CN113337004A - Novel phosphorus-nitrogen DOPO derivative flame retardant and synthetic method and application thereof - Google Patents
Novel phosphorus-nitrogen DOPO derivative flame retardant and synthetic method and application thereof Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 113
- 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 108
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 title claims abstract description 45
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical class C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 title claims 12
- 238000010189 synthetic method Methods 0.000 title description 3
- 239000003822 epoxy resin Substances 0.000 claims abstract description 29
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- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims abstract description 18
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002262 Schiff base Substances 0.000 claims abstract description 17
- 150000004753 Schiff bases Chemical class 0.000 claims abstract description 16
- 238000001308 synthesis method Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 10
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 10
- 229960004050 aminobenzoic acid Drugs 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000012046 mixed solvent Substances 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
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- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 238000000967 suction filtration Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 7
- 238000001953 recrystallisation Methods 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 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
- 238000002156 mixing Methods 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000002386 leaching Methods 0.000 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 12
- 239000011347 resin Substances 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 9
- 239000001301 oxygen Substances 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000654 additive Substances 0.000 abstract description 5
- 230000000996 additive effect Effects 0.000 abstract description 5
- 239000011159 matrix material Substances 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 239000002994 raw material Substances 0.000 description 5
- 239000002861 polymer material Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229960001701 chloroform Drugs 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000012815 thermoplastic material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- -1 phosphorus heterocyclic compound Chemical class 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 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
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910001853 inorganic hydroxide Inorganic materials 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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-
- 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
- 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
- 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)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a novel phosphorus-nitrogen DOPO derivative flame retardant, which has the following structural formula:the flame retardant is prepared by synthesizing corresponding Schiff base from 4-methoxybenzaldehyde and p-aminobenzoic acid, and then reacting with 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO). The flame retardant overcomes the defects of poor compatibility of an additive flame retardant and a matrix, easy loss in the using process, poor water resistance and the like, is applied to epoxy resin (EP-51), has good char formation property, can form a compact char layer, can obviously improve the limiting oxygen index LOI of the resin, achieves the level of V-0 in UL-94 when the flame retardant content is 5 percent (the P content is 0.3291 percent), and has good flame retardant effectFruit; the resin material has good thermal stability, and when the mass content of the flame retardant is 5 percent (the P content is 0.3291 percent), the resin material is stable at the temperature of below 320 ℃. Based on the novel phosphorus-nitrogen DOPO derivative flame retardant, the invention also provides a synthesis method and application of the novel phosphorus-nitrogen DOPO derivative flame retardant.
Description
Technical Field
The invention relates to the technical field of flame retardants, in particular to a novel phosphorus-nitrogen DOPO derivative flame retardant, a synthesis method thereof and application of the flame retardant in an epoxy resin polymer matrix.
Background
The high polymer material is widely applied due to the excellent performances of rich sources, easy processing, various varieties, excellent performance, low price and the like, but most of the high polymer materials are inflammable materials and are easy to cause fire, thereby causing serious loss of human lives and properties. Therefore, flame retardancy of polymer materials is a problem to be solved.
At present, the flame retardant mainly comprises a phosphorus flame retardant, a halogen flame retardant, a melamine flame retardant and an inorganic hydroxide flame retardant. For thermoplastic materials, the thermoplastic materials are usually added by a blending method, the addition amount is large, and the thermoplastic materials need to be blended with a base material during construction, so that some high polymer resins are difficult to crosslink or seriously degraded; for thermosetting materials, the method widely adopted at present is to add flame retardant into resin for curing, and the result is better dispersibility, but the defect is obvious, and the problem of compatibility with curing agent and resin is generally existed. Therefore, the reactive flame retardant capable of directly introducing flame retardant groups or elements into the polymer matrix chain segment is widely researched by numerous scholars at home and abroad due to good dispersibility, high flame retardant efficiency and lasting stability of the reactive flame retardant.
The 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) type flame retardant is an organic phosphorus heterocyclic compound, has high thermal stability, oxidation resistance and excellent water resistance, is a good reactive type and additive type flame retardant, is mainly used for flame retardance of polyester fibers, polyurethane foam plastics, thermosetting resin and adhesives, and is a hotspot for flame retardant development due to excellent flame retardant property, but most of the flame retardant needs high flame retardant dosage to play an effective flame retardant effect, the content of polycaprolactam flame retardant applied to Chinese patent CN201710681473 exceeds 15%, and the embodiment of applying the Chinese patent CN201711125311 to PBT also shows that the mechanical property of the composite material is influenced by the excessively high flame retardant dosage.
In view of the above, the present invention aims to provide a flame retardant which has a small addition amount, is compatible with a substrate, and exerts a long-lasting effect, thereby solving the above-mentioned technical problems.
Disclosure of Invention
The invention aims to solve the technical problem of providing a novel phosphorus-nitrogen DOPO derivative flame retardant which has good compatibility with a substrate and good long-acting flame retardant effect and is less in addition when applied to a high polymer material.
In order to solve the problems, the technical scheme of the invention is as follows:
a novel phosphorus-nitrogen DOPO derivative flame retardant has a structure shown as the following formula (I):
a synthetic method of a novel phosphorus-nitrogen DOPO derivative flame retardant comprises the following steps:
step S1, mixing 4-methoxybenzaldehyde and p-aminobenzoic acid according to the molar ratio of (1-3): (1-4) dissolving in a mixed solvent, adding a certain amount of an acid-binding agent to enable a reaction system to be in an alkaline environment, controlling the reaction temperature to be 0-50 ℃, stirring, reacting for 3-7 hours to obtain a large amount of yellow precipitates, and performing suction filtration, washing and drying to obtain pure Schiff base;
step S2, synthesizing Schiff base and DOPO according to the molar ratio (1-2): (1-4) adding the mixture into a mixed solvent, introducing inert gas, stirring, heating the mixed solution until the mixed solution becomes colorless and transparent, heating and refluxing for 3-5 hours to generate a large amount of white precipitates, and performing suction filtration and recrystallization after complete reaction to obtain the phosphorus-nitrogen DOPO derivative flame retardant.
Further, in step S1, the acid-binding agent is at least one of sodium hydroxide, potassium hydroxide, triethylamine, potassium tert-butoxide, sodium methoxide, pyridine, sodium ethoxide, and imidazole.
Further, in step S1 and step S2, the mixed solvent is two of methanol, ethanol, chloroform, tetrahydrofuran, dichloromethane, acetonitrile, dimethyl sulfoxide, 1, 4-dioxane, carbon tetrachloride, DMF, and DMAC, and the two solvents are mixed in a volume ratio of 1-3: 1-4.
Further, in step S2, the inert gas is one of nitrogen, argon, and helium.
Further, in step S1, the washing process uses ice water cooled solvent for multiple rinses.
Further, in step S2, a mixed solvent of ethyl acetate and petroleum ether is used for recrystallization, wherein the volume ratio of ethyl acetate to petroleum ether is (1-5): (1-3).
The invention also provides application of the novel phosphorus-nitrogen DOPO derivative flame retardant in the preparation process of epoxy resin.
Furthermore, the novel phosphorus-nitrogen DOPO derivative flame retardant is applied to the preparation process of the epoxy resin, and the addition amount of the novel phosphorus-nitrogen DOPO derivative flame retardant is 1-7% of the total amount of the epoxy resin.
Compared with the prior art, the novel phosphorus-nitrogen DOPO derivative flame retardant and the synthesis method and the application thereof have the advantages that:
the novel phosphorus-nitrogen DOPO derivative flame retardant is prepared by synthesizing corresponding Schiff base by using 4-methoxybenzaldehyde and P-aminobenzoic acid as raw materials and then reacting with 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), overcomes the defects of poor compatibility of an additive flame retardant and a matrix, easy loss in the using process, poor water resistance and the like, is applied to epoxy resin (EP-51), has good char formation property, can form a compact carbon layer, can obviously improve the limiting oxygen index LOI of resin, and has good flame retardant effect when the flame retardant content is 5 percent (the P content is 0.3291 percent), and UL-94 reaches V-0 level; the resin material has good thermal stability, and when the mass content of the flame retardant is 5 percent (the P content is 0.3291 percent), the resin material is stable at the temperature of below 320 ℃.
The novel phosphorus-nitrogen DOPO derivative flame retardant provided by the invention is simple in synthesis method, convenient to purify, high in yield, good in heating stability and convenient for industrial production.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is an infrared spectrum of a novel phosphorus-nitrogen DOPO derivative flame retardant synthesized by the invention;
FIG. 2 shows that the novel phosphorus-nitrogen DOPO derivative flame retardant synthesized by the invention1H-NMR chart;
FIG. 3 is a TG diagram of the flame retardant of various embodiments of the present invention applied to epoxy resin and a blank epoxy resin;
FIG. 4 is a DSC chart of the novel phosphorus-nitrogen DOPO derivative flame retardant synthesized by the present invention.
Detailed Description
The following description of the present invention is provided to enable those skilled in the art to better understand the technical solutions in the embodiments of the present invention and to make the above objects, features and advantages of the present invention more comprehensible.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual values, and between the individual values may be combined with each other to yield one or more new ranges of values, which ranges of values should be considered as specifically disclosed herein.
The synthesis method of the novel phosphorus-nitrogen DOPO derivative flame retardant has the following reaction formula:
specifically, the synthesis method comprises the following steps:
step S1, mixing 4-methoxybenzaldehyde and p-aminobenzoic acid according to the molar ratio of (1-3): (1-4) dissolving in a mixed solvent, adding a certain amount of an acid-binding agent to enable a reaction system to be in an alkaline environment, controlling the reaction temperature to be 0-50 ℃, stirring, reacting for 3-7 hours to obtain a large amount of yellow precipitates, and performing suction filtration, washing and drying to obtain pure Schiff base;
wherein the acid-binding agent is at least one of sodium hydroxide, potassium hydroxide, triethylamine, potassium tert-butoxide, sodium methoxide, pyridine, sodium ethoxide and imidazole;
the mixed solvent is two of methanol, ethanol, trichloromethane, tetrahydrofuran, dichloromethane, acetonitrile, dimethyl sulfoxide, 1, 4-dioxane, carbon tetrachloride, DMF and DMAC, and the two solvents are mixed according to the volume ratio of 1-3: 1-4;
the washing process adopts a solvent cooled by ice water for multiple times of leaching;
step S2, synthesizing Schiff base and DOPO according to the molar ratio (1-2): (1-4) adding the mixture into a mixed solvent, introducing inert gas, stirring, heating the mixed solution until the mixed solution becomes colorless and transparent, heating and refluxing for 3-5 hours to generate a large amount of white precipitates, and performing suction filtration and recrystallization after complete reaction to obtain the phosphorus-nitrogen DOPO derivative flame retardant;
wherein the mixed solvent is two of methanol, ethanol, trichloromethane, tetrahydrofuran, dichloromethane, acetonitrile, dimethyl sulfoxide, 1, 4-dioxane, carbon tetrachloride, DMF and DMAC, and the two solvents are mixed according to the volume ratio of 1-3: 1-4;
the inert gas is one of nitrogen, argon and helium;
carrying out recrystallization by adopting a mixed solvent of ethyl acetate and petroleum ether, wherein the volume ratio of the ethyl acetate to the petroleum ether is (1-5): (1-3).
The novel phosphorus-nitrogen DOPO derivative flame retardant and the synthesis method thereof provided by the invention are explained in detail according to specific examples below.
Example 1
A synthesis method of a novel phosphorus-nitrogen DOPO derivative flame retardant comprises the following reaction steps:
step S1, adding 0.1mol (13.6g) of 4-methoxybenzaldehyde and 0.1mol (13.7g) of p-aminobenzoic acid into a 125mL three-neck flask, adding 70mL of methanol, adding 0.2mol (8.0g) of sodium hydroxide as an acid-binding agent, controlling a certain temperature to react at about 20 ℃, electrically stirring, reacting for 4.0h, generating a large amount of yellow precipitates, performing suction filtration, rinsing with a solvent cooled by ice water for multiple times, and drying to obtain 22.7g of Schiff base, wherein the yield is about 89.1%;
step S2, adding 0.05mol (12.8g) of synthesized Schiff base and 0.1mol (21.6g) of DOPO into a mixed solvent of THF and DMF, introducing nitrogen, stirring electrically, heating to control the temperature to be 60-70 ℃, enabling the system to be uniform yellow, heating to react for about 40min, enabling the yellow to disappear, changing into a colorless transparent solution, then changing into a white milky solution, adding a new substance to the dotted plate, continuing to heat, enabling white precipitates to appear, reacting for 3-5 hours, enabling the raw materials to be almost completely reacted, performing suction filtration, and recrystallizing by using ethyl acetate to obtain 21.4g of relatively pure DOPO derivative flame retardant, wherein the yield is 90.9%.
Referring to fig. 1 and fig. 2, fig. 1 is an infrared spectrum of the novel phosphorus-nitrogen DOPO derivative flame retardant synthesized by the present invention; FIG. 2 shows that the novel phosphorus-nitrogen DOPO derivative flame retardant synthesized by the invention1H-NMR chart. The main absorption peaks of infrared absorption spectroscopy (IR) are: 3288(vs),3061(w), 2953(vs), 1697(vs),1605(vs),1510(m),1247(vs),1177(m),1031(m),920(vs), 752(vs),634(m),557(m),435 (w).
The results of the nuclear magnetic tests are as follows:1H-NMR(400MHz,DMSO-d6):δ3.81(1CH3),3.9(1CH),6.88(2CH),6.89(2CH),7.84(2CH),7.28(2CH),7.29(1CH),7.36(1CH),7.41(1CH),7.43(1CH),7.47(1CH),7.50(1CH),7.75(1CH),7.84(1CH),8.00(1CH),8.04(NH),12.71(OH)。
example 2
A synthesis method of a novel phosphorus-nitrogen DOPO derivative flame retardant comprises the following reaction steps:
step S1, adding 0.2mol (27.2g) of 4-methoxybenzaldehyde and 0.2mol (27.4g) of p-aminobenzoic acid into a 150mL three-neck flask, adding 100mL of ethanol, adding 0.2mol (11.2g) of triethylamine as an acid-binding agent, controlling a certain temperature to react at about 0 ℃, magnetically stirring, reacting for 4 hours, generating a large amount of yellow precipitates, performing suction filtration, rinsing with a solvent cooled by ice water for multiple times, and drying to obtain 44.3g of Schiff base, wherein the yield is 91.9%;
step S2, adding 0.1mol (24.1g) of synthesized Schiff base and 0.15mol (32.4g) of DOPO into a THF solvent, introducing argon, electrically stirring, heating and refluxing to obtain a yellow solution, changing the solution into colorless and transparent solution after 2 hours, then changing the solution into white milky solution, adding new substances to the solution, continuously heating to obtain white precipitates, reacting for 3-5 hours until the raw materials almost completely react, performing suction filtration, and recrystallizing with tetrahydrofuran to obtain 42.0g of relatively pure DOPO derivative flame retardant, wherein the yield is 92.0%.
Example 3
A synthesis method of a novel phosphorus-nitrogen DOPO derivative flame retardant comprises the following reaction steps:
step S1, adding 0.2mol (27.4g) of 4-methoxybenzaldehyde and 0.2mol (27.2g) of p-aminobenzoic acid into a 150mL three-neck flask, adding 90mL of methanol, adding 0.2mol (11.2g) of potassium hydroxide as an acid-binding agent, controlling a certain temperature to react at about 0 ℃, magnetically stirring, reacting for 5 hours, generating a large amount of yellow precipitates, performing suction filtration, rinsing with a solvent cooled by ice water for multiple times, and drying to obtain 47.5g of Schiff base with the yield of 93.10%;
step S2, adding 0.1mol (25.5g) of synthesized Schiff base and 0.2mol (43.2g) of DOPO into a solvent of DMF, introducing nitrogen, stirring electrically, heating to control the temperature to be 70-80 ℃, wherein the system is a yellow solution, the solution becomes colorless and transparent after 2 hours, then becomes a white milky solution, a new substance is generated on a spot plate, heating is continued, white precipitate appears, after 3-5 hours of reaction, the raw materials almost completely react, suction filtration is carried out, recrystallization is carried out by using a mixed solvent of ethyl acetate and petroleum ether (volume ratio is 1:1), 42.2g of relatively pure DOPO derivative flame retardant is obtained, and the yield is 89.60%.
Example 4
The novel phosphorus-nitrogen DOPO derivative flame retardant prepared in the embodiment 1-3 is applied to epoxy resin.
And (3) testing the combustion performance: weighing 25g of 4, 4-diaminodiphenylmethane in a 100mL beaker, heating and melting, cooling to about 100 ℃, adding 1%, 3%, 5% and 7% of flame retardants P1, P2 and P3 prepared in examples 1-3 with different mass contents, stirring and mixing uniformly, pouring 100g of epoxy resin which is weighed in a 75 ℃ water bath in advance into the beaker containing the curing agent and the flame retardants, stirring uniformly, quickly casting into a 130 x 6.5 x 3 national standard oxygen index sample strip and a 120 x 13 x 3.2 national standard vertical combustion sample strip mold, curing for 20 hours at room temperature, then curing for 3 hours at 100 ℃, then placing in a 160 ℃ vacuum drying oven for curing for 1 hour, naturally cooling to room temperature, and demolding to obtain a flame-retardant epoxy resin sample to be tested. The limit oxygen index was measured by JF 3-oxygen index meter, and UL-94 vertical burning performance test was carried out by FZ-5401 vertical burning meter, and the results are summarized in Table 1:
table 1: performance testing of flame-retardant epoxy resins
Wherein the weight percentages refer to the percentage of the additive relative to the total weight of the (epoxy resin Ep-51+ curing agent).
The determination of the limit oxygen index is based on the national standard method GB/T2406.2-2009, and the GB/T2408-2008 standard is adopted in the UL-94 vertical combustion test.
The epoxy resin (EP-51) is selected from epoxy resins CYD-128 (EP-51) of Baling, China petrochemical Co., Ltd.).
As can be seen from Table 1, the flame-retardant effect is markedly enhanced with an increase in the content of the flame retardant in EP, as compared with the blank EP (LOI:28.0, T:28 s; not extinguished on burning).
Compared with other flame retardants of the same type (for example, in the technology of Chinese patent CN201310008589, LOI of blank EP is 21, flame retardants of 7 wt%, 10 wt% and 12 wt% are respectively added, and the LOI values of the flame-retardant epoxy resin measured by the flame-retardant epoxy resin are respectively 27, 28.5 and 29, and UL-94V-0 level), the flame-retardant effect is enhanced.
In the chinese patent CN104109246A technology, the measured LOI values of flame retardant modified epoxy resin with 1%, 2%, 3% and 4% of different contents (w%) are respectively: 25.4, 26.3, 27.9 and 29.1, the LOI value of the invention is obviously increased, which shows that the flame retardant effect is enhanced.
Compared with the technology of Chinese patent CN201610304553 (the content of the flame retardant is 18.1%, and the P content reaches V-0 grade when 2.5% is reached), the flame retardant of the invention has 5% and the P content is only 0.3291 (W%), the flame retardant reaches V-0 grade when UL-94 test is carried out, and the flame retardant is slightly higher than Schiff base compounds of the same type (in Chinese patent CN110041370A, the P content is 0.34 (W%), the UL-94 test reaches V-0 grade, and the LOI value is 32.5), which shows that the flame retardant effect is good.
Example 5
TG tests were performed on the novel phosphorus-nitrogen DOPO derivative flame retardants prepared in examples 1 to 3 when applied to epoxy resins:
the TG tests were carried out in EP-51 using a thermogravimetric analyzer TGA (Q5000IR, TA instruments USA) for different examples, with different amounts of flame retardant: in the air atmosphere, the temperature is raised within the range of 0-900 ℃ at the speed of 20 ℃/min, and finally no polymer remains. Referring to fig. 3, which is a TG diagram of the flame retardant applied to epoxy resin and blank epoxy resin according to various embodiments of the present invention, it can be seen from fig. 3 that the decomposition temperature of blank EP is about 334 ℃, while that of P1, P2, and P3 are 334 ℃ (w% ═ 1%), 320 ℃ (w% > -5%) and 317 ℃ (w% > -7%), respectively, which illustrate that the thermal decomposition temperature is reduced but not greatly different with the increase of the content of the flame retardant.
The epoxy resin (EP-51) in this example was also selected from epoxy resins CYD-128 (EP-51) of Baling, China petrochemical Co., Ltd.).
Example 6
The novel phosphorus-nitrogen DOPO derivative flame retardant prepared in the examples 1 to 3 is applied to epoxy resin for heat resistance test:
for the different examples, the same flame retardant was applied in EP-51 in the absence of a differential scanning calorimeter under nitrogen using a DSC Q20 from TA Instruments (Ta Instruments) in the United states, at a rate of temperature increase: 10 ℃/min, temperature range: DSC test is carried out at 80-320 ℃. Referring to fig. 4, which is a DSC diagram of the new phosphorus-nitrogen DOPO derivative flame retardant synthesized by the present invention, it can be seen from fig. 4 that the glass transition temperature Tg of the pure EP without flame retardant is 118.3 ℃, while the glass transition temperature Tg of the EP containing schiff base DOPO phosphorus-nitrogen flame retardant is significantly changed with the increase of the content. When the flame retardant content was 3% (P content 0.1975%), Tg 128.5 ℃; tg 151.3 ℃ when the flame retardant content is 5% (P content 0.3291%); when the flame retardant content was 7% (P content 0.4607%), Tg 131.2 ℃; when the content of the novel flame retardant is 5%, the glass transition temperature Tg of the flame-retardant epoxy resin reaches the maximum (Tg of 151.31 ℃).
Compared with the prior art, the novel phosphorus-nitrogen DOPO derivative flame retardant and the synthesis method and the application thereof have the advantages that:
the novel phosphorus-nitrogen DOPO derivative flame retardant is prepared by synthesizing corresponding Schiff base by using 4-methoxybenzaldehyde and P-aminobenzoic acid as raw materials and then reacting with 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), overcomes the defects of poor compatibility of an additive flame retardant and a matrix, easy loss in the using process, poor water resistance and the like, is applied to epoxy resin (EP-51), has good char formation property, can form a compact carbon layer, can obviously improve the limiting oxygen index LOI of resin, and has good flame retardant effect when the flame retardant content is 5 percent (the P content is 0.3291 percent), and UL-94 reaches V-0 level; the resin material has good thermal stability, and when the mass content of the flame retardant is 5 percent (the P content is 0.3291 percent), the resin material is stable at the temperature of below 320 ℃.
The novel phosphorus-nitrogen DOPO derivative flame retardant provided by the invention is simple in synthesis method, convenient to purify, high in yield, good in heating stability and convenient for industrial production.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. Various changes, modifications, substitutions and alterations to these embodiments will occur to those skilled in the art without departing from the spirit and scope of the present invention.
Claims (9)
2. A synthesis method of a novel phosphorus-nitrogen DOPO derivative flame retardant is characterized by comprising the following steps:
step S1, mixing 4-methoxybenzaldehyde and p-aminobenzoic acid according to the molar ratio of (1-3): (1-4) dissolving in a mixed solvent, adding a certain amount of an acid-binding agent to enable a reaction system to be in an alkaline environment, controlling the reaction temperature to be 0-50 ℃, stirring, reacting for 3-7 hours to obtain a large amount of yellow precipitates, and performing suction filtration, washing and drying to obtain pure Schiff base;
step S2, synthesizing Schiff base and DOPO according to the molar ratio (1-2): (1-4) adding the mixture into a mixed solvent, introducing inert gas, stirring, heating the mixed solution until the mixed solution becomes colorless and transparent, heating and refluxing for 3-5 hours to generate a large amount of white precipitates, and performing suction filtration and recrystallization after complete reaction to obtain the phosphorus-nitrogen DOPO derivative flame retardant.
3. The method for synthesizing novel phosphorus-nitrogen DOPO derivative flame retardant according to claim 2, wherein in the step S1, the acid-binding agent is at least one of sodium hydroxide, potassium hydroxide, triethylamine, potassium tert-butoxide, sodium methoxide, pyridine, sodium ethoxide and imidazole.
4. The method for synthesizing novel phosphorus-nitrogen DOPO derivative flame retardant according to claim 2, wherein the mixed solvent is two of methanol, ethanol, chloroform, tetrahydrofuran, dichloromethane, acetonitrile, dimethyl sulfoxide, 1, 4-dioxane, carbon tetrachloride, DMF and DMAC in steps S1 and S2, and the two solvents are mixed in a volume ratio of 1-3: 1-4.
5. The method for synthesizing novel phosphorus-nitrogen DOPO derivative flame retardant according to claim 2, wherein in the step S2, the inert gas is one of nitrogen, argon and helium.
6. The method for synthesizing the novel phosphorus-nitrogen DOPO derivative flame retardant according to claim 2, wherein in the step S1, the washing process adopts an ice water cooled solvent for multiple times of leaching.
7. The synthesis method of the novel phosphorus-nitrogen DOPO derivative flame retardant as claimed in claim 2, wherein in the step S2, a mixed solvent of ethyl acetate and petroleum ether is adopted for recrystallization, wherein the volume ratio of ethyl acetate to petroleum ether is (1-5): (1-3).
8. Use of a novel phosphorus-nitrogen DOPO derivative flame retardant according to claim 1 in a process for the preparation of epoxy resins.
9. Use according to claim 8, characterized in that the novel phosphorus-nitrogen DOPO derivative flame retardant is added in an amount of 1-7% of the total amount of epoxy resin.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114409827A (en) * | 2022-01-29 | 2022-04-29 | 武汉工程大学 | Synthesis and performance of transparent epoxy resin material with high flame-retardant performance based on chitosan derivative |
CN115594507A (en) * | 2022-10-12 | 2023-01-13 | 郑州格瑞特高温材料有限公司(Cn) | Low-density microporous silicon nitride combined silicon carbide material and preparation method thereof |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1487946A (en) * | 2001-01-22 | 2004-04-07 | ���ٿƹɷݹ�˾ | Flame-proofing agents |
US20090215967A1 (en) * | 2008-02-21 | 2009-08-27 | National Chung Hsing University | Manufacture of novel epoxy resins semi-thermosets and their high tg thermosets for electronic applications |
-
2021
- 2021-04-19 CN CN202110418749.8A patent/CN113337004A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1487946A (en) * | 2001-01-22 | 2004-04-07 | ���ٿƹɷݹ�˾ | Flame-proofing agents |
US20090215967A1 (en) * | 2008-02-21 | 2009-08-27 | National Chung Hsing University | Manufacture of novel epoxy resins semi-thermosets and their high tg thermosets for electronic applications |
Non-Patent Citations (6)
Title |
---|
CHING HSUAN LIN ET AL.: "Phosphorus-Containing Epoxy Curing Agents via Imine Linkage", 《MACROMOL. CHEM. PHYS.》, vol. 208, 31 December 2007 (2007-12-31), pages 2628 - 2641 * |
CONG XIE ET AL.: "Improving Thermal and Flame-Retardant Properties of Epoxy Resins by a Novel Reactive Phosphorous-Containing Curing Agent", 《POLYMER ENGINEERING AND SCIENCE》, 31 December 2014 (2014-12-31), pages 1912 - 1200 * |
CORNELIU HAMCIUC ET AL.: "New fire-resistant epoxy thermosets: nonisothermal kinetic study and flammabilitybehavior", 《J POLYM ENG》, 5 December 2019 (2019-12-05), pages 21 - 29 * |
HUIJIN LIU ET AL.: "Novel Metal Coordinations in the Monolayers of an Amino-Acid-Derived Schiff Base at the Air-Water Interface and Langmuir-Blodgett Films", 《J. PHYS. CHEM.》, vol. 111, 31 December 2007 (2007-12-31), pages 17025 - 17031 * |
MENG ZHANG ET AL.: "Effects of a novel phosphorusenitrogen flame retardant on rosin-based rigid polyurethane foams", 《POLYMER DEGRADATION AND STABILITY》, vol. 120, 7 August 2015 (2015-08-07), pages 427 - 434 * |
YUAN-QIN XIONG ET AL.: "Synthesis of Novel Phosphorus-Containing Epoxy Hardeners and Thermal Stability and Flame-Retardant Properties of Cured Products", 《JOURNAL OF APPLIED POLYMER SCIENCE》, vol. 125, 7 January 2012 (2012-01-07), pages 1219 - 1225 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114409827A (en) * | 2022-01-29 | 2022-04-29 | 武汉工程大学 | Synthesis and performance of transparent epoxy resin material with high flame-retardant performance based on chitosan derivative |
CN114409827B (en) * | 2022-01-29 | 2023-11-24 | 武汉工程大学 | Synthesis and performance of transparent epoxy resin material with high flame retardant performance based on chitosan derivative |
CN115594507A (en) * | 2022-10-12 | 2023-01-13 | 郑州格瑞特高温材料有限公司(Cn) | Low-density microporous silicon nitride combined silicon carbide material and preparation method thereof |
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