CN104650349A - Halogen-free phosphorus-nitrogen flame retardant, preparation method thereof, flame-retarding polyester therewith and application of the flame-retarding polyester - Google Patents
Halogen-free phosphorus-nitrogen flame retardant, preparation method thereof, flame-retarding polyester therewith and application of the flame-retarding polyester Download PDFInfo
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Abstract
The invention discloses a halogen-free phosphorus-nitrogen flame retardant, a preparation method thereof, a flame-retarding polyester therewith and an application of the flame-retarding polyester. The preparation method includes following steps: (1) feeding a phosphorus-containing diacid compound and aliphatic dihydric alcohol into a reactor container; (2) slowly increasing the temperature to 50-200 DEG C and carrying a reaction at the temperature for 1-5 h to obtain a pre-polymer; and (3) adding a melamine derivative to the pre-polymer, continuously increasing the temperature to 150-230 DEG C, performing a reaction at normal pressure for 1-6 h and performing a vacuum reaction for 1-5 h to obtain the halogen-free phosphorus-nitrogen flame retardant, wherein a molar weight ratio of the phosphorus-containing diacid compound, the aliphatic dihydric alcohol to the melamine derivative is 1.0:1.0-2.0:0.5-1.0.
Description
Technical field
The present invention relates to a kind of bittern-free phosphorous-nitrogen fire retardant and preparation method thereof, a kind of containing this flame retardant polyester of bittern-free phosphorous-nitrogen fire retardant and the application of this flame retardant polyester.
Background technology
The method obtaining flame-retardant polymer at present mainly adds inorganic or organic fire-retardant by copolymerization or blended method in polymkeric substance.The flame retarding efficiency of inorganic combustion inhibitor is low, and reach desirable flame retardant effect must use in a large number, this greatly limits its application.Due to the above-mentioned shortcoming of inorganic combustion inhibitor, use more for organic fire-retardant is as halogenated flame retardant in flame-retardant polymer, it has, and addition is moderate, flame retarding efficiency advantages of higher, but halogenated flame retardant burning after can produce toxic substance, to environment and human body all harmful.
Organic fire-retardant also comprises halogen-free flame retardants, due to its there is low toxicity, low cigarette, feature is subject to applying more and more widely with polymer-based carbon compatability is good etc.In organic halogen-free agent, phosphorus nitrogen expansion type combustion inhibitor is the fire retardant systems that a class has development prospect.
Chinese patent CN1721423A discloses a kind of phosphorus nitrogen expansion type combustion inhibitor melamine salt of pentaerythritol bis (dihydrogen phosphate), but the synthesising reacting time synthesizing the intermediate product Pentaerythritol phosphate in this fire retardant process is long, and solvent is benzene, not only toxicity greatly also contaminate environment.Chinese patent CN101665515A disclose a kind of with carboxyethyl phenyl Hypophosporous Acid, 50 with there is P-N collaborative type flame-retardant compound that the compound of active amine is raw material and preparation method thereof, this flame-retardant compound poor heat resistance, heat decomposition temperature, at 210 ~ 235 DEG C, is difficult to meet polyester or the application requiring of nylon in some high temperature resistant fields.Chinese patent CN102321245A disclose a kind of with benzoguanamine and carboxyethyl phenyl Hypophosporous Acid, 50 for raw material is by the Benzoguanamine propyloic phenyl phosphinic acid condensation compound of two step synthesis, although the thermotolerance of this fire retardant improves a lot, two-step approach is unfavorable for suitability for industrialized production.
Summary of the invention
The invention provides a kind of bittern-free phosphorous-nitrogen fire retardant and preparation method thereof, the one-tenth carbon amounts of this fire retardant is high, and good flame resistance, and excellent heat stability can be applicable to the field requiring high temperature, and the technique of its preparation method is simple.
Technical solution of the present invention is:
A kind of bittern-free phosphorous-nitrogen fire retardant, comprises as shown in the formula 1 and formula 2 two kinds of structural units:
formula 1
formula 2
Wherein R
1structure be selected from such as formula the one in structure shown in 3 ~ formula 5:
formula 3
formula 4
formula 5
R in formula 1
2for the alkylidene group within carbonatoms 10; R in formula 2
3for aryl, virtue amino, the aryloxy of carbonatoms 6 ~ 12, or the alkyl within carbonatoms 10.
Concrete, R
2can be ethylidene, propylidene or its isomer, butylidene or its isomer, pentylidene or its isomer, hexylidene or its isomer, octylene or its isomer, cyclohexylidene etc., wherein alkylidene group shown in preferred ethylidene, propylidene, butylidene, hexylidene or formula 6
formula 6.
R
3can be methyl, ethyl, propyl group, Ren Ji, methoxyl group, oxyethyl group, cyclopropylamino, 18-alkylamino, phenyl, phenylamino, phenoxy group etc., wherein preferable methyl or phenyl.
The molecular weight of described fire retardant preferably controls within 500 ~ 20000g/mol scope, if the molecular weight of fire retardant is excessive, can affect the consistency of fire retardant and polymeric matrix when being that polymeric matrix carries out blended, better preferred molecular weight is the fire retardant of 500 ~ 15000g/mol.
The structure of bittern-free phosphorous-nitrogen fire retardant combines primarily of the structural unit shown in formula 1 and formula 2, the segment of such as fire retardant can be the block combination of structural unit shown in structural unit and 1 formula 2 shown in 1 formula 1, also can be the random combination of structural unit etc. shown in structural unit, 7 formulas 2 shown in structural unit, 4 formulas 1 shown in structural unit shown in 2 formulas 1,3 formulas 2.Consider uncertainty when each reaction chain connects in the chemical reaction of synthesis fire retardant, the structure of bittern-free phosphorous-nitrogen fire retardant of the present invention is more prone to rear a kind of random combination.
For the concrete structure of formula 1 and formula 2, be exemplified below:
formula 1A
formula 2A
formula 1B
formula 2B
formula 1C
formula 2C
formula 1D
formula 2D
formula 1E
formula 2E.
The preparation method of bittern-free phosphorous-nitrogen fire retardant of the present invention can adopt single stage method, concrete is: first will add in reaction vessel containing P diacid and aliphatic diol, slowly be warming up to 50 ~ 200 DEG C and normal pressure or vacuum reaction 1 ~ 5h at this temperature, obtain prepolymer; Then in above-mentioned prepolymer, add melamine derivative, continue to be warming up to 150 ~ 230 DEG C, synthesis under normal pressure 1 ~ 6h final vacuum reaction 1 ~ 5h, obtains phosphor nitrogen combustion inhibitor; The described mol ratio containing P diacid, aliphatic diol and melamine derivative is 1.0:1.0 ~ 2.0:0.5 ~ 1.0.
The described structural formula containing P diacid is selected from such as formula the one in compound shown in 6 ~ formula 8,
formula 6,
formula 7,
formula 8.
In 3 kinds of compounds shown in above-mentioned formula 6 ~ formula 8, the content of phenyl ring is all higher, and the carbon/hydrogen of phenyl ring is higher, and for fire retardant, high phenyl ring content can improve the carbon of integration compound/hydrogen ratio, can give the thermostability that fire retardant is high.
Aliphatic dihydric alcohol of the present invention is the hydrocarbon based diol of carbonatoms less than 10, that can enumerate has ethylene glycol, neopentyl glycol, 1,2-propylene glycol or 1,3-PD, Isosorbide-5-Nitrae-cyclohexanedimethanol, butyleneglycol or its isomer, pentanediol or its isomer, hexylene glycol or its isomer etc.From the viewpoint of reactive behavior and raw material sources, wherein preferred ethylene glycol, neopentyl glycol, 1,2-PD, 1,3-PD or Isosorbide-5-Nitrae-cyclohexanedimethanol.
Melamine derivative of the present invention is 2,4-diamino-6-Ren Ji-1,3,5-triazine, 2,4-diamino-6-methoxyl group-1,3,5-triazines, 2-cyclopropyl amino-4,6-diaminostilbene, 3,5-triazine, N-18-alkyl-1,3,5-triazine-4,6-diamines, benzoguanamine, methyl substituted melamine etc., wherein preferred 2-cyclopropyl amino-4,6-diaminostilbene, 3,5-triazine, 2,4-diamino-6-Ren Ji-1,3,5-triazine, benzoguanamine or methyl substituted melamine, most preferably benzoguanamine or methyl substituted melamine.
In the preparation method of bittern-free phosphorous-nitrogen fire retardant of the present invention, the mol ratio containing P diacid, aliphatic diol and melamine derivative by changing three kinds of compounds changes the ratio of acid source in fire retardant, carbon source and source of the gas, improves the flame retardant properties of fire retardant further.In method of the present invention, the mol ratio of above-mentioned three kinds of materials is 1.0:1.0 ~ 2.0:0.5 ~ 1.0.
In the preparation method of bittern-free phosphorous-nitrogen fire retardant, adding the temperature of reaction after reaction vessel containing P diacid and aliphatic diol is 50 ~ 200 DEG C, reaction times 1 ~ 5h.If temperature of reaction is too low, then the required reaction times extends, inefficiency; If temperature of reaction is too high, then become macromole containing P diacid with aliphatic diol direct polymerization, affect next step reaction.In the present invention, the temperature of reaction of this one-phase preferred is 60 ~ 180 DEG C, and the reaction times is 2 ~ 5h.
Melamine derivative is added wherein again after being obtained by reacting prepolymer containing P diacid and aliphatic diol, temperature of reaction now controls at 150 ~ 230 DEG C, if temperature too high particularly more than 230 DEG C time, melamine derivative can produce distillation, be difficult to the addition and the reactivity that control melamine derivative in the reaction, affect the flame retardant properties of bittern-free phosphorous-nitrogen fire retardant, also can cause the waste of reaction raw materials, raise the cost.In addition, when the reaction temperature is too low, the reaction of prepolymer and melamine derivative is carried out even not reacting comparatively slowly.In the present invention, the temperature of reaction of preferred prepolymer and melamine derivative is 180 ~ 220 DEG C, synthesis under normal pressure 2 ~ 5h, vacuum reaction 2 ~ 5h.
The invention also discloses a kind of flame retardant polyester containing above-mentioned bittern-free phosphorous-nitrogen fire retardant, carry out blending extrusion by above-mentioned preparation-obtained fire retardant and polyester and obtain, wherein the content of fire retardant counts 0.2% ~ 4.0% of final flame retardant polyester weight with phosphoric.Concrete, first drying is carried out in the vibrin section not containing flame-retardant composition, drying temperature is 80 ~ 150 DEG C, and after dry, the moisture content of section is at below 100ppm; Then dried polyester slice and fire retardant are dropped into blending extrusion in twin screw extruder, granulation by a certain percentage, obtain flame retardant polyester, what wherein the ratio of polyester slice and fire retardant accounted for final flame retardant polyester weight according to phosphoric in fire retardant 0.2% ~ 4.0% calculates.Polyester mentioned here can be polyethylene terephthalate (PET), Poly(Trimethylene Terephthalate) (PTT), polybutylene terephthalate (PBT) etc., also can containing, for example static inhibitor, containing various functional reagents such as sulfonic acid group compound, opalizer, anti ultraviolet agents in polyester.In the flame retardant polyester finally obtained, the content of fire retardant all accounts for 0.2% ~ 4.0% of flame retardant polyester weight in phosphoric, and preferably 0.5% ~ 4.0%.
Public technology was compared in the past, and outstanding advantage of the present invention is that synthesized fire retardant efficiency is high, becomes carbon good, and particularly thermostability aspect is with the obvious advantage, and heat decomposition temperature, at 295-320 DEG C, is applicable to the polymkeric substance that this class processing temperature of picture polyester is higher.In addition, this polyreaction is single step reaction, and only have a small amount of water to produce when prepolymer closes, the ethylene glycol produced when final minification gathers can be recycled, so substantially produce without the three wastes; And this polymerization reaction experiment device is simple, be applicable to suitability for industrialized production.Flame retardant polyester of the present invention is preparing fire-retardant fibre, the application in film and resin.
The evaluation method that the present invention relates to has:
(1) molecular weight determination (GPC):
By Waters 1515 type gel permeation chromatograph, make moving phase with tetrahydrofuran (THF), record number-average molecular weight M
w.
(2) limiting oxygen index(LOI) (LOI):
By JIS L 1,091 1999 E method, flame retardant polyester section or the fiber made or fabric are tested, evaluate its flame retardant properties by the limiting oxygen index(LOI) (LOI) of the fiber or fabric that measure section or establishment, the flame retardant resistance of the higher explanation flame retardant polyester of LOI value is better.
(3) thermal stability analysis
After putting into test sample, by thermogravimetric analyzer TGA(TA, Q500) be warmed up to 500 DEG C from 20 DEG C with 20 DEG C/min, draw the quality of sample and the function relation figure of temperature, the temperature when the mass loss of sample is 5% is designated as thermal weight loss temperature.
Embodiment
Embodiment 1
Compound shown in 1mol formula 6 and 1mol ethylene glycol are joined in developmental tube, is slowly warming up to 90 DEG C and reacts about 4h at this temperature, obtaining prepolymer.Then in above-mentioned prepolymer, add 1mol phenyl substituted melamine, continue to be warming up to 210 DEG C, after synthesis under normal pressure 4h, vacuum reaction 3h, after reacting completely, cooling obtains pale yellow transparent solid, and testing its number-average molecular weight is 3200g/mol.
Limiting viscosity is selected to be the PET polyester slice 1000g of 0.7dl/g, first section to be placed under hot air drier 80 DEG C of conditions dry 4 ~ 5 hours, to put under vacuum drying oven 120 DEG C of conditions dry 12 ~ 36 hours, after dry, the water-content of polyester slice is at below 100ppm again; Above-mentioned dried PET section is put into the hopper of twin screw extruder, hopper 1 adds PET polyester slice, and hopper 2 adds fire retardant, then carries out that mixing is extruded, granulation, and the addition of fire retardant counts the 1.5wt% of final fire-retardant polyester with phosphoric.
Miscible granulation process parameters is: twin screw extruder each district temperature, a district: 200 DEG C; 2nd district: 260 DEG C; 3rd district: 270 DEG C; 4th district: 270 DEG C; 5th district: 270 DEG C; 6th district: 270 DEG C; 7th district: 270 DEG C; 8th district: 270 DEG C; 9th district: 260 DEG C; Screw pressure: 0.2Mpa; Screw speed: 160rpm; After water-bath cooling, under dicing machine rotating speed is 80rpm pelletizing speed, cut into grain.
Embodiment 2
Compound shown in 1mol formula 6 and 1.5mol neopentyl glycol are joined in developmental tube, is slowly warming up to 130 DEG C and reacts about 4h at this temperature, obtaining prepolymer.Then in above-mentioned prepolymer, add 1mol phenyl substituted melamine, continue to be warming up to 200 DEG C, after synthesis under normal pressure 4h, vacuum reaction 4h, after reacting completely, cooling obtains pale yellow transparent solid, and testing its number-average molecular weight is 15000g/mol.
Flame retardant polyester is prepared with embodiment 1.
Embodiment 3
Compound shown in 1mol formula 6 and 2mol neopentyl glycol are joined in developmental tube, is slowly warming up to 180 DEG C and reacts about 3h at this temperature, obtaining prepolymer.Then in above-mentioned prepolymer, add 1mol methyl substituted melamine, continue to be warming up to 215 DEG C, after synthesis under normal pressure 5h, vacuum reaction 4h, after reacting completely, cooling obtains pale yellow transparent solid, and testing its number-average molecular weight is 11000g/mol.
Flame retardant polyester is prepared with embodiment 1.
Embodiment 4
Compound shown in 1mol formula 6 and 1.2mol 1,6-hexylene glycol are joined in developmental tube, is slowly warming up to 110 DEG C and reacts about 4h at this temperature, obtaining prepolymer.Then in above-mentioned prepolymer, add the methyl substituted melamine of 0.8 mol, continue to be warming up to 190 DEG C, after synthesis under normal pressure 5h, vacuum reaction 4h, after reacting completely, cooling obtains pale yellow transparent solid, and testing its number-average molecular weight is 11000g/mol.
Flame retardant polyester is prepared with embodiment 1.
Embodiment 5
Compound shown in 1mol formula 6 and 1mol ethylene glycol are joined in developmental tube, is slowly warming up to 100 DEG C and reacts about 4h at this temperature, obtaining prepolymer.Then in above-mentioned prepolymer, add the methyl substituted melamine of 1 mol, continue to be warming up to 180 DEG C, after synthesis under normal pressure 3h, vacuum reaction 2h, after reacting completely, cooling obtains pale yellow transparent solid, and testing its number-average molecular weight is 900g/mol.
Flame retardant polyester is prepared with embodiment 1.
Embodiment 6
Compound shown in 1mol formula 7 and 1mol ethylene glycol are joined in developmental tube, is slowly warming up to 90 DEG C and reacts about 4h at this temperature, obtaining prepolymer.Then in above-mentioned prepolymer, add 1mol phenyl substituted melamine, continue to be warming up to 210 DEG C, after synthesis under normal pressure 4h, vacuum reaction 3h, after reacting completely, cooling obtains pale yellow transparent solid, and testing its number-average molecular weight is 4500g/mol.
Flame retardant polyester is prepared with embodiment 1.
Embodiment 7
Compound shown in 1mol formula 7 and 1.5mol neopentyl glycol are joined in developmental tube, is slowly warming up to 130 DEG C and reacts about 4h at this temperature, obtaining prepolymer.Then in above-mentioned prepolymer, add 1mol phenyl substituted melamine, continue to be warming up to 200 DEG C, after synthesis under normal pressure 4h, vacuum reaction 4h, after reacting completely, cooling obtains pale yellow transparent solid, and testing its number-average molecular weight is 13000g/mol.
Flame retardant polyester is prepared with embodiment 1.
Embodiment 8
Compound shown in 1mol formula 7 and 2mol neopentyl glycol are joined in developmental tube, is slowly warming up to 200 DEG C and reacts about 2h at this temperature, obtaining prepolymer.Then in above-mentioned prepolymer, add 1mol methyl substituted melamine, continue to be warming up to 215 DEG C, after synthesis under normal pressure 5h, vacuum reaction 4h, after reacting completely, cooling obtains pale yellow transparent solid, and testing its number-average molecular weight is 14000g/mol.
Flame retardant polyester is prepared with embodiment 1.
Embodiment 9
Compound shown in 1mol formula 7 and 1.2mol 1,8-ethohexadiol are joined in developmental tube, is slowly warming up to 110 DEG C and reacts about 4h at this temperature, obtaining prepolymer.Then in above-mentioned prepolymer, add the methyl substituted melamine of 1mol, continue to be warming up to 190 DEG C, after synthesis under normal pressure 5h, vacuum reaction 4h, after reacting completely, cooling obtains pale yellow transparent solid, and testing its number-average molecular weight is 10000g/mol.
Flame retardant polyester is prepared with embodiment 1.
Embodiment 10
Compound shown in 1mol formula 7 and 1mol ethylene glycol are joined in developmental tube, is slowly warming up to 100 DEG C and reacts about 4h at this temperature, obtaining prepolymer.Then in above-mentioned prepolymer, add the methyl substituted melamine of 1mol, continue to be warming up to 210 DEG C, after synthesis under normal pressure 5h, vacuum reaction 5h, after reacting completely, cooling obtains pale yellow transparent solid, and testing its number-average molecular weight is 21000g/mol.
Flame retardant polyester is prepared with embodiment 1.
Embodiment 11
Compound shown in 1mol formula 8 and 1mol ethylene glycol are joined in developmental tube, is slowly warming up to 90 DEG C and reacts about 4h at this temperature, obtaining prepolymer.Then in above-mentioned prepolymer, add 1mol phenyl substituted melamine, continue to be warming up to 210 DEG C, after synthesis under normal pressure 4h, vacuum reaction 3h, after reacting completely, cooling obtains pale yellow transparent solid, and testing its number-average molecular weight is 6000g/mol.
Flame retardant polyester is prepared with embodiment 1.
Embodiment 12
Compound shown in 1mol formula 8 and 1.5mol neopentyl glycol are joined in developmental tube, is slowly warming up to 130 DEG C and reacts about 4h at this temperature, obtaining prepolymer.Then in above-mentioned prepolymer, add 1mol phenyl substituted melamine, continue to be warming up to 200 DEG C, after synthesis under normal pressure 4h, vacuum reaction 4h, after reacting completely, cooling obtains pale yellow transparent solid, and testing its number-average molecular weight is 15100g/mol.
Flame retardant polyester is prepared with embodiment 1.
Embodiment 13
Compound shown in 1mol formula 8 and 2mol BDO are joined in developmental tube, is slowly warming up to 135 DEG C and reacts about 3h at this temperature, obtaining prepolymer.Then in above-mentioned prepolymer, add 1mol methyl substituted melamine, continue to be warming up to 215 DEG C, after synthesis under normal pressure 5h, vacuum reaction 4h, after reacting completely, cooling obtains pale yellow transparent solid, and testing its number-average molecular weight is 14000g/mol.
Flame retardant polyester is prepared with embodiment 1.
Embodiment 14
Compound shown in 1mol formula 8 and 1.2mol 1,3-PD are joined in developmental tube, is slowly warming up to 110 DEG C and reacts about 4h at this temperature, obtaining prepolymer.Then in above-mentioned prepolymer, add the methyl substituted melamine of 0.8mol, continue to be warming up to 190 DEG C, after synthesis under normal pressure 5h, vacuum reaction 4h, after reacting completely, cooling obtains pale yellow transparent solid, and testing its number-average molecular weight is 12100g/mol.
Flame retardant polyester is prepared with embodiment 1.
Embodiment 15
Compound shown in 1mol formula 8 and 1mol neopentyl glycol are joined in developmental tube, is slowly warming up to 100 DEG C and reacts about 4h at this temperature, obtaining prepolymer.Then in above-mentioned prepolymer, add the benzoguanamine of 1mol, continue to be warming up to 210 DEG C, after synthesis under normal pressure 4h, vacuum reaction 3h, after reacting completely, cooling obtains pale yellow transparent solid, and testing its number-average molecular weight is 9000g/mol.
Flame retardant polyester is prepared with embodiment 1.
Comparative example 1
After completely water-soluble for 2-carboxyethyl phenyl Hypophosporous Acid, 50, add benzoguanamine, the completely rear filtration drying of stirring reaction, obtain reaction intermediate benzoguanamine carboxyethyl phenyl hypophosphite, wherein temperature of reaction 90 DEG C, 4 hours reaction times, the reaction mol ratio 1:1 of benzoguanamine and 2-carboxyethyl phenyl Hypophosporous Acid, 50; Above-mentioned reaction intermediate is warming up to 190 DEG C, 5 hours reaction times, makes intermediate carry out mass polymerization, obtain benzoguanamine carboxyethyl phenyl Hypophosporous Acid, 50 polycondensate, structure is shown in formula 9,
formula 9
Flame retardant polyester is prepared with embodiment 1.
Comparative example 2
Compound shown in formula 7 and ethylene glycol are mixed according to mol ratio 1:1.2, and atmospheric pressure reflux distills 3h at 210 DEG C; Add in above-mentioned solution by disposable for the catalytic antimony trioxide, at 230 DEG C of second vacuum distilling 3h; Vacuum distillation 8h at 260 DEG C, obtain product after polyreaction is complete, structure is shown in formula 10,
formula 10
Flame retardant polyester is prepared with embodiment 1.
Comparative example 3
By compound shown in formula 6, neopentyl glycol according to mol ratio 1:1 mixing, and is dissolved at 190 DEG C, to dissolve completely synthesis under normal pressure 5h at 210 DEG C; Add in above-mentioned solution by disposable for the catalytic antimony trioxide, vacuum distillation 8h at 260 DEG C, obtain product after polyreaction is complete, structure is shown in formula 11,
formula 11
Flame retardant polyester is prepared with embodiment 1.
Table 1
Claims (10)
1. a bittern-free phosphorous-nitrogen fire retardant, is characterized in that, this fire retardant comprises as shown in the formula 1 and formula 2 two kinds of structural units:
formula 1
formula 2
Wherein R
1structure be selected from such as formula the one in structure shown in 3 ~ formula 5:
formula 3
formula 4
formula 5
R in formula 1
2for the alkylidene group within carbonatoms 10; R in formula 2
3for aromatic base, virtue amino, the aryloxy of carbonatoms 6 ~ 12, or the alkyl within carbonatoms 10.
2. bittern-free phosphorous-nitrogen fire retardant according to claim 1, is characterized in that, R in formula 1
2for alkylidene group shown in ethylidene, propylidene, butylidene, hexylidene or formula 6,
formula 6,
R in formula 2
3for methyl or phenyl.
3. bittern-free phosphorous-nitrogen fire retardant according to claim 1, is characterized in that, the number-average molecular weight of this fire retardant is 500 ~ 20000g/mol.
4. a preparation method for bittern-free phosphorous-nitrogen fire retardant described in claim 1, is characterized in that, first will add in reaction vessel containing P diacid and aliphatic dihydric alcohol, is slowly warming up to 50 ~ 200 DEG C and reacts 1 ~ 5h at this temperature, obtaining prepolymer; Then in above-mentioned prepolymer, add melamine derivative, continue to be warming up to 150 ~ 230 DEG C, synthesis under normal pressure 1 ~ 6h final vacuum reaction 1 ~ 5h, obtains phosphor nitrogen combustion inhibitor; The described mol ratio containing P diacid, aliphatic dihydric alcohol and melamine derivative is 1.0:1.0 ~ 2.0:0.5 ~ 1.0.
5. the preparation method of bittern-free phosphorous-nitrogen fire retardant according to claim 4, is characterized in that, the described structure containing P diacid is selected from such as formula the one in compound shown in 7 ~ formula 9,
formula 7,
formula 8,
formula 9.
6. the preparation method of bittern-free phosphorous-nitrogen fire retardant according to claim 4 or 5, it is characterized in that, described aliphatic dihydric alcohol is ethylene glycol, neopentyl glycol, 1,2-PD, 1,3-PD and Isosorbide-5-Nitrae-cyclohexanedimethanol.
7. the preparation method of bittern-free phosphorous-nitrogen fire retardant according to claim 4 or 5, it is characterized in that, described melamine derivative is benzoguanamine or methyl substituted melamine.
8. the preparation method of bittern-free phosphorous-nitrogen fire retardant according to claim 4, it is characterized in that, the temperature of reaction containing P fire retardant and aliphatic dihydric alcohol is 60 ~ 180 DEG C, and the reaction times is 2 ~ 5h; The temperature of reaction of prepolymer and melamine derivative is 180 ~ 220 DEG C, synthesis under normal pressure 2 ~ 5h, vacuum reaction 2 ~ 5h.
9. the flame retardant polyester containing bittern-free phosphorous-nitrogen fire retardant described in claim 1, it is characterized in that, polyester and fire retardant are carried out blending extrusion, obtains flame retardant polyester, wherein the content of fire retardant counts 0.2% ~ 4.0% of final flame retardant polyester weight with phosphoric.
10. flame retardant polyester described in claim 9 is preparing a fire-retardant fibre, the application in film and resin.
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| CN201310583256.5A CN104650349A (en) | 2013-11-20 | 2013-11-20 | Halogen-free phosphorus-nitrogen flame retardant, preparation method thereof, flame-retarding polyester therewith and application of the flame-retarding polyester |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105155018A (en) * | 2015-07-22 | 2015-12-16 | 东华大学 | Copolymerized flame-retardant polyamide 66 fiber and preparation method thereof |
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| CN107980047A (en) * | 2015-05-28 | 2018-05-01 | 新加坡科意亚太有限公司 | Fire-retardant and self-catalysis polyester for polyurethane |
| CN114591623A (en) * | 2022-04-26 | 2022-06-07 | 华润化学材料科技股份有限公司 | High-impact-toughness flame-retardant nylon elastomer material and preparation method thereof |
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2013
- 2013-11-20 CN CN201310583256.5A patent/CN104650349A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107980047A (en) * | 2015-05-28 | 2018-05-01 | 新加坡科意亚太有限公司 | Fire-retardant and self-catalysis polyester for polyurethane |
| CN105155018A (en) * | 2015-07-22 | 2015-12-16 | 东华大学 | Copolymerized flame-retardant polyamide 66 fiber and preparation method thereof |
| CN106496551A (en) * | 2016-10-25 | 2017-03-15 | 成都拓利科技股份有限公司 | A kind of organophosphors system copolymerization Flameproof polyamide and preparation method thereof |
| CN114591623A (en) * | 2022-04-26 | 2022-06-07 | 华润化学材料科技股份有限公司 | High-impact-toughness flame-retardant nylon elastomer material and preparation method thereof |
| CN114591623B (en) * | 2022-04-26 | 2023-08-11 | 华润化学材料科技股份有限公司 | Flame-retardant nylon elastomer material with high impact toughness and preparation method thereof |
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