CN109265482A - Fire retardant phosphinylidyne-(N, N ', N ＂-three cage phosphate) triamine compound and preparation method thereof - Google Patents
Fire retardant phosphinylidyne-(N, N ', N ＂-three cage phosphate) triamine compound and preparation method thereof Download PDFInfo
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- CN109265482A CN109265482A CN201811145922.6A CN201811145922A CN109265482A CN 109265482 A CN109265482 A CN 109265482A CN 201811145922 A CN201811145922 A CN 201811145922A CN 109265482 A CN109265482 A CN 109265482A
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- phosphinylidyne
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- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 87
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 39
- 239000003063 flame retardant Substances 0.000 title claims abstract description 39
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 38
- 239000010452 phosphate Substances 0.000 title claims abstract description 38
- 150000001875 compounds Chemical class 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000047 product Substances 0.000 claims abstract description 49
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 47
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 32
- 150000001412 amines Chemical class 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000001914 filtration Methods 0.000 claims abstract description 25
- 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 compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 241000272517 Anseriformes Species 0.000 claims abstract description 21
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000706 filtrate Substances 0.000 claims abstract description 13
- 238000009413 insulation Methods 0.000 claims abstract description 13
- 239000008247 solid mixture Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 4
- 238000001291 vacuum drying Methods 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- QVLAWKAXOMEXPM-UHFFFAOYSA-N 1,1,1,2-tetrachloroethane Chemical group ClCC(Cl)(Cl)Cl QVLAWKAXOMEXPM-UHFFFAOYSA-N 0.000 claims description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- 238000005576 amination reaction Methods 0.000 claims description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- XFDJMIHUAHSGKG-UHFFFAOYSA-N chlorethoxyfos Chemical compound CCOP(=S)(OCC)OC(Cl)C(Cl)(Cl)Cl XFDJMIHUAHSGKG-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 16
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 229920000728 polyester Polymers 0.000 abstract description 5
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 abstract description 5
- 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 3
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 235000021317 phosphate Nutrition 0.000 description 32
- 238000000354 decomposition reaction Methods 0.000 description 13
- 238000001035 drying Methods 0.000 description 11
- 238000010792 warming Methods 0.000 description 10
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000003610 charcoal Substances 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 238000004079 fireproofing Methods 0.000 description 3
- -1 phosphamide compound Chemical class 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 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
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—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
- C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
-
- 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
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
-
- 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
- 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
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- 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)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of nitrogen phosphorus expansion type flame retardant phosphinylidyne-(N, N ', N ＂-three cage phosphate) 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 nitrogen phosphorus expansion type flame retardant phosphinylidyne-(- three cage phosphate of N, N ', N ") triamine compound and
A kind of preparation method, and in particular to N, N ', N "-three (1- oxygen -1- phospha -2,6,7- trioxa octyl<4>) phosphinylidyne amination
The preparation method of object is closed, which is suitable as polyester, polyurethane, epoxy resin, unsaturated-resin, polyvinyl chloride hydrocarbon etc.
The fire retardant of material.
Background technique
In recent decades, due to commonly used, lives and properties of the fire caused to people of inflammable high molecular material
Safety causes huge threat, thus promotes the promulgation and implementation of flame retardant regulation, while flame-retarded technology has also obtained quickly
Development.Now widely used fire retardant has halogen system, phosphorus system and inorganic fire retardants etc..Halogenated flame retardant is from 20th century 60
It is exactly the hot product in flame retardant area from age, such fire retardant is high-efficient, it is small to influence on the performance of material, and
It is moderate.But from after European Union's promulgation RoHS instruction in 1986, the use of halogenated flame retardant is restricted.Nitrogen phosphorus intumescent
Fire retardant has isolation heat and oxygen, inhibits smog, prevention melting drippage, the lot of advantages such as small toxicity, environmental requirement increasingly
It stringent today, is gradually valued by people, the research of organic nitrogen phosphorus expansion type flame retardant is had become and is most developed
One of direction of prospect.
The invention discloses a kind of nitrogen phosphorus expansion type flame retardant phosphinylidyne-(- three cage phosphate of N, N ', N ") triamine compounds
Preparation method.The present invention is to prepare the compound with young laying ducks in cage amine and phosphorus oxychloride, and simple process, equipment investment is few,
Easy to operate, at low cost, the yield of product is higher, is easily converted into industrialized production；Fire retardant of the present invention, it is preferable right to have
Claim property, with stable N-P key, decomposition temperature is higher, has the advantages that good compatibility with high molecular material.Therefore, this hair
Bright fire retardant has extraordinary development prospect.
Summary of the invention
It is an object of the present invention to propose a kind of-three (1- oxygen -1- phospha-of nitrogen phosphorus expansion type flame retardant N, N ', N "
2,6,7- trioxa octyls<4>) phosphamide compound, physical and chemical performance is stablized, and nontoxic, flame-retarded efficiency is high, with macromolecule material
Expect that compatibility is good, deficiency in the prior art can be overcome.
For achieving the above object, present invention employs following technical solutions:
A kind of nitrogen phosphorus expansion type flame retardant N, N ', N "-three (1- oxygen -1- phospha -2,6,7- trioxa octyl<4>) phosphorus
Amide compound, which is characterized in that the structure of the compound is shown below:
Another object of the present invention is to propose a kind of nitrogen phosphorus expansion type flame retardant phosphinylidyne-(- three cage phosphoric acid of N, N ', N "
Ester) triamine compound preparation method, this method simple process, equipment investment is few, easy to operate, at low cost, the yield of product
It is higher, it is easy to large-scale production, its technical solution is as follows:
This method are as follows: equipped with blender, thermometer, be connected to drying tube the reactor of efficient backflow device in, nitrogen
Under protection, a certain amount of organic solvent, the suitable molar ratio of material of control is added, young laying ducks in cage amine and triethylamine is added, it is cold
But to 10 DEG C, phosphorus oxychloride is dripped off in 1h, controls reaction temperature at 10 DEG C~20 DEG C, and temperature is risen after being added dropwise to 60-100
DEG C, after insulation reaction 2-6h, cold filtration is dried in vacuo, and the target product for obtaining yellow is mixed with the solid of triethylamine hydrochloride
Object is dissolved with the dimethyl sulfoxide that volume milliliter is 10-15 times of target product grams, filtering, and filtrate is evaporated to get target production
Product phosphinylidyne-(- three cage phosphate of N, N ', N ") triamine.
A certain amount of organic solvent as described above is tetrachloroethanes, dioxane, chloroform, dichloroethanes, diethylene glycol
Dimethyl ether or acetonitrile, dosage volume ml are 10-20 times of the quality grams of young laying ducks in cage.
Controlling suitable molar ratio of material as described above is phosphorus oxychloride: young laying ducks in cage amine: triethylamine=1: 3: 3-
1∶3.4∶3。
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:
Nitrogen phosphorus expansion type flame retardant phosphinylidyne-(- three cage phosphate of N, N ', N ") triamine compound of the present invention is pale yellow colored solid
Body, product yield 87.4%-92.2%, decomposition temperature: 260 ± 5 DEG C.It is suitable as polyester, polyurethane, epoxy resin,
The fire retardant of the materials such as unsaturated-resin, polyvinyl chloride has good compatibility with high molecular material, nitrogen phosphorus intumescent resistance
The preparation process principle of combustion agent phosphinylidyne-(- three cage phosphate of N, N ', N ") triamine compound is shown below:
Compared with prior art, the beneficial effects of the present invention are:
1. nitrogen phosphorus expansion type flame retardant phosphinylidyne-(- three cage phosphate of N, N ', N ") triamine compound flame-retarded efficiency of the present invention
Height, with preferable symmetry, with stable N-P key, decomposition temperature is high, there is preferable processing performance.The structure of product is equal
It is even, there is good compatibility with high molecular material,
2. the original that nitrogen phosphorus expansion type flame retardant phosphinylidyne-(- three cage phosphate of N, N ', N ") triamine compound of the present invention uses
Expect inherently a kind of excellent response type organic phosphine fire retardant of young laying ducks in cage amine, stable structure has polyester structure, with
Phosphorus oxychloride reaction, and the content of phosphorus is improved, multiamide structure is also introduced, assigning product and material has preferable phase
Capacitive.
3. nitrogen phosphorus expansion type flame retardant phosphinylidyne-(- three cage phosphate of N, N ', N ") triamine compound of the present invention and MCA, MPP
There is compounding synergistic function well, the cost of fire proofing can be effectively reduced, improve material environment.
4. the preparation work of nitrogen phosphorus expansion type flame retardant phosphinylidyne-(- three cage phosphate of N, N ', N ") triamine compound of the present invention
Skill is simple, and 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 light of nitrogen phosphorus expansion type flame retardant phosphinylidyne phosphinylidyne-(- three cage phosphate of N, N ', N ") triamine compound
Spectrogram；Fig. 1 shows in 1650cm-1Place is N-H stretching vibration peak, 1476.01cm-1Place is the P=O key on N-P=O key
Flexural vibrations peak, 1395.35cm-1Place is the flexural vibrations peak of the P=O key of key on O-P=O, 1075.06cm-1Place is P-
O-C stretching vibration peak, 979.02cm-1、619.59cm-1、506.16 cm-1For the characteristic absorption peak of cyclic structure.
Fig. 2 is the nuclear magnetic spectrum of nitrogen phosphorus expansion type flame retardant phosphinylidyne-(- three cage phosphate of N, N ', N ") triamine compound
Figure；Fig. 2 shows with deuterated water as solvent, is the peak H of-NH- at chemical shift δ 2.55；δ 4.41 is-CH2The peak H, then tie
Close infrared spectrum analyze as a result, synthesized compound is phosphinylidyne three (tri- cage phosphate of N, N, N-) amine.
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
In four-hole bottle, 100ml tetrachloroethanes, 4.95g young laying ducks in cage amine and 3.03g triethylamine is added, catches up with the sky in most bottle with nitrogen
Under the conditions of 10 DEG C, 1.54g phosphorus oxychloride about 1h is added drop-wise in there-necked flask for gas, controls reaction temperature at 10 DEG C~20 DEG C, drop
After adding, 80 DEG C, insulation reaction 2h are warming up to, later cold filtration, are dried in vacuo, obtain the target product and three second of yellow
The solid mixture of amine hydrochlorate is dissolved with 60ml dimethyl sulfoxide, and filtering, filtrate is evaporated, obtain target product phosphinylidyne-(N,
- three cage phosphate of N ', N ") triamine, yield 87.4%, decomposition temperature is 260 DEG C.
Embodiment 2 with blender, thermometer, dropping funel, connect drying tube high performance reflux condenser 250ml
In four-hole bottle, 100ml dioxane, 4.95g young laying ducks in cage amine and 3.03g triethylamine is added, catches up with the sky in most bottle with nitrogen
Under the conditions of 10 DEG C, 1.54g phosphorus oxychloride about 1h is added drop-wise in there-necked flask for gas, controls reaction temperature at 10 DEG C~20 DEG C, drop
After adding, 70 DEG C, insulation reaction 3h are warming up to, later cold filtration, are dried in vacuo, obtain the target product and three second of yellow
The solid mixture of amine hydrochlorate is dissolved with 60ml dimethyl sulfoxide, and filtering, filtrate is evaporated, obtain target product phosphinylidyne-(N,
- three cage phosphate of N ', N ") triamine, yield 89.1%, decomposition temperature is 260 DEG C.
Embodiment 3 with blender, thermometer, dropping funel, connect drying tube high performance reflux condenser 250ml
In four-hole bottle, 100ml chloroform, 4.95g young laying ducks in cage amine and 3.03g triethylamine is added, catches up with the air in most bottle with nitrogen,
Under the conditions of 10 DEG C, 1.54g phosphorus oxychloride about 1h is added drop-wise in there-necked flask, reaction temperature is controlled at 10 DEG C~20 DEG C, drips
Bi Hou is warming up to 60 DEG C, insulation reaction 4h, later cold filtration, and vacuum drying obtains the target product and triethylamine salt of yellow
The solid mixture of hydrochlorate is dissolved with 60ml dimethyl sulfoxide, and filtering, filtrate is evaporated, and obtains target product phosphinylidyne-(N, N ', N "-
Three cage phosphates) triamine, yield 91.9%, decomposition temperature is 260 DEG C.
Embodiment 4 with blender, thermometer, dropping funel, connect drying tube high performance reflux condenser 250ml
In four-hole bottle, 100ml dichloroethanes, 4.95g young laying ducks in cage amine and 3.03g triethylamine is added, catches up with the sky in most bottle with nitrogen
Under the conditions of 10 DEG C, 1.54g phosphorus oxychloride about 1h is added drop-wise in there-necked flask for gas, controls reaction temperature at 10 DEG C~20 DEG C, drop
After adding, 80 DEG C, insulation reaction 5h are warming up to, later cold filtration, are dried in vacuo, obtain the target product and three second of yellow
The solid mixture of amine hydrochlorate is dissolved with 60ml dimethyl sulfoxide, and filtering, filtrate is evaporated, obtain target product phosphinylidyne-(N,
- three cage phosphate of N ', N ") triamine, yield 92.1%, decomposition temperature is 260 DEG C.
Embodiment 5 with blender, thermometer, dropping funel, connect drying tube high performance reflux condenser 250ml
In four-hole bottle, 100ml dichloroethanes, 4.95g young laying ducks in cage amine and 3.03g triethylamine is added, catches up with the sky in most bottle with nitrogen
Under the conditions of 10 DEG C, 1.54g phosphorus oxychloride about 1h is added drop-wise in there-necked flask for gas, controls reaction temperature at 10 DEG C~20 DEG C, drop
After adding, 90 DEG C, insulation reaction 6h are warming up to, later cold filtration, are dried in vacuo, obtain the target product and three second of yellow
The solid mixture of amine hydrochlorate is dissolved with 60ml dimethyl sulfoxide, and filtering, filtrate is evaporated, obtain target product phosphinylidyne-(N,
- three cage phosphate of N ', N ") triamine, yield 92.2%, decomposition temperature is 260 DEG C.
Embodiment 6 with blender, thermometer, dropping funel, connect drying tube high performance reflux condenser 250ml
In four-hole bottle, 100ml diethylene glycol dimethyl ether, 4.95g young laying ducks in cage amine and 3.03g triethylamine is added, catches up with most bottle with nitrogen
Under the conditions of 10 DEG C, 1.54g phosphorus oxychloride about 1h is added drop-wise in there-necked flask for interior air, controls reaction temperature 10 DEG C~20
DEG C, after being added dropwise, 100 DEG C, insulation reaction 4h are warming up to, later cold filtration, are dried in vacuo, obtain the target product of yellow
With the solid mixture of triethylamine hydrochloride, 60ml dimethyl sulfoxide solubilized target product, filtering are used, filtrate is evaporated, and obtains target
Product phosphinylidyne-(- three cage phosphate of N, N ', N ") triamine, yield 89.3%, decomposition temperature are 260 DEG C.
Embodiment 7 with blender, thermometer, dropping funel, connect drying tube high performance reflux condenser 250ml
In four-hole bottle, 80ml dioxane, 5.12g young laying ducks in cage amine and 3.03g triethylamine is added, catches up with the sky in most bottle with nitrogen
Under the conditions of 10 DEG C, 1.54g phosphorus oxychloride about 1h is added drop-wise in there-necked flask for gas, controls reaction temperature at 10 DEG C~20 DEG C, drop
After adding, 90 DEG C, insulation reaction 4h are warming up to, later cold filtration, are dried in vacuo, obtain the target product and three second of yellow
The solid mixture of amine hydrochlorate dissolves purpose product, filtering with 60ml dimethyl sulfoxide, and filtrate is evaporated, and obtains purpose product phosphorus
Acyl-(- three cage phosphate of N, N ', N ") triamine, yield 90.4%, decomposition temperature are 260 DEG C.
Embodiment 8 with blender, thermometer, dropping funel, connect drying tube high performance reflux condenser 250ml
In four-hole bottle, 60ml acetonitrile, 5.33g young laying ducks in cage amine and 3.03g triethylamine is added, catches up with the air in most bottle with nitrogen, 10
Under the conditions of DEG C, 1.54g phosphorus oxychloride about 1h is added drop-wise in there-necked flask, reaction temperature is controlled at 10 DEG C~20 DEG C, is added dropwise
Afterwards, 70 DEG C, insulation reaction 4h are warming up to, later cold filtration, be dried in vacuo, obtain the target product and triethylamine hydrochloric acid of yellow
The solid mixture of salt dissolves purpose product with 60ml dimethyl sulfoxide, and filtering, filtrate is evaporated, obtain purpose product phosphinylidyne-(N,
- three cage phosphate of N ', N ") triamine, yield 91.0%, decomposition temperature is 260 DEG C.
Embodiment 9 with blender, thermometer, dropping funel, connect drying tube high performance reflux condenser 250ml
In four-hole bottle, 80ml tetrachloroethanes, 5.33g young laying ducks in cage amine and 3.03g triethylamine is added, catches up with the sky in most bottle with nitrogen
Under the conditions of 10 DEG C, 1.54g phosphorus oxychloride about 1h is added drop-wise in there-necked flask for gas, controls reaction temperature at 10 DEG C~20 DEG C, drop
After adding, 90 DEG C, insulation reaction 4h are warming up to, later cold filtration, are dried in vacuo, obtain the target product and three second of yellow
The solid mixture of amine hydrochlorate dissolves purpose product, filtering with 60ml dimethyl sulfoxide, and filtrate is evaporated, and obtains target product phosphorus
Acyl-(- three cage phosphate of N, N ', N ") triamine, yield 91.5%, decomposition temperature are 260 DEG C.
Embodiment 10 is with blender, thermometer, dropping funel, the high performance reflux condenser for connecing drying tube
In 250ml four-hole bottle, 80ml dioxane, 5.61g 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, 1.54g phosphorus oxychloride about 1h is added drop-wise in there-necked flask, controls reaction temperature 10 DEG C~20
DEG C, after being added dropwise, be warming up to 90 DEG C, insulation reaction 4h, later cold filtration, be dried in vacuo, obtain the target product of yellow with
The solid mixture of triethylamine hydrochloride is dissolved with 60ml dimethyl sulfoxide, and filtering, filtrate is evaporated, and obtains target product phosphinylidyne-
(- three cage phosphate of N, N ', N ") triamine, yield 92.0%, decomposition temperature are 260 DEG C.
Table 1 prepares embodiment main technologic parameters
The product phosphinylidyne-of above-mentioned preparation (- three cage phosphate of N, N ', N ") triamine is also applied to polyester by inventor
In PBT.Reference: the limit oxygen index of GB/T2406-2008 " Plastics Combustion method for testing performance-oxygen index method " sample.?
The product of different proportion is added in PBT, or after product is compounded in different proportions with MCA, MPP, then add in different proportions
Enter into PBT, at 230 DEG C, squeezed out with extruder, a length of 15cm is made, diameter is the batten of 3mm, and to its flame retardant property
It is tested, the LOI value measured is as shown in table 2 and table 3:
2 product phosphinylidyne of table-(- three cage phosphate of N, N ', N ") triamine is for the fire-retardant data in PBT
| Additive amount % | LOI% | Drip situation | At charcoal |
| 0 | 21 | Drippage | Not at charcoal |
| 10 | 23 | Drippage | Not at charcoal |
| 20 | 28 | Slow drippage | It is expanded at charcoal |
| 25 | 31 | Slow drippage | It is expanded at charcoal |
As shown in Table 2, when (- three cage phosphate of N, N ', N ") additive amount of the amine in PBT of phosphinylidyne three is 20%, the limit
Oxygen index value is 28%, has had reached fire retardant rank, and without melting drippage, carbon-forming performance is fine.
3 phosphinylidyne of table-(- three cage phosphate of N, N ', N ") triamine and MCA compounding are for the fire-retardant data in PBT
As shown in Table 3, product phosphinylidyne-(- three cage phosphate of N, N ', N ") triamine has with MCA compounding preferably cooperates with work
With, optimal additive amount proportion is 3: 2, and when total addition level is 25%, limit oxygen index does not melt drippage up to 33%,
The also price very third constellations of good carbon-forming performance and MCA is honest and clean, and the production cost of fire proofing can be greatly lowered.It thus can
To find out no matter triamine is single use product phosphinylidyne-(- three cage phosphate of N, N ', N "), or compounds with MCA, to PBT material
Material has preferable flame retardant effect.
4 phosphinylidyne of table-(- three cage phosphate of N, N ', N ") triamine and MPP compounding are for the fire-retardant data in PBT
As shown in Table 4, product phosphinylidyne-(- three cage phosphate of N, N ', N ") triamine has with MPP compounding preferably cooperates with work
With, optimal additive amount proportion is 1: 1, and when total addition level is 25%, limit oxygen index is up to 29%, though there is slight molten drop
Appearance, but have good carbon-forming performance, and the price of MPP is very cheap, being produced into for fire proofing can be greatly lowered
This.Thus it can be seen that no matter product phosphinylidyne-(- three cage phosphate of N, N ', N ") triamine is single use, or it is multiple with MPP
Match, has preferable flame retardant effect to PBT material.
Claims (3)
1. a kind of nitrogen phosphorus expansion type flame retardant phosphinylidyne-(- three cage phosphate of N, N ', N ") triamine compound, which is characterized in that the change
The structure for closing object is shown below:
2. a kind of three aminations of nitrogen phosphorus expansion type flame retardant phosphinylidyne-(- three cage phosphate of N, N ', N ") according to claim 1
Close the preparation method of object, which is characterized in that this method are as follows:
In the reactor equipped with blender, thermometer and reflux condensate device, under nitrogen protection, it is added a certain amount of organic molten
Agent, young laying ducks in cage amine and triethylamine are cooled to 10 DEG C, phosphorus oxychloride are added dropwise in 1h, and the molar ratio for controlling reaction mass is three
Chlorethoxyfos: young laying ducks in cage amine: triethylamine=1: 3: 3-1: 3.4: 3, dropping temperature is controlled at 10 DEG C~20 DEG C, after being added dropwise
Temperature is risen to 60-100 DEG C, after insulation reaction 2-6h, cold filtration, vacuum drying obtains the target product and triethylamine salt of yellow
The solid mixture of hydrochlorate dissolves purpose product, mistake with the dimethyl sulfoxide that volume milliliter is 10-15 times of target product grams
Filter, filtrate are evaporated to get target product phosphinylidyne-(- three cage phosphate of N, N ', N ") triamine；Young laying ducks in cage amine as described above
For 1- oxygen -1- phospha -2,6,7- trioxa octyl<4>amine, structural formula are as follows:
3. a kind of three aminations of nitrogen phosphorus expansion type flame retardant phosphinylidyne-(- three cage phosphate of N, N ', N ") according to claim 2
Close the preparation method of object, which is characterized in that a certain amount of organic solvent is tetrachloroethanes, dioxane, chloroform, dichloro
Ethane, diethylene glycol dimethyl ether, acetonitrile, dosage volume ml are 10-20 times of the quality grams of young laying ducks in cage.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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| CN101195642A (en) * | 2007-12-26 | 2008-06-11 | 北京理工大学 | Method for synthesizing fire resistant clathrate multi-ring phosphoric acid ester for engineering plastic |
| US20160102029A1 (en) * | 2014-07-15 | 2016-04-14 | John L. Lombardi | Oleo resins and phosphate esters for use in pyrotechnic formulations |
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|---|---|---|---|---|
| CN101195642A (en) * | 2007-12-26 | 2008-06-11 | 北京理工大学 | Method for synthesizing fire resistant clathrate multi-ring phosphoric acid ester for engineering plastic |
| US20160102029A1 (en) * | 2014-07-15 | 2016-04-14 | John L. Lombardi | Oleo resins and phosphate esters for use in pyrotechnic formulations |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN111978351B (en) * | 2020-08-06 | 2022-04-26 | 苏州科技大学 | Fire retardant cage-shaped organic silicon phosphoramide compound and preparation method thereof |
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