CN105461751A - Preparation method of high efficiency environment-friendly flame retardant - Google Patents
Preparation method of high efficiency environment-friendly flame retardant Download PDFInfo
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- CN105461751A CN105461751A CN201410425035.XA CN201410425035A CN105461751A CN 105461751 A CN105461751 A CN 105461751A CN 201410425035 A CN201410425035 A CN 201410425035A CN 105461751 A CN105461751 A CN 105461751A
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Abstract
The invention discloses a preparation method of a high efficiency environment-friendly flame retardant. The method comprises the steps of: (1) preparation of hexachlorocyclotriphosphazene: under the protection of nitrogen, adding a chlorobenzene solution into a reaction kettle, adding a mixture of zinc chloride and phosphorus pentachloride, adding a composite catalyst and pyridine in order, and carrying out reflux reaction, thus improving the conversion rate up to 85%; (2) preparation of hexaphenylamine cyclotriphosphazene: taking hexachlorocyclotriphosphazene, aniline and chlorobenzene, adding them into a reaction kettile, adding deionized water and a dispersant, starting stirring, carrying out reaction, filtration and drying; and (3) preparation of a flame retardant: adding hexaphenylamine cyclotriphosphazene into a mixed solution of ethanol and phenol, then adding magnesium hydroxide, diatomite and a silane coupling agent, and carrying out stirring, heating, reaction and centrifugal drying. A proper amount of chlorobenzene is adopted as ther solvent, has the characteristics of small toxicity, high boiling point and easy cyclic utilization, and reduces the cost. The prepared flame retardant has the characteristics of no toxicity and little smoke during buring, also has excellent durability, is beneficial to environmental protection, and is an environmental friendly flame retardant.
Description
Technical field
The invention belongs to fire retardant production technical field, be specifically related to a kind of preparation method of Efficient environment-friendlyflame flame retardant.
Background technology
Used conventional flame retardants, flame retarding efficiency is low, consumption is large, thus be degrading the excellent properties that polymer base is willing to have, the smoke which generated when increasing superpolymer burning or pyrolysis and toxic gas volume, increase the price of material, and cause the difficulty of fire-retardant high polymer processing and recovery aspect, therefore seeking efficient flame retardant system is the long-term targets of people.Phosphonitrile is that a class is alternately arranged forms with phosphorus, nitrogen element, and have the compound of stable phosphorus nitrogen skeleton structure, the phosphorus of its uniqueness, aza structure and high phosphorus, nitrogen content make it to have good thermostability and flame retardant resistance.When phosphonitrile has Halogen, a burning, the amount of being fuming is few, flame retarding efficiency is high, do not produce the advantages such as poisonous and corrosive gases and be considered to s-generation phosphorus-nitrogen expanding fire retardant, is the developing direction of fire retardant from now on.
Hexaaniline cyclotriphosphazene is one of phosphonitrile fire retardant reporting comparatively morning, to epoxy resin, ABS etc., there is good fire retardation, there is following problem at present in its synthesis: 1) solvent for use benzene or tetrahydrofuran (THF) toxicity large, high volatility, loss is large, and be unfavorable for recycle, solvent consumption is large, cost is high, and environmental pollution is serious; 2) product colour is dark, of poor quality.Therefore, for above problem, how to synthesize hexaaniline cyclotriphosphazene, improve product yield and quality, be applied in the production of fire retardant, make the fire retardant excellent effect obtained, have important practical significance.
Summary of the invention
For problems of the prior art, the object of the present invention is to provide a kind of preparation method of Efficient environment-friendlyflame flame retardant, improve transformation efficiency up to 85%, appropriate chlorobenzene is adopted to be solvent, toxicity is little, boiling point is higher, be easy to recycle, reduce cost, reaction conditions is gentle, improve product yield and quality, the feature that when fire retardant of preparation has a burning, nontoxic smog is few, has excellent weather resistance, is conducive to environmental protection, be a kind of environmental protection based flame retardant, the field such as plastics, rubber can be widely used in.
Technical scheme of the present invention is:
A preparation method for Efficient environment-friendlyflame flame retardant, is characterized in that, specifically comprises the steps:
(1) hexachlorocyclotriphosphazene processed: under nitrogen protection, chlorobenzene solution is added in reactor, interpolation 15-20% in mass ratio 2:5 gets the mixture of zinc chloride and phosphorus pentachloride, mass ratio is added successively for (0.01-0.03): the composite catalyst of 1 and pyridine in reactor, slowly be warming up to 118-123 DEG C of backflow, the lower insulation reaction 8-9h of backflow, cooling, filter, then go out chlorobenzene by vacuum distillation;
(2) hexaaniline cyclotriphosphazene processed: be that 1:1.5-1.8:6-7 weighs hexachlorocyclotriphosphazene, aniline and chlorobenzene according to mass ratio, join in reactor, add hexachlorocyclotriphosphazene quality 5-7 deionized water doubly and the dispersion agent of 0.003-0.005 times, start stirring, be heated to 90-110 DEG C, reaction 12-14h, is cooled to room temperature, filter, dry;
(3) fire retardant processed: the mixing solutions formed according to mol ratio 2:1 to ethanol and phenol, the above-mentioned obtained hexaaniline cyclotriphosphazene of 12-15% is added in mixing solutions, add the magnesium hydroxide of 5-7%, the diatomite of 6-8%, the silane coupling agent of 0.6-0.8% again, control mixing speed is 70-80rpm, slow raised temperature 90-120 DEG C, reaction 28-32h, is cooled to room temperature, centrifugal drying.
Further, in described step (1), composite catalyst is the mixture that ammonium chloride and iron(ic) chloride form according to mol ratio 2:3.
Further, in described step (2), dispersion agent is alkylphenol polyoxyethylene.
Beneficial effect of the present invention is:
The present invention, in the synthesis of hexachlorocyclotriphosphazene, with ammonium chloride and iron(ic) chloride for composite catalyst, avoids phosphorus pentachloride to be hydrolyzed; adopt nitrogen protection can take the HCl gas of reaction generation out of; promote that reaction is carried out to positive reaction direction, improve transformation efficiency further, up to 85%.
The present invention adopts appropriate chlorobenzene to be solvent, toxicity is little, boiling point is higher, be easy to recycle, reduce cost, under a small amount of dispersion agent exists, by the method for the nucleophilic substitution reaction synthesis hexaaniline cyclotriphosphazene of hexachlorocyclotriphosphazene and aniline, reaction conditions is gentle, improves product yield and quality.
Be rich in the composition such as diatomite and hexaaniline cyclotriphosphazene in fire retardant prepared by the present invention, turn waste into wealth, the feature that when having a burning, nontoxic smog is few, there is excellent weather resistance, be conducive to environmental protection, be a kind of environmental protection based flame retardant, the field such as plastics, rubber can be widely used in.
Embodiment
Embodiment 1
A preparation method for Efficient environment-friendlyflame flame retardant, is characterized in that, specifically comprises the steps:
(1) hexachlorocyclotriphosphazene processed: under nitrogen protection, 200g chlorobenzene solution is added in reactor, interpolation 30g in mass ratio 2:5 gets the mixture of zinc chloride and phosphorus pentachloride, the composite catalyst that to add mass ratio in reactor be successively 2g ammonium chloride and iron(ic) chloride forms according to mol ratio 2:3 and pyridine, slowly be warming up to 118 DEG C of backflows, the lower insulation reaction 8h of backflow, cooling, filter, then go out chlorobenzene by vacuum distillation;
(2) hexaaniline cyclotriphosphazene processed: be that 1:1.5:6 weighs 20g(0.35mol according to mass ratio) hexachlorocyclotriphosphazene, 30g(0.366mol) aniline and 120g chlorobenzene, join in reactor, add the deionized water of hexachlorocyclotriphosphazene quality 100g and the alkylphenol polyoxyethylene of 0.06g, start stirring, be heated to 100 DEG C, reaction 14h, is cooled to room temperature, filter, dry;
Interpretation of result: product weight 23.456g, fusing point 267-269 DEG C, content 99.0% (adopts
31measure, area normalization method), product yield 68.33%.
(3) fire retardant processed: the mixing solutions formed according to mol ratio 2:1 to ethanol and phenol, 12% above-mentioned obtained hexaaniline cyclotriphosphazene is added in mixing solutions, add the magnesium hydroxide of 5%, the diatomite of 6%, the silane coupling agent of 0.6% again, control mixing speed is 70rpm, slow raised temperature 90 DEG C, reaction 32h, is cooled to room temperature, centrifugal drying.
Embodiment 2
A preparation method for Efficient environment-friendlyflame flame retardant, is characterized in that, specifically comprises the steps:
(1) hexachlorocyclotriphosphazene processed: under nitrogen protection, 200g chlorobenzene solution is added in reactor, interpolation 36g in mass ratio 2:5 gets the mixture of zinc chloride and phosphorus pentachloride, composite catalyst and pyridine that ammonium chloride that mass ratio is 4g and iron(ic) chloride forms according to mol ratio 2:3 is added successively in reactor, slowly be warming up to 120 DEG C of backflows, the lower insulation reaction 8h of backflow, cooling, filter, then go out chlorobenzene by vacuum distillation;
(2) hexaaniline cyclotriphosphazene processed: be that 1:1.6:6.5 weighs 20g(0.35mol according to mass ratio) hexachlorocyclotriphosphazene, 32g(0.366mol) aniline and 130g chlorobenzene, join in reactor, add the alkylphenol polyoxyethylene of hexachlorocyclotriphosphazene quality 120g deionized water and 0.08g, start stirring, be heated to 90 DEG C, reaction 14h, is cooled to room temperature, filter, dry;
Interpretation of result: product weight 23.56g, fusing point 267-269 DEG C, content 99.0% (adopts
31measure, area normalization method), product yield 68.41%.
(3) fire retardant processed: the mixing solutions formed according to mol ratio 2:1 to ethanol and phenol, 13% above-mentioned obtained hexaaniline cyclotriphosphazene is added in mixing solutions, add the magnesium hydroxide of 6%, the diatomite of 7%, the silane coupling agent of 0.6-0.8% again, control mixing speed is 75rpm, slow raised temperature 110 DEG C, reaction 30h, is cooled to room temperature, centrifugal drying.
Embodiment 3
A preparation method for Efficient environment-friendlyflame flame retardant, is characterized in that, specifically comprises the steps:
(1) hexachlorocyclotriphosphazene processed: under nitrogen protection, 200g chlorobenzene solution is added in reactor, interpolation 40g in mass ratio 2:5 gets the mixture of zinc chloride and phosphorus pentachloride, composite catalyst and pyridine that ammonium chloride that mass ratio is 6g and iron(ic) chloride forms according to mol ratio 2:3 is added successively in reactor, slowly be warming up to 123 DEG C of backflows, the lower insulation reaction 8h of backflow, cooling, filter, then go out chlorobenzene by vacuum distillation;
(2) hexaaniline cyclotriphosphazene processed: be that 1:1.8:7 weighs 20g(0.35mol according to mass ratio) hexachlorocyclotriphosphazene, 36g(0.366mol) aniline and 140g chlorobenzene, aniline and chlorobenzene, join in reactor, add the deionized water of hexachlorocyclotriphosphazene quality 140g and the alkylphenol polyoxyethylene of 0.01g, start stirring, be heated to 110 DEG C, reaction 13h, be cooled to room temperature, filter, dry;
Interpretation of result: product weight 23.81g, fusing point 267-269 DEG C, content 99.0% (adopts
31measure, area normalization method), product yield 68.36%.
(3) fire retardant processed: the mixing solutions formed according to mol ratio 2:1 to ethanol and phenol, 15% above-mentioned obtained hexaaniline cyclotriphosphazene is added in mixing solutions, add the magnesium hydroxide of 7%, the diatomite of 8%, the silane coupling agent of 0.8% again, control mixing speed is 80rpm, slow raised temperature 120 DEG C, reaction 28h, is cooled to room temperature, centrifugal drying.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, although with reference to previous embodiment to invention has been detailed description, for a person skilled in the art, it still can be modified to the technical scheme described in foregoing embodiments, or carries out equivalent replacement to wherein portion of techniques feature.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (3)
1. a preparation method for Efficient environment-friendlyflame flame retardant, is characterized in that, specifically comprises the steps:
(1) hexachlorocyclotriphosphazene processed: under nitrogen protection, chlorobenzene solution is added in reactor, interpolation 15-20% in mass ratio 2:5 gets the mixture of zinc chloride and phosphorus pentachloride, mass ratio is added successively for (0.01-0.03): the composite catalyst of 1 and pyridine in reactor, slowly be warming up to 118-123 DEG C of backflow, the lower insulation reaction 8-9h of backflow, cooling, filter, then go out chlorobenzene by vacuum distillation;
(2) hexaaniline cyclotriphosphazene processed: be that 1:1.5-1.8:6-7 weighs hexachlorocyclotriphosphazene, aniline and chlorobenzene according to mass ratio, join in reactor, add hexachlorocyclotriphosphazene quality 5-7 deionized water doubly and the dispersion agent of 0.003-0.005 times, start stirring, be heated to 90-110 DEG C, reaction 12-14h, is cooled to room temperature, filter, dry;
(3) fire retardant processed: the mixing solutions formed according to mol ratio 2:1 to ethanol and phenol, the above-mentioned obtained hexaaniline cyclotriphosphazene of 12-15% is added in mixing solutions, add the magnesium hydroxide of 5-7%, the diatomite of 6-8%, the silane coupling agent of 0.6-0.8% again, control mixing speed is 70-80rpm, slow raised temperature 90-120 DEG C, reaction 28-32h, is cooled to room temperature, centrifugal drying.
2. the preparation method of a kind of Efficient environment-friendlyflame flame retardant according to claim 1, is characterized in that, in described step (1), composite catalyst is the mixture that ammonium chloride and iron(ic) chloride form according to mol ratio 2:3.
3. the preparation method of a kind of Efficient environment-friendlyflame flame retardant according to claim 1, is characterized in that, in described step (2), dispersion agent is alkylphenol polyoxyethylene.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109438755A (en) * | 2018-12-10 | 2019-03-08 | 苏州科技大学 | Five anilino- cyclotrinitrile phosphide of reactive flame retardant allyloxy and preparation method thereof |
| CN109575082A (en) * | 2018-12-10 | 2019-04-05 | 苏州科技大学 | Reactive flame retardant allyl amido pentaphene amido cyclotrinitrile phosphide and preparation method thereof |
| CN109651439A (en) * | 2018-12-10 | 2019-04-19 | 苏州科技大学 | Five alkoxycyclotriphosphderivative compound of reactive flame retardant allyl amido and preparation method thereof |
| CN109651441A (en) * | 2018-12-10 | 2019-04-19 | 苏州科技大学 | Five alkoxycyclotriphosphderivative compound of reactive flame retardant allyloxy and preparation method thereof |
| CN109734748A (en) * | 2018-12-10 | 2019-05-10 | 苏州科技大学 | Reactive flame retardant allyl amido pentaphene oxygroup cyclotrinitrile phosphide and preparation method thereof |
| CN109734749A (en) * | 2018-12-10 | 2019-05-10 | 苏州科技大学 | Five phenoxy group cyclotrinitrile phosphide of reactive flame retardant allyloxy and preparation method thereof |
| CN110467767A (en) * | 2019-07-25 | 2019-11-19 | 安徽电缆股份有限公司 | A kind of fire-retardant B1 grades of cable of 0.6/1kV |
-
2014
- 2014-08-27 CN CN201410425035.XA patent/CN105461751A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109438755A (en) * | 2018-12-10 | 2019-03-08 | 苏州科技大学 | Five anilino- cyclotrinitrile phosphide of reactive flame retardant allyloxy and preparation method thereof |
| CN109575082A (en) * | 2018-12-10 | 2019-04-05 | 苏州科技大学 | Reactive flame retardant allyl amido pentaphene amido cyclotrinitrile phosphide and preparation method thereof |
| CN109651439A (en) * | 2018-12-10 | 2019-04-19 | 苏州科技大学 | Five alkoxycyclotriphosphderivative compound of reactive flame retardant allyl amido and preparation method thereof |
| CN109651441A (en) * | 2018-12-10 | 2019-04-19 | 苏州科技大学 | Five alkoxycyclotriphosphderivative compound of reactive flame retardant allyloxy and preparation method thereof |
| CN109734748A (en) * | 2018-12-10 | 2019-05-10 | 苏州科技大学 | Reactive flame retardant allyl amido pentaphene oxygroup cyclotrinitrile phosphide and preparation method thereof |
| CN109734749A (en) * | 2018-12-10 | 2019-05-10 | 苏州科技大学 | Five phenoxy group cyclotrinitrile phosphide of reactive flame retardant allyloxy and preparation method thereof |
| CN110467767A (en) * | 2019-07-25 | 2019-11-19 | 安徽电缆股份有限公司 | A kind of fire-retardant B1 grades of cable of 0.6/1kV |
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