CN110511431B - Application of nitrogen-phosphorus efficient flame retardant containing benzoguanamine structure - Google Patents
Application of nitrogen-phosphorus efficient flame retardant containing benzoguanamine structure Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 83
- 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 75
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical group NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 title claims abstract description 71
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 title claims abstract description 40
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims abstract description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 16
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 claims abstract description 12
- LJUXFZKADKLISH-UHFFFAOYSA-N benzo[f]phosphinoline Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=P1 LJUXFZKADKLISH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- -1 melamine phosphaphenanthrene Chemical compound 0.000 claims abstract description 7
- 239000003822 epoxy resin Substances 0.000 claims description 29
- 229920000647 polyepoxide Polymers 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 16
- 229920005989 resin Polymers 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims description 7
- 239000002262 Schiff base Substances 0.000 claims description 6
- 150000004753 Schiff bases Chemical class 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical group C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 13
- 229920000877 Melamine resin Polymers 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 10
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 abstract description 10
- 230000002195 synergetic effect Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 238000003763 carbonization Methods 0.000 abstract 2
- 238000006467 substitution reaction Methods 0.000 abstract 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 9
- 238000002485 combustion reaction Methods 0.000 description 9
- 229910052698 phosphorus Inorganic materials 0.000 description 9
- 239000011574 phosphorus Substances 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
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- 239000001301 oxygen Substances 0.000 description 6
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- 239000002994 raw material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
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- 150000003141 primary amines Chemical class 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- ZTTFLCGNQCKBRY-UHFFFAOYSA-N O=C1c2ccccc2-c2ccccc2P1=O Chemical compound O=C1c2ccccc2-c2ccccc2P1=O ZTTFLCGNQCKBRY-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
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- 238000010292 electrical insulation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 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 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
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- 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
- C07F9/657181—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, at least, one ring oxygen atom being part of a (thio)phosphonic acid derivative
-
- 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
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention provides a nitrogen-phosphorus efficient flame retardant containing a benzoguanamine structure and synthesis and application thereof, and relates to the technical field of flame retardants. A nitrogen-phosphorus efficient flame retardant containing a benzoguanamine structure has the following structural formula:
the synthesis of the flame retardant comprises the following steps: (1) under the protection of nitrogen, adding benzoguanamine and salicylaldehyde into a solvent to obtain a benzoguanamine solution; (2) carrying out affinity substitution reaction on 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and salicylated melamine to obtain a salicylated melamine phosphaphenanthrene solution; (3) cooling the salicylidenemelamine phosphaphenanthrene solution to obtain the nitrogen-phosphorus efficient flame retardant containing the benzoguanamine structure. By utilizing the characteristics of the carbonization and the thermal stability of the benzoguanamine structure and the nitrogen-phosphorus conjugated synergistic flame retardance, the flame retardant with better carbonization rate and flame retardant effect is obtained, and the yield is high.
Description
Technical Field
The invention relates to the technical field of flame retardants, in particular to an application of a nitrogen-phosphorus efficient flame retardant containing a benzoguanamine structure.
Background
Resin is a common polymer material in daily life, and is applied to a plurality of technical fields due to good oxidation resistance and corrosion resistance. However, the resin is flammable and has low safety.
Epoxy resin is an important thermosetting plastic, and is widely applied to the fields of coatings, adhesives, electronic and electrical materials, engineering plastics, composite materials, civil engineering materials and the like due to good cohesiveness, electrical insulation and chemical stability. However, epoxy resin has a very low limiting oxygen index, is extremely easy to burn, and can continuously burn after a fire and generate a large amount of smoke. Its flammability limits its use in many fields. Therefore, it is crucial to impart good flame retardancy to EP.
In order to improve the flame retardant properties of epoxy resins, a common method is to add flame retardants. The traditional flame retardant contains halogen, and has the emission of smoke and toxic gas during combustion. In the prior art, the preparation of the flame retardant of the epoxy resin is often compounded with 9, 10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide (DOPO), but the carbon forming rate of the prepared flame retardant is lower and the flame retardant effect is poorer.
Disclosure of Invention
In view of the above, the invention provides an application of a nitrogen-phosphorus efficient flame retardant containing a benzoguanamine structure, which utilizes the characteristics of carbon formation and thermal stability of the benzoguanamine structure and nitrogen-phosphorus conjugate synergistic flame retardance to obtain a flame retardant with better carbon formation rate and flame retardant effect.
The invention relates to a nitrogen-phosphorus efficient flame retardant containing a benzoguanamine structure, which has the following structural formula:
the synthesis of the nitrogen-phosphorus efficient flame retardant containing the benzoguanamine structure comprises the following steps:
(1) under the protection of nitrogen, adding benzoguanamine and salicylaldehyde into a solvent according to the molar ratio of 1:2-2.5, reacting for 3-4 hours at 60-90 ℃, and carrying out Schiff base reaction to obtain a benzoguanamine solution, wherein DMF can be used as the solvent, and the reaction equation in the reaction process is as follows;
(2) adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide with the same molar weight as salicylaldehyde into the salicyloylated melamine solution to perform nucleophilic substitution reaction on the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and salicyloylated melamine, wherein the reaction time is 6-7 hours, the reaction temperature is 60-90 ℃, and the salicyloylated melamine phosphaphenanthrene solution is obtained, and the reaction equation is as follows;
(3) and cooling the salicylidenemelamine phosphaphenanthrene solution, cooling to room temperature, adding deionized water, separating out white solids, washing with the deionized water for 2-3 times after filtering, and drying at 60-70 ℃ for 10-12h to obtain the nitrogen-phosphorus efficient flame retardant containing the benzoguanamine structure.
The application of the nitrogen-phosphorus efficient flame retardant containing the benzoguanamine structure comprises the following steps: epoxy resin and a nitrogen-phosphorus efficient flame retardant containing a benzoguanamine structure are mixed according to the mass ratio of 100: 5-10, and stirring at 90-100 ℃; after vacuumizing, adding a curing agent with the mass of 0.15-0.2 times of that of the epoxy resin, and uniformly mixing to obtain a resin mixture; and pouring the resin mixture into a mold, and cooling to obtain an epoxy resin solid.
The curing agent may be a 4,4' diaminodiphenylmethane (DDM) curing agent.
The reaction process comprises the steps of firstly carrying out Schiff base reaction on benzoguanamine and salicylaldehyde to generate intermediate product of the benzoguanamine, then adding DOPO, carrying out nucleophilic substitution reaction on the benzoguanamine and the DOPO to generate the benzoguanamine phosphaphenanthrene (HDPD), namely a flame retardant, cooling to crystallize the benzoguanamine phosphaphenanthrene (HDPD), filtering and washing to obtain HDPD solid, namely the nitrogen-phosphorus efficient flame retardant containing a benzoguanamine structure.
The invention has the beneficial effects that: the benzoguanamine contains abundant primary amine, and the derivative formed by the reaction of the benzoguanamine and DOPO has the synergistic effect of nitrogen and phosphorus, so that the flame retardant effect of the DOPO can be promoted; the benzoguanamine and the salicylaldehyde are used as raw materials, so that the flame retardant has a benzoguanamine structure which has good carbon formation and thermal stability, and the epoxy resin thermosetting material containing the flame retardant can easily form a compact carbon layer in combustion, so that the contact between oxygen and internal materials is isolated, the flame retardant effect is achieved, and the flame retardant effect of the flame retardant is improved; the nitrogen-phosphorus conjugate synergistic flame retardant has large steric hindrance in the structure of the flame retardant, and is beneficial to improving the flame retardant effect; in addition, the benzoguanamine has the effect of promoting curing, hinders the melting of resin during combustion, resists flame and burns, has simple synthetic method and high yield up to 97 percent, does not contain halogen, and is green and environment-friendly.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of a nitrogen-phosphorus based efficient flame retardant containing a benzoguanamine structure provided in example 1 of the present invention;
FIG. 2 is a nuclear magnetic phosphorus spectrum of a nitrogen-phosphorus based efficient flame retardant containing a benzoguanamine structure provided in example 1 of the present invention;
FIG. 3 is an SEM image of the residue after burning of an epoxy resin to which a flame retardant of the present invention is not added;
FIG. 4 is an SEM image of the residue after burning of a flame retardant-containing epoxy resin solid prepared by using a high-efficiency nitrogen-phosphorus flame retardant containing a benzoguanamine structure as provided in example 1 of the present invention.
Detailed Description
The present invention will be described in detail with reference to specific embodiments.
Example 1
A nitrogen-phosphorus efficient flame retardant containing a benzoguanamine structure has the following structural formula:
the synthesis of the nitrogen-phosphorus efficient flame retardant containing the benzoguanamine structure in this embodiment includes the following steps:
(1) under the protection of nitrogen, adding benzoguanamine and salicylaldehyde into a solvent according to the molar ratio of 1:2, reacting for 3 hours at 60 ℃, and carrying out Schiff base reaction to obtain a benzoguanamine solution, wherein DMF can be used as the solvent, and the reaction equation in the reaction process is as follows;
(2) adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide with the same molar weight as salicylaldehyde into the salicyloylated melamine solution to perform nucleophilic substitution reaction on the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and salicyloylated melamine, wherein the reaction time is 6 hours, the reaction temperature is 60 ℃, and the salicyloylated melamine phosphaphenanthrene solution is obtained, and the reaction equation is as follows;
(3) and cooling the salicylidenemelamine phosphaphenanthrene solution, cooling to room temperature, adding deionized water, separating out white solids, washing with the deionized water for 2 times after filtering, and drying at 60 ℃ for 10 hours to obtain the nitrogen-phosphorus efficient flame retardant containing the benzoguanamine structure.
The application of the nitrogen-phosphorus efficient flame retardant containing the benzoguanamine structure comprises the following steps: epoxy resin and a nitrogen-phosphorus efficient flame retardant containing a benzoguanamine structure are mixed according to the mass ratio of 100: 5, mixing and stirring at 90 ℃; adding a DDM curing agent with the mass being 0.15 times of that of the epoxy resin after vacuumizing, and uniformly mixing to obtain a resin mixture; and pouring the resin mixture into a mold, and cooling to obtain an epoxy resin solid.
The flame retardant prepared in this example was subjected to nuclear magnetic hydrogen spectroscopy and nuclear magnetic phosphorus spectroscopy analysis, and the results are shown in fig. 1 and 2. FIG. 1 and FIG. 2 are respectively a drawing of a synthetic flame retardant HDPD1HNMR and phosphorus spectra. The hydrogen spectrum contains only three types of hydrogen, namely benzene ring, CH and OH, and the hydrogenExcept for solvent peaks, chemical shifts of the three types of hydrogen are only shown in the spectrogram, and the integral area is matched with the number ratio of the various types of hydrogen. In addition, the molecular structure only contains one kind of phosphorus, and the phosphorus spectrum only shows the chemical shift of one kind of phosphorus, and the shift is greatly different from the chemical shift of phosphorus element in the raw material DOPO. The yield was 96.8%.
The solid oxygen index test result of the prepared epoxy resin is 33.0, and the vertical combustion test result is V1 A rank.
FIG. 3 is an SEM image of the residue after burning of an epoxy resin to which a flame retardant of the present invention is not added; FIG. 4 SEM photograph of the residue after burning of the epoxy resin solid prepared in example 1 of the present invention. It can be seen that the solid epoxy resin in the examples has a compact surface layer after combustion, and can play a good role in isolating air, thereby being flame-retardant.
Example 2
A nitrogen-phosphorus efficient flame retardant containing a benzoguanamine structure has the following structural formula:
the synthesis of the nitrogen-phosphorus efficient flame retardant containing the benzoguanamine structure in this embodiment includes the following steps:
(1) under the protection of nitrogen, benzoguanamine and salicylaldehyde are mixed according to the molar ratio of 1:2-2.5
Adding the mixture into DMF, reacting for 4 hours at 90 ℃, and carrying out Schiff base reaction to obtain a salicylphenyl melamine solution;
(2) adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide with the same molar weight as salicylaldehyde into the salicylated melamine solution, and performing nucleophilic substitution reaction on the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and salicylated melamine for 7 hours at the reaction temperature of 90 ℃ to obtain the salicylated melamine phosphaphenanthrene solution;
(3) and cooling the salicylidenemelamine phosphaphenanthrene solution, cooling to room temperature, adding deionized water, separating out white solids, washing with the deionized water for 3 times after filtering, and drying at 70 ℃ for 12 hours to obtain the nitrogen-phosphorus efficient flame retardant containing the benzoguanamine structure.
The application of the nitrogen-phosphorus efficient flame retardant containing the benzoguanamine structure comprises the following steps: epoxy resin and a nitrogen-phosphorus efficient flame retardant containing a benzoguanamine structure are mixed according to the mass ratio of 100: 10 mixing and stirring at 100 ℃; adding a DDM curing agent with the mass being 0.2 times of that of the epoxy resin after vacuumizing, and uniformly mixing to obtain a resin mixture; and pouring the resin mixture into a mold, and cooling to obtain an epoxy resin solid.
The yield of the flame retardant is 97.2 percent, the solid oxygen index test result of the prepared epoxy resin is 35.5, and the vertical combustion test result is V0 A rank.
Example 3
A nitrogen-phosphorus efficient flame retardant containing a benzoguanamine structure has the following structural formula:
the synthesis of the nitrogen-phosphorus efficient flame retardant containing the benzoguanamine structure in this embodiment includes the following steps:
(1) under the protection of nitrogen, adding benzoguanamine and salicylaldehyde into a DMF solvent according to the molar ratio of 1:2.1, reacting for 3.5 hours at 70 ℃, and carrying out Schiff base reaction to obtain a benzoguanamine solution;
(2) adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide with the same molar weight as salicylaldehyde into the salicylated melamine solution to perform nucleophilic substitution reaction on the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and salicylated melamine, wherein the reaction time is 6.5 hours, and the reaction temperature is 80 ℃, so as to obtain the salicylated melamine phosphaphenanthrene solution;
(3) and cooling the salicylidenemelamine phosphaphenanthrene solution, cooling to room temperature, adding deionized water, separating out white solids, washing with the deionized water for 3 times after filtering, and drying at 65 ℃ for 11 hours to obtain the nitrogen-phosphorus efficient flame retardant containing the benzoguanamine structure.
The application of the nitrogen-phosphorus efficient flame retardant containing the benzoguanamine structure comprises the following steps: epoxy resin and a nitrogen-phosphorus efficient flame retardant containing a benzoguanamine structure are mixed according to the mass ratio of 100: 8, mixing and stirring at 95 ℃; adding a DDM curing agent with the mass being 0.17 times that of the epoxy resin after vacuumizing, and uniformly mixing to obtain a resin mixture; and pouring the resin mixture into a mold, and cooling to obtain an epoxy resin solid.
The yield of the flame retardant is 97.5 percent, the solid oxygen index test result of the prepared epoxy resin is 34.6, and the vertical combustion test result is V0 A rank.
The invention has the beneficial effects that: the benzoguanamine contains abundant primary amine, and the derivative formed by the reaction of the benzoguanamine and DOPO has the synergistic effect of nitrogen and phosphorus, so that the flame retardant effect of the DOPO can be promoted; the benzoguanamine and the salicylaldehyde are used as raw materials, so that the flame retardant has a benzoguanamine structure which has good carbon formation and thermal stability, and the epoxy resin thermosetting material containing the flame retardant can easily form a compact carbon layer in combustion, so that the contact between oxygen and internal materials is isolated, the flame retardant effect is achieved, and the flame retardant effect of the flame retardant is improved; the nitrogen-phosphorus conjugate synergistic flame retardant has large steric hindrance in the structure of the flame retardant, and is beneficial to improving the flame retardant effect; in addition, the benzoguanamine has the effect of promoting curing, hinders the melting of resin during combustion, resists flame and burns, has simple synthetic method and high yield up to 97 percent, does not contain halogen, and is green and environment-friendly.
The present invention is not limited to the above-described specific embodiments, and various modifications and variations are possible. Any modifications, equivalents, improvements and the like made to the above embodiments in accordance with the technical spirit of the present invention should be included in the scope of the present invention.
Claims (8)
1. The application of the nitrogen-phosphorus efficient flame retardant containing the benzoguanamine structure is characterized by comprising the following steps: epoxy resin and a nitrogen-phosphorus efficient flame retardant containing a benzoguanamine structure are mixed according to the mass ratio of 100: 5-10, and stirring at 90-100 ℃; adding a curing agent after vacuumizing, and uniformly mixing to obtain a resin mixture; pouring the resin mixture into a mold, and cooling to obtain an epoxy resin solid; the nitrogen-phosphorus efficient flame retardant containing the benzoguanamine structure has the following structural formula:
2. the use of the efficient fire retardant of claim 1, wherein the curing agent is 4,4' diaminodiphenylmethane.
3. The use of the efficient fire retardant of claim 2, wherein the amount of the curing agent is 0.15-0.2 times of the epoxy resin.
4. The use of the efficient fire retardant of claim 1, wherein the efficient fire retardant of the invention is synthesized by the following steps:
(1) under the protection of nitrogen, adding benzoguanamine and salicylaldehyde into a solvent, reacting for 3-4 hours at 60-90 ℃, and performing Schiff base reaction to obtain a benzoguanamine solution;
(2) adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide into the salicylated benzoguanamine solution to enable the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and the salicylated benzoguanamine to carry out nucleophilic substitution reaction for 6-7 hours to obtain the salicylated benzoguanamine phosphaphenanthrene solution;
(3) and cooling the salicylphenyl melamine phosphaphenanthrene solution, adding water, filtering and drying to obtain the nitrogen-phosphorus efficient flame retardant containing the benzoguanamine structure.
5. The application of the efficient nitrogen-phosphorus flame retardant containing the benzoguanamine structure as claimed in claim 4, wherein the molar ratio of the benzoguanamine to the salicylaldehyde is 1: 2-2.5.
6. The use of the efficient fire retardant of N-P series containing benzoguanamine structure as claimed in claim 4, wherein the molar amount of said 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is equal to the molar amount of said salicylaldehyde.
7. The use of the efficient N-P flame retardant containing a benzoguanamine structure as claimed in claim 4, wherein the reaction temperature of the nucleophilic substitution reaction in step (2) is 60-90 ℃.
8. The use of the efficient N-P flame retardant containing the benzoguanamine structure as claimed in claim 4, wherein the drying temperature in step (3) is 60-70 ℃ and the drying time is 10-12 h.
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| CN201910828940.2A CN110511431B (en) | 2019-09-03 | 2019-09-03 | Application of nitrogen-phosphorus efficient flame retardant containing benzoguanamine structure |
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| CN112961314B (en) * | 2021-03-15 | 2021-12-31 | 四川大学 | Preparation method of flame-retardant water-based polyurethane for impregnation of microfiber base cloth |
| CN113461734A (en) * | 2021-04-19 | 2021-10-01 | 衡阳师范学院 | Novel Schiff base DOPO phosphorus nitrogen-containing flame retardant and synthesis method and application thereof |
| WO2023096576A2 (en) * | 2021-11-23 | 2023-06-01 | Agency For Science, Technology And Research | Polymeric flame retardant synergist and the method of producing it and its formulation for polyamides |
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