CN104311818A - Novel phosphorus and nitrogen containing polymeric flame retardant and preparation method thereof - Google Patents
Novel phosphorus and nitrogen containing polymeric flame retardant and preparation method thereof Download PDFInfo
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- CN104311818A CN104311818A CN201410584675.5A CN201410584675A CN104311818A CN 104311818 A CN104311818 A CN 104311818A CN 201410584675 A CN201410584675 A CN 201410584675A CN 104311818 A CN104311818 A CN 104311818A
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Abstract
The invention relates to a novel phosphorus and nitrogen containing polymeric flame retardant and a preparation method thereof, namely a flame retardant and a preparation method thereof. The method comprises the following synthetic steps: firstly, dissolving an intermediate BHPPO by a solvent and adding into a reactor; then, successively adding cyanuric chloride and triethylamine in a certain proportion into the reactor container; carrying out reaction at 30-80 DEG C for 1-6 hors to remove the solvent; then carrying out reaction on a coarse product in a three-opening flask filled with 30-60mL of distilled water at 100 DEG C; and washing and drying to obtain the flame retardant. The prepared phosphorus and nitrogen containing flame retardant is halogen-free, good in charring property and relatively good in thermal stability, and can be used for flame retardance of polyolefin and epoxy resin materials. The preparation method provided by the invention is simple, easy to control and convenient 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, lowly poison future development.Compare traditional fire retardant exist due to it critical defects such as addition is large, the amount of being fuming large and it is poisonous to produce, corrosive gases just substitute by new generation of environment protection fire retardant.Wherein the most strikingly about phosphorus, nitrogen expansion type fire retardant, it is considered to be and realizes a non-halogen approach likely of fire retardant.
Phosphor-nitrogen expansion type combustion inhibitor is a kind of fire retardant being major ingredient with nitrogen, phosphorus, and it is not halogen-containing, is the environment friendly flame retardant of a class high-efficiency low-toxicity.This based flame retardant can foaming and intumescing when being heated, and can form fine and close foam layer of charcoal at material surface, the further degraded of internal layer superpolymer and combustiblematerials both can have been stoped to the release on surface, can completely cut off again extraneous thermal source and oxygen source, thus stop spreading of flame.Meanwhile, this based flame retardant has the advantages such as low cigarette, anti-molten drop, has become the important channel that fire retardant is non-halogen.Tradition phosphor-nitrogen expansion type combustion inhibitor, mainly based on Compositional type expanding fire retardant, though there is good flame retardant properties, also exists poor heat stability in use procedure, 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 effectively can realize " three sources " in the single component expansion type flame retardant of one and act on functional group play expandable flame retardant effect in single component molecule, show excellent flame retardant properties, and overcome traditional Compositional type expanding fire retardant thermostability low, with the drawback such as matrix poor compatibility, 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, also more and more higher to the requirement of the over-all properties of fire retardant, the fire-retardant rank of regulation should be reached, also will have good physical mechanical strength, non-aggressive, low cigarette, nontoxicity and thermostability etc.The developing direction of following fire retardant mainly contains the following aspects: non-halogen trend, press down fuming and nontoxic gas, the process that comes to the surface, miniaturization process, synergistic effect etc.
Summary of the invention
The object of the present invention is to provide a kind of novel phosphorus-containing, nitrogen aggretion type fire retardant and preparation method thereof, fire retardant contains phosphorus, nitrogen element, the effect of expansion type flame-retarding can be played, and there is the advantage of low toxicity, be conducive to environmental protection, and preparation method is simple, mild condition, is easy to control, without other additives, the product purity of gained is high, convenient post-treatment.
The object of the invention is 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: first join in reactor by intermediate B HPPO dissolution with solvents, again cyanuric chloride and triethylamine are successively joined in reaction vessel, react 1-6h at 30-80 DEG C after, except desolventizing, then crude product is put in 30-60mL distilled water is housed there-necked flask at 100 DEG C, react 2h, obtain final product, washing, drying, can obtain 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 the mixture of any one or its arbitrary proportion in ethyl acetate, Isosorbide-5-Nitrae dioxane, acetonitrile, acetone.
Described a kind of novel phosphorus-containing, nitrogen aggretion type fire retardant preparation method, described temperature of reaction is 30-80 DEG C; Reaction times 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 the mixing of any one or its arbitrary proportion in distilled water, ethyl acetate, acetonitrile, Isosorbide-5-Nitrae dioxane, acetone, dehydrated alcohol.
Advantage of the present invention and effect are:
1, aggretion type fire retardant provided by the invention contains phosphorus, nitrogen element, can play the effect of expansion type flame-retarding, and has the advantage of low toxicity, is conducive to environmental protection.
2, preparation method provided by the invention is simple, mild condition, is easy to control, and without other additives, the product purity of gained is high, convenient post-treatment.
3, phosphorous, nitrogen aggretion type fire retardant applied range provided by the invention, can be used for the fire-retardant of the polymerization system such as epoxy resin and polyolefine.
Accompanying drawing explanation
Fig. 1 is Inventive polymers structural formula.
Embodiment
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 of magnetic agitation, thermometer, reflux condensing tube, dropping funnel and device for absorbing tail gas) Resorcinol 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 hydrogenchloride is no longer released terminate reaction.Separatory is except removal xylene while hot, obtains reddish-brown clear viscous liquids.Excessive Resorcinol is removed with 50 DEG C of hot washes.Dry 24h in 80 DEG C of vacuum drying ovens, obtains white powdery solids after grinding, and temperature of initial decomposition is 306 DEG C, and fusing point is 159.5 DEG C, is intermediate B HPPO.
In the 100ml there-necked flask that magnetic agitation, reflux condensing tube and thermometer are housed, 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, have clear yellow viscous material to generate, then react 5h under 70 DEG C of conditions, obtain pasty state viscous product and be slightly soluble in ethyl acetate, after naturally cooling, then crude product is put in 30mL distilled water is housed there-necked flask at 100 DEG C, react 2h.Finally by product distilled water wash for several times to remove triethylamine hydrochloride, then by ethyl acetate washed product to remove excessive BHPPO.70 DEG C of vacuum-drying 24h, obtain translucent solid matter after the dry 4h of gas blower, obtain white powdery solids after grinding, be fire retardant, 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.
In the 100ml there-necked flask that magnetic agitation, reflux condensing tube and thermometer are housed, 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, bottom mixture, there is clear yellow viscous material to generate, then react 5h under 70 DEG C of conditions, underpressure distillation is except desolventizing 1,4 dioxane, obtain oyster white cheese shape material, then crude product is put in 40mL distilled water is housed there-necked flask at 100 DEG C, react 2h.Finally by product distilled water wash for several times to remove triethylamine hydrochloride, then by Isosorbide-5-Nitrae dioxane washed product to remove excessive BHPPO.70 DEG C of vacuum-drying 24h, obtain translucent solid matter after the dry 4h of gas blower, obtain white powdery solids, be fire retardant after grinding.
Embodiment 3:
Wherein the synthetic method of intermediate B HPPO is with example 1.
In the 100ml there-necked flask that magnetic agitation, reflux condensing tube and thermometer are housed, 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, bottom mixture, have clear yellow viscous material to generate, then react 5h under 70 DEG C of conditions, underpressure distillation removing solvent acetonitrile, obtain oyster white material, then crude product is put in 50mL distilled water is housed there-necked flask at 100 DEG C, react 2h.Finally by product distilled water wash for several times to remove triethylamine hydrochloride, then with acetonitrile wash 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 (7)
1. novel phosphorus-containing, a nitrogen aggretion type fire retardant, it is characterized in that, described polymer formulae is as follows:
In formula, n is the positive integer of 1-100.
2. a novel phosphorus-containing, nitrogen aggretion type fire retardant preparation method, it is characterized in that, the synthesis step of described the method is as follows: first join in reactor by intermediate B HPPO dissolution with solvents, again cyanuric chloride and triethylamine are successively joined in reaction vessel, react 1-6h at 30-80 DEG C after, except desolventizing, crude product is put in the there-necked flask that 30-60mL distilled water is housed again and reacts 2h at 100 DEG C, obtain final product, washing, drying, can obtain fire retardant.
3. a kind of novel phosphorus-containing according to claim 2, nitrogen aggretion type fire retardant preparation method, is characterized in that, the ratio of described cyanuric chloride and BHPPO and triethylamine is 1:1.1:1.1-1:1.5:1.5.
4. a kind of novel phosphorus-containing according to claim 2, nitrogen aggretion type fire retardant preparation method, is characterized in that, described solvent is the mixture of any one or its arbitrary proportion in ethyl acetate, Isosorbide-5-Nitrae dioxane, acetonitrile, acetone.
5. a kind of novel phosphorus-containing according to claim 2, nitrogen aggretion type fire retardant preparation method, it is characterized in that, described temperature of reaction is 30-80 DEG C; Reaction times is 1-6h.
6. a kind of novel phosphorus-containing according to claim 2, nitrogen aggretion type fire retardant preparation method, it is characterized in that, described solvent load is 10-30mL; The consumption of distilled water is 30-60mL.
7. a kind of novel phosphorus-containing according to claim 2, nitrogen aggretion type fire retardant preparation method, it is characterized in that, described cleaning solvent is the mixing of any one or its arbitrary proportion in distilled water, ethyl acetate, acetonitrile, Isosorbide-5-Nitrae dioxane, acetone, dehydrated alcohol.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106700084A (en) * | 2016-12-28 | 2017-05-24 | 浙江大学宁波理工学院 | Diphenolic acid-based polyphosphate ester flame retardant containing DOPO structure and preparation method of flame retardant |
| 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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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106700084A (en) * | 2016-12-28 | 2017-05-24 | 浙江大学宁波理工学院 | Diphenolic acid-based polyphosphate ester flame retardant containing DOPO structure and preparation method of flame retardant |
| 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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| CN104311818B (en) | 2016-09-28 |
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