CN107501326A - 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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- CN107501326A CN107501326A CN201710779926.9A CN201710779926A CN107501326A CN 107501326 A CN107501326 A CN 107501326A CN 201710779926 A CN201710779926 A CN 201710779926A CN 107501326 A CN107501326 A CN 107501326A
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- 0 C*C(***=I)[C@@]1c(cccc2)c2C(C)=C(C=CC)O[C@@]1O Chemical compound C*C(***=I)[C@@]1c(cccc2)c2C(C)=C(C=CC)O[C@@]1O 0.000 description 4
- VBQRUYIOTHNGOP-UHFFFAOYSA-N O=P1Oc(cccc2)c2-c2c1cccc2 Chemical compound O=P1Oc(cccc2)c2-c2c1cccc2 VBQRUYIOTHNGOP-UHFFFAOYSA-N 0.000 description 1
Classifications
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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, which provides a kind of compound and preparation method thereof, purposes and fire proofing, the compound, has flame-retarding characteristic, its can by the reaction of DOPO and chemical compounds I and compound ii reaction product, then with NH2RNH2React and obtain, and can apply to prepare fire proofing, with the addition of the fire proofing of the compound has splendid flame retardant effect.
Description
Technical field
The present invention relates to polymeric material field, in particular to a kind of compound and preparation method thereof, purposes and resistance
Combustible material.
Background technology
DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) is a kind of phosphorus phenanthrene class annular phosphate, is had
Good heat endurance and chemical stability.Based on the reactable of the P-H keys in DOPO, can respectively with double bond, carbonyl, Asia
Necleophilic reaction occurs for amino and epoxide group etc., prepares the addition type and reactive flame retardant of DOPO bases, and be widely used in epoxy
Resin (EP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT) (PBT), unsaturated polyester (UP) (UPR),
Poly- carbonic acid (PC), polyamide (PA), polyurethane (PU) Polymer material it is fire-retardant.In order to improve DOPO and substrate compatibility and
Its negative effect to material etc. is reduced, environmentally friendly and diversified DOPO based flameproofings turn into current study hotspot.
The content of the invention
It is an object of the invention to provide a kind of compound, and it has flame-retarding characteristic, can be widely used in high polymer material
Preparation field, and it has been used for flame retardant effect.
Another object of the present invention is to provide a kind of preparation method of above-claimed cpd.
It is still another object of the present invention to provide application of the above-claimed cpd in fire proofing is prepared.
It is still another object of the present invention to provide a kind of fire proofing, wherein containing above-claimed cpd and there is good resistance
Fire performance.
What embodiments of the invention were realized in：
A kind of compound, there is below formula structure：
Wherein, G C1-C10Alkyl or alkoxy, C2-C10Unsaturated alkyl or unsaturated hydrocarbons epoxide, C3-C7Cycloalkyl or
Cycloalkyloxy, phenyl, phenoxy group, naphthyl, naphthoxy,
Wherein, R1、R2And R3It is independently selected from C1-C6Alkyl, C2-C6Unsaturated alkyl, C1-C6Alkoxy, phenoxy group, benzene
Base or C3-C7Cycloalkyl；
Y is O or NH, Ar are phenyl or substituted-phenyl；Preferably 1,2- phenyl, 1,3- phenyl, 1,4- phenyl, 4,4'- connection
Phenyl, 2,4'- xenyls, 2,2'- xenyls, 1,4- naphthyls, 1,5- naphthyls, 1,6- naphthyls or 1,7- naphthyls.
R be 1,2- phenyl, 1,3- phenyl, 1,4- phenyl, 4,4'- xenyls, 2,4'- xenyls, 2,2'- xenyls, 1,
4- naphthyls, 1,5- naphthyls, 1,6- naphthyls, 1,7- naphthyls, benzhydryl, diphenyl sulfoxide base, diphenyl sulfone, C1-C12 alkyl, C2-
C12 unsaturated alkyls, phosphorous or siliceous C1-C16 alkyl.
Preferably, G is phenoxy group or phenyl, it is preferable that Ar is Isosorbide-5-Nitrae di-substituted-phenyl.
The present invention also provides purposes of the above-claimed cpd as fire retardant.
The preparation method of above-claimed cpd, including：Chemical compounds I is deposited with compound ii in acid binding agent and reacted at ambient,
Preferably, reaction temperature is -30 DEG C~120 DEG C, more preferably 10 DEG C~80 DEG C；Then reacted with compound III, it is preferable that anti-
Temperature is answered as -20 DEG C~160 DEG C, preferable 20 DEG C~80 DEG C, by reaction product and NH2RNH2Reacted.
Wherein, chemical compounds I isCompound ii is HY-Ar-CHO, and compound III is
A kind of fire proofing, including above-claimed cpd, it is preferable that also including resin, preferably resin is macromolecule resin,
Preferably also 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 polymer material, to improve the fire resistance of high polymer material.The compound is applied to prepare fire-retardant material
Material, such as during polyphosphazene polymer ester material, the fire resistance of material can be obviously improved.
In addition, the preparation method of above-claimed cpd provided by the invention, can be economical prepare the compound, and produce
Rate is high.Fire proofing containing the compound, there is good flame-retarding characteristic, be suitable for the application of in higher to flame retardant effect requirement
Application environment.
Embodiment
, below will be in the embodiment of the present invention to make the purpose, technical scheme and advantage of the embodiment of the present invention clearer
Technical scheme be clearly and completely described.Unreceipted actual conditions person, builds according to normal condition or manufacturer in embodiment
The condition of view is carried out.Agents useful for same or the unreceipted production firm person of instrument, it 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, there is below formula structure：
Wherein, G C1-C10Alkyl or alkoxy, C2-C10Unsaturated alkyl or unsaturated hydrocarbons epoxide, C3-C7Cycloalkyl or
Cycloalkyloxy, phenyl, phenoxy group, naphthyl, naphthoxy,
For example, G can be selected from C1-C6Alkyl or alkoxy or C7-C10Alkyl or alkoxy, C1-C6Unsaturated alkyl or not
Saturation oxyl or C7-C10Unsaturated alkyl or unsaturated hydrocarbons epoxide, C3-C6Cycloalkyl or C7Cycloalkyl.
Wherein, R1、R2And R3It is independently selected from C1-C6Alkyl, C1-C6Unsaturated alkyl, C1-C6Alkoxy,
Phenoxy group, phenyl or C3-C7Cycloalkyl.That is R1、R2And R3Can be that identical group can also be different bases from each other
Group.
Such as：R1、R2And R3It is independently selected from C1-C3Alkyl or C4-C6Alkyl,
C2-C3Unsaturated alkyl or C4-C6Unsaturated alkyl, C1-C3Alkoxy or C4-C6Alkoxy, phenoxy group, phenyl,
C3-C5Cycloalkyl or C6-C7Cycloalkyl.
Wherein, Y is O (oxygen) or NH, Ar are phenyl or substituted-phenyl, such as monosubstituted phenyl or polysubstituted phenyl, for
Polysubstituted phenyl, can be ortho position substitution, meta substitution or contraposition substitution.Preferably 1,2- phenyl, 1,3- phenyl, 1,4- benzene
Base, 4,4'- xenyls, 2,4'- xenyls, 2,2'- xenyls, 1,4- naphthyls, 1,5- naphthyls, 1,6- naphthyls or 1,7- naphthyls.
R be 1,2- phenyl, 1,3- phenyl, 1,4- phenyl, 4,4'- xenyls, 2,4'- xenyls, 2,2'- xenyls, 1,
4- naphthyls, 1,5- naphthyls, 1,6- naphthyls, 1,7- naphthyls, benzhydryl, diphenyl sulfoxide base, diphenyl sulfone, C1-C12Alkyl, C2-
C12Unsaturated alkyl, phosphorous or siliceous C1-C16Alkyl.
As the preferred embodiment of the present invention, G can for example be selected from phenoxy group or phenyl.
As the 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-claimed cpd can be prepared by the following method：
Chemical compounds I is deposited with compound ii in acid binding agent and reacted at ambient, it is preferable that the reaction temperature control of this step
For -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 can by reaction temperature control -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 it is feasible.
Acid binding agent can select organic base and/or inorganic base, can individually select organic base or inorganic base, can also be same
When using organic base and the mixture of inorganic base, such as:Organic base can select triethylamine, pyridine or N, accelerine
Deng.Inorganic base can select natrium carbonicum calcinatum or Anhydrous potassium carbonate etc..It should be appreciated that acid binding agent not necessarily one-component,
It can be the mixture of a variety of inorganic bases or the mixture of a variety of organic bases.
Wherein chemical compounds I isCompound ii is HY-Ar-CHO, the group representated by G, Y, Ar therein with
Group in above-claimed cpd is identical.
As the preferred embodiment of the present invention, the equivalent proportion of acid binding agent, compound ii and chemical compounds I is (2-2.5) ︰
(2-2.5) ︰ 1, preferable (2-2.1) ︰ (2-2.1) ︰ 1.
Reaction time is advisable with 1-30h, and preferable 2-6h is preferable.
Chemical compounds I reacts the reaction product (intermediate I) that can be prepared with compound ii：
Represented in the group and above-claimed cpd of the representatives such as G, Y, Ar therein
Group is identical.
As the preferred embodiment of the present invention, chemical compounds I and compound ii are reacted in organic solvent.It is preferred that
Ground, the organic solvent are selected from ether, dichloromethane, chloroform, tetrahydrofuran, dioxane, toluene, dimethylbenzene, N, N- diformazans
One or more in base formamide or glycol dimethyl ether.
Then product obtained by chemical compounds I and compound ii reaction is reacted with compound III, wherein, compound III is：Miscellaneous -10- phospho hetero phenanthrenes -10- the oxides (DOPO) of scientific name 9,10- dihydro-9-oxies.
Preferably, the reaction temperature control of this step is -20 DEG C~160 DEG C, and preferable 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, preferable 4-8h；
After being reacted with compound III, by reaction product and NH2RNH2Reacted.Group representated by wherein 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 present invention, reaction product and the compound III of chemical compounds I and compound ii are having
Reacted in solvent, so that reactant is directly more easy to haptoreaction.Preferably, the organic solvent can be selected from ether, two
Chloromethanes, chloroform, tetrahydrofuran, dioxane, toluene, dimethylbenzene, N,N-dimethylformamide, glycol dimethyl ether, ethanol,
One or more in butanol, ethylene glycol, glycol monoethyl ether, acetic acid.
Such as：Reacted by following reaction process：
Wherein, reaction product and NH2RNH2Reaction temperature be 20 DEG C -150 DEG C under the conditions of carry out, such as：Reaction is 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 is carried out under the conditions of 60 DEG C -130 DEG C.In addition, the reaction time can be controlled 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
Deposit in catalyst and carry out at ambient, it is preferable that the catalyst is selected from lewis acid, inorganic acid, organic acid and acid ion
One or more in 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 in 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：NH as reactant3And the weight sum of product obtained by step 2 reaction.
Further, the preferred embodiment as the compounds of this invention preparation method, change in reaction, the reaction product
With NH2RNH2Rate of charge be 1:2~8, preferably 1:2~3.Herein, reaction product refers to what is obtained in above-mentioned flow in step 2
Reaction product.
Above-mentioned compound can be used for being added into macromolecule resin etc. to prepare fire proofing, based on this, this hair
Bright also to provide a kind of fire proofing, it includes above-mentioned compound and macromolecule resin material, such as epoxy resin (EP), poly-
Ethylene glycol terephthalate (PET), polybutylene terephthalate (PBT) (PBT), unsaturated polyester (UP) (UPR), poly- carbonic acid (PC),
Polyamide (PA), polyurethane (PU) Polymer material.
Alternatively, can also include antioxidant in fire proofing, for example, 2,6- three-level butyl -4- methylphenols, three monooctyl esters,
Three last of the ten Heavenly stems esters, three (Lauryl Alcohol) esters and three (16 carbon alcohol) esters etc..
Alternatively, crosslinking agent can also be included in fire proofing.
The feature and performance of the present invention are described in further detail with reference to embodiments.
Embodiment 1
In with mechanical agitation, therm-param method, drying reactor in, add 2.0mol parahydroxyben-zaldehyde
(compound ii), 600.0mL dichloromethane (solvent) and 2.0mol triethylamine (acid binding agent), it is dispersed with stirring at room temperature uniformly
Afterwards, dropwise addition 1.0mol dichloro-phenyl phosphate (chemical compounds I) is started.Finish, filter, 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, separate organic layer (dichloromethane solvent and intermediate I) and add anhydrous sodium sulfate drying agent and dry 1h, be filtered to remove dry
Drying prescription, organic layer is distilled to recover dichloromethane, obtaining light yellow clear liquid i.e. intermediate I, (wherein, G is phenoxy group, and Y is
O, Ar are phenyl).
Intermediate I, the 2.0mol DOPO and 400.0mL ethanol that 1.0mol obtained above is added in reactor are molten
Agent, 40 DEG C of stirring reaction 6.0h, is down to room temperature, and filtering, filter cake obtains intermediate II -1 after being washed with ethanol (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)
Measure, test result are 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 substitute).
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).
1.0mol obtained above intermediate II -1 is added in reactor, (starting is former for 2.1mol 1,6- hexamethylene diamines
Material III), 800.0mL alcohol solvents and 0.05mol p-methyl benzenesulfonic acid (catalyst), 80 DEG C of stirring reaction 8.0h, be down to room
Temperature, filtering, filter cake obtain fire retardant 1a-1 after being washed with ethanol (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, obtained fire retardant 1a-1 structure is：
Embodiment 2
In with mechanical agitation, therm-param method, drying reactor in, add 3.0mol parahydroxyben-zaldehyde
(compound ii), 800.0mL toluene (solvent) and 3.0mol pyridine (acid binding agent), after being dispersed with stirring at 35 DEG C uniformly, open
1.5mol phenyl phosphonyl chloride (chemical compounds I) is slowly added dropwise in beginning.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, drier is filtered to remove, organic layer is distilled to recover
Toluene, residue are intermediate I (G is phenyl, and Y is oxygen, and Ar is phenyl ring).
Intermediate I, the 2.0mol DOPO and 550.0mL ethanol that 1.0mol obtained above is added in reactor are molten
Agent, 50 DEG C of stirring reaction 5.0h, is down to room temperature, and filtering, filter cake obtains intermediate II -2 after being washed with ethanol (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).
1.5mol obtained above intermediate II -2 is added in reactor, (starting is former for 3.0mol 1,6- hexamethylene diamines
Material III), 1000.0mL toluene solvants and 0.06mol acid-exchange resin (catalyst), 100 DEG C of stirring reaction 7.0h,
Be down to room temperature, filter, filter cake obtains fire retardant after being washed with toluene (G is phenyl, and Y is oxygen, and Ar is phenyl ring).
FTIR (KBr) tests are 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 Hes
949 (bound phosphate groups characteristic absorptions), 849 and 762 (phenyl ring is monosubstituted and contraposition substitutes).
Obtained fire retardant 1a-2 is carried out1H NMR (ppm, DMSO-d6) are tested, and 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 above test data it is known that fire retardant 1a-2 structural formula is：
Wherein G is phenyl, and Y O, Ar are phenyl ring.
Embodiment 3
Intermediate II -1 is prepared by method same as Example 1.
1.0mol intermediate II -1,2.0mol 4,4'- diaminodiphenyl-methane (initiation materials in reactor
III), 800.0mL toluene solvants and 0.10mol p-methyl benzenesulfonic acid (catalyst), 100 DEG C of stirring reaction 8.0h, is 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 the structure for judging fire retardant 1a-3 is：
Embodiment 4
Intermediate II -2 is prepared according to the method shown in embodiment 2.
1.2mol obtained above intermediate II -2,2.5mol 4,4'- diamino-diphenyls is added in reactor
The p-methyl benzenesulfonic acid (catalyst) of methane (initiation material III), 950.0mL glycol dinitrates ether solvents and 0.10mol, 80 DEG C
Stirring reaction 9.0h, room temperature is down to, 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 the structure for judging fire retardant 1a-4 is：
Embodiment 5
1.5mol intermediate II -1,3.5mol m-phenylene diamine (MPD) (initiation material III), 950.0mL second two in reactor
Diethylene glycol diethyl ether and 0.05mol p-methyl benzenesulfonic acid (catalyst), after 125 DEG C of stirring reaction 12h, room temperature is down to, filtered, filter cake
Flame-retardant monomer 1a-5 is obtained 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) tests are 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 the structure for judging fire retardant 1a-5 is：
Embodiment 6
1.5mol obtained above intermediate II -2,3.8mol m-phenylene diamine (MPD) (initiation material is added in reactor
III), 1000.0mL ethylene glycol solvents and 0.20mol to sulfuric acid (catalyst), after 120 DEG C of stirring reaction 7.0h, be down to room temperature,
Filtering, flame-retardant monomer 1a-6 is obtained 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) tests are 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 the structure for judging fire retardant 1a-6 is：
Embodiment 7
Step I：In with mechanical agitation, therm-param method, drying reactor in, add 2.2mol to amino
The triethylamine (acid binding agent) of benzaldehyde (initiation material II), 1200.0mL toluene (solvent) and 2.3mol, stirring point at 15 DEG C
After dissipating uniformly, start that 1.0mol dichloro-phenyl phosphate (initiation material I) is slowly added dropwise, finish, after continuing stirring reaction 4h, mistake
Filter, obtain 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, drier is filtered to remove, organic layer is distilled back
Receive toluene, residue is intermediate I -3 (G is phenyl, and Y NH, Ar are phenyl ring).
The structure of gained intermediate I -3 is：
Step III：Added in reactor 1.5mol obtained above intermediate I -3,3.0mol DOPO and
1500.0mL alcohol solvents, after 60 DEG C of stirring reaction 8.0h, room temperature is down to, filtered, filter cake obtains intermediate after being washed with ethanol
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 the structure for judging intermediate II -3 is：
Step IV：Hexamethylene diamine (the starting of 1.0mol obtained above intermediate II -3,4.0mol is added in reactor
Raw material III), 1200.0mL ethylene glycol diethyl ethers solvent and 0.30mol strong-acid ion exchange resin (catalyst), 125 DEG C are stirred
After mixing reaction 8.5h, room temperature is down to, 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, fire retardant 1b-1 structure is：
Embodiment 8
In with mechanical agitation, therm-param method, drying reactor in, add 4.1mol para aminotenzaldehyde
(initiation material II), 1200.0mL toluene (solvent) and 4.1mol triethylamine (acid binding agent), it is dispersed with stirring at 55 DEG C uniformly
Afterwards, start to be slowly added dropwise 2.0mol phenyl phosphonyl chloride (initiation material I).Finish, filter, 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,
Separate organic layer (toluene solvant and intermediate I -4) and add anhydrous sodium sulfate drying agent and dry 3h, be filtered to remove drier, 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
For：3382 (N-H), 3070 (phenyl ring C-H), 1715 (aldehyde radicals), 1584,1542 and 1464 (phenyl ring skeletons), 1288 (P=O),
1213rd, 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) are tested, and are surveyed
Test result is as follows：δ=9.914 (s, 2H), 6.672-7.729 (m, 13H), 4.462 (s, 2H).
Thus judge that intermediate I -4 is：
Intermediate I -4, the 2.1mol DOPO and 550.0mL ethanol that 1.0mol obtained above is added in reactor are molten
Agent, 50 DEG C of stirring reaction 4.0h, is down to room temperature, and filtering, filter cake obtains intermediate II -4 after being washed with ethanol (G is phenyl, and Y is
NH, X OH, Ar are phenyl ring).
FTIR (KBr), v/cm are carried out to intermediate II -4 (G is phenyl, and Y NH, X OH, Ar are phenyl ring)-1Test, survey
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 substitution).
Intermediate II -4 is carried out simultaneously1H NMR (ppm, DMSO-d6) are tested, and 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 is：
1.0mol obtained above intermediate II -4,5.0mol hexamethylene diamine (initiation material is added in reactor
III), 1200.0mL ethylene glycol diethyl ethers solvent and 0.30mol p-methyl benzenesulfonic acid (catalyst), 125 DEG C of stirring reaction 9.5h
Afterwards, room temperature is down to, 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 that fire retardant 1b-2 is：
Embodiment 9
Synthesize intermediate I -3 by the method in embodiment 7.And then continue in synthesizing according to the method in embodiment 7
Mesosome II -3 (G is phenoxy group, and Y NH, X OH, Ar are phenyl ring).
1.0mol obtained above intermediate II -3,6.5mol 4,4- diamino-diphenyl first is added in reactor
The strong-acid ion exchange resin (catalyst) of alkane (initiation material III), 1550.0mL xylene solvents and 0.45mol, 120 DEG C
After stirring reaction 10.5h, room temperature is down to, 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 the result for judging fire retardant 1b-3 is：
Embodiment 10
Synthesize intermediate I -4 by method described in embodiment 8, and and then continue to close according to method described in embodiment 8
Into obtaining intermediate II -4 (G is phenyl, and Y NH, X OH, Ar are phenyl ring).
1.0mol obtained above intermediate II -4,5.5mol 4,4- diamino-diphenyl first is added in reactor
The p-methyl benzenesulfonic acid (catalyst) of alkane (initiation material III), 1400.0mL ethylene glycol diethyl ethers solvent and 0.35mol, 120 DEG C
After stirring reaction 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 that fire retardant 1b-4 is：
Embodiment 11
Synthesize intermediate I -3 by the method in embodiment 7.And then continue in synthesizing according to the method in embodiment 7
Mesosome II -3 (G is phenoxy group, and Y NH, X OH, Ar are phenyl ring).
1.0mol obtained above intermediate II -3,3.5mol m-phenylene diamine (MPD) (initiation material is added in reactor
III), 1450.0mL xylene solvents and 0.40mol strong-acid ion exchange resin (catalyst), 125 DEG C of stirring reactions
After 11.5h, room temperature is down to, 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 and then continue to close according to method described in embodiment 8
Into obtaining intermediate II -4 (G is phenyl, and Y NH, X OH, Ar are phenyl ring).
1.0mol obtained above intermediate II -4,4.5mol m-phenylene diamine (MPD) (initiation material is added in reactor
III), 1350.0mL ethylene glycol diethyl ethers solvent and 0.30mol p-methyl benzenesulfonic acid (catalyst), 125 DEG C of stirring reactions
After 10.0h, room temperature is down to, 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 that fire retardant 1b-6 is：
Embodiment 13
Fire retardant 1b-1 is prepared with reference to the inventory and preparation process of each material in embodiment 7.Wherein differ only in
The reaction condition (temperature, pressure are different) of each step, the inventory of each reactions steps is same as Example 7, carries out 10 altogether
Group, the reaction condition of each group reaction are as shown in the table：
The each group reaction condition tables of data of 1 embodiment of table 13
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 different in rate of charge), 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 each group of 2 embodiment of table 10, the parameter list that feeds intake is reacted in step I
In the experiment of each group of 3 embodiment of table 10, the parameter list that feeds intake is reacted in step IV
Group wherein 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 proofing, by weight percentage, wherein containing epoxy resin (EP) 80%, implements
Fire retardant 1a-1 5% in example 1, in addition also containing antioxidant, crosslinking agent.
Embodiments described above is part of the embodiment of the present invention, rather than whole embodiments.The reality of the present invention
The detailed description for applying example is not intended to limit the scope of claimed invention, but is merely representative of the selected implementation of the present invention
Example.Based on the embodiment in the present invention, what those of ordinary skill in the art were obtained under the premise of creative work is not made
Every other embodiment, belongs to the scope of protection of the invention.
Claims (10)
1. a kind of compound, it is characterised in that there is below formula structure：
Wherein, G C1-C10Alkyl or alkoxy, C2-C10Unsaturated alkyl or unsaturated hydrocarbons epoxide, C3-C7Cycloalkyl or cycloalkanes
Epoxide, phenyl, phenoxy group, naphthyl, naphthoxy,
Wherein, R1、R2And R3It is independently selected from C1-C6Alkyl, C2-C6Unsaturated alkyl, C1-C6Alkoxy, phenoxy group, benzene
Base or C3-C7Cycloalkyl；
Y is O or NH, Ar are phenyl or substituted-phenyl；Preferably 1,2- phenyl, 1,3- phenyl, 1,4- phenyl, 4,4'- xenyls,
2,4'- xenyls, 2,2'- xenyls, 1,4- naphthyls, 1,5- naphthyls, 1,6- naphthyls or 1,7- naphthyls；
R is 1,2- phenyl, 1,3- phenyl, 1,4- phenyl, 4,4'- xenyls, 2,4'- xenyls, 2,2'- xenyls, 1,4- naphthalenes
Base, 1,5- naphthyls, 1,6- naphthyls, 1,7- naphthyls, benzhydryl, diphenyl sulfoxide base, diphenyl sulfone, C1-C12Alkyl, C2-C12No
Saturated hydrocarbyl, phosphorous or siliceous C1-C16Alkyl；
Preferably, G is phenoxy group or phenyl, it is preferable that Ar is Isosorbide-5-Nitrae di-substituted-phenyl.
2. purposes of the compound as claimed in claim 1 as fire retardant.
3. the preparation method of compound as claimed in claim 1, it is characterised in that including：Chemical compounds I and compound ii are existed
Acid binding agent is deposited to react at ambient, it is preferable that reaction temperature is -30 DEG C~120 DEG C, more preferably 10 DEG C~80 DEG C；Then with
Compound III is reacted, it is preferable that reaction temperature is -20 DEG C~160 DEG C, preferable 20 DEG C~80 DEG C；By reaction product with
NH2RNH2Reacted；
Wherein, chemical compounds I isCompound ii is HY-Ar-CHO, and compound III is
Preferably, the mol ratio of acid binding agent, compound ii and chemical compounds I is (2-2.5) ︰ (2-2.5) ︰ 1, are preferably (2-2.1) ︰
(2-2.1) ︰ 1.
4. the preparation method of compound as claimed in claim 3, it is characterised in that reaction product and the NH2RNH2Reaction
Carried out under the conditions of being 20 DEG C -150 DEG C in temperature, it is furthermore preferred that being carried out under the conditions of 60 DEG C -130 DEG C.
5. the preparation method of compound as claimed in claim 4, it is characterised in that reaction product and the NH2RNH2Reaction
Deposit in catalyst and carry out at ambient, it is preferable that the catalyst be selected from by lewis acid, inorganic acid, organic acid and it is acid from
Sub-exchange resin composition group in any one, it is highly preferred that the catalyst be selected from alchlor, the concentrated sulfuric acid, benzene sulfonic acid,
One or more in p-methyl benzenesulfonic acid and acid-exchange resin, most preferably, the catalyst are selected to methylbenzene
One or both of sulfonic acid and acid-exchange resin；
Preferably, the dosage of catalyst accounts for the 0.01%~20% of reactant gross weight, more preferably 5%~10%.
6. the preparation method of compound as claimed in claim 4, it is characterised in that the reaction product and the NH2RNH2's
Molar ratio is 1:2~8, preferably 1:2~3.
7. the preparation method of compound as claimed in claim 3, it is characterised in that the acid binding agent be selected from organic base and/or
Inorganic base, it is preferable that the organic base includes triethylamine, pyridine or DMA；
Preferably, the inorganic base includes natrium carbonicum calcinatum or Anhydrous potassium carbonate.
8. the preparation method of compound as claimed in claim 3, it is characterised in that chemical compounds I and compound ii are organic molten
Reacted in agent, it is preferable that the organic solvent is selected from ether, dichloromethane, chloroform, tetrahydrofuran, dioxane, first
One or more in benzene, dimethylbenzene, N,N-dimethylformamide or glycol dimethyl ether.
9. the preparation method of compound as claimed in claim 3, it is characterised in that the reaction production of chemical compounds I and compound ii
Thing is reacted in organic solvent with compound III, it is preferable that organic solvent is selected from ether, dichloromethane, chloroform, tetrahydrochysene furan
Mutter, dioxane, toluene, dimethylbenzene, N,N-dimethylformamide, glycol dimethyl ether, ethanol, butanol, ethylene glycol, ethylene glycol
One or more in monomethyl ether, acetic acid.
10. a kind of fire proofing, it is characterised in that including the compound described in claim 1, it is preferable that excellent also including resin
Selection of land, the resin are macromolecule resin, it is highly preferred that the resin include epoxy resin, polyethylene terephthalate,
Polybutylene terephthalate (PBT), unsaturated polyester (UP), poly- carbonic acid, polyamide or polyurethane.
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| CN111114064A (en) * | 2019-12-27 | 2020-05-08 | 中铁十八局集团北京工程有限公司 | Construction protection network device |
| CN111662332A (en) * | 2020-06-02 | 2020-09-15 | 桂林理工大学 | Organophosphorus flame retardant with active amino groups and preparation method and application thereof |
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