CN101602780A - The process for catalytic synthesis of hexachlorocyclotriphosphazene - Google Patents
The process for catalytic synthesis of hexachlorocyclotriphosphazene Download PDFInfo
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Abstract
The invention discloses a kind of process for catalytic synthesis of hexachlorocyclotriphosphazene, it is characterized in that by quaternary ammonium salt: anhydrous metal muriate: chlorobenzene: ammonium chloride: phosphorus pentachloride=1～2: 0.1～1: 5～10: 1～1.4: 1 mol ratio is got each raw material; With quaternary ammonium salt and anhydrous metal muriate and add in the reactor, under 80 ℃～120 ℃ temperature, stirring reaction 1h～2h, make ionic liquid; Again chlorobenzene, ammonium chloride and phosphorus pentachloride are added in the reactor, under 100 ℃～130 ℃ temperature, stirring reaction 1h～5h, obtain the reaction mixture material; With the reaction mixture material through separatory or/and filtration treatment, ionic liquid and the chlorobenzene solution that contains reaction product are separated, the chlorobenzene solution that will contain reaction product more promptly obtains the hexachlorocyclotriphosphazene product after through washing, underpressure distillation.The present invention is easy to operate and safe, cost is low, be easy to industrial production uses.
Description
Technical field
The invention belongs to the preparation method of 1,3,5-triaza-2,4,6-triphosphorines-three phosphabenzene compounds, relate to the process for catalytic synthesis of hexachlorocyclotriphosphazene.The hexachlorocyclotriphosphazene of this method preparation is suitable for the basic material of making to produce ring phosphonitrile and polyphosphonitrile material.
Background technology
Hexachlorocyclotriphosphazene claims the trimerization phosphonitrilic chloride again, molecular formula: Cl
6N
3P
3, molecular weight: 347.66, as the basic material of producing ring phosphonitrile and polyphosphonitrile material, be a kind of crucial fine-chemical intermediate, play a part very important to the development of phosphonitrile materials chemistry.
In the prior art, more about the preparation method of hexachlorocyclotriphosphazene both at home and abroad, wherein with inexpensive ammonium chloride and phosphorus pentachloride as reaction raw materials, as solvent, the method for select different catalyzer for use, synthesizing hexachlorocyclotriphosphazene with different synthesis techniques and isolation technique becomes the emphasis that many researchs are paid close attention to chlorobenzene or symmetric tetrachloroethane.Pass through to add metal chloride, metal organic acid salt or metal oxide, quinoline etc. as catalyzer as US4382914 (1983), US4795621 (1989), JP2004155616 (2004), adopt high temperature to drip modes such as phosphorus pentachloride solution, reaction 10h～20h, hexachlorocyclotriphosphazene content reaches 50%～90%, adopt this method yield 80%～98%, but long reaction time, by product is many, purity is low; Chinese patent application 200610017819.4 discloses a kind of " process for catalytic synthesis of hexa chloro cyclotripolyphosphazene ", system adopts the composite catalyst of being made up of metallic compound, pyridine thing repeatedly to add phosphorus pentachloride under reflux state in batches, reaction 3h～5h, distillation after filtration,, petroleum ether extraction, normal heptane recrystallization or distillation obtain hexachlorocyclotriphosphazene, productive rate 80%～90% adopts this procedure complexity, aftertreatment trouble, cost higher; Chinese patent application 200610116011.1 discloses a kind of " preparation of hexachlorocyclotriphosphazene and method of purification thereof ", proposition reacts chlorobenzene, acid binding agent (pyridine or triethylamine), phosphorus pentachloride, metal chloride, ammonium chloride to 1h～2h under refluxing, acid binding agent and hydrogenchloride are removed in the cooling washing, add the porous active material and soak 12h～24h, suction filtration, collect filtrate, underpressure distillation obtains product, yield can reach more than 95%, purity 65%～85%, adopt this method production cycle long, efficient is low, the tripolymer selectivity is lower, cost is higher; Chinese patent application 200710166213.1 discloses a kind of " a kind of novel process for preparing hexa chloro cyclotripolyphosphazene ", the novel composite catalyst that adopts transition metal chloride, transition metal oxide, pyridine compounds and their to form, by the reinforced method of substep, logical N2 dehydrochlorination, sherwood oil recrystallization, make the reaction times shorten to 2h～4h, productive rate reaches 85%～95%, and purity reaches 98%, the control requirement is high, safety issue is serious to adopt this method to feed in raw material, and cost is higher; People such as Chen Haiqun (" chemistry world ", 2008, (1): 34～37) reported a kind of synthetic hexachlorocyclotriphosphazene of improving one's methods, be raw material promptly with phosphorus pentachloride and ammonium chloride, it is synthetic that the pyridine that employing is equivalent to 2.5～3 times of phosphorus pentachloride weight is that acid binding agent carried out for two steps, productive rate is more than 85%, adopts that this method acid binding agent pyridine consumption is big, price is high, reclaim the pyridine complicated operation, cost is too high, and being difficult to is to produce to accept.
Ionic liquid because have high reactivity, highly selective, can reuse, characteristics safe in utilization; the an acidic catalyst such as sulfuric acid, aluminum chloride, zinc chloride that can replace traditional high pollution, high toxicity, highly corrosive; be considered to a kind of environment amenable catalyzer and solvent system more and more widely; successful Application in reaction such as acylations, polymerization, isomerization, asymmetric open loop, epoxidation becomes the focus of green synthetic chemistry research.But, adopt ionic liquid-catalyzed synthetic hexachlorocyclotriphosphazene not appear in the newspapers as yet.
Summary of the invention
Purpose of the present invention is intended to overcome above-mentioned deficiency of the prior art, and a kind of easy and simple to handle, safe and efficient, low-cost, process for catalytic synthesis of being easy to industrial hexachlorocyclotriphosphazene is provided.
Content of the present invention is: a kind of process for catalytic synthesis of hexachlorocyclotriphosphazene is characterized in that comprising the following steps:
A, raw material prepare: by quaternary ammonium salt: anhydrous metal muriate: chlorobenzene: ammonium chloride: phosphorus pentachloride=1～2: 0.1～1: 5～10: 1～1.4: 1 molar ratio is got raw material quaternary ammonium salt, anhydrous metal muriate, chlorobenzene, ammonium chloride and phosphorus pentachloride, and is standby;
B, preparation ionic liquid: get described quaternary ammonium salt of step a and anhydrous metal muriate and add in the reactor (for example: reactor, flask or other reactor), under 80 ℃～120 ℃ temperature, stirring reaction 1h～2h, make ionic liquid (such ion liquid fusing point can be again-10 ℃～100 ℃);
C, reaction: get the described chlorobenzene of step a (for solvent), ammonium chloride and phosphorus pentachloride again and add in the described reactor of step b, mix with ionic liquid, then under 100 ℃～130 ℃ temperature, stirring reaction 1h～5h, (in the actual production, in this time range, react to hydrogenchloride and no longer emit, reaction promptly finishes), obtain the reaction mixture material;
D, separation: with the reaction mixture material through separatory or/and filtration treatment [during lock out operation, if the temperature of reaction mixture material is higher than ion liquid fusing point, then takes the method for separatory that the chlorobenzene solution that lower floor's ionic liquid and upper strata contain reaction product is separated; Perhaps the temperature with the reaction mixture material is heated to above ion liquid fusing point, takes the method for separatory that the chlorobenzene solution that lower floor's ionic liquid and upper strata contain reaction product is separated again.During lock out operation, if the temperature of reaction mixture material is less than or equal to ion liquid fusing point, then take filtering method that ionic liquid (for solid state) is separated with the chlorobenzene solution that contains reaction product], described ionic liquid of step a and the chlorobenzene solution that contains reaction product are separated, the chlorobenzene solution that will contain reaction product more promptly obtains the hexachlorocyclotriphosphazene product after through washing, underpressure distillation (promptly removing the chlorobenzene that desolvates).This product purity (weight percentage of hexachlorocyclotriphosphazene) is more than 90%, and productive rate surpasses 95%.
In the content of the present invention: quaternary ammonium salt described in the step a be in tetrabutylammonium chloride, Tetrabutyl amonium bromide, trimethylamine hydrochloride, triethylamine hydrochloride or the pyridine hydrochloride any.
In the content of the present invention: the muriate of anhydrous metal described in the step a be in zinc chloride, iron(ic) chloride, magnesium chloride or the aluminum chloride any.
In the content of the present invention: the time of stirring reaction described in the step c is 1h～2h.
In the content of the present invention: the described washing of steps d is washing 2～5 times, and the weight of each washing is 0.5～1 times of chlorobenzene solution weight that contains reaction product.
In the content of the present invention: the ionic-liquid catalyst of the described Separation and Recovery of steps d can be reused.
Compared with prior art, the present invention has following characteristics and beneficial effect:
(1) the present invention adopts the ionic liquid of quaternary ammonium salt and anhydrous chloride formation as catalyst for reaction, the composite catalyst system that replaces traditional metal chloride, metal oxide, pyridine and other type can make the reaction times shorten to that 2h～4h, productive rate surpass 95%, the hexachlorocyclotriphosphazene product purity reaches more than 90%;
(2) ionic-liquid catalyst of the present invention's employing can be by simple separatory or/and filtration treatment be recyclable repeated use after reaction finishes, confirm through test, ionic-liquid catalyst repeated use 8 times, product yield and purity are not seen obvious reduction, thereby can reduce production costs greatly, help suitability for industrialized production and adopt;
(3) adopt the inventive method, need not post-processing operation repeatedly reinforced in batches, that be incubated dropping and complexity, reaction process is steady, and required equipment is simple, and production technique is simple, and is easy to operate and safe, practical.
Embodiment
Below by embodiment the present invention is specifically described; it is worthy of note that following examples only are applicable to that the present invention is further illustrated; can not be interpreted as limiting the scope of the invention; and the nonessential improved adjustment that the professional in present technique field makes according to above-mentioned content of the present invention should belong to protection scope of the present invention.
Embodiment 1:
Having agitator, thermometer, in the 500mL there-necked flask of reflux exchanger and hydrogen chloride gas absorption unit, add 55.6g (0.2mol) tetrabutylammonium chloride, 2.7g (0.02mol) zinc chloride, heat temperature raising to 100 ℃ reaction 1h, make ionic liquid, add 41.7g (0.2mol) phosphorus pentachloride then, 10.7g (0.2mol) ammonium chloride, the 150ml chlorobenzene is kept 100 ℃～130 ℃ reaction 2h, emits until no hydrogen chloride gas, material cools to 30 ℃ afterwards, tell supernatant liquid, lower floor's ionic liquid continues to use as secondary response under the catalyst supply mutually, and water is washed till neutrality with supernatant liquid then, decompression steams chlorobenzene (recovery), obtain white crystal, productive rate 96%, hexachlorocyclotriphosphazene content are 91%.
Embodiment 2:
Having agitator, thermometer, in the 500mL there-necked flask of reflux exchanger and hydrogen chloride gas absorption unit, add 64.5g (0.2mol) Tetrabutyl amonium bromide, 2.7g (0.02mol) zinc chloride, heat temperature raising to 80 ℃ reaction 1h, make ionic liquid, add 41.7g (0.2mol) phosphorus pentachloride then, 11.8g (0.22mol) ammonium chloride, the 140ml chlorobenzene is kept 100 ℃～130 ℃ reaction 2h, emits until no hydrogen chloride gas, material cools to 30 ℃ afterwards, tell supernatant liquid, lower floor's ionic liquid continues to use as secondary response under the catalyst supply mutually, and water is washed till neutrality with supernatant liquid then, decompression steams chlorobenzene (recovery), obtain white crystal, productive rate 96%, hexachlorocyclotriphosphazene content are 90%.
Embodiment 3:
Having agitator, thermometer, in the 500mL there-necked flask of reflux exchanger and hydrogen chloride gas absorption unit, add 19.1g (0.2mol) trimethylamine hydrochloride, 13.6g (0.1mol) zinc chloride, heat temperature raising to 120 ℃ reaction 2h, make ionic liquid, add 41.7g (0.2mol) phosphorus pentachloride then, 12.8g (0.24mol) ammonium chloride, the 100ml chlorobenzene is kept 100 ℃～130 ℃ reaction 2h, emits until no hydrogen chloride gas, material cools to below 60 ℃ afterwards, filter, collection of ions liquid solid filter residue continues to use as secondary response under the catalyst supply, and water is washed till neutrality with filtrate then, decompression steams chlorobenzene (recovery), obtain white crystal, productive rate 95%, hexachlorocyclotriphosphazene content are 91%.
Embodiment 4:
Having agitator, thermometer, in the 500mL there-necked flask of reflux exchanger and hydrogen chloride gas absorption unit, add 55g (0.4mol) triethylamine hydrochloride, 13.6g (0.1mol) zinc chloride, heat temperature raising to 100 ℃ reaction 2h, make ionic liquid, add 41.7g (0.2mol) phosphorus pentachloride then, 13.9g (0.26mol) ammonium chloride, the 130ml chlorobenzene is kept 100 ℃～130 ℃ back flow reaction 2h, emits until no hydrogen chloride gas, material cools to 30 ℃ afterwards, tell supernatant liquid, lower floor's ionic liquid continues to use as secondary response under the catalyst supply mutually, and water is washed till neutrality with supernatant liquid then, decompression steams chlorobenzene (recovery), obtain white crystal, productive rate 98%, hexachlorocyclotriphosphazene content are 91%.
Embodiment 5:
Having agitator, thermometer, in the 500mL there-necked flask of reflux exchanger and hydrogen chloride gas absorption unit, add 46.2g (0.4mol) pyridine hydrochloride, 10.9g (0.08mol) zinc chloride, heat temperature raising to 110 ℃ reaction 2h, make ionic liquid, add 41.7g (0.2mol) phosphorus pentachloride then, 15g (0.28mol) ammonium chloride, the 120ml chlorobenzene is kept 100 ℃～130 ℃ back flow reaction 2h, emits until no hydrogen chloride gas, material cools to below 80 ℃ afterwards, filter, collection of ions liquid solid filter residue continues to use as secondary response under the catalyst supply, and water is washed till neutrality with filtrate then, decompression steams chlorobenzene (recovery), obtain white crystal, productive rate 97%, hexachlorocyclotriphosphazene content are 92%.
Embodiment 6., 7,8,9,10:
Zinc chloride consumption among the embodiment 1,2,3,4,5 is brought up to 27.2g (0.2mol) system ionic liquid, and other is with embodiment 1,2,3,4,5 (summary), and productive rate 95%～98%, hexachlorocyclotriphosphazene content are 90%～92%.
Embodiment 11,12,13,14,15:
Replace zinc chloride and corresponding consumption thereof in the example 1,2,3,4,5 respectively with 3.2g (0.02mol) iron(ic) chloride, the system ionic liquid, reaction finishes the back material and cools to 30 ℃, the employing filter type is handled, other is respectively with embodiment 1,2,3,4,5 (summary), productive rate 95%～97%, hexachlorocyclotriphosphazene content are 90%～93%.
Embodiment 16,17,18,19,20:
Replace zinc chloride and corresponding consumption thereof in the example 1,2,3,4,5 respectively with 1.9g (0.02mol) magnesium chloride, the system ionic liquid, reaction finishes the back material and cools to 30 ℃, the employing filter type is handled, other is respectively with embodiment 1,2,3,4,5 (summary), productive rate 95%～99%, hexachlorocyclotriphosphazene content are 90%～93%.
Embodiment 21,22,23,24,25:
Replace zinc chloride and corresponding consumption thereof in the example 1,2,3,4,5 respectively with 2.7g (0.02mol) aluminum chloride, the system ionic liquid, reaction finishes the back material and cools to 30 ℃, the employing filter type is handled, other is respectively with embodiment 1,2,3,4,5 (summary), productive rate 95%～98%, hexachlorocyclotriphosphazene content are 90%～93%.
Embodiment 26,27,28,29,30:
Iron(ic) chloride consumption among the embodiment 11,12,13,14,15 is brought up to 32g (0.2mol), the system ionic liquid, reaction finishes the back material and cools to 30 ℃, the employing filter type is handled, other is with embodiment 1,2,3,4,5 (summary), productive rate 95%～99%, hexachlorocyclotriphosphazene content are 91%～96%.
Embodiment 31,32,33,34,35:
Magnesium chloride consumption among the embodiment 16,17,18,19,20 is brought up to 19.2g (0.2mol), the system ionic liquid, reaction finishes the back material and cools to 30 ℃, the employing filter type is handled, other is with embodiment 1,2,3,4,5 (summary), productive rate 95%～97%, hexachlorocyclotriphosphazene content are 90%～95%.
Embodiment 36,37,38,39,40:
Aluminum chloride consumption among the embodiment 21,22,23,24,25 is brought up to 26.7g (0.2mol), the system ionic liquid, reaction finishes the back material and cools to 30 ℃, the employing filter type is handled, other is with embodiment 1,2,3,4,5 (summary), productive rate 96%～99%, hexachlorocyclotriphosphazene content are 90%～94%.
Embodiment 41:
In embodiment 1, reacted layering residual have add 41.7g (0.2mol) phosphorus pentachloride in the ion liquid reactor, 10.7g (0.2mol) ammonium chloride, 130ml reclaims chlorobenzene, keep 100 ℃～130 ℃ reaction 1h, emit until no hydrogen chloride gas, material cools to 30 ℃ afterwards, tell supernatant liquid, lower floor's ionic liquid continues to use as secondary response under the catalyst supply mutually, water is washed till neutrality with supernatant liquid then, and decompression steams chlorobenzene (recovery), obtains white crystal, productive rate 97%, hexachlorocyclotriphosphazene content are 92%.
Embodiment 42:
After the ionic liquid that each embodiment reclaimed of embodiment 1～40 reused 8 times according to embodiment 41 described ionic liquids, with corresponding embodiment 1～40 (summary), productive rate all reached 95% respectively for other, and purity reaches 90%.
Embodiment 43:
A kind of process for catalytic synthesis of hexachlorocyclotriphosphazene comprises the following steps:
A, raw material prepare: by quaternary ammonium salt (tetrabutylammonium chloride): anhydrous metal muriate (zinc chloride): chlorobenzene: ammonium chloride: phosphorus pentachloride=1: 0.1: 5: 1: 1 molar ratio is got raw material quaternary ammonium salt (tetrabutylammonium chloride), anhydrous metal muriate (zinc chloride), chlorobenzene, ammonium chloride and phosphorus pentachloride, and is standby;
B, preparation ionic liquid: get described quaternary ammonium salt of step a (tetrabutylammonium chloride) and anhydrous metal muriate (zinc chloride) and add in the reactor, under 80 ℃～120 ℃ temperature, stirring reaction 1h, make ionic liquid;
C, reaction: get the described chlorobenzene of step a, ammonium chloride and phosphorus pentachloride again and add in the described reactor of step b, mix with ionic liquid, then under 100 ℃～130 ℃ temperature, stirring reaction 1h, obtain the reaction mixture material;
D, separation: the reaction mixture material is cooled to 30 ℃, tell supernatant liquid, lower floor's ionic liquid continues to use as secondary response under the catalyst supply mutually, the chlorobenzene solution that will contain reaction product more promptly obtains the hexachlorocyclotriphosphazene product through washing (wash 2 times, and the weight of each washing being 1 times of chlorobenzene solution weight that contains reaction product), underpressure distillation after (promptly except that desolvating chlorobenzene).This product purity (weight percentage of hexachlorocyclotriphosphazene) 91%, productive rate 96%.
Embodiment 44:
A kind of process for catalytic synthesis of hexachlorocyclotriphosphazene comprises the following steps:
A, raw material prepare: by quaternary ammonium salt (Tetrabutyl amonium bromide): anhydrous metal muriate (iron(ic) chloride): chlorobenzene: ammonium chloride: phosphorus pentachloride=2: 1: 10: 1.4: 1 molar ratio is got raw material quaternary ammonium salt (Tetrabutyl amonium bromide), anhydrous metal muriate (iron(ic) chloride), chlorobenzene, ammonium chloride and phosphorus pentachloride, and is standby;
B, preparation ionic liquid: get described quaternary ammonium salt of step a (Tetrabutyl amonium bromide) and anhydrous metal muriate (iron(ic) chloride) and add in the reactor, under 80 ℃～120 ℃ temperature, stirring reaction 2h, make ionic liquid;
C, reaction: get the described chlorobenzene of step a, ammonium chloride and phosphorus pentachloride again and add in the described reactor of step b, mix with ionic liquid, then under 100 ℃～130 ℃ temperature, stirring reaction 5h, obtain the reaction mixture material;
D, separation: the reaction mixture material is cooled to 30 ℃, the employing filter type is handled, filter residue is that ionic liquid continues to use as secondary response under the catalyst supply, the chlorobenzene solution that again filtrate is promptly contained reaction product promptly obtains the hexachlorocyclotriphosphazene product through washing (wash 5 times, and the weight of each washing being 0.5 times of chlorobenzene solution weight that contains reaction product), underpressure distillation after (promptly except that desolvating chlorobenzene).This product purity (weight percentage of hexachlorocyclotriphosphazene) 92%, productive rate 96%.
Embodiment 45:
A kind of process for catalytic synthesis of hexachlorocyclotriphosphazene comprises the following steps:
A, raw material prepare: by quaternary ammonium salt (tetrabutylammonium chloride): anhydrous metal muriate (magnesium chloride): chlorobenzene: ammonium chloride: phosphorus pentachloride=1.3: 0.3: 7: 1.1: 1 molar ratio is got raw material quaternary ammonium salt (tetrabutylammonium chloride), anhydrous metal muriate (magnesium chloride), chlorobenzene, ammonium chloride and phosphorus pentachloride, and is standby;
B, preparation ionic liquid: get described quaternary ammonium salt of step a (tetrabutylammonium chloride) and anhydrous metal muriate (magnesium chloride) and add in the reactor, under 80 ℃～120 ℃ temperature, stirring reaction 1.5h, make ionic liquid;
C, reaction: get the described chlorobenzene of step a, ammonium chloride and phosphorus pentachloride again and add in the described reactor of step b, mix with ionic liquid, then under 100 ℃～130 ℃ temperature, stirring reaction 2h, obtain the reaction mixture material;
D, separation: the reaction mixture material is cooled to room temperature, the employing filter type is handled, filter residue is that ionic liquid continues to use as secondary response under the catalyst supply, the chlorobenzene solution that again filtrate is promptly contained reaction product promptly obtains the hexachlorocyclotriphosphazene product through washing (wash 3 times, and the weight of each washing being 0.7 times of chlorobenzene solution weight that contains reaction product), underpressure distillation after (promptly except that desolvating chlorobenzene).This product purity (weight percentage of hexachlorocyclotriphosphazene) 91%, productive rate 97%.
Embodiment 46:
A kind of process for catalytic synthesis of hexachlorocyclotriphosphazene comprises the following steps:
A, raw material prepare: by quaternary ammonium salt (Tetrabutyl amonium bromide): anhydrous metal muriate (aluminum chloride): chlorobenzene: ammonium chloride: phosphorus pentachloride=1.6: 0.8: 8: 1.3: 1 molar ratio is got raw material quaternary ammonium salt, anhydrous metal muriate, chlorobenzene, ammonium chloride and phosphorus pentachloride, and is standby;
B, preparation ionic liquid: get described quaternary ammonium salt of step a (Tetrabutyl amonium bromide) and anhydrous metal muriate (aluminum chloride) and add in the reactor, under 80 ℃～120 ℃ temperature, stirring reaction 2h, make ionic liquid;
C, reaction: get the described chlorobenzene of step a, ammonium chloride and phosphorus pentachloride again and add in the described reactor of step b, mix with ionic liquid, then under 100 ℃～130 ℃ temperature, stirring reaction 4h, obtain the reaction mixture material;
D, separation: the reaction mixture material is cooled to room temperature, the employing filter type is handled, filter residue is that ionic liquid continues to use as secondary response under the catalyst supply, the chlorobenzene solution that again filtrate is promptly contained reaction product promptly obtains the hexachlorocyclotriphosphazene product through washing (wash 3 times, and the weight of each washing being 0.7 times of chlorobenzene solution weight that contains reaction product), underpressure distillation after (promptly except that desolvating chlorobenzene).This product purity (weight percentage of hexachlorocyclotriphosphazene) 92%, productive rate 98%.
The foregoing description all has described characteristics of content part of the present invention and beneficial effect.
The invention is not restricted to the foregoing description, content of the present invention is described all can implement and have described good result.
Claims (8)
1, a kind of process for catalytic synthesis of hexachlorocyclotriphosphazene is characterized in that comprising the following steps:
A, raw material prepare: by quaternary ammonium salt: anhydrous metal muriate: chlorobenzene: ammonium chloride: phosphorus pentachloride=1～2: 0.1～1: 5～10: 1～1.4: 1 molar ratio is got raw material quaternary ammonium salt, anhydrous metal muriate, chlorobenzene, ammonium chloride and phosphorus pentachloride, and is standby;
B, preparation ionic liquid: get described quaternary ammonium salt of step a and anhydrous metal muriate and add in the reactor, under 80 ℃～120 ℃ temperature, stirring reaction 1h～2h, make ionic liquid;
C, reaction: get the described chlorobenzene of step a, ammonium chloride and phosphorus pentachloride again and add in the described reactor of step b, mix with ionic liquid, then under 100 ℃～130 ℃ temperature, stirring reaction 1h～5h, obtain the reaction mixture material;
D, separation: with the reaction mixture material through separatory or/and filtration treatment, described ionic liquid of step a and the chlorobenzene solution that contains reaction product are separated, the chlorobenzene solution that will contain reaction product more promptly obtains the hexachlorocyclotriphosphazene product after through washing, underpressure distillation.
2, by the process for catalytic synthesis of the described hexachlorocyclotriphosphazene of claim 1, it is characterized in that: quaternary ammonium salt described in the step a be in tetrabutylammonium chloride, Tetrabutyl amonium bromide, trimethylamine hydrochloride, triethylamine hydrochloride or the pyridine hydrochloride any.
3, by the process for catalytic synthesis of claim 1 or 2 described hexachlorocyclotriphosphazenes, it is characterized in that: the muriate of anhydrous metal described in the step a be in zinc chloride, iron(ic) chloride, magnesium chloride or the aluminum chloride any.
4, by the process for catalytic synthesis of claim 1 or 2 described hexachlorocyclotriphosphazenes, it is characterized in that: the time of stirring reaction described in the step c is 1h～2h.
5, by the process for catalytic synthesis of the described hexachlorocyclotriphosphazene of claim 3, it is characterized in that: the time of stirring reaction described in the step c is 1h～2h.
6, by the process for catalytic synthesis of claim 1 or 2 described hexachlorocyclotriphosphazenes, it is characterized in that: the described washing of steps d is washing 2～5 times, and the weight of each washing is 0.5～1 times of chlorobenzene solution weight that contains reaction product.
7, by the process for catalytic synthesis of the described hexachlorocyclotriphosphazene of claim 3, it is characterized in that: the described washing of steps d is washing 2～5 times, and the weight of each washing is 0.5～1 times of chlorobenzene solution weight that contains reaction product.
8, by the process for catalytic synthesis of the described hexachlorocyclotriphosphazene of claim 4, it is characterized in that: the described washing of steps d is washing 2～5 times, and the weight of each washing is 0.5～1 times of chlorobenzene solution weight that contains reaction product.
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| CN102234108A (en) * | 2010-04-27 | 2011-11-09 | 北京理工大学 | Method for synthesizing hexachlorocyclo triphosphonitrile by phase-transfer catalysis |
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|---|---|---|---|---|
| CN102234108A (en) * | 2010-04-27 | 2011-11-09 | 北京理工大学 | Method for synthesizing hexachlorocyclo triphosphonitrile by phase-transfer catalysis |
| CN103570763A (en) * | 2012-07-23 | 2014-02-12 | 上海永鸿实业集团化学科技有限公司 | Novel method for synthesizing and purifying phosphonitrilic chloride trimer |
| CN103896985A (en) * | 2013-05-06 | 2014-07-02 | 深圳市华力兴工程塑料有限公司 | Synthesizing method and device of phosphonitrilic chloride trimer as well as preparation method of terphenyl cycloposphazene |
| CN103896985B (en) * | 2013-05-06 | 2016-09-21 | 深圳华力兴新材料股份有限公司 | The synthetic method of hexachlorocyclotriph,sphazene and synthesizer, and the preparation method of terphenyl basic ring phosphonitrile |
| CN107108673A (en) * | 2015-04-14 | 2017-08-29 | 山东泽世新材料科技有限公司 | A kind of fluorination process of hexachlorocyclotriph,sphazene and its derivative |
| CN105418348A (en) * | 2015-10-28 | 2016-03-23 | 辽宁石化职业技术学院 | Preparation method of 1,1-diphenyl ethane |
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