CN104311818B - A kind of phosphorous, nitrogen aggretion type fire retardant and preparation method thereof - Google Patents
A kind of phosphorous, nitrogen aggretion type fire retardant and preparation method thereof Download PDFInfo
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- CN104311818B CN104311818B CN201410584675.5A CN201410584675A CN104311818B CN 104311818 B CN104311818 B CN 104311818B CN 201410584675 A CN201410584675 A CN 201410584675A CN 104311818 B CN104311818 B CN 104311818B
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Abstract
A kind of novel phosphorus-containing, nitrogen aggretion type fire retardant and preparation method thereof, and one fire retardant and preparation method thereof, the synthesis step of the method is as follows: is first dissolved by intermediate B HPPO solvent and joins in reactor, again a certain proportion of Cyanuric Chloride and triethylamine are successively joined in reaction vessel, after reacting 1 6h at 30 80 DEG C, remove solvent, then crude product is put in the there-necked flask equipped with 30 60mL distilled water at 100 DEG C and reacts 2h, wash, be dried, i.e. can get fire retardant.Prepared phosphorous, nitrogen combustion inhibitor Halogen, become that charcoal is good, better heat stability.Can be used for the fire-retardant of TPO and epoxide resin material.The preparation method that the present invention provides is simple, it is easy to control, easy to operate.
Description
Technical field
The present invention relates to a kind of fire retardant and preparation method thereof, particularly relate to a kind of novel phosphorus-containing, nitrogen aggretion type fire retardant and preparation method thereof.
Background technology
In recent years, due to the enhancing of environmental consciousness, fire retardant towards non-halogen, press down fuming, low direction of poisoning is developed.Addition is big, the amount of being fuming is big and produces the critical defects such as poisonous, corrosive gas is just substituted by new generation of environment protection fire retardant owing to it exists to compare traditional fire retardant.The most strikingly about phosphorus, nitrogen expansion type fire retardant, it is considered to be and realizes the approach likely that fire retardant is non-halogen.
Phosphor-nitrogen expansion type combustion inhibitor is a kind of fire retardant with nitrogen, phosphorus as Main Ingredients and Appearance, and it does not contains halogen, is the environment friendly flame retardant of a class high-efficiency low-toxicity.This based flame retardant is expandable expansion when being heated, and can form the foam layer of charcoal of densification at material surface, the further degraded of internal layer high polymer and combustible both can have been stoped to the release on surface, can completely cut off again thermal source and the oxygen source in the external world, thus stop spreading of flame.Meanwhile, this based flame retardant has the advantages such as low cigarette, anti-molten drop, it has also become the important channel that fire retardant is non-halogen.Tradition phosphor-nitrogen expansion type combustion inhibitor is mainly based on Compositional type expanding fire retardant, though there being good fire resistance, but there is poor heat stability during using, facile hydrolysis, with the shortcoming such as matrix poor compatibility, seriously constrains its range of application.
At present, carbon-collecting source, acid source, source of the gas can effectively realize " three sources " effect functional group in one pack system intramolecular performance expandable flame retardant effect in the one pack system expansion type flame retardant of one, show excellent fire resistance, and overcome tradition Compositional type expanding fire retardant heat stability is low and the drawback such as matrix poor compatibility, it has also become the focus of current expansion type flame retardant area research.
Along with the development of the flame-retarded treatment technology of high polymer material, the requirement to the combination property of fire retardant is more and more higher, should reach the fire-retardant rank of regulation, also to have good physical mechanical strength, non-aggressive, low cigarette, avirulence and heat stability etc..The developing direction of following fire retardant mainly has the following aspects: non-halogen trend, press down fuming and non-toxic gas, the process that comes to the surface, miniaturization process, cooperative effect etc..
Summary of the invention
It is an object of the invention to provide a kind of novel phosphorus-containing, nitrogen aggretion type fire retardant and preparation method thereof, fire retardant contains phosphorus, nitrogen element, can play the effect of expansion type flame-retarding, and there is the advantage of low toxicity, beneficially environmental protection, and preparation method is simple, mild condition, it is easy to control, without other additives, the product purity of gained is high, convenient post-treatment.
It is an object of the invention to be achieved through the following technical solutions:
A kind of novel phosphorus-containing, nitrogen aggretion type fire retardant, described polymer formulae is as follows:
In formula, n is the positive integer of 1 100.
A kind of novel phosphorus-containing, nitrogen aggretion type fire retardant preparation method, the synthesis step of described the method is as follows: is first dissolved by intermediate B HPPO solvent and joins in reactor, again Cyanuric Chloride and triethylamine are successively joined in reaction vessel, after reacting 1 6h at 30 80 DEG C, remove solvent, then crude product is put in the there-necked flask equipped with 30 60mL distilled water at 100 DEG C and reacts 2h, obtain end product, wash, be dried, i.e. can get fire retardant.
Described a kind of novel phosphorus-containing, nitrogen aggretion type fire retardant preparation method, the ratio of described Cyanuric Chloride and BHPPO and triethylamine is 1:1.1:1.1 1:1.5:1.5.
Described a kind of novel phosphorus-containing, nitrogen aggretion type fire retardant preparation method, described solvent is any one in ethyl acetate, Isosorbide-5-Nitrae dioxane, acetonitrile, acetone or the mixture of its arbitrary proportion.
Described a kind of novel phosphorus-containing, nitrogen aggretion type fire retardant preparation method, described reaction temperature is 30 80 DEG C；Response time is 1 6h.
Described a kind of novel phosphorus-containing, nitrogen aggretion type fire retardant preparation method, described solvent load is 10 30mL；The consumption of distilled water is 30 60mL.
Described a kind of novel phosphorus-containing, nitrogen aggretion type fire retardant preparation method, described cleaning solvent is any one in distilled water, ethyl acetate, acetonitrile, Isosorbide-5-Nitrae dioxane, acetone, dehydrated alcohol or the mixing of its arbitrary proportion.
Advantages of the present invention with effect is:
1, the aggretion type fire retardant that the present invention provides contains phosphorus, nitrogen element, can play the effect of expansion type flame-retarding, and has the advantage of low toxicity, beneficially environmental protection.
2, the preparation method that the present invention provides is simple, mild condition, it is easy to control, and without other additives, the product purity of gained is high, convenient post-treatment.
3, phosphorous, the nitrogen aggretion type fire retardant applied range that the present invention provides, can be used for the fire-retardant of the polymerization system such as epoxy resin and polyolefin.
Accompanying drawing explanation
Fig. 1 is Inventive polymers structural formula.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1:
Under nitrogen protection; 13.213g(0.12mol is added in the 250ml four-hole boiling flask with magnetic agitation, thermometer, reflux condensing tube, Dropping funnel and device for absorbing tail gas) hydroquinone and 40ml dimethylbenzene; 9.749g(0.05mol is added in Dropping funnel) benzene phosphinylidyne dichloro; dilute with 20ml dimethylbenzene; in question response still, temperature reaches 130 DEG C; start to drip benzene phosphinylidyne dichloro, until hydrogen chloride no longer releases end reaction.Separatory removes dimethylbenzene while hot, obtains rufous clear viscous liquids.The hydroquinone of excess is removed with 50 DEG C of hot washes.Being dried 24h in 80 DEG C of vacuum drying ovens, obtain white powdery solids after grinding, temperature of initial decomposition is 306 DEG C, and fusing point is 159.5 DEG C, is intermediate B HPPO.
Equipped with in the 100ml there-necked flask of magnetic agitation, reflux condensing tube and thermometer, add BHPPO4.549g(0.0133mol), with 20ml acetic acid ethyl dissolution；Weigh Cyanuric Chloride 1.845g(0.01mol), add in there-necked flask；Weigh acid binding agent triethylamine 1.346g(0.0133mol again) add in there-necked flask；Now, bottom mixture, there is clear yellow viscous material to generate, then react 5h under the conditions of 70 DEG C, obtain pasty state viscous product and be slightly soluble in ethyl acetate, after natural cooling, then crude product is put in the there-necked flask equipped with 30mL distilled water at 100 DEG C, reacts 2h.Finally by product with distilled water wash for several times to remove triethylamine hydrochloride, then with ethyl acetate washed product to remove excessive BHPPO.70 DEG C of vacuum drying 24h, aerator obtains translucent solid matter, obtains white powdery solids, be fire retardant after grinding after being dried 4h, its fusing point is 157.3 DEG C, and thermogravimetric temperature of initial decomposition is 289.1 DEG C.Embodiment 2:
Wherein the synthetic method of intermediate B HPPO is with example 1.
Equipped with in the 100ml there-necked flask of magnetic agitation, reflux condensing tube and thermometer, add BHPPO5.13g(0.015mol), with 20ml1,4 dioxane solvent dissolve；Weigh Cyanuric Chloride 1.845g(0.01mol), add in there-necked flask；Weigh acid binding agent triethylamine 1.518g(0.015mol again) add in there-necked flask；Now, having clear yellow viscous material to generate bottom mixture, then react 5h under the conditions of 70 DEG C, decompression is distilled off solvent Isosorbide-5-Nitrae dioxane, obtains milky cheese shape material, then is put in by crude product in the there-necked flask equipped with 40mL distilled water and reacts 2h at 100 DEG C.Finally by product with distilled water wash for several times to remove triethylamine hydrochloride, then with Isosorbide-5-Nitrae dioxane washed product to remove excessive BHPPO.70 DEG C of vacuum drying 24h, aerator obtains translucent solid matter, obtains white powdery solids, be fire retardant after grinding after being dried 4h.
Embodiment 3:
Wherein the synthetic method of intermediate B HPPO is with example 1.
Equipped with in the 100ml there-necked flask of magnetic agitation, reflux condensing tube and thermometer, add BHPPO5.13g(0.015mol), dissolve with 20ml acetonitrile solvent；Weigh Cyanuric Chloride 1.845g(0.01mol), add in there-necked flask；Weigh acid binding agent triethylamine 1.518g(0.015mol again) add in there-necked flask；Now, having clear yellow viscous material to generate bottom mixture, then react 5h under the conditions of 70 DEG C, decompression is distilled off solvent acetonitrile, obtains milky material, then is put in by crude product in the there-necked flask equipped with 50mL distilled water and reacts 2h at 100 DEG C.Finally by product with distilled water wash for several times to remove triethylamine hydrochloride, then with acetonitrile washed product to remove excessive BHPPO.Obtain solid matter after 60 DEG C of vacuum drying 24h, obtain white powdery solids after grinding, be fire retardant.
Claims (2)
1. phosphorous, a nitrogen aggretion type fire retardant, it is characterised in that described polymer formulae is as follows:
In formula, n is the positive integer of 1 100.
2. phosphorous, a nitrogen aggretion type fire retardant preparation method, it is characterized in that, the synthesis step of described the method is as follows: is first dissolved by intermediate B HPPO solvent and joins in reactor, again Cyanuric Chloride and triethylamine are successively joined in reaction vessel, after reacting 1 6h at 30 80 DEG C, remove solvent, again crude product is put in the there-necked flask equipped with 30 60mL distilled water at 100 DEG C, reacts 2h, obtain end product, wash, be dried, i.e. can get fire retardant；
The ratio of described Cyanuric Chloride and BHPPO and triethylamine is 1:1.1:1.1 1:1.5:1.5；
Described solvent is any one in ethyl acetate, 1,4-dioxane, acetonitrile, acetone or the mixture of its arbitrary proportion；Described solvent load is 10 30mL.
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| CN104844803A (en) * | 2015-03-25 | 2015-08-19 | 沈阳化工大学 | Polymeric type phosphorus and nitrogen intumescent flame retardant and preparation method therefor |
| CN106700084B (en) * | 2016-12-28 | 2019-08-20 | 浙江大学宁波理工学院 | Bis-phenol acidic group fire retardant of polyphosphate of the structure containing DOPO and preparation method thereof |
| CN111592657A (en) * | 2020-05-29 | 2020-08-28 | 福建师范大学 | Phosphorus-modified ZIF-8 material and preparation method and application thereof |
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| US3364216A (en) * | 1965-10-18 | 1968-01-16 | American Cyanamid Co | 4, 6-diamino-s-triazinylethyl phosphines and phosphine oxides |
| GB8918881D0 (en) * | 1989-08-18 | 1989-09-27 | Minnesota Mining & Mfg | Flame retardants |
| CN101586033B (en) * | 2009-06-10 | 2012-07-04 | 中国科学院宁波材料技术与工程研究所 | Triazine carbonific containing aromatic chain structure and preparation method |
| CN102161763B (en) * | 2011-02-25 | 2013-11-06 | 中山大学 | Novel expansion-type charring agent for flame-retardant polyolefine material and synthesis method thereof |
| CN103254234B (en) * | 2013-06-05 | 2016-04-27 | 苏州科技学院 | Methyl triazinyl triphenyl hypophosphite compound and preparation method thereof |
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