CN102250384A - Preparation and application of flame retardant - Google Patents
Preparation and application of flame retardant Download PDFInfo
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- CN102250384A CN102250384A CN 201110128124 CN201110128124A CN102250384A CN 102250384 A CN102250384 A CN 102250384A CN 201110128124 CN201110128124 CN 201110128124 CN 201110128124 A CN201110128124 A CN 201110128124A CN 102250384 A CN102250384 A CN 102250384A
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- 0 CC=C(C=*)OP(NCCCCCCNP(OC=CC=C)(Oc1ccccc1)=O)(Oc1ccccc1)=O Chemical compound CC=C(C=*)OP(NCCCCCCNP(OC=CC=C)(Oc1ccccc1)=O)(Oc1ccccc1)=O 0.000 description 1
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Abstract
The invention relates to preparation and application of a flame retardant, and discloses a phosphorus-nitrogen flame retardant and a preparation method as well as application thereof. The phosphorus-nitrogen flame retardant, N,N'-di(diphenoxyl phosphoryl)-2,2'-hexamethylendiamine, has the structure which is as shown as a formula (I). The flame retardant is prepared by reacting diphenyl chlorophosphhate with hexamethylendiamine. In the invention, flame retardant modification is performed on a high molecular material by using the phosphorus-nitrogen flame retardant and polymer through melt blending; and through a synergistic flame retardant effect of phosphorus and nitrogen elements of the flame retardant, the flame retardant effect of the high molecular material is improved, the using amount of the flame retardant in the high molecular material is reduced, and the preparation cost of the flame retardant material is reduced.
Description
Technical field
The present invention relates to fire retardant and preparation method thereof, be specifically related to a kind of phosphorus-nitrogen containing flame retardant and its production and application, especially its application in the preparation flame retarded polymeric material.
Background technology
Along with the appearance that the mankind improve and limit, ban use of halogen flame regulation (WEEE, RoHS in 2006 in 2005, instructions such as EuP in 2007) environmental protection and healthy requirement, halogenated flame retardant is faced with great challenge.Expansion type flame retardant is as a kind of halogen-free flame retardants, along with rising, flame-retarded technology is widely used in flame-retardant polymer, when the superpolymer that contains this based flame retardant is heated, the surface can generate layer of even carbonaceous foam layer, play heat insulation, oxygen barrier, press down the effect of cigarette, and prevent to produce the molten drop phenomenon, have good flame retardancy.Expansion type flame retardant is main ignition-proof element with phosphorus nitrogen generally, two kinds of mixed type and one-pack types are arranged usually, the mixed type expanding fire retardant is with charcoal source, acid source, the composite by a certain percentage fire retardant of source of the gas compound, and the single component expansion type flame retardant is to collect acid source, charcoal source, source of the gas in same intramolecular fire retardant.Compare with the polycomponent expansion type flame retardant, have better thermostability and resistance to water soak, better matrix consistency and anti-surface transport and flame retarding efficiency be advantages of higher more.Phosphorus-nitrogen containing flame retardant provides a kind of new approach for the problem that solves above-mentioned flame-retardant modified macromolecular material existence.
Summary of the invention
The primary technical problem that the present invention will solve is to provide a kind of phosphorus-nitrogen containing flame retardant with flame retardant resistance.
Invent described phosphorus-nitrogen containing flame retardant, its structure is suc as formula shown in (I):
Second technical problem that the present invention will solve is to provide a kind of preparation method of above-mentioned phosphorus-nitrogen containing flame retardant.
The preparation method of described phosphorus-nitrogen containing flame retardant, method is as follows:
Diphenyl phosphate chloride shown in the formula (II) and hexanediamine reaction obtain the compound shown in the formula (I).
Below aforesaid method is elaborated.
The described reaction of the inventive method specifically can be carried out according to following: diphenyl phosphate chloride and hexanediamine, under the condition that solvent and acid binding agent exist, in 0～60 ℃ of reaction 2～15 hours, separate phosphorus-nitrogen containing flame retardant.
Described solvent is selected from one of the following: halogenated alkane, ester compound, ether compound, nitrile compounds; Preferred one of the following: 1,2-ethylene dichloride, trichloromethane, tetracol phenixin, methyl acetate, ethyl acetate, propyl acetate, butylacetate, isopropyl acetate, isobutyl acetate, pentyl acetate, ether, propyl ether, isopropyl ether, butyl ether, acetonitrile, propionitrile; One of more preferably following: trichloromethane, acetonitrile.
One of described acid binding agent is preferred following: triethylamine, pyridine, sodium bicarbonate, yellow soda ash, sodium hydroxide.
Described diphenyl phosphate chloride is recommended as 1.0: 2.0 with the amount of substance ratio that feeds intake of hexanediamine～and 4.5, preferred 1.0: 2.0～2.5.Described acid binding agent is 1.0～4.0: 1.0 with the amount of substance ratio that feeds intake of diphenyl phosphate chloride, preferred 2.5～3.0: 1.0.The volumetric usage of described solvent is recommended as 5～10ml/g in the quality of diphenyl phosphate chloride.
The temperature of reaction of the described reaction of method is preferably 30～50 ℃, and the reaction times is preferably 4～8 hours.
Method can adopt conventional separation method such as distillation to separate and obtain formula (I) compound after reaction finishes.
The 3rd technical problem that the present invention will solve is that described phosphorus-nitrogen containing flame retardant is applied to prepare flame retarded polymeric material, promptly makes described flame retarded polymeric material with described phosphorus-nitrogen containing flame retardant and polymkeric substance by melt blending.
The preparation method of described flame retarded polymeric material is specific as follows: phosphorus-nitrogen containing flame retardant shown in the formula (I) and polymkeric substance obtain described flame retarded polymeric material in 50～250 ℃ of melt blendings.
It is polyethylene, polypropylene, polyvinyl chloride, polystyrene, polymethylmethacrylate, ethylene-vinyl acetate copolymer (EVA), acrylonitrile-butadiene-styrene copolymer (ABS) that the present invention recommends described polymkeric substance
It is 5～30: 100 that the present invention recommends the mass ratio that feeds intake of described phosphorus-nitrogen containing flame retardant and polymkeric substance.
Compared with prior art, beneficial effect of the present invention is embodied in following several respects:
Fire retardant of the present invention is not halogen-containing, good flame retardation effect, applied widely, compliance with environmental protection requirements; The preparation manipulation of this fire retardant is easy, and is with low cost, is easy to industrialization.This fire retardant can prepare the high molecular fire retardant material by mechanical blending with polymkeric substance, reduces the fire retardant material preparation cost; Fire retardant of the present invention adopts non-halogen system, thereby has reduced " secondary harm " in the material combustion process; Fire retardant of the present invention utilizes phosphorus, the effect of nitrogen element cooperative flame retardant, improves the flame retardant effect to macromolecular material, reduces the usage quantity of fire retardant at macromolecular material, reduces the cost of fire retardant material.
Embodiment
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto:
Embodiment 1:N, N '-two (two phenoxy group phosphoryls)-2,2 '-hexanediamine synthetic
Mechanical stirring is being housed; thermometer; in the dry 250mL four-hole bottle of reflux condensing tube and dropping funnel; the diphenyl phosphate chloride and the 100mL chloroform that add 26.8g (0.1mol); back adding 20.0g (0.20mol) triethylamine stirs; cool off with frozen water; keeping reacting liquid temperature is 10 ℃; slow 3.0g (0.05mol) hexanediamine that drips and the mixed solution of 34mL chloroform; being warmed up to 40 ℃ after adding stirred 6 hours; revolve the steaming chloroform and get crude product, and use distilled water wash, get white solid N after the oven dry; (the two phenoxy group phosphoryls)-2 of N '-again; 2 '-hexanediamine, yield is 88%, purity is 95.3%.FT-IR(cm
-1)：3237，1251，1071，1006，923。
1H?NMR(CDCl
3)δ(ppm)：7.36～7.12(m，20H)，3.14～2.95(m，6H)，1.38(s，4H)，1.14(s，4H)。
Embodiment 2
N, the synthetic operation of N '-two (two phenoxy group phosphoryls)-2,2 '-hexanediamine is with embodiment 1.In the reaction of diphenyl phosphate chloride and hexanediamine, diphenyl phosphate chloride is 2.5: 1.0 with the amount of substance ratio that feeds intake of hexanediamine, the acid binding agent pyridine is 1.0: 1.0 with the amount of substance ratio that feeds intake of diphenyl phosphate chloride, solvent is selected acetonitrile for use, 10 ℃ of temperature of reaction, reaction times is 4 hours, and yield is 73.4%.
Embodiment 3
N, the synthetic operation of N '-two (two phenoxy group phosphoryls)-2,2 '-hexanediamine is with embodiment 1.In the reaction of diphenyl phosphate chloride and hexanediamine, diphenyl phosphate chloride is 3.5: 1.0 with the amount of substance ratio that feeds intake of hexanediamine, the acid binding agent sodium bicarbonate is 3.0: 1.0 with the amount of substance ratio that feeds intake of diphenyl phosphate chloride, solvent is selected ethyl acetate for use, 50 ℃ of temperature of reaction, reaction times is 8 hours, and yield is 86.4%.
Embodiment 4
N, the synthetic operation of N '-two (two phenoxy group phosphoryls)-2,2 '-hexanediamine is with embodiment 1.In the reaction of diphenyl phosphate chloride and hexanediamine, diphenyl phosphate chloride is 4.0: 1.0 with the amount of substance ratio that feeds intake of hexanediamine, acid binding agent sodium hydroxide is 1.5: 1.0 with the amount of substance ratio that feeds intake of diphenyl phosphate chloride, solvent is selected methylene dichloride for use, 0 ℃ of temperature of reaction, reaction times is 10 hours, and yield is 53.9%.
Embodiment 5
N, the synthetic operation of N '-two (two phenoxy group phosphoryls)-2,2 '-hexanediamine is with embodiment 1.In the reaction of diphenyl phosphate chloride and hexanediamine, diphenyl phosphate chloride is 4.5: 1.0 with the amount of substance ratio that feeds intake of hexanediamine, acid binding agent yellow soda ash is 2.5: 1.0 with the amount of substance ratio that feeds intake of diphenyl phosphate chloride, solvent is selected acetone for use, 60 ℃ of temperature of reaction, reaction times is 12 hours, and yield is 47.7%.
Embodiment 6
N, the synthetic operation of N '-two (two phenoxy group phosphoryls)-2,2 '-hexanediamine is with embodiment 1.In the reaction of diphenyl phosphate chloride and hexanediamine, diphenyl phosphate chloride is 4.5: 1.0 with the amount of substance ratio that feeds intake of hexanediamine, acid binding agent yellow soda ash is 2.8: 1.0 with the amount of substance ratio that feeds intake of diphenyl phosphate chloride, solvent is selected ether for use, 0 ℃ of temperature of reaction, reaction times is 2 hours, and yield is 31.7%.
Embodiment 7
N, the synthetic operation of N '-two (two phenoxy group phosphoryls)-2,2 '-hexanediamine is with embodiment 1.In the reaction of diphenyl phosphate chloride and hexanediamine, diphenyl phosphate chloride is 2.0: 1.0 with the amount of substance ratio that feeds intake of hexanediamine, acid binding agent yellow soda ash is 1.0: 1.0 with the amount of substance ratio that feeds intake of diphenyl phosphate chloride, solvent is selected propionitrile for use, 35 ℃ of temperature of reaction, reaction times is 5 hours, and yield is 67.4%.
Embodiment 8
N, the synthetic operation of N '-two (two phenoxy group phosphoryls)-2,2 '-hexanediamine is with embodiment 1.In the reaction of diphenyl phosphate chloride and hexanediamine, diphenyl phosphate chloride is 2.8: 1.0 with the amount of substance ratio that feeds intake of hexanediamine, the acid binding agent pyridine is 3.0: 1.0 with the amount of substance ratio that feeds intake of diphenyl phosphate chloride, solvent is selected tetrachloromethane for use, 60 ℃ of temperature of reaction, reaction times is 3 hours, and yield is 50.1%.
Embodiment 9
N, the synthetic operation of N '-two (two phenoxy group phosphoryls)-2,2 '-hexanediamine is with embodiment 1.In the reaction of diphenyl phosphate chloride and hexanediamine, diphenyl phosphate chloride is 2.4: 1.0 with the amount of substance ratio that feeds intake of hexanediamine, and solvent is selected butylacetate for use, 55 ℃ of temperature of reaction, and the reaction times is 9 hours, yield is 60.2%.
Embodiment 10: the preparation of fire retardant low-density polyethylene
The mass ratio that feeds intake is 5: 100 N; N '-two (two phenoxy group phosphoryls)-2,2 '-hexanediamine and new LDPE (film grade) pass through the single screw extrusion machine extruding pelletization down at 160 ℃ after high-speed mixer is pre-dispersed; the fire retardant low-density polyethylene that makes, the LOI of this material are 22.7.
Embodiment 11
The preparation manipulation of fire retardant low-density polyethylene is with embodiment 10, phosphorus-nitrogen containing flame retardant N, and the mass ratio that feeds intake of N '-two (two phenoxy group phosphoryls)-2,2 '-hexanediamine and new LDPE (film grade) is 10: 100, the LOI of the fire retardant low-density polyethylene of gained is 25.6.
Embodiment 12
The preparation manipulation of fire retardant low-density polyethylene is with embodiment 10, phosphorus-nitrogen containing flame retardant N, and the mass ratio that feeds intake of N '-two (two phenoxy group phosphoryls)-2,2 '-hexanediamine and new LDPE (film grade) is 20: 100, the LOI of the fire retardant low-density polyethylene of gained is 27.7.
Embodiment 13
The preparation manipulation of fire retardant low-density polyethylene is with embodiment 10, phosphorus-nitrogen containing flame retardant N, and the mass ratio that feeds intake of N '-two (two phenoxy group phosphoryls)-2,2 '-hexanediamine and new LDPE (film grade) is 30: 100, the LOI of the fire retardant low-density polyethylene of gained is 31.0.
Embodiment 14: the preparation of fire-retardant high density polyethylene(HDPE)
The mass ratio that feeds intake is 10: 100 N; N '-two (two phenoxy group phosphoryls)-2,2 '-hexanediamine and high density polyethylene(HDPE) pass through the single screw extrusion machine extruding pelletization down at 190 ℃ after high-speed mixer is pre-dispersed; the fire-retardant high density polyethylene(HDPE) that makes, the LOI of this material are 24.9.
Embodiment 15
The preparation manipulation of fire-retardant high density polyethylene(HDPE) is with embodiment 14, phosphorus-nitrogen containing flame retardant N, and the mass ratio that feeds intake of N '-two (two phenoxy group phosphoryls)-2,2 '-hexanediamine and high density polyethylene(HDPE) is 25: 100, the LOI of the fire retardant low-density polyethylene of gained is 30.1.
Embodiment 16: the preparation of fire retardant polystyrene
The mass ratio that feeds intake is 16: 100 N; N '-two (two phenoxy group phosphoryls)-2,2 '-hexanediamine and polystyrene pass through the single screw extrusion machine extruding pelletization down at 180 ℃ after high-speed mixer is pre-dispersed; the fire retardant polystyrene that makes, the LOI of this material are 24.8.
Embodiment 17
The preparation manipulation of fire retardant polystyrene is with embodiment 16, phosphorus-nitrogen containing flame retardant N, and the mass ratio that feeds intake of N '-two (two phenoxy group phosphoryls)-2,2 '-hexanediamine and polystyrene is 10: 100, the LOI of the fire retardant polystyrene of gained is 23.3.
Embodiment 18
The preparation manipulation of fire retardant polystyrene is with embodiment 16, phosphorus-nitrogen containing flame retardant N, and the mass ratio that feeds intake of N '-two (two phenoxy group phosphoryls)-2,2 '-hexanediamine and polystyrene is 28: 100, the LOI of the fire retardant polystyrene of gained is 28.9.
Embodiment 19: the preparation of fire-retardant polymethylmethacrylate
The mass ratio that feeds intake is 13: 100 N; N '-two (two phenoxy group phosphoryls)-2,2 '-hexanediamine and polymethylmethacrylate pass through the single screw extrusion machine extruding pelletization down at 190 ℃ after high-speed mixer is pre-dispersed; the fire-retardant polymethylmethacrylate that makes, the LOI of this material are 26.1.
Embodiment 20
The preparation manipulation of fire-retardant polymethylmethacrylate is with embodiment 19; phosphorus-nitrogen containing flame retardant N; the mass ratio that feeds intake of N '-two (two phenoxy group phosphoryls)-2,2 '-hexanediamine and polymethylmethacrylate is 22: 100, and the LOI of the fire-retardant polymethylmethacrylate of gained is 27.0.
Embodiment 21
The preparation manipulation of fire-retardant polymethylmethacrylate is with embodiment 19; phosphorus-nitrogen containing flame retardant N; the mass ratio that feeds intake of N '-two (two phenoxy group phosphoryls)-2,2 '-hexanediamine and polymethylmethacrylate is 26: 100, and the LOI of the fire-retardant polymethylmethacrylate of gained is 28.2.
Embodiment 22: the preparation of flame-proof ethylene-vinyl acetate copolymer
The mass ratio that feeds intake is 8: 100 N; N '-two (two phenoxy group phosphoryls)-2; 2 '-hexanediamine and ethylene-vinyl acetate copolymer be after high-speed mixer is pre-dispersed; pass through the single screw extrusion machine extruding pelletization down at 160 ℃; the flame-proof ethylene-vinyl acetate copolymer that makes, the LOI of this material are 22.2.
Embodiment 23
The preparation manipulation of flame-proof ethylene-vinyl acetate copolymer is with embodiment 22; phosphorus-nitrogen containing flame retardant N; N '-two (two phenoxy group phosphoryls)-2; 2 '-mass ratio that feeds intake of hexanediamine and ethylene-vinyl acetate copolymer is 17: 100, the LOI of the flame-proof ethylene-vinyl acetate copolymer of gained is 25.4.
Embodiment 24
The preparation manipulation of flame-proof ethylene-vinyl acetate copolymer is with embodiment 22; phosphorus-nitrogen containing flame retardant N; N '-two (two phenoxy group phosphoryls)-2; 2 '-mass ratio that feeds intake of hexanediamine and ethylene-vinyl acetate copolymer is 30: 100, the LOI of the flame-proof ethylene-vinyl acetate copolymer of gained is 28.9.
Embodiment 25: the preparation of fire-retardant acrylonitrile-butadiene diene-styrene copolymer
The mass ratio that feeds intake is 15: 100 N; N '-two (two phenoxy group phosphoryls)-2; 2 '-hexanediamine and acrylonitrile-butadiene-styrene copolymer be after high-speed mixer is pre-dispersed; pass through the single screw extrusion machine extruding pelletization down at 190 ℃; the fire-retardant acrylonitrile-butadiene diene-styrene copolymer that makes, the LOI of this material are 24.2.
Embodiment 26
The preparation manipulation of fire-retardant acrylonitrile-butadiene diene-styrene copolymer is with embodiment 25; phosphorus-nitrogen containing flame retardant N; N '-two (two phenoxy group phosphoryls)-2; 2 '-mass ratio that feeds intake of hexanediamine and acrylonitrile-butadiene-styrene copolymer is 25: 100, the LOI of the fire-retardant acrylonitrile-butadiene diene-styrene copolymer of gained is 28.4.
Embodiment 27
The preparation manipulation of fire-retardant acrylonitrile-butadiene diene-styrene copolymer is with embodiment 25; phosphorus-nitrogen containing flame retardant N; N '-two (two phenoxy group phosphoryls)-2; 2 '-mass ratio that feeds intake of hexanediamine and acrylonitrile-butadiene-styrene copolymer is 30: 100, the LOI of the fire-retardant acrylonitrile-butadiene diene-styrene copolymer of gained is 32.7.
Claims (10)
1. phosphorus-nitrogen containing flame retardant, its structure is suc as formula shown in (I):
2. the preparation method of phosphorus-nitrogen containing flame retardant as claimed in claim 1, method is as follows:
Diphenyl phosphate chloride shown in the formula (II) and hexanediamine reaction obtain the compound shown in the formula (I).
3. the preparation method of phosphorus-nitrogen containing flame retardant as claimed in claim 2, it is characterized in that described reaction is specific as follows: diphenyl phosphate chloride and hexanediamine, under the condition that solvent and acid binding agent exist, in 0～60 ℃ of reaction 2～12 hours, separate phosphorus-nitrogen containing flame retardant; Described solvent is selected from one of the following: halogenated alkane, ester compound, ether compound, nitrile compounds.
4. as the preparation method of claim 2 or 3 described phosphorus-nitrogen containing flame retardants, it is characterized in that the described diphenyl phosphate chloride and the amount of substance ratio that feeds intake of hexanediamine are 1.0: 2.0～4.5.
5. the preparation method of phosphorus-nitrogen containing flame retardant as claimed in claim 3, it is characterized in that described solvent is selected from one of the following: 1,2-ethylene dichloride, trichloromethane, tetracol phenixin, methyl acetate, ethyl acetate, propyl acetate, butylacetate, isopropyl acetate, isobutyl acetate, pentyl acetate, ether, propyl ether, isopropyl ether, butyl ether, acetonitrile, propionitrile.
6. the preparation method of phosphorus-nitrogen containing flame retardant as claimed in claim 3, it is one of following to it is characterized in that described acid binding agent is selected from: triethylamine, pyridine, sodium bicarbonate, yellow soda ash, sodium hydroxide, described acid binding agent is 1.0～4.0: 1.0 with the amount of substance ratio that feeds intake of diphenyl phosphate chloride.
7. phosphorus-nitrogen containing flame retardant as claimed in claim 1 is in the application of preparation in the flame retarded polymeric material, it is characterized in that it being that phosphorus-nitrogen containing flame retardant and polymkeric substance with shown in the formula (I) makes described flame retarded polymeric material by melt blending.
8. application as claimed in claim 7, it is characterized in that described flame retarded polymeric material specifically is prepared as follows: phosphorus-nitrogen containing flame retardant shown in the formula (I) and polymer melt blend obtain described flame retarded polymeric material.
9. as claim 7 or 8 described application, it is characterized in that described polymkeric substance is polyethylene, polypropylene, polyvinyl chloride, polystyrene, polymethylmethacrylate, ethylene-vinyl acetate copolymer, acrylonitrile-butadiene-styrene copolymer.
10. as claim 7 or 8 described application, it is characterized in that the mass ratio that feeds intake of described phosphorus-nitrogen containing flame retardant and polymkeric substance is 5～30: 100.
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| CN 201110128124 CN102250384A (en) | 2011-05-13 | 2011-05-13 | Preparation and application of flame retardant |
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| CN 201110128124 CN102250384A (en) | 2011-05-13 | 2011-05-13 | Preparation and application of flame retardant |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103265653A (en) * | 2013-04-15 | 2013-08-28 | 江苏德威新材料股份有限公司 | Fire retardant, preparation method thereof and application thereof in polyvinyl chloride (PVC) wire and cable materials |
| WO2013191227A1 (en) * | 2012-06-18 | 2013-12-27 | 大京化学株式会社 | Method for producing phosphoric acid ester amides |
| CN105315399A (en) * | 2015-04-16 | 2016-02-10 | 黄国波 | Highly-transparent flame-retardant modified organic glass and preparation method thereof |
| CN109081945A (en) * | 2018-09-18 | 2018-12-25 | 苏州科技大学 | - two young laying ducks in cage amine compounds of fire retardant phenyl phosphonic-N, N ' and preparation method thereof |
| CN109180732A (en) * | 2018-09-18 | 2019-01-11 | 苏州科技大学 | Fire retardant diphenyl time phosphono-N- young laying ducks in cage amine compounds and preparation method thereof |
| CN109232651A (en) * | 2018-09-18 | 2019-01-18 | 苏州科技大学 | - two young laying ducks in cage amine compounds of organic phosphine nitrogen combustion inhibitor phenyl Asia phosphono-N, N ' and preparation method thereof |
| CN109336930A (en) * | 2018-09-18 | 2019-02-15 | 苏州科技大学 | Fire retardant phenyl phosphono-N, N '-two young laying ducks in cage amine compounds and preparation method thereof |
| EP4209522A4 (en) * | 2020-10-29 | 2024-03-27 | LG Energy Solution, Ltd. | Flame retardant group-containing polymer, non-aqueous electrolyte battery separator comprising same, and non-aqueous electrolyte battery |
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| GB830714A (en) * | 1956-12-22 | 1960-03-16 | Benckiser Gmbh Joh A | A method for the preparation of di-amine-n-n-bis-phosphoric and thionophosphoric acid derivatives |
| JPS5419919A (en) * | 1977-07-14 | 1979-02-15 | Mitsubishi Rayon Co Ltd | Novel phosphoric acid amide, its preparation, and flame-retardants consisting of the compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB830714A (en) * | 1956-12-22 | 1960-03-16 | Benckiser Gmbh Joh A | A method for the preparation of di-amine-n-n-bis-phosphoric and thionophosphoric acid derivatives |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013191227A1 (en) * | 2012-06-18 | 2013-12-27 | 大京化学株式会社 | Method for producing phosphoric acid ester amides |
| CN103265653A (en) * | 2013-04-15 | 2013-08-28 | 江苏德威新材料股份有限公司 | Fire retardant, preparation method thereof and application thereof in polyvinyl chloride (PVC) wire and cable materials |
| CN103265653B (en) * | 2013-04-15 | 2015-05-27 | 江苏德威新材料股份有限公司 | Fire retardant, preparation method thereof and application thereof in polyvinyl chloride (PVC) wire and cable materials |
| CN105315399A (en) * | 2015-04-16 | 2016-02-10 | 黄国波 | Highly-transparent flame-retardant modified organic glass and preparation method thereof |
| CN109081945A (en) * | 2018-09-18 | 2018-12-25 | 苏州科技大学 | - two young laying ducks in cage amine compounds of fire retardant phenyl phosphonic-N, N ' and preparation method thereof |
| CN109180732A (en) * | 2018-09-18 | 2019-01-11 | 苏州科技大学 | Fire retardant diphenyl time phosphono-N- young laying ducks in cage amine compounds and preparation method thereof |
| CN109232651A (en) * | 2018-09-18 | 2019-01-18 | 苏州科技大学 | - two young laying ducks in cage amine compounds of organic phosphine nitrogen combustion inhibitor phenyl Asia phosphono-N, N ' and preparation method thereof |
| CN109336930A (en) * | 2018-09-18 | 2019-02-15 | 苏州科技大学 | Fire retardant phenyl phosphono-N, N '-two young laying ducks in cage amine compounds and preparation method thereof |
| EP4209522A4 (en) * | 2020-10-29 | 2024-03-27 | LG Energy Solution, Ltd. | Flame retardant group-containing polymer, non-aqueous electrolyte battery separator comprising same, and non-aqueous electrolyte battery |
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Application publication date: 20111123 |