CN110041370B - Preparation method and application of efficient flame retardant containing DOPO and aminopyrazine structures - Google Patents
Preparation method and application of efficient flame retardant containing DOPO and aminopyrazine structures Download PDFInfo
- Publication number
- CN110041370B CN110041370B CN201910410437.5A CN201910410437A CN110041370B CN 110041370 B CN110041370 B CN 110041370B CN 201910410437 A CN201910410437 A CN 201910410437A CN 110041370 B CN110041370 B CN 110041370B
- Authority
- CN
- China
- Prior art keywords
- aminopyrazine
- flame retardant
- structures
- dopo
- retardant containing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 82
- 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 73
- XFTQRUTUGRCSGO-UHFFFAOYSA-N pyrazin-2-amine Chemical group NC1=CN=CC=N1 XFTQRUTUGRCSGO-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 title claims abstract 15
- 239000003822 epoxy resin Substances 0.000 claims abstract description 26
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 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 17
- 239000002262 Schiff base Substances 0.000 claims abstract description 15
- 150000004753 Schiff bases Chemical class 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 13
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000007259 addition reaction Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 abstract description 20
- 239000001301 oxygen Substances 0.000 abstract description 20
- 238000002485 combustion reaction Methods 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 9
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 8
- 239000011574 phosphorus Substances 0.000 abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 238000001816 cooling Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 10
- 238000003760 magnetic stirring Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 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 5
- 238000010992 reflux Methods 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- -1 aminopyrazine compound Chemical class 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 231100000053 low toxicity Toxicity 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process 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
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000007039 two-step reaction 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
- 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
Landscapes
- 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)
- Fireproofing Substances (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a preparation method and application of a high-efficiency flame retardant containing DOPO and aminopyrazine structures, and relates to the technical field of flame retardants. The invention relates to a preparation method of a high-efficiency flame retardant containing DOPO and aminopyrazine structures, which comprises the following steps; (1) mixing aminopyrazine and terephthalaldehyde in a solvent, and carrying out Schiff base reaction, wherein the reaction equation is shown as the formula;
(2) adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and carrying out addition reaction on the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and Schiff base to generate the flame retardant DTPA containing the aminopyrazine structure, wherein the reaction equation is shown as the following formula.
The aminopyrazine fire retardant prepared by the invention has higher fire retardant efficiency, the phosphorus content is 0.09-0.34%, the fire retardant property of the material is improved, the oxygen index of the cured epoxy resin can be improved to 32.5%, the vertical combustion can reach UL-94V-0 level, and the using amount of the fire retardant is less under the condition of the same fire retardant effect.
Description
Technical Field
The invention relates to the technical field of flame retardants, and particularly relates to a preparation method and application of a high-efficiency flame retardant containing DOPO and aminopyrazine structures.
Background
Epoxy resins (EP) are widely used as a thermosetting polymer material for electronic and electric appliances, automobiles, packaging, printed circuit boards, adhesives, surface coatings, etc. because they have excellent electrical insulation properties, dimensional stability, high thermal stability, low shrinkage, strong adhesion, mechanical durability, etc. However, its use in many fields is limited due to its flammability. Therefore, it is crucial to impart good flame retardancy to EP.
A common method of improving the flame retardant properties of epoxy resins is the addition of flame retardants. The traditional halogen flame retardant has secondary damages such as smoke, toxic gas emission and the like during combustion, so that the safety of a human body is seriously threatened, the flame retardant effect is poor, the addition amount of the flame retardant is large during use, and the use cost is high.
Disclosure of Invention
In view of the above, the invention provides a preparation method and application of a high-efficiency flame retardant containing DOPO and aminopyrazine structures, which is halogen-free, low-toxicity, contains nitrogen atoms capable of forming a vapor source, has a good flame retardant effect, is free from smoke during combustion, and is low in addition during use.
The invention relates to a preparation method of a high-efficiency flame retardant containing DOPO and aminopyrazine structures, which comprises the following steps;
(1) adding aminopyrazine, terephthalaldehyde and a solvent into a 500mL three-neck flask with a condensing reflux pipe, magnetic stirring and a heating device for mixing, wherein the solvent can be ethanol, heating to 50-65 ℃, dissolving the aminopyrazine, the terephthalaldehyde by magnetic stirring, and carrying out Schiff base reaction at about 65 ℃, wherein the reaction equation is shown as the formula;
(2) adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), carrying out addition reaction on the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and Schiff base at 60-68 ℃ to generate a flame retardant DTPA containing an aminopyrazine structure, cooling to room temperature as shown in the following reaction formula, carrying out suction filtration to obtain a white solid, washing the white solid with deionized water for two to three times, washing with ethanol for two times, and drying in a vacuum drying oven at 55-60 ℃ for 10-14h to obtain a pure product.
Wherein, the mol ratio of the aminopyrazine, the terephthalaldehyde to the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1.8-2.2: 1: 2-2.3 to ensure that the reaction proceeds stoichiometrically.
The application of the high-efficiency flame retardant containing DOPO and aminopyrazine structures based on the above description comprises the following steps: mixing an epoxy resin, a curing agent and a flame retardant with an aminopyrazine structure according to a mass fraction ratio of 76.2-79.4: 19.8-20.4: 1-4; stirring uniformly at 90 ℃, pouring into a mold, cooling to room temperature, curing for 2h at 100 ℃ and 150 ℃ respectively, and curing to obtain the cured epoxy resin.
The flame retardant mechanism of the flame retardant of the invention is: the flame retardant contains aminopyrazine and a benzene ring structure, and NH is easily generated by decomposition3，CO2And the like, thereby playing the effect of diluting the combustible gas. And the allyl group generated simultaneously generates chain free radical reaction to carbon. In addition, the contained DOPO structure can be decomposed to generate PO and PO2+The free radicals capture active free radicals to generate a quenching effect, and polyphosphoric acid is formed to be used as an acid source, so that the thermosetting material rich in hydroxyl is dehydrated into carbon, the internal material is protected from being further damaged, and the combustion is delayed. Therefore, the flame retardant endows the epoxy resin with excellent flame retardant performance.
The structure of the aminopyrazine compound is known to be halogen-free and low-toxicity, and the aminopyrazine compound contains nitrogen atoms capable of forming a steam source. The synthetic reaction method is simple, has no other byproducts, mild reaction conditions, safe operation and low cost, the aminopyrazine flame retardant has higher flame retardant efficiency, the addition amount of the flame retardant is 1-4wt%, the phosphorus content is 0.09-0.34%, the flame retardant performance of the material can be improved by improving the phosphorus content in the material, the oxygen index of the cured epoxy resin can be improved to 32.5%, the vertical combustion passes through UL-94V-0 level, and the addition amount of the flame retardant is less under the condition of the same flame retardant effect.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of a flame retardant prepared by a preparation method of a high-efficiency flame retardant containing DOPO and aminopyrazine structures according to a specific embodiment of the invention;
fig. 2 is a nuclear magnetic phosphorus spectrum of the flame retardant prepared by the preparation method of the efficient flame retardant containing the DOPO and aminopyrazine structures, which is provided in the specific embodiment of the invention.
Detailed Description
The present invention will be described in detail with reference to specific embodiments. It should be noted that the following examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as those skilled in the art will be able to make insubstantial modifications and variations of this invention in light of the above teachings, and will nevertheless fall within the scope of this invention.
The Limiting Oxygen Index (LOI) in the examples was measured according to GB/T2406. sup. 1993 using an oxygen index measuring instrument type HC-2C, and the vertical combustion was measured according to GB/T2408-1996 using a vertical combustion instrument type CZF-2.
The Limiting Oxygen Index (LOI) refers to the minimum oxygen concentration required for a material to undergo flaming combustion in an oxygen-nitrogen mixture stream under specified conditions, and the limiting oxygen index refers to the fractional concentration of oxygen in the oxygen-nitrogen mixture when the polymer is just able to support its combustion. Is an index that characterizes the burning behavior of a material. The high limiting oxygen index indicates that the material is not easy to burn, the low oxygen index indicates that the material is easy to burn, and the oxygen index is considered to be a flammable material when the oxygen index is less than 22%, the oxygen index is between 22% and 27%, and the oxygen index is more than 27% and is considered to be a nonflammable material.
NR represents a non-graded flame retardancy, and V represents a vertical burn test, in which the energy levels of flame retardancy are classified into V-2, V-1, and V-0. V-2 is that after the sample is subjected to combustion test for 10 seconds twice, the flame is extinguished within 30 seconds, and absorbent cotton below 30cm can be ignited; v-1 is that after the sample is subjected to combustion test for 10 seconds twice, the flame is extinguished within 30 seconds, and absorbent cotton below 30cm cannot be ignited; v-0 is that after the sample is subjected to two 10-second combustion tests, the flame is extinguished within 10 seconds, and no combustible can fall off.
Comparative example
Adding 79.6% of epoxy resin and 20.4% of curing agent in mass percent into a flask, uniformly stirring at 90 ℃, pouring into a mold, cooling to room temperature, and curing at 100 ℃ and 150 ℃ for 2 hours respectively to obtain an epoxy resin cured product, wherein the oxygen index test result is 25.8%, and the vertical combustion grade is UL-94 NR grade.
Example one
The invention relates to a preparation method of a high-efficiency flame retardant containing DOPO and aminopyrazine structures, which comprises the following steps;
(1) adding 54mmol of aminopyrazine, 30mmol of terephthalaldehyde and a proper amount of solvent into a 500mL three-neck flask with a condensing reflux pipe, magnetic stirring and a heating device for mixing, wherein the solvent can be ethanol, heating to 50 ℃, dissolving by magnetic stirring, and carrying out Schiff base reaction at about 65 ℃, wherein the reaction equation is shown as the formula;
(2) adding 60mmol of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, carrying out addition reaction on the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and Schiff base at 60 ℃ to generate a flame retardant DTPA containing an aminopyrazine structure, cooling to room temperature as shown in the following formula, carrying out suction filtration to obtain a white solid, washing the obtained white solid with deionized water for two to three times, washing with ethanol for two times, and drying in a vacuum drying oven at 55 ℃ for 10 hours to obtain a pure product.
Referring to FIGS. 1 and 2, it can be seen from FIG. 1 that the peak at a chemical shift of 6.9 to 8.2ppm can be assigned to a hydrogen atom on an aromatic ring. The peak at 5.7ppm was assigned to the hydrogen atom on the imino group and the peak at 5.2ppm was assigned to the hydrogen atom on the chiral carbon. 2.5ppm and 3.2ppm are the chemical shifts of the solvents DMSO and water, respectively. In addition, the peak area is basically the same as the number of corresponding hydrogen atoms, which indicates the success of the synthesis.
In addition, the phosphorus spectrum of FIG. 2 shows, with the exception of the background, only one peak with a chemical shift of 29.5ppm, which can be assigned to a phosphorus atom, which corresponds to the chemical structure diagram with only one phosphorus in the structure.
Based on the application of the efficient flame retardant containing the DOPO and the aminopyrazine structures, the mass fraction ratio of the epoxy resin, the curing agent and the flame retardant containing the aminopyrazine structures is 79.4: 20.4: 1, stirring uniformly at 90 ℃, pouring into a mold, cooling to room temperature, curing at 100 ℃ and 150 ℃ for 2 hours respectively to obtain an epoxy resin cured product, wherein the limit oxygen index test result of (LOI) is 28.5%, and the vertical combustion grade is UL-94V-2 grade.
Example two
The invention relates to a preparation method of a high-efficiency flame retardant containing DOPO and aminopyrazine structures, which comprises the following steps;
(1) adding 66mmol of aminopyrazine, 30mmol of terephthalaldehyde and a proper amount of solvent into a 500mL three-neck flask with a condensing reflux pipe, magnetic stirring and a heating device for mixing, wherein the solvent can be ethanol, heating to 65 ℃, dissolving by magnetic stirring, and carrying out Schiff base reaction at about 65 ℃, wherein the reaction equation is shown as the formula;
(2) adding 69mmol of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, carrying out addition reaction on the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and Schiff base at 68 ℃ to generate a flame retardant DTPA containing an aminopyrazine structure, cooling to room temperature as shown in the following formula, carrying out suction filtration to obtain a white solid, washing the obtained white solid with deionized water for two to three times, washing with ethanol for two times, and drying in a vacuum drying oven at 60 ℃ for 14 hours to obtain a pure product.
Based on the application of the efficient flame retardant containing the DOPO and the aminopyrazine structures, the mass fraction ratio of the epoxy resin, the curing agent and the flame retardant containing the aminopyrazine structures is 77.8: 20.2: 2, stirring uniformly at 90 ℃, pouring into a mold, cooling to room temperature, curing at 100 ℃ and 150 ℃ for 2 hours respectively to obtain an epoxy resin cured product, wherein the limit oxygen index test result of (LOI) is 30.3%, and the vertical burning grade is UL-94V-1 grade.
EXAMPLE III
The invention relates to a preparation method of a high-efficiency flame retardant containing DOPO and aminopyrazine structures, which comprises the following steps;
(1) adding 60mmol of aminopyrazine, 30mmol of terephthalaldehyde and a proper amount of solvent into a 500mL three-neck flask with a condensing reflux pipe, magnetic stirring and a heating device for mixing, wherein the solvent can be ethanol, heating to 60 ℃, dissolving by magnetic stirring, and carrying out Schiff base reaction at about 65 ℃, wherein the reaction equation is shown as the formula;
(2) adding 60mmol of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, carrying out addition reaction on the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and Schiff base at 65 ℃ to generate a flame retardant DTPA containing an aminopyrazine structure, cooling to room temperature as shown in the following formula, carrying out suction filtration to obtain a white solid, washing the obtained white solid with deionized water for two to three times, washing with ethanol for two times, and drying in a vacuum drying oven at 58 ℃ for 12 hours to obtain a pure product.
Based on the application of the efficient flame retardant containing the DOPO and the aminopyrazine structures, the mass fraction ratio of the epoxy resin, the curing agent and the flame retardant containing the aminopyrazine structures is 77: 20: 3, stirring uniformly at 90 ℃, pouring into a mold, cooling to room temperature, curing at 100 ℃ and 150 ℃ for 2 hours respectively to obtain an epoxy resin cured product, wherein the limit oxygen index test result of (LOI) is 31.5%, and the vertical combustion grade is UL-94V-1 grade.
Example four
The invention relates to a preparation method of a high-efficiency flame retardant containing DOPO and aminopyrazine structures, which comprises the following steps;
(1) adding 58mmol of aminopyrazine, 30mmol of terephthalaldehyde and a proper amount of solvent into a 500mL three-neck flask with a condensing reflux pipe, magnetic stirring and a heating device for mixing, wherein the solvent can be ethanol, heating to 65 ℃, dissolving by magnetic stirring, and carrying out Schiff base reaction at about 65 ℃, wherein the reaction equation is shown as the formula;
(2) adding 60mmol of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, carrying out addition reaction on the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and Schiff base at 65 ℃ to generate a flame retardant DTPA containing an aminopyrazine structure, cooling to room temperature as shown in the following formula, carrying out suction filtration to obtain a white solid, washing the obtained white solid with deionized water for two to three times, washing with ethanol for two times, and drying in a vacuum drying oven at 55 ℃ for 12 hours to obtain a pure product.
Based on the application of the efficient flame retardant containing the DOPO and the aminopyrazine structures, the mass fraction ratio of the epoxy resin, the curing agent and the flame retardant containing the aminopyrazine structures is 76.2: 19.8: 4, stirring uniformly at 90 ℃, pouring into a mold, cooling to room temperature, curing at 100 ℃ and 150 ℃ for 2 hours respectively to obtain an epoxy resin cured product, wherein the limit oxygen index test result of (LOI) is 32.5%, and the vertical burning grade is UL-94V-0 grade.
Based on the application of the efficient flame retardant containing the DOPO and the aminopyrazine structures, the mass fraction ratio of the epoxy resin, the curing agent and the flame retardant containing the aminopyrazine structures is 76.2-79.4: 19.8-20.4: 1-4, stirring uniformly at 90 ℃, pouring into a mold, cooling to room temperature, curing at 100 ℃ and 150 ℃ for 2h respectively, and curing to obtain the cured epoxy resin.
The following table shows the data of monitoring the flame retardancy of the cured epoxy resins prepared in the comparative examples and examples
As can be seen from the data in the table, the flame retardant has good flame retardant effect when being applied, and belongs to flame retardant materials, and less flame retardant is added under the condition of the same flame retardant effect.
The aminopyrazine compound has the advantages of no halogen, low toxicity, nitrogen atom capable of forming a steam source, suitability for generation and processing, small influence on mechanical properties and no corrosion to a mould. The novel flame retardant is synthesized by two-step reaction by taking aminopyrazine and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) as main raw materials, and the synthetic method is simple, high in yield and good in flame retardant effect.
The synthetic reaction method is simple, has no other byproducts, mild reaction conditions, safe operation and low cost, the aminopyrazine flame retardant has higher flame retardant efficiency, the addition amount of the flame retardant is 1-4wt%, the phosphorus content is 0.09-0.34%, the flame retardant performance of the material can be improved by improving the phosphorus content in the material, the oxygen index of the cured epoxy resin can be improved to 32.5%, the vertical combustion can reach UL-94V-0 level, and the addition amount of the flame retardant is less under the condition of the same flame retardant effect.
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. A preparation method of a flame retardant containing DOPO and aminopyrazine structures is characterized by comprising the following steps;
(1) mixing aminopyrazine and terephthalaldehyde in a solvent, and carrying out Schiff base reaction, wherein the reaction equation is shown as the formula;
(2) adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to make 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and Schiff base produce addition reaction to produce fire retardant DTPA containing DOPO and aminopyrazine structure, and the reaction formula is shown in the following formula
2. The method for preparing a flame retardant containing DOPO and aminopyrazine structures according to claim 1, wherein the molar ratio of aminopyrazine, terephthalaldehyde, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1.8-2.2: 1: 2-2.3.
3. The preparation method of the flame retardant containing DOPO and aminopyrazine structures according to claim 1, wherein the reaction temperature of the Schiff base reaction is 65 ℃.
4. The preparation method of the flame retardant containing DOPO and aminopyrazine structures according to claim 1, wherein the reaction temperature of the addition reaction is 60-68 ℃.
5. The preparation method of the flame retardant containing DOPO and aminopyrazine structures according to claim 1, further comprising filtering, washing and drying.
6. The preparation method of the flame retardant containing the DOPO and the aminopyrazine structure according to claim 5, wherein the drying is carried out in a vacuum drying oven at 55-60 ℃ for 10-14 h.
7. The application of the flame retardant containing the DOPO and the aminopyrazine structures is characterized in that epoxy resin, a curing agent and the flame retardant containing the DOPO and the aminopyrazine structures are mixed and cured to obtain an epoxy resin cured product; the flame retardant containing DOPO and aminopyrazine structures is prepared by the preparation method of any one of claims 1-6.
8. The application of the flame retardant containing DOPO and aminopyrazine structures according to claim 7, wherein the mass fraction ratio of the epoxy resin to the curing agent to the flame retardant containing DOPO and aminopyrazine structures is 76.2-79.4: 19.8-20.4: 1-4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910410437.5A CN110041370B (en) | 2019-05-17 | 2019-05-17 | Preparation method and application of efficient flame retardant containing DOPO and aminopyrazine structures |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910410437.5A CN110041370B (en) | 2019-05-17 | 2019-05-17 | Preparation method and application of efficient flame retardant containing DOPO and aminopyrazine structures |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110041370A CN110041370A (en) | 2019-07-23 |
| CN110041370B true CN110041370B (en) | 2021-08-06 |
Family
ID=67282449
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910410437.5A Active CN110041370B (en) | 2019-05-17 | 2019-05-17 | Preparation method and application of efficient flame retardant containing DOPO and aminopyrazine structures |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110041370B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113337006A (en) * | 2021-04-19 | 2021-09-03 | 衡阳师范学院 | Novel Schiff base DOPO phosphorus-nitrogen-containing flame retardant and preparation method and application thereof |
| CN113429628B (en) * | 2021-07-20 | 2022-04-08 | 北京理工大学 | Expandable phytate flame retardant, flame-retardant epoxy resin, and preparation method and application thereof |
| CN113429629B (en) * | 2021-07-20 | 2023-02-28 | 衡阳师范学院 | Schiff-HCCP flame retardant, preparation method thereof and modified epoxy resin |
| CN113429627B (en) * | 2021-08-17 | 2023-02-28 | 衡阳师范学院 | P-aminobenzoic acid-condensed p-hydroxyl Schiff base/DOPO flame retardant, preparation method thereof and modified epoxy resin |
| CN114736429B (en) * | 2022-04-22 | 2023-07-21 | 北京理工大学重庆创新中心 | Flame retardant containing DOPO conjugated structure, high-efficiency flame-retardant epoxy resin and preparation method thereof |
| CN114836005A (en) * | 2022-06-16 | 2022-08-02 | 南京工业大学 | Preparation method of para-aminobenzonitrile derivative flame-retardant epoxy resin composite material |
| CN115612176A (en) * | 2022-10-21 | 2023-01-17 | 浙江工业大学 | Reactive flame retardant containing DOPO group and nitrogen-containing heterocycle and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838778A (en) * | 2012-10-09 | 2012-12-26 | 清华大学深圳研究生院 | Preparation method of nitrogen and phosphorus fire retardant, nitrogen and phosphorus fire retardant and application thereof |
| CN107400196A (en) * | 2017-08-04 | 2017-11-28 | 武汉工程大学 | A kind of application process of new reaction-type flame-retarding epoxy curing agent in epoxy-resin systems |
| CN107400197A (en) * | 2017-08-04 | 2017-11-28 | 武汉工程大学 | A kind of reaction-type flame-retarding epoxy curing agent and preparation method thereof |
| CN109485916A (en) * | 2018-11-20 | 2019-03-19 | 武汉工程大学 | A kind of synthesis and application of Aminopyrazine based flame retardant |
-
2019
- 2019-05-17 CN CN201910410437.5A patent/CN110041370B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838778A (en) * | 2012-10-09 | 2012-12-26 | 清华大学深圳研究生院 | Preparation method of nitrogen and phosphorus fire retardant, nitrogen and phosphorus fire retardant and application thereof |
| CN107400196A (en) * | 2017-08-04 | 2017-11-28 | 武汉工程大学 | A kind of application process of new reaction-type flame-retarding epoxy curing agent in epoxy-resin systems |
| CN107400197A (en) * | 2017-08-04 | 2017-11-28 | 武汉工程大学 | A kind of reaction-type flame-retarding epoxy curing agent and preparation method thereof |
| CN109485916A (en) * | 2018-11-20 | 2019-03-19 | 武汉工程大学 | A kind of synthesis and application of Aminopyrazine based flame retardant |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110041370A (en) | 2019-07-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110041370B (en) | Preparation method and application of efficient flame retardant containing DOPO and aminopyrazine structures | |
| Chen et al. | A novel flame retardant derived from DOPO and piperazine and its application in epoxy resin: Flame retardance, thermal stability and pyrolysis behavior | |
| Liu | Flame-retardant epoxy resins from novel phosphorus-containing novolac | |
| Xu et al. | Synthesis and characterization of a novel epoxy resin based on cyclotriphosphazene and its thermal degradation and flammability performance | |
| CN110734462A (en) | Synthesis and application of nitrogen-phosphorus efficient flame retardants containing benzimidazole structure | |
| You et al. | The synthesis and characterization of a novel phosphorus–nitrogen containing flame retardant and its application in epoxy resins | |
| CN110511431B (en) | Application of nitrogen-phosphorus efficient flame retardant containing benzoguanamine structure | |
| Xu et al. | Preparation of poly (phosphoric acid piperazine) and its application as an effective flame retardant for epoxy resin | |
| CN114426701B (en) | Preparation of P-N compound synergistic graphene oxide flame retardant and application of P-N compound synergistic graphene oxide flame retardant in epoxy resin | |
| Lin et al. | Synthesis, characterization, and properties of novel epoxy resins and cyanate esters | |
| CN111303483A (en) | Nitrogen-phosphorus efficient flame retardant containing p-hydroxybenzaldehyde and tryptamine structures, preparation method and application | |
| Ding et al. | Preparation and properties of halogen-free flame retardant epoxy resins with phosphorus-containing siloxanes | |
| Zhang et al. | A high‐efficiency DOPO‐based reactive flame retardant with bi‐hydroxyl for low‐flammability epoxy resin | |
| CN113429628B (en) | Expandable phytate flame retardant, flame-retardant epoxy resin, and preparation method and application thereof | |
| Wei et al. | Performance comparison of epoxy resins modified with diphenylphosphine oxide and DOPO | |
| CN105001451A (en) | Graphene containing DOPO group and preparation method thereof | |
| CN112048157A (en) | Preparation method of flame-retardant epoxy resin composite material | |
| Li et al. | Thermal and combustion behavior of phosphorus–nitrogen and phosphorus–silicon retarded epoxy | |
| Ribera et al. | Flame retardant epoxy resins based on diglycidyl ether of isobutyl bis (hydroxypropyl) phosphine oxide | |
| CN109503884B (en) | Tryptamine flame retardant and synthesis and application thereof | |
| CN113234228B (en) | Boron-containing polyphosphazene amide flame retardant with efficient flame retardance and smoke suppression as well as preparation method and application thereof | |
| CN107652324B (en) | Three-source-in-one expansion type fire retardant and its synthetic method and application | |
| CN110105395B (en) | Pyridine flame retardant and preparation method and application thereof | |
| TW201617401A (en) | DOPO derivative and composite of epoxy applied in high-frequency substrate | |
| CN115141230A (en) | Nitrogen-phosphorus flame retardant applied to epoxy resin and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |