CN109232978A - Fire retardant thiophosphoryl-(N, N ' ,-three young laying ducks in cage of N ") triamine compound and preparation method thereof - Google Patents
Fire retardant thiophosphoryl-(N, N ' ,-three young laying ducks in cage of N ") triamine compound and preparation method thereof Download PDFInfo
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- CN109232978A CN109232978A CN201811146069.XA CN201811146069A CN109232978A CN 109232978 A CN109232978 A CN 109232978A CN 201811146069 A CN201811146069 A CN 201811146069A CN 109232978 A CN109232978 A CN 109232978A
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- cage
- laying ducks
- young laying
- thiophosphoryl
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- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 85
- 241000272517 Anseriformes Species 0.000 title claims abstract description 59
- 239000003063 flame retardant Substances 0.000 title claims abstract description 39
- 150000001875 compounds Chemical class 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000000047 product Substances 0.000 claims abstract description 42
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 150000001412 amines Chemical class 0.000 claims abstract description 23
- 238000001914 filtration Methods 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000000706 filtrate Substances 0.000 claims abstract description 13
- 238000009413 insulation Methods 0.000 claims abstract description 13
- 238000001291 vacuum drying Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- WQYSXVGEZYESBR-UHFFFAOYSA-N thiophosphoryl chloride Chemical group ClP(Cl)(Cl)=S WQYSXVGEZYESBR-UHFFFAOYSA-N 0.000 claims description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 11
- -1 Alkane diethylene glycol dimethyl ether Chemical class 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- QVLAWKAXOMEXPM-UHFFFAOYSA-N 1,1,1,2-tetrachloroethane Chemical class ClCC(Cl)(Cl)Cl QVLAWKAXOMEXPM-UHFFFAOYSA-N 0.000 claims description 3
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical class ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims 1
- QCJQWJKKTGJDCM-UHFFFAOYSA-N [P].[S] Chemical compound [P].[S] QCJQWJKKTGJDCM-UHFFFAOYSA-N 0.000 claims 1
- 239000008247 solid mixture Substances 0.000 abstract description 22
- 229920000728 polyester Polymers 0.000 abstract description 5
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 abstract description 4
- 239000011347 resin Substances 0.000 abstract description 4
- 239000003822 epoxy resin Substances 0.000 abstract description 3
- 229920000647 polyepoxide Polymers 0.000 abstract description 3
- 239000004814 polyurethane Substances 0.000 abstract description 3
- 229920002635 polyurethane Polymers 0.000 abstract description 3
- 229920000915 polyvinyl chloride Polymers 0.000 abstract description 2
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 abstract 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 69
- 238000000354 decomposition reaction Methods 0.000 description 12
- 238000010992 reflux Methods 0.000 description 10
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- 239000011574 phosphorus Substances 0.000 description 8
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical class N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 6
- 239000003610 charcoal Substances 0.000 description 6
- 238000013329 compounding Methods 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 125000001863 phosphorothioyl group Chemical group *P(*)(*)=S 0.000 description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- XWBDWHCCBGMXKG-UHFFFAOYSA-N ethanamine;hydron;chloride Chemical compound Cl.CCN XWBDWHCCBGMXKG-UHFFFAOYSA-N 0.000 description 2
- 238000004079 fireproofing Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- BFZUFHPKKNHSAG-UHFFFAOYSA-N [N].[P].[S] Chemical compound [N].[P].[S] BFZUFHPKKNHSAG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001596 poly (chlorostyrenes) Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/5399—Phosphorus bound to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65748—Esters of oxyacids of phosphorus the cyclic phosphorus atom belonging to more than one ring system
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34928—Salts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Fireproofing Substances (AREA)
Abstract
The present invention relates to a kind of fire retardant thiophosphoryl-(- three young laying ducks in cage of N, N ', N ") triamine compounds and preparation method thereof, and the structure of the compound is shown below:
Description
Technical field
The present invention relates to a kind of fire retardant thiophosphoryl-(- three young laying ducks in cage of N, N ', N ") triamine compound and its preparations
Method, and in particular to a kind of fire retardant thiophosphoryl three [N, N ', N "-three (1- oxygen -1- phospha -2,6,7- trioxa octyl < 4
>)] amine compounds and preparation method thereof, which is suitable as polyester, polyurethane, epoxy resin, unsaturated-resin, polychlorostyrene
The fire retardant of the materials such as ethylene.
Background technique
With the continuous development of global economy, inflammable high molecular material has obtained a large amount of application, while flame-retarded technology
Cracking development is obtained.Now widely used fire retardant has halogen system, phosphorus system, nitrogenated flame retardant etc..Halogenated flame retardant is from 20
It being just widely applied from the sixties in century, application technology is more mature, but possessed toxicity when due to burning, from
After European Union in 1986 promulgates RoHS instruction, the use of halogenated flame retardant is restricted in certain fields.Phosphorus nitrogen system especially has
Machine phosphorus-nitrogen containing flame retardant is gradually valued by people because it has many advantages, such as low cigarette, low toxicity, to organic phosphorus-nitrogen containing flame retardant
Research and development have become most promising one of direction.
The invention discloses it is a kind of containing phosphorus, nitrogen, sulphur ignition-proof element organic fire-retardant thiophosphoryl-(N, N ',
- three young laying ducks in cage of N ") triamine compound and preparation method thereof.The present invention is with stable young laying ducks in cage amine and phosphorus thiochloride
For raw material, one-step method prepares the compound, and simple process, equipment investment is few, easy to operate, at low cost, easy industrialized production;This
Invention fire retardant has many advantages, such as that the height of amount containing ignition-proof element, stable structure, flame-retarded efficiency are high, good with material compatibility, thus this
Invention fire retardant has extraordinary application and development prospect.
Summary of the invention
It is an object of the present invention to propose a kind of fire retardant thiophosphoryl-(- three young laying ducks in cage of N, N ', N ") triamine
Compound, physical and chemical performance is stablized, nontoxic, and flame-retarded efficiency is high, good with high molecular material compatibility, can overcome in the prior art
It is insufficient.
For achieving the above object, present invention employs following technical solutions:
A kind of fire retardant thiophosphoryl-(- three young laying ducks in cage of N, N ', N ") triamine compound, which is characterized in that the chemical combination
The structure of object is shown below:
Another object of the present invention is to propose that one kind has fire retardant thiophosphoryl-(- three young laying ducks in cage of N, N ', N ") three
The preparation method of amine compounds, this method are single step reaction, and simple process is easy to operate, and equipment investment is few, is easy to scale metaplasia
It produces.Its technical solution is as follows:
This method are as follows: with blender, thermometer, dropping funel, be connected to drying tube efficient backflow device reaction
In device, suitable organic solvent, young laying ducks in cage amine and triethylamine is added, catches up with the air in most bottle with nitrogen, under the conditions of 10 DEG C,
Phosphorus thiochloride is added dropwise in 1h, the certain molar ratio of control material limits dropping temperature at 10 DEG C~20 DEG C, after being added dropwise, rises
Temperature is to 80-110 DEG C of insulation reaction 3-5h, and cold filtration, vacuum drying obtain the target product and triethylamine hydrochloride of yellow later
Solid mixture, dissolve purpose product with suitable dimethyl sulfoxide, filtering, filtrate is evaporated, and obtains target product thiophosphoryl-
(- three young laying ducks in cage of N, N ', N ") triamine.
It is tetrachloroethanes, dioxane, acetonitrile, dichloroethanes diethylene glycol that suitable organic solvent is added as described above
Dimethyl ether or ethylene glycol diethyl ether, dosage volume ml are 10-20 times of young laying ducks in cage amine grams.
The certain molar ratio of control material as described above is phosphorus thiochloride: young laying ducks in cage amine: triethylamine=1: 3: 3-1
∶3.4∶3。
Suitable dimethyl sulfoxide as described above is that the volume ml of addition dimethyl sulfoxide is the 10- of product theory grams
20 times.
Young laying ducks in cage amine as described above is 1- oxygen -1- phospha -2,6,7- trioxa octyl<4>amine, structural formula
Are as follows:
Organic phosphine fire retardant thiophosphoryl-(- three young laying ducks in cage of N, N ', N ") triamine of the present invention is yellow solid, product
Yield is 87.3%-93.3%, decomposition temperature: 264 DEG C.It is suitable as polyester, polyurethane, epoxy resin, unsaturated-resin,
The preparation process of the fire retardant of the materials such as polyvinyl chloride, polyvinyl acetate, the double phosphinylidyne young laying ducks in cage of the organic phosphine fire retardant is former
Reason is shown below:
Compared with prior art, the beneficial effects of the present invention are:
(1) fire retardant thiophosphoryl-(- three young laying ducks in cage of N, N ', N ") triamine compound of the present invention contains phosphorus sulphur nitrogen three
Kind ignition-proof element, effective ignition-proof element content is high, and mutual cooperative flame retardant efficiency is high, and cage ring structural symmetry is good, stable structure,
Decomposition temperature is high, there is preferable processing performance.
(2) the raw material cage that fire retardant thiophosphoryl-(- three young laying ducks in cage of N, N ', N ") triamine compound of the present invention uses
Inherently a kind of excellent response type organic phosphine fire retardant of shape phosphoric acid ester amine, stable structure are reacted with phosphorus thiochloride, and are improved
The content of phosphorus, also introduces effective ignition-proof element sulphur, forms multiamide polyester structure, assign product and material have compared with
Good compatibility and fire retardation.
(3) fire retardant thiophosphoryl-(- three young laying ducks in cage of N, N ', N ") triamine compound of the present invention has with MCA and MPP
Compounding synergistic function well provides beneficial support to improving the performance for improving fire proofing and reducing cost.
(4) preparation of organic phosphine fire retardant thiophosphoryl-(- three young laying ducks in cage of N, N ', N ") triamine compound of the present invention
Method is single step reaction, and simple process, equipment investment is few, easy to operate, at low cost, is easy to scale conversion and production.
Detailed description of the invention
Following attached drawing is provided in order to further illustrate the structure and performance spy of product.
Fig. 1 is the infrared spectrogram of thiophosphoryl-(- three young laying ducks in cage of N, N ', N ") triamine;
Fig. 1 shows 1650cm-1Place is N-H stretching vibration peak, 1481.01cm-1Place is the P=O key on N-P=S key
Flexural vibrations peak, 1399.35cm-1Place is the flexural vibrations peak of the P=O key of key on O-P=O, 1079.06cm-1Place is P-O-
C stretching vibration peak, 976.02cm-1、624.59cm-1、516.16cm-1For the characteristic absorption peak of cyclic structure.
Fig. 2 is the nuclear magnetic spectrum figure of thiophosphoryl-(- three young laying ducks in cage of N, N ', N ") triamine;
Fig. 2 shows with deuterated water as solvent, is the peak H on-NH- at chemical shift δ 2.60;δ 4.36 is-CH2H
Peak.
Specific embodiment
Below in conjunction with specific embodiment, technical scheme is described further.
Embodiment 1 with blender, thermometer, dropping funel, connect drying tube high performance reflux condenser 250ml tetra-
In mouthful bottle, 80ml acetonitrile, 4.95g young laying ducks in cage amine and 3.03g triethylamine is added, catches up with the air in most bottle with nitrogen, 10 DEG C
Under the conditions of, it being added drop-wise in reaction flask in 1.70g phosphorus thiochloride 1h, control dropping temperature is at 10 DEG C~20 DEG C, after being added dropwise,
80 DEG C of insulation reaction 3h are warming up to, are then cooled to 20 DEG C, are filtered, vacuum drying obtains the product and triethylamine hydrochloride of yellow
Solid mixture.Solid mixture with 60ml dimethyl sulfoxide dissolve, filtering, filtrate be evaporated the thio phosphorus phosphinylidyne-of product (N,
- three young laying ducks in cage of N ', N ") triamine.Yield is 87.3%, and decomposition temperature is 264 DEG C.
Embodiment 2 with blender, thermometer, dropping funel, connect drying tube high performance reflux condenser 250ml tetra-
In mouth bottle, 90ml dioxane, 4.95g young laying ducks in cage amine and 3.03g triethylamine is added, catches up with the air in most bottle with nitrogen,
It under the conditions of 10 DEG C, will be added drop-wise in reaction flask in 1.70g phosphorus thiochloride 1h, control dropping temperature at 10 DEG C~20 DEG C, drip
Bi Hou is warming up to 90 DEG C of insulation reaction 3h, is then cooled to 20 DEG C, filters, and vacuum drying obtains the product and triethylamine salt of yellow
The solid mixture of hydrochlorate.Solid mixture 70ml dimethyl sulfoxide dissolves, and filtering, filtrate is evaporated to obtain the thio phosphorus phosphinylidyne-of product
(- three young laying ducks in cage of N, N ', N ") triamine.Yield is 90.1%, and decomposition temperature is 264 DEG C.
Embodiment 3 with blender, thermometer, dropping funel, connect drying tube high performance reflux condenser 250ml tetra-
In mouth bottle, 90ml diethylene glycol dimethyl ether, 4.95g young laying ducks in cage amine and 3.03g triethylamine is added, is caught up in most bottle with nitrogen
Air under the conditions of 10 DEG C, will be added drop-wise in reaction flask in 1.70g phosphorus thiochloride 1h, control dropping temperature at 10 DEG C~20 DEG C, drop
After adding, 100 DEG C of insulation reaction 4h are warming up to, are then cooled to 20 DEG C, are filtered, vacuum drying obtains the product and three of yellow
The solid mixture of ethylamine hydrochloride.Solid mixture 80ml dimethyl sulfoxide dissolves, and filtering, filtrate is evaporated to obtain the thio phosphorus of product
Acyl-(- three young laying ducks in cage of N, N ', N ") triamine.Yield is 91.5%, and decomposition temperature is 264 DEG C.
Embodiment 4 with blender, thermometer, dropping funel, connect drying tube high performance reflux condenser 250ml tetra-
In mouth bottle, 100ml dichloroethanes, 4.95g young laying ducks in cage amine and 3.03g triethylamine is added, catches up with the air in most bottle with nitrogen,
It under the conditions of 10 DEG C, will be added drop-wise in reaction flask in 1.70g phosphorus thiochloride 1h, control dropping temperature at 10 DEG C~20 DEG C, drip
Bi Hou is warming up to 80 DEG C of insulation reaction 5h, is then cooled to 20 DEG C, filters, and vacuum drying obtains the product and triethylamine salt of yellow
The solid mixture of hydrochlorate.Solid mixture with 90ml dimethyl sulfoxide dissolve, filtering, filtrate be evaporated product thiophosphoryl-(N,
- three young laying ducks in cage of N ', N ") triamine.Yield is 91.0%, and decomposition temperature is 264 DEG C.
Embodiment 5 with blender, thermometer, dropping funel, connect drying tube high performance reflux condenser 250ml tetra-
In mouth bottle, 90ml ethylene glycol diethyl ether, 4.95g young laying ducks in cage amine and 3.03g triethylamine is added, catches up with the sky in most bottle with nitrogen
Gas under the conditions of 10 DEG C, will be added drop-wise in reaction flask in 1.70g phosphorus thiochloride 1h, is controlled dropping temperature at 10 DEG C~20 DEG C, is added dropwise
After, 90 DEG C of insulation reaction 5h are warming up to, are then cooled to 20 DEG C, are filtered, vacuum drying obtains the product and triethylamine of yellow
The solid mixture of hydrochloride.Solid mixture 100ml dimethyl sulfoxide dissolves, and filtering, filtrate is evaporated to obtain product thiophosphoryl-
(- three young laying ducks in cage of N, N ', N ") triamine.Yield is 92.2%, and decomposition temperature is 264 DEG C.
Embodiment 6 with blender, thermometer, dropping funel, connect drying tube high performance reflux condenser 250ml tetra-
In mouth bottle, 110ml tetrachloroethanes, 4.95g young laying ducks in cage amine and 3.03g triethylamine is added, catches up with the air in most bottle with nitrogen,
It under the conditions of 10 DEG C, will be added drop-wise in reaction flask in 1.70g phosphorus thiochloride 1h, control dropping temperature at 10 DEG C~20 DEG C, drip
Bi Hou is warming up to 110 DEG C of insulation reaction 4h, is then cooled to 20 DEG C, filters, and vacuum drying obtains the product and triethylamine of yellow
The solid mixture of hydrochloride.Solid mixture 60ml dimethyl sulfoxide dissolves, and filtering, filtrate is evaporated to obtain the thio phosphorus phosphorus of product
Acyl-(- three young laying ducks in cage of N, N ', N ") triamine.Yield is 89.3%, and decomposition temperature is 264 DEG C.
Embodiment 7 with blender, thermometer, dropping funel, connect drying tube high performance reflux condenser 250ml tetra-
In mouthful bottle, 80ml acetonitrile, 5.12g young laying ducks in cage amine and 3.03g triethylamine is added, catches up with the air in most bottle with nitrogen, 10 DEG C
Under the conditions of, it being added drop-wise in reaction flask in 1.70g phosphorus thiochloride 1h, control dropping temperature is at 10 DEG C~20 DEG C, after being added dropwise,
80 DEG C of insulation reaction 4h are warming up to, are then cooled to 20 DEG C, are filtered, vacuum drying obtains the product and triethylamine hydrochloride of yellow
Solid mixture.Solid mixture with 70ml dimethyl sulfoxide dissolve, filtering, filtrate be evaporated product thiophosphoryl-(N, N ',
- three young laying ducks in cage of N ") triamine.Yield is 90.4%, and decomposition temperature is 264 DEG C.
Embodiment 8 with blender, thermometer, dropping funel, connect drying tube high performance reflux condenser 250ml tetra-
In mouth bottle, 90ml diethylene glycol dimethyl ether, 5.33g young laying ducks in cage amine and 3.03g triethylamine is added, is caught up in most bottle with nitrogen
Air under the conditions of 10 DEG C, will be added drop-wise in reaction flask in 1.70g phosphorus thiochloride 1h, control dropping temperature at 10 DEG C~20 DEG C, drop
After adding, 100 DEG C of insulation reaction 4h are warming up to, are then cooled to 20 DEG C, are filtered, vacuum drying obtains the product and three of yellow
The solid mixture of ethylamine hydrochloride.Solid mixture 80ml dimethyl sulfoxide dissolves, and filtering, filtrate is evaporated to obtain the thio phosphorus of product
Acyl-(- three young laying ducks in cage of N, N ', N ") triamine.Yield is 91.9%, and decomposition temperature is 264 DEG C.
Embodiment 9 with blender, thermometer, dropping funel, connect drying tube high performance reflux condenser 250ml tetra-
In mouth bottle, 100ml dichloroethanes, 5.45g young laying ducks in cage amine and 3.03g triethylamine is added, catches up with the air in most bottle with nitrogen,
It under the conditions of 10 DEG C, will be added drop-wise in reaction flask in 1.70g phosphorus thiochloride 1h, control dropping temperature at 10 DEG C~20 DEG C, drip
Bi Hou is warming up to 80 DEG C of insulation reaction 4h, is then cooled to 20 DEG C, filters, and vacuum drying obtains the product and triethylamine salt of yellow
The solid mixture of hydrochlorate.Solid mixture with 90ml dimethyl sulfoxide dissolve, filtering, filtrate be evaporated product thiophosphoryl-(N,
- three young laying ducks in cage of N ', N ") triamine.Yield is 92.0%, and decomposition temperature is 264 DEG C.
Embodiment 10 with blender, thermometer, dropping funel, connect drying tube high performance reflux condenser 250ml
In four-hole bottle, 90ml dioxane, 5.61g young laying ducks in cage amine and 3.03g triethylamine is added, catches up with the sky in most bottle with nitrogen
Gas under the conditions of 10 DEG C, will be added drop-wise in reaction flask in 1.70g phosphorus thiochloride 1h, is controlled dropping temperature at 10 DEG C~20 DEG C, is added dropwise
After, 90 DEG C of insulation reaction 4h are warming up to, are then cooled to 20 DEG C, are filtered, vacuum drying obtains the product and triethylamine of yellow
The solid mixture of hydrochloride.Solid mixture 100ml dimethyl sulfoxide dissolves, and filtering, filtrate is evaporated to obtain product thiophosphoryl-
(- three young laying ducks in cage of N, N ', N ") triamine.Yield is 93.3%, and decomposition temperature is 264 DEG C.
Table 1 prepares embodiment main technologic parameters
The product thiophosphoryl-of above-mentioned preparation (- three young laying ducks in cage of N, N ', N ") triamine is also applied to by inventor
In polyester PBT.Reference: the limit oxygen of GB/T2406-2008 " Plastics Combustion method for testing performance-oxygen index method " sample refers to
Number.The product of different proportion is added in PBT, or after product is compounded in different proportions with MCA, MPP, then with different ratios
Example is added in PBT, at 230 DEG C, is squeezed out with extruder, and a length of 15cm is made, and diameter is the batten of 3mm, and fire-retardant to its
Performance is tested, and the LOI result measured is as shown in Table 2-4:
2 thiophosphoryl of table-(- three young laying ducks in cage of N, N ', N ") triamine is for the fire-retardant data in PBT
Additive amount % | LOI% | Drip situation | At charcoal |
0 | 20 | Fast drippage | Not at charcoal |
10 | 22 | Fast drippage | Not at charcoal |
20 | 28 | Slow drippage | At charcoal |
25 | 30 | Slow drippage | At charcoal |
As shown in Table 2, when phenyl time two (bis- cage phosphate of N, N-) additive amount of the amine in PBT of phosphinylidyne is 20%, pole
Limiting oxygen index value is 28%, has had reached fire retardant rank, though there is slight drippage, carbon-forming performance is fine.
3 product thiophosphoryl of table-(- three young laying ducks in cage of N, N ', N ") triamine and MCA compounding are for the fire-retardant number in PBT
According to
As shown in Table 3, product thiophosphoryl-(- three young laying ducks in cage of N, N ', N ") triamine has compounded preferable association with MCA
Same-action, there are also good dilatancy, optimal additive amount proportion is 3: 2, and when total addition level is 25%, limit oxygen index can
Up to 31%, illustrate that system has become nonflammable material at this time after compounding, and does not drip, and fine at charcoal, and the price of MCA is very
It is cheap, the production cost of fire proofing can be greatly lowered.Thus it can be seen that product thiophosphoryl-(- three caged of N, N ', N "
Phosphate) no matter triamine is single use, or compounds with MCA, there is preferable flame retardant effect to PBT material.
4 product thiophosphoryl of table-(- three young laying ducks in cage of N, N ', N ") triamine and MPP compounding are for the fire-retardant number in PBT
According to
As shown in Table 4, optimal additive amount proportion is 1: 1 after the compounding of the nitrogen phosphorus expansion type flame retardant product and MPP, pole
Limiting oxygen index value illustrates that system has formd nonflammable material at this time after compounding, but has the appearance of slight molten drop up to 28%.
It thus it can be seen that no matter product is single use, or is compounded with MPP, MCA, good anti-flammability is all had to PBT resin
Energy.
Claims (5)
1. a kind of fire retardant thiophosphoryl-(- three young laying ducks in cage of N, N ', N ") triamine compound, which is characterized in that the compound
Structure be shown below:
2. a kind of fire retardant thiophosphoryl-(- three young laying ducks in cage of N, N ', N ") triamine compound according to claim 1
Preparation method, which is characterized in that this method are as follows:
With blender, dropping funel, thermometer, be connected to drying tube the reactor of efficient backflow device in, be added appropriate
Organic solvent, young laying ducks in cage amine and triethylamine, catch up with the air in most bottle with nitrogen, under the conditions of 10 DEG C, trichlorine be added dropwise in 1h
Sulphur phosphorus, the certain molar ratio of control material limit dropping temperature at 10 DEG C~20 DEG C, after being added dropwise, are warming up to 80-110 DEG C
Insulation reaction 3-5h, cold filtration, vacuum drying, the target product for obtaining yellow are mixed with the solid of triethylamine hydrochloride later
Object dissolves purpose product, filtering with suitable dimethyl sulfoxide, and filtrate is evaporated, and obtains target product thiophosphoryl-(N, N ', N "-three
Young laying ducks in cage) triamine;Young laying ducks in cage amine as described above is 1- oxygen -1- phospha -2,6,7- trioxa octyl<4>amine,
Its structural formula are as follows:
3. a kind of fire retardant thiophosphoryl-(- three young laying ducks in cage of N, N ', N ") triamine compound according to claim 2
Preparation method, which is characterized in that the suitable organic solvent of the addition be tetrachloroethanes, dioxane, acetonitrile, two chloroethenes
Alkane diethylene glycol dimethyl ether or ethylene glycol diethyl ether, dosage volume ml are 10-20 times of young laying ducks in cage amine grams.
4. a kind of fire retardant thiophosphoryl-(- three young laying ducks in cage of N, N ', N ") triamine compound according to claim 2
Preparation method, which is characterized in that the certain molar ratio of control material as described above is phosphorus thiochloride: young laying ducks in cage amine:
Triethylamine=1: 3: 3-1: 3.4: 3.
5. a kind of fire retardant thiophosphoryl-(- three young laying ducks in cage of N, N ', N ") triamine compound according to claim 2
Preparation method, which is characterized in that as described above with suitable dimethyl sulfoxide be added dimethyl sulfoxide volume ml be
10-20 times of product theory grams.
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CN111978351A (en) * | 2020-08-06 | 2020-11-24 | 苏州科技大学 | Fire retardant cage-shaped organic silicon phosphoramide compound and preparation method thereof |
CN114315896A (en) * | 2021-12-09 | 2022-04-12 | 湖北大学 | 2- (diphenyl thiophosphoryl) succinate and synthesis method and application thereof |
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