WO2024113743A1 - Method for preparing hexachlorocyclotriphosphazene - Google Patents
Method for preparing hexachlorocyclotriphosphazene Download PDFInfo
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- WO2024113743A1 WO2024113743A1 PCT/CN2023/098547 CN2023098547W WO2024113743A1 WO 2024113743 A1 WO2024113743 A1 WO 2024113743A1 CN 2023098547 W CN2023098547 W CN 2023098547W WO 2024113743 A1 WO2024113743 A1 WO 2024113743A1
- Authority
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- WIPO (PCT)
- Prior art keywords
- hexachlorocyclotriphosphazene
- chlorobenzene
- chloride
- preparing
- phosphorus pentachloride
- Prior art date
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- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 22
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 110
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 40
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 32
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- OBYFVISULYVYNB-UHFFFAOYSA-N ClC1=CC=CC=C1.P(Cl)(Cl)(Cl)(Cl)Cl Chemical compound ClC1=CC=CC=C1.P(Cl)(Cl)(Cl)(Cl)Cl OBYFVISULYVYNB-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002608 ionic liquid Substances 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 22
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 20
- 239000007787 solid Substances 0.000 claims abstract description 20
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 18
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000047 product Substances 0.000 claims abstract description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 10
- 229910001510 metal chloride Inorganic materials 0.000 claims abstract description 9
- 239000002131 composite material Substances 0.000 claims abstract description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 51
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 34
- 238000002360 preparation method Methods 0.000 claims description 32
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 18
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 claims description 18
- 239000012046 mixed solvent Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 11
- 239000012065 filter cake Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 11
- 239000000706 filtrate Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 9
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 238000001953 recrystallisation Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 3
- 229910001626 barium chloride Inorganic materials 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims 1
- 238000004321 preservation Methods 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract 1
- 238000010189 synthetic method Methods 0.000 abstract 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 14
- 239000007788 liquid Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 5
- SSGDFGWGKPOYJO-UHFFFAOYSA-N ClC1=CC=CC=C1.ClP1(=NP(=NP(=N1)(Cl)Cl)(Cl)Cl)Cl Chemical compound ClC1=CC=CC=C1.ClP1(=NP(=NP(=N1)(Cl)Cl)(Cl)Cl)Cl SSGDFGWGKPOYJO-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- JPVZLJWGZYHBDD-UHFFFAOYSA-N chlorobenzene;trichlorophosphane Chemical compound ClP(Cl)Cl.ClC1=CC=CC=C1 JPVZLJWGZYHBDD-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
- C07F9/65815—Cyclic phosphazenes [P=N-]n, n>=3 n = 3
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Definitions
- the invention belongs to the technical field of flame retardant synthesis, and more specifically relates to a method for preparing hexachlorocyclotriphosphazene.
- Hexachlorocyclotriphosphazene is a very important reaction intermediate and the most basic compound in phosphazene chemistry. It is the basic raw material for the preparation of polyphosphazenes.
- the derivatives synthesized by the reaction of hexachlorocyclotriphosphazene can be used in high temperature resistant materials, biomedical materials, lubricants, coating materials, adhesives, etc.
- hexachlorocyclotriphosphazene derivatives are widely used as fire retardant materials, pesticides, preservatives, dyes and photographic materials.
- the most commonly used method is to react phosphorus pentachloride and ammonium chloride in the presence of a metal chloride or oxide catalyst, using chlorobenzene as a solvent, heating to a reflux temperature-keeping reaction to synthesize a crude hexachlorocyclotriphosphazene, and then filtering, changing the solvent, extracting with concentrated sulfuric acid, diluting and crystallizing, filtering, and drying to obtain a finished hexachlorocyclotriphosphazene.
- the crude hexachlorocyclotriphosphazene synthesized by this method has a low purity, a low yield of the finished product, and the generated sulfuric acid waste liquid is not good for the environment.
- Patent CN201310166628 uses ammonium chloride and phosphorus pentachloride to react solid-solid to synthesize hexachlorocyclotriphosphazene. This reaction is carried out in the absence of solvent, the reaction speed is slow, and it is difficult to react completely, and the yield is low.
- Patent CN104945438 puts phosphorus pentachloride, ammonium chloride, magnesium chloride, pyridine and chlorobenzene in proportion at one time, then heats to 130-140°C for reaction for 9-11 hours, filters after the reaction is complete, removes chlorobenzene by vacuum distillation, cools to 10-15°C, and then filters to obtain hexachlorocyclotriphosphazene.
- the heat preservation time of this process is too long, and the byproduct linear phosphazene will increase with the extension of the heat preservation time.
- the object of the present invention is to provide a method for preparing hexachlorocyclotriphosphazene, wherein the finished product obtained by the method has high purity and high yield.
- the invention discloses a method for preparing hexachlorocyclotriphosphazene, comprising the following steps:
- chlorobenzene is added to a four-necked flask with a condenser and a drying tube, and powdered ammonium chloride and an ionic liquid catalyst solution are added while stirring.
- the temperature is raised to 118-122° C., and the phosphorus pentachloride chlorobenzene solution of step 1) is added dropwise.
- the temperature is raised to 130-135° C. and the mixture is kept warm for 2-3 hours to obtain a chlorobenzene solution of a crude hexachlorocyclotriphosphazene product.
- the hydrogen chloride generated by the reaction is absorbed by water to prepare 30% hydrochloric acid;
- the present invention also limits the dropwise addition time of the phosphorus pentachloride chlorobenzene solution in step 2) to 8-12 hours.
- the present invention also defines that the volume ratio of ethyl acetate to n-hexane in the recrystallization solvent in step 4) is 6-10:3, preferably 7:3; the mass ratio of the mixed solvent of ethyl acetate and n-hexane to the mixed solid phosphazene is 1-1.5:1, preferably 1.3:1; the vacuum drying temperature is 60-75°C, preferably 70°C, the vacuum drying time is 6-8 hours, and the pressure is negative pressure above -0.098MPa.
- the present invention also limits the feeding amount of the mixed solvent of ethyl acetate and n-hexane to 1.2-1.5 times the weight of the mixed solid phosphazene, preferably 1.3 times.
- the present invention also defines the preparation process of the ionic liquid catalyst as follows: under nitrogen protection, chlorobenzene, composite metal chloride powder and pyridine are added, the temperature is raised to 80-100°C while stirring, and hydrogen chloride gas is introduced until the solid is dissolved and clear to obtain an ionic liquid catalyst solution; the weight ratio of phosphorus pentachloride, ammonium chloride, composite metal chloride and pyridine is 1000:300-500:10-20:30-50; the composite metal chloride is any two of barium chloride, zinc chloride, aluminum chloride, magnesium chloride, ferric chloride or calcium chloride.
- the present invention has the following advantages:
- the invention adopts ionic liquid as a catalyst, phosphorus pentachloride and ammonium chloride as raw materials, and performs a reaction by dropwise adding phosphorus pentachloride, and then performs post-treatment and recrystallization to obtain the product hexachlorocyclotriphosphazene of the invention.
- the heat preservation time of the reaction is short, and the increase of by-products is effectively avoided.
- the obtained finished product has high purity and high yield, and the yield is more than 90%, and the purity is also greater than 99%.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Disclosed in the present invention is a method for preparing hexachlorocyclotriphosphazene. A synthetic method for hexachlorocyclotriphosphazene comprises the following steps: (1) mixing and stirring chlorobenzene, composite metal chloride powder and pyridine, introducing hydrogen chloride until the solid is dissolved, and preparing an ionic liquid catalyst for later use; (2) stirring and dissolving phosphorus pentachloride and chlorobenzene to obtain a phosphorus pentachloride chlorobenzene solution; and (3) under the protection of nitrogen, mixing chlorobenzene, ammonium chloride and the ionic liquid catalyst, heating, dropwise adding the phosphorus pentachloride chlorobenzene solution, performing heat preservation reaction after dropwise adding to obtain a hexachlorocyclotriphosphazene crude chlorobenzene solution, and performing post-treatment to obtain hexachlorocyclotriphosphazene. According to the present invention, a self-prepared ionic liquid is used as a catalyst for reaction, the reaction time is short, and the generation of byproducts is effectively avoided, such that the purity of an obtained finished product is greater than 99%, the purity is also greater than 99%, and the method is suitable for industrial application.
Description
本发明属于阻燃剂合成技术领域，更具体涉及一种六氯环三磷腈的制备方法。The invention belongs to the technical field of flame retardant synthesis, and more specifically relates to a method for preparing hexachlorocyclotriphosphazene.
六氯环三磷腈是一种非常重要的反应中间体，也是磷腈化学中最基本的化合物，为制备聚磷腈的基础原料。通过六氯环三磷腈反应合成的衍生物可应用于耐高温材料、生物医用材料、润滑剂、涂层材料、粘合剂等方面。同时，六氯环三磷腈衍生物被广泛应用为防火阻燃剂材料、杀虫剂、防腐剂、染料及摄影用材料等方面。Hexachlorocyclotriphosphazene is a very important reaction intermediate and the most basic compound in phosphazene chemistry. It is the basic raw material for the preparation of polyphosphazenes. The derivatives synthesized by the reaction of hexachlorocyclotriphosphazene can be used in high temperature resistant materials, biomedical materials, lubricants, coating materials, adhesives, etc. At the same time, hexachlorocyclotriphosphazene derivatives are widely used as fire retardant materials, pesticides, preservatives, dyes and photographic materials.
目前，采用较多的方法是五氯化磷与氯化铵在金属氯化物或氧化物催化剂作用下，氯苯为溶剂，升温至回流保温反应合成六氯环三磷腈粗品，再经过滤、更换溶剂、浓硫酸萃取、稀释析晶、过滤、烘干，得六氯环三磷腈成品。此方法合成六氯环三磷腈粗品纯度低，得到成品收率低，且产生的硫酸废液对环境不好。At present, the most commonly used method is to react phosphorus pentachloride and ammonium chloride in the presence of a metal chloride or oxide catalyst, using chlorobenzene as a solvent, heating to a reflux temperature-keeping reaction to synthesize a crude hexachlorocyclotriphosphazene, and then filtering, changing the solvent, extracting with concentrated sulfuric acid, diluting and crystallizing, filtering, and drying to obtain a finished hexachlorocyclotriphosphazene. The crude hexachlorocyclotriphosphazene synthesized by this method has a low purity, a low yield of the finished product, and the generated sulfuric acid waste liquid is not good for the environment.
专利CN201310166628采用氯化铵和五氯化磷固-固反应合成六氯环三磷腈，此反应在无溶剂条件下反应，反应速度较慢，且很难反应完全，收率低。Patent CN201310166628 uses ammonium chloride and phosphorus pentachloride to react solid-solid to synthesize hexachlorocyclotriphosphazene. This reaction is carried out in the absence of solvent, the reaction speed is slow, and it is difficult to react completely, and the yield is low.
专利CN104945438一次性按比例投入投入五氯化磷、氯化铵、氯化镁、吡啶、氯苯，然后升温至130-140℃反应9-11小时，反应完全后，过滤，减压蒸馏脱氯苯，冷却至10-15℃，再过滤得六氯环三磷腈。此工艺保温时间过长，副产物线性磷腈会随保温时间延长而增加。Patent CN104945438 puts phosphorus pentachloride, ammonium chloride, magnesium chloride, pyridine and chlorobenzene in proportion at one time, then heats to 130-140°C for reaction for 9-11 hours, filters after the reaction is complete, removes chlorobenzene by vacuum distillation, cools to 10-15°C, and then filters to obtain hexachlorocyclotriphosphazene. The heat preservation time of this process is too long, and the byproduct linear phosphazene will increase with the extension of the heat preservation time.
发明内容Summary of the invention
针对现有技术的不足，本发明的目的在于提供一种六氯环三磷腈的制备方法，此方法制得的成品纯度高，收率高。In view of the shortcomings of the prior art, the object of the present invention is to provide a method for preparing hexachlorocyclotriphosphazene, wherein the finished product obtained by the method has high purity and high yield.
本发明公开了一种六氯环三磷腈的制备方法，包括以下步骤：The invention discloses a method for preparing hexachlorocyclotriphosphazene, comprising the following steps:
1)五氯化磷氯苯溶液的制备：在氮气保护下，将五氯化磷与氯苯混合并升温至80-90℃搅拌至溶解，得到五氯化磷氯苯溶液保温待用；1) Preparation of phosphorus pentachloride chlorobenzene solution: under nitrogen protection, phosphorus pentachloride and chlorobenzene are mixed and heated to 80-90° C. and stirred until dissolved to obtain phosphorus pentachloride chlorobenzene solution, which is kept warm for standby use;
2)在氮气保护下，往带冷凝管、干燥管的四口瓶中投入氯苯，开启搅拌下，投入粉末状的氯化铵和离子液体催化剂溶液，升温至118-122℃，开始滴加步骤1)的五氯化磷氯苯溶液，滴毕升温至130-135℃保温反应2-3小时，得六氯环三磷腈粗品氯苯溶液，反应所生成的氯化氢经水吸收制成30％盐酸；2) Under nitrogen protection, chlorobenzene is added to a four-necked flask with a condenser and a drying tube, and powdered ammonium chloride and an ionic liquid catalyst solution are added while stirring. The temperature is raised to 118-122° C., and the phosphorus pentachloride chlorobenzene solution of step 1) is added dropwise. After the addition is completed, the temperature is raised to 130-135° C. and the mixture is kept warm for 2-3 hours to obtain a chlorobenzene solution of a crude hexachlorocyclotriphosphazene product. The hydrogen chloride generated by the reaction is absorbed by water to prepare 30% hydrochloric acid;
3)后处理：反应结束后将步骤2)的六氯环三磷腈粗品氯苯溶液冷却至35-40℃，过滤，
滤液减压蒸馏回收氯苯，冷却得到混合固体磷腈；3) Post-treatment: After the reaction is completed, the chlorobenzene solution of the crude hexachlorocyclotriphosphazene in step 2) is cooled to 35-40°C, filtered, The filtrate is subjected to reduced pressure distillation to recover chlorobenzene, and cooled to obtain a mixed solid phosphazene;
4)重结晶：向步骤3)的混合固体磷腈中加入乙酸乙酯与正己烷的混合溶剂，升温回流0.5-1.2小时，冷却至0-5℃，抽滤，滤饼真空干燥，粉碎得纯度大于99％的六氯环三磷腈成品。4) Recrystallization: Add a mixed solvent of ethyl acetate and n-hexane to the mixed solid phosphazene in step 3), heat and reflux for 0.5-1.2 hours, cool to 0-5°C, filter, vacuum dry the filter cake, and pulverize to obtain a hexachlorocyclotriphosphazene product with a purity greater than 99%.
进一步地，本发明还限定了步骤2)中五氯化磷氯苯溶液的滴加时间为8-12小时。Furthermore, the present invention also limits the dropwise addition time of the phosphorus pentachloride chlorobenzene solution in step 2) to 8-12 hours.
进一步地，本发明还限定了步骤4)中的重结晶溶剂中乙酸乙酯与正己烷的体积比为6-10：3，优选为7：3；乙酸乙酯与正己烷的混合溶剂与混合固体磷腈的质量比为1-1.5:1，优选为1.3:1；真空干燥温度为60-75℃，优选为70℃，真空干燥时间为6-8小时，压力为负压-0.098MPa以上。Furthermore, the present invention also defines that the volume ratio of ethyl acetate to n-hexane in the recrystallization solvent in step 4) is 6-10:3, preferably 7:3; the mass ratio of the mixed solvent of ethyl acetate and n-hexane to the mixed solid phosphazene is 1-1.5:1, preferably 1.3:1; the vacuum drying temperature is 60-75°C, preferably 70°C, the vacuum drying time is 6-8 hours, and the pressure is negative pressure above -0.098MPa.
进一步地，本发明还限定了乙酸乙酯与正己烷的混合溶剂的投料量为混合固体磷腈重量的1.2-1.5倍，优选为1.3倍。Furthermore, the present invention also limits the feeding amount of the mixed solvent of ethyl acetate and n-hexane to 1.2-1.5 times the weight of the mixed solid phosphazene, preferably 1.3 times.
更进一步地，本发明还限定了离子液体催化剂的制备过程为：在氮气保护下，投入氯苯、复合金属氯化物粉末和吡啶，搅拌下升温至80-100℃通入氯化氢气体，直至固体溶解清亮，得到离子液体催化剂溶液；五氯化磷、氯化铵、复合金属氯化物及吡啶的投料重量比为1000：300-500：10-20：30-50；复合金属氯化物为氯化钡、氯化锌、氯化铝、氯化镁、氯化铁或氯化钙中的任意两种。Furthermore, the present invention also defines the preparation process of the ionic liquid catalyst as follows: under nitrogen protection, chlorobenzene, composite metal chloride powder and pyridine are added, the temperature is raised to 80-100°C while stirring, and hydrogen chloride gas is introduced until the solid is dissolved and clear to obtain an ionic liquid catalyst solution; the weight ratio of phosphorus pentachloride, ammonium chloride, composite metal chloride and pyridine is 1000:300-500:10-20:30-50; the composite metal chloride is any two of barium chloride, zinc chloride, aluminum chloride, magnesium chloride, ferric chloride or calcium chloride.
通过采用上述工艺技术，与现有技术相比，本发明优点如下：By adopting the above process technology, compared with the prior art, the present invention has the following advantages:
本发明通过采用离子液体为催化剂，以五氯化磷和氯化铵为原料，采用滴加五氯化磷的方式进行反应，再后处理、重结晶得到本发明的产物六氯环三磷腈，反应的保温时间短，有效避免了副产物的增加，得到成品纯度高，收率高，其收率为90％以上，纯度也大于99％。The invention adopts ionic liquid as a catalyst, phosphorus pentachloride and ammonium chloride as raw materials, and performs a reaction by dropwise adding phosphorus pentachloride, and then performs post-treatment and recrystallization to obtain the product hexachlorocyclotriphosphazene of the invention. The heat preservation time of the reaction is short, and the increase of by-products is effectively avoided. The obtained finished product has high purity and high yield, and the yield is more than 90%, and the purity is also greater than 99%.
以下结合实施例对本发明作进一步说明，但本发明的保护范围并不仅限于此。The present invention is further described below in conjunction with embodiments, but the protection scope of the present invention is not limited thereto.
实施例1六氯环三磷腈的制备Example 1 Preparation of hexachlorocyclotriphosphazene
1)离子液体催化剂的制备：氮气保护下，向100ml四口瓶中投入50g氯苯，氯化镁、氯化锌粉末15g，吡啶40g，搅拌，控制温度80-100℃，通入氯化氢气体，直至液体清亮，待用；1) Preparation of ionic liquid catalyst: Under nitrogen protection, add 50g chlorobenzene, 15g magnesium chloride and zinc chloride powder, and 40g pyridine into a 100ml four-necked bottle, stir, control the temperature at 80-100°C, and introduce hydrogen chloride gas until the liquid is clear, and set aside;
2)五氯化磷氯苯溶液的制备：在氮气保护下，将五氯化磷1000g与氯苯1000g升温至80-90℃搅拌至溶解，保温待用；2) Preparation of phosphorus pentachloride chlorobenzene solution: under nitrogen protection, heat 1000 g of phosphorus pentachloride and 1000 g of chlorobenzene to 80-90° C., stir until dissolved, and keep warm for later use;
3)六氯环三磷腈制备：在氮气保护下，往带冷凝管、干燥管的5L四口瓶中投入氯苯
1000g，开搅拌，再投入粉末状的氯化铵400g、步骤1)的离子液体催化剂，升温至120℃，开始滴加步骤2)的五氯化磷氯苯溶液，滴加8小时，滴毕，升温至132℃保温反应3小时，得六氯环三磷腈粗品氯苯溶液，反应所生成的氯化氢水吸收制成30％盐酸；3) Preparation of hexachlorocyclotriphosphazene: Under nitrogen protection, add chlorobenzene into a 5L four-necked bottle with a condenser and a drying tube. 1000g, start stirring, then add 400g of powdered ammonium chloride and the ionic liquid catalyst of step 1), raise the temperature to 120°C, start dripping the phosphorus pentachloride chlorobenzene solution of step 2), drip for 8 hours, and after the dripping is completed, raise the temperature to 132°C and keep the temperature for 3 hours to obtain a chlorobenzene solution of crude hexachlorocyclotriphosphazene, and absorb the hydrogen chloride water generated by the reaction to prepare 30% hydrochloric acid;
3)反应结束，步骤2)的六氯环三磷腈粗品氯苯溶液冷却至40℃，过滤，滤液减压蒸馏回收氯苯，得固体混合磷腈548g；加入混合溶剂(乙酸乙酯：正己烷＝7：3)712g，加热回流1小时，冷却至5℃，抽滤，滤饼在70℃，真空-0.098MPa下干燥6小时，粉碎，得504g成品，纯度99.2％，收率90.6％。3) After the reaction is completed, the chlorobenzene solution of the crude hexachlorocyclotriphosphazene in step 2) is cooled to 40°C, filtered, and the filtrate is distilled under reduced pressure to recover chlorobenzene to obtain 548g of solid mixed phosphazene; 712g of a mixed solvent (ethyl acetate: n-hexane = 7:3) is added, heated to reflux for 1 hour, cooled to 5°C, filtered, and the filter cake is dried at 70°C under vacuum -0.098MPa for 6 hours, crushed, and 504g of a finished product is obtained with a purity of 99.2% and a yield of 90.6%.
实施例2六氯环三磷腈的制备方法Example 2 Preparation method of hexachlorocyclotriphosphazene
1)离子液体催化剂的制备：氮气保护下，向100ml四口瓶中投入50g氯苯，氯化铁、氯化铝粉末15g，吡啶42g，搅拌，控制温度80-100℃，通入氯化氢气体，直至液体清亮，待用；1) Preparation of ionic liquid catalyst: Under nitrogen protection, add 50g chlorobenzene, 15g ferric chloride and aluminum chloride powder, and 42g pyridine into a 100ml four-necked bottle, stir, control the temperature at 80-100°C, and introduce hydrogen chloride gas until the liquid is clear, and set aside;
2)五氯化磷氯苯溶液的制备：在氮气保护氛围下，将五氯化磷1000g与氯苯1000g升温至80-90℃搅拌至溶解，保温待用；2) Preparation of phosphorus pentachloride chlorobenzene solution: Under a nitrogen atmosphere, heat 1000 g of phosphorus pentachloride and 1000 g of chlorobenzene to 80-90° C., stir until dissolved, and keep warm for later use;
3)六氯环三磷腈制备：在氮气保护氛围下，往带冷凝管、干燥管的5L四口瓶中投入氯苯1000g，开搅拌，再投入粉末状的氯化铵450g、离子液体催化剂，升温至120℃，开始滴加五氯化磷氯苯溶液，滴加9小时，滴毕，升温至132℃保温反应2.5小时，得六氯环三磷腈粗品氯苯溶液，反应所生成的氯化氢水吸收制成30％盐酸；3) Preparation of hexachlorocyclotriphosphazene: In a nitrogen atmosphere, 1000 g of chlorobenzene was added to a 5L four-necked bottle with a condenser and a drying tube, and stirred. Then, 450 g of powdered ammonium chloride and an ionic liquid catalyst were added. The temperature was raised to 120° C., and phosphorus pentachloride chlorobenzene solution was added dropwise for 9 hours. After the addition was completed, the temperature was raised to 132° C. and the reaction was kept warm for 2.5 hours to obtain a crude hexachlorocyclotriphosphazene chlorobenzene solution. The hydrogen chloride water generated by the reaction was absorbed to prepare 30% hydrochloric acid;
4)反应结束，冷却至40℃，过滤，滤液减压蒸馏回收氯苯，得固体混合磷腈545g；加入混合溶剂(乙酸乙酯：正己烷＝7：3)708.5g，加热回流1小时，冷却至5℃，抽滤，滤饼在70℃，真空-0.098MPa下干燥6小时，粉碎，得502g成品，纯度99.4％，收率90.2％。4) After the reaction was completed, the mixture was cooled to 40°C, filtered, and the filtrate was distilled under reduced pressure to recover chlorobenzene to obtain 545g of solid mixed phosphazene; 708.5g of a mixed solvent (ethyl acetate: n-hexane = 7:3) was added, heated to reflux for 1 hour, cooled to 5°C, filtered, and the filter cake was dried at 70°C under vacuum -0.098MPa for 6 hours, crushed, and 502g of a finished product was obtained with a purity of 99.4% and a yield of 90.2%.
实施例3六氯环三磷腈的制备方法Example 3 Preparation method of hexachlorocyclotriphosphazene
1)离子液体催化剂的制备：氮气保护下，向100ml四口瓶中投入50g氯苯，氯化钡、氯化钙粉末20g，吡啶50g，搅拌，控制温度80-100℃，通入氯化氢气体，直至液体清亮，待用；1) Preparation of ionic liquid catalyst: Under nitrogen protection, add 50g chlorobenzene, 20g barium chloride and calcium chloride powder, and 50g pyridine into a 100ml four-necked bottle, stir, control the temperature at 80-100°C, and introduce hydrogen chloride gas until the liquid is clear, and set aside;
2)五氯化磷氯苯溶液的制备：在氮气保护氛围下，将五氯化磷1000g与氯苯1000g升温至80-90℃搅拌至溶解，保温待用；2) Preparation of phosphorus pentachloride chlorobenzene solution: Under a nitrogen atmosphere, heat 1000 g of phosphorus pentachloride and 1000 g of chlorobenzene to 80-90° C., stir until dissolved, and keep warm for later use;
3)六氯环三磷腈制备：在氮气保护氛围下，往带冷凝管、干燥管的5L四口瓶中投入氯苯1000g，开搅拌，再投入粉末状的氯化铵500g、离子液体催化剂，升温至120℃，开始滴加五氯化磷氯苯溶液，滴加11小时，滴毕，升温至132℃保温反应2.5小时，得六氯环三磷腈粗品氯苯溶液，反应所生成的氯化氢水吸收制成30％盐酸；
3) Preparation of hexachlorocyclotriphosphazene: In a nitrogen atmosphere, 1000 g of chlorobenzene was added to a 5L four-necked bottle with a condenser and a drying tube, and stirred. Then, 500 g of powdered ammonium chloride and an ionic liquid catalyst were added. The temperature was raised to 120° C., and phosphorus pentachloride chlorobenzene solution was added dropwise for 11 hours. After the addition was completed, the temperature was raised to 132° C. and the reaction was kept warm for 2.5 hours to obtain a crude chlorobenzene solution of hexachlorocyclotriphosphazene. The hydrogen chloride water generated by the reaction was absorbed to prepare 30% hydrochloric acid;
4)反应结束，冷却至40℃，过滤，滤液减压蒸馏回收氯苯，得固体混合磷腈550g；加入混合溶剂(乙酸乙酯：正己烷＝7：3)715g，加热回流1小时，冷却至5℃，抽滤，滤饼在70℃，真空-0.098MPa下干燥6小时，粉碎，得508g成品，纯度99.5％，收率91.3％。4) After the reaction is completed, the mixture is cooled to 40°C, filtered, and the filtrate is distilled under reduced pressure to recover chlorobenzene to obtain 550g of solid mixed phosphazene; 715g of a mixed solvent (ethyl acetate: n-hexane = 7:3) is added, heated to reflux for 1 hour, cooled to 5°C, filtered, and the filter cake is dried at 70°C under vacuum -0.098MPa for 6 hours, crushed, and 508g of a finished product is obtained, with a purity of 99.5% and a yield of 91.3%.
实施例4六氯环三磷腈的制备方法Example 4 Preparation method of hexachlorocyclotriphosphazene
1)离子液体催化剂的制备：氮气保护下，向100ml四口瓶中投入50g氯苯，氯化镁、氯化铁粉末10g，吡啶35g，搅拌，控制温度80-100℃，通入氯化氢气体，直至液体清亮，待用；1) Preparation of ionic liquid catalyst: Under nitrogen protection, add 50g chlorobenzene, 10g magnesium chloride and ferric chloride powder, and 35g pyridine into a 100ml four-necked bottle, stir, control the temperature at 80-100°C, and introduce hydrogen chloride gas until the liquid is clear, and set aside;
2)五氯化磷氯苯溶液的制备：在氮气保护氛围下，将五氯化磷1000g与氯苯1000g升温至80-90℃搅拌至溶解，保温待用；2) Preparation of phosphorus pentachloride chlorobenzene solution: Under a nitrogen atmosphere, heat 1000 g of phosphorus pentachloride and 1000 g of chlorobenzene to 80-90° C., stir until dissolved, and keep warm for later use;
3)六氯环三磷腈制备：在氮气保护氛围下，往带冷凝管、干燥管的5L四口瓶中投入氯苯1000g，开搅拌，再投入粉末状的氯化铵350g、离子液体催化剂，升温至120℃，开始滴加五氯化磷氯苯溶液，滴加10小时，滴毕，升温至132℃保温反应2小时，得六氯环三磷腈粗品氯苯溶液，反应所生成的氯化氢水吸收制成30％盐酸；3) Preparation of hexachlorocyclotriphosphazene: In a nitrogen atmosphere, 1000 g of chlorobenzene was added to a 5L four-necked bottle with a condenser and a drying tube, and stirred. Then 350 g of powdered ammonium chloride and an ionic liquid catalyst were added. The temperature was raised to 120° C. and phosphorus pentachloride chlorobenzene solution was added dropwise for 10 hours. After the addition was completed, the temperature was raised to 132° C. and the reaction was kept warm for 2 hours to obtain a crude hexachlorocyclotriphosphazene chlorobenzene solution. The hydrogen chloride water generated by the reaction was absorbed to prepare 30% hydrochloric acid;
4)反应结束，冷却至40℃，过滤，滤液减压蒸馏回收氯苯，得固体混合磷腈542g；加入混合溶剂(乙酸乙酯：正己烷＝7：3)704.6g，加热回流1小时，冷却至5℃，抽滤，滤饼在70℃，真空-0.098MPa下干燥8小时，粉碎，得501g成品，纯度99.3％，收率90％。4) After the reaction is completed, the mixture is cooled to 40°C, filtered, and the filtrate is distilled under reduced pressure to recover chlorobenzene to obtain 542g of solid mixed phosphazene; 704.6g of a mixed solvent (ethyl acetate: n-hexane = 7:3) is added, heated to reflux for 1 hour, cooled to 5°C, filtered, and the filter cake is dried at 70°C under vacuum -0.098MPa for 8 hours, crushed, and 501g of a finished product is obtained with a purity of 99.3% and a yield of 90%.
比较例1(采用单一氯化盐作催化剂)Comparative Example 1 (using a single chloride salt as a catalyst)
1)离子液体催化剂的制备：氮气保护下，向100ml四口瓶中投入50g氯苯，氯化镁粉末15g，吡啶40g，搅拌，控制温度80-100℃，通入氯化氢气体，直至液体清亮，待用；1) Preparation of ionic liquid catalyst: Under nitrogen protection, add 50g chlorobenzene, 15g magnesium chloride powder, and 40g pyridine into a 100ml four-necked bottle, stir, control the temperature at 80-100°C, and introduce hydrogen chloride gas until the liquid becomes clear, and set aside;
2)五氯化磷氯苯溶液的制备：在氮气保护氛围下，将五氯化磷1000g与氯苯1000g升温至80-90℃搅拌至溶解，保温待用；2) Preparation of phosphorus pentachloride chlorobenzene solution: Under a nitrogen atmosphere, heat 1000 g of phosphorus pentachloride and 1000 g of chlorobenzene to 80-90° C., stir until dissolved, and keep warm for later use;
3)六氯环三磷腈制备：在氮气保护氛围下，往带冷凝管、干燥管的5L四口瓶中投入氯苯1000g，开搅拌，再投入粉末状的氯化铵400g、离子液体催化剂，升温至120℃，开始滴加五氯化磷氯苯溶液，滴加8小时，滴毕，升温至132℃保温反应3小时，得六氯环三磷腈粗品氯苯溶液，反应所生成的氯化氢水吸收制成30％盐酸；3) Preparation of hexachlorocyclotriphosphazene: In a nitrogen atmosphere, 1000 g of chlorobenzene was added to a 5L four-necked bottle with a condenser and a drying tube, and stirred. Then, 400 g of powdered ammonium chloride and an ionic liquid catalyst were added. The temperature was raised to 120° C., and phosphorus pentachloride chlorobenzene solution was added dropwise for 8 hours. After the addition was completed, the temperature was raised to 132° C. and the reaction was kept warm for 3 hours to obtain a crude hexachlorocyclotriphosphazene chlorobenzene solution. The hydrogen chloride water generated by the reaction was absorbed to prepare 30% hydrochloric acid;
4)反应结束，冷却至40℃，过滤，滤液减压蒸馏回收氯苯，得固体混合磷腈528g；加入混合溶剂(乙酸乙酯：正己烷＝7：3)686.4g，加热回流1小时，冷却至5℃，抽滤，滤饼在70℃，真空-0.098MPa下干燥6小时，粉碎，得478成品，纯度99.1％，收率85.9％。4) After the reaction was completed, the mixture was cooled to 40°C, filtered, and the filtrate was distilled under reduced pressure to recover chlorobenzene to obtain 528 g of solid mixed phosphazene; 686.4 g of mixed solvent (ethyl acetate: n-hexane = 7:3) was added, heated to reflux for 1 hour, cooled to 5°C, filtered, and the filter cake was dried at 70°C under vacuum -0.098 MPa for 6 hours, crushed, and 478 finished products were obtained with a purity of 99.1% and a yield of 85.9%.
比较例2(氯化磷氯苯与氯化铵的投料质量比为1000:280)Comparative Example 2 (the mass ratio of phosphorus chloride chlorobenzene to ammonium chloride is 1000:280)
1)离子液体催化剂的制备：氮气保护下，向100ml四口瓶中投入50g氯苯，氯化镁、氯化
锌粉末15g，吡啶40g，搅拌，控制温度80-100℃，通入氯化氢气体，直至液体清亮，待用；1) Preparation of ionic liquid catalyst: Under nitrogen protection, 50g chlorobenzene, magnesium chloride, and chloride were added into a 100ml four-necked bottle. Zinc powder 15g, pyridine 40g, stir, control the temperature at 80-100℃, pass hydrogen chloride gas until the liquid is clear, and set aside;
2)五氯化磷氯苯溶液的制备：在氮气保护氛围下，将五氯化磷1000g与氯苯1000g升温至80-90℃搅拌至溶解，保温待用；2) Preparation of phosphorus pentachloride chlorobenzene solution: Under a nitrogen atmosphere, heat 1000 g of phosphorus pentachloride and 1000 g of chlorobenzene to 80-90° C., stir until dissolved, and keep warm for later use;
3)六氯环三磷腈制备：在氮气保护氛围下，往带冷凝管、干燥管的5L四口瓶中投入氯苯1000g，开搅拌，再投入粉末状的氯化铵280g、离子液体催化剂，升温至120℃，开始滴加五氯化磷氯苯溶液，滴加9小时，滴毕，升温至132℃保温反应3小时，得六氯环三磷腈粗品氯苯溶液，反应所生成的氯化氢水吸收制成30％盐酸；3) Preparation of hexachlorocyclotriphosphazene: In a nitrogen atmosphere, 1000 g of chlorobenzene was added to a 5L four-necked bottle with a condenser and a drying tube, and stirred. Then, 280 g of powdered ammonium chloride and an ionic liquid catalyst were added. The temperature was raised to 120° C., and phosphorus pentachloride chlorobenzene solution was added dropwise for 9 hours. After the addition was completed, the temperature was raised to 132° C. and the reaction was kept warm for 3 hours to obtain a crude hexachlorocyclotriphosphazene chlorobenzene solution. The hydrogen chloride water generated by the reaction was absorbed to prepare 30% hydrochloric acid;
4)反应结束，冷却至40℃，过滤，滤液减压蒸馏回收氯苯，得固体混合磷腈520g；加入混合溶剂(乙酸乙酯：正己烷＝7：3)676g，加热回流1小时，冷却至5℃，抽滤，滤饼在70℃，真空-0.098MPa下干燥6小时，粉碎，得466成品，纯度99.1％，收率82.3％。4) After the reaction is completed, the mixture is cooled to 40°C, filtered, and the filtrate is distilled under reduced pressure to recover chlorobenzene to obtain 520 g of solid mixed phosphazene; 676 g of a mixed solvent (ethyl acetate: n-hexane = 7:3) is added, heated to reflux for 1 hour, cooled to 5°C, filtered, and the filter cake is dried at 70°C under vacuum -0.098 MPa for 6 hours, crushed, and 466 finished product is obtained with a purity of 99.1% and a yield of 82.3%.
比较例3(重结晶用的混合溶剂(乙酸乙酯：正己烷＝6：4))Comparative Example 3 (Mixed solvent for recrystallization (ethyl acetate:n-hexane=6:4))
1)离子液体催化剂的制备：氮气保护下，向100ml四口瓶中投入50g氯苯，氯化镁、氯化锌粉末15g，吡啶40g，搅拌，控制温度80-100℃，通入氯化氢气体，直至液体清亮，待用；1) Preparation of ionic liquid catalyst: Under nitrogen protection, add 50g chlorobenzene, 15g magnesium chloride and zinc chloride powder, and 40g pyridine into a 100ml four-necked bottle, stir, control the temperature at 80-100°C, and introduce hydrogen chloride gas until the liquid is clear, and set aside;
2)五氯化磷氯苯溶液的制备：在氮气保护氛围下，将五氯化磷1000g与氯苯1000g升温至80-90℃搅拌至溶解，保温待用；2) Preparation of phosphorus pentachloride chlorobenzene solution: Under a nitrogen atmosphere, heat 1000 g of phosphorus pentachloride and 1000 g of chlorobenzene to 80-90° C., stir until dissolved, and keep warm for later use;
3)六氯环三磷腈制备：在氮气保护氛围下，往带冷凝管、干燥管的5L四口瓶中投入氯苯1000g，开搅拌，再投入粉末状的氯化铵400g、离子液体催化剂，升温至120℃，开始滴加五氯化磷氯苯溶液，滴加10小时，滴毕，升温至132℃保温反应3小时，得六氯环三磷腈粗品氯苯溶液，反应所生成的氯化氢水吸收制成30％盐酸；反应结束，冷却至40℃，过滤，滤液减压蒸馏回收氯苯，得固体混合磷腈547g；加入混合溶剂(乙酸乙酯：正己烷＝6：4)686.4g，加热回流1小时，冷却至5℃，抽滤，滤饼在70℃，真空-0.098MPa下干燥6小时，粉碎，得503g成品，纯度97.8％，收率90.4％。3) Preparation of hexachlorocyclotriphosphazene: In a nitrogen atmosphere, 1000 g of chlorobenzene was added to a 5L four-necked bottle with a condenser and a drying tube, and stirred. Then, 400 g of powdered ammonium chloride and an ionic liquid catalyst were added. The temperature was raised to 120° C., and phosphorus pentachloride chlorobenzene solution was added dropwise for 10 hours. After the addition was completed, the temperature was raised to 132° C. and the mixture was kept warm for 3 hours to obtain a crude chlorobenzene solution of hexachlorocyclotriphosphazene. The hydrogen chloride water generated by the reaction was absorbed to prepare 30% hydrochloric acid. After the reaction was completed, the mixture was cooled to 40° C., filtered, and the filtrate was decompressed and distilled to recover chlorobenzene to obtain 547 g of solid mixed phosphazene. 686.4 g of a mixed solvent (ethyl acetate: n-hexane = 6:4) was added, the mixture was heated to reflux for 1 hour, cooled to 5° C., filtered, and the filter cake was dried at 70° C. under vacuum -0.098 MPa for 6 hours, crushed, and 503 g of a finished product was obtained, with a purity of 97.8% and a yield of 90.4%.
比较例4(以复合氯化金属盐为催化剂)Comparative Example 4 (using composite metal chloride as catalyst)
1)五氯化磷氯苯溶液的制备：在氮气保护氛围下，将五氯化磷1000g与氯苯1000g升温至80-90℃搅拌至溶解，保温待用；1) Preparation of phosphorus pentachloride chlorobenzene solution: Under a nitrogen atmosphere, heat 1000 g of phosphorus pentachloride and 1000 g of chlorobenzene to 80-90° C., stir until dissolved, and keep warm for later use;
2)六氯环三磷腈制备：在氮气保护氛围下，往带冷凝管、干燥管的5L四口瓶中投入氯苯1000g，开搅拌，再投入粉末状的氯化铵400g、氯化镁、氯化锌粉末15g、吡啶40g，升温至120℃，开始滴加五氯化磷氯苯溶液，滴加10小时，滴毕，升温至132℃保温反应3小
时，得六氯环三磷腈粗品氯苯溶液，反应所生成的氯化氢水吸收制成30％盐酸；反应结束，冷却至40℃，过滤，滤液减压蒸馏回收氯苯，得固体混合磷腈503g；加入混合溶剂(乙酸乙酯：正己烷＝7：3)653.9g，加热回流1小时，冷却至5℃，抽滤，滤饼在70℃，真空-0.098MPa下干燥6小时，粉碎，得441g成品，纯度99％，收率79.3％。
2) Preparation of hexachlorocyclotriphosphazene: In a nitrogen atmosphere, 1000 g of chlorobenzene was added to a 5L four-necked bottle with a condenser and a drying tube, and stirred. Then, 400 g of powdered ammonium chloride, magnesium chloride, 15 g of zinc chloride powder, and 40 g of pyridine were added. The temperature was raised to 120°C, and phosphorus pentachloride chlorobenzene solution was added dropwise for 10 hours. After the addition was completed, the temperature was raised to 132°C and kept warm for 3 hours. When the reaction is completed, a chlorobenzene solution of crude hexachlorocyclotriphosphazene is obtained, and the hydrogen chloride water generated by the reaction is absorbed to prepare 30% hydrochloric acid; after the reaction is completed, the mixture is cooled to 40°C, filtered, and the filtrate is distilled under reduced pressure to recover chlorobenzene to obtain 503g of solid mixed phosphazene; 653.9g of a mixed solvent (ethyl acetate:n-hexane=7:3) is added, heated to reflux for 1 hour, cooled to 5°C, filtered, and the filter cake is dried at 70°C under vacuum -0.098MPa for 6 hours, crushed, and 441g of a finished product is obtained with a purity of 99% and a yield of 79.3%.
Claims (10)
- 一种六氯环三磷腈的制备方法，其特征在于包括以下步骤：A method for preparing hexachlorocyclotriphosphazene, characterized in that it comprises the following steps:1)五氯化磷氯苯溶液的制备：在氮气保护下，将五氯化磷与氯苯混合并升温至80-90℃搅拌至溶解，得到五氯化磷氯苯溶液保温待用；1) Preparation of phosphorus pentachloride chlorobenzene solution: under nitrogen protection, phosphorus pentachloride and chlorobenzene are mixed and heated to 80-90° C. and stirred until dissolved to obtain phosphorus pentachloride chlorobenzene solution, which is kept warm for standby use;2)在氮气保护下，往带冷凝管、干燥管的四口瓶中投入氯苯，开启搅拌下，投入粉末状的氯化铵和离子液体催化剂溶液，升温至118-122℃，开始滴加步骤1)的五氯化磷氯苯溶液，滴毕升温至130-135℃保温反应2-3小时，得六氯环三磷腈粗品氯苯溶液，反应所生成的氯化氢经水吸收制成30％盐酸；2) Under nitrogen protection, chlorobenzene is added to a four-necked flask with a condenser and a drying tube, and powdered ammonium chloride and an ionic liquid catalyst solution are added while stirring. The temperature is raised to 118-122° C., and the phosphorus pentachloride chlorobenzene solution of step 1) is added dropwise. After the addition is completed, the temperature is raised to 130-135° C. and the mixture is kept warm for 2-3 hours to obtain a chlorobenzene solution of a crude hexachlorocyclotriphosphazene product. The hydrogen chloride generated by the reaction is absorbed by water to prepare 30% hydrochloric acid;3)后处理：反应结束后将步骤2)的六氯环三磷腈粗品氯苯溶液冷却至35-40℃，过滤，滤液减压蒸馏回收氯苯，冷却得到混合固体磷腈；3) Post-treatment: After the reaction is completed, the crude chlorobenzene solution of hexachlorocyclotriphosphazene in step 2) is cooled to 35-40° C., filtered, and the filtrate is distilled under reduced pressure to recover chlorobenzene, and cooled to obtain a mixed solid phosphazene;4)重结晶：向步骤3)的混合固体磷腈中加入乙酸乙酯与正己烷的混合溶剂，升温回流0.5-1.2小时，冷却至0-5℃，抽滤，滤饼真空干燥，粉碎得纯度大于99％的六氯环三磷腈成品。4) Recrystallization: Add a mixed solvent of ethyl acetate and n-hexane to the mixed solid phosphazene in step 3), heat and reflux for 0.5-1.2 hours, cool to 0-5°C, filter, vacuum dry the filter cake, and pulverize to obtain a hexachlorocyclotriphosphazene product with a purity greater than 99%.
- 根据权利要求1所述的一种六氯环三磷腈的制备方法，其特征在于步骤2)中五氯化磷氯苯溶液的滴加时间为8-12小时。The method for preparing hexachlorocyclotriphosphazene according to claim 1, characterized in that the phosphorus pentachloride chlorobenzene solution in step 2) is added dropwise for 8-12 hours.
- 根据权利要求1所述的一种六氯环三磷腈的制备方法，其特征在于步骤4)中的重结晶溶剂中乙酸乙酯与正己烷的体积比为6-10：3，优选为7：3。The method for preparing hexachlorocyclotriphosphazene according to claim 1, characterized in that the volume ratio of ethyl acetate to n-hexane in the recrystallization solvent in step 4) is 6-10:3, preferably 7:3.
- 根据权利要求1所述的一种六氯环三磷腈的制备方法，其特征在于步骤4)中的乙酸乙酯与正己烷的混合溶剂与混合固体磷腈的质量比为1-1.5:1，优选为1.3:1。The method for preparing hexachlorocyclotriphosphazene according to claim 1, characterized in that the mass ratio of the mixed solvent of ethyl acetate and n-hexane to the mixed solid phosphazene in step 4) is 1-1.5:1, preferably 1.3:1.
- 根据权利要求1所述的一种六氯环三磷腈的制备方法，其特征在于步骤4)中的真空干燥温度为60-75℃，优选为70℃，压力为负压-0.098MPa以上。The method for preparing hexachlorocyclotriphosphazene according to claim 1, characterized in that the vacuum drying temperature in step 4) is 60-75° C., preferably 70° C., and the pressure is negative pressure above -0.098 MPa.
- 根据权利要求1所述的一种六氯环三磷腈的制备方法，其特征在于步骤4)中的滤饼真空干燥时间为6-8小时。The method for preparing hexachlorocyclotriphosphazene according to claim 1, characterized in that the vacuum drying time of the filter cake in step 4) is 6-8 hours.
- 根据权利要求1-6任一项所述的一种六氯环三磷腈的制备方法，其特征在于乙酸乙酯与正己烷的混合溶剂的投料量为混合固体磷腈重量的1.2-1.5倍，优选为1.3倍。A method for preparing hexachlorocyclotriphosphazene according to any one of claims 1 to 6, characterized in that the feeding amount of the mixed solvent of ethyl acetate and n-hexane is 1.2-1.5 times the weight of the mixed solid phosphazene, preferably 1.3 times.
- 根据权利要求1-6任一项所述的一种六氯环三磷腈的制备方法，其特征在于离子液体催化剂的制备过程为：在氮气保护下，投入氯苯、复合金属氯化物粉末和吡啶，搅拌下升温至80-100℃通入氯化氢气体，直至固体溶解清亮，得到离子液体催化剂溶液。A method for preparing hexachlorocyclotriphosphazene according to any one of claims 1 to 6, characterized in that the preparation process of the ionic liquid catalyst is: under nitrogen protection, chlorobenzene, composite metal chloride powder and pyridine are added, the temperature is raised to 80-100° C. under stirring, and hydrogen chloride gas is introduced until the solid is dissolved and clear to obtain an ionic liquid catalyst solution.
- 根据权利要求8所述的一种六氯环三磷腈的制备方法，其特征在于五氯化磷、氯化铵、复合金属氯化物及吡啶的投料重量比为1000：300-500：10-20：30-50。The method for preparing hexachlorocyclotriphosphazene according to claim 8 is characterized in that the weight ratio of phosphorus pentachloride, ammonium chloride, composite metal chloride and pyridine is 1000:300-500:10-20:30-50.
- 根据权利要求8所述的一种六氯环三磷腈的制备方法，其特征在于复合金属氯化物为氯 化钡、氯化锌、氯化铝、氯化镁、氯化铁或氯化钙中的任意两种。 The method for preparing hexachlorocyclotriphosphazene according to claim 8, characterized in that the composite metal chloride is chlorine Any two of barium chloride, zinc chloride, aluminum chloride, magnesium chloride, iron chloride or calcium chloride.
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| CN103554186A (en) * | 2013-10-30 | 2014-02-05 | 威海金威化学工业有限责任公司 | Preparation method of phosphonitrilic chloride trimer |
| CN109134544A (en) * | 2018-07-24 | 2019-01-04 | 潍坊医学院 | A kind of phosphorus nitrile compounds, the composition including the phosphorus nitrile compounds, the fire retardant comprising it and application |
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| CN101602780A (en) * | 2009-06-26 | 2009-12-16 | 四川东材科技集团股份有限公司 | The process for catalytic synthesis of hexachlorocyclotriphosphazene |
| CN103554186A (en) * | 2013-10-30 | 2014-02-05 | 威海金威化学工业有限责任公司 | Preparation method of phosphonitrilic chloride trimer |
| CN109134544A (en) * | 2018-07-24 | 2019-01-04 | 潍坊医学院 | A kind of phosphorus nitrile compounds, the composition including the phosphorus nitrile compounds, the fire retardant comprising it and application |
Non-Patent Citations (2)
| Title |
|---|
| "China Master's Theses Full-Text Database", 1 April 2011, HENAN UNIVERSITY OF TECHNOLOGY, China, article WU, YONG: "Synthesis and Study of Cyclotriphosphazene Derivatives Containing Oxygen Group and Their Flame-Retardant for Epoxy Resin", pages: 1 - 110, XP009555091 * |
| SUN DE, XU ZHENLIANG: "Synthesis of Hexachlorocyclotriphosphazene Catalyzed by [Py]Cl-ZnCl2 Ionic Liquid", HUAXUE FANYING GONGCHENG YU GONGYI - CHEMICAL REACTION ENGINEERING AND TECHNOLOGY, ZHEJIANG DAXUE XUEBAO BIANJIBU, HANGZHOU,, CN, vol. 26, no. 5, 31 October 2010 (2010-10-31), CN , pages 472 - 476, XP009555271, ISSN: 1001-7631 * |
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