrinsic flame retardant epoxy resin prepared by the steps can reach 31.6%, and the vertical burning grade can pass UL-94V-0 grade when the addition amount is 5%.
Compared with the prior art, the invention has the following advantages:
(1) the intrinsic flame retardant used in the intrinsic flame retardant epoxy resin provided by the invention is a phosphorus-containing triazole intrinsic flame retardant synthesized by adopting diphenylphosphine chloride and 3-amino-1, 2, 4-triazole as raw materials, contains phosphorus-nitrogen flame retardant elements and has a flame retardant synergistic effect.
(2) The phosphorous triazole compound used in the intrinsic flame-retardant epoxy resin provided by the invention has good compatibility with an epoxy matrix, is a reactive flame retardant, has high-efficiency flame-retardant property for the epoxy resin, and can pass UL-94V-0 level when the vertical combustion level is 5%.
(3) The intrinsic flame-retardant epoxy resin provided by the invention has the characteristics of simple preparation method, high efficiency, no halogen contained in the flame retardant, no toxic gas generated during combustion, environmental friendliness and high efficiency.
Detailed Description
The intrinsic flame retardant epoxy resin and the preparation method thereof provided by the present invention are specifically described by the following examples, but the embodiments of the present invention are not limited thereto, and the examples should not be construed as limiting the present invention.
The synthesis method of the intrinsic flame retardant containing the phosphorus triazole compound used in the following examples is as follows:
adding a certain amount of 3-amino-1, 2, 4-triazole and acetonitrile into a three-neck flask provided with a thermometer and a mechanical stirrer, after the raw materials are uniformly mixed, adding an acid-binding agent, after the raw materials are completely dissolved, dropwise adding an acetonitrile solution of diphenyl phosphoryl chloride into the three-neck flask at normal temperature, stirring while dropwise adding, after dropwise adding, heating and refluxing for a period of time, cooling to room temperature after reaction is completed, carrying out suction filtration, taking a filter cake, washing for 3 times with deionized water, washing for 1 time with absolute ethyl alcohol, finally drying in a drying oven at 70 ℃ for 12 hours, and drying in a vacuum drying oven at 60 ℃ for 5 hours to finally obtain the intrinsic flame retardant, namely the phosphorus-containing triazole compound.
Example 1
Reacting 100 parts by weight of epoxy resin and 2.5 parts by weight of phosphorus-containing triazole compound at 100 ℃ for 20 minutes; then adding 25 parts by weight of 4, 4' -diaminodiphenylmethane, and stirring to obtain a uniform epoxy solution; vacuumizing the epoxy solution to remove bubbles, and pouring the epoxy solution into a preheated mold for thermosetting; and naturally cooling to room temperature after curing, and demolding to obtain the intrinsic flame-retardant epoxy resin material.
The prepared epoxy resin sample specimens were subjected to a limiting oxygen index test and a vertical burning test. The dimension of a limit oxygen index test sample strip is 120mm multiplied by 6mm multiplied by 3.2 mm; the vertical burning sample bar size is 130 mm. times.13 mm. times.3.2 mm. The test results are shown in table 1.
Example 2
Reacting 100 parts by weight of epoxy resin and 2.5 parts by weight of phosphorus-containing triazole compound at 120 ℃ for 15 minutes; then adding 25 parts by weight of 4, 4' -diaminodiphenylmethane, and stirring to obtain a uniform epoxy solution; vacuumizing the epoxy solution to remove bubbles, and pouring the epoxy solution into a preheated mold for thermosetting; and naturally cooling to room temperature after curing, and demolding to obtain the intrinsic flame-retardant epoxy resin material.
The prepared epoxy resin sample specimens were subjected to a limiting oxygen index test and a vertical burning test. The dimension of a limit oxygen index test sample strip is 120mm multiplied by 6mm multiplied by 3.2 mm; the vertical burning sample bar size is 130 mm. times.13 mm. times.3.2 mm. The test results are shown in table 1.
Example 3
Reacting 100 parts by weight of epoxy resin and 2.5 parts by weight of phosphorus-containing triazole compound at 140 ℃ for 10 minutes; then adding 25 parts by weight of 4, 4' -diaminodiphenylmethane, and stirring to obtain a uniform epoxy solution; vacuumizing the epoxy solution to remove bubbles, and pouring the epoxy solution into a preheated mold for thermosetting; and naturally cooling to room temperature after curing, and demolding to obtain the intrinsic flame-retardant epoxy resin material.
The prepared epoxy resin sample specimens were subjected to a limiting oxygen index test and a vertical burning test. The dimension of a limit oxygen index test sample strip is 120mm multiplied by 6mm multiplied by 3.2 mm; the vertical burning sample bar size is 130 mm. times.13 mm. times.3.2 mm. The test results are shown in table 1.
Example 4
Reacting 100 parts by weight of epoxy resin and 2.5 parts by weight of phosphorus-containing triazole compound at 140 ℃ for 10 minutes; then adding 22 parts by weight of 4, 4' -diaminodiphenylmethane, and stirring to obtain a uniform epoxy solution; vacuumizing the epoxy solution to remove bubbles, and pouring the epoxy solution into a preheated mold for thermosetting; and naturally cooling to room temperature after curing, and demolding to obtain the intrinsic flame-retardant epoxy resin material.
The prepared epoxy resin sample specimens were subjected to a limiting oxygen index test and a vertical burning test. The dimension of a limit oxygen index test sample strip is 120mm multiplied by 6mm multiplied by 3.2 mm; the vertical burning sample bar size is 130 mm. times.13 mm. times.3.2 mm. The test results are shown in table 1.
Example 5
Reacting 100 parts by weight of epoxy resin and 5 parts by weight of phosphorus-containing triazole compound at 120 ℃ for 18 minutes; then adding 22 parts by weight of 4, 4' -diaminodiphenylmethane, and stirring to obtain a uniform epoxy solution; vacuumizing the epoxy solution to remove bubbles, and pouring the epoxy solution into a preheated mold for thermosetting; and naturally cooling to room temperature after curing, and demolding to obtain the intrinsic flame-retardant epoxy resin material.
The prepared epoxy resin sample specimens were subjected to a limiting oxygen index test and a vertical burning test. The dimension of a limit oxygen index test sample strip is 120mm multiplied by 6mm multiplied by 3.2 mm; the vertical burning sample bar size is 130 mm. times.13 mm. times.3.2 mm. The test results are shown in table 1.
Example 6
Reacting 100 parts by weight of epoxy resin and 5 parts by weight of phosphorus-containing triazole compound at 130 ℃ for 15 minutes; then adding 22 parts by weight of 4, 4' -diaminodiphenylmethane, and stirring to obtain a uniform epoxy solution; vacuumizing the epoxy solution to remove bubbles, and pouring the epoxy solution into a preheated mold for thermosetting; and naturally cooling to room temperature after curing, and demolding to obtain the intrinsic flame-retardant epoxy resin material.
The prepared epoxy resin sample specimens were subjected to a limiting oxygen index test and a vertical burning test. The dimension of a limit oxygen index test sample strip is 120mm multiplied by 6mm multiplied by 3.2 mm; the vertical burning sample bar size is 130 mm. times.13 mm. times.3.2 mm. The test results are shown in table 1.
Example 7
Reacting 100 parts by weight of epoxy resin and 5 parts by weight of phosphorus-containing triazole compound at 140 ℃ for 10 minutes; then adding 22 parts by weight of 4, 4' -diaminodiphenylmethane, and stirring to obtain a uniform epoxy solution; vacuumizing the epoxy solution to remove bubbles, and pouring the epoxy solution into a preheated mold for thermosetting; and naturally cooling to room temperature after curing, and demolding to obtain the intrinsic flame-retardant epoxy resin material.
The prepared epoxy resin sample specimens were subjected to a limiting oxygen index test and a vertical burning test. The dimension of a limit oxygen index test sample strip is 120mm multiplied by 6mm multiplied by 3.2 mm; the vertical burning sample bar size is 130 mm. times.13 mm. times.3.2 mm. The test results are shown in table 1.
Example 8
Reacting 100 parts by weight of epoxy resin and 7.5 parts by weight of phosphorus-containing triazole compound at 130 ℃ for 15 minutes; then adding 20 parts by weight of 4, 4' -diaminodiphenylmethane, and stirring to obtain a uniform epoxy solution; vacuumizing the epoxy solution to remove bubbles, and pouring the epoxy solution into a preheated mold for thermosetting; and naturally cooling to room temperature after curing, and demolding to obtain the intrinsic flame-retardant epoxy resin material.
The prepared epoxy resin sample specimens were subjected to a limiting oxygen index test and a vertical burning test. The dimension of a limit oxygen index test sample strip is 120mm multiplied by 6mm multiplied by 3.2 mm; the vertical burning sample bar size is 130 mm. times.13 mm. times.3.2 mm. The test results are shown in table 1.
Example 9
Reacting 100 parts by weight of epoxy resin and 7.5 parts by weight of phosphorus-containing triazole compound at 140 ℃ for 10 minutes; then adding 20 parts by weight of 4, 4' -diaminodiphenylmethane, and stirring to obtain a uniform epoxy solution; vacuumizing the epoxy solution to remove bubbles, and pouring the epoxy solution into a preheated mold for thermosetting; and naturally cooling to room temperature after curing, and demolding to obtain the intrinsic flame-retardant epoxy resin material.
The prepared epoxy resin sample specimens were subjected to a limiting oxygen index test and a vertical burning test. The dimension of a limit oxygen index test sample strip is 120mm multiplied by 6mm multiplied by 3.2 mm; the vertical burning sample bar size is 130 mm. times.13 mm. times.3.2 mm. The test results are shown in table 1.
Example 10
Reacting 100 parts by weight of epoxy resin and 7.5 parts by weight of phosphorus-containing triazole compound at 140 ℃ for 10 minutes; then adding 22 parts by weight of 4, 4' -diaminodiphenylmethane, and stirring to obtain a uniform epoxy solution; vacuumizing the epoxy solution to remove bubbles, and pouring the epoxy solution into a preheated mold for thermosetting; and naturally cooling to room temperature after curing, and demolding to obtain the intrinsic flame-retardant epoxy resin material.
The prepared epoxy resin sample specimens were subjected to a limiting oxygen index test and a vertical burning test. The dimension of a limit oxygen index test sample strip is 120mm multiplied by 6mm multiplied by 3.2 mm; the vertical burning sample bar size is 130 mm. times.13 mm. times.3.2 mm. The test results are shown in table 1.
Example 11
Reacting 100 parts by weight of epoxy resin and 10 parts by weight of phosphorus-containing triazole compound at 130 ℃ for 20 minutes; then adding 20 parts by weight of 4, 4' -diaminodiphenylmethane, and stirring to obtain a uniform epoxy solution; vacuumizing the epoxy solution to remove bubbles, and pouring the epoxy solution into a preheated mold for thermosetting; and naturally cooling to room temperature after curing, and demolding to obtain the intrinsic flame-retardant epoxy resin material.
The prepared epoxy resin sample specimens were subjected to a limiting oxygen index test and a vertical burning test. The dimension of a limit oxygen index test sample strip is 120mm multiplied by 6mm multiplied by 3.2 mm; the vertical burning sample bar size is 130 mm. times.13 mm. times.3.2 mm. The test results are shown in table 1.
Example 12
Reacting 100 parts by weight of epoxy resin and 10 parts by weight of phosphorus-containing triazole compound at 140 ℃ for 10 minutes; then adding 20 parts by weight of 4, 4' -diaminodiphenylmethane, and stirring to obtain a uniform epoxy solution; vacuumizing the epoxy solution to remove bubbles, and pouring the epoxy solution into a preheated mold for thermosetting; and naturally cooling to room temperature after curing, and demolding to obtain the intrinsic flame-retardant epoxy resin material.
The prepared epoxy resin sample specimens were subjected to a limiting oxygen index test and a vertical burning test. The dimension of a limit oxygen index test sample strip is 120mm multiplied by 6mm multiplied by 3.2 mm; the vertical burning sample bar size is 130 mm. times.13 mm. times.3.2 mm. The test results are shown in table 1.
Example 13
Reacting 100 parts by weight of epoxy resin and 10 parts by weight of phosphorus-containing triazole compound at 140 ℃ for 10 minutes; then adding 22 parts by weight of 4, 4' -diaminodiphenylmethane, and stirring to obtain a uniform epoxy solution; vacuumizing the epoxy solution to remove bubbles, and pouring the epoxy solution into a preheated mold for thermosetting; and naturally cooling to room temperature after curing, and demolding to obtain the intrinsic flame-retardant epoxy resin material.
The prepared epoxy resin sample specimens were subjected to a limiting oxygen index test and a vertical burning test. The dimension of a limit oxygen index test sample strip is 120mm multiplied by 6mm multiplied by 3.2 mm; the vertical burning sample bar size is 130 mm. times.13 mm. times.3.2 mm. The test results are shown in table 1.
Comparative example 1
Uniformly stirring 100 parts by weight of epoxy resin at 100 ℃; and then adding 22 parts by weight of 4, 4' -diaminodiphenylmethane, stirring to obtain a uniform pure epoxy solution, vacuumizing the pure epoxy solution to remove bubbles, pouring the pure epoxy solution into a preheated mold for thermosetting, naturally cooling to room temperature after curing, and demolding to obtain the pure epoxy resin material.
The prepared pure epoxy resin sample strips are subjected to a limiting oxygen index test and a vertical burning test. The dimension of a limit oxygen index test sample strip is 120mm multiplied by 6mm multiplied by 3.2 mm; the vertical burning sample bar size is 130 mm. times.13 mm. times.3.2 mm. The test results are shown in table 1.
TABLE 1 formulation of intrinsic type flame retardant epoxy resin and its oxygen index and vertical burning test results
Claims (7)
1. The preparation method of the intrinsic flame-retardant epoxy resin is characterized by comprising the following steps: reacting epoxy resin and a reactive flame retardant at a certain temperature for a period of time; then adding a hardening agent, and stirring until a uniform epoxy solution is obtained; then vacuumizing the epoxy solution to remove bubbles, and pouring the epoxy solution into a preheated mold for thermosetting; cooling to room temperature after solidification, and demolding to obtain the intrinsic flame-retardant epoxy resin;
the reactive flame retardant is a phosphorus-containing triazole compound, and the structural formula of the reactive flame retardant is as follows:
2. the method of claim 1, wherein the epoxy resin is bisphenol A epoxy resin.
3. The method of claim 1, wherein the hardener is 4, 4' -diaminodiphenylmethane.
4. The preparation method of the intrinsic flame-retardant epoxy resin as claimed in claim 1, wherein the weight ratio of the reactive flame retardant to the epoxy resin is 2.5-10: 100.
5. the method for preparing the intrinsic flame-retardant epoxy resin as claimed in claim 1, wherein the weight ratio of the hardener to the epoxy resin is 20-25: 100.
6. the method for preparing the intrinsic flame-retardant epoxy resin as claimed in claim 1, wherein the reaction temperature of the epoxy resin and the reactive flame retardant is 100-140 ℃ and the reaction time is 10-20 minutes.
7. An intrinsically flame-retardant epoxy resin obtainable by the process according to any one of claims 1 to 6.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003160712A (en) * | 2001-11-27 | 2003-06-06 | Daihachi Chemical Industry Co Ltd | Flame-retardant epoxy resin composition |
| US6809130B2 (en) * | 2002-12-06 | 2004-10-26 | Industrial Technology Research Institute | Halogen-free, phosphorus-free flame-retardant advanced epoxy resin and an epoxy composition containing the same |
| CN104311876A (en) * | 2014-11-07 | 2015-01-28 | 东北林业大学 | Polymerization type phosphorus-containing flame retardant as well as preparation method and application thereof as epoxy resin flame retardant |
| CN106751470A (en) * | 2016-11-24 | 2017-05-31 | 福建师范大学 | A kind of preparation method of activeness and quietness fire retarding epoxide resin |
| CN111548479A (en) * | 2020-05-18 | 2020-08-18 | 福建师范大学 | Phosphine-modified triazole flame-retardant co-curing agent for epoxy resin and preparation method thereof |
-
2021
- 2021-06-24 CN CN202110703387.7A patent/CN113336920A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003160712A (en) * | 2001-11-27 | 2003-06-06 | Daihachi Chemical Industry Co Ltd | Flame-retardant epoxy resin composition |
| US6809130B2 (en) * | 2002-12-06 | 2004-10-26 | Industrial Technology Research Institute | Halogen-free, phosphorus-free flame-retardant advanced epoxy resin and an epoxy composition containing the same |
| CN104311876A (en) * | 2014-11-07 | 2015-01-28 | 东北林业大学 | Polymerization type phosphorus-containing flame retardant as well as preparation method and application thereof as epoxy resin flame retardant |
| CN106751470A (en) * | 2016-11-24 | 2017-05-31 | 福建师范大学 | A kind of preparation method of activeness and quietness fire retarding epoxide resin |
| CN111548479A (en) * | 2020-05-18 | 2020-08-18 | 福建师范大学 | Phosphine-modified triazole flame-retardant co-curing agent for epoxy resin and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| HANS-GEORG HENNING等: ""Metallkomplexe einiger 2-Diphenylphosphinylamino-N-heterocyclen"", 《ZEITSCHRIFT FÜR CHEMIE》, vol. 13, no. 1, 1 January 1973 (1973-01-01), pages 16 - 17 * |
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