JPH03193793A - Production of tris(trihaloneopentyl)phosphate - Google Patents
Production of tris(trihaloneopentyl)phosphateInfo
- Publication number
- JPH03193793A JPH03193793A JP1333466A JP33346689A JPH03193793A JP H03193793 A JPH03193793 A JP H03193793A JP 1333466 A JP1333466 A JP 1333466A JP 33346689 A JP33346689 A JP 33346689A JP H03193793 A JPH03193793 A JP H03193793A
- Authority
- JP
- Japan
- Prior art keywords
- phosphate
- tris
- trihaloneopentyl
- alcohol
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000007983 Tris buffer Substances 0.000 title claims description 33
- 229910019142 PO4 Inorganic materials 0.000 title claims description 32
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims description 32
- 239000010452 phosphate Substances 0.000 title claims description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000002904 solvent Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011574 phosphorus Substances 0.000 claims abstract description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 13
- 238000009835 boiling Methods 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 9
- QEJPOEGPNIVDMK-UHFFFAOYSA-N 3-bromo-2,2-bis(bromomethyl)propan-1-ol Chemical compound OCC(CBr)(CBr)CBr QEJPOEGPNIVDMK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011541 reaction mixture Substances 0.000 claims abstract description 6
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 45
- 239000013078 crystal Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 25
- 239000007864 aqueous solution Substances 0.000 claims description 14
- -1 dibromo-chloroneopentyl alcohol Chemical compound 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 7
- 230000002378 acidificating effect Effects 0.000 claims description 6
- BHYQWBKCXBXPKM-UHFFFAOYSA-N tris[3-bromo-2,2-bis(bromomethyl)propyl] phosphate Chemical group BrCC(CBr)(CBr)COP(=O)(OCC(CBr)(CBr)CBr)OCC(CBr)(CBr)CBr BHYQWBKCXBXPKM-UHFFFAOYSA-N 0.000 claims description 5
- RBFSNPHHISIOGN-UHFFFAOYSA-N tris(1,1,3-trichloro-2,2-dimethylpropyl) phosphate Chemical compound ClCC(C)(C)C(Cl)(Cl)OP(=O)(OC(Cl)(Cl)C(C)(C)CCl)OC(Cl)(Cl)C(C)(C)CCl RBFSNPHHISIOGN-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- DXCFADYCHVMCJW-UHFFFAOYSA-N tris(1,3-dibromo-1-chloro-2,2-dimethylpropyl) phosphate Chemical compound BrCC(C)(C)C(Cl)(Br)OP(=O)(OC(Cl)(Br)C(C)(C)CBr)OC(Cl)(Br)C(C)(C)CBr DXCFADYCHVMCJW-UHFFFAOYSA-N 0.000 claims 1
- OUWSTQZBWYSZBV-UHFFFAOYSA-N tris(3-bromo-1,1-dichloro-2,2-dimethylpropyl) phosphate Chemical compound BrCC(C)(C)C(Cl)(Cl)OP(=O)(OC(Cl)(Cl)C(C)(C)CBr)OC(Cl)(Cl)C(C)(C)CBr OUWSTQZBWYSZBV-UHFFFAOYSA-N 0.000 claims 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 9
- 239000011347 resin Substances 0.000 abstract description 8
- 229920005989 resin Polymers 0.000 abstract description 8
- 239000003063 flame retardant Substances 0.000 abstract description 7
- 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 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 5
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 abstract description 4
- 229940117389 dichlorobenzene Drugs 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract description 4
- UXCDUFKZSUBXGM-UHFFFAOYSA-N phosphoric tribromide Chemical compound BrP(Br)(Br)=O UXCDUFKZSUBXGM-UHFFFAOYSA-N 0.000 abstract description 4
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 17
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 10
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 235000002639 sodium chloride Nutrition 0.000 description 4
- 229950011008 tetrachloroethylene Drugs 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012433 hydrogen halide Substances 0.000 description 3
- 229910000039 hydrogen halide Inorganic materials 0.000 description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 150000002366 halogen compounds Chemical class 0.000 description 2
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- WVPKAWVFTPWPDB-UHFFFAOYSA-M dichlorophosphinate Chemical compound [O-]P(Cl)(Cl)=O WVPKAWVFTPWPDB-UHFFFAOYSA-M 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- NVTPMUHPCAUGCB-UHFFFAOYSA-L pentyl phosphate Chemical compound CCCCCOP([O-])([O-])=O NVTPMUHPCAUGCB-UHFFFAOYSA-L 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、可燃性材料に難燃性を付与するために用いら
れるトリス（トリハロネオペンチル）ホスフェートの製
造方法に関する。７特に、高純度であり、溶融時に着色
しにくいトリス（トリハロネオペンチル）ホスフェート
を、安全に、かつ生産効率よ（製造し得る方法に関する
。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing tris (trihaloneopentyl) phosphate, which is used to impart flame retardancy to combustible materials. In particular, the present invention relates to a method for safely and efficiently producing tris (trihaloneopentyl) phosphate, which has high purity and is resistant to coloration when melted.
（従来の技術）
電気製品、自動車用内装品、繊維製品などに用いられる
樹脂材料は、可燃性であり、これらを難燃化する方法お
して、ハロゲン化合物を難燃剤として使用し、これを樹
脂組成物に添加する方法が知られている。しかし、一般
にハロゲン化合物は紫外線および可視光線に対して不安
定であり、最終製品の変色の原因となる。(Prior art) Resin materials used in electrical products, automobile interior parts, textile products, etc. are flammable, and the method of making them flame retardant is to use halogen compounds as flame retardants and add them to the resin composition. There are known methods of adding it to foods. However, halogen compounds are generally unstable to ultraviolet and visible light, causing discoloration of the final product.
ハロゲン含有化合物のなかで、トリス（トリハロネオペ
ンチル）ホスフェートを使用することが比較的有利であ
ることが知られている。このトリス（トリハロネオペン
チル）ホスフェートは、紫外線および可視光線に対して
安定であり製品の変色が少ない。さらに、この化合物は
樹脂材料の可塑性を増加させるため、加工性および衝撃
強度を改善する効果もある。Among halogen-containing compounds, it is known to be relatively advantageous to use tris(trihaloneopentyl) phosphate. This tris (trihaloneopentyl) phosphate is stable against ultraviolet and visible light and causes little discoloration of the product. Furthermore, since this compound increases the plasticity of the resin material, it also has the effect of improving processability and impact strength.
このように難燃剤として有用なトリス（トリハロネオペ
ンチル）ホスフェートは、一般にトリハロネオペンチル
アルコールと、オキシ塩化リンあるいはオキシ臭化リン
などのオキシハロゲン化リンとの反応によって得られる
。Tris(trihaloneopentyl) phosphate, which is thus useful as a flame retardant, is generally obtained by reacting trihaloneopentyl alcohol with a phosphorus oxyhalide such as phosphorus oxychloride or phosphorus oxybromide.
例えば、特公昭４５−３６８９４号公報には、テトラク
ロロエチレンを溶剤として上記の反応を行い、この反応
によって生成するハロゲン化水素を、ピリジンを捕捉剤
として除去する方法が開示されている。この反応におい
ては、反応混合物を冷却水に流し込み、トリス（トリハ
ロネオペンチル）ホスフェートの結晶を析出させて回収
している。この方法ではハロゲン化水素捕捉剤として使
用するピリジンが高価であり、さらに、生成するピリジ
ン塩を除去するために、多量の水で洗浄する必要があり
、生産効率が低い。For example, Japanese Patent Publication No. 45-36894 discloses a method in which the above reaction is carried out using tetrachlorethylene as a solvent, and hydrogen halide produced by this reaction is removed using pyridine as a scavenger. In this reaction, the reaction mixture is poured into cooling water to precipitate and collect tris(trihaloneopentyl)phosphate crystals. In this method, pyridine used as a hydrogen halide scavenger is expensive, and furthermore, it is necessary to wash with a large amount of water to remove the generated pyridine salt, resulting in low production efficiency.
特公昭４６−６８６５号公報では、触媒として塩化アル
ミニウムを、溶剤としてクロロベンゼンを用いている。Japanese Patent Publication No. 46-6865 uses aluminum chloride as a catalyst and chlorobenzene as a solvent.
特開昭６２−１８７４７δ号公報には、溶剤としてテト
ラクロロエチレンなどの、ハロゲン化水素に対して実質
的に不活性な溶剤を用い、必要に応じて生成したスラリ
ー状の反応液を塩酸水で洗浄する方法が開示されている
。しかし、反応液を冷却して結晶を析出させる場合、反
応液の流動性を保つために生成物の３〜５倍の体積の溶
剤を必要とする。したがって反応液の容積が大きくなる
ため大型の反応容器を必要とし、生産性が著しく低下す
る。さらに生成物の純度が低いため、難燃剤として使用
した場合に、樹脂製品が着色する。特開昭６２−１８７
４７８号公報の方法では、触媒などの不純物を除去して
生成物の純度を向上させるために、スラリー状態の反応
液を多量の塩酸水で２〜３回洗浄しているが、このよう
な方法では精製時の溶積が大きくなり、上記と同じ理由
で生産性が低下する。JP-A-62-18747δ discloses that a solvent substantially inert to hydrogen halides, such as tetrachloroethylene, is used as a solvent, and if necessary, a slurry-like reaction solution produced is washed with hydrochloric acid water. A method is disclosed. However, when crystals are precipitated by cooling the reaction solution, a volume of solvent 3 to 5 times the volume of the product is required to maintain the fluidity of the reaction solution. Therefore, the volume of the reaction solution increases, requiring a large reaction container, which significantly reduces productivity. Furthermore, the low purity of the product causes coloring of resin products when used as a flame retardant. Japanese Patent Publication No. 62-187
In the method of Publication No. 478, in order to remove impurities such as the catalyst and improve the purity of the product, the reaction liquid in a slurry state is washed with a large amount of hydrochloric acid water two to three times, but such a method In this case, the elution volume during purification increases, and productivity decreases for the same reason as above.
このように、従来のトリス（トリハロネオペンチル）ホ
スフェートの製造方法は安全性、生成物の純度および生
産性に問題があり、工業的に実施する方法としては不十
分なものである。As described above, the conventional method for producing tris(trihaloneopentyl) phosphate has problems in safety, product purity, and productivity, and is insufficient as a method for industrial implementation.
（発明が解決しようとする課題）
本発明は、上記従来の問題を解決するものであり、その
目的とするところは、安全に、かつ高い生産性で高純度
のトリス（トリハロネオペンチル）ホスフェートを製造
する方法を提供することにある。(Problems to be Solved by the Invention) The present invention solves the above-mentioned conventional problems, and its purpose is to produce highly purified tris (trihaloneopentyl) phosphate safely and with high productivity. The purpose is to provide a manufacturing method.
（課題を解決するための手段および作用）本発明のトリ
ス（トリハロネオペンチル）ホスフェートの製造方法は
、下記の一般式（１）で示されるトリハロネオペンチル
アルコールとオキシハロゲン化リンとを高沸点溶剤に溶
解させ、触媒の存在下に反応させて、下記の一般式（Ｉ
ｆ）で示されるトリス（トリハロネオペンチル）ホスフ
ェートを得る工程を包含し、そのことにより上記目的が
達成される：
Ｈ２Ｘ
上記式（Ｉ）および（ｎ）において、Ｘは、それぞれ独
立して、臭素または塩素である。(Means and Effects for Solving the Problems) The method for producing tris(trihaloneopentyl)phosphate of the present invention comprises combining trihaloneopentyl alcohol represented by the following general formula (1) and phosphorus oxyhalide in a high boiling point solvent. and reacted in the presence of a catalyst to form the following general formula (I
f), whereby the above object is achieved: H2X In the above formulas (I) and (n), X is each independently bromine Or chlorine.
さらに本発明のトリス（トリハロネオペンチル）ホスフ
ェートの製造方法は、前記反応終了後の反応混合液に水
、または中性、アルカリ性あるいは酸性の水溶液を該混
合液に対して０．００１〜１００重量％の盟で添加し、
トリス（トリハロネオペンチル）ホスフェートの結晶を
得る工程を包含し、そのことにより上記目的が達成され
る。Further, in the method for producing tris(trihaloneopentyl) phosphate of the present invention, water or a neutral, alkaline or acidic aqueous solution is added to the reaction mixture in an amount of 0.001 to 100% by weight based on the mixture. Added with the alliance of
The method includes a step of obtaining crystals of tris(trihaloneopentyl)phosphate, thereby achieving the above object.
本発明の方法に用いられるトリハロネオペンチルアルコ
ールとしては、トリブロモネオペンチルアルコール、ト
リクロロネオペンチルアルコール、ジブロモ−クロロネ
オペンチルアルコール、またはプロモージクロロネオペ
ンチルアルコールが用いられる。As the trihaloneopentyl alcohol used in the method of the present invention, tribromoneopentyl alcohol, trichloroneopentyl alcohol, dibromo-chloroneopentyl alcohol, or promo-dichloroneopentyl alcohol is used.
本発明の方法に使用されるオキシハロゲン化リンとして
はオキシ塩化リンまたはオキシ臭化リンが用いられる。As the phosphorus oxyhalide used in the method of the present invention, phosphorus oxychloride or phosphorus oxybromide is used.
これらのオキシハロゲン化リンは、上記トリハロネオペ
ンチルアルコール３モルに対して１モルの割合で使用さ
れる。オキシハロゲン化リンが過剰であると、反応時に
、トリハロネオペンチルホスホロジクロリデート、ビス
（トリハロネオペンチル）ホスホロクロリデートなどの
中間生成物の生成割合が高くなる。オキシハロゲン化リ
ンが過少であると、未反応のトリハロネオペンチルアル
コールが残存し、いずれの場合にも生成物の純度が低い
。These phosphorus oxyhalides are used in a ratio of 1 mole to 3 moles of the trihaloneopentyl alcohol. If the phosphorus oxyhalide is in excess, the rate of intermediate products such as trihaloneopentyl phosphorodichloridate and bis(trihaloneopentyl)phosphorochloridate will increase during the reaction. If the amount of phosphorus oxyhalide is too small, unreacted trihaloneopentyl alcohol will remain, and in either case, the purity of the product will be low.
本発明の方法では、高沸点溶剤としてクロロベンゼン、
ジクロロベンゼン、テトラクロロエチレン、トルエン、
キシレン、イソプロピルベンゼン、ジメチルスルホキシ
ド、ジフェニルエーテルなどが用いられる。好ましくは
、ジクロロベンゼン、特に好ましくは、０−ジクロロベ
ンゼンが使用される。溶剤の使用量は、反応によって生
成し得るトリス（トリハロネオペンチル）ホスフェート
の容量の１０００以上であればよく、好ましくは、トリ
ス（トリハロネオペンチル）ホスフェートの容量に対し
て１．０〜２．０倍である・
本発明の方法に使用される触媒としては、塩化アルミニ
ウム、塩化マグネシウム、四塩化チタン、塩化亜鉛、塩
化スズ、硫酸マグネシウム、マグネシウム、アルミニウ
ムなどがある。これらの化合物を２種以上混合して使用
してもよい。特に塩化アルミニウムが好ましい。使用量
はオキシハロゲン化リンに対して０．１重量％以上、好
ましくは０．５〜２，０重量％の範囲である。In the method of the present invention, chlorobenzene is used as a high boiling point solvent.
dichlorobenzene, tetrachloroethylene, toluene,
Xylene, isopropylbenzene, dimethyl sulfoxide, diphenyl ether, etc. are used. Preference is given to using dichlorobenzene, particularly preferably 0-dichlorobenzene. The amount of the solvent used may be 1000 or more of the capacity of tris(trihaloneopentyl) phosphate that can be produced by the reaction, and preferably 1.0 to 2.0 to the capacity of tris(trihaloneopentyl) phosphate. Catalysts used in the method of the present invention include aluminum chloride, magnesium chloride, titanium tetrachloride, zinc chloride, tin chloride, magnesium sulfate, magnesium, aluminum, and the like. Two or more of these compounds may be used in combination. Particularly preferred is aluminum chloride. The amount used is 0.1% by weight or more, preferably from 0.5 to 2.0% by weight, based on the phosphorus oxyhalide.
本発明の方法においては、好ましくは、反応終了後の反
応液を、水、または中性、アルカリ性あるいは酸性の水
溶液に接触させる。中性水溶液としては、塩化ナトリウ
ム、硫酸ナトリウム、塩化カリウム、硫酸カリウム、塩
化アンモニウム、硫酸アンモニウム等の中性塩の水溶液
が用いられる。In the method of the present invention, the reaction solution after the reaction is preferably brought into contact with water or a neutral, alkaline or acidic aqueous solution. As the neutral aqueous solution, an aqueous solution of a neutral salt such as sodium chloride, sodium sulfate, potassium chloride, potassium sulfate, ammonium chloride, ammonium sulfate, etc. is used.
アルカリ性水溶液としては、水酸化ナトリウム、水酸化
カリウム、炭酸ナトリウム、炭酸カリウム、アンモニア
な・どの水溶液が使用される。酸性水溶液としては、塩
酸、硫酸、酢酸、シコウ酸などの水溶液が用いられる。As the alkaline aqueous solution, an aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia, etc. is used. As the acidic aqueous solution, an aqueous solution of hydrochloric acid, sulfuric acid, acetic acid, sikolic acid, etc. is used.
特に、塩化ナトリウム、炭酸ナトリウム、塩酸の水溶液
が好ましい。そして、これらの水溶液は、１０重量％以
下の濃度であることが好ましい。水または上記水溶液の
使用量は生成し得るトリス（トリハロネオペンチル）ホ
スフェートに対して０．００１−１００重量％以上で、
好ましくは、１〜２０重量％、さらに好ましくは、５〜
１５重量％の範囲である。Particularly preferred are aqueous solutions of sodium chloride, sodium carbonate, and hydrochloric acid. The concentration of these aqueous solutions is preferably 10% by weight or less. The amount of water or the aqueous solution used is 0.001-100% by weight or more based on the tris(trihaloneopentyl) phosphate that can be produced,
Preferably 1 to 20% by weight, more preferably 5 to 20% by weight
It is in the range of 15% by weight.
本発明の方法では、以下のようにして、トリス（トリハ
ロネオペンチル）ホスフェートが製造される。まず、上
記トリハロネオペンチルアルコール、オキシハロゲン化
リンおよび触媒を高沸点溶剤に溶解させる。あるいは、
トリハロネオペンチルアルコールを高沸点溶剤に溶解さ
せ、その混合物に、触媒をオキシハロゲン化リンに溶解
させたものを添加してもよい。得られた混合物を室温か
ら溶剤の沸点以下の温度で還流して反応を行う。In the method of the present invention, tris(trihaloneopentyl) phosphate is produced as follows. First, the trihaloneopentyl alcohol, phosphorus oxyhalide, and catalyst are dissolved in a high boiling point solvent. or,
The trihaloneopentyl alcohol may be dissolved in a high boiling point solvent and a catalyst dissolved in phosphorous oxyhalide may be added to the mixture. The resulting mixture is refluxed at a temperature ranging from room temperature to the boiling point of the solvent to carry out the reaction.
反応温度が低いと生成したトリス（トリハロネオペンチ
ル）ホスフェートが、結晶として析出するので、できる
限り高い温度で反応を実施することが好ましい。例えば
、溶剤として０−ジクロロベンゼンを使用する場合は、
０−ジクロロベンゼンの沸点が１８０℃であるので１０
０−１８０℃の温度で反応を行うことが好ましい。反応
終了後、反応系に溶解しているハロゲン化水素を除去し
て反応を完結させるために、反応系内を減圧してもよい
。If the reaction temperature is low, the tris(trihaloneopentyl) phosphate produced will precipitate as crystals, so it is preferable to carry out the reaction at as high a temperature as possible. For example, when using 0-dichlorobenzene as a solvent,
Since the boiling point of 0-dichlorobenzene is 180℃, 10
Preferably, the reaction is carried out at a temperature of 0-180°C. After the reaction is completed, the pressure inside the reaction system may be reduced in order to remove the hydrogen halide dissolved in the reaction system and complete the reaction.
このようにして得られた反応混合液に、水、または上記
中性、アルカリ性あるいは酸性の水溶液を接触させる。The reaction mixture thus obtained is brought into contact with water or the above-mentioned neutral, alkaline or acidic aqueous solution.
接触時の温度は、室温からジクロロベンゼンの沸点以下
の、生成物の結晶が析出しない温度が使用され得る。し
かし、接触温度が１００°Ｃを大きく上回ると、水蒸気
による事故が発生する可能性があるので、好ましくは、
８０〜１２０℃で接触を行う。接触時間は特に制限しな
いが、５〜３０分が好ましい。接触した混合液は、その
まま冷却して結晶を析出させ固体成分を濾過などの方法
で分離するか、あるいは接触後−旦装置して、水層を取
り除いてから、結晶を析出させて固体成分を分離しても
よい。得られた結晶は、そのまま乾燥して用いるか、あ
るいは、水、メタノール、エタノールなどのトリス（ト
リハロネオペンチル）ホスフェートを溶解しない溶剤で
洗浄した後乾燥して用いる。The temperature during contact may be from room temperature to below the boiling point of dichlorobenzene, at which crystals of the product do not precipitate. However, if the contact temperature greatly exceeds 100°C, accidents due to water vapor may occur, so preferably,
Contacting is carried out at 80-120°C. The contact time is not particularly limited, but is preferably 5 to 30 minutes. The contacted mixture can be cooled as it is to precipitate crystals and the solid component can be separated by a method such as filtration, or alternatively, after the contact, it can be placed in an apparatus to remove the aqueous layer, and then the crystals can be precipitated and the solid component can be separated. May be separated. The obtained crystals are used after being dried as they are, or after being washed with a solvent that does not dissolve tris (trihaloneopentyl) phosphate, such as water, methanol, or ethanol, and then dried.
本発明の方法によれば、溶剤として高沸点溶剤を用いて
いるため、反応温度を高くすることができ、溶剤が少量
であっても、生成物が析出することがなく安全に反応を
行うことが可能である。さらに本発明の方法では、反応
後の反応液を、水、または中性、アルカリ性あるいは酸
性の水溶液に接触させることにより、反応液の流動性が
著しく向上する。したがって、接触後冷却して結晶を析
出させる場合に、結晶が触媒などの不純物を取り込むこ
とがなく、高純度の結晶が得られる。例えば、得られる
トリス（トリハロネオペンチル）ホスフェートは、９５
％以上の収率で９９．５％以上の高純度である。さらに
溶剤の使用量も従来の方法に比べて１／２〜１１５に減
少させることができる。そして、本発明の方法では、上
記のように、溶媒の使用量が大幅に低減されるため、生
産性が向上する。According to the method of the present invention, since a high boiling point solvent is used as the solvent, the reaction temperature can be raised, and even if the amount of solvent is small, the reaction can be carried out safely without precipitation of the product. is possible. Further, in the method of the present invention, the fluidity of the reaction liquid is significantly improved by contacting the reaction liquid after the reaction with water or a neutral, alkaline or acidic aqueous solution. Therefore, when the crystals are precipitated by cooling after contact, the crystals do not take in impurities such as the catalyst, and highly pure crystals can be obtained. For example, the tris(trihaloneopentyl) phosphate obtained is 95
It has a high purity of 99.5% or more with a yield of 99.5% or more. Furthermore, the amount of solvent used can be reduced to 1/2 to 115 times compared to conventional methods. In addition, in the method of the present invention, as described above, the amount of solvent used is significantly reduced, so that productivity is improved.
例えば、下記式で表される容積効率は、従来の方法に比
べて２〜３倍になる。For example, the volumetric efficiency expressed by the following formula is 2 to 3 times that of the conventional method.
ここで、反応容器の容量はＩＩＬを１０００ｇとして計
算した。Here, the capacity of the reaction vessel was calculated with IIL being 1000 g.
本発明の方法では、上記の容積効率は７０％以上であり
、特開昭６２−１８７４７８号公報の方法を用いた場合
は、２９．４％であった。In the method of the present invention, the above-mentioned volumetric efficiency was 70% or more, and when the method of JP-A-62-187478 was used, it was 29.4%.
このように本発明の方法によれば、安全に、かつ高い生
産性で高純度のトリス（トリノ〜ロネオベンチル）ホス
フェートを製造することができる。As described above, according to the method of the present invention, highly purified tris(trino-roneobentyl) phosphate can be produced safely and with high productivity.
そしてこのような高純度のトリス（トリノ〜ロネオベン
チル）ホスフェートを、樹脂材料に添加することによっ
て、樹脂材料などの可燃性材料に優れた耐熱性を付与す
ることができる。さらにトリス（トリハロネオペンチル
）ホスフェートが高純度であるため、溶融時の着色が少
なく、樹脂材料の色を損なうことがなく、難燃剤として
好適に使用される。By adding such high-purity tris (trino-roneobentyl) phosphate to a resin material, excellent heat resistance can be imparted to a combustible material such as a resin material. Furthermore, since tris (trihaloneopentyl) phosphate is highly pure, it exhibits little coloration when melted and does not impair the color of the resin material, making it suitable for use as a flame retardant.
（実施例）
以下に本発明の実施例について述べるが、本発明はこれ
らの実施例に限定されるものではない。(Examples) Examples of the present invention will be described below, but the present invention is not limited to these Examples.
１皿皿上
ＩＡの４つロフラスコに攪拌機、温度計、滴下ロート、
および水スクラバーを連結したコンデンサーを取り付け
、このフラスコに、７６２ｇのトリブロモネオペンチル
アルコール、１０７５ｇのＯ−ジクロロベンゼンおよび
１．２ｇの塩化アルミニウムを入れ、加熱、混合した。A stirrer, a thermometer, a dropping funnel,
A condenser connected to a water scrubber was attached, and 762 g of tribromoneopentyl alcohol, 1075 g of O-dichlorobenzene and 1.2 g of aluminum chloride were placed in the flask and heated and mixed.
反応液の温度が１００℃に達した時点で、オキシ塩化リ
ン１２０ｇを約３０分間に渡って添加した。このとき発
生した塩酸ガスを水スクラノイーへ導いた。オキシ塩化
リンの添加が終了した後、反応液の温度を徐々に１６０
℃まで上昇させて反応を完結させた。次いで反応液を８
５℃まで冷却し、５０ｇの水を添加し、この混合液を約
１５分間８５℃で攪拌接触した後、室温まで冷却して結
晶を析出させた。When the temperature of the reaction solution reached 100° C., 120 g of phosphorus oxychloride was added over about 30 minutes. The hydrochloric acid gas generated at this time was introduced into the water skranoy. After the addition of phosphorus oxychloride is completed, the temperature of the reaction solution is gradually increased to 160℃.
The reaction was completed by increasing the temperature to ℃. Then, the reaction solution was
The mixture was cooled to 5° C., 50 g of water was added, the mixture was stirred and contacted at 85° C. for about 15 minutes, and then cooled to room temperature to precipitate crystals.
析出した結晶を濾過により分離し、メタノール３００ｇ
で洗浄した後１００°Ｃにて減圧乾燥した。得られた結
晶は、白色の針状結晶であり、収量は７７３ｇ、収率は
９７％であった。液体クロマトグラフィーで分析したと
ころ、得られた結晶は純度９９．８％のトリス（トリブ
ロモネオペンチル）ホスフェートであった。そして融点
は１８１〜１８２℃であった。得られた結晶の収量、収
率、純度、融点、溶融時の色、および容積効率を下表に
示す。後述の実施例２〜５、および比較例１〜２で得ら
れた生成物についての結果も同時に下表に示す。Separate the precipitated crystals by filtration and add 300 g of methanol.
After washing with water, it was dried under reduced pressure at 100°C. The obtained crystals were white needle-shaped crystals, and the yield was 773 g, 97%. Analysis by liquid chromatography revealed that the obtained crystals were tris (tribromoneopentyl) phosphate with a purity of 99.8%. And the melting point was 181-182°C. The yield, yield, purity, melting point, color upon melting, and volumetric efficiency of the obtained crystals are shown in the table below. The results for the products obtained in Examples 2 to 5 and Comparative Examples 1 to 2, which will be described later, are also shown in the table below.
爽五皿ユ
０−ジクロロベンゼンに代えてテトラクロロエチレンを
用い、反応終了後反応液に、水に代えて１％塩化ナトリ
ウム水溶液を添加したこと以外は、実施例１と同様にし
てトリス（トリブロモネオペンチル）ホスフェートの白
色の結晶を得た。Tris (tribromone) was prepared in the same manner as in Example 1, except that tetrachloroethylene was used instead of O-dichlorobenzene, and after the reaction, a 1% aqueous sodium chloride solution was added to the reaction solution instead of water. White crystals of pentyl phosphate were obtained.
爽血五ユ
反応終了後反応液に、水に代えて１％炭酸ナトリウム水
溶液を添加したこと以外は、実施例１と同様にしてトリ
ス（トリブロモネオペンチル）ホスフェートの白色の結
晶を得た。White crystals of tris (tribromoneopentyl) phosphate were obtained in the same manner as in Example 1, except that 1% aqueous sodium carbonate solution was added to the reaction solution instead of water after the completion of the reaction.
夾血皿土
０−ジクロロベンゼンに代工てクロロヘ：／ セ：、ｔ
ｙｇ−用い、反応終了後反応液に、水に代えて１％塩
酸を添加したこと以外は、実施例１と同様にしてトリス
（トリブロモネオペンチル）ホスフェートの白色の結晶
を得た。Substituting 0-dichlorobenzene for chlorobenzene:/Se:,t
White crystals of tris (tribromoneopentyl) phosphate were obtained in the same manner as in Example 1, except that 1% hydrochloric acid was added to the reaction solution instead of water after the reaction was completed.
１皿匹旦
トリブロモネオペンチルアルコール７６２ｇに代工てト
リクロロネオペンチルアルコール７４３ｇヲ、オキシ塩
化リン１２０ｇの代えてオキシ臭化リン３７１ｇを、Ｍ
［として塩化アルミニウム１．２ｇに代えて塩化マグネ
シウム２ｇを用いたこと以外は、実施例１と同様にして
トリス（トリクロロネオペンチル）ホスフェートの白色
の結晶を得た。得られた結晶の融点は１５７〜１５８℃
であった
友Δ匠上
３Ｌの４つロフラスコに攪拌機、温度計、滴下ロート、
および水スクラバーを連結したコンデンサーを取り付け
、このフラスコに、７６２ｇのトリブロモネオペンチル
アルコール、１０７５ｇのクロロベンゼンおよび１．２
ｇの塩化アルミニウムを入れ、加熱、混合した。反応液
の温度が１００℃に達した時点で、オキシ塩化リン１２
０ｇを約３０分間に渡って添加した。For each dish, replace 762 g of tribromoneopentyl alcohol with 743 g of trichloroneopentyl alcohol, replace 120 g of phosphorus oxychloride with 371 g of phosphorus oxybromide,
White crystals of tris (trichloroneopentyl) phosphate were obtained in the same manner as in Example 1, except that 2 g of magnesium chloride was used in place of 1.2 g of aluminum chloride. The melting point of the obtained crystals is 157-158℃
My friend ΔTakumi had a 3L four-loaf flask with a stirrer, a thermometer, a dropping funnel,
and a condenser connected to a water scrubber, the flask was charged with 762 g of tribromoneopentyl alcohol, 1075 g of chlorobenzene and 1.2
g of aluminum chloride was added, heated and mixed. When the temperature of the reaction solution reached 100°C, phosphorus oxychloride 12
0g was added over approximately 30 minutes.
このとき、発生した塩酸ガスを水スクラバーへ導いた。At this time, the generated hydrochloric acid gas was led to a water scrubber.
オキシ塩化リンの添加が終了した後、反応液の温度を徐
々に１３０℃まで上昇させて反応を完結させた。次いで
反応液を８５℃まで冷却し、追加溶媒として２５００ｇ
のクロロベンゼンを添加した後、室温まで冷却して結晶
を析出させた。析出した結晶を濾過により分離し、メタ
ノール３００ｇで洗浄した後１００℃にて減圧乾燥した
。得られた結晶は、白色の針状結晶であり、トリス（ト
リブロモネオペンチル）ホスフェートの収率は９２％、
結晶の純度は９６％であった。そして融点は１７９〜１
８０℃であった。After the addition of phosphorus oxychloride was completed, the temperature of the reaction solution was gradually raised to 130° C. to complete the reaction. The reaction solution was then cooled to 85°C, and 2500 g of additional solvent was added.
After adding chlorobenzene, the mixture was cooled to room temperature to precipitate crystals. The precipitated crystals were separated by filtration, washed with 300 g of methanol, and then dried under reduced pressure at 100°C. The obtained crystals were white needle-like crystals, and the yield of tris (tribromoneopentyl) phosphate was 92%.
The purity of the crystals was 96%. And the melting point is 179-1
The temperature was 80°C.
友Δ匹主
トリブロモネオペンチルアルコール７６２ｇに代えでト
リクロロネオペンチルアルコール７４３ｇを用い、触媒
として塩化アルミニウムに代えて塩化マグネシウム２ｇ
を用い、反応温度を１２５℃とし、反応溶剤および追加
溶剤として０−ジクロロベンゼンを用いたこと以外は、
比較例１と同様にして、トリス（トリクロロネオペンチ
ル）ホスフェートの結晶を得た。743 g of trichloroneopentyl alcohol was used instead of 762 g of tribromoneopentyl alcohol, and 2 g of magnesium chloride was used instead of aluminum chloride as a catalyst.
except that the reaction temperature was 125 °C and 0-dichlorobenzene was used as the reaction solvent and additional solvent.
Crystals of tris(trichloroneopentyl)phosphate were obtained in the same manner as in Comparative Example 1.
（以下余白）
（発明の効果）
このように本発明によれば、トリハロネオペンチルアル
コールとオキシハロゲン化リンとの反応の完結度が良好
であり、高収率でトリス（トリハロネオペンチル）ホス
フェートを得ることが可能である。かつ、反応終了後の
反応液に過剰の溶剤を添加する必要がないため容積効率
が高く、著しく生産性を向上させることができる。本発
明の方法は、溶剤として高沸点溶剤を用いているため、
反応温度を高く設定することが可能であり、反応中に生
成物の結晶が析出して突沸現象を起こすことがなく安全
に作業を行うことができる。さらに本発明の方法によっ
て得られるトリス（トリハロネオペンチル）ホスフェー
トは高純度であり、溶融時の着色が少なく樹脂材料の難
燃剤として好適に使用される。(The following is a blank space) (Effects of the Invention) As described above, according to the present invention, the reaction between trihaloneopentyl alcohol and phosphorus oxyhalide has a good degree of completion, and tris(trihaloneopentyl) phosphate can be produced in high yield. It is possible to obtain. In addition, since there is no need to add an excessive amount of solvent to the reaction solution after the reaction is completed, volumetric efficiency is high and productivity can be significantly improved. Since the method of the present invention uses a high boiling point solvent as a solvent,
It is possible to set the reaction temperature high, and the work can be carried out safely without crystals of the product precipitating during the reaction and causing a bumping phenomenon. Further, the tris(trihaloneopentyl) phosphate obtained by the method of the present invention has high purity, exhibits little coloring when melted, and is suitably used as a flame retardant for resin materials.
以上that's all
Claims (1)
チルアルコールとオキシハロゲン化リンとを高沸点溶剤
に溶解させ、触媒の存在下に反応させて、下記の一般式
（II）で示されるトリス（トリハロネオペンチル）ホス
フェートを得る工程を包含する、 トリス（トリハロネオペンチル）ホスフェートの製造方
法： ▲数式、化学式、表等があります▼（ I ） ▲数式、化学式、表等があります▼（II） 上記式（ I ）および（II）において、Ｘは、それぞれ
独立して、臭素または塩素である。 ２、前記反応終了後の反応混合液に水、または中性、ア
ルカリ性あるいは酸性の水溶液を該混合液に対して０．
００１〜１００重量％の量で添加し、トリス（トリハロ
ネオペンチル）ホスフェートの結晶を得る工程を包含す
る、 請求項１に記載のトリス（トリハロネオペンチル）ホス
フェートの製造方法。 ３、前記トリハロネオペンチルアルコールが、トリブロ
モネオペンチルアルコール、トリクロロネオペンチルア
ルコール、ジブロモ−クロロネオペンチルアルコール、
およびブロモ−ジクロロネオペンチルアルコールでなる
群からから選択される少なくとも１種である、請求項１
に記載のトリス（トリハロネオペンチル）ホスフェート
の製造方法。 ４、前記トリス（トリハロネオペンチル）ホスフェート
が、トリス（トリブロモネオペンチル）ホスフェート、
トリス（トリクロロネオペンチル）ホスフェート、トリ
ス（ジブロモクロロネオペンチル）ホスフェート、およ
びトリス（ブロモジクロロネオペンチル）ホスフェート
でなる群から選択される少なくとも１種である、請求項
１に記載のトリス（トリハロネオペンチル）ホスフェー
トの製造方法。[Claims] 1. Trihaloneopentyl alcohol represented by the following general formula (I) and phosphorus oxyhalide are dissolved in a high boiling point solvent and reacted in the presence of a catalyst to obtain the following general formula (I). A method for producing tris(trihaloneopentyl) phosphate, which includes the process of obtaining tris(trihaloneopentyl)phosphate represented by II): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲Mathematical formulas, chemical formulas, tables, etc. ▼(II) In the above formulas (I) and (II), X is each independently bromine or chlorine. 2. Add water or a neutral, alkaline, or acidic aqueous solution to the reaction mixture after the completion of the reaction at a ratio of 0.0% to the mixture.
The method for producing tris(trihaloneopentyl) phosphate according to claim 1, comprising the step of adding the tris(trihaloneopentyl) phosphate in an amount of 001 to 100% by weight to obtain crystals of tris(trihaloneopentyl)phosphate. 3. The trihaloneopentyl alcohol is tribromoneopentyl alcohol, trichlorneopentyl alcohol, dibromo-chloroneopentyl alcohol,
and bromo-dichloroneopentyl alcohol.
A method for producing tris (trihaloneopentyl) phosphate as described in . 4. The tris (trihaloneopentyl) phosphate is tris (tribromoneopentyl) phosphate,
The tris(trihaloneopentyl) according to claim 1, which is at least one selected from the group consisting of tris(trichloroneopentyl) phosphate, tris(dibromochloroneopentyl) phosphate, and tris(bromodichloroneopentyl) phosphate. ) Method for producing phosphate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1333466A JPH0768258B2 (en) | 1989-12-22 | 1989-12-22 | Method for producing tris (trihaloneopentyl) phosphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1333466A JPH0768258B2 (en) | 1989-12-22 | 1989-12-22 | Method for producing tris (trihaloneopentyl) phosphate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03193793A true JPH03193793A (en) | 1991-08-23 |
| JPH0768258B2 JPH0768258B2 (en) | 1995-07-26 |
Family
ID=18266394
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1333466A Expired - Fee Related JPH0768258B2 (en) | 1989-12-22 | 1989-12-22 | Method for producing tris (trihaloneopentyl) phosphate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0768258B2 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5393812A (en) * | 1993-08-31 | 1995-02-28 | Hercules Incorporated | Flame retardant, light stable composition |
| US5710309A (en) * | 1995-06-08 | 1998-01-20 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Process for producing tris (tribromoneopentyl) phosphate |
| WO2000006584A1 (en) * | 1998-07-27 | 2000-02-10 | Daihachi Chemical Industry Co., Ltd. | Process for producing halogen-containing phosphate ester |
| US6204404B1 (en) | 1997-06-06 | 2001-03-20 | Daihachi Chemical Industry Co., Ltd. | Process for preparing ester compounds |
| JP2011190371A (en) * | 2010-03-15 | 2011-09-29 | Asahi Kasei Chemicals Corp | Resin composition |
| CN104672278A (en) * | 2015-03-24 | 2015-06-03 | 宜兴市中正化工有限公司 | Method for synthesizing tri(tribromoneopentyl alcohol) phosphate |
| JP2016069479A (en) * | 2014-09-29 | 2016-05-09 | 出光ライオンコンポジット株式会社 | Polyolefin-based flame-retardant resin composition |
| CN105646571B (en) * | 2016-01-26 | 2018-11-06 | 寿光市泰源化工有限公司 | It is a kind of to be easy to the three of industrialized production（Tribromoneoamyl alcohol base）Phosphate synthesis method |
| CN112778356A (en) * | 2020-12-26 | 2021-05-11 | 山东日兴新材料股份有限公司 | One-pot synthesis process of tri (tribromoneopentyl) phosphate flame retardant |
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| CA802242A (en) * | 1968-12-24 | The Dow Chemical Company | Brominated pentaerythritol phosphates | |
| GB1146173A (en) * | 1966-06-18 | 1969-03-19 | Geigy Uk Ltd | Production of triaryl phosphates |
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| US4897502A (en) * | 1987-02-09 | 1990-01-30 | Fmc Corporation | Process for making solid polyhalotriaryl phosphate esters |
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA802242A (en) * | 1968-12-24 | The Dow Chemical Company | Brominated pentaerythritol phosphates | |
| GB1146173A (en) * | 1966-06-18 | 1969-03-19 | Geigy Uk Ltd | Production of triaryl phosphates |
| JPS5110236A (en) * | 1974-07-12 | 1976-01-27 | Mitsubishi Motors Corp | Enjinno hijoteishisochi |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5393812A (en) * | 1993-08-31 | 1995-02-28 | Hercules Incorporated | Flame retardant, light stable composition |
| US5710309A (en) * | 1995-06-08 | 1998-01-20 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Process for producing tris (tribromoneopentyl) phosphate |
| US6204404B1 (en) | 1997-06-06 | 2001-03-20 | Daihachi Chemical Industry Co., Ltd. | Process for preparing ester compounds |
| WO2000006584A1 (en) * | 1998-07-27 | 2000-02-10 | Daihachi Chemical Industry Co., Ltd. | Process for producing halogen-containing phosphate ester |
| US6211396B1 (en) | 1998-07-27 | 2001-04-03 | Daihachi Chemical Industry Co., Ltd. | Process for producing halogen-containing phosphate ester |
| JP2011190371A (en) * | 2010-03-15 | 2011-09-29 | Asahi Kasei Chemicals Corp | Resin composition |
| JP2016069479A (en) * | 2014-09-29 | 2016-05-09 | 出光ライオンコンポジット株式会社 | Polyolefin-based flame-retardant resin composition |
| CN104672278A (en) * | 2015-03-24 | 2015-06-03 | 宜兴市中正化工有限公司 | Method for synthesizing tri(tribromoneopentyl alcohol) phosphate |
| CN105646571B (en) * | 2016-01-26 | 2018-11-06 | 寿光市泰源化工有限公司 | It is a kind of to be easy to the three of industrialized production（Tribromoneoamyl alcohol base）Phosphate synthesis method |
| CN112778356A (en) * | 2020-12-26 | 2021-05-11 | 山东日兴新材料股份有限公司 | One-pot synthesis process of tri (tribromoneopentyl) phosphate flame retardant |
| CN112778356B (en) * | 2020-12-26 | 2022-07-01 | 山东日兴新材料股份有限公司 | One-pot synthesis process of tri (tribromoneopentyl) phosphate flame retardant |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0768258B2 (en) | 1995-07-26 |
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