CN113105506A - Phosphaphenanthrene derivative flame retardant and preparation method thereof - Google Patents
Phosphaphenanthrene derivative flame retardant and preparation method thereof Download PDFInfo
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- CN113105506A CN113105506A CN202110515876.XA CN202110515876A CN113105506A CN 113105506 A CN113105506 A CN 113105506A CN 202110515876 A CN202110515876 A CN 202110515876A CN 113105506 A CN113105506 A CN 113105506A
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 55
- 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 52
- LJUXFZKADKLISH-UHFFFAOYSA-N benzo[f]phosphinoline Chemical class C1=CC=C2C3=CC=CC=C3C=CC2=P1 LJUXFZKADKLISH-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 29
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000007810 chemical reaction solvent Substances 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- DVKXIAKROYARSW-UHFFFAOYSA-N 6-sulfido-6H-benzo[c][2,1]benzoxaphosphinin-6-ium Chemical compound S=P1Oc2ccccc2-c2ccccc12 DVKXIAKROYARSW-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 2
- 150000007530 organic bases Chemical group 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 abstract description 7
- 239000011593 sulfur Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 4
- 239000011574 phosphorus Substances 0.000 abstract description 4
- 229910052736 halogen Inorganic materials 0.000 abstract description 2
- 150000002367 halogens Chemical class 0.000 abstract description 2
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical group C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 17
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- 238000002844 melting Methods 0.000 description 9
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- 239000007787 solid Substances 0.000 description 9
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- 239000007789 gas Substances 0.000 description 7
- 239000012467 final product Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000012429 reaction media Substances 0.000 description 4
- 238000007259 addition reaction Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- -1 aldehyde ketone Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000307 polymer substrate Polymers 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Chemical group 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- OTYNBGDFCPCPOU-UHFFFAOYSA-N phosphane sulfane Chemical compound S.P[H] OTYNBGDFCPCPOU-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000004151 quinonyl group Chemical group 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000007280 thionation reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/5398—Phosphorus bound to sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- 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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- 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 provides a phosphaphenanthrene derivative flame retardant and a preparation method thereof, wherein the chemical structural formula of the phosphaphenanthrene derivative flame retardant is as follows:
the phosphaphenanthrene derivative flame retardant disclosed by the invention has the advantages that the sulfur element is introduced into the DOPO structure, the flame retardant effect of phosphorus is enhanced, the condensed phase flame retardant capability of the flame retardant is improved, the MAH-DOPS flame retardant effect is good, the halogen is not contained, and the environment friendliness is facilitated.
Description
Technical Field
The invention relates to the field of preparation of flame retardants, and particularly relates to a phosphaphenanthrene derivative flame retardant and a preparation method thereof.
Background
The phosphaphenanthrene flame retardant is widely applied to polymer base materials such as epoxy resin, polyester, polycarbonate and the like due to the advantages of environmental friendliness, high carbon content, good compatibility, lasting flame retardance and the like. The 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) is used as an important phosphaphenanthrene intermediate, the molecular structure of the DOPO contains active P-H bonds, and the DOPO and unsaturated groups such as quinone, aldehyde ketone, epoxy group, carbon-carbon double bond, carbonyl group, carbon-nitrogen double bond and the like are subjected to addition reaction to prepare a series of reactive or additive phosphaphenanthrene derivative flame retardants.
However, DOPO only plays a flame retardant role in the gas phase, and has an insignificant promoting effect on the generation of carbon residue on the polymer substrate, and the promotion of the flame retardant effect is limited.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a phosphaphenanthrene derivative flame retardant, and a flame-retardant composite material prepared from the flame retardant has the advantages of high flame-retardant efficiency, compact carbon layer, low toxicity during combustion and the like.
The second purpose of the invention is to provide a preparation method of the phosphaphenanthrene derivative flame retardant, the preparation method is convenient to operate, simple and feasible, the reaction conditions are mild, the industrial production is convenient to realize, and the operation route is very worthy of subsequent popularization and application.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides a phosphaphenanthrene derivative flame retardant, which has a chemical structural formula as follows:
the chemical structural formula is abbreviated as MAH-DOPS, and the chemical formula is C16H11O4PS。
The novel flame retardant overcomes the defects of low flame retardant efficiency, large addition amount, insufficient promotion of carbon residue generation of a polymer substrate and the like of the traditional flame retardant, improves the compatibility problem of the flame retardant and the substrate, is convenient to produce and use, has high flame retardant efficiency, low smoke and low toxicity, has excellent processing performance and wide application range, and obtains the flame retardant composite material with good flame retardant performance and mechanical property.
Preferably, as a further implementable variant, it is produced mainly from Maleic Anhydride (MAH) and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-sulphide (DOPS) as starting materials. MAH itself is a heterocyclic compound containing unsaturated double bonds, and is easy to have addition reaction with P-H in DOPS.
The specific reaction process is as follows:
preferably, as a further implementable aspect, the molar ratio of the MAH and the DOPS is (0.9-1.5):1, in addition to which the molar ratio may be 1.0:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, and so on.
In the scheme of the invention, P ═ O in DOPO is subjected to thionation, and the phosphorus-sulfur composite compound DOPS can be obtained. Firstly, the sulfur element is used as a flame retardant element, the flame retardant effect of phosphorus can be improved by introducing the sulfur element into the phosphaphenanthrene flame retardant, and the sulfur-containing compound can release H under the condition of high temperature2SO4Strong acid, etc. to promote the dehydration and carbonization of the base material, so that the flame retardant can exert excellent flame retardant performance in a condensed phase; secondly, a sulfur atomThe agent helps to inhibit the dripping behavior of the flame-retardant modified base material; thirdly, the reactivity of the P-H bond in the compound DOPS after the sulfur element is introduced into the structure of DOPO is increased, and the compound DOPS is easier to generate addition reaction with unsaturated groups to generate DOPS derivatives.
Preferably, as a further implementable scheme, the raw materials further comprise a reaction solvent, and the reaction solvent comprises any one or a mixture of several of toluene, xylene, tetrahydrofuran and ethyl acetate. The reaction solvent serves as a reaction medium.
Preferably, as a further implementable variant, the reaction catalyst is an organic base, more preferably triethylamine.
The invention provides a specific structure of the phosphaphenanthrene derivative flame retardant, and also provides a preparation method of the phosphaphenanthrene derivative flame retardant, which comprises the following steps:
all raw materials are subjected to catalytic reaction in the presence of a reaction solvent, the reaction temperature is 60-90 ℃, and the reaction time is 6-14 h.
Preferably, as a further practical embodiment, the product obtained by the reaction is washed with an organic solvent and then dried under vacuum.
Preferably, as a further practical scheme, the organic solvent comprises any one or a mixture of ethanol, propanol, isopropanol, dichloromethane, chloroform and petroleum ether.
The method takes the MAH and the DOPS as raw materials, synthesizes the flame retardant MAH-DOPS by a direct addition method, has rapid reaction and high synthesis efficiency, removes residual MAH raw materials by a method of washing with an organic solvent, and purifies the product, wherein the organic solvent adopted by the method has lower solubility to the MAH-DOPS and higher solubility to impurities; the method provided by the invention can be used for obtaining MAH-DOPS powder with high purity and high yield.
Preferably, as a further practicable embodiment, the mass of the organic solvent added is 15 to 30 times the mass of the maleic anhydride.
Preferably, as a further implementable solution, the temperature of the vacuum drying is 40-60 ℃ and the time is 4-8 h.
Compared with the prior art, the invention has the beneficial effects that:
(1) in the scheme of the invention, the sulfur element is introduced into the DOPO structure, so that the flame retardant effect of phosphorus is improved, and the condensed phase flame retardant capability of the phosphorus is improved;
(2) the flame retardant disclosed by the invention is good in flame retardant effect, does not contain halogen, and is beneficial to environmental protection;
(3) the preparation method of the flame retardant is simple, the reaction conditions are easy to control, the reaction is rapid, and the synthesis efficiency is high;
(4) the novel reactive phosphaphenanthrene derivative flame retardant prepared by the invention can be applied to substrates such as epoxy resin, polyester, polycarbonate and the like, obtains a flame-retardant composite material with good flame retardant property and mechanical property, has a wide application range, and can meet the use requirements of different fields.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:
FIG. 1 is an infrared spectrum of a phosphaphenanthrene derivative flame retardant product provided in example 1 of the present invention;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of the phosphaphenanthrene derivative flame retardant product provided in example 1 of the present invention.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
(1) Weighing MAH and DOPS according to the molar ratio of 1.5: 1;
(2) organic solvent toluene is used as a reaction medium, so that reactants can fully react;
(3) adding weighed DOPS into a four-neck flask with a thermometer, a stirrer and a shielding gas inlet and outlet, adding a proper amount of solvent and triethylamine catalyst, installing a reflux condensing device, introducing shielding gas, and heating to 60 ℃ under the stirring condition. After the DOPS is completely dissolved, adding the MAH into the reaction system for 5 times, and after the addition is finished, continuing the reflux reaction for 14 hours.
(4) After the reaction is finished, performing suction filtration, collecting a filter cake, adding an organic solvent absolute ethyl alcohol as a washing solvent, wherein the using amount of the washing solvent is 30 times of the mass of the MAH, filtering the white powder by using a Buchner funnel, repeatedly washing for 2 times, and performing vacuum drying at 60 ℃ for 8 hours to finally obtain a product MAH-DOPS which is a white powdery solid, wherein the melting point (m.p.) of the product is 199.2 ℃, the yield is 94.1%, the conversion rate is 94.5%, the purity is more than 99.0%, and a specific product confirmation map is shown in a figure 1-a figure 2.
The infrared spectrum of MAH-DOPS is shown in FIG. 1, wherein 3440.39cm-1The product is not completely dried due to absorption peak of water; 2925.47cm-1The position is a stretching vibration absorption peak of C-H on a benzene ring, 1785.91, 1856.51cm-1The peak is the antisymmetric stretching vibration absorption peak of carbonyl C ═ O on the acid anhydride group, 1259.04cm-1Is the absorption peak of stretching vibration of C-O bond in cyclic acid anhydride, 1579.41cm-1A stretching vibration absorption peak at P-Ph of 1185.56cm-1The absorption peak at position is the absorption peak of the P-O-Ph bond, 936.80cm-1Absorption peak of stretching vibration at P ═ S bond, 759.82cm-1Is a characteristic absorption peak of ortho-substitution on a benzene ring.
Example 2
(1) Weighing MAH and DOPS according to the molar ratio of 0.9: 1;
(2) the tetrahydrofuran which is an organic solvent is used as a reaction medium, so that reactants can fully react;
(3) adding weighed DOPS into a four-neck flask with a thermometer, a stirrer and a shielding gas inlet and outlet, adding a proper amount of solvent and triethylamine catalyst, installing a reflux condensing device, introducing shielding gas, and heating to 90 ℃ under the stirring condition. After the DOPS is completely dissolved, adding the MAH into the reaction system for 3 times, and after the addition is finished, continuing the reflux reaction for 6 hours.
(4) And after the reaction is finished, carrying out suction filtration, collecting a filter cake, adding an organic solvent absolute ethyl alcohol as a washing solvent, wherein the using amount of the washing solvent is 15 times of the mass of the MAH, filtering the white powder by using a Buchner funnel, repeatedly washing for 5 times, and carrying out vacuum drying at 40 ℃ for 4 hours to finally obtain a product MAH-DOPS which is a white powdery solid, wherein the melting point (m.p.) of the product is 199.2 ℃, the yield is 94.1%, the conversion rate is 94.3%, and the purity is more than 99.0%.
Example 3
(1) Weighing MAH and DOPS according to the molar ratio of 1.2: 1;
(2) the tetrahydrofuran which is an organic solvent is used as a reaction medium, so that reactants can fully react;
(3) adding weighed DOPS into a four-neck flask with a thermometer, a stirrer and a shielding gas inlet and outlet, adding a proper amount of solvent and triethylamine catalyst, installing a reflux condensing device, introducing shielding gas, and heating to 80 ℃ under the stirring condition. After the DOPS is completely dissolved, adding the MAH into the reaction system for 3 times, and after the addition is finished, continuing the reflux reaction for 10 hours.
(4) And after the reaction is finished, carrying out suction filtration, collecting a filter cake, adding an organic solvent absolute ethyl alcohol as a washing solvent, wherein the using amount of the washing solvent is 20 times of the mass of the MAH, filtering the white powder by using a Buchner funnel, repeatedly washing for 4 times, and carrying out vacuum drying at 50 ℃ for 6 hours to finally obtain a product MAH-DOPS which is a white powdery solid, wherein the melting point (m.p.) of the product is 199.6 ℃, the yield is 95.3%, the conversion rate is 95.5%, and the purity is more than 99.0%.
Example 4
The specific procedure was as in example 3 except that MAH and DOPS were weighed at a molar ratio of 0.6:1, and the final product MAH-DOPS was a white powdery solid with a melting point (m.p.) of 199.6 ℃, a yield of 92.2%, a conversion of 92.6%, and a purity of > 99.0%.
Example 5
The specific procedure was as in example 3 except that MAH and DOPS were weighed at a molar ratio of 2:1 to give a white powdery solid as the final product MAH-DOPS, with a melting point (m.p.) of 199.6 ℃, a yield of 91.5%, a conversion of 91.6%, and a purity of > 99.0%.
Example 6
The specific procedure was identical to example 3, except that the reaction temperature was 40 ℃ and the final product MAH-DOPS was a white powdery solid, the melting point (m.p.) of the product was 199.6 ℃, the yield was 91.7%, the conversion was 91.8% and the purity was > 99.0%.
Example 7
The specific procedure was identical to example 3, except that the reaction temperature was 100 ℃ and the final product MAH-DOPS was a white powdery solid, the melting point (m.p.) of the product was 199.6 ℃, the yield was 91.9%, the conversion was 92.0% and the purity was > 99.0%.
Example 8
The specific procedure was identical to example 3, except that the reaction time was 2h, and the final product MAH-DOPS was a white powdery solid with a melting point (m.p.) of 199.6 ℃, a yield of 89.1%, a conversion of 89.3% and a purity of > 99.0%.
Example 9
The specific procedure was identical to example 3, except that the reaction time was 17h, and the final product MAH-DOPS was a white powdery solid with a melting point (m.p.) of 199.6 ℃, a yield of 91.1%, a conversion of 91.7% and a purity of > 99.0%.
In conclusion, for the phosphaphenanthrene derivative flame retardant product of the present invention, it is advantageous to control the respective operation parameters during the preparation process to improve the yield of the product, and therefore it is preferable to control the respective operation parameters within appropriate ranges.
While particular embodiments of the present invention have been illustrated and described, it would be obvious that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
Claims (10)
1. A phosphaphenanthrene derivative flame retardant is characterized in that the chemical structural formula of the phosphaphenanthrene derivative flame retardant is as follows:
2. the phosphaphenanthrene derivative flame retardant as claimed in claim 1, which is prepared mainly from maleic anhydride and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-sulfide.
3. The phosphaphenanthrene derivative flame retardant of claim 1, wherein the molar ratio of the maleic anhydride and the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-sulfide is (0.9-1.5): 1.
4. The phosphaphenanthrene derivative flame retardant of claim 1, wherein the raw materials further comprise a reaction solvent, and the reaction solvent comprises any one or a mixture of toluene, xylene, tetrahydrofuran and ethyl acetate.
5. The phosphaphenanthrene derivative flame retardant of claim 1, wherein the reaction catalyst is an organic base, preferably triethylamine.
6. The method for preparing phosphaphenanthrene derivative flame retardants according to any of claims 1 to 5, characterized by comprising the steps of:
all raw materials are subjected to catalytic reaction in the presence of a reaction solvent, the reaction temperature is 60-90 ℃, and the reaction time is 6-14 h.
7. The process according to claim 6, wherein the product obtained by the reaction is washed with an organic solvent and then dried under vacuum.
8. The preparation method according to claim 7, wherein the organic solvent comprises one or more of ethanol, propanol, isopropanol, dichloromethane, chloroform and petroleum ether.
9. The production method according to claim 7, wherein the mass of the organic solvent added is 15 to 30 times the mass of the maleic anhydride.
10. The method according to claim 7, wherein the temperature of the vacuum drying is 40-60 ℃ and the time is 4-8 hours.
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| CN116004065A (en) * | 2023-02-14 | 2023-04-25 | 安徽盾卫工业防护材料有限公司 | Tunnel diffuse reflection coating and preparation method thereof |
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| WO2012142634A1 (en) * | 2011-04-18 | 2012-10-26 | Sunpor Kunststoff Gesellschaft M.B.H. | Flame-retardant expandable polymers |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116004065A (en) * | 2023-02-14 | 2023-04-25 | 安徽盾卫工业防护材料有限公司 | Tunnel diffuse reflection coating and preparation method thereof |
| CN116004065B (en) * | 2023-02-14 | 2023-10-27 | 安徽盾卫工业防护材料有限公司 | Tunnel diffuse reflection coating and preparation method thereof |
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