CN107400197A - A kind of reaction-type flame-retarding epoxy curing agent and preparation method thereof - Google Patents
A kind of reaction-type flame-retarding epoxy curing agent and preparation method thereof Download PDFInfo
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- CN107400197A CN107400197A CN201710661206.2A CN201710661206A CN107400197A CN 107400197 A CN107400197 A CN 107400197A CN 201710661206 A CN201710661206 A CN 201710661206A CN 107400197 A CN107400197 A CN 107400197A
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- reaction
- curing agent
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- epoxy curing
- type flame
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Classifications
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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
- C08G59/5046—Amines heterocyclic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
-
- 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
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
Abstract
The invention discloses a kind of reaction-type flame-retarding epoxy curing agent and preparation method thereof, the curing agent obtains intermediate product by p-phenylenediamine and terephthaldehyde's aldehyde reaction, then is reacted and be made by intermediate product and DOPO.It contains two active aminos and two imino groups simultaneously, available for cured epoxy resin；And contain P, N ignition-proof element, can cooperative flame retardant.The present invention has the advantages that raw material are easy to get, preparation technology is simple, separating-purifying is easy, is easy to large-scale promotion application.
Description
Technical field
The present invention relates to technical field of flame retardant, and in particular to a kind of reaction-type flame-retarding epoxy curing agent and its preparation
Method.
Background technology
In the last few years, with the environmental protection of people and the continuous improvement of awareness of safety, epoxide resin material it is fire-retardant
Constantly develop to green direction.Nitrogenous, phosphorus and silicon compound are environmentally friendly fire proofings, in its combustion process hardly
Noxious material is produced, and its fire resistance is no less than halogen-containing flame retardant, and when compound is simultaneously containing two kinds or more resistances
When firing element, flame retardant effect can greatly improve.
Though the synthesis of aldimine class and poly methylene imine class compound early has report, it is used for the fire-retardant nearest of epoxy resin
Just get along with, it is that condensation occurs with amino with aldehyde radical and obtains that it, which reacts, is broadly divided into two classes：Single aldehyde radical reaction generation aldimine
Class and more aldehyde radicals reaction generation poly methylene imine class.Tigelaar and Donghua University Wang Peng thesis for the doctorate all use equimolar amounts
P-phenylenediamine synthesized with terephthaldehyde's aldehyde reaction and contain nitrogen oligomer, then can be final to synthesize DOPO bases with DOPO addition reactions
Containing nitrogen oligomer.Li Gucai, Sun Dechao and Xiao Ling p-phenylenediamine are with single aldehyde compound with 1：2 reaction, then with DOPO additions
Reaction, has synthesized R end group DOPO type fire retardants.But they are the functional group reactionses with equimolar amounts, rather than equimolar amounts
Functional group reactionses are not reported in the epoxy.
The content of the invention
It is an object of the invention to provide a kind of reaction-type flame-retarding epoxy curing agent, its chemical structural formula is：
Another object of the present invention is to provide the preparation method of above-mentioned reaction-type flame-retarding epoxy curing agent, this method
Specially：Under protective atmosphere, p-phenylenediamine and terephthalaldehyde is reacted in solvent orange 2 A and obtain intermediate product；In protection gas
Under atmosphere, intermediate product is reacted with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) in solvent B and obtain
Final product.
According to such scheme, the solvent orange 2 A is any one in ethanol, ether, tetrahydrofuran, deionized water.
According to such scheme, the solvent B is any one in dimethylbenzene or N ' dinethylformamides (DMF).
According to such scheme, the mol ratio of p-phenylenediamine and terephthalaldehyde is (5-7):1.
According to such scheme, the mol ratio of intermediate product and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is
1:(2-2.4)。
According to such scheme, first p-phenylenediamine is dissolved in solvent orange 2 A when preparing intermediate product, leads to protective gas, stirring adds
Heat reacts 4-6h to terephthalaldehyde is added dropwise after 90-100 DEG C, reaction terminate after through cooling down, filtering, recrystallizing and 80 DEG C dry
Dry 24h produces intermediate product.
According to such scheme, when preparing final product by 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, in
Between product be dissolved in solvent B, lead to protective gas, be heated with stirring to 110-140 DEG C, react 6-12h, reaction is cooled to room after terminating
Temperature, final product is produced in 80 DEG C of dry 24h after washing suction filtration is multiple.
In such scheme, the protective atmosphere is N2。
Compared with prior art, the invention has the advantages that：
1. halogen-free flameproof element P, N are incorporated into molecule, the effect of cooperative flame retardant is played, is obtained a kind of new, not
The flame retardant curing agent to appear in the newspapers, crosslinking curing effect can be both played, halogen-free flameproof effect can be played again.
2. compared to existing R end groups DOPO type fire retardants, the curing agent that the present invention synthesizes contains can be anti-with epoxy resin
The active H answered is substantially more, then solidifying dosage can be reduced relatively, can so reduce the influence to the mechanical performance of solidfied material.
3. the DOPO bases of report are difficult to control containing nitrogen oligomer, mixture, the novel flame-retardant that the present invention synthesizes generally are
Loss of the curing agent to amino will also be lacked containing nitrogen oligomer compared to DOPO bases, and preparation method is simple, mild condition, separation
Purification is easy, will have good application prospect in the solidification of epoxy resin and flame retardant area.
Brief description of the drawings
Fig. 1 is intermediate product prepared by the embodiment of the present invention 11H-NMR spectrum.
Fig. 2 is reaction-type flame-retarding epoxy curing agent prepared by the embodiment of the present invention 11H-NMR spectrum.
Embodiment
To make those of ordinary skill in the art fully understand technical scheme and beneficial effect, below in conjunction with specific
Embodiment is further described.
A kind of reaction-type flame-retarding epoxy curing agent, the curing agent are given birth to by terephthalaldehyde and p-phenylenediamine reaction first
Into intermediate, then reacted and obtained under conditions of DMF makees solvent with DOPO by gained intermediate, specific reaction equation is as follows：
Embodiment 1
(1) to equipped with thermometer, condensing reflux, magnetic agitation, dropping funel and N2Add in the 250ml four-hole boiling flasks being passed through
Enter 20mL deionized waters, 0.01mol p-phenylenediamine, be stirred and heated to 95 DEG C and be completely dissolved it, then dripped into flask
Add 0.05mol terephthalaldehydes, in N24h is reacted under protection atmosphere.
(2) after question response terminates, reactant mixture is placed in sub-cooled in refrigerator, suction filtration obtains crude product.Spend again
Ionized water dissolves and heated, and then cools down recrystallization with same method, is repeated 3 times, finally in 80 DEG C in vacuum drying chamber
Lower dry 24h, obtains intermediate product.
(3) to equipped with thermometer, condensing reflux, magnetic agitation and N20.02mol is added in the 250ml three-necked flasks being passed through
DOPO, 0.01mol intermediate product and 10mL DMF, progressively heating is completely dissolved it, in 110 DEG C, N2Reacted under protection atmosphere
6h。
(4) after question response terminates, room temperature is cooled to, adds a large amount of deionized waters thereto, stirs and filters and slightly produced
Product, repeated washing filter 3 times, finally dry 24h at 80 DEG C in vacuum drying chamber, obtain final product, as novel trans
Answer type antiflaming epoxy resin curing agent.
Fig. 1 and Fig. 2 is respectively intermediate product and final product prepared by the embodiment of the present invention 11H-NMR spectrum.From figure
In can be seen that the hydrocarbon of intermediate product carbon-to-nitrogen double bon is 8.39ppm, and the chemical shift herein on final product disappears, right
Chemical shift at 3.9ppm and 7.47ppm two should be generated, it can be verified that the product obtained according to the inventive method hinders for response type
Fire epoxy curing agent.
Embodiment 2
(1) to equipped with thermometer, condensing reflux, magnetic agitation, dropping funel and N2Add in the 250ml four-hole boiling flasks being passed through
Enter 20mL deionized waters, 0.01mol p-phenylenediamine, be stirred and heated to 95 DEG C and be completely dissolved it, then dripped into flask
Add 0.07mol terephthalaldehydes, in N24h is reacted under protection atmosphere, intermediate product is obtained through separating-purifying.
(2) to equipped with thermometer, condensing reflux, magnetic agitation and N2Added in the 250ml three-necked flasks being passed through
0.024mol DOPO, 0.01mol intermediate products and 10mL DMF, progressively heating is completely dissolved it, in 110 DEG C, N2Protect atmosphere
Lower reaction 6h is enclosed, novel reaction type antiflaming epoxy resin curing agent is obtained through separating-purifying.
Embodiment 3
(1) to equipped with thermometer, condensing reflux, magnetic agitation, dropping funel and N2Add in the 250ml four-hole boiling flasks being passed through
Enter 20mL deionized waters, 0.01mol p-phenylenediamine, be stirred and heated to 95 DEG C and be completely dissolved it, then dripped into flask
Add 0.07mol terephthalaldehydes, in N26h is reacted under protection atmosphere, intermediate product is obtained through separating-purifying.
(2) to equipped with thermometer, condensing reflux, magnetic agitation and N2Added in the 250ml three-necked flasks being passed through
0.024mol DOPO, 0.01mol intermediate products and 10mL DMF, progressively heating is completely dissolved it, in 140 DEG C, N2Protect atmosphere
Lower reaction 6h is enclosed, novel reaction type antiflaming epoxy resin curing agent is obtained through separating-purifying.
Embodiment 4
(1) to equipped with thermometer, condensing reflux, magnetic agitation, dropping funel and N2Add in the 250ml four-hole boiling flasks being passed through
Enter 20mL deionized waters, 0.01mol p-phenylenediamine, be stirred and heated to 95 DEG C and be completely dissolved it, then dripped into flask
Add 0.07mol terephthalaldehydes, in N26h is reacted under protection atmosphere, intermediate product is obtained through separating-purifying.
(2) to equipped with thermometer, condensing reflux, magnetic agitation and N2Added in the 250ml three-necked flasks being passed through
0.024mol DOPO, 0.01mol intermediate products and 10mL DMF, progressively heating is completely dissolved it, in 140 DEG C, N2Protect atmosphere
Lower reaction 12h is enclosed, novel reaction type antiflaming epoxy resin curing agent is obtained through separating-purifying.
Application examples
Epoxy resin E51 is chosen, by itself and 10wt% new reaction-type flame-retarding epoxy curing agent, 1wt% DMP-
30 or imidazoles (in terms of epoxy resin quality), organic solvent DMF and filler are well mixed.Above-mentioned mixed liquor is injected homemade
In silica gel mould, 60 DEG C of precuring 1h are heated to, are allowed to be molded.120 DEG C of solidification 2h are heated the mixture to, make curing agent abundant
Cured epoxy resin, then proceed to be warming up to 180 DEG C of solidify afterwards 2h, glue-joint strength and epoxy resin are improved to eliminate internal stress
The combination property of solidfied material.
Test by contrast, the more typical curing agent of the reaction-type flame-retarding epoxy curing agent synthesized by the present invention (such as
Methacrylamide etc.) for, fire resistance has obtained larger lifting, and UL94 flame retardant ratings refer to up to V-0 ranks, limit oxygen
Number LOI has reached fire retardant rank up to more than 27%.
Claims (9)
1. a kind of reaction-type flame-retarding epoxy curing agent, it is characterised in that its chemical structural formula is：
2. a kind of preparation method of reaction-type flame-retarding epoxy curing agent, it is characterised in that comprise the following steps：In protection gas
Under atmosphere, p-phenylenediamine and terephthalaldehyde is reacted in solvent orange 2 A and obtain intermediate product；Under protective atmosphere, make intermediate product
Reacted with the miscellaneous -10- phospho hetero phenanthrenes -10- oxides of 9,10- dihydro-9-oxies in solvent B and obtain final product.
A kind of 3. preparation method of reaction-type flame-retarding epoxy curing agent as claimed in claim 2, it is characterised in that：It is described
Solvent orange 2 A is any one in ethanol, ether, tetrahydrofuran, deionized water.
A kind of 4. preparation method of reaction-type flame-retarding epoxy curing agent as claimed in claim 2, it is characterised in that：It is described
Solvent B is any one in dimethylbenzene or N ' dinethylformamides.
A kind of 5. preparation method of reaction-type flame-retarding epoxy curing agent as claimed in claim 2, it is characterised in that：To benzene
The mol ratio of diamines and terephthalaldehyde is (5-7):1.
A kind of 6. preparation method of reaction-type flame-retarding epoxy curing agent as claimed in claim 2, it is characterised in that：It is middle
The mol ratio of product and the miscellaneous -10- phospho hetero phenanthrenes -10- oxides of 9,10- dihydro-9-oxies is 1:(2-2.4).
A kind of 7. preparation method of reaction-type flame-retarding epoxy curing agent as claimed in claim 2, it is characterised in that：Prepare
First p-phenylenediamine is dissolved in solvent orange 2 A during intermediate product, leads to protective gas, terephthaldehyde is added dropwise after being heated with stirring to 90-100 DEG C
Aldehyde, reacts 4-6h, reaction terminate after through cooling down, filtering, recrystallizing, 80 DEG C of dry 24h produce intermediate product.
A kind of 8. preparation method of reaction-type flame-retarding epoxy curing agent as claimed in claim 2, it is characterised in that：Prepare
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, intermediate product are dissolved in solvent B during final product, lead to protection gas
Body, 110-140 DEG C is heated with stirring to, reacts 6-12h, reaction is cooled to room temperature after terminating, at 80 DEG C after repeatedly washing filters
Dry 24h and produce final product.
A kind of 9. preparation method of reaction-type flame-retarding epoxy curing agent as claimed in claim 2, it is characterised in that：It is described
Protective atmosphere is N2。
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109096471A (en) * | 2018-07-27 | 2018-12-28 | 武汉工程大学 | A kind of novel P-N-Si cooperative resistance combustion epoxy curing agent and preparation method thereof |
| CN109096472A (en) * | 2018-07-27 | 2018-12-28 | 武汉工程大学 | A kind of application of novel P-N-Si cooperative resistance combustion epoxy curing agent in epoxy-resin systems |
| CN109912650A (en) * | 2019-04-16 | 2019-06-21 | 中国科学院宁波材料技术与工程研究所 | A kind of phosphorus-nitrogen system biology based flameproofing and its synthetic method and application |
| CN110041370A (en) * | 2019-05-17 | 2019-07-23 | 武汉工程大学 | A kind of preparation method and applications of the efficient flame-retarding agent containing DOPO and Aminopyrazine structure |
| CN110105395A (en) * | 2019-04-16 | 2019-08-09 | 皖西学院 | A kind of pyridine fire retardant and its preparation method and application |
| CN110218355A (en) * | 2019-07-04 | 2019-09-10 | 武汉工程大学 | A kind of pyridine fire retardant and its synthesis and application |
| WO2020108310A1 (en) * | 2018-11-28 | 2020-06-04 | 苏州生益科技有限公司 | Flame-retardant resin prepolymer and resin composition, prepreg and laminate prepared by using same |
| WO2020108351A1 (en) * | 2018-11-28 | 2020-06-04 | 苏州生益科技有限公司 | Flame-retardant resin composition and prepreg and laminate prepared therefrom |
| CN113429626A (en) * | 2021-06-24 | 2021-09-24 | 中国民用航空飞行学院 | Cross-linkable flame retardant containing bis-DOPO bis-phthalonitrile, and preparation method and application thereof |
| CN115536601A (en) * | 2022-10-14 | 2022-12-30 | 重庆交通大学 | Curing agent capable of resisting flame, strengthening and toughening epoxy resin, epoxy resin material and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101830929A (en) * | 2010-05-17 | 2010-09-15 | 中科院广州化学有限公司 | Phosphorus-containing hydroquinone derivative, phosphorus-containing flame-retardant epoxy resin, preparation method and application thereof |
| CN104592549A (en) * | 2015-02-03 | 2015-05-06 | 上海交通大学 | Phosphorus-containing reaction-type fire retardant as well as synthesis method and application thereof |
| CN104693421A (en) * | 2015-03-27 | 2015-06-10 | 厦门大学 | Self-inflaming-retarding epoxy resin curing agent containing phosphorus-nitrogen and preparation method thereof |
-
2017
- 2017-08-04 CN CN201710661206.2A patent/CN107400197A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101830929A (en) * | 2010-05-17 | 2010-09-15 | 中科院广州化学有限公司 | Phosphorus-containing hydroquinone derivative, phosphorus-containing flame-retardant epoxy resin, preparation method and application thereof |
| CN104592549A (en) * | 2015-02-03 | 2015-05-06 | 上海交通大学 | Phosphorus-containing reaction-type fire retardant as well as synthesis method and application thereof |
| CN104693421A (en) * | 2015-03-27 | 2015-06-10 | 厦门大学 | Self-inflaming-retarding epoxy resin curing agent containing phosphorus-nitrogen and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| PENG WANG ET AL.: "Flame retardancy and mechanical properties of epoxy thermosets modified with a novel DOPO-based oligomer", 《POLYMER DEGRADATION AND STABILITY》 * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109096472A (en) * | 2018-07-27 | 2018-12-28 | 武汉工程大学 | A kind of application of novel P-N-Si cooperative resistance combustion epoxy curing agent in epoxy-resin systems |
| CN109096471B (en) * | 2018-07-27 | 2020-11-27 | 武汉工程大学 | P-N-Si synergistic flame-retardant epoxy resin curing agent and preparation method thereof |
| CN109096472B (en) * | 2018-07-27 | 2020-11-27 | 武汉工程大学 | Application of P-N-Si synergistic flame-retardant epoxy resin curing agent in epoxy resin system |
| CN109096471A (en) * | 2018-07-27 | 2018-12-28 | 武汉工程大学 | A kind of novel P-N-Si cooperative resistance combustion epoxy curing agent and preparation method thereof |
| WO2020108310A1 (en) * | 2018-11-28 | 2020-06-04 | 苏州生益科技有限公司 | Flame-retardant resin prepolymer and resin composition, prepreg and laminate prepared by using same |
| WO2020108351A1 (en) * | 2018-11-28 | 2020-06-04 | 苏州生益科技有限公司 | Flame-retardant resin composition and prepreg and laminate prepared therefrom |
| CN110105395A (en) * | 2019-04-16 | 2019-08-09 | 皖西学院 | A kind of pyridine fire retardant and its preparation method and application |
| CN109912650A (en) * | 2019-04-16 | 2019-06-21 | 中国科学院宁波材料技术与工程研究所 | A kind of phosphorus-nitrogen system biology based flameproofing and its synthetic method and application |
| CN109912650B (en) * | 2019-04-16 | 2022-12-13 | 中国科学院宁波材料技术与工程研究所 | Phosphorus-nitrogen series bio-based flame retardant and synthetic method and application thereof |
| CN110041370A (en) * | 2019-05-17 | 2019-07-23 | 武汉工程大学 | A kind of preparation method and applications of the efficient flame-retarding agent containing DOPO and Aminopyrazine structure |
| CN110041370B (en) * | 2019-05-17 | 2021-08-06 | 武汉工程大学 | Preparation method and application of efficient flame retardant containing DOPO and aminopyrazine structures |
| CN110218355A (en) * | 2019-07-04 | 2019-09-10 | 武汉工程大学 | A kind of pyridine fire retardant and its synthesis and application |
| CN110218355B (en) * | 2019-07-04 | 2021-07-16 | 武汉工程大学 | Pyridine flame retardant and synthesis and application thereof |
| CN113429626A (en) * | 2021-06-24 | 2021-09-24 | 中国民用航空飞行学院 | Cross-linkable flame retardant containing bis-DOPO bis-phthalonitrile, and preparation method and application thereof |
| CN113429626B (en) * | 2021-06-24 | 2022-05-27 | 中国民用航空飞行学院 | Cross-linkable flame retardant containing bis-DOPO bis-phthalonitrile, and preparation method and application thereof |
| CN115536601A (en) * | 2022-10-14 | 2022-12-30 | 重庆交通大学 | Curing agent capable of resisting flame, strengthening and toughening epoxy resin, epoxy resin material and application |
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Application publication date: 20171128 |