CN1962816A - Process for preparing unimolecular P-N type expansive flame retardant - Google Patents
Process for preparing unimolecular P-N type expansive flame retardant Download PDFInfo
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- CN1962816A CN1962816A CN 200610070585 CN200610070585A CN1962816A CN 1962816 A CN1962816 A CN 1962816A CN 200610070585 CN200610070585 CN 200610070585 CN 200610070585 A CN200610070585 A CN 200610070585A CN 1962816 A CN1962816 A CN 1962816A
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Abstract
The invention discloses a preparing method of single-molecular phosphorus-nitrogen inflatable fire retardant, which is characterized by the following: reacting polyatomic alcohol and phosphoric acid to obtain the intermediate; reacting with melamine in the organic solvent to generate fire retardant; simplifying the manufacturing procedure; saving cost; possessing good compatibility with macromolecule without halogen.
Description
Technical field
The present invention relates to the preparation method of fire retardant, be specifically related to a kind of preparation method of unimolecular P-N type expansive flame retardant.
Background technology
Phosphorus-nitrogen expansion type fire retardant (IFR) is not halogen-containing, with phosphorus, nitrogen, carbon is main component, P-N cooperative flame retardant effect can take place when being heated, the charcoal layer that generates even compact adsorbs the polymkeric substance that fusion is caught fire, prevent its drippage propagating flame, and can generate non-flammable gases and completely cut off the required oxygen that burns away.Simultaneously, it has advantages such as low toxicity, few cigarette, addition be less relatively, can be compatible preferably with processed material, do not influence the thermostability of material, and be applicable to the fire-retardant of most of macromolecular materials.IFR is one of active research focus very in the current flame retardant area, is regarded as realizing the fire retardant the most potential non-halogen based flame retardant.
The preparation of IFR mainly is that the compound that contains carbon source, acid source and source of the gas is composite both at home and abroad at present, wherein the most important thing is tetramethylolmethane, ammonium polyphosphate, trimeric cyanamide are combined into IFR and use, and ammonium polyphosphate has certain moisture, and the composite IFR and the consistency of material are poor, influence the processing and the use properties of material.Contain among the unit molecule IFR preparation method of three components existing, most ofly limited their use because of production cost is high.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of preparation method of unimolecular P-N type expansive flame retardant is proposed, to overcome fire retardant in the prior art and material compatibility is poor, use halogen containing flame-retardant to cause the problem such as expensive of environmental pollution and preparation unit molecule IFR.
Unimolecular P-N type expansive flame retardant preparation method of the present invention, step is as follows:
(1) polyvalent alcohol and phosphoric acid are pressed mass ratio mixing stirring in 1: 1～1: 5, reacted 1-3 hour down, get the intermediate PAPE at 70-100 ℃,
(2) trimeric cyanamide is dispersed in the organic solvent, adds the intermediate PAPE, the mass ratio of polyvalent alcohol and trimeric cyanamide is 1: 0.5～1: 3, reacts 0.5-2 hour down at 60-90 ℃.
Preferably, the mass ratio of above-mentioned steps (1) polyvalent alcohol and phosphoric acid is 1: 1.5-1: 3.
Preferably, described polyvalent alcohol is tetramethylolmethane or dipentaerythritol or tripentaerythritol.
Preferably, organic solvent is methyl alcohol or ethanol.
Preferably, the mass ratio of polyvalent alcohol and trimeric cyanamide is 1: 0.8-1: 2.
Phosphoric acid consumption of the present invention crosses that low then polyol reaction is incomplete, reduces productive rate, and the too high meeting of consumption increases side reaction.The temperature of reaction of polyvalent alcohol and phosphoric acid is controlled at 70-100 ℃, and the reaction times was controlled at 1-3 hour.The low time of temperature of reaction is short, reacts incomplete productive rate and reduces; The too high time of temperature of reaction is oversize, and side reaction increases, and energy consumption is big, has strengthened production cost.
The present invention uses cheap organic solvent, promotes the reaction of intermediate PAPE and trimeric cyanamide, and not loss of organic solvent can be recycled before and after reaction.
The trimeric cyanamide consumption affects the turgidity and the surplus charcoal rate of product, and turgidity and surplus charcoal rate are to weigh the standard of expansion type flame retardant flame retardant properties quality.The temperature of reaction of trimeric cyanamide and PAPE is controlled at 60-90 ℃, and the reaction times was controlled at 0.5-2 hour.Oversize increase side reaction of too high time of temperature of reaction and production cost.The low time of temperature of reaction is short, reacts incomplete productive rate and reduces.
Preparation technology of the present invention is simple, prepares unimolecular P-N type expansive flame retardant by using cheap acid source phosphoric acid and organic solvent, has effectively reduced production cost.Product turgidity and surplus charcoal amount height, molecular weight is big, addition is few, and is good with macromolecular material consistencies such as polyethylene, polypropylene, the macromolecular material Halogen low toxicity that obtains, and flame retardant properties is good.
Embodiment
The present invention will be further described below in conjunction with embodiment, but be not limited thereto.
Embodiment 1
Add 34g tetramethylolmethane and 43.2g phosphoric acid in a beaker, be heated to 70 ℃ with heating jacket, reaction is 1 hour under the vigorous stirring.Add 350ml methyl alcohol in a there-necked flask, place 70 ℃ of water-baths, refluxing to stir down adds the 25.2g trimeric cyanamide, after waiting to be uniformly dispersed, adds pentaerythritol phosphate, continues stirring reaction and finishes after 0.5 hour, obtains product after suction filtration, washing, the drying.The methyl alcohol distillation is reclaimed and is reused.
Accurately take by weighing the 0.5g fire retardant, put into the 100ml crucible, place retort furnace to be warming up to 500 ℃, insulation 10min tests its turgidity and surplus charcoal rate.The detected result turgidity is 75cm
3/ g, surplus charcoal rate is 35.35%.The polyethylene that weighs up in proportion after plasticizing on 160 ℃ the duplex roller, is added the mixing again 10min of 30% fire retardant, and 185 ℃ of shaped by fluid pressures on thermocompressor are made the thick sample of 3.2mm with omnipotent sampling machine, test its combustionproperty and mechanical property.The detected result oxygen index is up to standard, and tensile strength is 13Mpa.
Embodiment 2
Add 34g dipentaerythritol and 57.6g phosphoric acid in a beaker, be heated to 90 ℃ with heating jacket, reaction is 2 hours under the vigorous stirring.Add 400ml ethanol in a there-necked flask, place 80 ℃ of water-baths, refluxing to stir down adds the 31.5g trimeric cyanamide, after waiting to be uniformly dispersed, adds the dipentaerythritol phosphoric acid ester, continues stirring reaction and finishes after 1 hour, obtains product after suction filtration, washing, the drying.Ethanol distillation reclaims to be reused.
Accurately take by weighing the 0.5g fire retardant, put into the 100ml crucible, place retort furnace to be warming up to 500 ℃, insulation 10min tests its turgidity and surplus charcoal rate.The detected result turgidity is 77cm
3/ g, surplus charcoal rate is 38.54%.The polyethylene that weighs up in proportion after plasticizing on 160 ℃ the duplex roller, is added the mixing again 10min of 30% fire retardant, and 185 ℃ of shaped by fluid pressures on thermocompressor are made the thick sample of 3.2mm with omnipotent sampling machine, test its combustionproperty and mechanical property.The detected result oxygen index is up to standard, and tensile strength is 13.2Mpa.
Embodiment 3
Add 34g tetramethylolmethane and 57.6g phosphoric acid in a beaker, be heated to 90 ℃ with heating jacket, reaction is 2 hours under the vigorous stirring.Add 500ml ethanol in a there-necked flask, place 85 ℃ of water-baths, refluxing to stir down adds the 47.3g trimeric cyanamide, after waiting to be uniformly dispersed, adds pentaerythritol phosphate, continues stirring reaction and finishes after 1 hour, obtains product after suction filtration, washing, the drying.Ethanol distillation reclaims to be reused.
Accurately take by weighing the 0.5g fire retardant, put into the 100ml crucible, place retort furnace to be warming up to 500 ℃, insulation 10min tests its turgidity and surplus charcoal rate.The detected result turgidity is 83cm
3/ g, surplus charcoal rate is 40.24%.The polyethylene that weighs up in proportion after plasticizing on 160 ℃ the duplex roller, is added the mixing again 10min of 30% fire retardant, and 185 ℃ of shaped by fluid pressures on thermocompressor are made the thick sample of 3.2mm with omnipotent sampling machine, test its combustionproperty and mechanical property.The detected result oxygen index is up to standard, and tensile strength is 14Mpa.The principal character absorption peak of the infrared spectra of product is as follows: 3350.6cm
-1(N-H), 3160.2cm
-1(-OH), 2961.9cm
-1, 2886.8cm
-1(C-H), 1276.8cm
-1(P=O), 1016.5cm
-1(P-O-C).The thermal weight loss of product: product begins to decompose about 300 ℃, weightlessness about 7.7% during to 370 ℃, this stage mainly is oxygen acid and the catalytic esterification that generates phosphorus, is the weightless more stage from 370 ℃ to 490 ℃, mainly is that trimeric cyanamide decomposes generation NO, NH
3Deng non-flammable gases, continuing to heat up further generates the stable charcoal layer with P-N-O with the P contained compound effect.
Embodiment 4
Add 34g tripentaerythritol and 57.6g phosphoric acid in a beaker, be heated to 90 ℃ with heating jacket, reaction is 2 hours under the vigorous stirring.Add 600ml methyl alcohol in a there-necked flask, place 90 ℃ of water-baths, refluxing to stir down adds the 63g trimeric cyanamide, after waiting to be uniformly dispersed, adds the tripentaerythritol phosphoric acid ester, continues stirring reaction and finishes after 1.5 hours, obtains product after suction filtration, washing, the drying.The methyl alcohol distillation is reclaimed and is reused.
Accurately take by weighing the 0.5g fire retardant, put into the 100ml crucible, place retort furnace to be warming up to 500 ℃, insulation 10min tests its turgidity and surplus charcoal rate.The detected result turgidity is 81cm
3/ g, surplus charcoal rate is 41.70%.The polyethylene that weighs up in proportion after plasticizing on 160 ℃ the duplex roller, is added the mixing again 10min of 30% fire retardant, and 185 ℃ of shaped by fluid pressures on thermocompressor are made the thick sample of 3.2mm with omnipotent sampling machine, test its combustionproperty and mechanical property.The detected result oxygen index is up to standard, and tensile strength is 13Mpa.
Embodiment 5
Add 34g dipentaerythritol and 72g phosphoric acid in a beaker, be heated to 90 ℃ with heating jacket, reaction is 2.5 hours under the vigorous stirring.Add 500ml ethanol in a there-necked flask, place 80 ℃ of water-baths, refluxing to stir down adds the 47.3g trimeric cyanamide, after waiting to be uniformly dispersed, adds the dipentaerythritol phosphoric acid ester, continues stirring reaction and finishes after 1 hour, obtains product after suction filtration, washing, the drying.Ethanol distillation reclaims to be reused.
Accurately take by weighing the 0.5g fire retardant, put into the 100ml crucible, place retort furnace to be warming up to 500 ℃, insulation 10min tests its turgidity and surplus charcoal rate.The detected result turgidity is 78cm
3/ g, surplus charcoal rate is 39.69%.The polyethylene that weighs up in proportion after plasticizing on 160 ℃ the duplex roller, is added the mixing again 10min of 30% fire retardant, and 185 ℃ of shaped by fluid pressures on thermocompressor are made the thick sample of 3.2mm with omnipotent sampling machine, test its combustionproperty and mechanical property.The detected result oxygen index is up to standard, and tensile strength is 12.5Mpa.
Claims (5)
1. the preparation method of a unimolecular P-N type expansive flame retardant, step is as follows:
(1) polyvalent alcohol and phosphoric acid are pressed mass ratio mixing stirring in 1: 1～1: 5, reacted 1-3 hour down, get the intermediate PAPE at 70-100 ℃,
(2) trimeric cyanamide is dispersed in the organic solvent, adds the intermediate PAPE, the mass ratio of polyvalent alcohol and trimeric cyanamide is 1: 0.5～1: 3, reacts 0.5-2 hour down at 60-90 ℃.
2, the preparation method of unimolecular P-N type expansive flame retardant according to claim 1, the mass ratio that it is characterized in that polyvalent alcohol and phosphoric acid is 1: 1.5-1: 3.
3, the preparation method of unimolecular P-N type expansive flame retardant according to claim 1 is characterized in that described polyvalent alcohol is tetramethylolmethane, dipentaerythritol or tripentaerythritol.
4, the preparation method of unimolecular P-N type expansive flame retardant according to claim 1 is characterized in that organic solvent is methyl alcohol or ethanol.
5, the preparation method of unimolecular P-N type expansive flame retardant according to claim 1, the mass ratio that it is characterized in that polyvalent alcohol and trimeric cyanamide is 1: 0.8-1: 2.
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| CN 200610070585 CN1962816A (en) | 2006-12-06 | 2006-12-06 | Process for preparing unimolecular P-N type expansive flame retardant |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111393734A (en) * | 2020-04-23 | 2020-07-10 | 四川轻化工大学 | Halogen-free flame retardant, halogen-free flame-retardant low-density polyethylene material and preparation method thereof |
| CN112853753A (en) * | 2019-11-28 | 2021-05-28 | 天津工业大学 | Phosphorus-aluminum-nitrogen synergistic phosphorus-nitrogen expansion halogen-free flame retardant and preparation technology thereof |
-
2006
- 2006-12-06 CN CN 200610070585 patent/CN1962816A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112853753A (en) * | 2019-11-28 | 2021-05-28 | 天津工业大学 | Phosphorus-aluminum-nitrogen synergistic phosphorus-nitrogen expansion halogen-free flame retardant and preparation technology thereof |
| CN111393734A (en) * | 2020-04-23 | 2020-07-10 | 四川轻化工大学 | Halogen-free flame retardant, halogen-free flame-retardant low-density polyethylene material and preparation method thereof |
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