CN103319538A

CN103319538A - Preparation method of hexaphenoxy cyclotriphosphazene

Info

Publication number: CN103319538A
Application number: CN2013102792922A
Authority: CN
Inventors: 储晓建
Original assignee: NANTONG TAITONG CHEMICAL TECHNOLOGY Co Ltd
Current assignee: NANTONG TAITONG CHEMICAL TECHNOLOGY Co Ltd
Priority date: 2013-07-04
Filing date: 2013-07-04
Publication date: 2013-09-25

Abstract

The invention relates to the technical field of hexaphenoxy cyclotriphosphazene and in particular relates to a preparation method of the hexaphenoxy cyclotriphosphazene. The preparation method of hexaphenoxy cyclotriphosphazene comprises a phosphonitrilic chloride trimer synthesizing process and a hexaphenoxy cyclotriphosphazene synthesizing process, wherein the phosphonitrilic chloride trimer is used as the main material, the product yield is as high as 98%l and the hexaphenoxy cyclotriphosphazene has the characteristics of being high in flame retardant efficiency, good in stability, easy to process, extremely small in material physical performance interference, capable of improving the water resistance of epoxy resin and the like. Besides, the preparation method of the hexaphenoxy cyclotriphosphazene is short in reaction time in a production process, high in solvent recovery rate, low in cost, less in pollution, capable of extensively used for epoxy resin flame retardant and used for flame retardant of PC (Poly Carbonate), PBT (Polybutylece Terephthalate) and PA (Poly Amine).

Description

The preparation method of hexaphenoxycyclotriphosphazene

Technical field

The present invention relates to the hexaphenoxycyclotriphosphazene technical field, be specifically related to the preparation method of hexaphenoxycyclotriphosphazene.

Background technology

At present, environment-friendly type combustion inhibitor special hexaphenoxycyclotriphosphazene, its synthesis material is mainly phenol and hexachlorocyclotriphosphazene.The chemical structure of phosphonitrile has determined that it has excellent flame retardant effect and good thermotolerance.In phosphorus flame retardant, phosphazene flame retardant is BACN, it is high that hexaphenoxycyclotriphosphazene has a flame retarding efficiency, good stability, easy processed-type, minimum on the material property impact, can improve the characteristics such as water-resisting type of Resins, epoxy, therefore not only be useful on the fire retardant of Resins, epoxy, can also be used for PC, PBT, the fire retardant of PA, even the phosphazene flame retardant of certain structure can be used for ABS fire-retardant (reporting) abroad, and the halogen-free flameproof of ABS is global problem, if the ABS halogen-free flame retardants can be succeeded in developing, market demand can surpass tons up to ten thousand in a short time.Because the fire retardant of Resins, epoxy now or take brominated epoxy resin as main, particularly domestic those low side electronic products of doing all are as fire retardant with brominated epoxy.But along with environmental protection pressure is increasing, particularly external client's environmental requirement, halogen-free flameproof must be trend of the times.Therefore the demand of brominated epoxy can reduce rapidly, and the demand of phosphorus flame retardant promotes rapidly.

Summary of the invention

The preparation method who the purpose of this invention is to provide that a kind of flame retarding efficiency is high, good stability, energy consumption are low, pollutes little hexaphenoxycyclotriphosphazene.

In order to solve the existing problem of background technology, the present invention is by the following technical solutions: the preparation method of hexaphenoxycyclotriphosphazene, comprise hexachlorocyclotriphosphazene synthesis procedure and hexaphenoxycyclotriphosphazene synthesis procedure, and concrete steps are as follows:

(1), hexachlorocyclotriphosphazene synthesis procedure

In reactor, add successively weight part phosphorus pentachloride 600～700kg, ammonium chloride 100～300kg, behind catalyzer magnesium chloride 4～8kg, the agent pyridine 20～40kg, add again solvent chlorobenzene 800～1200kg, stir temperature rising reflux reaction 10 hours, be cooled to 30～50 ℃, remove by filter the salt of excessive ammonium chloride and catalyzer and generation, the solution precipitation that reduces pressure again reclaims chlorobenzene, be cooled to 10 ℃, refilter to get hexachlorocyclotriphosphazene.

(2), hexaphenoxycyclotriphosphazene synthesis procedure

First chlorobenzene, liquid caustic soda are pumped into corresponding header tank, in reactor, add chlorobenzene 700～800kg, phenol 400～600kg by weight again, add 30% sodium hydroxide solution, 600～800kg after the stirring and dissolving, stirring heated up after 30 minutes removes moisture, add catalyzer Tetrabutyl amonium bromide 30～50kg after the dehydration fully, drip again chlordene ring three phosphorus cyanogen 200～400kg after the stirring and dissolving, be dissolved in the chlorobenzene, add rear back flow reaction 14～18 hours.

After reaction is finished reaction solution is cooled to 80 ℃, adding is mixed with alkali lye 1400～1600kg of 5%, stirs 1～2 hour, divides the phase of anhydrating; Organic addition is mixed with 5% sulfuric acid, 1400～1600kg, reacts and divides the phase of anhydrating after 30 minutes; Organic addition water 1400～1600kg washs, and stirs and divides the phase of anhydrating after 1～2 hour; Organic phase is carried out the underpressure distillation desolvation, reclaims lower batch of chlorobenzene and applies mechanically, and then adds dehydrated alcohol 200～400kg, cools to 10～20 ℃ of crystallizations, filters, and filter cake with dry after the alcohol washing, gets the product hexaphenoxycyclotriphosphazene again.

Wherein, main chemical equation is as follows:

The present invention has following beneficial effect: the preparation method of hexaphenoxycyclotriphosphazene of the present invention, take hexachlorocyclotriphosphazene as main raw material, its product yield is up to more than 98%, has that flame retarding efficiency is high, a good stability, easily processed-type,, the characteristics such as water-resisting type that can improve Resins, epoxy minimum on the material property impact.In addition, the present invention in process of production the reaction times short, solvent recovering rate is high, cost is low, stains fewly, is widely used in the fire retardant of Resins, epoxy, and is used for PC, PBT, the fire retardant of PA.

Embodiment

Below the present invention will be further described in detail.

Embodiment one:

The preparation method of hexaphenoxycyclotriphosphazene comprises hexachlorocyclotriphosphazene synthesis procedure and hexaphenoxycyclotriphosphazene synthesis procedure, and concrete steps are as follows:

(1), hexachlorocyclotriphosphazene synthesis procedure

In reactor, add successively weight part phosphorus pentachloride 600kg, ammonium chloride 100kg, behind catalyzer magnesium chloride 4kg, the agent pyridine 20kg, add again solvent chlorobenzene 800kg, stir temperature rising reflux reaction 10 hours, be cooled to 30 ℃, remove by filter the salt of excessive ammonium chloride and catalyzer and generation, the solution precipitation that reduces pressure again reclaims chlorobenzene, be cooled to 10 ℃, refilter to get hexachlorocyclotriphosphazene.

(2), hexaphenoxycyclotriphosphazene synthesis procedure

First chlorobenzene, liquid caustic soda are pumped into corresponding header tank, in reactor, add chlorobenzene 700kg, phenol 400kg by weight again, add 30% sodium hydroxide solution 600kg after the stirring and dissolving, stirring heated up after 30 minutes removes moisture, add catalyzer Tetrabutyl amonium bromide 30kg after the dehydration fully, drip again chlordene ring three phosphorus cyanogen 200kg after the stirring and dissolving, be dissolved in the chlorobenzene, add rear back flow reaction 14 hours.

After reaction is finished reaction solution is cooled to 80 ℃, adding is mixed with 5% alkali lye 1400kg, stirs 1 hour, divides the phase of anhydrating; Organic addition is mixed with 5% sulfuric acid 1400kg, reacts and divides the phase of anhydrating after 30 minutes; Organic addition water 1400kg washs, and stirs and divides the phase of anhydrating after 1 hour; Organic phase is carried out the underpressure distillation desolvation, reclaims lower batch of chlorobenzene and applies mechanically, and then adds dehydrated alcohol 200kg, cools to 10 ℃ of crystallizations, filters, and filter cake with dry after the alcohol washing, gets the product hexaphenoxycyclotriphosphazene again.

In the present embodiment, when generating, chlordene ring three phosphorus cyanogen produce hydrogenchloride; The finished product production reaction hydrogenchloride is produced sodium-chlor by the solid acid of sodium hydroxide, only has a small amount of hydrogenchloride discharging, chlorobenzene, ethanol have a small amount of volatilization waste gas to produce when reinforced, chlorobenzene, ethanol distillation reclaim has non-condensable gas to produce, product drying has ethanol waste gas to produce, alkali is molten, acid minute go after molten water respectively after the recoverys salt such as crystallization filtration waste water advance again the sewage works processing, filter residue and the distillation slag outer processing of all entrusting, thereby little to environmental pollution.

Embodiment two:

The preparation method of hexaphenoxycyclotriphosphazene is characterized in that, comprises hexachlorocyclotriphosphazene synthesis procedure and hexaphenoxycyclotriphosphazene synthesis procedure, and concrete steps are as follows:

(1), hexachlorocyclotriphosphazene synthesis procedure

(2), hexaphenoxycyclotriphosphazene synthesis procedure

First chlorobenzene, liquid caustic soda are pumped into corresponding header tank, in reactor, add chlorobenzene 750kg, phenol 500kg by weight again, add 30% sodium hydroxide solution 700kg after the stirring and dissolving, stirring heated up after 30 minutes removes moisture, add catalyzer Tetrabutyl amonium bromide 40kg after the dehydration fully, drip again chlordene ring three phosphorus cyanogen 300kg after the stirring and dissolving, be dissolved in the chlorobenzene, add rear back flow reaction 16 hours.

After reaction is finished reaction solution is cooled to 80 ℃, adding is mixed with 5% alkali lye 1500kg, stirs 1.5 hours, divides the phase of anhydrating; Organic addition is mixed with 5% sulfuric acid 1500kg, reacts and divides the phase of anhydrating after 30 minutes; Organic addition water 1500kg washs, and stirs and divides the phase of anhydrating after 1.5 hours; Organic phase is carried out the underpressure distillation desolvation, reclaims lower batch of chlorobenzene and applies mechanically, and then adds dehydrated alcohol 300kg, cools to 15 ℃ of crystallizations, filters, and filter cake with dry after the alcohol washing, gets the product hexaphenoxycyclotriphosphazene again.

Embodiment three:

(1), hexachlorocyclotriphosphazene synthesis procedure

In reactor, add successively weight part phosphorus pentachloride 700kg, ammonium chloride 300kg, behind catalyzer magnesium chloride 8kg, the agent pyridine 40kg, add again solvent chlorobenzene 1200kg, stir temperature rising reflux reaction 10 hours, be cooled to 50 ℃, remove by filter the salt of excessive ammonium chloride and catalyzer and generation, the solution precipitation that reduces pressure again reclaims chlorobenzene, be cooled to 10 ℃, refilter to get hexachlorocyclotriphosphazene.

(2), hexaphenoxycyclotriphosphazene synthesis procedure

First chlorobenzene, liquid caustic soda are pumped into corresponding header tank, in reactor, add chlorobenzene 800kg, phenol 600kg by weight again, add 30% sodium hydroxide solution 800kg after the stirring and dissolving, stirring heated up after 30 minutes removes moisture, add catalyzer Tetrabutyl amonium bromide 50kg after the dehydration fully, drip again chlordene ring three phosphorus cyanogen 400kg after the stirring and dissolving, be dissolved in the chlorobenzene, add rear back flow reaction 18 hours.

After reaction is finished reaction solution is cooled to 80 ℃, adding is mixed with 5% alkali lye 1600kg, stirs 2 hours, divides the phase of anhydrating; Organic addition is mixed with 5% sulfuric acid 1600kg, reacts and divides the phase of anhydrating after 30 minutes; Organic addition water 1600kg washs, and stirs and divides the phase of anhydrating after 2 hours; Organic phase is carried out the underpressure distillation desolvation, reclaims lower batch of chlorobenzene and applies mechanically, and then adds dehydrated alcohol 400kg, cools to 20 ℃ of crystallizations, filters, and filter cake with dry after the alcohol washing, gets the product hexaphenoxycyclotriphosphazene again.

Explanation is at last, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, other modifications that those of ordinary skills make technical scheme of the present invention or be equal to replacement, only otherwise break away from the spirit and scope of technical solution of the present invention, all should be encompassed in the middle of the claim scope of the present invention.

Claims

1. the preparation method of hexaphenoxycyclotriphosphazene is characterized in that, comprises hexachlorocyclotriphosphazene synthesis procedure and hexaphenoxycyclotriphosphazene synthesis procedure, and concrete steps are as follows:

(1), hexachlorocyclotriphosphazene synthesis procedure

In reactor, add successively weight part phosphorus pentachloride 600～700 kg, ammonium chloride 100～300kg, behind catalyzer magnesium chloride 4～8kg, the agent pyridine 20～40kg, add again solvent chlorobenzene 800～1200kg, stir temperature rising reflux reaction 10 hours, be cooled to 30～50 ℃, remove by filter the salt of excessive ammonium chloride and catalyzer and generation, the solution precipitation that reduces pressure again reclaims chlorobenzene, be cooled to 10 ℃, refilter to get hexachlorocyclotriphosphazene;

(2), hexaphenoxycyclotriphosphazene synthesis procedure

First chlorobenzene, liquid caustic soda are pumped into corresponding header tank, in reactor, add chlorobenzene 700～800kg, phenol 400～600kg by weight again, add 30% sodium hydroxide solution, 600～800kg after the stirring and dissolving, stirring heated up after 30 minutes removes moisture, add catalyzer Tetrabutyl amonium bromide 30～50kg after the dehydration fully, drip again chlordene ring three phosphorus cyanogen 200～400kg after the stirring and dissolving, be dissolved in the chlorobenzene, add rear back flow reaction 14～18 hours;