CN110372745A - A kind of flame-retardant compound and its preparation method and application - Google Patents
A kind of flame-retardant compound and its preparation method and application Download PDFInfo
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- CN110372745A CN110372745A CN201910724650.3A CN201910724650A CN110372745A CN 110372745 A CN110372745 A CN 110372745A CN 201910724650 A CN201910724650 A CN 201910724650A CN 110372745 A CN110372745 A CN 110372745A
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- flame
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- retardant
- triphenylamines
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- -1 flame-retardant compound Chemical class 0.000 title claims abstract description 26
- 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 class 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 claims abstract description 24
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical class C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 claims description 29
- 239000003054 catalyst Substances 0.000 claims description 16
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 16
- 238000005654 Michaelis-Arbuzov synthesis reaction Methods 0.000 claims description 14
- GEFYZZRKUPFYLH-UHFFFAOYSA-N 2-iodo-n,n-diphenylaniline Chemical class IC1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 GEFYZZRKUPFYLH-UHFFFAOYSA-N 0.000 claims description 12
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical group Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 8
- YPIANBZIVBPMJS-UHFFFAOYSA-N 2-bromo-n,n-diphenylaniline Chemical class BrC1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 YPIANBZIVBPMJS-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical class Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 11
- 239000000654 additive Substances 0.000 abstract description 4
- 230000000996 additive effect Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 238000002485 combustion reaction Methods 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 48
- 238000006243 chemical reaction Methods 0.000 description 28
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 12
- 238000009833 condensation Methods 0.000 description 11
- 230000005494 condensation Effects 0.000 description 11
- 239000000047 product Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 7
- 238000002390 rotary evaporation Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 125000002346 iodo group Chemical group I* 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 239000001230 potassium iodate Substances 0.000 description 6
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 description 6
- 229940093930 potassium iodate Drugs 0.000 description 6
- 235000006666 potassium iodate Nutrition 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical class [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- QCMYYKRYFNMIEC-UHFFFAOYSA-N COP(O)=O Chemical class COP(O)=O QCMYYKRYFNMIEC-UHFFFAOYSA-N 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 238000007445 Chromatographic isolation Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- ASWXNYNXAOQCCD-UHFFFAOYSA-N dichloro(triphenyl)-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1P(Cl)(C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 ASWXNYNXAOQCCD-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000003008 phosphonic acid esters Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4021—Esters of aromatic acids (P-C aromatic linkage)
-
- 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4075—Esters with hydroxyalkyl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
- C08K5/5353—Esters of phosphonic acids containing also nitrogen
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of flame-retardant compounds and the preparation method and application thereof, belong to technical field of flame retardant.Flame-retardant compound provided by the invention has structure shown in formula 1, for completely new fire-retardant kind, it is good with the compatibility of high molecular material, it is a kind of expansion type flame retardant of efficient halogen-free, with excellent flame retardant property, when additive amount is 10%, the oxygen index (OI) of PVC material can be made to reach 29.5%, vertical combustion UL94 reaches V0 rank.Preparation method provided by the invention has the advantages that at low cost, yield is high, can be realized industrialized production.The present invention also provides application of the above-mentioned flame-retardant compound in flame retardant area.
Description
Technical field
The present invention relates to technical field of flame retardant more particularly to a kind of flame-retardant compound and preparation method thereof.
Background technique
Phosphonic acid ester fire retardant is the important species of phosphorus flame retardant, has additive amount few, compatible with high molecular material
Property it is good and flame-retardant modified after it is small to the Effect on Mechanical Properties of material the advantages that, be a kind of Green Flammability having a extensive future
Agent.Further, since being rich in P-C key, not facile hydrolysis, thus thermal stability with higher and hydrolytic stability in its structure, extensively
It is general to be applied to the flame-retardant modified of the high molecular materials such as polyurethane flexible foam, epoxy resin.The fire retardant of more new varieties is provided,
Great impetus is played to the development of fire retardant.
Summary of the invention
The purpose of the present invention is to provide a kind of new flame-retardant compound and its preparation method and application, chemical combination of the invention
The compatibility of object and high molecular material is good, is a kind of expansion type flame retardant of efficient halogen-free, has excellent flame retardant property.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of flame-retardant compounds, have structure shown in formula 1:
The present invention provides the preparation methods of flame-retardant compound described in above scheme, comprising the following steps:
By 4 ', 4, ", 4 " '-three halogenated triphenylamines carry out Arbuzov with Trimethyl phosphite and react, and obtain with shown in formula 1
The flame-retardant compound of structure;
Preferably, described 4 ', 4 ", 4 " molar ratio of '-three halogenated triphenylamines and Trimethyl phosphite is 1:(40~60).
Preferably, described 4 ', 4 ", 4 " '-three halogenated triphenylamines are 4 ', 4 ", 4 " '-three iodo triphenylamines or 4 ', 4 ", 4 " '-
Three bromo triphenylamines.
Preferably, the temperature of the Arbuzov reaction is 145~155 DEG C.
Preferably, the time of the Arbuzov reaction is 4~6h.
Preferably, the Arbuzov reaction carries out under catalysts conditions, and the catalyst is palladium chloride, bi triphenyl
Phosphine dichloride palladium, palladium acetate or Dehydrated nickel chloride.
Preferably, described 4 ', 4 ", 4 " molar ratio of '-three halogenated triphenylamines and catalyst is 1:(0.15~0.30).
Preferably, the Arbuzov reaction carries out under inert gas existence condition.
The present invention provides application of the flame-retardant compound described in above scheme in flame retardant area.
The present invention provides a kind of flame-retardant compounds, have structure shown in formula 1:
Flame-retardant compound of the invention is completely new fire-retardant kind, good with the compatibility of high molecular material, is a kind of efficient
The expansion type flame retardant of Halogen has excellent flame retardant property.When flame-retardant compound additive amount of the present invention is 10%, can make
The oxygen index (OI) of PVC material reaches 29.5%, and vertical combustion UL94 reaches V0 rank.
The present invention provides the preparation method of above-mentioned flame-retardant compound, has the advantages that at low cost, yield is high, can be realized
Industrialized production.
Detailed description of the invention
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of embodiment 1.
Specific embodiment
The present invention provides a kind of flame-retardant compounds, have structure shown in formula 1:
According to IUPAC naming rule, the title of the compound with structure shown in formula 1 are as follows: 4 ', 4 ", 4 " '-triphosphines
Sour methyl esters triphenylamine.
The present invention provides the preparation methods of flame-retardant compound described in above scheme, comprising the following steps:
By 4 ', 4, ", 4 " '-three halogenated triphenylamines carry out Arbuzov with Trimethyl phosphite and react, and obtain with shown in formula 1
The flame-retardant compound of structure;
In the present invention, described 4 ', 4 ", 4 " molar ratio of '-three halogenated triphenylamines and Trimethyl phosphite is preferably 1:
(40~60), further preferably 1:50.In the present invention, described 4 ', 4 ", 4 " '-three halogenated triphenylamines are preferably 4 ', 4 ",
4 " '-three iodo triphenylamines or 4 ', 4 ", 4 " '-three bromo triphenylamines, due to 4 ', 4 ", 4 " the reaction difficulty of '-three bromo triphenylamines
Than 4 ', 4 ", 4 " '-three iodo triphenylamines are big, therefore the present invention more preferably uses 4 ', 4 ", 4 " '-three iodo triphenylamines.
In the present invention, described 4 ', 4 ", 4 " structure of '-three iodo triphenylamines is as shown in Equation 2:
The present invention is to described 4 ', 4 ", 4 " source of '-three halogenated triphenylamines does not have particular/special requirement, can use this field skill
Commercial goods known to art personnel, or be voluntarily prepared.The present invention, which preferably passes through, to be voluntarily prepared, and is produced into reducing
This.When voluntarily preparing, described 4 ', 4 ", 4 " '-three iodo triphenylamines are preferably according to document Chemistry of materials,
2005,17 (11): the preparation of method disclosed in 3031-3039, specifically includes the following steps: being equipped with spherical condensation tube, stirrer
Three-necked flask in sequentially add triphenylamine, potassium iodide and acetic acid, be heated to 115~125 DEG C reflux, then in batches by Potassiumiodate
It is added in reaction flask, 3~5h of isothermal reaction, reaction solution is first become brown and finally become colorless again from colourless, stops heating, cooling
To room temperature, rotary evaporation falls acetic acid, and saturated sodium thiosulfate solution is added and methylene chloride is extracted, the anhydrous sulphur of organic phase
Sour sodium is dry, is concentrated to get faint yellow solid, re-crystallizing in ethyl acetate, obtains faint yellow platelet, as 4 ', and 4 ", 4 " '-three iodos
Triphenylamine.Each specific dosage of substance is referring to above-mentioned document, and which is not described herein again.
In the present invention, the temperature of the Arbuzov reaction is preferably 145~155 DEG C, and further preferably 150 DEG C;Institute
The time for stating Arbuzov reaction is preferably 4~6h, further preferably 5h.
In the present invention, the Arbuzov reaction preferably carries out under catalysts conditions.
In the present invention, the catalyst is preferably palladium chloride, bis-triphenylphosphipalladium palladium dichloride, palladium acetate or anhydrous chlorination
Nickel, further preferably bis-triphenylphosphipalladium palladium dichloride.The present invention does not have particular/special requirement to the source of the catalyst, can be used
Commercial goods well known in the art or method well known in the art are prepared.When catalyst selects bis-triphenylphosphipalladium palladium dichloride
When, it is preferred to use method well known in the art is prepared, to reduce production cost.In the present invention, described 4 ', 4 ", 4 " '-
The molar ratio of three halogenated triphenylamines and catalyst is preferably 1:(0.15~0.30).
In the present invention, the Arbuzov reaction preferably carries out under inert gas existence condition.The present invention is to described lazy
The type of property gas does not have particular/special requirement, using inert gas well known to those skilled in the art, be specifically as follows nitrogen,
Argon gas etc., to save cost, preferably nitrogen.
In the present invention, the Arbuzov reaction preferably carries out under agitation.Rate of the present invention to the stirring
There is no particular/special requirement, using the stirring rate of this field routine.
After the Arbuzov reaction, the present invention is it is also preferable to include reaction product system to be cooled to room temperature, to reaction product
System is separated, and the flame-retardant compound with structure shown in formula 1 is obtained.In the present invention, the separation preferably includes following
Step: filtering out catalyst, and rotary evaporation removes extra Trimethyl phosphite, obtains light yellow viscous liquid, will be described light
Yellow viscous liquid obtains the flame-retardant compound with structure shown in formula 1 after carrying out pillar layer separation.
The present invention provides application of the flame-retardant compound described in above scheme in flame retardant area.The present invention is to the application
Mode there is no particular/special requirement, using application mode well known in the art.
Flame-retardant compound provided by the invention and the preparation method and application thereof is carried out specifically below with reference to embodiment
It is bright, but they cannot be interpreted as limiting the scope of the present invention.
The raw material condition that Examples 1 to 5 is used is as shown in table 1.
Summarize in the 1 raw materials used source of each embodiment of table
Embodiment 1
4 ', 4 ", the 4 " preparation (2 compound of formula) of '-three iodo triphenylamines
Spherical condensation tube is being housed, is sequentially adding triphenylamine 2.45g, 3.65g iodate in the 250mL three-necked flask of stirrer
Potassium, acetic acid 100mL are heated to flowing back, and then by 6 batches of addition reaction flasks of 2.35g Potassiumiodate point, 0.6g or so is added in every batch of,
Isothermal reaction 4h, reaction solution first from it is colourless become brown finally again become colorless, stop heating, be cooled to room temperature, spin off acetic acid,
100mL saturated sodium thiosulfate solution is added and 150mL methylene chloride is extracted, organic phase is dry with anhydrous sodium sulfate, dense
Contracting obtains faint yellow solid 6.11g, and re-crystallizing in ethyl acetate obtains faint yellow platelet 5.80g, yield 93.00%.(Mp:169℃)
4 ', 4 ", 4 " '-tri methylene phosphonic acid methyl esters triphenylamine preparation (1 compound of formula)
Spherical condensation tube is being housed, is sequentially adding 2g 4 ' in the 50mL three-necked flask of stirrer, 4 ", 4 " '-three iodos three
Aniline, 20mL Trimethyl phosphite and 0.34g Pd (PPh3)2Cl2, 150 DEG C of isothermal reaction 5h, reaction are tied in a nitrogen atmosphere
Beam is cooled to room temperature, and filters out catalyst, and rotary evaporation removes extra Trimethyl phosphite, obtains light yellow viscous liquid
2g, pillar layer separation obtain target product 1.47g, yield 81%.Nucleus magnetic hydrogen spectrum test is carried out to products therefrom, as a result such as Fig. 1
Shown, specific data are as follows:
1H NMR(DCCl3, δ, ppm): 7.7 (dd, 6H, J=7.62Hz), 7.2 (dd, 6H, J=16.86Hz), 3.8 (d,
18H, J=22.14Hz);
Test result proves that product is the flame-retardant compound with structure shown in formula 1.
Embodiment 2
4 ', 4 ", the 4 " preparation (2 compound of formula) of '-three iodo triphenylamines
Spherical condensation tube is being housed, is sequentially adding triphenylamine 2.45g, 3.65g iodate in the 250mL three-necked flask of stirrer
Potassium, acetic acid 100mL are heated to flowing back, and then 3.20g Potassiumiodate is added portionwise in reaction flask, isothermal reaction 4h, and reaction solution is first
Become brown from colourless and finally become colorless again, stopped heating, be cooled to room temperature, spin off acetic acid, saturated sodium thiosulfate is added
Solution and methylene chloride are extracted, and organic phase is dry with anhydrous sodium sulfate, are concentrated to get faint yellow solid 6.20g, acetic acid second
Ester recrystallization, obtains faint yellow platelet 5.85g, yield 93.90%.(Mp:169℃)
4 ', 4 ", 4 " '-tri methylene phosphonic acid methyl esters triphenylamine preparation (1 compound of formula)
Spherical condensation tube is being housed, is sequentially adding 2g 4 ' in the 50mL three-necked flask of stirrer, 4 ", 4 " '-three iodos three
Aniline, 20mL Trimethyl phosphite and 0.17g PdCl2, 150 DEG C of isothermal reaction 4h, reaction terminate in a nitrogen atmosphere, cooling
To room temperature, catalyst is filtered out, rotary evaporation removes extra Trimethyl phosphite, obtains light yellow viscous liquid 1.93g, column
Chromatographic isolation obtains target product 1.27g, yield 70%.
Embodiment 3
4 ', 4 ", the 4 " preparation (2 compound of formula) of '-three iodo triphenylamines
Spherical condensation tube is being housed, is sequentially adding triphenylamine 4.90g, 7.30g iodate in the 500mL three-necked flask of stirrer
Potassium, acetic acid 200mL are heated to flowing back, and then 6.40g Potassiumiodate is added portionwise in reaction flask, isothermal reaction 4h, and reaction solution is first
Become brown from colourless and finally become colorless again, stopped heating, be cooled to room temperature, spin off acetic acid, saturated sodium thiosulfate is added
Solution and methylene chloride are extracted, and organic phase is dry with anhydrous sodium sulfate, are concentrated to get faint yellow solid 12.50g, acetic acid second
Ester recrystallization, obtains faint yellow platelet 11.77g, yield 94.50%.(Mp:169℃)
4 ', 4 ", 4 " '-tri methylene phosphonic acid methyl esters triphenylamine preparation (1 compound of formula)
Spherical condensation tube is being housed, is sequentially adding 2.00g4 ' in the 50mL three-necked flask of stirrer, 4 ", 4 " '-three iodos
Triphenylamine, 20mL Trimethyl phosphite and the anhydrous NiCl of 0.12g2, 150 DEG C of isothermal reaction 5h, reaction terminate in a nitrogen atmosphere,
It being cooled to room temperature, filters out catalyst, rotary evaporation removes extra Trimethyl phosphite, light yellow viscous liquid 2g is obtained,
Pillar layer separation obtains target product 1.31g, yield 72%.
Embodiment 4
4 ', 4 ", the 4 " preparation (2 compound of formula) of '-three iodo triphenylamines
Spherical condensation tube is being housed, is sequentially adding triphenylamine 4.9g, 6.63g iodate in the 500mL three-necked flask of stirrer
Potassium, acetic acid 200mL are heated to flowing back, and then 4.28g Potassiumiodate is added portionwise in reaction flask, isothermal reaction 4h, and reaction solution is first
Become brown from colourless and finally become colorless again, stopped heating, be cooled to room temperature, spin off acetic acid, saturated sodium thiosulfate is added
Solution and methylene chloride are extracted, and organic phase is dry with anhydrous sodium sulfate, are concentrated to get faint yellow solid 10.21g, acetic acid second
Ester recrystallization, obtains faint yellow platelet 9.51g, yield 76.32%.(Mp:169℃)
4 ', 4 ", 4 " '-tri methylene phosphonic acid methyl esters triphenylamine preparation (1 compound of formula)
Spherical condensation tube is being housed, is sequentially adding 2.00g4 ' in the 50mL three-necked flask of stirrer, 4 ", 4 " '-three iodos
Triphenylamine, 20mL Trimethyl phosphite and 0.13g Pd (OAc)2, 150 DEG C of isothermal reaction 5h, reaction terminate in a nitrogen atmosphere,
It is cooled to room temperature, filters out catalyst, rotary evaporation removes extra Trimethyl phosphite, obtains light yellow viscous liquid
2.10g, pillar layer separation obtain target product 1.42g, yield 78%.
Embodiment 5
4 ', 4 ", the 4 " preparation (2 compound of formula) of '-three iodo triphenylamines
Spherical condensation tube is being housed, is sequentially adding triphenylamine 3.0g, 4.45g iodate in the 250mL three-necked flask of stirrer
Potassium, acetic acid 200mL are heated to flowing back, and then 2.82g Potassiumiodate is added portionwise in reaction flask, isothermal reaction 4h, and reaction solution is first
Become brown from colourless and finally become colorless again, stopped heating, be cooled to room temperature, spin off acetic acid, saturated sodium thiosulfate is added
Solution and methylene chloride are extracted, and organic phase is dry with anhydrous sodium sulfate, are concentrated to get faint yellow solid 7.11g, acetic acid second
Ester recrystallization, obtains faint yellow platelet 6.92g, yield 91.00%.(Mp:169℃)
4 ', 4 ", 4 " '-tri methylene phosphonic acid methyl esters triphenylamine preparation (1 compound of formula)
Spherical condensation tube is being housed, is sequentially adding 4.0g4 ' in the 100mL three-necked flask of stirrer, 4 ", 4 " '-three iodos
Triphenylamine, 30mL Trimethyl phosphite and 0.68g Pd (PPh3)2Cl2, 150 DEG C of isothermal reaction 5h, reaction are tied in a nitrogen atmosphere
Beam is cooled to room temperature, and filters out catalyst, and rotary evaporation removes extra Trimethyl phosphite, obtains light yellow viscous liquid
4.2g, pillar layer separation obtain target product 3.02g, yield 83%.
Using the product of embodiment 1 as reference substance, embodiment 2~5 uses the production of TLC (thin-layered chromatography) and embodiment 1
Object carries out control verifying, it was demonstrated that the product of embodiment 2~5 is the flame-retardant compound of 1 structure of formula.
The flame-retardant compound that Examples 1 to 5 is obtained mixes, and carries out flame retardant property test, and test result is shown: when fire-retardant
When the additive amount of compound is 10%, the oxygen index (OI) of PVC material can be made to reach 29.5%, vertical combustion UL94 reaches V0 rank,
Illustrate that flame-retardant compound provided by the invention has excellent flame retardant property.
As seen from the above embodiment, the present invention provides a kind of new flame-retardant compounds, the compatibility with high molecular material
It is good, it is a kind of expansion type flame retardant of efficient halogen-free, there is excellent flame retardant property.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of flame-retardant compound, which is characterized in that have structure shown in formula 1:
2. the preparation method of flame-retardant compound described in claim 1, which comprises the following steps:
By 4 ', 4, ", 4 " '-three halogenated triphenylamines carry out Arbuzov with Trimethyl phosphite and react, and obtain with structure shown in formula 1
Flame-retardant compound;
3. preparation method according to claim 2, which is characterized in that described 4 ', 4 ", 4 " '-three halogenated triphenylamines and phosphorous
The molar ratio of sour trimethyl is 1:(40~60).
4. preparation method according to claim 2 or 3, which is characterized in that described 4 ', 4 ", 4 " '-three halogenated triphenylamines are
4 ', 4 ", 4 " '-three iodo triphenylamines or 4 ', 4 ", 4 " '-three bromo triphenylamines.
5. preparation method according to claim 2, which is characterized in that the temperature of the Arbuzov reaction is 145~155
℃。
6. preparation method according to claim 5, which is characterized in that the time of the Arbuzov reaction is 4~6h.
7. according to preparation method described in claim 2,3,5 or 6, which is characterized in that the Arbuzov reaction is in catalyst item
It is carried out under part, the catalyst is palladium chloride, bis-triphenylphosphipalladium palladium dichloride, palladium acetate or Dehydrated nickel chloride.
8. preparation method according to claim 7, which is characterized in that described 4 ', 4 ", 4 " '-three halogenated triphenylamines and catalysis
The molar ratio of agent is 1:(0.15~0.30).
9. preparation method according to claim 2, which is characterized in that in inert gas, there are items for the Arbuzov reaction
It is carried out under part.
10. application of the flame-retardant compound described in claim 1 in flame retardant area.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111040250A (en) * | 2019-12-27 | 2020-04-21 | 叶丹平 | Composite flame retardant for plastics |
CN111057349A (en) * | 2019-12-27 | 2020-04-24 | 叶丹平 | Environment-friendly flame-retardant plastic, preparation method and application |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103980314A (en) * | 2014-05-26 | 2014-08-13 | 中北大学 | Compound with a plurality of active groups and preparation method of compound |
CN109134847A (en) * | 2017-06-27 | 2019-01-04 | 中国科学院化学研究所 | A kind of multi-component copolymer virtue amide and its preparation method and application containing side group |
-
2019
- 2019-08-07 CN CN201910724650.3A patent/CN110372745B/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103980314A (en) * | 2014-05-26 | 2014-08-13 | 中北大学 | Compound with a plurality of active groups and preparation method of compound |
CN109134847A (en) * | 2017-06-27 | 2019-01-04 | 中国科学院化学研究所 | A kind of multi-component copolymer virtue amide and its preparation method and application containing side group |
Non-Patent Citations (3)
Title |
---|
杜朝军等: "《新型磷氮阻燃剂合成与性质研究》", 31 May 2017 * |
王彦林等: ""无溶剂法合成2,4,6-三(O,O-二甲基磷酰基)-1,3,5,-三嗪的研究"", 《化学世界》 * |
胡新利等: ""阻燃剂三嗪三苯基次膦酸甲酯的合成及应用研究"", 《化学世界》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111040250A (en) * | 2019-12-27 | 2020-04-21 | 叶丹平 | Composite flame retardant for plastics |
CN111057349A (en) * | 2019-12-27 | 2020-04-24 | 叶丹平 | Environment-friendly flame-retardant plastic, preparation method and application |
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