CN111763351A - Reactive phosphaphenanthrene/phosphite ester biradical flame retardant, preparation method and application thereof - Google Patents
Reactive phosphaphenanthrene/phosphite ester biradical flame retardant, preparation method and application thereof Download PDFInfo
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- CN111763351A CN111763351A CN202010390988.2A CN202010390988A CN111763351A CN 111763351 A CN111763351 A CN 111763351A CN 202010390988 A CN202010390988 A CN 202010390988A CN 111763351 A CN111763351 A CN 111763351A
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- phosphite
- phosphaphenanthrene
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- phosphite ester
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- 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 93
- 239000003063 flame retardant Substances 0.000 title claims abstract description 93
- LJUXFZKADKLISH-UHFFFAOYSA-N benzo[f]phosphinoline Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=P1 LJUXFZKADKLISH-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 150000008301 phosphite esters Chemical class 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229920005830 Polyurethane Foam Polymers 0.000 claims abstract description 22
- 239000011496 polyurethane foam Substances 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- -1 dialdehyde compound Chemical class 0.000 claims abstract description 15
- 239000002131 composite material Substances 0.000 claims abstract description 10
- 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 abstract 3
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- 239000006260 foam Substances 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 7
- 229920001228 polyisocyanate Polymers 0.000 claims description 7
- 239000005056 polyisocyanate Substances 0.000 claims description 7
- 229920005862 polyol Polymers 0.000 claims description 7
- 150000003077 polyols Chemical class 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000005187 foaming Methods 0.000 claims description 5
- 239000004088 foaming agent Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 5
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 claims description 4
- KUMNEOGIHFCNQW-UHFFFAOYSA-N diphenyl phosphite Chemical compound C=1C=CC=CC=1OP([O-])OC1=CC=CC=C1 KUMNEOGIHFCNQW-UHFFFAOYSA-N 0.000 claims description 4
- CHJUOCDSZWMLRU-UHFFFAOYSA-N oxo(dipropoxy)phosphanium Chemical compound CCCO[P+](=O)OCCC CHJUOCDSZWMLRU-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- UMHJEEQLYBKSAN-UHFFFAOYSA-N Adipaldehyde Chemical compound O=CCCCCC=O UMHJEEQLYBKSAN-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
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 claims description 2
- WSMYVTOQOOLQHP-UHFFFAOYSA-N Malondialdehyde Chemical compound O=CCC=O WSMYVTOQOOLQHP-UHFFFAOYSA-N 0.000 claims description 2
- OOLBRPUFHUSCOS-UHFFFAOYSA-N Pimelic dialdehyde Chemical compound O=CCCCCCC=O OOLBRPUFHUSCOS-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- PCSMJKASWLYICJ-UHFFFAOYSA-N Succinic aldehyde Chemical compound O=CCCC=O PCSMJKASWLYICJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- RQKYHDHLEMEVDR-UHFFFAOYSA-N oxo-bis(phenylmethoxy)phosphanium Chemical compound C=1C=CC=CC=1CO[P+](=O)OCC1=CC=CC=C1 RQKYHDHLEMEVDR-UHFFFAOYSA-N 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims 8
- 238000000034 method Methods 0.000 claims 7
- 239000000463 material Substances 0.000 abstract description 9
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- 238000002485 combustion reaction Methods 0.000 abstract description 7
- 230000002195 synergetic effect Effects 0.000 abstract description 6
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 13
- 239000002585 base Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 7
- 238000004786 cone calorimetry Methods 0.000 description 6
- 229920002635 polyurethane Polymers 0.000 description 6
- 239000004814 polyurethane Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000203 mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical group CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011241 protective layer Substances 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
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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)
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
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Abstract
The invention discloses a reactive phosphaphenanthrene/phosphite ester biradical flame retardant, a preparation method thereof and application of a complex system in flame-retardant rigid polyurethane foam, belonging to the technical field of flame-retardant materials. The flame retardant with the bistatic synergistic effect is synthesized by the dialdehyde compound, the organic phosphite ester and the DOPO, is an environment-friendly flame retardant with high efficiency and high thermal stability, and a composite system of the flame retardant can promote the hard polyurethane foam to quickly form carbon during combustion, form a continuous and compact carbon layer, effectively reduce the release of heat and enable the hard polyurethane foam to have excellent flame retardant property.
Description
Technical Field
The invention belongs to the technical field of flame-retardant materials, and particularly relates to a reactive phosphaphenanthrene/phosphite ester biradical flame retardant, a preparation method thereof and application of a complex system in flame-retardant rigid polyurethane foam.
Background
The hard polyurethane foam has excellent physical and mechanical properties, electrical properties, mechanical properties, acid and alkali resistance and strong bonding force with various materials, so the hard polyurethane foam is widely used in the fields of automobile industry, household appliance industry, building industry and the like. However, the polyurethane material is flammable in air and decomposes to generate a large amount of toxic smoke, which may cause fire and cause casualties and great economic loss, etc., thereby limiting the further development of polyurethane foam. At present, the flame retardant most commonly applied to polyurethane foam is mainly a phosphorus-containing additive flame retardant such as phosphite flame retardant, the flame retardant is mainly used for improving the flame retardant performance of the polyurethane foam through gas-phase flame retardance, but most of the flame retardant is liquid and has the defects of poor heat resistance, easy precipitation and the like, and when the flame retardant is singly used, the prepared polyurethane material has poor stability.
In recent years, researchers have been working on designing and developing flame retardants with good flame retardant efficiency and little influence on the performance of the base material, and have been working on obtaining a good flame retardant effect of the base material with a low addition amount. Among them, the double-base synergistic flame retardant has received much attention from researchers, and its research results have been published in many journals such as Macromolecules, polymers, Polymer degradation and stability, and Journal of Applied Polymer Science. In addition, the environment-friendly flame retardant is 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), and has higher reactivity and good flame retardant effect, so that the preparation of the novel high-efficiency phosphaphenanthrene derivative flame retardant by taking the DOPO as a raw material becomes a research hotspot in the flame retardant field in recent years.
The phosphite flame retardant and the DOPO play a flame retardant role simultaneously in a physical blending mode, so certain disadvantages are undoubtedly brought: the polarity of phosphite ester is greatly different from that of a polymer matrix, the phosphite ester is easy to agglomerate, the problem of poor compatibility is easy to occur, meanwhile, the organic small molecular flame retardant is easy to migrate, and in addition, the mechanical property of the material is reduced due to the fact that the addition amount is too large. Therefore, the phosphite ester and the phosphaphenanthrene group are combined in one molecular unit through chemical bonds to form a reactive phosphaphenanthrene/phosphite ester double-base flame retardant, which not only solves the problems, but also enhances the double-base synergistic effect of the phosphite ester and the phosphaphenanthrene, and improves the flame retardant efficiency.
Disclosure of Invention
Aiming at the problems existing at present, the invention provides a novel environmentally-friendly phosphaphenanthrene/phosphite ester biradical flame retardant with biradical synergistic effect, a preparation method thereof and application of a complex system in flame-retardant rigid polyurethane foam. The reactive phosphaphenanthrene/phosphite ester biradical flame retardant has good thermal stability, and the complex system containing the phosphaphenanthrene/phosphite ester biradical flame retardant has higher flame retardant efficiency and can obviously improve the flame retardant property of hard polyurethane foam.
The flame retardant with different flame retardant mechanisms is selected, and the flame retardant is compounded to generate a good synergistic effect, so that a more obvious flame retardant effect is obtained, and the safety performance of the product is improved. The phosphaphenanthrene/phosphite ester double-base flame retardant has both hydroxyl group and flame retardant group, and in the reaction process with isocyanate group in polyurethane, the phosphaphenanthrene group and phosphite ester group are connected to the main chain of the molecular structure of polyurethane to hinder the combustion. In addition, Expandable Graphite (EG) forms a vermicular carbon layer on the surface of a matrix after being decomposed by heat, thereby playing an excellent condensed phase blocking role. The two reaction processes are continuously carried out, so that a compact phosphoric acid compound protective layer is formed on the outer surface of the flame-retardant RPUF carbon layer, and the compactness of the surface carbon layer is improved to isolate oxygen and heat.
The invention adopts the following technical scheme:
a reactive phosphaphenanthrene/phosphite diester-based flame retardant has a general structural formula shown as the following formula:
wherein R and R' are both alkyl or aryl.
The invention also discloses a synthetic method of the reactive phosphaphenanthrene/phosphite ester biradical flame retardant, and the synthetic route is as follows:
(1)
(2)
the specific preparation method comprises the following steps:
(1) adding a dialdehyde compound and an organic solvent into a reaction vessel, stirring and dissolving the dialdehyde compound and the organic solvent at 50 ℃, and then adding a certain amount of basic catalyst into the solution; b. dropping organic phosphite ester solution dissolved in proper amount of organic solvent into flask at certain speed, and raising the temperature of the system to react for certain time after dropping.
(2) Then adding DOPO into the reaction system obtained in the step (1) to continue the reaction for 8 to 12 hours. After the reaction is finished, cooling to room temperature, and carrying out reduced pressure distillation and drying to obtain the reactive phosphaphenanthrene/phosphite ester biradical flame retardant.
In the above technical scheme, preferably, the molar ratio of the dialdehyde compound and the organic phosphite ester in the step (1) is 1:1-1:3, preferably 1:1-1: 1.5; the dialdehyde compound is one of terephthalaldehyde, malonaldehyde, succinaldehyde, 3-diphenyl glutaraldehyde, hexanedial and heptanedial;
preferably, the organic solvent in the steps (1) a and (b) is one or more of methanol, ethanol, propanol, diethyl ether and dipropylene glycol dimethyl ether; the dosage of the organic solvent is as follows: 5-30ml (more preferably 7-20ml) of solvent per 1g of dialdehyde compound in a and 5-50ml (more preferably 10-35ml) of solvent per 1g of organic phosphite in b;
preferably, the basic catalyst in the step (1) is one of triethylamine, sodium ethoxide, sodium hydroxide, potassium hydroxide, sodium bicarbonate, potassium bicarbonate, pyridine, 4-dimethylaminopyridine and N, N-diisopropylethylamine; the catalyst is used in such an amount that the molar ratio of organophosphite to catalyst is from 1:1 to 1:3, more preferably from 1:1 to 1: 2.5;
preferably, the organic phosphite in the step (1) is one of dimethyl phosphite, diethyl phosphite, di-n-propyl phosphite, diphenyl phosphite and dibenzyl phosphite; the dropping speed of the organic phosphite ester solution is 0.2-5ml/min, and more preferably 0.5-3 ml/min; after the organic phosphite ester solution is dripped, the system is heated to a certain temperature and reacts for a certain time: raising the temperature to 60-120 ℃ for reaction for 5-15h, more preferably 70-90 ℃ for reaction for 10-15 h;
preferably, the molar ratio of DOPO in step (2) to organophosphite in step (1) is from 1:1 to 1:3, preferably from 1:1 to 1: 1.5.
The invention also provides a halogen-free composite flame-retardant system containing the phosphaphenanthrene/phosphite ester biradical flame retardant, and the components of the composite system comprise: the phosphaphenanthrene/phosphite double-base flame retardant and expandable graphite.
In the above technical scheme, preferably, the phosphaphenanthrene/phosphite double-base flame retardant in the complex system: the mass ratio of the expandable graphite is 3:1-1: 1.
The invention also provides flame-retardant rigid polyurethane foam, and the preparation method comprises the following steps:
(1) mixing polyether polyol, water, a foaming agent, a foam stabilizer, a catalyst and the halogen-free composite flame retardant, and mechanically stirring for 3-5 min at normal temperature until the raw materials are uniformly mixed;
(2) and adding the polyisocyanate into the system, stirring, pouring into a prepared mould for natural foaming, and curing the foam to obtain the flame-retardant rigid polyurethane foam.
The mass ratio of the polyisocyanate to the polyether polyol in the step (1) is 1-1.6: 1.
The invention has the beneficial effects that:
1. the reactive phosphaphenanthrene/phosphite ester biradical flame retardant combines a phosphaphenanthrene group and an organic phosphite ester in the same molecular unit through chemical bonds to form a biradical synergistic effect, and the phosphaphenanthrene group and the phosphite ester group are connected to a main chain of a polyurethane molecular structure through reaction to hinder the combustion of the polyurethane molecular structure, so that the flame retardant efficiency is improved.
2. The reactive phosphaphenanthrene/phosphite ester biradical flame retardant has high thermal stability, moisture absorption resistance and matrix compatibility, is an efficient and high-thermal-stability environment-friendly flame retardant, and a composite system of the reactive phosphaphenanthrene/phosphite ester biradical flame retardant can promote hard polyurethane foam to quickly form carbon during combustion, form a continuous, complete and compact carbon layer, effectively reduce the release of heat and enable the hard polyurethane foam to have excellent flame retardant property.
3. The efficient and environment-friendly flame-retardant rigid polyurethane foam plastic prepared by the phosphaphenanthrene/phosphite double-base flame retardant and the composite system thereof has the advantages of sufficient raw material sources, low cost, simple preparation method, easily controlled industrial conditions and suitability for industrial production.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a nuclear magnetic resonance carbon spectrum of a phosphaphenanthrene/phosphite biradical flame retardant prepared in example 1;
FIG. 2 is an IR spectrum of a phosphaphenanthrene/phosphite biradical flame retardant prepared in example 1;
fig. 3 is a photograph of carbon residue after cone calorimetry testing of the flame retarded RPUF in example 1.
Detailed Description
The present invention will be described in further detail with reference to examples and the accompanying tables, but the embodiments of the present invention are not limited thereto.
Example 1
Adding 21.48g of terephthalaldehyde and 120ml of ethanol into a reaction vessel, stirring and dissolving the terephthalaldehyde at 50 ℃, and then adding 24ml of triethylamine into the solution; dissolving 22.10g diethyl phosphite in 300ml ethanol, after combustion, dripping the diethyl phosphite solution into the flask at the speed of 1ml/min, and after the dripping is finished, raising the temperature of the system to 90 ℃ for reaction for 8 h; then 34.56g of DOPO was added to the reaction system for 15 hours; after the reaction is finished, cooling to room temperature, and carrying out reduced pressure distillation and drying to obtain a reactive phosphaphenanthrene/phosphite ester biradical flame retardant; adding 72 parts of polyether polyol, 48 parts of phosphaphenanthrene/phosphite double-base flame retardant, 22 parts of expandable graphite, 0.9 part of water, 9 parts of foaming agent, 2.2 parts of foam stabilizer and 2.8 parts of catalyst into a 600mL plastic beaker, stirring for 3-5 min by using an electric stirrer until the raw materials are uniformly mixed, then quickly adding 108 parts of polyisocyanate into the beaker, simultaneously quickly stirring for 10s by using the electric stirrer, then quickly pouring the obtained mixture into a prepared mould for natural foaming, and obtaining the flame-retardant rigid polyurethane foam after foam curing.
Example 2
22.47g of terephthalaldehyde and 150ml of propanol were added to a reaction vessel and dissolved with stirring at 50 ℃ and then 20ml of sodium ethoxide was added to the solution; 26.42g of di-n-propyl phosphite is dissolved in 300ml of propanol, after combustion, the di-n-propyl phosphite solution is dripped into a flask at the speed of 1.5ml/min, and after dripping is finished, the system is raised to 90 ℃ for reaction for 10 hours; 38.88g of DOPO were subsequently added to the reaction system for 12 h; after the reaction is finished, cooling to room temperature, and carrying out reduced pressure distillation and drying to obtain a reactive phosphaphenanthrene/phosphite ester biradical flame retardant; according to the mass percent, 80 parts of polyether polyol, 40 parts of phosphaphenanthrene/phosphite double-base flame retardant, 20 parts of expandable graphite, 0.6 part of water, 10 parts of foaming agent, 2.5 parts of foam stabilizer and 2.5 parts of catalyst are added into a 600mL plastic beaker, stirred for 3-5 min by an electric stirrer until the raw materials are uniformly mixed, then 120 parts of polyisocyanate is rapidly added into the beaker, and simultaneously rapidly stirred for 10s by the electric stirrer, then the obtained mixture is rapidly poured into a prepared mould for natural foaming, and after foam curing, the flame-retardant rigid polyurethane foam can be obtained.
Example 3
11.53g of adipaldehyde and 100ml of diethyl ether are added to a reaction vessel and dissolved with stirring at 50 ℃ and then 18ml of N, N-diisopropylethylamine is added to the solution; 37.47g of diphenyl phosphite is dissolved in 350ml of diethyl ether, after combustion, the diphenyl phosphite solution is dripped into a flask at the speed of 2ml/min, and after the dripping is finished, the system is raised to 90 ℃ for reaction for 12 hours; subsequently, 41.04g of DOPO was added to the reaction system for 15 hours; after the reaction is finished, cooling to room temperature, and carrying out reduced pressure distillation and drying to obtain a reactive phosphaphenanthrene/phosphite ester biradical flame retardant; according to the mass, 70 parts of polyether polyol, 30 parts of phosphaphenanthrene/phosphite double-base flame retardant, 20 parts of expandable graphite, 0.8 part of water, 8 parts of foaming agent, 3 parts of foam stabilizer and 2 parts of catalyst are added into a 600mL plastic beaker in proportion, an electric stirrer is used for stirring for 3-5 min until the raw materials are uniformly mixed, 105 parts of polyisocyanate is quickly added into the beaker, the electric stirrer is used for quickly stirring for 10s, the obtained mixed material is quickly poured into a prepared mould for natural foaming, and the flame-retardant rigid polyurethane foam can be obtained after foam curing.
Comparative example
The flame retardant rigid polyurethane foam prepared from the phosphaphenanthrene/phosphite bis-based flame retardant and expandable graphite of example 1 was tested for flame retardant properties and pure RPUF was used as a control for comparison with the flame retardant sample of example 1. The specific test results are shown in table 1 and fig. 3.
Table 1 shows the cone calorimetry test results of example 1 and the control, wherein RPUF is the cone calorimetry test result of the control, and PDEP/EG/RPUF is the cone calorimetry test result of example 1. FIG. 3 is a photomicrograph of carbon residue after cone calorimetry testing of example 1.
TABLE 1 Cone calorimetry test results for the control and example 1
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several equivalent substitutions or obvious modifications, which are equivalent in performance or use, should be considered to fall within the scope of the present invention without departing from the spirit of the invention.
Claims (10)
1. A reactive phosphaphenanthrene/phosphite diester-based flame retardant has a general structural formula shown as the following formula:
wherein R and R' are both alkyl or aryl.
2. A method for preparing the phosphaphenanthrene/phosphite biradical flame retardant of claim 1, which comprises the following steps:
(1) adding a dialdehyde compound and an organic solvent into a reaction vessel, stirring and dissolving the dialdehyde compound and the organic solvent at 50 ℃, and then adding a certain amount of basic catalyst into the solution; b. dripping organic phosphite ester solution dissolved in a proper amount of organic solvent into a flask at a certain speed, and after finishing dripping, raising the temperature of the system to react for a certain time;
(2) and (2) adding DOPO into the reaction system obtained in the step (1) to continue to react for 8-12h, cooling to room temperature after the reaction is finished, and carrying out reduced pressure distillation and drying to obtain the reactive phosphaphenanthrene/phosphite ester biradical flame retardant.
3. The method for preparing phosphaphenanthrene/phosphite biradical flame retardant according to claim 2, characterized in that: the molar ratio of the dialdehyde compound and the organic phosphite ester in the step (1) is 1:1-1:3, preferably 1:1-1: 1.5; the dialdehyde compound is one of terephthalaldehyde, malonaldehyde, succinaldehyde, 3-diphenyl glutaraldehyde, hexanedial and heptanedial.
4. The method for preparing phosphaphenanthrene/phosphite biradical flame retardant according to claim 2, characterized in that: the organic solvent in the steps (1) a and b is selected from one or more of methanol, ethanol, propanol, diethyl ether and dipropylene glycol dimethyl ether; the dosage of the organic solvent is as follows: in a, 5 to 30ml of solvent per 1g of dialdehyde compound, preferably 7 to 20ml of solvent per 1g of dialdehyde compound, and in b, 5 to 50ml of solvent per 1g of organophosphite, preferably 10 to 35ml per 1g of organophosphite.
5. The method for preparing phosphaphenanthrene/phosphite biradical flame retardant according to claim 2, characterized in that: the basic catalyst in the step (1) is one of triethylamine, sodium ethoxide, sodium hydroxide, potassium hydroxide, sodium bicarbonate, potassium bicarbonate, pyridine, 4-dimethylaminopyridine and N, N-diisopropylethylamine; the molar ratio of organophosphite to catalyst is from 1:1 to 1:3, preferably from 1:1 to 1: 2.5.
6. The method for preparing phosphaphenanthrene/phosphite biradical flame retardant according to claim 2, characterized in that: the organic phosphite ester in the step (1) is one of dimethyl phosphite, diethyl phosphite, di-n-propyl phosphite, diphenyl phosphite and dibenzyl phosphite; the dropping speed of the organic phosphite ester solution is 0.2-5ml/min, preferably 0.5-3 ml/min; after the organic phosphite ester solution is dripped, the temperature of the system is raised to 60-120 ℃ for reaction for 5-15h, preferably 70-90 ℃ for reaction for 10-15 h.
7. The method for preparing phosphaphenanthrene/phosphite biradical flame retardant according to claim 2, characterized in that: the molar ratio of DOPO in step (2) to the organophosphite in step (1) is from 1:1 to 1:3, preferably from 1:1 to 1: 1.5.
8. A halogen-free composite flame retardant system comprising the phosphaphenanthrene/phosphite biradical flame retardant of claim 1 or prepared by the method of any one of claims 2-7 and expandable graphite.
9. The halogen-free composite flame retardant system according to claim 8, wherein the mass ratio of the phosphaphenanthrene/phosphite double-based flame retardant to the expandable graphite is 3:1-1: 1.
10. A flame-retardant rigid polyurethane foam is characterized by being prepared by adopting the halogen-free composite flame-retardant system as defined in claim 9, and the preparation method comprises the following steps:
(1) mixing polyether polyol, water, a foaming agent, a foam stabilizer, a catalyst and a halogen-free composite flame retardant, and mechanically stirring at normal temperature until the raw materials are uniformly mixed;
(2) and (2) adding polyisocyanate into the system, wherein the mass ratio of the polyisocyanate to the polyether polyol in the step (1) is 1-1.6:1, stirring, pouring into a mould for natural foaming, and curing the foam to obtain the flame-retardant rigid polyurethane foam.
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| EP4011891A1 (en) * | 2020-12-09 | 2022-06-15 | Covestro Deutschland AG | Method for the preparation of flame-resistant pur/pir foams |
| CN116516679A (en) * | 2023-03-30 | 2023-08-01 | 苏州大学 | Durable flame-retardant anti-dripping coating nylon 6 fabric and preparation method thereof |
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| CN116516679A (en) * | 2023-03-30 | 2023-08-01 | 苏州大学 | Durable flame-retardant anti-dripping coating nylon 6 fabric and preparation method thereof |
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