CN109180735A - A kind of preparation method of phosphonium flame retardant - Google Patents
A kind of preparation method of phosphonium flame retardant Download PDFInfo
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- CN109180735A CN109180735A CN201811209599.4A CN201811209599A CN109180735A CN 109180735 A CN109180735 A CN 109180735A CN 201811209599 A CN201811209599 A CN 201811209599A CN 109180735 A CN109180735 A CN 109180735A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000003063 flame retardant Substances 0.000 title claims abstract description 12
- 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 8
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 title claims abstract description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- AFTOJIAPXHGBGH-UHFFFAOYSA-N bis(2-oxopyridin-1-yl) carbonate Chemical compound C1=CC=CC(=O)N1OC(=O)ON1C=CC=CC1=O AFTOJIAPXHGBGH-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000003871 sulfonates Chemical class 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical class C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims description 16
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 12
- 150000007530 organic bases Chemical class 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000007524 organic acids Chemical class 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- CZXGXYBOQYQXQD-UHFFFAOYSA-N methyl benzenesulfonate Chemical compound COS(=O)(=O)C1=CC=CC=C1 CZXGXYBOQYQXQD-UHFFFAOYSA-N 0.000 claims description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- -1 Toluenesulfonic acid esters compound Chemical class 0.000 claims description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 6
- 235000019253 formic acid Nutrition 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 5
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 claims description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 4
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 235000011054 acetic acid Nutrition 0.000 claims description 4
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 4
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 229940113088 dimethylacetamide Drugs 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 2
- BSZXAFXFTLXUFV-UHFFFAOYSA-N 1-phenylethylbenzene Chemical compound C=1C=CC=CC=1C(C)C1=CC=CC=C1 BSZXAFXFTLXUFV-UHFFFAOYSA-N 0.000 claims description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 229940043279 diisopropylamine Drugs 0.000 claims description 2
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 claims description 2
- VRZVPALEJCLXPR-UHFFFAOYSA-N ethyl 4-methylbenzenesulfonate Chemical compound CCOS(=O)(=O)C1=CC=C(C)C=C1 VRZVPALEJCLXPR-UHFFFAOYSA-N 0.000 claims description 2
- XDRMBCMMABGNMM-UHFFFAOYSA-N ethyl benzenesulfonate Chemical compound CCOS(=O)(=O)C1=CC=CC=C1 XDRMBCMMABGNMM-UHFFFAOYSA-N 0.000 claims description 2
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- BUZMJVBOGDBMGI-UHFFFAOYSA-N 1-phenylpropylbenzene Chemical compound C=1C=CC=CC=1C(CC)C1=CC=CC=C1 BUZMJVBOGDBMGI-UHFFFAOYSA-N 0.000 claims 1
- WRLRISOTNFYPMU-UHFFFAOYSA-N [S].CC1=CC=CC=C1 Chemical compound [S].CC1=CC=CC=C1 WRLRISOTNFYPMU-UHFFFAOYSA-N 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 150000004702 methyl esters Chemical class 0.000 claims 1
- JTTWNTXHFYNETH-UHFFFAOYSA-N propyl 4-methylbenzenesulfonate Chemical compound CCCOS(=O)(=O)C1=CC=C(C)C=C1 JTTWNTXHFYNETH-UHFFFAOYSA-N 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 description 6
- 238000004679 31P NMR spectroscopy Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000006840 diphenylmethane group Chemical group 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- MBABOKRGFJTBAE-UHFFFAOYSA-N methyl methanesulfonate Chemical compound COS(C)(=O)=O MBABOKRGFJTBAE-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- OCNPXKLQSGAGKT-UHFFFAOYSA-N propyl benzenesulfonate Chemical compound CCCOS(=O)(=O)C1=CC=CC=C1 OCNPXKLQSGAGKT-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003459 sulfonic acid esters Chemical class 0.000 description 1
- 238000003786 synthesis 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
- C07F9/547—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)
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of preparation method of phosphonium flame retardant, and using CDOP and ethylene glycol as reaction raw materials, compound of formula I is prepared under the catalysis of sulfonates compounds and acid.This method is easy to operate, high income, while high-melting-point content of isomer is high in product.
Description
Technical field
The invention belongs to flame retardant areas, and in particular to a kind of preparation method of DOPO derivative flame retardant.
Background technique
Phosphonium flame retardant has significant application value, and especially high-melting-point phosphonium flame retardant has a vast market.
Patent WO2011123389A1 reports a kind of very potential DOPO derivative compound I, the patent with
The derivative that DOPO and ethylene glycol (EG) they are the Material synthesis DOPO, but contain low melting point isomers in product, limiting it makes
With.
Chinese patent 201310281306.4 reports a kind of intermediate CDOP to synthesize DOPO as raw material and ethylene glycol
Reaction, directly prepares high-purity, single product without enantiomter, and this method has certain excellent on product configuration
Gesture, but yield still needs to be further increased.
Lin Zang et al. discloses a kind of DOP-Cl (i.e. CDOP) and alcohol compound THIC in triethylamine and to toluene
The lower reaction of methylmesylate catalysis generates the method (Polym.Adv.Technol.2011,22,1182-1191) of following compound.
The application in view of the above shortcomings of the prior art, provides a kind of new preparation method, this method is with CDOP and second
Glycol is reaction raw materials, compound of formula I is prepared under sulfonates compounds catalysis, not only high-melting-point isomers contains product
Amount is high, and high income, is conducive to industrialized production, realizes large-scale application.
Summary of the invention
The present invention provides a kind of preparation method of organic phosphorus right agent of resistance of DOPO analog, is that reaction is former with CDOP and ethylene glycol
Compound of formula I is prepared under sulfonates compounds catalysis in material.This method is easy to operate, high income, while high in product
Fusing point content of isomer is high.
In order to solve the above-mentioned technical problem, invention provides the following technical solutions:
A kind of preparation method of DOPO analog fire retardant shown in Formulas I:
Raw material ethylene glycol is added in organic solvent, organic base is added, controls temperature between -10 DEG C to 10 DEG C, drop
Add the organic solvent solution of CDOP, drop finishes, and reacts at room temperature 0.5-2h；Then catalyst sulfonates compounds are added, are warming up to
100-220 DEG C of reaction 2-8h, after reaction, post-treated to obtain DOPO analog shown in Formulas I, reaction equation is as follows:
In an embodiment of invention, while catalyst sulfonates compounds are added, it is additionally added organic acid.
As preferred scheme is invented, the sulfonates compounds are selected from p-methyl benzenesulfonic acid ester type compound, benzene sulfonic acid
Ester type compound；Further preferred methyl benzene sulfonate, ethyl benzenesulfonat, methyl tosylate, ethyl p-toluenesulfonate, to first
Benzene sulfonic acid propyl ester.
Further, the organic base in triethylamine, diethylamine, diisopropylamine, diisopropyl ethyl amine one
Kind is a variety of.
Preferably, the organic acid is selected from formic acid, acetic acid, propionic acid, butyric acid, methanesulfonic acid, ethanesulfonic acid, p-methyl benzenesulfonic acid, benzene
Sulfonic acid.
As preferred scheme is invented, the organic solvent is toluene, ethylo benzene, dimethylbenzene, diphenyl-methane, two phenylpropyl alcohols
Alkane, diphenylethane, diphenyl ether, diethylbenzene, dimethyl sulfoxide, n,N-Dimethylformamide, dimethyl acetamide, N- methylpyrrole
Alkanone, glycol dimethyl ether, one of ethylene glycol diethyl ether or combination.
As preferred scheme is invented, the organic solvent is preferably diphenyl-methane, N-Methyl pyrrolidone, diformazan Asia
Sulfone, n,N-Dimethylformamide, dimethyl acetamide.
Further, it in an embodiment of invention, operates: raw material ethylene glycol being added to organic as follows
In solvent, organic base is added, controls temperature between -10 DEG C to 10 DEG C, the organic solvent solution of CDOP is added dropwise, drop finishes, room temperature
React 0.5-2h；Then sulfonates compounds and organic acid is added, is warming up to 170-200 DEG C of reaction 2-6h, after reaction,
It is post-treated to obtain DOPO analog shown in Formulas I.
As an embodiment of invention, in the reaction, the molar ratio of ethylene glycol and CDOP are 1:(2-3).
As an embodiment of invention, the molar ratio of organic base and CDOP are as follows: (1-3): 1, preferably (1.5-2): 1.
As the preferred embodiment of invention, the molar ratio of sulfonates compounds and CDOP are as follows: (0.1-0.4): 1, preferably
(0.2-0.3):1。
As the preferred embodiment of invention, the molar ratio of organic acid and organic base are as follows: (1.2-3): 1, preferably (1.5-2): 1.
Preferably, the post-processing are as follows: reaction solution is cooled to 50 DEG C, and solvent chosen from the followings: ethyl alcohol, acetone, first is added
Alcohol, isopropanol stir, and filter, washing, DOPO analog fire retardant shown in dry Formulas I.
Beneficial effects of the present invention, the present invention use sulfonic acid esters derivative for catalyst, improve yield, reach 90%
More than, while also having higher degree, especially high-melting-point content of isomer higher (can be 98.9% or more), be conducive to this
The industrialized production and application of fire retardant.
Specific embodiment
Embodiment 1
Raw material ethylene glycol 3.12g is added in 20ml diphenyl-methane, be added triethylamine 15g, control temperature at -10 DEG C extremely
Between 10 DEG C, the diphenyl-methane solution (23.68g is dissolved in 50ml diphenyl-methane) of CDOP is added dropwise, drop finishes, and reacts at room temperature 2h；Then
Methyl tosylate 3.75g and formic acid 10g is added, is warming up to 180 DEG C of reaction 3h, is cooled to 50 DEG C, 100ml methanol is added,
Stirring is filtered, and washing obtains DOPO analog shown in 20.93g Formulas I, yield 90%,31P-NMR shows high-melting-point isomers
Ratio is 98.7%, 297-298 DEG C of fusing point.
Embodiment 2
Raw material ethylene glycol 6.21g is added in 45ml diphenyl-methane, be added triethylamine 32g, control temperature at -10 DEG C extremely
Between 10 DEG C, the diphenyl-methane solution (47.50g is dissolved in 100ml diphenyl-methane) of CDOP is added dropwise, drop finishes, and reacts at room temperature 0.5h；So
Methyl benzene sulfonate 6.42g and formic acid 25.46g is added afterwards, is warming up to 170 DEG C of reaction 3h, is cooled to 50 DEG C, 180ml ethyl alcohol is added,
Stirring is filtered, and washing obtains DOPO analog shown in 43.24g Formulas I, yield 94%,31P-NMR shows high-melting-point isomers
Ratio is 99.8%, 300-301 DEG C of fusing point.
Embodiment 3
Raw material ethylene glycol 3.12g is added in 25ml diphenyl-methane, be added triethylamine 16g, control temperature at -10 DEG C extremely
Between 10 DEG C, the diphenyl-methane solution (23.85g is dissolved in 50ml diphenyl-methane) of CDOP is added dropwise, drop finishes, and reacts at room temperature 1h；Then
Methyl tosylate 3.92g and acetic acid 15.6g is added, is warming up to 200 DEG C of reaction 5h, is cooled to 50 DEG C, 100ml third is added
Ketone stirs, and filters, and washing obtains DOPO analog shown in 20.81g Formulas I,31P-NMR shows that high-melting-point isomer proportion is
99.2%.
Embodiment 4
Raw material ethylene glycol 6.20g is added in 50ml diphenyl-methane, be added triethylamine 34g, control temperature at -10 DEG C extremely
Between 10 DEG C, the diphenyl-methane solution (47.88g is dissolved in 100ml diphenyl-methane) of CDOP is added dropwise, drop finishes, and reacts at room temperature 1.5h；So
Methyl benzene sulfonate 6.42g and acetic acid 32.52g is added afterwards, is warming up to 180 DEG C of reaction 4h, is cooled to 50 DEG C, 200ml isopropyl is added
Alcohol stirs, and filters, and washing obtains DOPO analog shown in 44.25g Formulas I,31P-NMR shows that high-melting-point isomer proportion is
99.7%.
Embodiment 5
In the identical situation of other reaction conditions, different catalysts are combined to product high-melting-point isomer proportion and receipts
Rate has certain influence, the results are shown in Table 1, and generally speaking, the catalytic effect of methyl benzene sulfonate is better than methyl tosylate；In addition,
By acid adding, high-melting-point isomer proportion can be improved, but yield is influenced smaller.
Table 1
| Catalyst | High-melting-point isomer proportion | Yield |
| Methyl tosylate | 96.5% | 91% |
| Methyl tosylate+formic acid | 98.9% | 90.6% |
| Methyl benzene sulfonate | 97.2% | 93.02% |
| Methyl benzene sulfonate+formic acid | 99.8% | 93.56% |
Although the contents of the present invention are had been described in detail by above preferred embodiment, but it should be appreciated that above-mentioned
Description be not considered as limitation of the present invention.The changes that any person skilled in the art can think of should all fall in this
In the protection scope of application.
Claims (10)
1. a kind of preparation method of phosphonium flame retardant includes the following steps: for raw material ethylene glycol to be added in organic solvent, it is added
Organic base controls temperature between -10 DEG C to 10 DEG C, and the organic solvent solution of CDOP is added dropwise, and drop finishes, and reacts at room temperature 0.5-2h；
Then catalyst sulfonates compounds are added, are warming up to 100-220 DEG C of reaction 2-8h, it is after reaction, post-treated to obtain Formulas I
Shown in DOPO analog, reaction equation is as follows:
2. preparation method according to claim 1, it is characterised in that: when catalyst sulfonates compounds are added, also
Organic acid is added.
3. -2 described in any item preparation methods according to claim 1, it is characterised in that: the sulfonates compounds be selected from pair
Toluenesulfonic acid esters compound, benzene sulfonic acid ester type compound；Further preferred methyl benzene sulfonate, ethyl benzenesulfonat, to toluene sulphur
Sour methyl esters, ethyl p-toluenesulfonate, propyl p-toluenesulfonate.
4. preparation method according to claim 1-3, it is characterised in that: the organic base be selected from triethylamine,
One of diethylamine, diisopropylamine, diisopropyl ethyl amine are a variety of.
5. preparation method according to claim 1-4, it is characterised in that: the organic acid be selected from formic acid, acetic acid,
Propionic acid, butyric acid, methanesulfonic acid, ethanesulfonic acid, p-methyl benzenesulfonic acid, benzene sulfonic acid.
6. preparation method according to claim 1-5, it is characterised in that: the organic solvent is toluene, second
Base benzene, dimethylbenzene, diphenyl-methane, diphenyl propane, diphenylethane, diphenyl ether, diethylbenzene, dimethyl sulfoxide, N, N- dimethyl methyl
Amide, dimethyl acetamide, N-Methyl pyrrolidone, glycol dimethyl ether, one of ethylene glycol diethyl ether or combination.
7. preparation method according to claim 1-6, it is characterised in that: be added to raw material ethylene glycol organic molten
In agent, organic base is added, controls temperature between -10 DEG C to 10 DEG C, the organic solvent solution of CDOP is added dropwise, drop finishes, and room temperature is anti-
Answer 0.5-2h；Then sulfonates compounds and organic acid is added, is warming up to 170-200 DEG C of reaction 2-6h, after reaction, warp
Post-process to obtain DOPO analog shown in Formulas I.
8. preparation method according to claim 1-7, it is characterised in that: in the reaction, ethylene glycol and CDOP
Molar ratio be 1:(2-3)；The molar ratio of organic base and CDOP are as follows: (1-3): 1, preferably (1.5-2): 1.
9. preparation method according to claim 1-8, which is characterized in that sulfonates compounds and CDOP's rubs
That ratio are as follows: (0.1-0.4): 1, preferably (0.2-0.3): 1；The molar ratio of organic acid and organic base are as follows: (1.2-3): 1, preferably
(1.5-2):1。
10. -9 described in any item preparation methods according to claim 1, which is characterized in that the post-processing are as follows: reaction solution is cooling
To 50 DEG C, solvent chosen from the followings: ethyl alcohol, acetone, methanol, isopropanol is added, stirs, filters, washing, shown in dry Formulas I
DOPO analog fire retardant.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112125930A (en) * | 2020-10-16 | 2020-12-25 | 寿光卫东化工有限公司 | Preparation method of aryl-containing bis-DOPO compound |
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| JPH11106619A (en) * | 1997-10-03 | 1999-04-20 | Saitou Kaseihin Kenkyusho:Kk | Flame retardant polyester and its production |
| CN102971333A (en) * | 2010-03-31 | 2013-03-13 | 雅宝公司 | Process for preparation of DOPO-derived compounds and compositions thereof |
| CN103408594A (en) * | 2013-07-05 | 2013-11-27 | 江苏雅克科技股份有限公司 | Preparation method of high-purity DOPO (9,10-dihydro-9-oxa-10- phosphaphenanthrene-10-oxide) derivative |
| CN103980310A (en) * | 2014-05-30 | 2014-08-13 | 天津久日化学股份有限公司 | Preparation method of phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11106619A (en) * | 1997-10-03 | 1999-04-20 | Saitou Kaseihin Kenkyusho:Kk | Flame retardant polyester and its production |
| CN102971333A (en) * | 2010-03-31 | 2013-03-13 | 雅宝公司 | Process for preparation of DOPO-derived compounds and compositions thereof |
| CN103408594A (en) * | 2013-07-05 | 2013-11-27 | 江苏雅克科技股份有限公司 | Preparation method of high-purity DOPO (9,10-dihydro-9-oxa-10- phosphaphenanthrene-10-oxide) derivative |
| CN103980310A (en) * | 2014-05-30 | 2014-08-13 | 天津久日化学股份有限公司 | Preparation method of phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112125930A (en) * | 2020-10-16 | 2020-12-25 | 寿光卫东化工有限公司 | Preparation method of aryl-containing bis-DOPO compound |
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