CN107501326B - A kind of compound and preparation method thereof, purposes and fire proofing - Google Patents
A kind of compound and preparation method thereof, purposes and fire proofing Download PDFInfo
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- CN107501326B CN107501326B CN201710779926.9A CN201710779926A CN107501326B CN 107501326 B CN107501326 B CN 107501326B CN 201710779926 A CN201710779926 A CN 201710779926A CN 107501326 B CN107501326 B CN 107501326B
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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 System
- 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
- C07F9/65746—Esters of oxyacids of phosphorus the molecule containing more than one cyclic phosphorus atom
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- 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
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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- 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
- C08K5/5399—Phosphorus bound to nitrogen
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- 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
Abstract
The present invention provides a kind of compound and preparation method thereof, purposes and fire proofing, which has flame-retarding characteristic, can reacting by DOPO and chemical compounds I and compound ii reaction product, then with NH2RNH2It reacts and obtains, and can be applied to prepare fire proofing, the fire proofing for being added to the compound has splendid flame retardant effect.
Description
Technical field
The present invention relates to polymeric material fields, in particular to a kind of compound and preparation method thereof, purposes and resistance
Combustible material.
Background technique
DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) is a kind of phosphorus phenanthrene class annular phosphate, is had
Good thermal stability and chemical stability.Based on the reactable of the P-H key in DOPO, can respectively with double bond, carbonyl, Asia
Necleophilic reaction occurs for amino and epoxy group etc., prepares the addition type and reactive flame retardant of DOPO base, and be widely used in epoxy
Resin (EP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT) (PBT), unsaturated polyester (UP) (UPR),
The high molecular materials such as poly- carbonic acid (PC), polyamide (PA), polyurethane (PU) it is fire-retardant.In order to improve DOPO and substrate compatibility and
Its negative effect etc. to material is reduced, environmentally friendly and diversified DOPO based flameproofing becomes current research hotspot.
Summary of the invention
The purpose of the present invention is to provide a kind of compounds can be widely used in high molecular material with flame-retarding characteristic
Preparation field, and it has been used for flame retardant effect.
Another object of the present invention is to provide a kind of preparation methods of above compound.
A further object of the present invention is to provide above compounds to prepare the application in fire proofing.
A further object of the present invention is to provide a kind of fire proofings, wherein containing above compound and having good resistance
Fire performance.
The embodiment of the present invention is achieved in that
A kind of compound has following general formula structure:
Wherein, G C1-C10Alkyl or alkoxy, C3-C7Naphthenic base or cycloalkyloxy,Wherein, R1、R2With
R3It is independently selected from C1-C6Alkyl, C1-C6Alkoxy, phenoxy group, phenyl or C3-C7Naphthenic base；
Y is O or NH, and Ar is phenyl, substituted-phenyl, 4,4'- xenyl, 2,4'- xenyl, 2,2'- xenyl, Isosorbide-5-Nitrae-naphthalene
Base, 1,5- naphthalene, 1,6- naphthalene or 1,7- naphthalene；Substituted-phenyl is preferably that 1,2- phenyl, 1,3- phenyl or Isosorbide-5-Nitrae-phenyl, Ar take
Dai Jiwei chlorine or bromine.
R is 1,2- phenyl, 1,3- phenyl, Isosorbide-5-Nitrae-phenyl, 4,4 '-xenyls, 2,4 '-xenyls, 2,2 '-xenyls, 1,
4- naphthalene, 1,6- naphthalene, 1,7- naphthalene, benzhydryl, diphenyl sulfoxide base, diphenyl sulfone, C1-C12 alkyl, contains 1,5- naphthalene
Phosphorus or siliceous C1-C16 alkyl.
Preferably, G is phenoxy group or phenyl, it is preferable that Ar is Isosorbide-5-Nitrae di-substituted-phenyl.
Purposes the present invention also provides above compound as fire retardant.
The preparation method of above compound, comprising: compound I is deposited with compound II in acid binding agent and is reacted at ambient,
Preferably, reaction temperature is -30 DEG C~120 DEG C, more preferably 10 DEG C~80 DEG C；Then it is reacted with compound III, it is preferable that
Reaction temperature be -20 DEG C~160 DEG C, preferred 20 DEG C~80 DEG C, by reaction product and NH2RNH2It is reacted.
Wherein, compound I isCompound II is HY-Ar-CHO, and compound III is
A kind of fire proofing, including above compound, it is preferable that it further include resin, preferably resin is macromolecule resin,
It preferably further include antioxidant or crosslinking agent.
The beneficial effect of the embodiment of the present invention is:
Compound provided by the invention has excellent flame-retarding characteristic, can be widely used in various types of resins or others
In material, especially high molecular material, to improve the flame retardant property of high molecular material.The compound is applied to prepare fire-retardant material
Material, such as when polyphosphazene polymer ester material, the flame retardant property of material can be obviously improved.
In addition, the preparation method of above compound provided by the invention, can be economical prepare the compound, and produce
Rate is high.Fire proofing containing the compound has good flame-retarding characteristic, is suitable for the application of in more demanding to flame retardant effect
Application environment.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Compound of the embodiment of the present invention and preparation method thereof, purposes and fire proofing are specifically described below.
A kind of compound has following general formula structure:
Wherein, G C1-C10Alkyl or alkoxy, C2-C10Unsaturated alkyl or unsaturated hydrocarbons oxygroup, C3-C7Naphthenic base or
Cycloalkyloxy,
For example, G can be selected from C1-C6Alkyl or alkoxy or C7-C10Alkyl or alkoxy, C1-C6Unsaturated alkyl or not
It is saturated oxyl or C7-C10Unsaturated alkyl or unsaturated hydrocarbons oxygroup, C3-C6Naphthenic base or C7Naphthenic base.
Wherein, R1、R2And R3It is independently selected from C1-C6Alkyl, C1-C6Unsaturated alkyl, C1-C6Alkoxy,
Phenoxy group, phenyl or C3-C7Naphthenic base.That is R1、R2And R3It can be identical group from each other and be also possible to different bases
Group.
Such as: R1、R2And R3It is independently selected from C1-C3Alkyl or C4-C6Alkyl, C2-C3Unsaturated alkyl or C4-C6No
Saturated hydrocarbyl, C1-C3Alkoxy or C4-C6Alkoxy, phenoxy group, phenyl, C3-C5Naphthenic base or C6-C7Naphthenic base.
Wherein, Y is O (oxygen) or NH, Ar are phenyl, substituted-phenyl, 4,4'- xenyl, 2,4'- xenyl, 2,2'- biphenyl
Base, Isosorbide-5-Nitrae-naphthalene, 1,5- naphthalene, 1,6- naphthalene or 1,7- naphthalene, such as monosubstituted phenyl or polysubstituted phenyl, for polysubstituted
Phenyl can be ortho position substitution, meta position replaces or contraposition replaces.Substituted-phenyl is preferably 1,2- phenyl, 1,3- phenyl or 1,4-
Phenyl.
R be 1,2- phenyl, 1,3- phenyl, 1,4- phenyl, 4,4'- xenyl, 2,4'- xenyl, 2,2'- xenyl, 1,
4- naphthalene, 1,5- naphthalene, 1,6- naphthalene, 1,7- naphthalene, benzhydryl, diphenyl sulfoxide base, diphenyl sulfone, C1-C12Alkyl, C2-
C12Unsaturated alkyl, phosphorous or siliceous C1-C16Alkyl.
As a preferred embodiment of the present invention, G can for example be selected from phenoxy group or phenyl.
As a preferred embodiment of the present invention, Ar for example can be Isosorbide-5-Nitrae di-substituted-phenyl, such as Isosorbide-5-Nitrae dichlorophenyl, 1,
4 dibromo phenyls etc..
Above compound can be prepared by the following method:
Chemical compounds I is deposited with compound ii in acid binding agent and is reacted at ambient, it is preferable that the reaction temperature of this step controls
It is -30 DEG C~120 DEG C, more preferably control is 10 DEG C~80 DEG C, it is further preferred that may be controlled to 30 DEG C~60 DEG C.
Such as reaction temperature can be controlled in -30 DEG C, -20 DEG C, -10 DEG C, 0 DEG C, 10 DEG C, 20 DEG C, 30 DEG C, 40 DEG C, 50
DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 100 DEG C, 120 DEG C etc., in actual fabrication process, specific reaction temperature might have certain upper
Lower deviation and feasible.
Acid binding agent can choose organic base and/or inorganic base, it can individually selection organic base or inorganic base, it can also be same
When using organic base and inorganic base mixture, such as: organic base can choose triethylamine, pyridine or n,N-Dimethylaniline
Deng.Inorganic base can choose natrium carbonicum calcinatum or Anhydrous potassium carbonate etc..It should be appreciated that acid binding agent not necessarily one-component,
Its mixture that can be a variety of inorganic bases, is also possible to the mixture of a variety of organic bases.
Wherein compound I isCompound II is HY-Ar-CHO, group representated by G, Y, Ar therein with
Group in above compound is identical.
As a preferred embodiment of the present invention, the equivalent proportion of acid binding agent, compound II and compound I is (2-2.5):
(2-2.5): 1, preferred (2-2.1): (2-2.1): 1.
Reaction time is advisable with 1-30h, and preferred 2-6h is preferable.
Compound I reacts the reaction product (intermediate compound I) that can be prepared with compound II are as follows:
It is represented in the group and above compound of the representatives such as G, Y, Ar therein
Group is identical.
As a preferred embodiment of the present invention, compound I and compound II are reacted in organic solvent.It is preferred that
Ground, the organic solvent are selected from ether, methylene chloride, chloroform, tetrahydrofuran, dioxane, toluene, dimethylbenzene, N, N- diformazan
One or more of base formamide or glycol dimethyl ether.
Then product obtained by chemical compounds I being reacted with compound ii is reacted with compound III, wherein compound III are as follows:Miscellaneous -10- phospho hetero phenanthrene -10- the oxide (DOPO) of scientific name 9,10- dihydro-9-oxy.
Preferably, the reaction temperature control of this step is -20 DEG C~160 DEG C, and preferred control is 0 DEG C~100 DEG C, more excellent
The control of choosing is 20 DEG C~80 DEG C.Such as by reaction temperature control -20 DEG C, -10 DEG C, 0 DEG C, 10 DEG C, 30 DEG C, 50 DEG C, 70 DEG C,
90 DEG C, 100 DEG C, 120 DEG C, 140 DEG C, 160 DEG C etc..
Reaction time is preferably controlled in 1-30h, preferred 4-8h；
After being reacted with compound III, by reaction product and NH2RNH2It is reacted.Wherein group representated by R and above R
It is identical.
Reaction time is preferably controlled to 1-30h, and preferred control is preferred in 3-6h.
In a part of embodiment of the invention, the reaction product and compound III of chemical compounds I and compound ii are having
It is reacted in solvent, so that reactant is directly easier to haptoreaction.Preferably, which can be selected from ether, two
Chloromethanes, chloroform, tetrahydrofuran, dioxane, toluene, dimethylbenzene, N,N-dimethylformamide, glycol dimethyl ether, ethyl alcohol,
One or more of butanol, ethylene glycol, glycol monoethyl ether, acetic acid.
Such as: it is reacted by reaction process below:
Wherein, reaction product and NH2RNH2Reaction temperature be 20 DEG C -150 DEG C under the conditions of carry out, such as: reaction 20
DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C of conditions
Lower progress, it is furthermore preferred that reaction carries out under the conditions of 60 DEG C -130 DEG C.In addition, the reaction time can control in 1-30h, preferably
For 3-6h.
As the preferred embodiment of the compounds of this invention preparation method, reaction product and NH2RNH2Reaction response can be with
It deposits in catalyst and carries out at ambient, it is preferable that the catalyst is selected from lewis acid, inorganic acid, organic acid and acid ion
One or more of exchanger resin, it is highly preferred that the catalyst be selected from alchlor, the concentrated sulfuric acid, benzene sulfonic acid, to methylbenzene
One or more of sulfonic acid and acid-exchange resin, most preferably, the catalyst are selected from p-methyl benzenesulfonic acid and acid
One or both of property ion exchange resin.
As the preferred embodiment of the compounds of this invention preparation method, reaction product and NH2RNH2Reaction response in,
The dosage of catalyst accounts for the 0.01%~20% of reactant gross weight, more preferably 5%~10%, such as 6%, 7%, 8%, 9%
Deng.Wherein reactant gross weight refers to: the NH as reactant3And the sum of the weight of product obtained by step 2 reaction.
Further, the preferred embodiment as the compounds of this invention preparation method is changed in reaction, the reaction product
With NH2RNH2Feed ratio be 1:2~8, preferably 1:2~3.Herein, reaction product refers in above-mentioned process obtained in step 2
Reaction product.
Above-mentioned compound can be used for being added into macromolecule resin etc. to prepare fire proofing, be based on this, this hair
It is bright that a kind of fire proofing is also provided comprising above-mentioned compound and macromolecule resin material, for example (,) it is epoxy resin (EP), poly-
Ethylene glycol terephthalate (PET), polybutylene terephthalate (PBT) (PBT), unsaturated polyester (UP) (UPR), poly- carbonic acid (PC),
The high molecular materials such as polyamide (PA), polyurethane (PU).
Optionally, can also include antioxidant in fire proofing, such as 2,6- three-level butyl -4- methylphenol, three monooctyl esters,
Three last of the ten Heavenly stems esters, three (Lauryl Alcohol) esters and three (16 carbon alcohol) esters etc..
It optionally, can also include crosslinking agent in fire proofing.
Feature and performance of the invention are described in further detail with reference to embodiments.
Embodiment 1
In with mechanical stirring, therm-param method, drying reactor in, the parahydroxyben-zaldehyde of 2.0mol is added
The methylene chloride (solvent) of (compound ii), 600.0mL and the triethylamine (acid binding agent) of 2.0mol are dispersed with stirring uniformly at room temperature
Afterwards, start the dichloro-phenyl phosphate (chemical compounds I) that 1.0mol is added dropwise.It finishes, filters, obtain dichloromethane solution and (contain in solution
Have intermediate I and remaining triethylamine hydrochloride), dichloromethane solution is washed with water to the neutral triethylamine salt for removing remnants
Hydrochlorate separates organic layer (dichloromethane solvent and intermediate I) and anhydrous sodium sulfate desiccant dryness 1h is added, is filtered to remove dry
Organic layer is distilled to recover methylene chloride by drying prescription, and obtaining light yellow clear liquid i.e. intermediate I, (wherein, G is phenoxy group, and Y is
O, Ar are phenyl).
DOPO the and 400.0mL ethyl alcohol of intermediate I, 2.0mol that 1.0mol obtained above is added in reactor is molten
Agent, 40 DEG C are stirred to react 6.0h, are down to room temperature, filtering, and intermediate II -1 is obtained after filter cake ethanol washing, and (wherein, G is benzene oxygen
Base, Y are oxygen, and Ar is phenyl).
FTIR (KBr) is carried out to obtained flame retardant intermediate II -1 (G is phenoxy group, and Y is oxygen, and X OH, Ar are phenyl)
Measurement, test result is as follows: v/cm-1: 3266 (O-H), 2935 (saturation C-H), 1592,1498,1481 and 1430 (phenyl ring bones
Frame), 1198-1298 (P=O), 1156 (C-O), 968 and 929 (bound phosphate groups characteristic absorptions), 845 and 756 (phenyl ring list takes
Generation and contraposition replace).
Obtained intermediate II -1 (G is phenoxy group, and Y is oxygen, and X OH, Ar are phenyl ring) is carried out1H NMR (ppm,
DMSO-d6) test, test result is as follows: δ=6.692-7.753 (m, 29H), 5.107 (d, 2H), 3.411 (s, 2H).
The intermediate II -1 of 1.0mol obtained above, 1,6- hexamethylene diamine (the starting original of 2.1mol are added in reactor
Material III), the p-methyl benzenesulfonic acid (catalyst) of 800.0mL alcohol solvent and 0.05mol, 80 DEG C are stirred to react 8.0h, are down to room
Temperature filters, and obtains fire retardant 1a-1 after filter cake ethanol washing (G is phenoxy group, and Y is oxygen, and Ar is phenyl ring).
Obtained fire retardant 1a-1 is carried out1H NMR (ppm, DMSO-d6) test, test result is as follows: δ=6.668-
7.824 (m, 29H), 4.216 (dd, 2H), 2.581-2.723 (m, 8H), 2.447 (s, 2H), 2.108 (s, 4H), 1.382-
1.613 (m, 8H), 1.154-1.301 (m, 8H).
It can be determined that by above-mentioned test result, the structure of obtained fire retardant 1a-1 are as follows:
Embodiment 2
In with mechanical stirring, therm-param method, drying reactor in, the parahydroxyben-zaldehyde of 3.0mol is added
The toluene (solvent) of (compound ii), 800.0mL and the pyridine (acid binding agent) of 3.0mol are opened after being dispersed with stirring at 35 DEG C uniformly
Begin the phenyl phosphonyl chloride (chemical compounds I) that 1.5mol is slowly added dropwise.Finish, filter, obtain toluene solution (containing intermediate I with
Remaining pyridine hydrochloride), toluene solution is washed with water to the neutral pyridine hydrochloride for removing remnants, separates organic layer (first
Benzene solvent and intermediate I) and anhydrous magnesium sulfate desiccant dryness 1h is added, it is filtered to remove desiccant, organic layer is distilled to recover
Toluene, residue, that is, intermediate I (G is phenyl, and Y is oxygen, and Ar is phenyl ring).
DOPO the and 550.0mL ethyl alcohol of intermediate I, 2.0mol that 1.0mol obtained above is added in reactor is molten
Agent, 50 DEG C are stirred to react 5.0h, are down to room temperature, filtering, and obtaining intermediate II -2 after filter cake ethanol washing, (G is phenyl, and Y is
Oxygen, Ar are phenyl ring).
Intermediate II -2 is carried out1H NMR (ppm, DMSO-d6) test, test result is as follows: δ=6.672-7.698 (m,
29H), 5.015-5.108 (d, 2H), 2.721 (s, 2H).
The intermediate II -2 of 1.5mol obtained above, 1,6- hexamethylene diamine (the starting original of 3.0mol are added in reactor
Material III), the acid-exchange resin (catalyst) of 1000.0mL toluene solvant and 0.06mol, 100 DEG C are stirred to react 7.0h,
It is down to room temperature, filters, filter cake obtains fire retardant after being washed with toluene (G is phenyl, and Y is oxygen, and Ar is phenyl ring).
FTIR (KBr) test is carried out to obtained fire retardant 1a-2, test result is as follows: v/cm-1: 3352 (O-H), 2947
(saturation C-H), 1598,1521,1471 and 1450 (phenyl ring skeletons), 1262-1287 (P=O), 1216 (C-O), 958 and 949
(bound phosphate groups characteristic absorption), 849 and 762 (phenyl ring is monosubstituted and contraposition replaces).
Obtained fire retardant 1a-2 is carried out1H NMR (ppm, DMSO-d6) test, test result is as follows: δ=6.683-
7.851 (m, 29H), 4.226 (dd, 2H), 2.579-2.730 (m, 8H), 2.439 (s, 2H), 2.118 (s, 4H), 1.402-
1.624 (m, 8H), 1.161-1.311 (m, 8H).
By the above test data it is known that the structural formula of fire retardant 1a-2 are as follows:
Wherein G is phenyl, and Y O, Ar are phenyl ring.
Embodiment 3
Intermediate II -1 is prepared by method same as Example 1.
In reactor the intermediate II -1 of 1.0mol, 2.0mol 4,4'- diaminodiphenyl-methane (starting material
III), the p-methyl benzenesulfonic acid (catalyst) of 800.0mL toluene solvant and 0.10mol, 100 DEG C are stirred to react 8.0h, are down to room
Temperature, filtering, filter cake obtain flame-retardant monomer 1a-3 after being washed with toluene (G is phenoxy group, and Y is oxygen, and Ar is phenyl ring).
Obtained fire retardant 1a-3 is carried out1H NMR (ppm, DMSO-d6) test, test result is as follows: δ=6.209-
7.801 (m, 45H), 4.105-4.156 (m, 6H), 4.071-4.096 (dd, 2H), 3.970-4.072 (d, 4H).
Thus judge the structure of fire retardant 1a-3 are as follows:
Embodiment 4
Intermediate II -2 is prepared according to method shown in embodiment 2.
The intermediate II -2 of 1.2mol obtained above, the 4,4'- diamino-diphenyl of 2.5mol are added in reactor
The p-methyl benzenesulfonic acid (catalyst) of methane (starting material III), 950.0mL glycol dinitrate ether solvents and 0.10mol, 80 DEG C
It is stirred to react 9.0h, is down to room temperature, is filtered, filter cake obtains flame-retardant monomer 1a-4 after being washed with toluene (G is phenyl, and Y is oxygen, Ar
For phenyl ring).
Obtained fire retardant 1a-3 is carried out1H NMR (ppm, DMSO-d6) test, test result is as follows: δ=6.320-
7.812 (m, 45H), 4.012-4.031 (dd, 2H), 3.807-3.892 (m, 4H), 3.043-3.066 (m, 6H).
Thus judge the structure of fire retardant 1a-4 are as follows:
Embodiment 5
The intermediate II -1 of 1.5mol, the m-phenylene diamine (MPD) (starting material III) of 3.5mol, 950.0mL second two in reactor
The p-methyl benzenesulfonic acid (catalyst) of diethylene glycol diethyl ether and 0.05mol, after 125 DEG C are stirred to react 12h, is down to room temperature, filtering, filter cake
Obtain flame-retardant monomer 1a-5 after the washing of spent glycol diethyl ether (G is phenoxy group, and Y is oxygen, and Ar is phenyl ring)
1H NMR (ppm, DMSO-d6) test is carried out to obtained fire retardant 1a-5, test result is as follows: δ=5.951-
8.120 (m, 37H), 4.011-4.034 (dd, 2H), 3.443 (s, 4H).3.231 (s, 2H).
Thus judge the structure of fire retardant 1a-5 are as follows:
Embodiment 6
The intermediate II -2 of 1.5mol obtained above, the m-phenylene diamine (MPD) (starting material of 3.8mol are added in reactor
III), 1000.0mL ethylene glycol solvent and 0.20mol are down to room temperature after 120 DEG C are stirred to react 7.0h to sulfuric acid (catalyst),
Filtering obtains flame-retardant monomer 1a-6 after the washing of filter cake spent glycol (G is phenyl, and Y is oxygen, and Ar is phenyl ring).
1H NMR (ppm, DMSO-d6) test is carried out to obtained fire retardant 1a-6, test result is as follows: δ=5.906-
8.102 (m, 37H), 3.981-3.998 (dd, 2H), 3.383 (s, 4H).3.135 (s, 2H).
Thus judge the structure of fire retardant 1a-6 are as follows:
Embodiment 7
Step I: in mechanical stirring, therm-param method, drying reactor in, be added 2.2mol to amino
The triethylamine (acid binding agent) of benzaldehyde (starting material II), the toluene (solvent) of 1200.0mL and 2.3mol, stirring point at 15 DEG C
After dissipating uniformly, starts the dichloro-phenyl phosphate (starting material I) that 1.0mol is slowly added dropwise, finish, continue after being stirred to react 4h, mistake
Filter obtains toluene solution (containing intermediate I -3 and remaining triethylamine hydrochloride).
Step II: toluene solution is washed with water to the neutral triethylamine hydrochloride for removing remnants, separates organic layer (toluene
Solvent and intermediate I -3) and anhydrous magnesium sulfate desiccant dryness 2.5h is added, it is filtered to remove desiccant, organic layer is distilled back
Receive toluene, residue, that is, intermediate I -3 (G is phenyl, and Y NH, Ar are phenyl ring).
The structure of gained intermediate I -3 are as follows:
Step III: be added in reactor the intermediate I -3 of 1.5mol obtained above, the DOPO of 3.0mol and
1500.0mL alcohol solvent after 60 DEG C are stirred to react 8.0h, is down to room temperature, filtering, obtains intermediate after filter cake ethanol washing
II -3 (G is phenyl, and Y NH, X OH, Ar are phenyl ring).
Intermediate II -3 is carried out1H NMR (ppm, DMSO-d6) test, test result is as follows: δ=6.592-7.704 (m,
29H), 4.872-4.788 (dd, 2H), 4.212-4.279 (s, 2H), 2.724 (s, 2H).
Thus judge the structure of intermediate II -3 are as follows:
Step IV: the intermediate II -3 of 1.0mol obtained above, the hexamethylene diamine (starting of 4.0mol being added in reactor
Raw material III), the strong-acid ion exchange resin (catalyst) of 1200.0mL ethylene glycol diethyl ether solvent and 0.30mol, 125 DEG C are stirred
After mixing reaction 8.5h, it is down to room temperature, is filtered, obtaining fire retardant 1b-1 after the washing of filter cake spent glycol diethyl ether, (G is phenyl, and Y is
NH, Ar are phenyl ring).
Obtained fire retardant 1b-1 is carried out1H NMR (ppm, DMSO-d6) test, test result is as follows: δ=6.762-
8.095 (m, 29H), 4.116 (dd, 2H), 2.612-2.634 (m, 8H), 2.405 (s, 2H), 2.201 (s, 4H), 1.346-
1.531 (m, 8H), 1.148-1.363 (m, 8H).
Thus judge, the structure of fire retardant 1b-1 are as follows:
Embodiment 8
In with mechanical stirring, therm-param method, drying reactor in, the para aminotenzaldehyde of 4.1mol is added
The toluene (solvent) of (starting material II), 1200.0mL and the triethylamine (acid binding agent) of 4.1mol are dispersed with stirring at 55 DEG C uniformly
Afterwards, start the phenyl phosphonyl chloride (starting material I) that 2.0mol is slowly added dropwise.It finishes, filters, obtain toluene solution (in containing
Mesosome I -4 and remaining triethylamine hydrochloride), toluene solution is washed with water to the neutral triethylamine hydrochloride for removing remnants,
It separates organic layer (toluene solvant and intermediate I -4) and anhydrous sodium sulfate desiccant dryness 3h is added, be filtered to remove desiccant, it will
Organic layer is distilled to recover toluene, and residue is intermediate I -4 (G is phenyl, and Y NH, Ar are phenyl ring).
To the carry out FTIR (KBr), v/cm of intermediate I -4 (G is phenyl, and Y NH, Ar are phenyl ring)-1Test, test result
Are as follows: 3382 (N-H), 3070 (phenyl ring C-H), 1715 (aldehyde radicals), 1584,1542 and 1464 (phenyl ring skeletons), 1288 (P=O),
1213,1160 and 1056 (C-O and C-N), 986 (bound phosphate groups characteristic absorptions), 858 and 756 (phenyl ring is monosubstituted and contraposition takes
Generation).
Intermediate I -4 (G is phenyl, and Y NH, Ar are phenyl ring) is carried out simultaneously1H NMR (ppm, DMSO-d6) test, is surveyed
Test result is as follows: δ=9.914 (s, 2H), 6.672-7.729 (m, 13H), 4.462 (s, 2H).
Thus judge intermediate I -4 are as follows:
DOPO the and 550.0mL ethyl alcohol of intermediate I -4,2.1mol that 1.0mol obtained above is added in reactor is molten
Agent, 50 DEG C are stirred to react 4.0h, are down to room temperature, filtering, and obtaining intermediate II -4 after filter cake ethanol washing, (G is phenyl, and Y is
NH, X OH, Ar are phenyl ring).
FTIR (KBr) is carried out to intermediate II -4 (G is phenyl, and Y NH, X OH, Ar are phenyl ring), v/cm-1Test is surveyed
Test result is as follows: 3289-3432 (O-H and N-H), 2965 (saturation C-H), 1584,1558,1476 and 1423 (phenyl ring skeletons),
1256,1293 (P=O), 1216 (C-O), 982 and 965 (bound phosphate groups characteristic absorptions), 862 and 753 (phenyl ring it is monosubstituted and
Contraposition replaces).
Intermediate II -4 is carried out simultaneously1H NMR (ppm, DMSO-d6) test, test result is as follows: δ=6.541-
7.628 (m, 29H), 4.657-4.692 (dd, 2H), 4.314 (s, 2H), 3.021 (s, 2H).
Thus judge, intermediate II -4 are as follows:
The intermediate II -4 of 1.0mol obtained above, the hexamethylene diamine (starting material of 5.0mol are added in reactor
III), the p-methyl benzenesulfonic acid (catalyst) of 1200.0mL ethylene glycol diethyl ether solvent and 0.30mol, 125 DEG C are stirred to react 9.5h
Afterwards, it is down to room temperature, is filtered, obtaining fire retardant 1b-2 after the washing of filter cake spent glycol diethyl ether, (G is phenyl, and Y NH, Ar are benzene
Ring).
Obtained fire retardant 1b-2 is carried out1H NMR (ppm, DMSO-d6) test, test result is as follows: δ=6.246-
8.073 (m, 29H), 4.316 (dd, 2H), 2.601-2.621 (m, 8H), 2.445 (s, 2H), 2.221 (s, 4H), 1.329-
1.530 (m, 8H), 1.152-1.353 (m, 8H).
Thus judge fire retardant 1b-2 are as follows:
Embodiment 9
Synthesize intermediate I -3 by the method in embodiment 7.And then in continuing to synthesize according to the method in embodiment 7
Mesosome II -3 (G is phenoxy group, and Y NH, X OH, Ar are phenyl ring).
The intermediate II -3 of 1.0mol obtained above, the 4,4- diamino-diphenyl first of 6.5mol are added in reactor
The strong-acid ion exchange resin (catalyst) of alkane (starting material III), 1550.0mL xylene solvent and 0.45mol, 120 DEG C
After being stirred to react 10.5h, it is down to room temperature, is filtered, filter cake obtains fire retardant 1b-3 after being washed with dimethylbenzene (G is phenoxy group, and Y is
NH, Ar are phenyl ring).
Obtained fire retardant 1b-3 is carried out1H NMR (ppm, DMSO-d6) test, test result is as follows: δ=6.113-
8.201 (m, 45H), 4.116-4.206 (m, 6H), 4.062-4.087 (dd, 2H), 3.956-4.026 (d, 4H).
Thus judge the result of fire retardant 1b-3 are as follows:
Embodiment 10
Synthesize intermediate I -4 by method described in embodiment 8, and continues to close according to method described in embodiment 8 in turn
At obtaining intermediate II -4 (G is phenyl, and Y NH, X OH, Ar are phenyl ring).
The intermediate II -4 of 1.0mol obtained above, the 4,4- diamino-diphenyl first of 5.5mol are added in reactor
The p-methyl benzenesulfonic acid (catalyst) of alkane (starting material III), 1400.0mL ethylene glycol diethyl ether solvent and 0.35mol, 120 DEG C
After being stirred to react 12.5h, be down to room temperature, filter, filter cake spent glycol diethyl ether washing after obtain fire retardant 1b-4 (G is phenyl,
Y is NH, and Ar is phenyl ring).
Obtained fire retardant 1b-4 is carried out1H NMR (ppm, DMSO-d6) test, test result is as follows: δ=6.113-
8.201 (m, 45H), 4.116-4.206 (m, 6H), 4.062-4.087 (dd, 2H), 3.956-4.026 (d, 4H).
Thus judge fire retardant 1b-4 are as follows:
Embodiment 11
Synthesize intermediate I -3 by the method in embodiment 7.And then in continuing to synthesize according to the method in embodiment 7
Mesosome II -3 (G is phenoxy group, and Y NH, X OH, Ar are phenyl ring).
The intermediate II -3 of 1.0mol obtained above, the m-phenylene diamine (MPD) (starting material of 3.5mol are added in reactor
III), the strong-acid ion exchange resin (catalyst) of 1450.0mL xylene solvent and 0.40mol, 125 DEG C are stirred to react
After 11.5h, it is down to room temperature, is filtered, filter cake obtains fire retardant 1b-5 after being washed with dimethylbenzene (G is phenoxy group, and Y NH, Ar are benzene
Ring).
Fire retardant 1b-5 is carried out1H NMR (ppm, DMSO-d6) test, test result is as follows: δ=6.010-8.208 (m,
37H), 4.302-4.328 (dd, 2H), 4.243 (s, 4H).4.103 (s, 2H).
Embodiment 12
Synthesize intermediate I -4 by method described in embodiment 8, and continues to close according to method described in embodiment 8 in turn
At obtaining intermediate II -4 (G is phenyl, and Y NH, X OH, Ar are phenyl ring).
The intermediate II -4 of 1.0mol obtained above, the m-phenylene diamine (MPD) (starting material of 4.5mol are added in reactor
III), the p-methyl benzenesulfonic acid (catalyst) of 1350.0mL ethylene glycol diethyl ether solvent and 0.30mol, 125 DEG C are stirred to react
After 10.0h, it is down to room temperature, is filtered, obtaining fire retardant 1b-6 after the washing of filter cake spent glycol diethyl ether, (G is phenyl, Y NH, Ar
For phenyl ring).
Fire retardant 1b-6 is carried out1H NMR (ppm, DMSO-d6) test, test result is as follows: δ=6.032-8.198 (m,
37H), 4.310-4.326 (dd, 2H), 4.250 (s, 4H), 4.118 (s, 2H).
Thus judge fire retardant 1b-6 are as follows:
Embodiment 13
Fire retardant 1b-1 is prepared referring to the inventory and preparation step of each substance in embodiment 7.Wherein difference is only that
The reaction condition (temperature, pressure are different) of each step, the inventory of each reaction step is same as Example 7, carries out 10 altogether
The reaction condition of group, each group reaction is as shown in the table:
1 embodiment of table, 13 each group reaction condition tables of data
Fire retardant 1b-1 has been prepared after reaction.
Embodiment 14
According to the reaction condition of each step in embodiment 7, (reaction temperature, reaction pressure are same as Example 7, difference
It is in feed ratio difference), while 10 groups of experiments are carried out, the inventory of each group experiment is as shown in table 2 and table 3:
In the experiment of 2 embodiment of table, 10 each group, the parameter list that feeds intake is reacted in step I
In the experiment of 3 embodiment of table, 10 each group, the parameter list that feeds intake is reacted in step IV
Wherein the group in table 2 and table 3 is in one-to-one relationship.And fire retardant 1b-1 is prepared after reacting.
Embodiment 15
The present embodiment provides a kind of fire proofings, by weight percentage, wherein containing epoxy resin (EP) 80%, implement
In addition fire retardant 1a-1 5% in example 1 also contains antioxidant, crosslinking agent.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.Reality of the invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of selected implementation of the invention
Example.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (31)
1. a kind of compound, which is characterized in that have following general formula structure:
Wherein, G C1-C10Alkyl or alkoxy, C3-C7Naphthenic base or cycloalkyloxy,Wherein, R1、R2With
R3It is independently selected from C1-C6Alkyl, C1-C6Alkoxy, phenoxy group, phenyl or C3-C7Naphthenic base；
Y is O or NH, and Ar is phenyl, Isosorbide-5-Nitrae dichlorophenyl, Isosorbide-5-Nitrae dibromo phenyl, 4,4'- xenyl, 2,4'- xenyl, 2,2'- connection
Phenyl, 1,4- naphthalene, 1,5- naphthalene, 1,6- naphthalene or 1,7- naphthalene；
R is 1,2- phenyl, 1,3- phenyl, 1,4- phenyl, 4,4'- xenyl, 2,4'- xenyl, 2,2'- xenyl, 1,4- naphthalene
Base, 1,5- naphthalene, 1,6- naphthalene, 1,7- naphthalene, benzhydryl, diphenyl sulfoxide base, diphenyl sulfone, C1-C12It is alkyl, phosphorous or contain
Silicon C1-C16Alkyl.
2. compound as described in claim 1, G is phenoxy group or phenyl.
3. such as purposes of the described in any item compounds of claim 1-2 as fire retardant.
4. such as the preparation method of the described in any item compounds of claim 1-2 characterized by comprising by chemical compounds I and change
It closes object II and is deposited in acid binding agent and reacted at ambient, then reacted with compound III, by reaction product and NH2RNH2It is reacted；
Wherein, chemical compounds I isCompound ii is HY-Ar-CHO, and compound III is
5. the preparation method of compound as claimed in claim 4, chemical compounds I and compound ii reaction temperature are -30 DEG C~120
℃。
6. the preparation method of compound as claimed in claim 5, chemical compounds I and compound ii reaction temperature are 10 DEG C~80
℃。
7. the preparation method of compound as claimed in claim 4 deposits chemical compounds I and compound ii at ambient in acid binding agent
After reaction, the reaction temperature reacted with compound III is -20 DEG C~160 DEG C.
8. the preparation method of compound as claimed in claim 7 deposits chemical compounds I and compound ii at ambient in acid binding agent
After reaction, the reaction temperature reacted with compound III is 20 DEG C~80 DEG C.
9. the preparation method of compound as claimed in claim 4, which is characterized in that acid binding agent, compound ii and chemical compounds I
Molar ratio is (2-2.5) ︰ (2-2.5) ︰ 1.
10. the preparation method of compound as claimed in claim 9, which is characterized in that acid binding agent, compound ii and chemical compounds I
Molar ratio be (2-2.1) ︰ (2-2.1) ︰ 1.
11. the preparation method of compound as claimed in claim 4, which is characterized in that reaction product and the NH2RNH2It is anti-
It should be carried out under the conditions of temperature is 20 DEG C -150 DEG C.
12. the preparation method of compound as claimed in claim 11, which is characterized in that reaction product and the NH2RNH2It is anti-
It should be carried out under the conditions of temperature is 60 DEG C -130 DEG C.
13. the preparation method of compound as claimed in claim 11, which is characterized in that reaction product and the NH2RNH2It is anti-
It should deposit in catalyst and carry out at ambient.
14. the preparation method of compound as claimed in claim 13, which is characterized in that the catalyst is selected from by Louis
Acid, inorganic acid, organic acid and acid-exchange resin composition group in any one or a few.
15. the preparation method of compound as claimed in claim 14, which is characterized in that the catalyst be selected from alchlor,
One or more of the concentrated sulfuric acid, benzene sulfonic acid, p-methyl benzenesulfonic acid and acid-exchange resin.
16. the preparation method of compound as claimed in claim 15, which is characterized in that the catalyst is selected to methylbenzene sulphur
One or both of acid and acid-exchange resin.
17. the preparation method of compound as claimed in claim 13, which is characterized in that the dosage of the catalyst accounts for reactant
The 0.01%~20% of total weight.
18. the preparation method of compound as claimed in claim 17, which is characterized in that the dosage of the catalyst accounts for reactant
The 5%~10% of total weight.
19. the preparation method of compound as claimed in claim 11, which is characterized in that the reaction product and the NH2RNH2
Molar ratio be 1:2~8.
20. the preparation method of compound as claimed in claim 19, which is characterized in that the reaction product and the NH2RNH2
Molar ratio be 1:2~3.
21. the preparation method of compound as claimed in claim 4, which is characterized in that the acid binding agent be selected from organic base and/or
Inorganic base.
22. the preparation method of compound as claimed in claim 21, which is characterized in that the organic base includes triethylamine, pyrrole
Pyridine or N, accelerine.
23. the preparation method of compound as claimed in claim 21, which is characterized in that the inorganic base includes natrium carbonicum calcinatum
Or Anhydrous potassium carbonate.
24. the preparation method of compound as claimed in claim 4, which is characterized in that chemical compounds I and compound ii are organic molten
It is reacted in agent.
25. the preparation method of compound as claimed in claim 24, which is characterized in that the organic solvent is selected from ether, two
In chloromethanes, chloroform, tetrahydrofuran, dioxane, toluene, dimethylbenzene, N,N-dimethylformamide or glycol dimethyl ether
It is one or more of.
26. the preparation method of compound as claimed in claim 4, which is characterized in that chemical compounds I reacts production with compound ii
Object is reacted in organic solvent with compound III.
27. the preparation method of compound as claimed in claim 26, which is characterized in that the organic solvent is selected from ether, two
Chloromethanes, chloroform, tetrahydrofuran, dioxane, toluene, dimethylbenzene, N,N-dimethylformamide, glycol dimethyl ether, ethyl alcohol,
One or more of butanol, ethylene glycol, glycol monoethyl ether, acetic acid.
28. a kind of fire proofing, which is characterized in that including compound described in claim 1.
29. fire proofing as claimed in claim 28, which is characterized in that the fire proofing further includes resin.
30. fire proofing as claimed in claim 29, which is characterized in that the resin is macromolecule resin.
31. fire proofing as claimed in claim 30, which is characterized in that the resin include epoxy resin, unsaturated polyester (UP),
Poly- carbonic acid, polyamide or polyurethane.
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