CN113337006A - Novel Schiff base DOPO phosphorus-nitrogen-containing flame retardant and preparation method and application thereof - Google Patents
Novel Schiff base DOPO phosphorus-nitrogen-containing flame retardant and preparation method and application thereof Download PDFInfo
- Publication number
- CN113337006A CN113337006A CN202110418782.0A CN202110418782A CN113337006A CN 113337006 A CN113337006 A CN 113337006A CN 202110418782 A CN202110418782 A CN 202110418782A CN 113337006 A CN113337006 A CN 113337006A
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- schiff base
- dopo
- novel
- phosphorus nitrogen
- 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.)
- Pending
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 95
- 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 91
- 239000002262 Schiff base Substances 0.000 title claims abstract description 77
- 150000004753 Schiff bases Chemical class 0.000 title claims abstract description 76
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 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 22
- 239000003822 epoxy resin Substances 0.000 claims abstract description 29
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000009776 industrial production Methods 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 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
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 239000012046 mixed solvent Substances 0.000 claims description 13
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 12
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 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
- 238000002156 mixing Methods 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
- 239000005457 ice water Substances 0.000 claims description 8
- 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
- 238000001035 drying Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 238000001914 filtration Methods 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
- 238000002386 leaching Methods 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
- 229960001701 chloroform Drugs 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000004017 vitrification Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 8
- 230000006872 improvement Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000003115 biocidal effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- -1 phosphorus heterocyclic compound Chemical class 0.000 description 2
- 230000001737 promoting effect Effects 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
- 239000004593 Epoxy Substances 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 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
- 238000004458 analytical method Methods 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000005389 magnetism Effects 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
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000001766 physiological effect Effects 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
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000012827 research and development 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
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009333 weeding Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- 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
Landscapes
- 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)
- Fireproofing Substances (AREA)
Abstract
The invention discloses a novel Schiff base DOPO phosphorus nitrogen-containing flame retardant, which has the following structure:
the invention also provides a preparation method of the novel Schiff base DOPO phosphorus nitrogen-containing flame retardant. The invention also provides application of the novel Schiff base DOPO phosphorus nitrogen-containing flame retardant. The invention has the following beneficial effects: the novel flame retardant containing Schiff base DOPO phosphorus nitrogen prepared by the preparation method provided by the invention has high yield which can reach more than 89%; after the novel phosphorus-nitrogen flame retardant containing Schiff base DOPO is applied to epoxy resin, the flame retardant effect of the epoxy resin can be obviously improved; the novel flame retardant containing Schiff base DOPO phosphorus nitrogen provided by the invention is used for vitrification conversion of EPThe temperature change is promoted to be increased; the preparation method of the novel Schiff base DOPO phosphorus nitrogen-containing flame retardant provided by the invention has the advantages of simple steps, high purity and yield of the prepared flame retardant, and convenience 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 Schiff base DOPO phosphorus nitrogen-containing flame retardant and a preparation method and application thereof.
[ background of the invention ]
The 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) type flame retardant is an organic phosphorus heterocyclic compound, can directly introduce a flame retardant group or element into a reaction type flame retardant of a high molecular matrix chain segment, and is widely researched by numerous scholars at home and abroad due to good dispersibility and high flame retardant efficiency. The flame retardant is mainly used for flame retardance of polyester fibers, polyurethane foam plastics, thermosetting resins and adhesives, and due to the excellent flame retardant property of the flame retardant, derived structures of the flame retardant are hot spots for research and development of flame retardants.
Schiff base mainly refers to an imine or azomethine characteristic group compound containing carbon-nitrogen double bonds, and due to the unique physical material properties of light, electricity, magnetism and the like, good coordination chemical properties and unique physiological activities of antibiosis, anticancer, weeding and the like, the Schiff base brings about extensive theoretical and application research of people. Schiff base can also be used as a good ligand, can be used for identifying and identifying metal ions and quantitatively analyzing the content of the metal ions, and has attracted extensive attention in the analysis field, in the application fields, the research on the antibiosis and bacteriostasis of the Schiff base is a hotspot of the current research, most of the researches are concentrated on a simple Schiff base complex, and the research reports on the application of the Schiff base complex and DOPO to the flame retardance of high polymer materials are less.
[ summary of the invention ]
The invention discloses a novel Schiff base-containing DOPO phosphorus-nitrogen flame retardant, and 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 Schiff base DOPO phosphorus nitrogen containing flame retardant has the following structure 1:
the invention also provides a preparation method of the novel Schiff base DOPO phosphorus nitrogen-containing flame retardant, which comprises the following steps:
step one, di-p-aminobenzaldehyde and p-aminobenzoic acid are mixed according to the molar ratio of (1-3): (1-2) dissolving in a solvent, adding a certain amount of an acid-binding agent to enable a reaction system to be in an alkaline environment, controlling a certain temperature to react, stirring, reacting for 3-6 hours, leaching when a large amount of yellow precipitates appear, rinsing with a solvent cooled by ice water for multiple times, and drying to obtain pure Schiff base;
step two, mixing the Schiff base and the DOPO according to the proportion (1-3): (1-2) adding the mixture into a mixed solvent, introducing inert gas, stirring, heating and refluxing for 3-5 hours, filtering after a large amount of white precipitates appear, and performing suction filtration by using the following components in a molar ratio of (1-5): (1-3) recrystallizing a mixed solvent formed by mixing ethyl acetate and petroleum ether to obtain a pure flame retardant containing Schiff base DOPO, wherein the reaction equation of the pure flame retardant containing the Schiff base DOPO is as shown in the following formula 2:
as a preferable improvement of the invention, the acid-binding agent comprises at least one of sodium hydroxide, potassium hydroxide, triethylamine, potassium tert-butoxide, sodium methoxide, pyridine, sodium ethoxide and imidazole.
As a preferable improvement 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 mixed solvent comprises at least two of methanol, ethanol, chloroform, tetrahydrofuran, dichloromethane, acetonitrile, dimethyl sulfoxide, 1, 4-dioxane, carbon tetrachloride, DMF and DMAC, and is mixed according to the volume ratio of (1-4) to (1-3).
As a preferred modification of the present invention, the inert gas includes one of nitrogen, argon, and helium.
As a preferred improvement of the present invention, in the step one, the temperature is controlled as follows: 0 to 50 ℃.
The invention also provides an application of the novel flame retardant containing Schiff base DOPO phosphorus nitrogen, and the novel flame retardant containing Schiff base DOPO phosphorus nitrogen is applied to epoxy resin.
The invention also provides application of the novel flame retardant containing Schiff base DOPO phosphorus nitrogen, and the novel flame retardant containing Schiff base DOPO phosphorus nitrogen is applied to flame-retardant materials in industrial production.
The invention has the beneficial effects that:
1. the novel flame retardant containing Schiff base DOPO phosphorus nitrogen prepared by the preparation method provided by the invention has high yield which can reach more than 89%;
2. after the novel phosphorus-nitrogen flame retardant containing Schiff base DOPO is applied to epoxy resin, the flame retardant effect of the epoxy resin can be obviously improved;
3. the novel flame retardant containing Schiff base DOPO phosphorus nitrogen provided by the invention has a promoting effect on the improvement of EP glass transition temperature;
4. the preparation method of the novel Schiff base DOPO phosphorus nitrogen-containing flame retardant provided by the invention has the advantages of simple steps, high purity and yield of the prepared flame retardant, and convenience 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 Schiff base DOPO phosphorus nitrogen-containing flame retardant prepared by the invention;
FIG. 2 is a graph of H-NMR of a novel Schiff base DOPO phosphorus nitrogen containing flame retardant prepared in accordance with the present invention;
FIG. 3 is a TG diagram of the novel Schiff base DOPO phosphorus nitrogen-containing flame retardant applied to epoxy resin and blank epoxy resin;
FIG. 4 is a DSC chart of the novel Schiff base DOPO 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 Schiff base DOPO phosphorus nitrogen-containing flame retardant, which has the following structure 1:
the invention also provides a preparation method of the novel Schiff base DOPO phosphorus nitrogen-containing flame retardant, which comprises the following steps:
step one, di-p-aminobenzaldehyde and p-aminobenzoic acid are mixed according to the molar ratio of (1-3): (1-2) dissolving in a solvent, adding a certain amount of an acid-binding agent to enable a reaction system to be in an alkaline environment, controlling a certain temperature to react, stirring, reacting for 3-6 hours, leaching when a large amount of yellow precipitates appear, rinsing with a solvent cooled by ice water for multiple times, and drying to obtain pure Schiff base;
specifically, the solvent includes any one of methanol, ethanol, chloroform, tetrahydrofuran, dichloromethane, acetonitrile, dimethyl sulfoxide, 1, 4-dioxane, carbon tetrachloride, DMF, and DMAC. The acid-binding agent comprises at least one of sodium hydroxide, potassium hydroxide, triethylamine, potassium tert-butoxide, sodium methoxide, pyridine, sodium ethoxide and imidazole, and the temperature is controlled as follows: 0 to 50 ℃.
Step two, mixing the Schiff base and the DOPO according to the proportion (1-3): (1-2) adding the mixture into a mixed solvent, introducing inert gas, stirring, heating and refluxing for 3-5 hours, filtering after a large amount of white precipitates appear, and performing suction filtration by using the following components in a molar ratio of (1-5): (1-3) recrystallizing a mixed solvent formed by mixing ethyl acetate and petroleum ether to obtain a pure flame retardant containing Schiff base DOPO, wherein the reaction equation of the pure flame retardant containing the Schiff base DOPO is as shown in the following formula 2:
specifically, the mixed solvent comprises at least two of methanol, ethanol, chloroform, tetrahydrofuran, dichloromethane, acetonitrile, dimethyl sulfoxide, 1, 4-dioxane, carbon tetrachloride, DMF and DMAC, and is mixed according to a volume ratio of (1-4) to (1-3). The inert gas comprises one of nitrogen, argon and 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 Schiff base DOPO phosphorus nitrogen-containing flame retardant, which comprises the following steps:
step one, adding 0.1mol (14.9g) of di-p-aminobenzaldehyde and 0.1mol (13.6g) of p-aminobenzoic acid into a 125mL three-neck flask, adding 70mL of ethanol, adding 0.2mol (11.2g) of potassium hydroxide as an acid binding agent, controlling a certain temperature to react at about 20 ℃, electrically 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 23.3g of Schiff base, wherein the yield is about 87.1%;
and step two, adding 0.05mol (13.4g) 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 ℃, 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, a white precipitate appears, after 3-5 hours of reaction, the raw materials almost completely react, cooling and suction filtration are carried out, and recrystallization is carried out by using a mixed solvent formed by mixing ethyl acetate and petroleum ether according to the molar ratio of 1:1, 22.0g of pure flame retardant containing Schiff base DOPO is obtained, and the yield is 91.0%.
Wherein, the main absorption peaks of IR are: 3281(vs),2876(m), 2803(m), 1686(vs),1651(vs),1587(vs),1520(vs),1431(m),1285(vs),1231(vs),1177(m),920(vs),748(vs),635(m),563(m),529 (m).
The results of the nuclear magnetic tests are as follows: δ 3.9(1H), 3.02(6H), 6.71(2H), 6.88(2CH), 7.10(2CH), 7.84(2CH), 7.29(1CH), 7.36(1CH), 7.43(1CH), 7.47(1CH), 7.50(1CH), 7.75(1CH), 8.00(1CH), 8.04(NH), 12.71 (OH).
Example 2
The invention provides a preparation method of a novel Schiff base DOPO phosphorus nitrogen-containing flame retardant, which comprises the following steps:
step one, adding 0.2mol (29.8g) of di-p-aminobenzaldehyde and 0.2mol (27.2g) of p-aminobenzoic acid into a 150mL three-neck flask, adding 110mL of methanol, adding 0.2mol (11.2g) of sodium hydroxide 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 48.3g of Schiff base, wherein the yield is 90.1%;
and step two, adding 0.1mol (26.8g) of synthesized Schiff base and 0.15mol (32.4g) of DOPO into a DMF solvent, introducing argon, electrically stirring, heating and refluxing to obtain a yellow solution, wherein the solution becomes colorless and transparent after 2 hours and then becomes a white milky solution, generating a new substance on a spot plate, continuously heating to obtain a white precipitate, almost completely reacting the raw materials after 3-5 hours, cooling with ice water, performing suction filtration, and recrystallizing by using a mixed solvent formed by mixing ethyl acetate and petroleum ether according to a molar ratio of 1:1 to obtain 44.0g of pure flame retardant containing Schiff base DOPO, wherein the yield is 92.0%.
Example 3
The invention provides a preparation method of a novel Schiff base DOPO phosphorus nitrogen-containing flame retardant, which comprises the following steps:
step one, adding 0.2mol (29.8g) of di-p-aminobenzaldehyde and 0.2mol (27.2g) of p-aminobenzoic acid into a 150mL three-neck flask, adding 110mL of methanol, adding 0.2mol (11.2g) of sodium hydroxide as an acid binding agent, controlling a certain temperature to react at about 5 ℃, 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 48.0g of Schiff base, wherein the yield is 89.55%;
and step two, adding 0.1mol (24.1g) of synthesized Schiff base and 0.2mol (43.2g) of DOPO into a solvent of THF, introducing nitrogen, electrically stirring, heating to control the temperature to be 60-70 ℃, wherein the system is a yellow solution, the solution becomes colorless and transparent after 2 hours and then becomes a white milky solution, generating new substances on a panel, continuously heating to generate white precipitates, after 3-5 hours of reaction, almost completely reacting the raw materials, cooling with ice water, performing suction filtration, and recrystallizing by using a mixed solvent of ethyl acetate and petroleum ether to obtain 43.4g of pure flame retardant containing the Schiff base DOPO, wherein the yield is 89.71%.
Example 4
The novel Schiff base DOPO phosphorus nitrogen-containing 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
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 1, as the content of the flame retardant in the epoxy resin (EP) increases, the flame retardant effect is obviously enhanced compared with that of the blank EP (LOI:28.0, T:28 s; not extinguished during burning), compared with other flame retardants of the same type (for example, Chinese patent CN201310008589, blank EP: LOI: 21, 7%, 10% and 12% flame retardant with different contents (W%) are added, the LOI values of the flame retardant modified epoxy resin measured are respectively 27, 28.5 and 29, further, for example, Chinese patent CN104109246A, 1%, 2%, 3% and 4% flame retardant with different contents (W%) are respectively 25.4, 26.3, 27.9 and 29.1, the flame retardant effect is enhanced, compared with that of Chinese patent CN 201604553 (the flame retardant content is 18.1%, the P content is 2.5%, the flame retardant content reaches V-0 level), the flame retardant content is 5%, and the P content is only 0.318% (W%) and the UL-0-94 level is tested, slightly higher than the same type of Schiff base compound (the P content in Chinese patent CN110041370A is only 0.34 (W%), UL-94 test reaches V-0 level, LOI value is 32.5), which shows that the flame retardant effect is good, and LOI value is higher, UL-94 can reach V-0 level, and can be used as a flame retardant material for industrial production.
Example 5
TG tests were performed on the novel Schiff base DOPO phosphorus nitrogen containing flame retardants prepared in examples 1 to 3 when applied to epoxy resins.
The TG tests were carried out using a thermogravimetric analyzer TGA (Q5000IR, TA instruments USA) for different examples, with the same content of flame retardant applied in the epoxy resin EP-51: 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, P2 were 318 ℃ (w% ═ 5%) and 321 ℃ (w% ═ 7%), respectively, indicating that the thermal decomposition temperature decreased first and then increased as the amount of flame retardant was increased.
Example 6
The novel Schiff base DOPO phosphorus nitrogen-containing flame retardant prepared in the embodiment 1-3 is applied to epoxy resin for heat resistance test.
For the different examples, the same amount of flame retardant was applied to epoxy resin EP-51 under nitrogen atmosphere using a differential scanning calorimeter with a TA instruments DSC Q20 (TaInstructions) in the United states, 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 Tg of the schiff base DOPO phosphorus nitrogen containing flame retardant EP increases and then decreases with increasing content, from Tg of 172 ℃ at 5% to Tg of 122 ℃ at 7% content, indicating that the novel flame retardant has an accelerating effect on the increase of the glass transition temperature of EP. In addition, the thermal stability is good, and the decomposition is complete, and the stability is below 318 ℃.
The invention has the beneficial effects that:
1. the novel flame retardant containing Schiff base DOPO phosphorus nitrogen prepared by the preparation method provided by the invention has high yield which can reach more than 89%;
2. after the novel phosphorus-nitrogen flame retardant containing Schiff base DOPO is applied to epoxy resin, the flame retardant effect of the epoxy resin can be obviously improved;
3. the novel flame retardant containing Schiff base DOPO phosphorus nitrogen provided by the invention has a promoting effect on the improvement of EP glass transition temperature;
4. the preparation method of the novel Schiff base DOPO phosphorus nitrogen-containing flame retardant provided by the invention has the advantages of simple steps, high purity and yield of the prepared flame retardant, and convenience 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 Schiff base DOPO phosphorus nitrogen containing flame retardant is characterized by having the following structure 1:
2. a preparation method of a novel Schiff base DOPO phosphorus nitrogen-containing flame retardant is characterized by comprising the following steps:
step one, di-p-aminobenzaldehyde and p-aminobenzoic acid are mixed according to the molar ratio of (1-3): (1-2) dissolving in a solvent, adding a certain amount of an acid-binding agent to enable a reaction system to be in an alkaline environment, controlling a certain temperature to react, stirring, reacting for 3-6 hours, leaching when a large amount of yellow precipitates appear, rinsing with a solvent cooled by ice water for multiple times, and drying to obtain pure Schiff base;
step two, mixing the Schiff base and the DOPO according to the proportion (1-3): (1-2) adding the mixture into a mixed solvent, introducing inert gas, stirring, heating and refluxing for 3-5 hours, filtering after a large amount of white precipitates appear, and performing suction filtration by using the following components in a molar ratio of (1-5): (1-3) recrystallizing a mixed solvent formed by mixing ethyl acetate and petroleum ether to obtain a pure flame retardant containing Schiff base DOPO, wherein the reaction equation of the pure flame retardant containing the Schiff base DOPO is as shown in the following formula 2:
3. the preparation method of the novel schiff base DOPO phosphorus nitrogen containing flame retardant as claimed in claim 2, wherein: 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 schiff base DOPO phosphorus nitrogen containing flame retardant as claimed in claim 2, wherein: 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 schiff base DOPO phosphorus nitrogen containing flame retardant as claimed in claim 2, wherein: the mixed solvent comprises at least two of methanol, ethanol, trichloromethane, tetrahydrofuran, dichloromethane, acetonitrile, dimethyl sulfoxide, 1, 4-dioxane, carbon tetrachloride, DMF and DMAC, and is mixed according to the volume ratio of (1-4) to (1-3).
6. The preparation method of the novel schiff base DOPO phosphorus nitrogen containing flame retardant as claimed in claim 2, wherein: the inert gas comprises one of nitrogen, argon and helium.
7. The preparation method of the novel schiff base DOPO phosphorus nitrogen containing flame retardant as claimed in claim 2, wherein: in the first step, the control temperature is: 0 to 50 ℃.
8. Use of a novel schiff base-containing DOPO phosphorus nitrogen flame retardant as defined in claim 1 or 2, wherein: the novel Schiff base DOPO phosphorus nitrogen-containing flame retardant is applied to epoxy resin.
9. Use of a novel schiff base-containing DOPO phosphorus nitrogen flame retardant as defined in claim 1 or 2, wherein: the novel Schiff base DOPO phosphorus nitrogen-containing flame retardant is applied to the flame retardant material in industrial production.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110418782.0A CN113337006A (en) | 2021-04-19 | 2021-04-19 | Novel Schiff base DOPO phosphorus-nitrogen-containing flame retardant and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110418782.0A CN113337006A (en) | 2021-04-19 | 2021-04-19 | Novel Schiff base DOPO phosphorus-nitrogen-containing flame retardant and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113337006A true CN113337006A (en) | 2021-09-03 |
Family
ID=77468110
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110418782.0A Pending CN113337006A (en) | 2021-04-19 | 2021-04-19 | Novel Schiff base DOPO phosphorus-nitrogen-containing flame retardant and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113337006A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114106545A (en) * | 2021-10-12 | 2022-03-01 | 安徽坤涂新材料科技有限公司 | Heat-insulating flame-retardant polycarbonate sheet 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 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002138096A (en) * | 2000-10-27 | 2002-05-14 | Dainippon Ink & Chem Inc | Phenol compound including phosphorus, manufacturing method therefor, and epoxy resin composition using the same |
| TW200936602A (en) * | 2008-02-21 | 2009-09-01 | Nat Univ Chung Hsing | Manufacture of advanced epoxy resins and their high Tg thermosets for electronic applications |
| JP2011148901A (en) * | 2010-01-21 | 2011-08-04 | Manac Inc | Phosphorus-containing diamine and phosphorus-containing polyimide obtained therefrom |
| CN107033329A (en) * | 2017-04-12 | 2017-08-11 | 武汉理工大学 | A kind of halogen-free flameproof epoxy hardener and preparation method thereof |
| CN110041370A (en) * | 2019-05-17 | 2019-07-23 | 武汉工程大学 | A kind of preparation method and applications of the efficient flame-retarding agent containing DOPO and Aminopyrazine structure |
| CN110734462A (en) * | 2019-09-14 | 2020-01-31 | 武汉工程大学 | Synthesis and application of nitrogen-phosphorus efficient flame retardants containing benzimidazole structure |
-
2021
- 2021-04-19 CN CN202110418782.0A patent/CN113337006A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002138096A (en) * | 2000-10-27 | 2002-05-14 | Dainippon Ink & Chem Inc | Phenol compound including phosphorus, manufacturing method therefor, and epoxy resin composition using the same |
| TW200936602A (en) * | 2008-02-21 | 2009-09-01 | Nat Univ Chung Hsing | Manufacture of advanced epoxy resins and their high Tg thermosets for electronic applications |
| JP2011148901A (en) * | 2010-01-21 | 2011-08-04 | Manac Inc | Phosphorus-containing diamine and phosphorus-containing polyimide obtained therefrom |
| CN107033329A (en) * | 2017-04-12 | 2017-08-11 | 武汉理工大学 | A kind of halogen-free flameproof epoxy hardener and preparation method thereof |
| CN110041370A (en) * | 2019-05-17 | 2019-07-23 | 武汉工程大学 | A kind of preparation method and applications of the efficient flame-retarding agent containing DOPO and Aminopyrazine structure |
| CN110734462A (en) * | 2019-09-14 | 2020-01-31 | 武汉工程大学 | Synthesis and application of nitrogen-phosphorus efficient flame retardants containing benzimidazole structure |
Non-Patent Citations (2)
| Title |
|---|
| CORNELIU HAMCIUC ET AL: ""New fire-resistant epoxy thermosets: nonisothermal kinetic study and flammabilitybehavior"", 《J POLYM ENG》 * |
| SALVATORE FAILLA ET AL: ""METHYL-AMINO-PHOSPHONIC ACID DI-ALKYL ESTERS CONTAINING FREE CARBOXYLIC GROUPS. SYNTHESIS AND CHARACTERIZATION"", 《PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114106545A (en) * | 2021-10-12 | 2022-03-01 | 安徽坤涂新材料科技有限公司 | Heat-insulating flame-retardant polycarbonate sheet 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 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu | Flame-retardant epoxy resins from novel phosphorus-containing novolac | |
| CN107090083B (en) | Nitrogen-phosphorus-silicon copolymer with double-layer silsesquioxane as main chain and preparation method and application thereof | |
| CN108440598B (en) | Preparation method and application of sulfur-nitrogen-phosphorus composite flame retardant | |
| CN113337006A (en) | Novel Schiff base DOPO phosphorus-nitrogen-containing flame retardant and preparation method and application thereof | |
| CN110510605A (en) | A kind of richness nitrogen groups functionalization graphene, preparation method and application | |
| CN104725665B (en) | A kind of spiro-phosphate fire retardant containing s-triazine structure, preparation method and applications | |
| CN113264961A (en) | Novel phosphorus-nitrogen-containing DOPO flame retardant and preparation method and application thereof | |
| CN113429627B (en) | P-aminobenzoic acid-condensed p-hydroxyl Schiff base/DOPO flame retardant, preparation method thereof and modified epoxy resin | |
| CN110183727B (en) | Benzothiazole nitrogen phosphorus sulfur ternary synergistic flame retardant containing double DOPO units, and preparation method and application thereof | |
| CN109021287B (en) | Phosphorus-nitrogen-sulfur type flame retardant and application thereof in epoxy resin | |
| CN104558683A (en) | DOPO-containing cyclic phosphate flame retardant as well as preparation method and application thereof | |
| CN113461734A (en) | Novel Schiff base DOPO phosphorus nitrogen-containing flame retardant and synthesis method and application thereof | |
| CN109134544A (en) | A kind of phosphorus nitrile compounds, the composition including the phosphorus nitrile compounds, the fire retardant comprising it and application | |
| CN104231309A (en) | Oxaphosphaphenanthrene flame retardant, preparation method and application thereof | |
| CN113337004A (en) | Novel phosphorus-nitrogen DOPO derivative flame retardant and synthetic method and application thereof | |
| CN107216354A (en) | The preparation method of the six degree of functionality epoxy resin based on the phosphonitrile of ring three | |
| CN110128702A (en) | Benzene sulphones nitrogen phosphorus sulphur synergistic flame retardant containing double DOPO, preparation method and applications | |
| CN113264960A (en) | Novel phosphorus-nitrogen flame retardant containing Schiff base DOPO derivative and preparation method and application thereof | |
| CN111606948B (en) | Efficient phosphine-nitrogen flame retardant and preparation method and application thereof | |
| CN113512233A (en) | Novel nitrogen-phosphorus flame retardant containing furyl DOPO and preparation method and application thereof | |
| CN110128474B (en) | Preparation method and application of nitrogen-phosphorus-sulfur ternary synergistic flame retardant bis-DOPO thiazole compound | |
| CN114409827B (en) | Synthesis and performance of transparent epoxy resin material with high flame retardant performance based on chitosan derivative | |
| CN113429629B (en) | Schiff-HCCP flame retardant, preparation method thereof and modified epoxy resin | |
| CN113337005A (en) | Novel thienyl-containing DOPO flame retardant and synthesis method and application thereof | |
| CN107501526B (en) | DOPO type epoxy resin curing agent 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 |