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 PDF

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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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cage
phosphinylidyne
phosphate
triamine
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魏怀鑫
沈敏杰
王彦林
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Suzhou University of Science and Technology
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02Phosphorus compounds
    • C07F9/547Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564Heterocyclic 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
    • C07F9/6571Heterocyclic 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
    • C07F9/6574Esters of oxyacids of phosphorus
    • C07F9/65748Esters of oxyacids of phosphorus the cyclic phosphorus atom belonging to more than one ring system
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/34Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477Six-membered rings
    • C08K5/3492Triazines
    • C08K5/34924Triazines containing cyanurate groups; Tautomers thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/49Phosphorus-containing compounds
    • C08K5/51Phosphorus bound to oxygen
    • C08K5/52Phosphorus bound to oxygen only
    • C08K5/521Esters of phosphoric acids, e.g. of H3PO4
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/49Phosphorus-containing compounds
    • C08K5/5399Phosphorus bound to nitrogen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/02Flame 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

Fire retardant phosphinylidyne-(- three cage phosphate of N, N ', N ") triamine compound and its preparation Method
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.
CN201811145922.6A 2018-09-18 2018-09-18 Fire retardant phosphinylidyne-(N, N ', N "-three cage phosphate) triamine compound and preparation method thereof Pending CN109265482A (en)

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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

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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 examiner, † Cited by third party
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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Application publication date: 20190125