CN116444800A - Preparation method of oligomeric phosphonate flame retardant - Google Patents
Preparation method of oligomeric phosphonate flame retardant Download PDFInfo
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- CN116444800A CN116444800A CN202310228254.8A CN202310228254A CN116444800A CN 116444800 A CN116444800 A CN 116444800A CN 202310228254 A CN202310228254 A CN 202310228254A CN 116444800 A CN116444800 A CN 116444800A
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 48
- 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 44
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 16
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 238000009835 boiling Methods 0.000 claims abstract description 8
- 239000002608 ionic liquid Substances 0.000 claims abstract description 8
- -1 1-butyl-3-methylimidazole ion Chemical class 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 150000001450 anions Chemical class 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 239000011830 basic ionic liquid Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 20
- 239000000047 product Substances 0.000 abstract description 11
- 238000006735 epoxidation reaction Methods 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000012467 final product Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000003381 stabilizer Substances 0.000 abstract description 2
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 229920005830 Polyurethane Foam Polymers 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 239000011496 polyurethane foam Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HCGMDEACZUKNDY-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;acetate Chemical compound CC(O)=O.CCCCN1CN(C)C=C1 HCGMDEACZUKNDY-UHFFFAOYSA-N 0.000 description 1
- BXOAIZOIDUQOFA-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;hydroxide Chemical compound [OH-].CCCC[N+]=1C=CN(C)C=1 BXOAIZOIDUQOFA-UHFFFAOYSA-M 0.000 description 1
- ZXLOSLWIGFGPIU-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;acetate Chemical compound CC(O)=O.CCN1CN(C)C=C1 ZXLOSLWIGFGPIU-UHFFFAOYSA-N 0.000 description 1
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 1
- SQPFPKSOPRMSDP-UHFFFAOYSA-N C(CCC)N1CN(C=C1)C.O Chemical compound C(CCC)N1CN(C=C1)C.O SQPFPKSOPRMSDP-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910004856 P—O—P Inorganic materials 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- GTRSAMFYSUBAGN-UHFFFAOYSA-N tris(2-chloropropyl) phosphate Chemical compound CC(Cl)COP(=O)(OCC(C)Cl)OCC(C)Cl GTRSAMFYSUBAGN-UHFFFAOYSA-N 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
Classifications
-
- 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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/093—Polyol derivatives esterified at least twice by phosphoric acid groups
-
- 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
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
- C08G79/04—Phosphorus linked to oxygen or to oxygen and carbon
-
- 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
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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 belongs to the technical field of synthesis of flame retardants, and relates to a preparation method of an oligomeric phosphonate flame retardant, which comprises the following steps: (1) Reacting phosphorus pentoxide with triethyl phosphate in a nitrogen atmosphere and a water bath to obtain colorless transparent reaction liquid; (2) Cooling the reaction liquid, stirring and adding water in a nitrogen atmosphere, and reacting to obtain an intermediate; (3) Transferring the intermediate into a closed reaction kettle, adding alkaline ionic liquid, introducing ethylene oxide, controlling the temperature at 65-75 ℃, introducing nitrogen, reacting, and removing low boiling point after the reaction is finished to obtain the oligomeric phosphonate. According to the invention, the alkaline ionic liquid is added in the epoxidation reaction stage, so that the alkaline ionic liquid is not only the catalyst for the epoxidation reaction, but also the acid value stabilizer of the final product, the separation is not needed, the final application effect of the product is not affected, the acid value of the product is lower than 0.1mgKOH/g within half a year, the problem of acid return of the phosphonate flame retardant is solved, and the stability of the quality of the oligomeric phosphonate flame retardant is improved.
Description
Technical Field
The invention belongs to the technical field of synthesis of flame retardants, and particularly relates to a preparation method of an oligomeric phosphonate flame retardant.
Background
Polyurethane foams are widely used in various aspects of life, but their flammability also brings serious hazard, so flame-retardant modified polyurethane foams are attracting attention of researchers.
The organic phosphine flame retardant has high flame retardant efficiency and good thermal stability, and a plurality of varieties have plasticizing, antioxidation and other functions, thus being a hot spot in the research of flame retardants. The oligomeric phosphonate is polymerized by monophosphonate, has the characteristics of larger molecular weight, higher phosphorus content, low volatility, no odor, hydrolysis resistance, low atomization, low yellow core and the like, and is very suitable for flame retardant modification of polyurethane foam materials.
Patent US 5608100a proposes a method for synthesizing a reactive oligomeric phosphonate, wherein phosphorus pentoxide reacts with a phosphate in the presence of phosphorous acid to obtain a polyphosphate with a high average degree of condensation. Through partial hydrolysis or alcoholysis, selective cleavage of P-O-P bond occurs, and ring-opening reaction of epoxy compound is carried out at 70-140 ℃ to obtain the final product. In the reaction conditions adopted by the patent, the temperature is too high when the epoxy compound is introduced, the oxidation degree of the material state in the process is difficult, and the industrial production has certain difficulty.
Patent CN 103204876a discloses a preparation method of an oligomeric organic phosphine flame retardant, dimethyl methylphosphonate reacts with phosphorus pentoxide, then hydroxyl-containing compound and trialkyl phosphite are added, ethylene oxide is introduced into a reaction kettle to react to obtain a product, the acid value of the product obtained by the method is 5 mgKOH/g-25 mgKOH/g, the high acid value can prevent the normal function of an amine catalyst used in the foaming reaction, and the foam cannot rise, or the pore size is inappropriate, or the foam is sticky and fragile.
Patent CN112250705A discloses a reactive oligomeric phosphate flame retardant, a preparation method and application thereof, wherein the flame retardant is mainly formed by two-step reaction of phosphorus pentoxide, phosphorus (phosphonate), phosphoric acid and epoxy compound, and the acid value of the product is less than 1mgKOH/g.
The stability problem of the flame retardant is ignored in the above patent, the phosphonate flame retardant prepared by the method disclosed in the above patent has the phenomenon of acid reversion, and the acid value gradually increases after long-time storage, which causes poisoning of a catalyst for polyurethane foaming, so that the problem of acid reversion of the phosphonate flame retardant is solved, the stability of the phosphonate flame retardant is ensured, and the method has important practical significance for production, storage and application of the phosphonate flame retardant.
Disclosure of Invention
The invention aims to provide a preparation method of an oligomeric phosphonate flame retardant with low acid value and high stability, so as to solve the problems in the prior art.
In order to achieve the technical purpose, the technical scheme of the invention comprises the following steps:
a method for preparing an oligomeric phosphonate flame retardant, comprising the following steps:
(1) Slowly adding phosphorus pentoxide into triethyl phosphate in a nitrogen atmosphere and a water bath, stirring, keeping the temperature at or below 40 ℃, heating to 60 ℃ after the addition, reacting for 1h, heating to 90 ℃, and reacting for 5h to obtain colorless transparent reaction liquid;
(2) Cooling the reaction liquid, stirring in a nitrogen atmosphere, slowly adding water, keeping the temperature at or below 40 ℃, heating to 70 ℃ after the addition is finished, and reacting for 3 hours to obtain an intermediate;
(3) Transferring the intermediate into a closed reaction kettle, adding alkaline ionic liquid, introducing ethylene oxide, controlling the temperature at 65-75 ℃, introducing nitrogen after the feeding is finished, maintaining the pressure at 0.5Mpa, reacting for 2 hours, and removing low boiling point to obtain the oligomeric phosphonate flame retardant. The reaction equation is as follows:
as a modification, in the step (3), the basic ionic liquid contains cations and anions.
Preferably, the cation is one or two of 1-butyl-3-methylimidazole ion, 1-ethyl-3-methylimidazole ion, 1, 3-dibutylimidazole ion and 1, 3-dimethylimidazole ion; the anions are one or two of hydroxide ions, acetate ions, tetrafluoroborate ions and hexafluorophosphate ions.
As a modification, in the step (1), the molar ratio of the phosphorus pentoxide to the triethyl phosphate is 1:1.2.
As an improvement, in the step (2), the water is added in an amount of 0.5-2 mol.
As an improvement, in the step (3), the adding amount of the alkaline ionic liquid is 0.05-0.5% of the adding amount of the intermediate.
As an improvement, in the step (3), the addition amount of the ethylene oxide is 70% -90% of the total mass of the phosphorus pentoxide and the triethyl phosphate.
By adopting the technical scheme, the invention has the beneficial effects that:
according to the preparation method of the oligomeric phosphonate flame retardant, the alkaline ionic liquid is added in the epoxidation reaction stage, so that the oligomeric phosphonate flame retardant is not only a catalyst for the epoxidation reaction, but also an acid value stabilizer of a final product, separation is not needed, the final application effect of the product is not affected, the acid value of the product is lower than 0.1mgKOH/g in half a year, the temperature is not high when the epoxy compound is introduced in the epoxidation reaction stage, the industrial production is facilitated, the problem of acid return of the phosphonate flame retardant is solved, the stability of the quality of the oligomeric phosphonate flame retardant is improved, and the preparation method has important practical significance for the production, the storage and the application of the phosphonate flame retardant.
Detailed Description
The invention is further described below in connection with the following detailed description.
Example 1
In a nitrogen atmosphere and a water bath, 284g of phosphorus pentoxide is slowly added into a four-neck flask filled with 436.8g of triethyl phosphate, the four-neck flask is mechanically stirred, the temperature is kept to be not higher than 40 ℃, after the addition is finished, the temperature is firstly increased to 60 ℃ for reaction for 1h, then the temperature is increased to 90 ℃ for reaction for 5h, and a colorless transparent viscous reaction solution is obtained. And cooling the reaction liquid to room temperature, mechanically stirring in a nitrogen atmosphere, slowly adding 18g of water, keeping the temperature not higher than 40 ℃, heating to 70 ℃ after the addition is finished, and reacting for 3 hours to obtain an intermediate. Transferring the intermediate into a closed reaction kettle, adding 0.5g of 1-butyl-3-methylimidazole hydroxide ([ Bmim ] OH), introducing 520g of ethylene oxide, controlling the temperature to 65 ℃, introducing nitrogen after the end of feeding, keeping the pressure at 0.5Mpa, reacting for 2 hours, removing low boiling point to obtain 1162.8g of oligomeric phosphonate, wherein the acid value is 0.076mgKOH/g, and the hydroxyl value is 122.4mgKOH/g.
Example 2
In a nitrogen atmosphere and a water bath, 284g of phosphorus pentoxide is slowly added into a four-neck flask filled with 436.8g of triethyl phosphate, the four-neck flask is mechanically stirred, the temperature is kept to be not higher than 40 ℃, after the addition is finished, the temperature is firstly increased to 60 ℃ for reaction for 1h, then the temperature is increased to 90 ℃ for reaction for 5h, and a colorless transparent viscous reaction solution is obtained. And cooling the reaction liquid to room temperature, mechanically stirring in a nitrogen atmosphere, slowly adding 27g of water, keeping the temperature not higher than 40 ℃, heating to 70 ℃ after the addition is finished, and reacting for 3 hours to obtain an intermediate. The intermediate was transferred to a closed reaction vessel and 0.9g of 1-butyl-3-methylimidazole tetrafluoroborate ([ Bmim) was added]BF 4 ) 546g of ethylene oxide is introduced, the temperature is controlled at 70 ℃, nitrogen is introduced after the feeding is finished, the pressure is kept at 0.5Mpa, the reaction is carried out for 2 hours, the boiling point is removed, 1193.7g of oligomeric phosphonate is obtained, the acid value is 0.073mgKOH/g, and the hydroxyl value is 142.8 mgKOH/g.
Example 3
In a nitrogen atmosphere and a water bath, 284g of phosphorus pentoxide is slowly added into a four-neck flask filled with 436.8g of triethyl phosphate, the four-neck flask is mechanically stirred, the temperature is kept to be not higher than 40 ℃, after the addition is finished, the temperature is firstly increased to 60 ℃ for reaction for 1h, then the temperature is increased to 90 ℃ for reaction for 5h, and a colorless transparent viscous reaction solution is obtained. And cooling the reaction liquid to room temperature, mechanically stirring in a nitrogen atmosphere, slowly adding 36g of water, keeping the temperature not higher than 40 ℃, heating to 70 ℃ after the addition is finished, and reacting for 3 hours to obtain an intermediate. Transferring the intermediate into a closed reaction kettle, adding 1.4g of 1-ethyl-3-methylimidazole acetate ([ Emim ] OAC), introducing 592g of ethylene oxide, controlling the temperature at 68 ℃, introducing nitrogen after the end of feeding, keeping the pressure at 0.5Mpa, reacting for 2 hours, removing low boiling point to obtain 1270.1g of oligomeric phosphonate, and obtaining the oligomeric phosphonate with an acid value of 0.069mgKOH/g and a hydroxyl value of 172.1mgKOH/g.
Example 4
In a nitrogen atmosphere and a water bath, 284g of phosphorus pentoxide is slowly added into a four-neck flask filled with 436.8g of triethyl phosphate, the four-neck flask is mechanically stirred, the temperature is kept to be not higher than 40 ℃, after the addition is finished, the temperature is firstly increased to 60 ℃ for reaction for 1h, then the temperature is increased to 90 ℃ for reaction for 5h, and a colorless transparent viscous reaction solution is obtained. And cooling the reaction liquid to room temperature, mechanically stirring in a nitrogen atmosphere, slowly adding 9g of water, keeping the temperature not higher than 40 ℃, heating to 70 ℃ after the addition is finished, and reacting for 3 hours to obtain an intermediate. The intermediate was transferred to a closed reaction vessel and 0.7g of 1, 3-dimethylimidazole hexafluorophosphate ([ Dnim ] was added]PF 6 ) 506g of ethylene oxide is introduced, the temperature is controlled at 72 ℃, nitrogen is introduced after the feeding is finished, the pressure is kept at 0.5Mpa, the reaction is carried out for 2 hours, the boiling point is removed, 1147.4g of oligomeric phosphonate is obtained, the acid value is 0.082mgKOH/g, and the hydroxyl value is 114.5mgKOH/g.
Example 5
In a nitrogen atmosphere and a water bath, 284g of phosphorus pentoxide is slowly added into a four-neck flask filled with 436.8g of triethyl phosphate, the four-neck flask is mechanically stirred, the temperature is kept to be not higher than 40 ℃, after the addition is finished, the temperature is firstly increased to 60 ℃ for reaction for 1h, then the temperature is increased to 90 ℃ for reaction for 5h, and a colorless transparent viscous reaction solution is obtained. And cooling the reaction liquid to room temperature, mechanically stirring in a nitrogen atmosphere, slowly adding 30g of water, keeping the temperature not higher than 40 ℃, heating to 70 ℃ after the addition is finished, and reacting for 3 hours to obtain an intermediate. The intermediate was transferred to a closed reaction vessel and 0.9g of 1-butyl-3-methylimidazole acetate ([ Bmim) was added]OAC) and 0.8g of 1, 3-dibutylimidazole tetrafluoroborate ([ Bbim)]BF 4 ) 603g of ethylene oxide is introduced, the temperature is controlled at 75 ℃, nitrogen is introduced after the feeding is finished, the pressure is kept at 0.5Mpa, the reaction is carried out for 2 hours, the boiling point is removed, 1278g of oligomeric phosphonate is obtained, the acid value is 0.057mgKOH/g, and the hydroxyl value is 159.8mgKOH/g.
Comparative example 1
Tris (2-chloropropyl) phosphate flame retardant (TCPP), a common commercial product, is an additive flame retardant.
Comparative example 2
Reference is made to the synthesis of patent CN112250705 a: 200g of triethyl phosphate is weighed and placed in a four-neck flask provided with a mechanical stirrer and a thermometer, nitrogen is introduced for protection, 135.52g of phosphorus pentoxide is added, water bath is carried out and stirring is carried out, the liquid temperature is controlled to be not higher than 45 ℃, and after the addition is finished, the reaction is carried out at 85 ℃ for 4 hours. Then cooling to below 60 ℃, dropwise adding 35.52g (total mole amount of phosphoric acid and water is 0.6 mol) of 85% phosphoric acid by mass fraction, controlling the liquid temperature to be 60 ℃, and after the dropwise adding is finished, carrying out heat preservation reaction for 1h at 65 ℃. And (3) the liquid temperature is reduced to 20 ℃, 228.91g of propylene oxide is slowly added dropwise under vigorous stirring, the dropping temperature is not more than 25 ℃, the reaction liquid is quickly transferred to a high-pressure reaction kettle after the dropping is finished, an air inlet valve of the reaction kettle is opened, a nitrogen pressure reducing valve is regulated to control the pressure to be 0.5Mpa, the temperature is set to be 70 ℃ for 2 hours, and colorless transparent oily liquid, namely the reactive oligomeric phosphate flame retardant, has an acid value of 0.78mgKOH/g and a hydroxyl value of 174.6 mgKOH/g, is obtained.
Stability test
The stability test was carried out by putting 2 comparative examples and 5 examples into an oven at 60℃for six months, and the acid value (unit: mgKOH/g) of the product was measured at each interval of one month, and the results are shown in Table 1:
TABLE 1
| Time | Initial initiation | 1 month | 2 months of | For 3 months | For 4 months | For 5 months | 6 months of |
| Comparative example 1 | 0.071 | 0.073 | 0.077 | 0.078 | 0.082 | 0.083 | 0.086 |
| Comparative example 2 | 0.78 | 2.56 | 8.22 | 13.15 | 15.28 | 19.17 | 22.36 |
| Example 1 | 0.076 | 0.069 | 0.072 | 0.078 | 0.085 | 0.079 | 0.087 |
| Example 2 | 0.073 | 0.067 | 0.071 | 0.071 | 0.078 | 0.082 | 0.086 |
| Example 3 | 0.069 | 0.063 | 0.065 | 0.069 | 0.071 | 0.075 | 0.083 |
| Example 4 | 0.082 | 0.079 | 0.081 | 0.084 | 0.089 | 0.091 | 0.097 |
| Example 5 | 0.057 | 0.055 | 0.061 | 0.062 | 0.065 | 0.071 | 0.075 |
Application example
The stability and application properties of the prepared flame retardant were examined by using 2 comparative examples and 5 examples of flame retardants for preparing flame retardant polyurethane rigid foams.
The test idea is as follows: in order to examine the stability and application performance of the product, the raw materials are respectively prepared and foamed immediately, foamed after being stored for one week at room temperature and foamed after being stored for two weeks at room temperature, and the parameters are compared. Compared with comparative example 1, the flame retardant detection of all the tests of the series is better structural flame retardant products if the flame retardant effect of the same additive amount is the same.
The test method comprises the following steps: after 5g of sample and 25g of detection white material are uniformly mixed at room temperature (20 ℃), 30g of black material (PM 200) is added, and the mixture is stirred electrically for 5 seconds, and parameters such as foaming phenomenon, foaming time, foam strength, cell shrinkage, flame retardant property and the like are recorded. The specific results are shown in Table 2:
TABLE 2
From the results of the stability and application performance tests of the examples and comparative examples of Table 2, it can be seen that the stability and application effect of the product of the present invention reach the level of the additive flame retardant (comparative example 1), which is superior to comparative example 2.
The above-described embodiments of the present invention do not limit the scope of the present invention. Any other corresponding changes and modifications made in accordance with the technical idea of the present invention shall be included in the scope of the claims of the present invention.
Claims (7)
1. The preparation method of the oligomeric phosphonate flame retardant is characterized by comprising the following steps of:
(1) Slowly adding phosphorus pentoxide into triethyl phosphate in a nitrogen atmosphere and a water bath, stirring, keeping the temperature at or below 40 ℃, heating to 60 ℃ after the addition, reacting for 1h, heating to 90 ℃, and reacting for 5h to obtain colorless transparent reaction liquid;
(2) Cooling the reaction liquid, stirring in a nitrogen atmosphere, slowly adding water, keeping the temperature at or below 40 ℃, heating to 70 ℃ after the addition is finished, and reacting for 3 hours to obtain an intermediate;
(3) Transferring the intermediate into a closed reaction kettle, adding alkaline ionic liquid, introducing ethylene oxide, controlling the temperature at 65-75 ℃, introducing nitrogen after the feeding is finished, maintaining the pressure at 0.5Mpa, reacting for 2 hours, and removing low boiling point to obtain the oligomeric phosphonate flame retardant.
2. The method for preparing an oligomeric phosphonate flame retardant according to claim 1, wherein in step (3), the basic ionic liquid contains cations and anions.
3. The method for preparing the oligomeric phosphonate flame retardant according to claim 2, wherein the cation is one or two of 1-butyl-3-methylimidazole ion, 1-ethyl-3-methylimidazole ion, 1, 3-dibutylimidazole ion and 1, 3-dimethylimidazole ion; the anions are one or two of hydroxide ions, acetate ions, tetrafluoroborate ions and hexafluorophosphate ions.
4. The method for preparing an oligomeric phosphonate flame retardant according to claim 1, wherein in step (1), the molar ratio of phosphorus pentoxide to triethyl phosphate is 1:1.2.
5. The method for preparing an oligomeric phosphonate flame retardant according to claim 1, wherein in the step (2), the water is added in an amount of 0.5 to 2mol.
6. The method for preparing an oligomeric phosphonate flame retardant according to claim 1, wherein in the step (3), the addition amount of the alkaline ionic liquid is 0.05-0.5% of the addition amount of the intermediate.
7. The method for preparing an oligomeric phosphonate flame retardant according to claim 1, wherein in the step (3), the addition amount of the ethylene oxide is 70% -90% of the total mass of phosphorus pentoxide and triethyl phosphate.
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