CN116355285A - Phosphorus-containing triazole flame retardant, preparation method thereof and application thereof in epoxy resin - Google Patents
Phosphorus-containing triazole flame retardant, preparation method thereof and application thereof in epoxy resin Download PDFInfo
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- CN116355285A CN116355285A CN202310642312.1A CN202310642312A CN116355285A CN 116355285 A CN116355285 A CN 116355285A CN 202310642312 A CN202310642312 A CN 202310642312A CN 116355285 A CN116355285 A CN 116355285A
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 88
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 70
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000011574 phosphorus Substances 0.000 title claims abstract description 69
- 150000003852 triazoles Chemical class 0.000 title claims abstract description 34
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 30
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 11
- PKWIYNIDEDLDCJ-UHFFFAOYSA-N guanazole Chemical compound NC1=NNC(N)=N1 PKWIYNIDEDLDCJ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 150000001412 amines Chemical class 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 229940126062 Compound A Drugs 0.000 claims abstract description 11
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 239000011261 inert gas Substances 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 8
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052734 helium Inorganic materials 0.000 claims description 5
- 239000001307 helium Substances 0.000 claims description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000000034 method Methods 0.000 claims 6
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 5
- 125000000524 functional group Chemical group 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000004593 Epoxy Substances 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000009472 formulation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IBDMRHDXAQZJAP-UHFFFAOYSA-N dichlorophosphorylbenzene Chemical compound ClP(Cl)(=O)C1=CC=CC=C1 IBDMRHDXAQZJAP-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- 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 Table
- 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
- 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 Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having three nitrogen atoms as the only ring hetero atoms
- C07F9/6518—Five-membered rings
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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
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/5399—Phosphorus bound to nitrogen
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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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Life Sciences & Earth Sciences (AREA)
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- General Health & Medical Sciences (AREA)
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Abstract
The invention discloses a phosphorus-containing triazole flame retardant, a preparation method thereof and application thereof in epoxy resin, wherein the preparation method of the phosphorus-containing triazole flame retardant comprises the steps of mixing 3, 5-diamino-1, 2, 4-triazole and organic amine in a solvent, and dripping a mixed solution of a phosphorus-containing compound A or a phosphorus-containing compound B and the solvent into a reaction system for reaction to obtain the phosphorus-containing triazole flame retardant. The invention prepares the phosphorus-containing flame retardant by utilizing two amino functional groups in the 3, 5-diamino-1, 2, 4-triazole structure and various phosphorus-containing structures to react, and the prepared phosphorus-containing flame retardant has better flame retardant effect in a condensed phase or a gas phase, and is suitable for flame retardant treatment of various polymers.
Description
Technical Field
The invention belongs to the technical field of phosphorus-containing flame retardants, and particularly relates to a phosphorus-containing triazole flame retardant, a preparation method thereof and application thereof in epoxy resin.
Background
Epoxy resins (EP) have now become the most versatile thermosetting resin materials through continued development since the first synthesis in the thirty-second of the twentieth century. Has the characteristics of excellent mechanical property, difficult shrinkage and expansion, corrosion resistance and the like, and has been widely applied to adhesives, coatings for protection and decoration, packaging materials for the field of electronic and electric appliances, composite materials for use in construction, automobiles, aerospace and the like. However, since epoxy resin is extremely easy to burn and does not self-extinguish after being ignited, the epoxy resin is exposed to great fire risks in the environments of electronic and electrical appliances, aerospace, trains, high-speed rail, ships and the like.
The phosphorus flame retardant has the excellent properties of low smoke, low toxicity, stable carbon layer formation after combustion, and the like, wherein the generated carbon layer can inhibit the diffusion of internal thermal decomposition products to a gas phase. The nitrogen-containing flame retardant generates inert gas during combustion to inhibit flame combustion, but has poor flame retardant effect when used alone, and nitrogen and phosphorus are generally used in combination to improve flame retardant efficiency. Phosphorus-nitrogen based flame retardants are a hot spot of current research due to their unique flame retardancy and thermal stability. The 3, 5-diamino-1, 2, 4-triazole has 5 nitrogen atoms in the structure, two amino functional groups and strong structural designability, has potential application value in the aspect of constructing the high-efficiency flame retardant, and can react with various phosphorus-containing structures to prepare the phosphorus-containing flame retardant.
Disclosure of Invention
The invention aims to provide a phosphorus-containing triazole flame retardant, a preparation method thereof and application thereof in epoxy resin, wherein the phosphorus-containing triazole flame retardant can react with various phosphorus-containing structures by utilizing two amino functional groups in a 3, 5-diamino-1, 2, 4-triazole structure, and the prepared phosphorus-containing flame retardant has good flame retardant effect in a condensed phase or a gas phase and is suitable for flame retardant treatment of various polymers.
In order to achieve the above purpose, the invention adopts the following technical scheme: a phosphorus-containing triazole flame retardant has a chemical structural formula shown in the following formula I or II:
wherein in formula I, R 1 The chemical structure of (a) is selected from any one of the following structures:
、
、/>
；
in the formula II, R 2 The chemical structure of (a) is selected from any one of the following structures:
、/>
、/>
。
the preparation method of the phosphorus-containing triazole flame retardant comprises the steps of mixing 3, 5-diamino-1, 2, 4-triazole and organic amine in a solvent, and dripping the mixed solution of the phosphorus-containing compound A and the solvent into a reaction system for reaction to obtain the phosphorus-containing triazole flame retardant;
the structure of the phosphorus-containing compound A is selected from any one of the following structures:
、
、/>
；
the preparation method of the phosphorus-containing triazole flame retardant is characterized by comprising the following steps of: 3, 5-diamino-1, 2, 4-triazole and organic amine are mixed in a solvent, and the mixed solution of the phosphorus-containing compound B and the solvent is dripped into a reaction system to react, so that the phosphorus-containing triazole flame retardant is obtained;
the structure of the phosphorus-containing compound B is selected from any one of the following structuresOne or two of:
、/>
、
。
further, the organic amine is selected from any one or more of triethylamine, cyclohexylamine and hexamethylenediamine; the solvent is selected from one or more of dichloromethane, chloroform and diethyl ether.
Further, the reaction is carried out under the protection of inert gas, and the inert gas is selected from any one of nitrogen, argon and helium.
Further, the molar ratio of the 3, 5-diamino-1, 2, 4-triazole to the organic amine is 1:2-2.2, the molar ratio of the 3, 5-diamino-1, 2, 4-triazole to the phosphorus-containing compound A is 1:2-2.2, the reaction temperature is-15-5 ℃, and the reaction time is 4-24 hours.
Further, the molar ratio of the 3, 5-diamino-1, 2, 4-triazole to the triethylamine is 1:1-1.2, and the molar ratio of the 3, 5-diamino-1, 2, 4-triazole to the phosphorus-containing compound B is 1:1-1.2. The reaction temperature is 60-80 ℃ and the reaction time is 4-24 hours.
The application of the phosphorus-containing triazole flame retardant in flame-retardant cured epoxy tree.
The beneficial effects of the invention are as follows: according to the invention, two amino functional groups in the 3, 5-diamino-1, 2, 4-triazole structure are utilized to react with various phosphorus-containing structures to prepare the phosphorus-containing flame retardant, and when the flame retardant is combusted, the flame retardant can promote the formation of a carbon layer in a condensed phase, and the obtained compact carbon layer plays a physical shielding role, so that the exchange of a matrix and external gas and heat is isolated, and the combustion of a matrix material is further inhibited; in the gas phase, the flame retardant is decomposed to generate radicals, and the radicals such as H.HO.and the like in the flame are trapped and eliminated, thereby suppressing the progress of combustion. Therefore, the prepared phosphorus-containing flame retardant has better flame retardant effect in both a condensed phase and a gas phase, and is suitable for flame retardant treatment of various polymers.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of the product of example 1 of the present invention;
FIG. 2 is a nuclear magnetic resonance chromatogram of the product of example 1 of the present invention;
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of the product of example 2 of the present invention;
FIG. 4 is a nuclear magnetic resonance chromatogram of the product of example 2 of the present invention;
FIG. 5 is a thermogravimetric analysis curve of each sample in example 3 of the present invention;
FIG. 6 is a graph showing the heat release rate in a cone calorimeter for each sample of example 3 of the present invention;
FIG. 7 is an enlarged view of a portion of FIG. 1 in accordance with the present invention;
fig. 8 is an enlarged view of a portion of fig. 3 in accordance with the present invention.
Detailed Description
In order that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention will be rendered by reference to the appended drawings. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The present invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit of the invention, whereby the invention is not limited to the specific embodiments disclosed below.
The preparation method of the phosphorus-containing triazole flame retardant comprises the steps of mixing 3, 5-diamino-1, 2, 4-triazole and organic amine in a solvent, dropwise adding a mixed solution of a phosphorus-containing compound A and the solvent into a reaction system for reaction under the protection of inert gas, wherein the reaction temperature is-15-5 ℃ and the reaction time is 4-24 hours, and obtaining the phosphorus-containing triazole flame retardant; illustratively, the reaction temperature is-15 ℃, -10 ℃, -5 ℃, 0 ℃,5 ℃, and the reaction time is 4 hours, 10 hours, 18 hours, 24 hours.
The structure of the phosphorus-containing compound A is selected from any one of the following structures:
、
、/>
。
the molar ratio of the 3, 5-diamino-1, 2, 4-triazole to the organic amine is 1:2-2.2, and the molar ratio of the 3, 5-diamino-1, 2, 4-triazole to the phosphorus-containing compound A is 1:2-2.2.
Illustratively, the molar ratio of 3, 5-diamino-1, 2, 4-triazole to organic amine is 1:2;1:2.1;1:2.2; the mol ratio of the 3, 5-diamino-1, 2, 4-triazole to the phosphorus-containing compound A is 1:2;1:2.1;1:2.2.
The organic amine is selected from any one or more of triethylamine, cyclohexylamine and hexamethylenediamine.
The solvent is selected from one or more of dichloromethane, chloroform and diethyl ether.
The inert gas is selected from any one of nitrogen, argon and helium.
The preparation method of the phosphorus-containing triazole flame retardant comprises the steps of mixing 3, 5-diamino-1, 2, 4-triazole and organic amine in a solvent, dripping the mixed solution of phosphorus-containing compound B and the solvent into a reaction system for reaction, wherein the reaction temperature is 60-80 ℃ and the reaction time is 4-24 hours, and obtaining the phosphorus-containing triazole flame retardant; illustratively, the reaction temperature is 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, and the reaction time is 4 hours, 10 hours, 18 hours, 24 hours.
The saidThe structure of the phosphorus-containing compound B is selected from any one of the following structures:
、/>
、
。
the molar ratio of the 3, 5-diamino-1, 2, 4-triazole to the organic amine is 1:1-1.2, and the molar ratio of the 3, 5-diamino-1, 2, 4-triazole to the phosphorus-containing compound B is 1:1-1.2; illustratively, the molar ratio of 3, 5-diamino-1, 2, 4-triazole to organic amine is 1:1;1:1.1;1:1.2, wherein the molar ratio of the 3, 5-diamino-1, 2, 4-triazole to the phosphorus-containing compound B is 1:1;1:1.1;1:1.2.
Further, the organic amine is selected from any one or more of triethylamine, cyclohexylamine and hexamethylenediamine; the solvent is selected from one or more of dichloromethane, chloroform and diethyl ether.
Further, the reaction is carried out under the protection of inert gas, and the inert gas is selected from any one of nitrogen, argon and helium.
Examples
The present disclosure is more particularly described in the following examples that are intended as illustrations only, since various modifications and changes within the scope of the present disclosure will be apparent to those skilled in the art. Unless otherwise indicated, all parts, percentages, and ratios reported in the examples below are by weight, and all reagents used in the examples are commercially available or were obtained synthetically according to conventional methods and can be used directly without further treatment, as well as the instruments used in the examples.
Example 1:
22.27 of g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 300 ml of methylene chloride were added to a 500 ml three-neck flask and stirred under ice-bath and nitrogen. Subsequently 17.29 of g of carbon tetrachloride was added dropwise to the reaction system, and stirring was continued until the reaction system solution became clear. The ice bath was removed, 5.06 g of 3, 5-diamino-1, 2, 4-triazole was added to the three-necked flask at room temperature and 11.24 g of triethylamine was added dropwise to the flask. After the reaction was continued for 12 h, the precipitate was removed by filtration, and the resulting solution was dried by spin-drying the solvent to obtain flame retardant a.
The obtained flame retardant a is characterized by nuclear magnetic resonance hydrogen spectrum and phosphorus spectrum, and is prepared by the following steps of 1 In H-NMR (400 MHz, DMSO-d6, ppm), the characteristic peak of N-H in the triazole structure was found at the 5.75 ppm position, while the signal between 7.18 and 8.20 ppm was found to be the characteristic peak of the aromatic structure in 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. At the position of 31 In the P-NMR spectrum, only one characteristic peak at the 5.80 ppm position appears, indicating that there is only one chemical environment of phosphorus atoms in the synthesized compound. The product is a phosphorus-containing flame retardant containing a triazole structure.
Example 2:
5.45 g of 3, 5-diamino-1, 2, 4-triazole, 10.12 g of triethylamine and 100 ml of methylene chloride were added to a 250 ml three-neck flask and stirred under ice-bath and helium conditions. A mixed solution of 11.75, 11.75 g of phenylphosphonic dichloride and 50, 50 ml of dichloromethane was added dropwise to the flask, followed by continuous reflux stirring at 60 ℃ for 24, 24 h. The solid obtained after filtration is washed by deionized water and dried to obtain the flame retardant b.
The obtained flame retardant b is characterized by nuclear magnetic resonance hydrogen spectrum and phosphorus spectrum, and is prepared by the following steps of 1 In H-NMR (400 MHz, DMSO-d6, ppm), the 8.90 ppm position is the characteristic peak of active hydrogen in N-H in triazole structure, and between 7.25 and 7.72 ppm is the characteristic peak of aromatic in phenylphosphonyl structure. And at 31 In the P-NMR spectrum, a distinct characteristic peak appears at the 12.21 ppm position, corresponding to the chemical shift of the phosphorus atom of the product. The product is a phosphorus-containing flame retardant containing a triazole structure.
Example 3: preparation of flame-retardant epoxy resin and oxygen index and vertical combustion experimental result thereof
This example prepares a flame retardant epoxy resin according to the formulation of table 1:
table 1 flame retardant epoxy resin formulation
Note that: the epoxy resin is bisphenol A type epoxy resin curing agent which is 4,4' -diaminodiphenyl methane.
Accurately weighing the epoxy resin and the flame retardant, adding the epoxy resin and the flame retardant into a flask, and heating and stirring at 100 ℃. The curing agent was melted in a 100 ℃ oven, then added to the flask and stirred well, and immediately poured into the mold after 1 minute. The curing conditions were 100 ℃/2 hours +150 ℃/2 hours. And cooling to room temperature after the solidification is completed, and obtaining epoxy resin sample bars. The oxygen index and vertical burn data for the epoxy resin bars of the different formulations are shown in table 2:
TABLE 2 oxygen index and vertical Combustion test results for flame retardant epoxy resins
As can be seen from the data in Table 2, the epoxy resin samples were low in oxygen index and no grade in the vertical burning test, while the prepared flame retardant epoxy resins all had better flame retardant efficiency with a greater improvement in oxygen index, and wherein the flame retardant epoxy resin-2 reached V-0 grade in the vertical burning test.
In addition, the flame retardant epoxy resin-3 and the flame retardant epoxy resin-4, although containing different mass fractions of the flame retardant b, show the same oxygen index value, probably because the flame retardant b content is higher in the samples of the flame retardant epoxy resin-3 and the flame retardant epoxy resin-4, the flame retardant ability that the flame retardant b can exert when burning is saturated, and then it has been difficult to enhance the flame retardant property of the epoxy resin by increasing the content of the flame retardant b.
The thermogravimetric analysis of each sample under nitrogen is shown in figure 5. As can be seen from the graph, the epoxy resin sample had a lower amount of carbon residue at 800 ℃ and a greater maximum mass loss rate. For the flame-retardant epoxy resin sample, the carbon residue at 800 ℃ is improved to a certain extent compared with the epoxy resin, and the maximum mass loss rate of the flame-retardant epoxy resin sample is greatly reduced, which indicates that the flame retardant a and the flame retardant b have the function of promoting the formation of carbon.
The heat release rate profile of each sample in the cone calorimeter test is shown in figure 6. As can be seen from the graph, the peak value of the heat release rate of the epoxy resin sample is larger and reaches 1300 kW/m 2 About, the peak heat release rate of the flame-retardant epoxy resin is reduced to different degrees, wherein the peak heat release rate of the flame-retardant epoxy resin-4 is only 800 kW/m 2 About, it is explained that both flame retardant a and flame retardant b have a good flame retardant effect on epoxy resin.
The information on the reagents used in the present invention is also shown in the following table:
the above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and to implement the same, but are not intended to limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.
Claims (10)
1. The phosphorus-containing triazole flame retardant is characterized by having a chemical structural formula as shown in the following formula I or II:
wherein in formula I, R 1 The chemical structure of (a) is selected from any one of the following structures:
、
、/>
；
in the formula II, R 2 The chemical structure of (a) is selected from any one of the following structures:
、/>
、/>
。
2. the method for preparing the phosphorus-containing triazole flame retardant according to claim 1, wherein: 3, 5-diamino-1, 2, 4-triazole and organic amine are mixed in a solvent, and the mixed solution of the phosphorus-containing compound A and the solvent is dripped into a reaction system to react, so as to obtain the phosphorus-containing triazole flame retardant;
the structure of the phosphorus-containing compound A is selected from any one of the following structures:
、/>
、
。
3. the method for preparing the phosphorus-containing triazole flame retardant according to claim 1, wherein: 3, 5-diamino-1, 2, 4-triazole and organic amine are mixed in a solvent, and the mixed solution of the phosphorus-containing compound B and the solvent is dripped into a reaction system to react, so that the phosphorus-containing triazole flame retardant is obtained;
the structure of the phosphorus-containing compound B is selected from any one of the following structures:
、/>
、/>
。
4. a process for preparing a phosphorus-containing triazole flame retardant as claimed in claim 2 or 3, characterized in that: the organic amine is selected from any one or more of triethylamine, cyclohexylamine and hexamethylenediamine; the solvent is selected from one or more of dichloromethane, chloroform and diethyl ether.
5. A process for preparing a phosphorus-containing triazole flame retardant as claimed in claim 2 or 3, characterized in that: the reaction is carried out under the protection of inert gas, and the inert gas is selected from any one of nitrogen, argon and helium.
6. The method for preparing the phosphorus-containing triazole flame retardant according to claim 2, wherein: the reaction temperature is-15 to 5 ℃ and the reaction time is 4 to 24 hours.
7. The method for preparing the phosphorus-containing triazole flame retardant according to claim 2, wherein: the molar ratio of the 3, 5-diamino-1, 2, 4-triazole to the organic amine is 1:2-2.2, and the molar ratio of the 3, 5-diamino-1, 2, 4-triazole to the phosphorus-containing compound A is 1:2-2.2.
8. The method for preparing the phosphorus-containing triazole flame retardant according to claim 3, wherein: the reaction temperature is 60-80 ℃ and the reaction time is 4-24 hours.
9. The method for preparing the phosphorus-containing triazole flame retardant according to claim 3, wherein: the molar ratio of the 3, 5-diamino-1, 2, 4-triazole to the organic amine is 1:1-1.2, and the molar ratio of the 3, 5-diamino-1, 2, 4-triazole to the phosphorus-containing compound B is 1:1-1.2.
10. Use of the phosphorus-containing triazole flame retardant according to claim 1 in flame-retardant cured epoxy resins.
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| Title |
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| WEIJIE ZHANG ET AL.: ""Synthesis and flame retardant efficiency study of two phosphorus-nitrogen type flame retardants containing triazole units"", 《POLYMER DEGRADATION AND STABILITY》, vol. 208, pages 110236 * |
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