CN109627491A - It is a kind of using catechol as the phosphate flame retardant of skeleton and its environment-friendly preparation method thereof - Google Patents
It is a kind of using catechol as the phosphate flame retardant of skeleton and its environment-friendly preparation method thereof Download PDFInfo
- Publication number
- CN109627491A CN109627491A CN201811540593.5A CN201811540593A CN109627491A CN 109627491 A CN109627491 A CN 109627491A CN 201811540593 A CN201811540593 A CN 201811540593A CN 109627491 A CN109627491 A CN 109627491A
- Authority
- CN
- China
- Prior art keywords
- catechol
- skeleton
- flame retardant
- phosphate flame
- environment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000003063 flame retardant Substances 0.000 title claims abstract description 29
- 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 23
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 22
- 239000010452 phosphate Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 35
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 13
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 9
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 7
- 238000005292 vacuum distillation Methods 0.000 claims description 7
- 239000002841 Lewis acid Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 150000007517 lewis acids Chemical class 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims description 5
- -1 alkyl pyridine Chemical compound 0.000 claims description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 150000002460 imidazoles Chemical class 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 230000006837 decompression Effects 0.000 claims description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000002608 ionic liquid Substances 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 125000005270 trialkylamine group Chemical group 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 4
- 239000011574 phosphorus Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 235000019504 cigarettes Nutrition 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 206010003497 Asphyxia Diseases 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000005654 Michaelis-Arbuzov synthesis reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- RFXSFVVPCLGHAU-UHFFFAOYSA-N benzene;phenol Chemical group C1=CC=CC=C1.OC1=CC=CC=C1.OC1=CC=CC=C1 RFXSFVVPCLGHAU-UHFFFAOYSA-N 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- BZCGWAXQDLXLQM-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O.ClP(Cl)(Cl)=O BZCGWAXQDLXLQM-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/527—Cyclic esters
-
- 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
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65742—Esters of oxyacids of phosphorus non-condensed with carbocyclic rings or heterocyclic rings or ring systems
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention discloses a kind of using catechol as the phosphate flame retardant of skeleton and its environment-friendly preparation method thereof.A kind of novel halogen-free phosphorus-containing based flame retardant has been synthesized by two-step process using catechol, phosphorus oxychloride and alcohol or phenol as raw material in the present invention.The fire retardant not only good flame retardation effect, and it is environment friendly and pollution-free.Meanwhile raw material of the invention is simple and easy to get, and it is low in cost, there is very strong practicability.
Description
Technical field
The present invention relates to fire-retardant FRW field, in particular to it is a kind of using catechol as the phosphate flame retardant of skeleton and
Its environment-friendly preparation method thereof.
Background technique
In recent years, increasing substantially with the increasingly strict and plastic products yield of fire safety standard, the overwhelming majority can
Combustion or inflammable material need to promote its anti-flammability by addition fire retardant, to prevent the hidden danger such as fire.In addition to this, high score
Sub- material can also generate the toxic gases such as toluene, hydrogen chloride in burning, so that majority is because of death by suffocation when fire occurs.And
Fire retardant is then the effective auxiliary agent for changing high molecular material combustibility, and original flammable, inflammable material is made to have flame retardancy, disappear
Cigarette and self-extinguishment, can greatly fire preventing, preferably satisfaction safety in production and life requirement.Phosphate is as a kind of
Phosphorous ester type compound, it is many kinds of, it is widely used.According to the difference of added functional group, phosphate may be used as drug
Precursor, intermediate；It is used as the various additives such as adhesive, dispersing agent, curing agent, surfactant and fire retardant.
Phosphate has the advantages that low cigarette, nontoxic as a kind of organic halogen-free phosphorus-containing fire retardant agent in combustion, when use
It is more environmentally friendly, be recognized be alternative halogen containing flame-retardant one of staple product, have good development prospect.
It is mentioned in the documents such as Aleksandrsaka, Jan Michalski during Arbuzov Reaction mechanism obtains
Mesosome；GB1175211 mentions the substitution catechol ester obtained with phosphoric acid or phosphorus pentoxide；It is mentioned in the documents such as Von J
There is a unstable catechol esters chloride to dissociate to obtain intermediate；It is mentioned in CN 102086215B: the first step,
In chloroform, under the catalysis of triethylamine, heating makes catechol and phosphorus oxychloride reaction, and cyclization chemical combination is obtained after vacuum distillation
Object；Second step under the catalysis of triethylamine, above-mentioned ring compound is reacted with phloroglucin heating, decompression is steamed in chloroform
It evaporates and with being obtained after inorganic neutralizing treatment between three (1,3- dioxa -2- phospha -2- oxo -1,2- dihydro benzofuran) phosphoric acid
Benzenetriol ester.The use of chloroform and triethylamine increases subsequent processing steps.
Summary of the invention
It is good that the object of the present invention is to provide a kind of flame retardant properties, and the New-type halide-free for saving cost contains phosphorus type flame retardant,
The present invention can realize the green syt of this new flame retardant to avoid excessive postprocessing working procedures.
The present invention is achieved in the following ways: a kind of using catechol as the phosphate flame retardant of skeleton, it has
Structural formula shown in formula (1):
。
It is a further object to provide the environment-friendly preparation method thereofs of above-mentioned new flame retardant.
A kind of to prepare above-mentioned using catechol as the environment-friendly preparation method thereof of the phosphate flame retardant of skeleton, it includes following step
Rapid: the first step, under catalysts conditions, catechol is directly reacted with phosphorus oxychloride, is obtained among phosphoryl chloride phosphorus oxychloride after vacuum distillation
Body；Second step, in the molten state, phosphinylidyne chloromethylated intermediate and single phenol, diphenol, monohydric alcohol or diol reaction are obtained with adjacent benzene
Diphenol is the phosphate of skeleton.
Reaction temperature in the first step reaction is 10 ~ 100 DEG C, and the reaction time is 2 ~ 8 h.
Reaction temperature in the second step reaction is 50 ~ 180 DEG C, and the reaction time is 2 ~ 10 h.
The temperature of the vacuum distillation is 100 DEG C hereinafter, the time is 10-60 min.
In the first step reaction, the molar ratio of catechol and phosphorus oxychloride is 1:1 ~ 1:6.
In second step reaction, phosphinylidyne chloromethylated intermediate and single phenol, diphenol, monohydric alcohol or dihydric alcohol molar ratio be 1:1 ~
1:5.
In the first step reaction, catalyst [A]-x [Lewis acid], wherein A is amine and its derivative, imidazoles and its spreads out
Biology or pyridine and its derivatives；X is 0.2-2%, and x is the molar ratio of Lewis acid and A when synthesizing ionic liquid.
In the first step reaction, amine and its derivative are trialkylamine, and wherein alkyl is methyl, ethyl, propyl, fourth
Base, amyl, hexyl, heptyl, octyl, nonyl, isopropyl, isobutyl group or isopentyl；Imidazole and its derivants are imidazoles, N- alkyl
Imidazoles or 1,3- dialkylimidazolium, wherein alkyl is methyl, ethyl, propyl or butyl；Pyridine and its derivatives are pyridine, alkane
Yl pyridines or haloalkylpyridin, wherein alkyl is methyl, ethyl, propyl or butyl, and halogeno-group is chloro or bromo.It is described
Lewis acid is MgCl2、ZnCl2、SnCl2、AlCl3、FeCl3And TiCl4。
In the first step reaction, catalytic amount is the 0.001% ~ 0.01% of catechol quality.
It is reacted under negative pressure when raw material is single phenol or diphenol in the second step reaction, pressure is -0.01 ~ 0.01
MPa。
The utility model has the advantages that the present invention has synthesized a kind of novel halogen-free phosphorus-containing based flame retardant, starting point is obtained by Thermogravimetric Data
When solution temperature is 205 DEG C, when temperature reaches 800 DEG C, residual carbon content is 25% or more, and traditional phosphate resistance such as BDP, RDP
Agent remaining carbon is fired 20% hereinafter, illustrating good flame retardation effect of the present invention；Synthetic method of the present invention is environment friendly and pollution-free, and raw material is simple
It is easy to get, it is low in cost, there is very strong practicability.
Shown in reaction equation of the present invention descends:
Specific embodiment
By the following specific examples further illustrate the invention, but is not used to limit practical range of the invention.
Embodiment 1
Take the catechol of 91.8 g (0.8 mol) be placed in equipped with electric mixer, thermometer, condenser pipe four-neck flask in,
Then the phosphorus oxychloride and 0.009 g BMIMCl-AlCl of 141.1 g (0.92 mol) is added3, reaction temperature is 10 DEG C, instead
8 h are answered, 10 min are evaporated under reduced pressure after reaction and remove excessive phosphorus oxychloride；The phenol of 112.9 g (1.2 mol) is added, controls
Reaction temperature is 180 DEG C, 2 h of -0.01MPa Depressor response, obtains brown solid, and yield is the % of 90 % ~ 95.It is obtained by Thermogravimetric Data
When initial decomposition temperature is 205 DEG C out, when temperature reaches 800 DEG C, residual carbon content 26%.
Embodiment 2
Take the catechol of 91.8 g (0.8 mol) be placed in equipped with electric mixer, thermometer, condenser pipe four-neck flask in,
Then the phosphorus oxychloride and 0.0009 g BMIMCl-AlCl of 490.7g (3.2mol) is added3, 50 DEG C are warming up to, 6 h are reacted,
Vacuum distillation removes excessive phosphorus oxychloride after reaction；The ethyl alcohol of 110.6 g (2.4 mol) is added, control reaction temperature is 70
DEG C, 10 h of -0.01MPa Depressor response obtains brown solid, and yield is the % of 90 % ~ 95.Show that temperature is decomposed in starting by Thermogravimetric Data
When degree is 205 DEG C, when temperature reaches 800 DEG C, residual carbon content 25%.
Embodiment 3
Take the catechol of 91.8 g (0.8 mol) be placed in equipped with electric mixer, thermometer, condenser pipe four-neck flask in,
Then the phosphorus oxychloride and 0.009 g BMIMCl-AlCl of 736.0g (4.8mol) is added3, 100 DEG C are warming up to, 2 h are reacted,
100 DEG C or less 60 min of vacuum distillation remove excessive phosphorus oxychloride after reaction；The ethyl alcohol of 36.9 g (0.8 mol) is added,
Controlling reaction temperature is 50 DEG C, 2 h of -0.01MPa Depressor response, obtains brown solid, and yield is the % of 90 % ~ 95.By thermogravimetric number
According to obtain initial decomposition temperature be 205 DEG C when, when temperature reaches 800 DEG C, residual carbon content 26%.
Embodiment 4
Take the catechol of 91.8 g (0.8 mol) be placed in equipped with electric mixer, thermometer, condenser pipe four-neck flask in,
Then the phosphorus oxychloride and 0.0009 g Et of 490.7g (3.2mol) is added3NHCl-AlCl3, 50 DEG C are warming up to, 6 h are reacted,
It is evaporated under reduced pressure 30 min after reaction and removes excessive phosphorus oxychloride；It is warming up between 180 DEG C of 264.3 g of addition (2.4 mol)
Benzenediol, 0.01MPa react 10 h, obtain brown solid, and yield is the % of 90 % ~ 95.Show that temperature is decomposed in starting by Thermogravimetric Data
When degree is 205 DEG C, when temperature reaches 800 DEG C, residual carbon content 26%.
Embodiment 5
Take the catechol of 91.8 g (0.8 mol) be placed in equipped with electric mixer, thermometer, condenser pipe four-neck flask in,
Then the phosphorus oxychloride and 0.009 g Et of 141.1 g (0.92 mol) is added3NHCl-AlCl3, 100 DEG C are warming up to, reaction 2
H, 100 DEG C or less 10 min of vacuum distillation remove excessive phosphorus oxychloride after reaction；Cool to 90 DEG C of 248.3 g (4.0 of addition
Mol ethylene glycol), 0.01MPa react 5 h, obtain brown solid, and yield is the % of 90 % ~ 95.Starting is obtained by Thermogravimetric Data
When decomposition temperature is 205 DEG C, when temperature reaches 800 DEG C, residual carbon content 26%.
Embodiment 6
Take the catechol of 91.8 g (0.8 mol) be placed in equipped with electric mixer, thermometer, condenser pipe four-neck flask in,
Then the phosphorus oxychloride and 0.0009 g Et of 736.0g (4.8mol) is added3NHCl-AlCl3, control reaction temperature is 20 DEG C,
8 h are reacted, 60 min are evaporated under reduced pressure after reaction and remove excessive phosphorus oxychloride；It is warming up to 140 DEG C of 273.9 g (1.2 of addition
Mol bisphenol-A), 0.01MPa react 5 h, obtain brown solid, and yield is the % of 90 % ~ 95.Starting point is obtained by Thermogravimetric Data
When solution temperature is 205 DEG C, when temperature reaches 800 DEG C, residual carbon content 26%.
Claims (10)
1. a kind of using catechol as the phosphate flame retardant of skeleton, which is characterized in that it has structural formula shown in formula (1):
。
2. a kind of prepare using catechol as the environment-friendly preparation method thereof of the phosphate flame retardant of skeleton described in claim 1, special
Sign is it the following steps are included: the first step, under catalysts conditions, catechol is directly reacted with phosphorus oxychloride, and decompression is steamed
Phosphinylidyne chloromethylated intermediate is obtained after evaporating；Second step, in the molten state, phosphinylidyne chloromethylated intermediate and single phenol, diphenol, monohydric alcohol or binary
Alcohol reaction, obtains a kind of using catechol as the phosphate of skeleton.
3. according to claim 2 using catechol as the environment-friendly preparation method thereof of the phosphate flame retardant of skeleton, feature exists
In the reaction temperature in the first step reaction is 10 ~ 100 DEG C, and the reaction time is 2 ~ 8 h.
4. according to claim 2 using catechol as the phosphate flame retardant environment-friendly preparation method thereof of skeleton, which is characterized in that
Reaction temperature in the second step reaction is 50 ~ 180 DEG C, and the reaction time is 2 ~ 10 h；The second step reaction is under negative pressure
It is reacted, pressure is -0.01 ~ 0.01 MPa.
5. according to claim 2 using catechol as the phosphate flame retardant environment-friendly preparation method thereof of skeleton, which is characterized in that
The temperature of the vacuum distillation is 100 DEG C hereinafter, the time is 10-60 min.
6. according to claim 2 using catechol as the phosphate flame retardant environment-friendly preparation method thereof of skeleton, which is characterized in that
In the first step reaction, the molar ratio of catechol and phosphorus oxychloride is 1:1 ~ 1:6.
7. according to claim 2 using catechol as the phosphate flame retardant environment-friendly preparation method thereof of skeleton, which is characterized in that
In the second step reaction, the molar ratio of phosphinylidyne chloromethylated intermediate and single phenol, diphenol, monohydric alcohol or dihydric alcohol is 1:1 ~ 1:5.
8. according to claim 2 using catechol as the phosphate flame retardant environment-friendly preparation method thereof of skeleton, which is characterized in that
In first step reaction, catalyst is [A]-x [Lewis acid], wherein A be amine and its derivative, imidazole and its derivants or
Pyridine and its derivatives；X is 0.2-2%, and x is the molar ratio of Lewis acid and A when synthesizing ionic liquid.
9. according to claim 9 using catechol as the phosphate flame retardant environment-friendly preparation method thereof of skeleton, which is characterized in that
The amine and its derivative are trialkylamine, wherein alkyl be methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl,
Nonyl, isopropyl, isobutyl group or isopentyl；Imidazole and its derivants be imidazoles, N- alkyl imidazole or 1,3- dialkylimidazolium,
Wherein alkyl is methyl, ethyl, propyl or butyl；Pyridine and its derivatives be pyridine, alkyl pyridine or haloalkylpyridin,
Middle alkyl is methyl, ethyl, propyl or butyl, and halogeno-group is chloro or bromo；The Lewis acid is MgCl2、ZnCl2、
SnCl2、AlCl3、FeCl3Or TiCl4。
10. according to claim 2 using catechol as the phosphate flame retardant environment-friendly preparation method thereof of skeleton, feature exists
In in the first step reaction, catalytic amount is the 0.001% ~ 0.01% of catechol quality.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811540593.5A CN109627491A (en) | 2018-12-17 | 2018-12-17 | It is a kind of using catechol as the phosphate flame retardant of skeleton and its environment-friendly preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811540593.5A CN109627491A (en) | 2018-12-17 | 2018-12-17 | It is a kind of using catechol as the phosphate flame retardant of skeleton and its environment-friendly preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109627491A true CN109627491A (en) | 2019-04-16 |
Family
ID=66074659
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811540593.5A Pending CN109627491A (en) | 2018-12-17 | 2018-12-17 | It is a kind of using catechol as the phosphate flame retardant of skeleton and its environment-friendly preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109627491A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110642884A (en) * | 2019-10-08 | 2020-01-03 | 山东瑞兴阻燃科技有限公司 | Phosphate flame retardant with catechol as skeleton and green preparation method thereof |
| CN114249762A (en) * | 2021-12-10 | 2022-03-29 | 江苏三吉利化工股份有限公司 | Method for preparing high-performance phosphate ester flame retardant from benzenediol tar |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH101451A (en) * | 1996-06-14 | 1998-01-06 | Sankyo Kagaku Kk | Production of 3,4-dihydroxybenzaldehyde or 3-alkyloxy-4-hydroxybenzaldehyde |
| CN102086215A (en) * | 2010-12-27 | 2011-06-08 | 江汉大学 | Novel fire retardant tri(1,3-dioxa-2-phospho hetero-2-oxo-1,2-indane) m-cresyl phosphate and preparation method thereof |
| CN102617635A (en) * | 2012-02-23 | 2012-08-01 | 四川大学 | Method for preparing organic phosphorous flame retardant with hydroquinone phosphate as framework |
| CN103394375A (en) * | 2013-07-15 | 2013-11-20 | 响水雅克化工有限公司 | Ionic liquid catalyst and preparation method of same |
-
2018
- 2018-12-17 CN CN201811540593.5A patent/CN109627491A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH101451A (en) * | 1996-06-14 | 1998-01-06 | Sankyo Kagaku Kk | Production of 3,4-dihydroxybenzaldehyde or 3-alkyloxy-4-hydroxybenzaldehyde |
| CN102086215A (en) * | 2010-12-27 | 2011-06-08 | 江汉大学 | Novel fire retardant tri(1,3-dioxa-2-phospho hetero-2-oxo-1,2-indane) m-cresyl phosphate and preparation method thereof |
| CN102617635A (en) * | 2012-02-23 | 2012-08-01 | 四川大学 | Method for preparing organic phosphorous flame retardant with hydroquinone phosphate as framework |
| CN103394375A (en) * | 2013-07-15 | 2013-11-20 | 响水雅克化工有限公司 | Ionic liquid catalyst and preparation method of same |
Non-Patent Citations (2)
| Title |
|---|
| HANS GROΒ: "Darstellung und Reaktionen von Phosphorsaure-o-phenylenesterhalogeniden und Phosphorsaure-o-phenylenester", 《GROΒ, KATZWINKEL UND GLOEDE》 * |
| TORU KOIZUMI: "THE HYDROLYSISO F HETEROATOCMO NTAININGB ENZOPHOSPHOLES", 《TETRAHEDRON LETTERS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110642884A (en) * | 2019-10-08 | 2020-01-03 | 山东瑞兴阻燃科技有限公司 | Phosphate flame retardant with catechol as skeleton and green preparation method thereof |
| CN114249762A (en) * | 2021-12-10 | 2022-03-29 | 江苏三吉利化工股份有限公司 | Method for preparing high-performance phosphate ester flame retardant from benzenediol tar |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109627491A (en) | It is a kind of using catechol as the phosphate flame retardant of skeleton and its environment-friendly preparation method thereof | |
| TW201639861A (en) | Flame retardant compounds, hardeners and polyphenol-based epoxy resins | |
| CN103980313A (en) | Phosphorus-nitrogen synergistic flame-retardant polyalcohol and preparation method thereof | |
| CN109206665B (en) | A kind of hybrid modification hypo-aluminum orthophosphate and preparation method thereof | |
| CN104140559A (en) | Application of cyclophosphazene compound in preparation of resin as fire retardant | |
| CN106496570B (en) | A kind of phosphorus-nitrogen containing and the hyperbranched poly phosphamide carbon forming agent of benzene ring structure and preparation method thereof | |
| CN102181015B (en) | Method for synthesizing reactive halogen-free flame-retardant unsaturated polyester resin | |
| WO2020019596A1 (en) | Phosphazene compound, composition comprising phosphazene compound, flame retardant comprising same, and use thereof | |
| CN112341670A (en) | Environment-friendly surface flame retardant and preparation method thereof | |
| CN111704687B (en) | Application of polymer as anti-dripping flame retardant | |
| Huang et al. | Rigid and steric hindering bisphosphate flame retardants for polycarbonate | |
| CN103772740A (en) | Phosphorus-containing flame retardant and preparation method thereof | |
| CN105801624A (en) | Intumescent flame retardant containing phosphorus, nitrogen and sulfur and preparation method of intumescent flame retardant | |
| CN109161242B (en) | Solvent-free two-component polyurethane waterproof coating with flame-retardant smoke-suppression effect | |
| CN101565431A (en) | Process for synthetizing phosphoester oligopolymer BDP | |
| CN105061502B (en) | Synthesis method of bis(2-carboxylethyl)phosphonic acid | |
| CN109776780B (en) | Phosphorus-containing flame-retardant PTT and preparation method and application thereof | |
| CN110922637A (en) | DOPO derivative flame-retardant photo-thermal stabilizer and preparation method and application thereof | |
| CN104017163A (en) | Applications of cyclic phosphorus-nitrogen synergic halogen-free flame retardant | |
| CN102604157B (en) | Flame retardant and preparation method thereof | |
| TW201619222A (en) | HMF-based phenol formaldehyde resin | |
| CN113929968B (en) | Resveratrol-based flame retardant and preparation method and application thereof | |
| CN107663350A (en) | A kind of method that modified polyvinyl chloride and modified oxidized antimony prepare fire proofing | |
| KR100483652B1 (en) | Process for the preparation of condensed phosphoric acid esters | |
| CN102952290B (en) | The preparation method of synergistic intumescent flame retardant |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190416 |
|
| RJ01 | Rejection of invention patent application after publication |