CN105753900A - Synthesis method of aromatic amide phosphate compound and flame retardant containing compound - Google Patents

Synthesis method of aromatic amide phosphate compound and flame retardant containing compound Download PDF

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CN105753900A
CN105753900A CN201610164120.4A CN201610164120A CN105753900A CN 105753900 A CN105753900 A CN 105753900A CN 201610164120 A CN201610164120 A CN 201610164120A CN 105753900 A CN105753900 A CN 105753900A
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compound
formula
aromatic
phosphoric ester
alkyl
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浜田申
浜田申一
浜田智子
唐成见
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YWK CHEMICALS (TAICANG) CO Ltd
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YWK CHEMICALS (TAICANG) CO Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/22—Amides of acids of phosphorus
    • C07F9/24—Esteramides
    • C07F9/2454—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/247—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic of aromatic amines (N-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
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/22—Amides of acids of phosphorus
    • C07F9/24—Esteramides
    • C07F9/2454—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/12—Organic materials containing phosphorus

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Abstract

The invention discloses a one-pot synthesis method of an aromatic amide phosphate compound. Firstly, phosphorus trioxyhalogen and a monophenol compound or a bisphenol compound react in the presence of a lewis acid catalyst to produce a mono- and/or poly-halogenated phosphate ester compound; secondarily, the mono- and/or poly-halogenated phosphate ester compound and at least one amine compound of a monoamine compound with one primary amino group and/or secondary amino group in molecules and a diamine compound with two primary amino groups and/or secondary amino groups in molecules are subjected to a dehydrohalogenation reaction in the presence of lewis base, and the aromatic amide phosphate compound is produced; finally, the aromatic amide phosphate compound is purified, and a target product is obtained. The one-pot synthesis method has the advantages that with the adoption of one-pot, an intermediate, namely, the mono- and/or poly-halogenated phosphate ester compound, obtained through the reaction is not required to be distilled and/or rectified and purified, required energy consumption is greatly reduced, required production equipment is greatly simplified, corrosive damage of equipment is greatly reduced, the whole process is simple and practical, the production cost is low, the environmental pressure is small, and the product quality is high.

Description

The synthetic method of a kind of aromatic phosphoric ester amide compound and the fire retardant containing this compound
Technical field
The invention belongs to technical field of organic synthesis, be specifically related to " cooking different foods in one pot " synthetic method of a kind of aromatic phosphoric ester amide compound and the fire retardant containing this compound.
Background technology
At present, phosphorus-nitrogen (P-N) expanding fire retardant becomes carbon and quality retention mechanism and partial gas phase fire retardant mechanism with its solid phase, fire-retardant process can not only reduce the HRR of material, improve flame retardant effect, zest and corrosive gas and the shortcoming of a large amount of poison gas is easily discharged when also overcoming halogenated flame retardant burning, at textile, leather, polyester fiber, coating, cable, need in the industries such as engineering plastics fire-retardant product is increasingly widely applied, wherein aromatic phosphoric acid esteramides is one of representative compound of phosphorus-nitrogen (P-N) expanding fire retardant.
Root it is documented, it is available for the manufacture method of industrialized production aromatic phosphoric acid esteramides at present, it is essentially all the list and/or many halogenated phosphates and aminated compounds generation amidation process that are obtained by phenolic compound and phosphorus oxychloride reaction, and dehydrohalogenation obtains purpose product aromatic phosphoric acid esteramides.Relatively more documents and patent all focus on the reaction of single and/or many halogenated phosphates and aminated compounds, but, in fact the obtained price of single and/or many halogenated phosphate is only the key controlling such production of chemicals cost.
The preparation method that patent CN201110424421 discloses a kind of diphenyl phosphoryl amino benzenes compounds, it adopts the list and/or many halophosphoric acids ester admixture that after first distilling, rectification phenolic compound and phosphorus oxychloride reaction obtain, and utilizes obtained high-purity halophosphoric acid phenolic ester that aromatic phosphoric acid esteramides is synthesized again with aminated compounds.Owing in the mixture that phenolic compound and phosphorus oxychloride reaction obtain, each composition boiling point is significantly high, whole distillation and distillation process are required for high temperature, fine vacuum, energy consumption high (constituting about the 50% of production cost), equipment corrosion is serious, and the production cycle is longer.
Patent 201380032297 discloses the manufacture method of a kind of phosphoric ester amides class, more than its halogenated phosphate adopting 1 equivalent and 0.5 equivalent and less than the aminated compounds of 2.0 equivalents, at temperature more than 130 DEG C, the at least one material adopting the aromatic hydrocarbon of boiling point more than 130 DEG C, halogenated aromatic hydrocarbon, aliphatic hydrocarbon and aromatic ether apoplexy due to endogenous wind makes solvent, and under reduced pressure synthesizes aromatic phosphoric acid esteramides.It equally exists, and halogenated phosphate obtains, storage is not easy, high boiling solvent recycling trouble, and need also exist for high temperature, fine vacuum, particularly the same with patent CN201110424421, it is required for the high temperature heat-conduction boiler heating system of a set of complexity and a set of high temperature rectifying device.
All weak points in view of aforementioned production technology, particularly because producing, equipment is excessively complicated, energy resource consumption is too high, ultimately result in aryl phosphate ester amide compound production cost to remain high, making it reduce difficulty as the use cost of fire retardant, its popularization and application widely are very restricted.Therefore, it is necessary to develop the aromatic phosphoric acid esteramides production technology of a kind of low energy consumption, the requirement of low equipment performance, low cost.
Summary of the invention
Goal of the invention: in order to overcome the deficiencies in the prior art, it is an object of the invention to provide that a kind of technique is simple, energy consumption is low, equipment requirements is low, with low cost and be suitable to the aromatic phosphoric acid esteramides production technology of industrialized production.
Technical scheme: in order to solve above-mentioned technical problem, the technical solution adopted in the present invention is:
The invention provides " cooking different foods in one pot " synthetic method of a kind of aromatic phosphoric ester amide compound, the method at least comprises the following steps:
(1) in the presence of a lewis acid catalyst, make to be selected from single phenolic compounds of formula (Ia) and/or at least one phenolic compound in the bisphenol compound of formula (Ib) and three oxyhalogen phosphorus reactions, generate single and/or many halophosphate compound.
Its formula of (Ia) includes formula (Ia1)、(Ia2) and (Ia3) representated by single phenolic compounds, formula (Ib) includes formula (Ib1) and (Ib2) representated by bisphenol compound, described phenolic compound formula (Ia), (Ib) phenyl ring on have zero～multiple in the reaction for the alkyl of inactive substituent group, cycloalkyl, aryl alkyl or aryl.
(2) list without distillation and/or rectification purification making to obtain in step (1) and/or many halophosphate compound directly and have in molecule in the monoamine compound of a primary amino radical and/or secondary amino group and molecule and have at least one amines in the diamine compound of two primary amino radicals and/or secondary amino group, under lewis base exists, there is de-hydrogen halide, generate aromatic phosphoric ester amide compound.
Wherein monoamine compound includes formula (IIa1) shown in aromatic series monoamine compound and formula (IIa2) shown in aliphatic monoamine compound:
Formula (IIa1) in, Ar1Represent aryl, Y1Represent hydrogen atom, alkyl, alkenyl, cycloalkyl, aryl or aryl alkyl, Y1During for aryl, Y1With Ar1Can identical can also differ.
Formula (IIa2) in, Ay1Represent alkyl, alkenyl, cycloalkyl or aryl alkyl, Y2Represent hydrogen atom, alkyl, alkenyl, cycloalkyl or aryl alkyl；Or, Ay1With Y2Can being collectively forming 5～7 rings, now, above-mentioned ring can include oxygen atom and/or nitrogen-atoms as the atom forming this ring, and wherein, when the looped atom of shape is nitrogen-atoms, this nitrogen-atoms does not have hydrogen atom bonded thereto.
Wherein diamine compound includes formula (IIb1) shown in aromatic diamine compound and formula (IIb2) shown in aliphatic diamine compound:
Formula (IIb1) in, Ar2Represent respectively with the divalent group comprising aromatic rings of two nitrogen atom bondings in molecule, Y3And Y4Represent hydrogen atom, alkyl, alkenyl, cycloalkyl, aryl or aryl alkyl, Y independently of one another3And Y4Can identical can also differ.
Formula (IIb2) in, Ay2Represent alkylidene or ring alkylidene, the Y optionally on carbon atom or between carbon atom with aromatic group5And Y6Represent hydrogen atom, alkyl, alkenyl, cycloalkyl or aryl alkyl independently of one another；Or, Ay2With Y55～7 rings or Ay can be collectively forming2With Y65～7 rings or Ay can be collectively forming2With Y5And Y6It is collectively forming 5～7 rings.
(3) after, described single and/or many halophosphate compound is reacted with aminated compounds and is terminated, adjusting the ratio of solvent/solute, solid in rising temperature for dissolving reaction system, with acid water and/or caustic water wash under keeping warm mode, then concentrating organic facies, crystallization purifying obtains purpose product.
In above-mentioned formula (Ia), (Ib), (IIa), (IIb), (IVa) and (IVb), its preferred carbon number of alkyl represented independently of one another is 1～12, the alkyl of more preferably 1～6, particularly preferably 1～4, the alkyl of carbon number more than 3 can be straight-chain can also be branched, as this alkyl, for instance methyl, ethyl, propyl group, isopropyl, butyl, the tert-butyl group, amyl group, hexyl, octyl group, nonyl, dodecyl etc. can be listed
Deng, wherein methyl, isopropyl and the tert-butyl group are preferred.
In above-mentioned formula (Ia), (Ib), (IIa), (IIb), (IVa) and (IVb), its cycloalkyl represented independently of one another is the optional cycloalkyl that total carbon atom number is 5～20, preferably 5～12 on the looped carbon atom of shape with or without alkyl alternatively base, as concrete example, cyclopenta, methylcyclopentyl, cyclohexyl, methylcyclohexyl, Dimethylcyclohexyl, trimethylcyclohexyl, ethylcyclohexyl etc. can be listed, it is preferred to cyclohexyl.
In above-mentioned formula (Ia), (Ib), (IIa), (IIb), (IVa) and (IVb), its preferred carbon number of aryl represented independently of one another is the aryl of 6～18, such as phenyl, naphthyl, xenyl etc., wherein preferred phenyl.These aryl optionally can have one or more alkyl on aromatic ring, but preferably 1～3 and its carbon number are the alkyl of 1～4, and this to have reaction be the aryl such as tolyl, xylyl of inactive substituent group, methyl naphthyl etc..
In above-mentioned formula (Ia), (Ib), (IIa), (IIb), (IVa) and (IVb), its aryl alkyl represented independently of one another is preferably benzyl or phenethyl, their phenyl can have one or above but preferably 1～3 and its carbon number are the low alkyl group of 1～4.
In above-mentioned formula (Ia), (Ib), (IIa), (IIb), (IVa) and (IVb), its preferred carbon number of alkenyl represented independently of one another is the pi-allyl of 3～6, include, for example out pi-allyl, crotyl etc., additionally pi-allyl can also optionally have reaction is inactive heterocyclic radical alternatively base, it is preferred to pi-allyl.
At above-mentioned formula (IIa1) and (IIb1) in, Ar1、Ar2The preferred carbon number of aryl represented independently of one another is the aryl of 6～18, such as phenyl, naphthyl, xenyl etc., wherein preferred phenyl.These aryl optionally can have one or more alkyl on aromatic ring, but preferably 1～3 and its carbon number are the alkyl of 1～4, and this to have reaction be the aryl such as tolyl, xylyl of inactive substituent group, methyl naphthyl etc..
Therefore, above-mentioned formula (IIa in the present invention2) in the aliphatic monoamine compound that relates to, methylamine can be listed, ethamine, n-propylamine, 2-aminopropane., n-butylamine, isobutyl amine, tert-butylamine, hexylamine, heptyl amice, 2 ethyl hexylamine, ring is amine, piperidines, benzylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-iso-butylmanice, two tert-butylamines, diamylamine, dihexylamine, two (2-ethylhexyl) amine, hexanamine, dibenzylamine, allylamine, morpholine, piperidines, alkyl substituted piperidine compounds etc., and any two or more mixture in them, wherein tert-butylamine, cyclohexylamine, morpholine is preferred.
Above-mentioned formula (IIa in the present invention1) in the aromatic series monoamine compound that relates to, specifically can be exemplified as aniline, ortho-aminotoluene, meta-aminotoluene, para-totuidine, 2,3-dimethylaniline, 2,4-dimethylaniline, 3,4-dimethylaniline, 2,6-dimethylaniline, 1-naphthylamine, 2-naphthylamine, 2-xenylamine, 3-xenylamine, 4-xenylamine, N-alkyl substituted benzene amine, nitroaniline compounds, amino substituted pyridine compounds etc., wherein aniline is most preferred.
At above-mentioned formula (IIb2) in the aliphatic diamine compound that relates to, Ay2Representing the chain alkylidene at least containing a carbon atom, the preferred carbon number of this alkylidene is the scope of 1～6, concrete such as methylene, ethylidene, propylidene, butylidene etc.；Ay2Represent the alkylidene on carbon atom or between carbon atom with aromatic group, such as phenyl methine, diphenyl methine, 1-phenyl-ethylene, 1,2-diphenylethylene etc.；Ay2Can enumerate out such as cyclohexylene, cyclohexylidene base etc. when representing ring alkylidene；Formula (IIb2) in, Ay2And Y55～7 rings or Ay can be collectively forming2And Y6It is collectively forming 5～7 rings or Ay2And Y5、Y65～7 rings can be collectively forming.Therefore formula (IIb2) the middle aliphatic diamine compound represented, can list as ethylenediamine, propane diamine, butanediamine, 1,5-pentanediamine, 1,6-hexamethylene diamine, 1,3-diaminourea Pentamethylene., 1,4-diaminourea Pentamethylene., 1,3-diamino-cyclohexane, Isosorbide-5-Nitrae-diamino-cyclohexane, 1, double; two (amino methyl) hexamethylene of 3-, 1, double; two (amino methyl) hexamethylene of 4-, 1,3-double; two (2,2 '-amino-ethyl) benzene, 1,4-double; two (2,2 '-amino-ethyl) benzene, 4-amino piperidine, piperazine or substituted-piperazinyl etc., wherein ethylenediamine, piperazine are preferred, it is particularly preferred to piperazine.
At above-mentioned formula (IIb1) in the aromatic diamine compound that relates to, there is the divalent group Ar of aromatic rings2With 2 nitrogen atom bondings in the molecule forming diamine compound, this divalent group Ar with aromatic rings2Preferred a kind of form be arlydene, as preferred concrete example, this arlydene can optionally have the alkyl of carbon number 0～6 or to reacting for other group inactive, such as m-diaminobenzene., the diaminobenzene class replaced without alkyl on the phenyl ring such as p-phenylenediamine, 2, 4-diaminotoluene, 2, the phenyl ring such as 6-diaminotoluene have the diaminobenzene class that alkyl replaces, 1, the diaminonaphthalene classes such as 8-diaminourea, 4, 4 '-benzidine (has another name called benzidine, benzidine), 3, 3 '-dimethylbenzidine (has another name called o-tolidine), 3, the benzidine classes such as 3 '-dimethoxy benzidine (has another name called adjacent dianisidine)；This divalent group Ar with aromatic rings2Another form preferred, the group shown in below formula (V) structure can be listed:
Divalent group X in logical formula V represent optional from alkylidene (such as CH2-、-C(CH3)2-etc.), ring alkylidene, oxygen atom (-O-), sulphur atom (-S-), disulfide group, sulfoxide group (-SO-), sulfuryl (-SO2-) and carbonyl (-CO-) in any one, as preferred concrete example, such as double, two (4-aminophenyl) methane (namely 4, 4 '-diaminodiphenyl-methane), 1, double, two (4-aminophenyl) ethane of 1-, 1, double, two (4-aminophenyl) ethane of 2-, 1, double, two (4-aminophenyl) propane of 1-, 2, double, two (4-aminophenyl) propane of 2-, 1, double, two (4-aminophenyl) butane of 1-, 4, 4 '-diaminourea triphenyl methane, 4, 4 '-diamino-diphenyl hexamethylene, 4, 4 '-diaminourea-3, 3 '-dimethyl diphenyl hexamethylene, 4, 4 '-diaminodiphenyl ether, 4, 4 '-diaminourea diphenyl sulfoxide, 4, 4 '-DADPS etc..The above-mentioned preferred p-phenylenediamine of aromatic series diamino compounds, double; two (4-aminophenyl) methane (having another name called 4,4 '-diaminodiphenyl-methane or methylene-dianiline (MDA)), 4,4' diaminodiphenyl sulfone.
nullIn above-mentioned formula (I) and (II)，The instantiation of its involved aromatic hydroxy compound includes phenol、(o-，M-or p-) methylphenol、(o-，M-or p-) ethyl-phenol、(o-，M-or p-) n-pro-pyl phenol、(o-，M-or p-) isopropyl-phenol、(o-，M-or p-) normal-butyl phenol、(o-，M-or p-) sec-butyl phenol、(o-，M-or p-) tert-butyl phenol、(o-，M-or p-) isobutyl group phenol、(o-，M-or p-) tert-butyl group-2-methylphenol、(o-，M-or p-) tert-butyl-4-methyl-Phenol、(o-，M-or p-) amyl phenol、(o-，M-or p-) hexylphenol、(o-，M-or p-) heptylphenol、(o-，M-or p-) octyl phenol、(o-，M-or p-) nonyl phenol、(2,3-，2,4-，2,5-，2,6-，3,4-or 3,5-) xylenol、(2,3-，2,4-，2,5-，2,6-，3,4-or 3,5-) diethyl phenol、(2,3-，2,4-，2,5-，2,6-，3,4-or 3,5-) diη-propyl phenol、(2,3-，2,4-，2,5-，2,6-，3,4-or 3,5-) diisopropyl phenol、(2,3-，2,4-，2,5-，2,6-，3,4-or 3,5-) di-n-butyl phenol、(2,3-，2,4-，2,5-，2,6-，3,4-or 3,5-) di sec-butylphenol、(2,3-，2,4-，2,5-，2,6-，3,4-or 3,5-) two tertiary base phenol、(2,3，5-，2,4，5-，2,3,4-，2,3，6-，2,4，6-or 3,45-) pseudocuminol、(2,3，5-，2,4，5-，2,3,4-，2,3，6-，2,4，6-or 3,45-) triethyl group phenol、2,3，5-，2,4，5-，2,3,4-，2,3，6-，2,4，6-or 3,45-) tripropyl phenol、2,3，5-，2,4，5-，2,3,4-，2,3，6-，2,4，6-or 3,45-) tri-butyl-phenol、1-naphthols、Beta naphthal、P-phenylphenol、O-phenylphenol etc..These aromatic hydroxy compounds, from commercially available and cost consideration, phenol, methylphenol, tert-butyl phenol, xylenol and o-phenylphenol are preferred, wherein particularly preferably phenol and o-phenylphenol.
In above-mentioned formula (I) and (II), the instantiation of its involved aroma dihydroxy compound include catechol, p-tert-butyl catechol, 2,2 '-xenol etc., wherein preferred catechol.
The method of " cooking different foods in one pot " of the present invention synthesis aromatic phosphoric ester amide compound, the mol ratio of wherein said single phenolic compounds and three oxyhalogen phosphorus is preferably 1.95～2.00:1, preferred mol ratio is 1.98～1.99:1, the mol ratio of described o-phenyl phenol compounds and described bisphenol compound and three oxyhalogen phosphorus is preferably 0.90～1.20:1, preferred mol ratio is 0.98～1.05:1, described lewis acid is any one in aluminum trichloride (anhydrous), anhydrous magnesium chloride or anhydrous zinc chloride, preferred anhydrous magnesium chloride, its consumption is common by general document.
The method of " cooking different foods in one pot " of the present invention synthesis aromatic phosphoric ester amide compound, the reaction of wherein said phenolic compound and three oxyhalogen phosphorus carries out preferably under the organic solvent that reaction is inertia is existed, preferred solvent is halogenated hydrocarbons and/or aromatic hydrocarbon, particularly preferably solvent made by 1,2 dichloroethanes and/or toluene.Under the organic solvent that reaction is inertia is existed, phenolic compound and phosphorus oxychloride react the monochloro that generates can be higher by 3～5% than solventless method for the content of di(2-ethylhexyl)phosphate phenolic ester, and the content of tricresyl phosphate phenolic ester reduces by 3～5% accordingly, be conducive to synthesis and the purification of follow-up aromatic phosphoric ester amide compound.Halogenated hydrocarbons and/or aromatic hydrocarbon is selected to make solvent and can reduce the residual quantity of product free chlorine hydrogen, can reduce reaction temperature more than 20 DEG C to reaction temperature is (conventional steam temperature) within 100 DEG C simultaneously, due to 1,2-dichloroethanes and/or aromatic hydrocarbon have price advantage and the solubility property of aromatic phosphoric ester amide compound is moderate, be conducive to purifying products, therefore particularly preferably 1,2 dichloroethanes and/or aromatic hydrocarbon make solvent.
The method of " cooking different foods in one pot " of the present invention synthesis aromatic phosphoric ester amide compound, wherein said lewis base preferably is selected from pyridine, containing at least one in the tertiary amine compounds representated by pyridine ring reagent or formula (III), more preferably N, at least one in accelerine, trimethylamine or triethylamine, owing to triethylamine is all three to replace in tertiary amine compounds and have price advantage especially and industrial source is extensive, so particularly preferably triethylamine.
R in formula (III)1、R2And R3From representing alkyl, alkenyl, cycloalkyl, aryl or aryl alkyl, R independently1、R2And R3Can identical can also differ.
The method of " cooking different foods in one pot " of the present invention synthesis aromatic phosphoric ester amide compound, in the reaction of wherein said single and/or many halophosphate compound and aminated compounds, the mode preferably added by lewis base particularly trisubstituted tertiary amine compounds in single and/or many halophosphate compound mixture with aminated compounds carries out, this feed way can suppress the generation of by-product, be conducive to the generation of aromatic phosphoric ester amide compound, its the highest yield can reach about 70% (calculating with the phenolic compound put into), higher by about 10～20% than the method that conventional documents is recorded.
The method of " cooking different foods in one pot " of the present invention synthesis aromatic phosphoric ester amide compound, in the reaction of wherein said single and/or many halophosphate compound and aminated compounds, reaction temperature is 0～100 DEG C, preferably 15～50 DEG C, more preferably 20～40 DEG C, temperature is too low is unfavorable for that reaction carries out, and too high, halophosphate compound facile hydrolysis also generates by-product.
The method of " cooking different foods in one pot " of the present invention synthesis aromatic phosphoric ester amide compound, wherein said single and/or many halophosphate compound is reacted with aminated compounds after terminating, it is warming up to 30～100 DEG C, preferably 50～80 DEG C, more preferably 60～70 DEG C, dissolve solid in reaction system, then respectively with acid water and/or caustic water wash, finally concentrate organic facies, crystallization, purification obtain aromatic phosphoric acid esteramides purpose compound.Treatment method can remove the list of residual and/or many halophosphoric acids phenolic ester and hydrolyzate, residual aniline, Amine from Tertiary Amine Hydrochloride and by-product simultaneously, and method is simple, and products obtained therefrom quality is good, is more suitable for industrialized production than the scheme mentioned in conventional documents.Described acid water is preferably hydrochloric acid, and described alkaline water is preferably aqueous sodium carbonate.
The method of " cooking different foods in one pot " of the present invention synthesis aromatic phosphoric ester amide compound, at least one in aminated compounds optimization aromatic monoamine compound that wherein said and single and/or many halogenated phosphates react, aromatic diamine compound, ring-type monoamine compound, cyclic diamine compound, more preferably aniline, morpholine, piperazine, p-phenylenediamine, 4,4 '-diaminodiphenyl-methane, 4, at least one in 4 '-DADPS.
Heretofore described aromatic phosphoric ester amide compound flame-retardant additive, it contains at least one compound in aforesaid aromatic phosphoric ester amide compound, total content >=85.0% of wherein said aromatic phosphoric ester amide compound, more preferably >=91.0%.Here aromatic phosphoric ester amide compound at least includes in P/N=1:1 in molecule (mol ratio) and molecule two kinds of P/N=1:2 (mol ratio), it is possible to also include some polymer.
Heretofore described aromatic phosphoric ester amide compound flame-retardant additive, aromatic phosphoric ester amide compound content >=85.0% of P/N=1:1 (mol ratio) in preferably described aromatic phosphoric ester amide compound molecule, more preferably >=91.0%；In wherein said molecule, the aromatic phosphoric ester amide compound of P/N=1:1 (mol ratio) including: the aromatic series biphosphonate amide compound representated by formula (IVa) and/or the aromatic series four phosphoric ester amides compound representated by formula (IVb)；
Wherein said formula (IVa) includes (IVa1) and (IVa2), formula (IVb) includes (IVb1) and (IVb2), the R in formula (IVa) and (IVb)4And R5Represent the phenolic group of single phenolic compounds in formula (Ia), R4And R5Can be the same or different；R in wherein said formula (IVa) and (IVb)4And R5Group can also form 5～7 rings thus the phenolic group of the diphenols compound represented in formula (Ib).
Heretofore described aromatic phosphoric ester amide compound flame-retardant additive, more preferably aromatic series biphosphonate amide compound content >=91.0% representated by described formula (IVa), and the aromatic series phosplate diamide compound representated by logical formula V, its content≤8.0%.
Wherein said logical formula V includes formula (V1) and (V2), the R in logical formula V represents the phenolic group of the single phenolic compounds in formula (Ia).
At aromatic phosphoric ester amide compound content >=85.0%, particularly >=91.0%, and when adding same dosage fire retardant, the aromatic phosphoric ester amide compound that in molecule, the flame retardant effect of the aromatic phosphoric ester amide compound of P/N=1:1 (mol ratio) and quality of materials are better than in molecule P/N=1:2 (mol ratio).
Beneficial effect: compared with prior art, the invention have the advantage that
1, adopt " cooking different foods in one pot ", react obtained intermediate list and/or many halophosphate compound need not be distilled and/or rectification purification, greatly reduce the required energy expended in production；
2, greatly simplifie the equipment produced required for this series products, and equipment corrosion damage is substantially reduced；
3, the recycling problem of single halophosphate compound is eliminated, simultaneously need to the yield of the by-product of the phosphoric acid triaryl phenolic ester recycled have also been obtained great reduction；
4, whole features simple and practical process, production cost is greatly lowered, and environmental protection pressure is little, and product quality is high.
Technical solution novelty in the present invention is unique, remarkable in economical benefits.
Detailed description of the invention:
Below in conjunction with the specific embodiment with preferably flame retardant effect, it is further elucidated with the present invention, it should be understood that these embodiments are merely to illustrate the present invention rather than restriction the scope of the present invention, after having read the present invention, the amendment of the various equivalent form of values of the present invention is all fallen within the application claims limited range by those skilled in the art.
Embodiment 1～3
The configuration stirring of 100ml four-hole bottle, thermometer, condensing tube, drying tube and acidic tail gas absorbing device, add phosphorus oxychloride 30.67g, anhydrous magnesium chloride 0.80g, it is warming up to interior temperature more than 70 DEG C, dropping phenol 36.71g/1,2-dichloroethanes 36.71g solution, time for adding more than 2 hours.Dropwise, be incubated 90～100 DEG C reaction 2 hours or more than, in HPLC control detection phenol residual≤0.1% (Area%) after be down to room temperature, obtain DCM/DPCP solution for standby.
The configuration stirring of 250ml four-hole bottle, thermometer, condensing tube and drying tube, add aniline 20.00g, 1,2-dichloroethanes 100.00g, and stirring is lower drips aforementioned DCM/DPCP solution, and during dropping, interior temperature is maintained at≤20 DEG C.Dropwise, be warming up to interior temperature more than 30 DEG C, drip triethylamine 20.00g/1,2-dichloroethanes 20.00g solution, dropwise, be incubated 30～40 DEG C and react 2 hours.It is warming up to interior temperature 60～70 DEG C, dissolves solid in reaction system.Wash 3 times with 30.00g/ insulation of 5% hydrochloric acid water 60～70 DEG C, being acidity to aqueous phase.Wash 3 times with 30.00g/ insulation of 5% aqueous sodium carbonate 60～70 DEG C again, being alkalescence to aqueous phase.Washing complete, concentrating under reduced pressure organic facies distillates to no liquid, adds 1,2-dichloroethanes 15.00g/ water 15.00g mixed liquor, is cooled to 5 DEG C of crystallization below 2 hours, filters, and washing is dry, obtains anilino-diphenyl phosphoester (being called for short DPPP).Result such as following table (calculates yield) in reference count for phenol:
Embodiment 4
The configuration stirring of 100ml four-hole bottle, thermometer, condensing tube, drying tube and acidic tail gas absorbing device, add phosphorus oxychloride 30.67g, anhydrous magnesium chloride 0.80g, it is warming up to interior temperature more than 85 DEG C, dropping phenol 37.27g/1,2-dichloroethanes 40.00g solution, time for adding more than 2 hours.Dropwise, be incubated 90～100 DEG C reaction 2 hours or more than, in HPLC control detection phenol residual≤0.1% (Area%) after be down to room temperature, obtain DCM/DPCP solution for standby.
The configuration stirring of 250ml four-hole bottle, thermometer, condensing tube and drying tube, add Piperazine anhydrous 9.26g, 1,2-dichloroethanes 200.00g, and stirring is lower drips aforementioned DCM/DPCP solution, and during dropping, interior temperature is maintained at≤20 DEG C.Dropwise, be warming up to interior temperature more than 30 DEG C, drip triethylamine 10.00g/1,2-dichloroethanes 20.00g solution, dropwise, be incubated 30～40 DEG C and react 2 hours.It is warming up to interior temperature 60～70 DEG C, dissolves solid in reaction system.Wash 3 times with 30.00g/ insulation of 5% hydrochloric acid water 60～70 DEG C, being acidity to aqueous phase.Wash 3 times with 30.00g/ insulation of 5% aqueous sodium carbonate 60～70 DEG C again, being alkalescence to aqueous phase.Wash complete, concentrating under reduced pressure organic facies distillates to no liquid, add 1,2-dichloroethanes 15.00g/ water 15.00g mixed liquor, be cooled to 5 DEG C of crystallization below 2 hours, filter, washing, dry, obtain 1, double; two (diphenyl phosphoester) 72.35g of 4-piperazinyl, yield 66.37% (calculating yield in reference count for phenol).
Embodiment 5
Using p-phenylenediamine 11.63g to replace Piperazine anhydrous, all the other operations, with embodiment 4, obtain double; two (diphenyl phosphoester)-Isosorbide-5-Nitrae-to benzene two phosphamide 71.75g, yield 63.29% (calculating yield in reference count for phenol).
Embodiment 6
Use 4,4 '-diaminodiphenyl-methane 21.32g replaces Piperazine anhydrous, and all the other operations, with embodiment 4, obtain double; two (diphenyl phosphoester)-4,4 '-diphenylmethane group two phosphamide 84.60g, yield 64.48% (calculating yield in reference count for phenol).
Embodiment 7
Using 4,4 '-DADPS 26.70g replaces Piperazine anhydrous, and all the other operations, with embodiment 4, obtain double; two (diphenyl phosphoester)-4,4 '-diphenyl sulfone two phosphamide 93.54g, yield 66.29% (calculating yield in reference count for phenol).
Embodiment 8
The configuration stirring of 100ml four-hole bottle, thermometer, condensing tube, drying tube and acidic tail gas absorbing device, add phosphorus oxychloride 30.67g, anhydrous magnesium chloride 0.80g, it is warming up to interior temperature 90 DEG C, dropping alpha-Naphthol 57.24g/1,2-dichloroethanes 60.00g solution, time for adding 3～4 hours.Dropwise, be incubated 90～100 DEG C of reactions 2 hours or more than, in HPLC, after control detection alpha-Naphthol residual≤0.1% (Area%), to be down to room temperature standby.
The configuration stirring of 250ml four-hole bottle, thermometer, condensing tube and drying tube, add morpholine 18.74g, 1,2-dichloroethanes 120.00g, and the lower dichloroethane solution dripping aforementioned chlorophosphate naphthol ester of stirring, during dropping, interior temperature is maintained at≤30 DEG C.Dropwising, continue dropping triethylamine 20.00g/1,2-dichloroethanes 20.00g solution, then insulation 40 DEG C is reacted 2 hours.It is warming up to interior temperature 60～70 DEG C, dissolves solid in reaction system.Wash 3 times with 30.00g/ insulation of 5% hydrochloric acid water 60～70 DEG C, being acidity to aqueous phase.Wash 3 times with 30.00g/ insulation of 5% aqueous sodium carbonate 60～70 DEG C again, being alkalescence to aqueous phase.Wash complete, concentrating under reduced pressure organic facies distillates to no liquid, add 1,2-dichloroethanes 15.00g/ water 15.00g mixed liquor, be cooled to 5 DEG C of crystallization below 2 hours, filter, washing, dry, obtain di(2-ethylhexyl)phosphate naphthol ester phosphinylidyne morpholine 58.44g, yield 70.19% (calculating yield in reference count for phenol), HPLC (Area%) 92.1308%.
Embodiment 9
The configuration stirring of 100ml four-hole bottle, thermometer, condensing tube, drying tube and acidic tail gas absorbing device, add phosphorus oxychloride 30.67g, anhydrous magnesium chloride 0.80g, it is warming up to interior temperature 90 DEG C, dropping Catechol 2 2.02g/1,2-dichloroethanes 45.00g solution, time for adding 2 hours.Dropwise insulation 90～100 DEG C to react more than 2 hours, HPLC is down to room temperature after control detection catechol residual≤0.1% (Area%) standby.
The configuration stirring of 250ml four-hole bottle, thermometer, condensing tube and drying tube, add p-phenylenediamine 10.82g, 1,2-dichloroethanes 120.00g, and the lower dichloroethane solution dripping aforementioned chlorophosphate naphthol ester of stirring, during dropping, interior temperature is maintained at≤30 DEG C.Dropwising, continue dropping triethylamine 10.00g/1,2-dichloroethanes 20.00g solution, then insulation 70 DEG C is reacted 2 hours.Add 1,2-dichloroethanes 50g and dissolve solid in reaction system.Wash 3 times with 30.00g/ insulation of 5% hydrochloric acid water 60～70 DEG C, being acidity to aqueous phase.Wash 3 times with 30.00g/ insulation of 5% aqueous sodium carbonate 60～70 DEG C again, being alkalescence to aqueous phase.Wash complete, concentrating under reduced pressure organic facies distillates to no liquid, add 1,2-dichloroethanes 15.00g/ water 15.00g mixed liquor, be cooled to 5 DEG C of crystallization below 2 hours, filter, washing, dry, obtain phosphamide compound 74.41g, yield 90.24% (calculating yield in reference count for catechol), HPLC (Area%) 95.3108%.
Embodiment 10
The configuration stirring of 100ml four-hole bottle, thermometer, condensing tube, drying tube and acidic tail gas absorbing device, add phosphorus oxychloride 31.28g, aluminum trichloride (anhydrous) 0.50g, be warming up to interior temperature 90 DEG C, dropping o-phenyl phenol 34.04g/ toluene 35.00g solution, time for adding 2 hours.Dropwise, be incubated 100 DEG C of reactions, HPLC is down to room temperature after control detection o-phenyl phenol residual≤0.1% (Area%) standby.
The configuration stirring of 250ml four-hole bottle, thermometer, condensing tube and drying tube, add morpholine 17.42g, toluene 150.00g, the lower dropping aforementioned (9 of stirring, 10-dihydro-9-oxy assorted-10-phospho hetero phenanthrene-10-oxide) phosphoryl chloride phosphorus oxychloride/toluene solution, during dropping, interior temperature is maintained at≤30 DEG C.Dropwising, be warming up to 50 DEG C, drip triethylamine 20.00g/ toluene 20.00g solution, then insulation 50 DEG C is reacted 2 hours.It is warming up to interior temperature 70 DEG C and dissolves solid in reaction system.Wash 3 times with 30.00g/ insulation of 5% hydrochloric acid water 60～70 DEG C, being acidity to aqueous phase.Wash 3 times with 30.00g/ insulation of 5% aqueous sodium carbonate 60～70 DEG C again, being alkalescence to aqueous phase.Wash complete, concentrating under reduced pressure organic facies distillates to no liquid, add toluene 15.00g/ water 15.00g mixed liquor, it is cooled to 5 DEG C of crystallization below 2 hours, filters, washing, dry, obtain phosphinylidyne morpholine amines 57.24g, yield 95.00% (calculating yield in reference count for o-phenyl phenol), HPLC (Area%) 96.5289%.

Claims (10)

1. the synthetic method of an aromatic phosphoric ester amide compound, it is characterised in that including:
(1) in the presence of a lewis acid catalyst, make to be selected from single phenolic compounds of formula (I a) and/or at least one phenolic compound in the bisphenol compound of formula (I b) and three oxyhalogen phosphorus reactions, generate single and/or many halophosphate compound.
Its formula of (I a) includes formula (I a1)、(Ⅰa2) and (I a3) representated by single phenolic compounds, formula (I b) includes formula (I b1) and (I b2) representated by bisphenol compound, described phenolic compound formula (I a), (I b) phenyl ring on have zero～multiple in the reaction for the alkyl of inactive substituent group, cycloalkyl, aryl alkyl or aryl.
(2) list without distillation and/or rectification purification making to obtain in step (1) and/or many halophosphate compound directly and have in molecule in the monoamine compound of a primary amino radical and/or secondary amino group and molecule and have at least one amines in the diamine compound of two primary amino radicals and/or secondary amino group, under lewis base exists, there is de-hydrogen halide, generate aromatic phosphoric ester amide compound.
Wherein monoamine compound includes formula (IIa1) shown in aromatic series monoamine compound and formula (IIa2) shown in aliphatic monoamine compound:
Formula (IIa1) in, Ar1Represent aryl, Y1Represent hydrogen atom, alkyl, alkenyl, cycloalkyl, aryl or aryl alkyl, Y1During for aryl, Y1With Ar1Can identical can also differ.
Formula (IIa2) in, Ay1Represent alkyl, alkenyl, cycloalkyl or aryl alkyl, Y2Represent hydrogen atom, alkyl, alkenyl, cycloalkyl or aryl alkyl；Or, Ay1With Y2Can being collectively forming 5～7 rings, now, above-mentioned ring can include oxygen atom and/or nitrogen-atoms as the atom forming this ring, and wherein, when the looped atom of shape is nitrogen-atoms, this nitrogen-atoms does not have hydrogen atom bonded thereto.
Wherein diamine compound includes formula (IIb1) shown in aromatic diamine compound and formula (IIb2) shown in aliphatic diamine compound:
Formula (IIb1) in, Ar2Represent respectively with the divalent group comprising aromatic rings of two nitrogen atom bondings in molecule, Y3And Y4Represent hydrogen atom, alkyl, alkenyl, cycloalkyl, aryl or aryl alkyl, Y independently of one another3And Y4Can identical can also differ.
Formula (IIb2) in, Ay2Represent alkylidene or ring alkylidene, the Y optionally on carbon atom or between carbon atom with aromatic group5And Y6Represent hydrogen atom, alkyl, alkenyl, cycloalkyl or aryl alkyl independently of one another；Or, Ay2With Y55～7 rings or Ay can be collectively forming2With Y65～7 rings or Ay can be collectively forming2With Y5And Y6It is collectively forming 5～7 rings.
2. the synthetic method of aromatic phosphoric ester amide compound according to claim 1, it is characterised in that: the mol ratio of described single phenolic compounds and three oxyhalogen phosphorus is 1.90～2.00:1；The mol ratio of described o-phenyl phenol compounds and described bisphenol compound and three oxyhalogen phosphorus is 0.90～1.20:1.
3. the synthetic method of aromatic phosphoric ester amide compound according to claim 1, it is characterized in that: the reaction of described phenolic compound and three oxyhalogen phosphorus carries out under the organic solvent that reaction is inertia is existed, and described organic solvent is halogenated hydrocarbons and/or aromatic hydrocarbon；Its reaction temperature is 70～120 DEG C.
4. the synthetic method of aromatic phosphoric ester amide compound according to claim 1, it is characterised in that: described lewis base preferably is selected from pyridine, containing at least one in the tertiary amine compounds representated by pyridine ring reagent or formula (III),
R in formula (III)1、R2And R3From representing alkyl, alkenyl, cycloalkyl, aryl or aryl alkyl, R independently1、R2And R3Can identical can also differ.
5. the synthetic method of aromatic phosphoric ester amide compound according to claim 4, it is characterized in that: described single and/or many halophosphate compound is with the reaction of aminated compounds, and the mode added by lewis base particularly trisubstituted tertiary amine compounds in single and/or many halophosphate compound mixture with aminated compounds carries out；Its reaction temperature is 0～100 DEG C.
6. the synthetic method of aromatic phosphoric ester amide compound according to claim 1, it is characterized in that: described single and/or many halophosphate compound is reacted with aminated compounds after terminating, it is warming up to 30～100 DEG C, dissolve solid in reaction system, then respectively with acid water and/or caustic water wash, organic facies is finally concentrated, crystallization purifying obtains aromatic phosphoric acid esteramides purpose compound；Described acid water is hydrochloric acid, and described alkaline water is aqueous sodium carbonate.
7. the synthetic method of aromatic phosphoric ester amide compound according to claim 1, it is characterised in that: the aminated compounds that described and single and/or many halogenated phosphates react is at least one in aromatic series monoamine compound, aromatic diamine compound, ring-type monoamine compound, cyclic diamine compound.
8. an aromatic phosphoric ester amide compound flame-retardant additive, it is characterized in that: this flame-retardant additive contains at least one compound in the aromatic phosphoric ester amide compound described in claim 1, content >=85.0% of wherein said aromatic phosphoric ester amide compound.
9. a kind of aromatic phosphoric ester amide compound flame-retardant additive according to claim 8, it is characterized in that: P/N=1:1 (mol ratio) in described aromatic phosphoric ester amide compound molecule, including: the aromatic series biphosphonate amide compound representated by formula (IVa) and/or the aromatic series four phosphoric ester amides compound representated by formula (IVb)；
Wherein said formula (IVa) includes (IVa1) and (IVa2), formula (IVb) includes (IVb1) and (IVb2), the R in formula (IVa) and (IVb)4And R5Represent the phenolic group of single phenolic compounds in formula (I a), R4And R5Can be the same or different；R in wherein said formula (IVa) and (IVb)4And R5Group can also form 5～7 rings thus the phenolic group of the diphenols compound represented in formula (I b).
10. a kind of aromatic phosphoric ester amide compound flame-retardant additive according to claim 9, it is characterized in that: aromatic series biphosphonate amide compound content >=91.0% representated by described formula (IVa), and the aromatic series phosplate diamide compound representated by formula (V), its content≤8.0%；
Wherein said formula (V) includes formula (V1) and (V2), the R in formula (V) represents the phenolic group of the single phenolic compounds in formula (I a).
CN201610164120.4A 2016-03-22 2016-03-22 Synthesis method of aromatic amide phosphate compound and flame retardant containing compound Pending CN105753900A (en)

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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
CN113717515A (en) * 2021-08-23 2021-11-30 安徽瑞琦塑胶科技有限公司 Antistatic heat-insulating plastic pipe and preparation method thereof

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CN102558228A (en) * 2011-12-19 2012-07-11 和夏化学(太仓)有限公司 Process for preparing diphenyl diphenoxy phosphoryl aniline compound
CN104395329A (en) * 2012-06-18 2015-03-04 大京化学株式会社 Method for producing phosphoric acid ester amides

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CN1358728A (en) * 2001-10-30 2002-07-17 上海晟霖新材料科技有限公司 Process for one-stage synthesizing substituted diaryl organic metal phosphate
CN102558228A (en) * 2011-12-19 2012-07-11 和夏化学(太仓)有限公司 Process for preparing diphenyl diphenoxy phosphoryl aniline compound
CN104395329A (en) * 2012-06-18 2015-03-04 大京化学株式会社 Method for producing phosphoric acid ester amides

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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
CN113717515A (en) * 2021-08-23 2021-11-30 安徽瑞琦塑胶科技有限公司 Antistatic heat-insulating plastic pipe and preparation method thereof

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