CN101985455A - Method for synthesizing flame retardant hexaphenoxy cyclotriphosphazene - Google Patents
Method for synthesizing flame retardant hexaphenoxy cyclotriphosphazene Download PDFInfo
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Abstract
The invention discloses a method for synthesizing a flame retardant hexaphenoxy cyclotriphosphazene. The method is characterized by comprising the following steps of: performing a one-pot reaction on hexachlorocyclotriphosphazene, phenol, alkali metal hydroxides and other raw materials in a solvent system consisting of aromatic hydrocarbon or aryl halide and water by adopting noncyclic polyether as a catalyst at the temperature of between 20 and 30 DEG C for 3 to 5 hours; heating to the temperature of between 80 and 100 DEG C, reacting for 3 to 5 hours; reclaiming hydrated aromatic hydrocarbon or aryl halide through cooling, separation, washing and depressed pressure distillation after the reaction is completed; and cooling and coagulating the residues to obtain a white crystal solid powder product, wherein the yield is over 95 percent. The method has the characteristics of short reaction time, low cost, good quality and the like, is simple and safe in operation, and is environmentally-friendly and suitable for industrial production and application.
Description
Technical field
The invention belongs to the preparation method of three phosphorus atom, relate to a kind of synthetic method of fire retardant hexaphenoxycyclotriphosphazene as the compound of ring hetero atom.
Background technology
Hexaphenoxycyclotriphosphazene is as the typical case of cyclic phosphazene compound representative, has heat-resisting height, hydrolytic resistance excellence,, outstanding feature such as flame retarding efficiency remarkable good with the macromolecular material consistency, become one of focus of present halogen-free flameproof research.
Many about the Study of synthesis method report of hexaphenoxycyclotriphosphazene both at home and abroad, be broadly divided into three types.First method adopts the catalysis of inorganic salt acid binding agent, reacts in hydrophilic organic solvent, and aftertreatment needs just can obtain product with the hydrophobic solvent refinement treatment.Adopt anhydrous phosphoric acid potassium or Anhydrous potassium carbonate to make acid binding agent as Chinese patent application 00122363.1, in acetonitrile or acetone, add substituted phenol, hexachlorocyclotriphosphazene back flow reaction 1h～15h, after cold filtration steams and desolventizes, use acetic acid ethyl dissolution again, alkali cleaning, washing, drying remove ethyl acetate and obtain different aryloxy ring three phosphonitriles; And people (" Journal of Applied Polymer Science " such as GABINO A.CARRIEDO, 1996,59:1879～1884) report joins raw materials such as hexachlorocyclotriphosphazene, phenol, salt of wormwood in the acetone together, reaction 3h, remove solvent, with after the toluene extraction, wash 3 times, dried over sodium sulfate, filtration, distillating recovering solvent obtains product.The acid binding agent catalysis that this employing is dissimilar, in acetone, acetonitrile isopolarity solvent, react the solvent-refined method of aftertreatment secondary, good product quality, but yield generally is lower than 70%, and the aftertreatment complexity, solvent and acid binding agent consumption are quite big, and loss is serious, particularly the solvent price is expensive, reclaim difficulty, cause cost high, be difficult to accept for producing.
Second method adopts catalyzer quaternary ammonium salt (or season phosphonium salt) to carry out phase-transfer-catalyzed reactions in the solvent system that water and non-polar organic solvent are formed, reaction only finish need layering, washing, drying, remove post-processing step such as solvent and can obtain product.As people such as Y.W.Chen-Yang (" Ind.Eng.Chem.Res. ", 1991,30:1314～1319) reported in the aqueous solution of phenol and sodium hydroxide, the chloroparaffin solution that adds the hexachlorocyclotriphosphazene that contains the phase-transfer catalyst quaternary ammonium salt, more than the reaction 8h, cool off layering, washing, drying then, remove solvent and obtain product; U.S. Pat 4600791 then employing in the aqueous solution of phenol, potassium hydroxide, quaternary ammonium salt (or season phosphonium salt), dropping contains high boiling chloroparaffin (or chlorinated aromatic hydrocarbons) solution of hexachlorocyclotriphosphazene, behind the reaction 21h, standing demix, removes solvent and obtains product a pickling, alkali cleaning, washing, drying.This phase transfer catalysis process speed of response is slow, long reaction time, and product quality is poor, low substituent foreign matter content height, yield has only 70%～80%, and quaternary ammonium salt or season the phosphonium salt catalyst levels big, cost an arm and a leg, be difficult to recycle, cause cost to rise, be unfavorable for that industry transforms.
The third method then need not catalyzer, but will react proceed step by step, prepare phenates earlier, and then react with hexachlorocyclotriphosphazene, reaction finishes and obtains product through suitable aftertreatment purification, as U.S. Pat 6518836, US6627122 adopts sodium Metal 99.5 and phenol to react 6h in tetrahydrofuran (THF) to make the phenol sodium solution, this phenol sodium solution is added drop-wise in the middle of the chlorobenzene solution that contains hexachlorocyclotriphosphazene then, behind the reaction 15h, concentrate organic phase, once more with chlorobenzene dissolving, repeatedly alkali cleaning afterwards, pickling, washing, remove the product of solvent, yield reaches 98.5%, though this method yield is higher, and sodium Metal 99.5, the use of sodium hydride can cause reaction to be difficult to control, increased danger, while long reaction time, operating process are complicated, and particularly aftertreatment quite bothers, the three wastes are more, are unfavorable for environmental protection; In order to reduce the operational danger of using sodium Metal 99.5 to bring, other has research to replace sodium Metal 99.5 (or sodium hydride) and phenol reactant with potassium hydroxide (or sodium hydroxide), people's (" Guangzhou chemical industry " such as build as Kong Xiang, 2008,36 (2): 31～33) report reacts phenol and sodium hydroxide and makes phenol sodium in tetrahydrofuran (THF), drip the tetrahydrofuran solution of hexachlorocyclotriphosphazene, behind the reaction 48h, distilling off solvent, washing repeatedly, get product behind the recrystallization, yield is 95%, though this method product yield is higher, but solvents tetrahydrofurane costs an arm and a leg, and be easy to oxidation and generate explosive superoxide, safety issue is more outstanding, and the water-containing tetrahydrofuran that uses the back to form reclaims to purify and is difficult for; And people such as Yang Mingshan (" Chinese plastics ", 2009,23 (8): 35～38) report is with phenol, potassium hydroxide adds toluene after 110 ℃ of reaction 2h generate phenol potassium, the toluene solution that splashes into hexachlorocyclotriphosphazene reacts 10h again at 110 ℃, suction filtration removes waste residue then, and the potassium hydroxide solution that filtrate is used different concns again is extracting and washing repeatedly, and last underpressure distillation removes solvent and obtains product.Though this method danger reduces greatly, the reaction times is shorter, and waste liquid amount is big, and environmental protection pressure is big, product quality relatively poor (only can obtain yellow thickness oily produce product, the quality better products should be a white crystalline solid), and not mentioned product yield.
In sum, the synthetic method of existing hexaphenoxycyclotriphosphazene respectively has characteristics, but more or less have long reaction time, complicated operation, separation purification trouble, product yield and quality is low, energy consumption is high, cost is high and pollute problems such as big, being difficult to is that industrial production is accepted.
Summary of the invention
Purpose of the present invention is intended to overcome above-mentioned deficiency of the prior art, adopt straight-chain polyether to make catalyzer, one pot reaction, thus provide a kind of easy and simple to handle, the reaction times is short, yield is high, good product quality, pollution less, the synthetic method of low, the practical fire retardant hexaphenoxycyclotriphosphazene of cost.
Content of the present invention is: a kind of synthetic method of fire retardant hexaphenoxycyclotriphosphazene is characterized in that may further comprise the steps:
A, batching: with alkali metal hydroxide, water, solvent aromatic hydrocarbons or halogenated aryl hydrocarbon, phenol, catalyst polyethylene glycol and hexachlorocyclotriphosphazene is feed composition, and by alkali metal hydroxide: water: solvent aromatic hydrocarbons or halogenated aryl hydrocarbon: phenol: catalyst polyethylene glycol: hexachlorocyclotriphosphazene is 6～9: 20～30: 10～25: 6: 0.01～0.1: 1 molar ratio is got each component;
B, reaction: each component is added in the reactor successively, under 20 ℃～30 ℃ temperature, react 3h～5h, rise to then under 80 ℃～100 ℃ the temperature and react 3h～5h again, after reaction finishes the material cooling is left standstill;
C, aftertreatment: isolate the organic layer in the reacting rear material, after water washs 2～5 times (being preferably to neutrality) with this organic layer, aqueous aromatic hydrocarbons or the halogenated aryl hydrocarbon in this organic layer reclaimed in distillation, again resistates is cooled off, condenses, obtains the white crystalline pressed powder, be fire retardant hexaphenoxycyclotriphosphazene product, yield＞95%.
In the content of the present invention: alkali metal hydroxide described in the step a can be any in potassium hydroxide, the sodium hydroxide.
In the content of the present invention: catalyst polyethylene glycol described in the step a can be any in the straight-chain polyethers such as poly(oxyethylene glycol) 400, Polyethylene Glycol-600, polyoxyethylene glycol 800, cetomacrogol 1000, polyethylene glycol 1500, Macrogol 2000.
In the content of the present invention: aromatic hydrocarbons of solvent described in the step a or halogenated aryl hydrocarbon can be any in toluene, dimethylbenzene, chlorobenzene, the orthodichlorobenzene.
In the content of the present invention: water described in the step a is preferably distilled water or deionized water.
In the content of the present invention: the moisture aromatic hydrocarbons or the halogenated aryl hydrocarbon that pass through the distillation recovery described in the step c, the drying-free dehydration can be used for reaction once more.
Compared with prior art, the present invention has following characteristics and beneficial effect:
(1) the present invention adopts the method for straight-chain polyether as catalyst for reaction, the synthetic fire retardant hexaphenoxycyclotriphosphazene product of one pot reaction, easy and simple to handle, reaction times shortens to 6h～10h, avoided in existing synthetic ten thousand methods problems in various degree the problem includes: grow complicated operation, reaction time, problem such as energy consumption is high, pollution is big;
(2) adopt the present invention, need not to increase extra solvent treatment in the aftertreatment handles, need not to increase pickling, alkali cleaning, drying and other steps, only need to carry out the product that simple operationss such as separatory, washing, distillation can obtain better quality and yield to having reacted material, simplify separation and purification mode and step greatly, helped realizing suitability for industrialized production more;
(3) the straight-chain polyether catalyzer determined of the present invention belongs to inexpensive and environment amenable degradable material, and consumption is few, cost is low, and catalyzed reaction is effective, and reaction finishes, can conveniently remove by simple washing, have than existing method catalyst system therefor excellent characteristics more;
(4) aromatic hydrocarbons or the halogenated aryl hydrocarbon solvent determined of the present invention, the organic solvent that all belongs to inexpensive, safety, low toxicity, by obtaining aqueous aromatic hydrocarbons or halogenated aryl hydrocarbon after the simple distillation recovery, can be used for reaction once more, to the no negative impact of reaction, so solvent need not secondary refining, solvent recovering rate can reach more than 90%, help more reducing cost, reduce pollution environment;
(5) product preparation process of the present invention is simple, yield＞95%, and good product quality pollutes and lacks, and cost is low, and is for industrial production provides a kind of feasible synthetic method, practical;
(6) the fire retardant hexaphenoxycyclotriphosphazene of the inventive method preparation is used for the halogen-free flameproof of glass cloth laminated board, veneer sheet excellent combination property (seeing the following form), fire retardant glass cloth laminated board than existing other types has better cost performance, meet the Rohs of European Union instruction, satisfy export requirement, have favorable economic benefit and market outlook.
Halogen-free flameproof veneer sheet performance
Embodiment
Embodiment given below intends so that the invention will be further described; but can not be interpreted as it is limiting the scope of the invention; the person skilled in art to some nonessential improvement and adjustment that the present invention makes, still belongs to protection scope of the present invention according to the content of the invention described above.
Embodiment 1:
Having agitator, thermometer, in the 500mL there-necked flask of reflux exchanger, add 33.6g (0.6mol) potassium hydroxide successively, 36g water, 230g toluene, 56.4g (0.6mol) phenol, 4g (0.01mol) poly(oxyethylene glycol) 400,34.8g (0.1mol) hexachlorocyclotriphosphazene adds in the reactor successively, at first keep reaction 5h at 20 ℃～30 ℃, rise to 80 ℃～90 ℃ reaction 5h then, system cooled to below 30 ℃ after reaction finished, standing demix, the pale brown look organic phase in upper strata is washed to neutrality for 3 times with 300g moisture altogether, the about 220g of toluene is reclaimed in distillation, resistates is poured out while hot, obtain 66.4g white crystalline pressed powder after the cooling, be fire retardant hexaphenoxycyclotriphosphazene product, yield 95.8%.
Embodiment 2:
The potassium hydroxide dosage is become 50.4g (0.9mol), and the water yield becomes 54g, and other obtains product 66.6g with embodiment 1, summary, and yield is 96.1%.
Embodiment 3:
Potassium hydroxide is replaced by sodium hydroxide, and dosage becomes 24g (0.6mol), and other obtains product 65.9g with embodiment 1, summary, and yield is 95.1%.
Embodiment 4:
Potassium hydroxide is replaced by sodium hydroxide, and dosage becomes 36g (0.9mol), and other obtains product 66.1g with embodiment 2, summary, and yield is 95.4%.
Embodiment 5:
Change toluene into dimethylbenzene, dosage becomes 212g, at first keeps reaction 4h at 20 ℃～30 ℃, rises to 80 ℃～90 ℃ reaction 5h then, and other is with embodiment 1,2,3 or 4, summary, and product yield reaches 95%.
Embodiment 6:
Change toluene into chlorobenzene, dosage becomes 169g, at first keeps reaction 3h at 20 ℃～30 ℃, rises to 90 ℃～100 ℃ reaction 4h then, and other is with embodiment 1,2,3 or 4, summary, and product yield reaches 95%.
Embodiment 7:
Change toluene into orthodichlorobenzene, dosage becomes 147g, at first keeps reaction 3h at 20 ℃～30 ℃, rises to 90 ℃～100 ℃ reaction 3h then, and other is with embodiment 1,2,3 or 4, summary, and product yield reaches 95%.
Embodiment 8:
Poly(oxyethylene glycol) 400 is replaced by Polyethylene Glycol-600, and dosage becomes 4.8g (0.008mol), and other is with embodiment 1,2,3,4,5,6 or 7, summary, and product yield reaches 95%.
Embodiment 9:
Poly(oxyethylene glycol) 400 is replaced by polyoxyethylene glycol 800, and dosage becomes 4.8g (0.006mol), and other is with embodiment 1,2,3,4,5,6 or 7, summary, and product yield reaches 95%.
Embodiment 10:
Poly(oxyethylene glycol) 400 is replaced by cetomacrogol 1000, and dosage becomes 4g (0.004mol), and other is with embodiment 1,2,3,4,5,6 or 7, summary, and product yield reaches 95%.
Embodiment 11:
Poly(oxyethylene glycol) 400 is replaced by polyethylene glycol 1500, and dosage becomes 3g (0.002mol), and other is with embodiment 1,2,3,4,5,6 or 7, summary, and product yield reaches 95%.
Embodiment 12:
Poly(oxyethylene glycol) 400 is replaced by Macrogol 2000, and dosage becomes 2g (0.001mol), and other is with embodiment 1,2,3,4,5,6 or 7, summary, and product yield reaches 95%.
Embodiment 13:
Moisture aromatic hydrocarbons or halogenated aryl hydrocarbon solvent that distillation is reclaimed are directly used in reaction, other with embodiment 1,2,3,4,5,6,7,8,9,10,11 or 12, slightly, repeats 10 uses after, no abnormality seen, product yield all reach 95%.
Embodiment 14:
A kind of synthetic method of fire retardant hexaphenoxycyclotriphosphazene may further comprise the steps:
A, batching: with alkali metal hydroxide, water, solvent aromatic hydrocarbons or halogenated aryl hydrocarbon, phenol, catalyst polyethylene glycol and hexachlorocyclotriphosphazene is feed composition, and by alkali metal hydroxide: water: solvent aromatic hydrocarbons or halogenated aryl hydrocarbon: phenol: catalyst polyethylene glycol: hexachlorocyclotriphosphazene is 6: 20: 10:: 6: 0.01: 1 molar ratio is got each component;
B, reaction: each component is added in the reactor successively, under 20 ℃～30 ℃ temperature, react 3h, rise to then under 80 ℃～100 ℃ the temperature and react 5h again, after reaction finishes the material cooling is left standstill;
C, aftertreatment: isolate the organic layer in the reacting rear material, after water washs 2 times with this organic layer, aqueous aromatic hydrocarbons or the halogenated aryl hydrocarbon in this organic layer reclaimed in distillation, again resistates cooled off, condense, obtain the white crystalline pressed powder, be fire retardant hexaphenoxycyclotriphosphazene product.
Embodiment 15:
A kind of synthetic method of fire retardant hexaphenoxycyclotriphosphazene may further comprise the steps:
A, batching: with alkali metal hydroxide, water, solvent aromatic hydrocarbons or halogenated aryl hydrocarbon, phenol, catalyst polyethylene glycol and hexachlorocyclotriphosphazene is feed composition, and by alkali metal hydroxide: water: solvent aromatic hydrocarbons or halogenated aryl hydrocarbon: phenol: catalyst polyethylene glycol: hexachlorocyclotriphosphazene is 9: 30: 25:: 6: 0.1: 1 molar ratio is got each component;
B, reaction: each component is added in the reactor successively, under 20 ℃～30 ℃ temperature, react 5h, rise to then under 80 ℃～100 ℃ the temperature and react 3h again, after reaction finishes the material cooling is left standstill;
C, aftertreatment: isolate the organic layer in the reacting rear material, after water washs 5 times with this organic layer, aqueous aromatic hydrocarbons or the halogenated aryl hydrocarbon in this organic layer reclaimed in distillation, again resistates cooled off, condense, obtain the white crystalline pressed powder, be fire retardant hexaphenoxycyclotriphosphazene product.
Embodiment 16:
A kind of synthetic method of fire retardant hexaphenoxycyclotriphosphazene may further comprise the steps:
A, batching: with alkali metal hydroxide, water, solvent aromatic hydrocarbons or halogenated aryl hydrocarbon, phenol, catalyst polyethylene glycol and hexachlorocyclotriphosphazene is feed composition, and by alkali metal hydroxide: water: solvent aromatic hydrocarbons or halogenated aryl hydrocarbon: phenol: catalyst polyethylene glycol: hexachlorocyclotriphosphazene is 8: 25: 15: 6: 0.05: 1 molar ratio is got each component;
B, reaction: each component is added in the reactor successively, under 20 ℃～30 ℃ temperature, react 4h, rise to then under 80 ℃～100 ℃ the temperature and react 4h again, after reaction finishes the material cooling is left standstill;
C, aftertreatment: isolate the organic layer in the reacting rear material, after water washs 4 times with this organic layer, aqueous aromatic hydrocarbons or the halogenated aryl hydrocarbon in this organic layer reclaimed in distillation, again resistates cooled off, condense, obtain the white crystalline pressed powder, be fire retardant hexaphenoxycyclotriphosphazene product.
Embodiment 17-23:
A kind of synthetic method of fire retardant hexaphenoxycyclotriphosphazene may further comprise the steps:
A, batching: with alkali metal hydroxide, water, solvent aromatic hydrocarbons or halogenated aryl hydrocarbon, phenol, catalyst polyethylene glycol and hexachlorocyclotriphosphazene is feed composition, and the molar ratio of each component sees the following form among each embodiment:
B, reaction: each component is added in the reactor successively, under 20 ℃～30 ℃ temperature, react 3h～5h, rise to then under 80 ℃～100 ℃ the temperature and react 3h～5h again, after reaction finishes the material cooling is left standstill;
C, aftertreatment: isolate the organic layer in the reacting rear material, after water washs 2～5 times with this organic layer, aqueous aromatic hydrocarbons or the halogenated aryl hydrocarbon in this organic layer reclaimed in distillation, again resistates cooled off, condense, obtain the white crystalline pressed powder, be fire retardant hexaphenoxycyclotriphosphazene product.
Among the foregoing description 14-23: alkali metal hydroxide described in the step a can be any in potassium hydroxide, the sodium hydroxide;
Among the foregoing description 14-23: catalyst polyethylene glycol described in the step a can be any in poly(oxyethylene glycol) 400, Polyethylene Glycol-600, polyoxyethylene glycol 800, cetomacrogol 1000, polyethylene glycol 1500, the Macrogol 2000;
Among the foregoing description 14-23: aromatic hydrocarbons of solvent described in the step a or halogenated aryl hydrocarbon can be any in toluene, dimethylbenzene, chlorobenzene, the orthodichlorobenzene;
Among the foregoing description 14-23: water described in the step a is preferably distilled water or deionized water.
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 (5)
1. the synthetic method of a fire retardant hexaphenoxycyclotriphosphazene is characterized in that may further comprise the steps:
A, batching: with alkali metal hydroxide, water, solvent aromatic hydrocarbons or halogenated aryl hydrocarbon, phenol, catalyst polyethylene glycol and hexachlorocyclotriphosphazene is feed composition, and by alkali metal hydroxide: water: solvent aromatic hydrocarbons or halogenated aryl hydrocarbon: phenol: catalyst polyethylene glycol: hexachlorocyclotriphosphazene is 6～9: 20～30: 10～25: 6: 0.01～0.1: 1 molar ratio is got each component;
B, reaction: each component is added in the reactor successively, under 20 ℃～30 ℃ temperature, react 3h～5h, rise to then under 80 ℃～100 ℃ the temperature and react 3h～5h again, after reaction finishes the material cooling is left standstill;
C, aftertreatment: isolate the organic layer in the reacting rear material, after water washs 2～5 times with this organic layer, aqueous aromatic hydrocarbons or the halogenated aryl hydrocarbon in this organic layer reclaimed in distillation, again resistates cooled off, condense, obtain the white crystalline pressed powder, be fire retardant hexaphenoxycyclotriphosphazene product.
2. by the synthetic method of the described fire retardant hexaphenoxycyclotriphosphazene of claim 1, it is characterized in that: alkali metal hydroxide described in the step a is any in potassium hydroxide, the sodium hydroxide.
3. by the synthetic method of the described fire retardant hexaphenoxycyclotriphosphazene of claim 1, it is characterized in that: catalyst polyethylene glycol described in the step a is any in poly(oxyethylene glycol) 400, Polyethylene Glycol-600, polyoxyethylene glycol 800, cetomacrogol 1000, polyethylene glycol 1500, the Macrogol 2000.
4. by the synthetic method of the described fire retardant hexaphenoxycyclotriphosphazene of claim 1, it is characterized in that: aromatic hydrocarbons of solvent described in the step a or halogenated aryl hydrocarbon are any in toluene, dimethylbenzene, chlorobenzene, the orthodichlorobenzene.
5. by the synthetic method of the described fire retardant hexaphenoxycyclotriphosphazene of claim 1, it is characterized in that: water described in the step a is distilled water or deionized water.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103539820A (en) * | 2013-10-30 | 2014-01-29 | 威海金威化学工业有限责任公司 | Preparation method of hexaphenoxycyclotriphosphazene |
| CN103588815A (en) * | 2013-11-25 | 2014-02-19 | 济南泰星精细化工有限公司 | Preparation method of hexaphenoxy cyclotriphosphazene fire retardant |
| CN108690081A (en) * | 2018-05-22 | 2018-10-23 | 济南泰星精细化工有限公司 | A kind of preparation method of hexaphenoxycyclotriphosphazene |
| CN109422774A (en) * | 2017-08-30 | 2019-03-05 | 张家港市国泰华荣化工新材料有限公司 | The preparation method of five fluorine ethoxy basic rings, three phosphonitrile |
| CN110759947A (en) * | 2019-11-07 | 2020-02-07 | 山东省海洋化工科学研究院 | Synthesis method of hexaphenoxycyclotriphosphazene |
| CN111848684A (en) * | 2020-08-11 | 2020-10-30 | 威海金威化学工业有限责任公司 | Method for separating mixed phenoxy phosphazene from hexaphenoxy cyclotriphosphazene crystallization mother liquor |
| CN112708392A (en) * | 2020-12-25 | 2021-04-27 | 深圳德邦界面材料有限公司 | Low-volatility high-shielding silver-nickel conductive adhesive and preparation method thereof |
| CN116444976A (en) * | 2023-05-22 | 2023-07-18 | 沭阳亿彩泡塑有限公司 | Polyurethane foam plastic and preparation method and application thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103539820A (en) * | 2013-10-30 | 2014-01-29 | 威海金威化学工业有限责任公司 | Preparation method of hexaphenoxycyclotriphosphazene |
| CN103588815A (en) * | 2013-11-25 | 2014-02-19 | 济南泰星精细化工有限公司 | Preparation method of hexaphenoxy cyclotriphosphazene fire retardant |
| CN109422774A (en) * | 2017-08-30 | 2019-03-05 | 张家港市国泰华荣化工新材料有限公司 | The preparation method of five fluorine ethoxy basic rings, three phosphonitrile |
| CN109422774B (en) * | 2017-08-30 | 2021-03-30 | 张家港市国泰华荣化工新材料有限公司 | Preparation method of pentafluoroethoxy cyclotriphosphazene |
| CN108690081A (en) * | 2018-05-22 | 2018-10-23 | 济南泰星精细化工有限公司 | A kind of preparation method of hexaphenoxycyclotriphosphazene |
| CN110759947A (en) * | 2019-11-07 | 2020-02-07 | 山东省海洋化工科学研究院 | Synthesis method of hexaphenoxycyclotriphosphazene |
| CN111848684A (en) * | 2020-08-11 | 2020-10-30 | 威海金威化学工业有限责任公司 | Method for separating mixed phenoxy phosphazene from hexaphenoxy cyclotriphosphazene crystallization mother liquor |
| CN112708392A (en) * | 2020-12-25 | 2021-04-27 | 深圳德邦界面材料有限公司 | Low-volatility high-shielding silver-nickel conductive adhesive and preparation method thereof |
| CN116444976A (en) * | 2023-05-22 | 2023-07-18 | 沭阳亿彩泡塑有限公司 | Polyurethane foam plastic and preparation method and application thereof |
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