CN113512233A - Novel nitrogen-phosphorus flame retardant containing furyl DOPO and preparation method and application thereof - Google Patents
Novel nitrogen-phosphorus flame retardant containing furyl DOPO and preparation method and application thereof Download PDFInfo
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- CN113512233A CN113512233A CN202110417842.7A CN202110417842A CN113512233A CN 113512233 A CN113512233 A CN 113512233A CN 202110417842 A CN202110417842 A CN 202110417842A CN 113512233 A CN113512233 A CN 113512233A
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- flame retardant
- dopo
- phosphorus flame
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 91
- 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 87
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- -1 furyl DOPO Chemical compound 0.000 title claims abstract 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000003822 epoxy resin Substances 0.000 claims abstract description 21
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 19
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011574 phosphorus Substances 0.000 claims abstract description 14
- 238000009776 industrial production Methods 0.000 claims abstract description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 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
- 239000011261 inert gas Substances 0.000 claims description 9
- 238000000967 suction filtration Methods 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 6
- 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 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
- 229960004050 aminobenzoic acid Drugs 0.000 claims description 6
- 229960001701 chloroform Drugs 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 4
- UPSIAUXDGWYOFJ-UHFFFAOYSA-N formaldehyde;furan Chemical compound O=C.C=1C=COC=1 UPSIAUXDGWYOFJ-UHFFFAOYSA-N 0.000 claims description 3
- 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
- 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
- 239000000463 material Substances 0.000 claims description 2
- 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 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 125000002541 furyl group Chemical group 0.000 description 27
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000009477 glass transition Effects 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 239000004593 Epoxy Chemical group 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000000034 method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 1
- 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
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000002743 phosphorus functional group Chemical group 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 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)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention discloses a novel nitrogen-phosphorus flame retardant containing furyl DOPO, which has the following structure:
the invention also provides a preparation method of the novel nitrogen and phosphorus flame retardant containing furyl DOPO. The invention also provides application of the novel nitrogen and phosphorus flame retardant containing furyl DOPO. The invention has the following beneficial effects: the yield of the novel nitrogen-phosphorus flame retardant containing furyl DOPO prepared by the preparation method provided by the invention is high and can reach more than 89%; after the novel nitrogen-phosphorus flame retardant containing furyl DOPO is applied to epoxy resin, the flame retardant effect of the epoxy resin can be obviously improved; the novel nitrogen-phosphorus flame retardant containing furyl DOPO converts EP vitrifactionThe temperature change is promoted to be increased; the preparation method of the novel nitrogen-phosphorus flame retardant containing furyl DOPO provided by the invention has simple steps, and the prepared flame retardant has high purity and yield and is convenient for industrial production.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of flame retardant design, in particular to a novel nitrogen and phosphorus flame retardant containing furyl DOPO and a preparation method and application thereof.
[ background of the invention ]
The epoxy resin has excellent water resistance, solvent resistance and chemical corrosion resistance, has good mechanical property and dielectric property, can be used for a resin matrix of a high-performance composite material, and has wide application prospect in the fields of aerospace, home decoration buildings, microelectronic packaging materials, ornaments and the like. However, the main disadvantage of epoxy resins is their flammability, which limits their effective use in many fields. Therefore, the development of the flame retardant modification research of the epoxy resin is an important way for improving the application field of the epoxy resin.
The 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) is used as a novel flame retardant intermediate, on one hand, the molecular structure contains a biphenyl ring and a phenanthrene ring structure, and particularly, a lateral phosphorus group is introduced in a mode of a cyclic O ═ P-O bond, so that the flame retardant has higher thermal stability and chemical stability than a common acyclic organic phosphate flame retardant system; on the other hand, the structure of the flame retardant has P-H bonds, so that the flame retardant has activity on olefin, epoxy bonds and carbonyl groups, can react with various compounds including furfural and derivatives thereof, such as aldehyde, Schiff base and the like to generate a plurality of flame retardant derivatives with unique performance, and can form stable combination with a plurality of polymer resin substrates needing flame retardant modification, such as epoxy resin and the like through chemical bonds, so that the migration or precipitation of the flame retardant in the processing and using processes of polymer products is avoided, and the flame retardant effect on the polymer products can be stably maintained.
[ summary of the invention ]
The invention discloses a novel nitrogen-phosphorus flame retardant containing furyl DOPO as well as a preparation method and application thereof, which can solve the technical problems related to the background technology.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a novel nitrogen-phosphorus flame retardant containing furyl DOPO has the following structure 1:
the invention also provides a preparation method of the novel nitrogen-phosphorus flame retardant containing furyl DOPO, which comprises the following steps: furan formaldehyde, p-aminobenzoic acid and DOPO are mixed according to the molar ratio of (1-2): (1-3): (1-4) adding the mixture into a three-neck flask with electric stirring, adding a certain amount of mixed solvent and an acid-binding agent to enable a reaction system to be in an alkaline environment, introducing inert gas, controlling a certain temperature to react, stirring, reacting for 3-8 h, performing suction filtration when a large amount of light yellow precipitates appear, almost completely reacting the raw materials of the point plate, performing suction filtration, and recrystallizing by using the mixed solvent to obtain a pure furyl-DOPO nitrogen and phosphorus flame retardant, wherein the reaction equation of the flame retardant is as follows in formula 2:
as a preferable improvement of the present invention, the acid-binding agent includes at least one of sodium hydroxide, potassium hydroxide, triethylamine, potassium tert-butoxide, sodium methoxide, pyridine, sodium ethoxide, and imidazole.
As a preferable modification of the present invention, the solvent includes any one of methanol, ethanol, chloroform, tetrahydrofuran, dichloromethane, acetonitrile, dimethyl sulfoxide, 1, 4-dioxane, carbon tetrachloride, DMF, and DMAC.
As a preferable improvement of the invention, the solvent comprises any two of methanol, ethanol, chloroform, tetrahydrofuran, dichloromethane, acetonitrile, dimethyl sulfoxide, 1, 4-dioxane, carbon tetrachloride, DMF and DMAC, and the volume ratio of the two components is 1-4: 1-3.
As a preferred modification of the present invention, the inert gas is one of nitrogen, argon or helium.
As a preferred improvement of the present invention, the reaction temperature is controlled to be: 50 to 110 ℃.
The invention also provides application of the novel nitrogen and phosphorus flame retardant containing the furyl DOPO, and the novel nitrogen and phosphorus flame retardant containing the furyl DOPO is applied to epoxy resin.
The invention also provides application of the novel nitrogen and phosphorus flame retardant containing the furyl DOPO, and the novel nitrogen and phosphorus flame retardant containing the furyl DOPO is applied to flame retardant materials in industrial production.
The invention has the beneficial effects that:
1. the yield of the novel nitrogen-phosphorus flame retardant containing furyl DOPO prepared by the preparation method provided by the invention is high and can reach more than 89%;
2. after the novel nitrogen-phosphorus flame retardant containing furyl DOPO is applied to epoxy resin, the flame retardant effect of the epoxy resin can be obviously improved;
3. the novel nitrogen-phosphorus flame retardant containing furyl DOPO has a promoting effect on the improvement of the glass transition temperature of EP;
4. the preparation method of the novel nitrogen-phosphorus flame retardant containing furyl DOPO provided by the invention has simple steps, and the prepared flame retardant has high purity and yield and is convenient for industrial production.
[ description of the 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 are briefly introduced below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without inventive efforts, wherein:
FIG. 1 is an infrared spectrum of a novel furyl-DOPO phosphorus-nitrogen containing flame retardant prepared by the invention;
FIG. 2 is a H-NMR chart of the novel furyl-DOPO phosphorus-nitrogen containing flame retardant prepared by the invention;
FIG. 3 is a TG plot of various embodiments of the present invention applied to epoxy and epoxy blanks;
FIG. 4 is a DSC chart of the novel furyldiPO phosphorus-nitrogen containing flame retardant applied to epoxy resin.
[ detailed description ] embodiments
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 invention provides a novel nitrogen-phosphorus flame retardant containing furyl DOPO, which has the following structure 1:
the invention also provides a preparation method of the novel nitrogen-phosphorus flame retardant containing furyl DOPO, which comprises the following steps: furan formaldehyde, p-aminobenzoic acid and DOPO are mixed according to the molar ratio of (1-2): (1-3): (1-4) adding the mixture into a three-neck flask with electric stirring, adding a certain amount of mixed solvent and an acid-binding agent to enable a reaction system to be in an alkaline environment, introducing inert gas, controlling a certain temperature to react at 50-110 ℃, stirring, reacting for 3-8 h, performing suction filtration when a large amount of light yellow precipitates appear, almost completely reacting the raw materials of the point plate, performing suction filtration, and recrystallizing by using the mixed solvent to obtain a pure furyl-DOPO nitrogen and phosphorus flame retardant, wherein the reaction equation of the formula is as follows 2:
specifically, the acid-binding agent includes at least one of sodium hydroxide, potassium hydroxide, triethylamine, potassium tert-butoxide, sodium methoxide, pyridine, sodium ethoxide, and imidazole. The solvent comprises any one of methanol, ethanol, trichloromethane, tetrahydrofuran, dichloromethane, acetonitrile, dimethyl sulfoxide, 1, 4-dioxane, carbon tetrachloride, DMF and DMAC. In another embodiment, the solvent comprises any two of methanol, ethanol, chloroform, tetrahydrofuran, dichloromethane, acetonitrile, dimethyl sulfoxide, 1, 4-dioxane, carbon tetrachloride, DMF and DMAC, and the volume ratio of the two components is 1-4: 1-3. The inert gas is one of nitrogen, argon or helium.
The present invention will be described in detail with reference to specific embodiments.
Example 1
The invention provides a preparation method of a novel nitrogen and phosphorus flame retardant containing furyl DOPO, which comprises the following steps:
adding 0.2mol (19.2g) of furaldehyde, 0.2mol (27.2g) of p-aminobenzoic acid and 0.2mol (43.2g) of DOPO into a 250mL three-neck flask, adding into a mixed solvent of 150mL THF and DMF, adding 0.3mol (12.0g) of sodium hydroxide as an acid binding agent, introducing inert gas, controlling a certain temperature to react at about 70 ℃, introducing nitrogen, electrically stirring, reacting for 5 hours, allowing a large amount of light yellow precipitates to appear, dotting the raw materials on the plate, performing suction filtration, rinsing with a solvent cooled by ice water for multiple times, and drying to obtain 76.90g of furyl DOPO flame retardant with the yield of about 89.20%.
Wherein, the main absorption peaks of IR are: 3281(vs),1703(vs),1603(vs),1530(m),1385(m),1240(vs),1091(m),929(vs),844(m),752(m),543 (m).
The results of the nuclear magnetic tests are as follows: δ 4.1(1H), 6.88(2CH), 7.84(2CH), 7.56(1CH), 6.39(1CH), 6.29(1CH), 7.29(1CH), 7.50(1CH), 7.47(1CH), 7.36(1CH), 7.41(1CH), 7.43(1CH), 7.75(1CH), 8.00(1CH), 8.04(NH), 12.71 (OH).
Example 2
The invention provides a preparation method of a novel nitrogen and phosphorus flame retardant containing furyl DOPO, which comprises the following steps:
adding 0.1mol (9.6g) of furfural, 0.1mol (13.6g) of p-aminobenzoic acid and 0.2mol (43.2g) of DOPO into a 150mL three-neck flask, adding 70mL of THF solvent, adding 0.2mol (8.0g) of sodium hydroxide as an acid binding agent, introducing inert gas, controlling a certain temperature to react at about 60 ℃, introducing argon, electrically stirring, reacting for 5 hours, allowing a large amount of light yellow precipitates to appear, almost completely reacting raw materials in a spot plate, performing suction filtration, rinsing with ice water cooled solvent for multiple times, and drying to obtain 39.4g of furyl DOPO flame retardant, wherein the yield is about 91.40%.
Example 3
The invention provides a preparation method of a novel nitrogen and phosphorus flame retardant containing furyl DOPO, which comprises the following steps:
adding 0.1mol (9.6g) of furfural, 0.1mol (13.6g) of p-aminobenzoic acid and 0.15mol (32.40g) of DOPO into a 125mL three-neck flask, adding 70mL of DMF solvent, adding 0.2mol (11.2g) of potassium hydroxide as an acid binding agent, introducing inert gas, controlling a certain temperature to react at about 80 ℃, introducing nitrogen, electrically stirring, reacting for 4 hours, allowing a large amount of light yellow precipitates to appear, almost completely reacting raw materials in a spot plate, performing suction filtration, rinsing with ice water cooled solvent for multiple times, and drying to obtain 39.2g of furan-based DOPO flame retardant, wherein the yield is about 90.90%.
Example 4
The novel nitrogen-phosphorus flame retardant containing furyl DOPO prepared in the examples 1 to 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
a. Weight percent refers to the percentage of additive relative to the total weight of (epoxy EP-51+ curing agent);
b. the determination of the limit oxygen index refers to a national standard method GB/T2406.2-2009, and a UL-94 vertical combustion test adopts a GB/T2408-2008 standard.
As can be seen from the above table, as the content of the flame retardant in EP increases, the flame retardant effect is obviously enhanced compared with blank EP (LOI:28.0, T:28 s; not extinguished during combustion), and compared with other flame retardants of the same type (CN201310008589, blank EP: LOI of 21, and 7%, 10% and 12% of flame retardants with different contents (W%) are added, the LOI values of the flame-retardant modified epoxy resin measured by the method are respectively 27, 28.5 and 29), compared with CN201610304553 (flame retardant content of 18.1%, P content of 2.5% reaches V-0 level), the flame retardant content is 5%, and the P content is only 0.3360 (W%), and UL-94 test reaches V-0 level, which indicates that the flame retardant effect is good.
Example 5
TG tests were performed on the novel nitrogen and phosphorus flame retardants containing furyl DOPO 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 the different examples, with the same content 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 (see figure 3). As can be seen from fig. 3, the decomposition temperature of the blank EP was about 334 ℃, while P1 and P2 were 321 ℃ (w% ═ 5%) and 329.5 ℃ (w% ═ 7%), respectively, indicating that the thermal decomposition temperature increased with increasing flame retardant content, indicating that the addition of flame retardant promoted the thermal decomposition of the modified epoxy resin.
Example 6
The novel nitrogen-phosphorus flame retardant containing furyl DOPO 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 under nitrogen atmosphere using a differential scanning calorimeter with TA Instruments DSC Q20, USA, at a rate of temperature rise: 10 ℃/min, temperature range: DSC test at 80-320 deg.C: (see FIG. 4). From fig. 4, it can be seen that the glass transition temperature Tg of pure EP without added flame retardant is 118.3 ℃, while the glass transition temperature of the furan-based DOPO phosphorus nitrogen containing flame retardant EP increases and then decreases with increasing content, from Tg of 147 ℃ at 5% to Tg of 116 ℃ at 7% content, indicating that the novel flame retardant has a promoting effect on the increase of the glass transition temperature of EP.
The invention has the beneficial effects that:
1. the yield of the novel nitrogen-phosphorus flame retardant containing furyl DOPO prepared by the preparation method provided by the invention is high and can reach more than 89%;
2. after the novel nitrogen-phosphorus flame retardant containing furyl DOPO is applied to epoxy resin, the flame retardant effect of the epoxy resin can be obviously improved;
3. the novel nitrogen-phosphorus flame retardant containing furyl DOPO has a promoting effect on the improvement of the glass transition temperature of EP;
4. the preparation method of the novel nitrogen-phosphorus flame retardant containing furyl DOPO provided by the invention has simple steps, and the prepared flame retardant has high purity and yield and is 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)
1. A novel nitrogen-phosphorus flame retardant containing furyl DOPO is characterized by having the following structure 1:
2. a preparation method of a novel nitrogen-phosphorus flame retardant containing furyl DOPO is characterized by comprising the following steps: furan formaldehyde, p-aminobenzoic acid and DOPO are mixed according to the molar ratio of (1-2): (1-3): (1-4) adding the mixture into a three-neck flask with electric stirring, adding a certain amount of mixed solvent and an acid-binding agent to enable a reaction system to be in an alkaline environment, introducing inert gas, controlling a certain temperature to react, stirring, reacting for 3-8 h, performing suction filtration when a large amount of light yellow precipitates appear, almost completely reacting the raw materials of the point plate, performing suction filtration, and recrystallizing by using the mixed solvent to obtain a pure furyl-DOPO nitrogen and phosphorus flame retardant, wherein the reaction equation of the flame retardant is as follows in formula 2:
3. the preparation method of the novel nitrogen-phosphorus flame retardant containing furyl DOPO according to claim 2, characterized in that: the acid-binding agent comprises at least one of sodium hydroxide, potassium hydroxide, triethylamine, potassium tert-butoxide, sodium methoxide, pyridine, sodium ethoxide and imidazole.
4. The preparation method of the novel nitrogen-phosphorus flame retardant containing furyl DOPO according to claim 2, characterized in that: the solvent comprises any one of methanol, ethanol, trichloromethane, tetrahydrofuran, dichloromethane, acetonitrile, dimethyl sulfoxide, 1, 4-dioxane, carbon tetrachloride, DMF and DMAC.
5. The preparation method of the novel nitrogen-phosphorus flame retardant containing furyl DOPO according to claim 2, characterized in that: the solvent comprises any two of methanol, ethanol, trichloromethane, tetrahydrofuran, dichloromethane, acetonitrile, dimethyl sulfoxide, 1, 4-dioxane, carbon tetrachloride, DMF and DMAC, and is combined according to the volume ratio of 1-4: 1-3.
6. The preparation method of the novel nitrogen-phosphorus flame retardant containing furyl DOPO according to claim 2, characterized in that: the inert gas is one of nitrogen, argon or helium.
7. The preparation method of the novel nitrogen-phosphorus flame retardant containing furyl DOPO according to claim 2, characterized in that: the reaction temperature was controlled as follows: 50 to 110 ℃.
8. Use of a novel nitrogen phosphorus flame retardant containing furanyl DOPO as claimed in claim 1 or 2, wherein: the novel nitrogen-phosphorus flame retardant containing furyl DOPO is applied to epoxy resin.
9. Use of a novel nitrogen phosphorus flame retardant containing furanyl DOPO as claimed in claim 1 or 2, wherein: the novel nitrogen-phosphorus flame retardant containing furyl DOPO is applied to the flame-retardant material in industrial production.
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