CN103739877A - Phosphorus-nitrogen flame retardant and preparation method thereof - Google Patents
Phosphorus-nitrogen flame retardant and preparation method thereof Download PDFInfo
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- CN103739877A CN103739877A CN201410008892.XA CN201410008892A CN103739877A CN 103739877 A CN103739877 A CN 103739877A CN 201410008892 A CN201410008892 A CN 201410008892A CN 103739877 A CN103739877 A CN 103739877A
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Abstract
The invention provides a phosphorus-nitrogen flame retardant and a preparation method thereof. The phosphorus-nitrogen flame retardant is synthesized through condensation and addition and electrophilic addition reaction of the raw materials including organic amines, hypophosphorous acid and fatty aldehydes in the presence of acid catalysts, wherein the organic amines are one or more than one of primary diamines with molecular formula of NH2RNH2, wherein R is -(CH2)m<->, -[CH2CH2NH]pCH2CH2<-> or -C6H4<->, m and p are positive integers, m is not more than 6 and not less than 2, and p is not more than 4 and not less than 1; fatty aldehydes are one or more than one of formaldehyde, acetaldehyde, propionaldehyde or butyraldehyde; the adopted acid catalysts can be one or more than one of hydrochloric acid, sulfuric acid or nitric acid. The mole ratio of the organic amines to hypophosphorous acid to fatty aldehydes adopted in the preparation process is preferably 1:(2-5):(2-5), the reaction temperature is preferably 70-90 DEG C, and the reaction time is preferably 2-6 hours.
Description
One, technical field
The present invention relates to fire retardant and preparation method thereof, particularly phosphorus-nitrogen type fire retardant and preparation method thereof, belongs to flame retardant area.
Two, background technology
Polymkeric substance is widely used in industrial production and people's daily life, but most polymers is all inflammable, in air, running into burning things which may cause a fire disaster metropolitan is lighted and is burnt, the melting dropping that burning produces other combustiblematerialss that can also ignite, people's the security of the lives and property is caused to huge threat and harm, therefore the fire-retardant problem of polymkeric substance is subject to extensive concern, and polymkeric substance becomes focus with fire retardant research and development.
Along with countries in the world environmental protection policy is put into effect, the green of fire retardant and environmental protection are the development trends of current fire retardant, and the environmental protection fire retarding agents such as phosphorus flame retardant, nitrogenated flame retardant become the exploitation focus of fire retardant.Phosphorus flame retardant can be brought into play the fire-retardant and condensed phase fire retardation of gas phase simultaneously, during burning, can form charring layer at polymer surfaces, and generation is covered in the thick liquid film of coke layer, reduced heat and mass transfer between the gentle solid phase of oxygen, played oxygen barrier, heat insulation effect, secondly after phosphorus flame retardant heat absorption, decomposed, there is stronger dehydration property, the water vapour generating absorbs large calorimetric, reduces temperature, thereby reaches flame retardant effect.Nitrogenated flame retardant is subject to heat release CO
2, NO
2, N
2, NH
3, H
2the non-flammable gases such as O, cover and are looped around around polymkeric substance, can water down the inflammable gas of burning situation, dilution oxygen concn and cut off contacting of polymkeric substance and oxygen in air, and can catch high energy free radical, and the burning of inhibition polymkeric substance, thus bring into play flame retardant effect.
Adopt P contained compound and nitrogenous compound to synthesize by chemical reaction the phosphorus-nitrogen type fire retardants phosphorous, two kinds of elements of nitrogen of simultaneously holding concurrently, by the synergy between phosphorus, two kinds of ignition-proof elements of nitrogen, can bring into play good flame retardant effect, have the flame-retarding characteristic of phosphorus flame retardant and nitrogenated flame retardant concurrently, will be the new direction of fire retardant from now on.
Three, summary of the invention
The object of this invention is to provide a kind of novel phosphorus-nitrogen type fire retardant and preparation method thereof.
The technical solution that realizes the object of the invention is: a kind of phosphorus-nitrogen type fire retardant is to take organic amine, Hypophosporous Acid, 50 and alkanoic under acid catalysis, to react the synthetic fire retardant that includes phosphorus and two kinds of elements of nitrogen as raw material; Wherein, organic amine is that molecular formula is NH
2rNH
2one or more binary primary amine, R is-(CH
2)
m-,-[CH
2cH
2nH]
pcH
2cH
2-or-C
6h
4-, m and p are positive integer and 6>=m>=2,4>=p>=1; Alkanoic is one or more in formaldehyde, acetaldehyde, propionic aldehyde or butyraldehyde.
A kind of preparation method of phosphorus-nitrogen type fire retardant is that adopting organic amine, Hypophosporous Acid, 50 and alkanoic is that raw material reacts the synthetic phosphorus-nitrogen type fire retardant that includes phosphorus and two kinds of elements of nitrogen under acid catalysis; Wherein, organic amine is that molecular formula is NH
2rNH
2one or more binary primary amine, R is-(CH
2)
m-,-[CH
2cH
2nH]
pcH
2cH
2-or-C
6h
4-, m and p are positive integer and 6>=m>=2,4>=p>=1; Alkanoic is one or more in formaldehyde, acetaldehyde, propionic aldehyde or butyraldehyde.
The preparation method's of phosphorus-nitrogen type fire retardant of the present invention reaction process is: organic amine, Hypophosporous Acid, 50 and alkanoic are added in reactor and add acid catalyst, rise to required temperature of reaction and carry out condensation addition and electrophilic addition reaction, reaction finishes to obtain phosphorus-nitrogen type fire retardant by filtering, washing.
The acid catalyst that the preparation method of phosphorus-nitrogen type fire retardant of the present invention adopts is one or more in hydrochloric acid, sulfuric acid or nitric acid.In the preparation method of phosphorus-nitrogen type fire retardant of the present invention, the mol ratio of organic amine, Hypophosporous Acid, 50 and alkanoic is preferably 1: (2～5): (2～5).The temperature of reaction that the preparation method of phosphorus-nitrogen type fire retardant of the present invention adopts is preferably 70～90 ℃.The reaction times that the preparation method of phosphorus-nitrogen type fire retardant of the present invention adopts is preferably 2～6 hours.
Compared with prior art, the present invention has significant advantage.The present invention adopts cheap raw material organic amine, Hypophosporous Acid, 50 and alkanoic by simple reaction process (condensation addition and electrophilic addition reaction), to prepare the New Phosphorus nitrogen type flame retardant that simultaneously contains phosphorus and two kinds of ignition-proof elements of nitrogen, reaction conditions is gentle, productive rate is higher, and phosphorus-nitrogen type fire retardant of the present invention is not halogen-containing, it is eco-friendly BACN.
Four, embodiment
Phosphorus-nitrogen type fire retardant of the present invention is to take organic amine, Hypophosporous Acid, 50 and alkanoic under acid catalysis, to react the synthetic fire retardant that includes phosphorus and two kinds of elements of nitrogen as raw material; Wherein, organic amine is that molecular formula is NH
2rNH
2one or more binary primary amine, R is-(CH
2)
m-,-[CH
2cH
2nH]
pcH
2cH
2-or-C
6h
4-, m and p are positive integer and 6>=m>=2,4>=p>=1; Alkanoic is one or more in formaldehyde, acetaldehyde, propionic aldehyde or butyraldehyde.
The molecular formula of phosphorus-nitrogen type fire retardant of the present invention is roughly:
In formula: n is 0 or positive integer; P is 0,1,2 or 3
The preparation method of phosphorus-nitrogen type fire retardant of the present invention is: adopting organic amine, Hypophosporous Acid, 50 and alkanoic is that raw material reacts the synthetic phosphorus-nitrogen type fire retardant that includes phosphorus and two kinds of elements of nitrogen under acid catalysis; Wherein, organic amine is that molecular formula is NH
2rNH
2one or more binary primary amine, R can be-(CH
2)
m-,-[CH
2cH
2nH]
pcH
2cH
2-or-C
6h
4-, m and p are positive integer and 6>=m>=2,4>=p>=1; Alkanoic is one or more in formaldehyde, acetaldehyde, propionic aldehyde or butyraldehyde.
Organic amine of the present invention can be that molecular formula is NH
2rNH
2a kind of binary primary amine, can be also that molecular formula is NH
2rNH
2the mixing binary primary amine of two or more binary primary amines.NH
2rNH
2can be quadrol, propylene diamine, butanediamine, pentamethylene diamine, hexanediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamine or phenylenediamines.
The preparation method's of phosphorus-nitrogen type fire retardant of the present invention reaction process is: organic amine, Hypophosporous Acid, 50 and alkanoic are added in reactor and add acid catalyst, rise to required temperature of reaction and carry out condensation addition and electrophilic addition reaction, reaction finishes to obtain phosphorus-nitrogen type fire retardant by filtering, washing.
The chemical equation of phosphorus-nitrogen type fire retardant preparation process of the present invention is roughly (in formula, symbol is the same):
Phosphorus-nitrogen type fire retardant preparation process of the present invention can add a small amount of unary primary amine, and such as methylamine, ethamine, propylamine, butylamine etc., the molecular formula of unary primary amine can be expressed as NH
2r
1, R here
1for alkyl or aryl.At this moment unary primary amine can be used as the molecular weight regulator of phosphorus-nitrogen type fire retardant of the present invention, as end group.Therefore, the at this moment aforementioned molecular formula of phosphorus-nitrogen type fire retardant of the present invention and the Q of chemical equation
1except aforementioned, described can also be
(now aforesaid n is positive integer, non-vanishing), Q
2except aforementioned, described can also be
The acid catalyst that the preparation method of phosphorus-nitrogen type fire retardant of the present invention adopts can be one or more in hydrochloric acid, sulfuric acid or nitric acid.The H that in reaction system, acid catalyst provides
+concentration is preferably 0.001-0.02mol/L, now reacts gained yield larger.The mol ratio of organic amine, Hypophosporous Acid, 50 and alkanoic that the preparation method of phosphorus-nitrogen type fire retardant of the present invention adopts preferably 1: (2～5): (2～5).The temperature of reaction that the preparation method of phosphorus-nitrogen type fire retardant of the present invention adopts is preferably between 70～90 ℃, and the reaction times is preferably between 2～6 hours.
Embodiment 1 adds the mol ratio of quadrol, Hypophosporous Acid, 50 and formaldehyde raw material quadrol, Hypophosporous Acid, 50 and the formaldehyde solution of 1: 3: 3 (30% concentration) in reactor, and adds the hydrochloric acid soln (H that in system, hydrochloric acid provides
+concentration is 0.004mol/L), after stirring, temperature rises to 75 ℃ of reactions 4 hours, and reaction finishes rear filtration, and filter cake is used to acetone, methylene dichloride and deionized water wash successively, through vacuum-drying, obtains deep yellow solid, is phosphorus-nitrogen type fire retardant of the present invention.Use it for fire retarding epoxide resin, while adopting synthetic phosphorus-nitrogen type fire retardant here separately, consumption 18% can be so that horizontal firing rank reaches FH-1 level.
Embodiment 2 adds the mol ratio of diethylenetriamine, Hypophosporous Acid, 50 and formaldehyde raw material diethylenetriamine, Hypophosporous Acid, 50 and the formaldehyde solution of 1: 3: 4 (30% concentration) in reactor, and add hydrochloric acid-sulfuric acid mixture liquid (36% concentrated hydrochloric acid of hydrochloric acid-sulfuric acid mixture liquid: 98% vitriol oil is 5: 1 (mass ratio), the H that in system, hydrochloric acid-sulfuric acid mixture liquid provides
+concentration is 0.006mol/L), after stirring, temperature rises to 85 ℃ of reactions 3 hours, and reaction finishes rear filtration, and filter cake is used to acetone, methylene dichloride and deionized water wash successively, through vacuum-drying, obtains deep yellow solid, is phosphorus-nitrogen type fire retardant of the present invention.Use it for fire retarding epoxide resin, while adopting synthetic phosphorus-nitrogen type fire retardant here separately, consumption 20% can be so that horizontal firing rank reaches FH-1 level.
The present invention adopts the quadrol of foregoing other organic amine alternate embodiments 1 or the diethylenetriamine of embodiment 2 can synthesize equally the corresponding phosphorus-nitrogen type fire retardant with flame retardant effect, adopts the formaldehyde of acetaldehyde, propionic aldehyde, butyraldehyde or mixed aldehyde alternate embodiment 1 and embodiment 2 can synthesize equally the corresponding phosphorus-nitrogen type fire retardant with flame retardant effect.
Claims (7)
1. a phosphorus-nitrogen type fire retardant, is characterized in that: be to take organic amine, Hypophosporous Acid, 50 and alkanoic under acid catalysis, to react the synthetic fire retardant that includes phosphorus and two kinds of elements of nitrogen as raw material; Wherein, organic amine is that molecular formula is NH
2rNH
2one or more binary primary amine, R is-(CH
2)
m-,-[CH
2cH
2nH]
pcH
2cH
2-or-C
6h
4-, m and p are positive integer and 6>=m>=2,4>=p>=1 here; Alkanoic is one or more in formaldehyde, acetaldehyde, propionic aldehyde or butyraldehyde.
2. a preparation method for phosphorus-nitrogen type fire retardant, is characterized in that: adopting organic amine, Hypophosporous Acid, 50 and alkanoic is that raw material reacts the synthetic phosphorus-nitrogen type fire retardant that includes phosphorus and two kinds of elements of nitrogen under acid catalysis; Wherein, organic amine is that molecular formula is NH
2rNH
2one or more binary primary amine, R is-(CH
2)
m-,-[CH
2cH
2nH]
pcH
2cH
2-or-C
6h
4-, m and p are positive integer and 6>=m>=2,4>=p>=1 here; Alkanoic is one or more in formaldehyde, acetaldehyde, propionic aldehyde or butyraldehyde.
3. the preparation method of phosphorus-nitrogen type fire retardant according to claim 2, it is characterized in that: organic amine, Hypophosporous Acid, 50 and alkanoic are added in reactor and add acid catalyst, rise to required temperature of reaction and carry out condensation addition and electrophilic addition reaction, reaction finishes to obtain phosphorus-nitrogen type fire retardant by filtering, washing.
4. according to the preparation method of phosphorus-nitrogen type fire retardant described in claim 2 or 3, it is characterized in that: the acid catalyst of employing is one or more in hydrochloric acid, sulfuric acid or nitric acid.
5. according to the preparation method of phosphorus-nitrogen type fire retardant described in claim 2～4 any one, it is characterized in that: the mol ratio of organic amine, Hypophosporous Acid, 50 and alkanoic is 1: (2～5): (2～5).
6. according to the preparation method of phosphorus-nitrogen type fire retardant described in claim 2～5 any one, it is characterized in that: temperature of reaction is 70～90 ℃.
7. according to the preparation method of phosphorus-nitrogen type fire retardant described in claim 2～6 any one, it is characterized in that: the reaction times is 2～6 hours.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104109246A (en) * | 2014-06-20 | 2014-10-22 | 南京航空航天大学 | P-N intumescent flame retardant and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101027343A (en) * | 2004-09-22 | 2007-08-29 | 罗狄亚英国有限公司 | Aminophosphinate polymers |
-
2014
- 2014-01-09 CN CN201410008892.XA patent/CN103739877A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101027343A (en) * | 2004-09-22 | 2007-08-29 | 罗狄亚英国有限公司 | Aminophosphinate polymers |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104109246A (en) * | 2014-06-20 | 2014-10-22 | 南京航空航天大学 | P-N intumescent flame retardant and preparation method thereof |
| CN104109246B (en) * | 2014-06-20 | 2016-08-17 | 南京航空航天大学 | A kind of P-N expanding fire retardant and preparation method thereof |
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Application publication date: 20140423 |