CN101560399A - Phosphorus flame retardant, preparation method thereof and application in PU flame retardance - Google Patents
Phosphorus flame retardant, preparation method thereof and application in PU flame retardance Download PDFInfo
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- CN101560399A CN101560399A CNA2009100397053A CN200910039705A CN101560399A CN 101560399 A CN101560399 A CN 101560399A CN A2009100397053 A CNA2009100397053 A CN A2009100397053A CN 200910039705 A CN200910039705 A CN 200910039705A CN 101560399 A CN101560399 A CN 101560399A
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Abstract
The invention discloses phosphorus flame retardant, a preparation method thereof and application in PU flame retardance. The flame retardant is magnesium hydrogen phosphate flame retardant and is prepared by the double decomposition reaction of magnesium chloride and disodium hydrogen phosphate. By utilizing the functions of dehydration, carbonization and expansion of phosphoric acid which is one of the high-temperature decomposition products of the magnesium hydrogen phosphate, the invention blocks the heat transmission and greatly reduces the generation of inflammable gas, thereby greatly improving the flame retarding efficiency. The phosphorus flame retardant does not include halogen, is nontoxic and environment-friendly and generates low smoke; and compared with the traditional halogen flame retardant, the phosphorus flame retardant has lower market cost. The phosphorus flame retardant has the main component of magnesium hydrogen phosphate, can be added to base materials with various colors, can not change the characteristics of the base materials, and also has the advantages of no precipitation, low addition and easy processing.
Description
Technical field
The present invention relates to flame retardant area, be specifically related to a kind of phosphorus flame retardant and preparation method thereof and the application in PU is fire-retardant.
Background technology
Macromolecular material has also brought potential fire safety evaluating problem when the widespread use of every field brings huge interests for people's production and life, in order to reduce the generation of fire, countries in the world all are being devoted to research and are being used fire retardant and fire retardant material.
Fire retardant is a kind of auxiliary agent that can improve the flame retardancy or the self-extinguishing of combustiblematerials, is the auxiliary agent that is only second to the softening agent consumption in the additives for plastics.Fire retardant need possess following condition usually:
(1) heat decomposition temperature will be higher than the processing temperature (approximately exceeding about 160 ℃) of superpolymer;
(2) intermiscibility is good, can with the superpolymer uniform mixing, do not separate out;
(3) its other performances that apply object there is not serious detrimentally affect, as mechanical property, processing characteristics, melting index and every intensity etc.;
(4) production cost is low, nontoxic, does not discharge poisonous and corrosive gases during burning.
In fact, any one matter all is difficult to satisfy above-mentioned various condition, and good fire retardant often uses by two or more materials are collaborative, thereby requires people to seek effective fire retardant, also will study its optimum formula.
The fire retardant of old brand---halogen containing flame-retardant is emitted a large amount of hydrogen halides when material combustion, and then suction formation has the haloid acid of severe corrosive and causes the secondary public hazards, fire retardant Halogen cry grows to even greater heights now, halogen containing flame-retardant is difficult in 21 century and obtains large development, and the inorganic fire retardant that contains combination water, as Al (OH)
3, Mg (OH)
2Deng will developing to miniaturization and nanometer direction, single fire retardant will be substituted by compound fire retardant with synergistic effect, and the BACN of 21 century will be Halogen, efficient, low cigarette, low toxicity, multi-functional composite fire retardant
In each based flame retardant, phosphorus flame retardant occupies critical role, it has not only overcome the defective that Halogen type fire retardant combustion fumes is big, emit poisonous and corrosive gases, improved simultaneously the shortcoming that the high addition of inorganic combustion inhibitor has a strong impact on the physical and mechanical properties of material again, accomplished that high flame retardant, low cigarette, low toxicity, non-corrosiveness gas produce.
The fire retardant mechanism of phosphorus flame retardant is: the fire retardant decomposes produces phosphoric acid, metaphosphoric acid, poly-metaphosphoric acid on the one hand, these phosphoric acid have the intensive dehydration property, can make the polymer surfaces dehydration carbonization, and simple substance carbon can not produce the combustion by evaporation and the decomposition combustion of flame, so, have fire retardation; Fire retardant is subjected to thermogenesis PO free radical on the other hand, can absorb H in a large number, the HO free radical, thus interrupt combustion reactions.
Phosphorus flame retardant is according to the The Nomenclature Composition and Structure of Complexes of phosphorus flame retardant, and can be divided into inorganic phosphorus flame retardant and organic phosphorus flame retardant two big classes: the inorganic phosphorus flame retardant comprises red phosphorus, phosphoric acid salt and ammonium polyphosphate etc.; Organic phosphorus flame retardant comprises phosphoric acid ester, phosphorous acid ester, phosphonic acid ester and squama salt etc.
Inorganic combustion inhibitor is with a long history, mainly is phosphoric acid salt such as red phosphorus, ammonium polyphosphate, primary ammonium phosphate, and decomposes goes out phosphoric acid, metaphosphoric acid and H
2O etc., and promote into the surface that charcoal is overlying on base material and play fire-retardant effect, be applied to PVC, nylon epoxy resin, polyester and polymeric amide etc.
Red phosphorus is a kind of fire retardant of excellent property, has efficient, as to press down cigarette, low toxicity flame retardant effect, red phosphorus is 400 ℃ of decomposes, depolymerization forms white phosphorus, white phosphorus is oxidized to the oxygen acid of the phosphorus of viscosity in the presence of steam, this class acid promptly is covered in by the fire retardant material surface, impels material surface to quicken dehydration carbonization again, forms the charcoal layer.Liquid film and charcoal layer can play accumulation of heat, stop the effect of gaseous interchange, and protection lower floor is no longer continued oxidation, plays fire retardation.But the easy in actual applications moisture absorption, oxidation are also emitted hypertoxic gas, the dust explosive, in process operation processes such as, molding mixing, there is ignition hazard with resin, and it is scarlet, easily make color articles, suction easily is with the polymkeric substance poor compatibility, should not be uniformly dispersed, cause the base material physicals to descend.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of white powder is provided, can add in the plastics of any color phosphorus flame retardant halogen-containing, nontoxic and not with low cost to.
Another object of the present invention is to provide the preparation method of above-mentioned phosphorus flame retardant.
Another object of the present invention is to provide the application of above-mentioned phosphorus flame retardant in PU is fire-retardant.
Above-mentioned purpose of the present invention is achieved by following scheme:
A kind of phosphorus flame retardant, this phosphorus flame retardant belongs to the inorganic salts fire retardant, is specially the secondary magnesium phosphate fire retardant, and secondary magnesium phosphate is the white powder material, thereby can add in any coloured goods.
Above-mentioned phosphorus flame retardant can adopt by magnesium chloride and Sodium phosphate dibasic and carry out replacement(metathesis)reaction generation white powder precipitation---Sodium phosphate dibasic, thereby prepare required phosphorus flame retardant, wherein, the reaction consumption of magnesium chloride and Sodium phosphate dibasic can adopt 4: 3 mass ratio.
The preparation method of above-mentioned phosphorus flame retardant comprises the steps:
(1) magnesium chloride and Sodium phosphate dibasic are carried out replacement(metathesis)reaction between salt and the salt, generate the white powder precipitation, this white powder precipitation is secondary magnesium phosphate;
(2) reaction solution is removed in operations such as the dehydration of employing this area routine, oven dry, only obtains exsiccant white powder---secondary magnesium phosphate, promptly prepares phosphorus flame retardant of the present invention.
In the above-mentioned steps (1), taking by weighing magnesium chloride and Sodium phosphate dibasic respectively earlier, is solvent with water, and dissolving prepares the magnesium chloride brine and the Sodium phosphate dibasic aqueous solution respectively.
In the above-mentioned steps (1), replacement(metathesis)reaction adopts routine operation, in order to accelerate replacement(metathesis)reaction speed, can also adopt and carry out replacement(metathesis)reaction under 90～100 ℃ temperature.
In the above-mentioned steps (1), when the white precipitate of replacement(metathesis)reaction generation no longer increases, illustrate that promptly replacement(metathesis)reaction finishes.
In the above-mentioned steps (2), after replacement(metathesis)reaction finishes, can carry out processed to entire reaction end product system earlier, in the time of dehydration 90%, dry processing again, finally obtain exsiccant white powder material, be phosphorus flame retardant of the present invention.
In the above-mentioned steps (2), can also simultaneously the white powder material that obtains be pulverized,, help mixing of fire retardant of the present invention and other goods so more as being crushed to 1000～2000 orders in oven dry.
Traditional cable adopts PUC as lapping usually, so but because poisonous the getting more and more now of PUC is to adopt the PU parcel, the fire retardant that phosphorus flame retardant of the present invention mainly can be used for PU plays flame retardant effect effectively.
Phosphorus flame retardant of the present invention is used for not playing fire retardation in other class plastic cement, only plays the good flame effect in PU is fire-retardant.
Compared with prior art, the present invention has following beneficial effect:
1. phosphorus flame retardant of the present invention, its main component are secondary magnesium phosphate, and therefore secondary magnesium phosphate can add in the base material of any color from as white, thereby have solved the drawback that easily makes color articles when conventional flame retardant is used red phosphorus;
2. phosphorus flame retardant of the present invention, thus one of secondary magnesium phosphate high-temperature decomposition product utilized---and dehydration, carbonization and the expansion of phosphoric acid stop heat passage, and reduce the generation of inflammable gas in a large number, improve flame retarding efficiency greatly;
3. phosphorus flame retardant of the present invention is not halogen-containing, asepsis environment-protecting, low cigarette;
4. phosphorus flame retardant of the present invention is compared with traditional halogen flame, and its market cost is lower;
5. phosphorus flame retardant of the present invention is to utilize magnesium chloride and Sodium phosphate dibasic to carry out replacement(metathesis)reaction preparation and get, and is not only with low cost, simple to operate, and the whole process of preparation environment-protecting asepsis;
6. the main component of phosphorus flame retardant of the present invention is a secondary magnesium phosphate, secondary magnesium phosphate can add in the base material of any color, and can not change the character of base material in the adding base material, traditional fire retardant contains the mineral powder, can cause the hardening phenomenon of base material, and fire retardant of the present invention is water miscible so can not produce hardening phenomenon, the halogen-free flame retardants of the market development now also exists and can separate out after joining in the base material in addition, and to PU to no effect, addition is big and problem such as bad processing, and phenomenon can not appear separating out in the present invention, and addition is not easy to processing very much yet.
Embodiment
Below in conjunction with specific embodiment the present invention is done description further, but specific embodiment is not done any qualification to the present invention.
Embodiment 1
The phosphorus flame retardant of present embodiment is the secondary magnesium phosphate fire retardant, by magnesium chloride and the Sodium phosphate dibasic mass ratio according to 4: 3, carries out the replacement(metathesis)reaction preparation and gets, and its preparation method specifically comprises the steps:
(1) be respectively solvent with water with magnesium chloride and Sodium phosphate dibasic, dissolving prepares the magnesium chloride brine and the Sodium phosphate dibasic aqueous solution, and two salts solutions are stirred fully dissolving mixing under 90 ℃ temperature, carries out replacement(metathesis)reaction;
(2) when the white powder of replacement(metathesis)reaction precipitation no longer increased, system carried out processed with the entire reaction end-body, and then 180 ℃ of oven dry and be crushed to 1000 orders, obtained exsiccant white powder material, was the phosphorus flame retardant of present embodiment.
Embodiment 2
The phosphorus flame retardant of present embodiment is the secondary magnesium phosphate fire retardant, by magnesium chloride and the Sodium phosphate dibasic mass ratio according to 4: 3, carries out the replacement(metathesis)reaction preparation and gets, and its preparation method specifically comprises the steps:
(1) be respectively solvent with water with magnesium chloride and Sodium phosphate dibasic, dissolving prepares the magnesium chloride brine and the Sodium phosphate dibasic aqueous solution, and two salts solutions are stirred fully dissolving mixing under 100 ℃ temperature, carries out replacement(metathesis)reaction;
(2) when the white powder of replacement(metathesis)reaction precipitation no longer increased, system carried out processed with the entire reaction end-body, and then 180 ℃ of oven dry and be crushed to 2000 orders, obtained exsiccant white powder material, was the phosphorus flame retardant of present embodiment.
Embodiment 3
The phosphorus flame retardant of present embodiment is the secondary magnesium phosphate fire retardant, by magnesium chloride and the Sodium phosphate dibasic mass ratio according to 4: 3, carries out the replacement(metathesis)reaction preparation and gets, and its preparation method specifically comprises the steps:
(1) be respectively solvent with water with magnesium chloride and Sodium phosphate dibasic, dissolving prepares the magnesium chloride brine and the Sodium phosphate dibasic aqueous solution, and two salts solutions are stirred fully dissolving mixing under 90 ℃ temperature, carries out replacement(metathesis)reaction;
(2) when the white powder of replacement(metathesis)reaction precipitation no longer increased, system carried out processed with the entire reaction end-body, and then 250 ℃ of oven dry and be crushed to 1500 orders, obtained exsiccant white powder material, was the phosphorus flame retardant of present embodiment.
The test of embodiment 4 flame retardant propertiess
Present embodiment is tested the flame retardant properties of embodiment 1, embodiment 2 and embodiment 3 preparation gained phosphorus flame retardants.
According to the phosphorus flame retardant that adds 13% (mass percent) among 100 parts the PU, phosphorus flame retardant to embodiment 1～embodiment 3 preparations carries out the test of vertical combustion respectively, the phosphorus flame retardant of three embodiment all can reach U.S. UL-94 standard V-0 level as a result, and burning the time is white cigarette.
Simultaneously with traditional halogen flame according to the fire retardant that adds 12% (mass percent) among 100 parts the PU, also carry out the test of vertical combustion, halogen flame also can reach U.S. UL-94 standard V-0 level as a result, but in halogen flame when burning, discharge black smoke, and the cost of halogen flame retardant agent prescription doubles above than the cost of the present invention phosphorus flame retardant.
Therefore, phosphorus flame retardant of the present invention not only can reach good flame retardant effect, and cost is low, and is nontoxic Environmental protection.
Claims (7)
1, a kind of phosphorus flame retardant is characterized in that this fire retardant is the secondary magnesium phosphate fire retardant.
2,, it is characterized in that described fire retardant is by magnesium chloride and Sodium phosphate dibasic prepared in reaction and get according to the described phosphorus flame retardant of claim 1.
3, according to the described phosphorus flame retardant of claim 2, the mass ratio that it is characterized in that described magnesium chloride and Sodium phosphate dibasic is 4: 3.
4, a kind of method for preparing the described phosphorus flame retardant of claim 1 is characterized in that this method comprises the steps:
(1) prepares the magnesium chloride brine and the Sodium phosphate dibasic aqueous solution respectively, carry out replacement(metathesis)reaction after two solution are mixed;
(2) with the reaction product of above-mentioned replacement(metathesis)reaction after dehydration or oven dry are handled, obtain exsiccant white powder material and be required phosphorus flame retardant.
5,, it is characterized in that in the described step (1), the temperature of replacement(metathesis)reaction is 90～100 ℃ according to the described preparation method of claim 4.
6,, it is characterized in that in the described step (2) that the reaction product of replacement(metathesis)reaction is also carried out pulverization process except that dehydration or oven dry processing according to the described preparation method of claim 4.
7, the application of the described phosphorus flame retardant of claim 1 in PU is fire-retardant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100397053A CN101560399A (en) | 2009-05-22 | 2009-05-22 | Phosphorus flame retardant, preparation method thereof and application in PU flame retardance |
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|---|---|---|---|
| CNA2009100397053A CN101560399A (en) | 2009-05-22 | 2009-05-22 | Phosphorus flame retardant, preparation method thereof and application in PU flame retardance |
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| CNA2009100397053A Pending CN101560399A (en) | 2009-05-22 | 2009-05-22 | Phosphorus flame retardant, preparation method thereof and application in PU flame retardance |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105801905A (en) * | 2016-04-22 | 2016-07-27 | 东源顺亨塑胶阻燃材料厂 | Phosphorus synergistic flame retardant and manufacturing method and application thereof |
| CN111440433A (en) * | 2020-03-18 | 2020-07-24 | 博硕科技(江西)有限公司 | Halogen-free flame-retardant smoke-inhibiting anti-dripping thermoplastic polyurethane elastomer composite material and preparation method thereof |
-
2009
- 2009-05-22 CN CNA2009100397053A patent/CN101560399A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105801905A (en) * | 2016-04-22 | 2016-07-27 | 东源顺亨塑胶阻燃材料厂 | Phosphorus synergistic flame retardant and manufacturing method and application thereof |
| CN105801905B (en) * | 2016-04-22 | 2018-03-13 | 东源顺亨塑胶阻燃材料厂 | A kind of phosphorus system synergistic flame retardant and its manufacture method and application |
| CN111440433A (en) * | 2020-03-18 | 2020-07-24 | 博硕科技(江西)有限公司 | Halogen-free flame-retardant smoke-inhibiting anti-dripping thermoplastic polyurethane elastomer composite material and preparation method thereof |
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Application publication date: 20091021 |