EP2205614A1 - Procédé pour la production continue d'un composé organophosphoré et utilisation de ce composé - Google Patents

Procédé pour la production continue d'un composé organophosphoré et utilisation de ce composé

Info

Publication number
EP2205614A1
EP2205614A1 EP08840907A EP08840907A EP2205614A1 EP 2205614 A1 EP2205614 A1 EP 2205614A1 EP 08840907 A EP08840907 A EP 08840907A EP 08840907 A EP08840907 A EP 08840907A EP 2205614 A1 EP2205614 A1 EP 2205614A1
Authority
EP
European Patent Office
Prior art keywords
stage
general formula
catalyst
hydrolysis
phenylphenol
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.)
Withdrawn
Application number
EP08840907A
Other languages
German (de)
English (en)
Inventor
Andreas Kaplan
René Gisler
Christopher Kohl
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EMS Patent AG
Original Assignee
EMS Patent AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by EMS Patent AG filed Critical EMS Patent AG
Priority to EP08840907A priority Critical patent/EP2205614A1/fr
Publication of EP2205614A1 publication Critical patent/EP2205614A1/fr
Withdrawn legal-status Critical Current

Links

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
    • C07F9/6571—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 oxygen atoms as the only ring hetero atoms
    • C07F9/657163—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 oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
    • C07F9/65719—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 oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and, at least, one ring oxygen atom being part of a (thio)phosphonous acid derivative

Definitions

  • Organophosphorus compounds in particular 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) or their derivatives have been known in the prior art for many years and are preferably used as additives for polymers.
  • DOPO and its derivatives as flame retardants for polymers, e.g. Polyester, polyamides, epoxy resins, has proven to be advantageous.
  • JP 5017979 describes a process for the preparation of DOPO and its use as an additive in polymers. Furthermore, in JP 59-222496 from 1984 a method for the production of DOPO is known and its use as a flame retardant.
  • DOPO or its derivatives as an additive, in particular as a halogen-free flame retardant for polymers, there is a Great interest in a procedurally simple, economical and safe manufacturing process for DOPO and its derivatives. Difficulties in the production of DOPO cause phosphorus-containing by-products such as phosphorous acid, phosphines, too
  • Discontinuous production processes known as batch production processes for DOPO, have hitherto been known in the prior art. Such a batch process is e.g. described in JP 5017979.
  • the object of the present invention to provide a new continuous production process of DOPO and its derivatives.
  • the continuous production process is intended to enable a simple and safe procedure and to deliver products of constant quality, high purity and high yield.
  • Step 3 Hydrolysis of the product from Step 2.
  • yi and y 2 which may be the same or different, may be hydrogen or halogen atoms, alkyl groups having Ci to Ci 8 , alkoxy groups having Ci to Ci 8 , aryl groups, aryloxy groups, acyl groups, nitro groups or cyano groups, wherein the
  • Step 2 cyclization of the intermediate from Step 1 in the presence of a catalyst and recycling of unreacted phosphorus trihalide,
  • Step 3 Hydrolysis of the distillate from Step 2 to the intermediate of the general formula (II)
  • Stage 3.1 Discharge of the intermediate of general formula (II) in the form of dandruff, and
  • Step 4 Drying and Cyclization of Intermediate (II) to the End Product of General Formula (I)
  • the reaction temperature is preferably from 25 to 180 ° C., more preferably from 25 to 85 ° C.
  • the catalyst is used in an amount of 0.01 to 0.06 mol, preferably 0.02 to 0.04 mol based on 1 mol of o-phenylphenol or 3-60 wt .-%, preferably 10-40 % By weight, more preferably 15-20 Wt .-% based on o-phenylphenol, used.
  • ionic liquids or ion exchangers can be used as the catalyst. These show a high selectivity, lead to a strong reduction of the reaction time and are easily separable at the end of the 1st stage. The separated catalyst remains in stage 1 or is returned to stage 1.
  • Tetrachloroferrate (III) Tetrachloroferrate (III), hexafluorophosphate, hexafluoroonantimonate, trifluoromethanesulfate, alkylsulfonate, benzenesulfonate or bis (trifluoromethylsulfonyl) imide, with chloride being preferred.
  • Preferred ionic liquids are l-butyl-3- methylimidazolium chloride (m.p. about 70 0 C), 1-decyl-3-methylimidazolium chloride (liquid at 20 0 C), l-ethyl-3-methylimidazolium chloride (m.p.
  • the ion exchangers can be used in the form of solid particles, solid membranes, papers or layers. These are anion exchangers or chelate resins whose matrix is e.g. from phenol-formaldehyde condensates, copolymers of styrene and divinylbenzene, copolymers of methacrylates and di-vinylbenzene, cellulose, crosslinked dextran or crosslinked agarose.
  • the functional groups fixed to the matrix are e.g.
  • Halide ions are preferably used as counterions in the anion exchangers.
  • Type I ion exchangers are used which are macroporous and strongly basic, have halide ions as the counterion and in which the support is a copolymer of styrene and divinylbenzene. Chloride is particularly preferably used as the halide ion.
  • Ion exchangers especially anion exchangers or chelate resins, are preferably used as catalysts over ionic liquids.
  • the cyclization can be made smaller and thus less expensive since the monoester (e.g., DOPCl) has fewer by-products after the 1st stage (e.g., diesters, triesters, o-phenylphenol).
  • the monoester e.g., DOPCl
  • the 1st stage e.g., diesters, triesters, o-phenylphenol.
  • the aforementioned by-products must therefore not be converted over a longer reaction time in the cyclization in DOPCl, which is incomplete and therefore also unsatisfactory.
  • the lower phase is the molten product in the open form of general formula (II) and the upper, aqueous phase contains the split-off HX.
  • the hydrolysis can be carried out with or without an additional inert, aromatic solvent.
  • the content of ortho-phenylphenol is at most 0.5 wt .-%, preferably at most 0.3 wt .-%, more preferably at most 0.1 wt .-%.
  • Buffer containers may be installed between the individual stages of the production process according to the invention in order to temporarily store the intermediates of the individual process stages under inert gas until they are introduced into the following stage.
  • the advantage is that due to the continuous operation, smaller quantities of material are in the system and thus smaller mass flows have to be mastered. This makes it possible to respond to disruptions faster and also the risk of "going through” the reaction is minimized.
  • the invention furthermore relates to an organophosphorus compound of the formula I in which the radicals indicated in formula I are those indicated above
  • the ion exchange resins used for the esterification were dried before starting the reaction in a convection oven at 110 0 C to constant weight.
  • the HCl gas escaping at the top was passed through an intensive condenser and freed of entrained phosphorus trichloride, which was returned to the column.
  • the product obtained is of high purity, which is reflected in a mono / diester ratio of 18: 1 and the absence of triester.
  • the space-time yield of about 0.37 kg / h and reaction space can be further increased.
  • esterification product which was obtained analogously to Example 9, was added 0.4 g (2.9 mmol) of anhydrous zinc chloride in a boiling flask equipped with stirrer, thermometer and dropping funnel with ball cooler mounted under nitrogen atmosphere and heated to reflux temperature. After reaching the reflux temperature, the tap of the dropping funnel was adjusted so that a constant reaction temperature of 170 0 C was maintained by phosphorus trichloride reflux. The HCl gas formed during the cyclization was passed overhead in a neutralization solution using a continuous stream of nitrogen. The course of the reaction was monitored by gas chromatography and by back-titration of the neutralization solution. After 180 minutes, the reaction was complete and HCl evolution ceased. The tap of the dropping funnel was closed and the remaining phophortrichloride distilled off before the reaction mixture was cooled and analyzed by gas chromatography. The Product was orange and had a content of DOPCl of 88.2%.

Landscapes

  • 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)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne la production de composés organophosphorés, en particulier de 9,10-dihydro-9-oxa-10-phosphaphénanthrène-10-oxyde (DOPO), ou de leurs dérivés qui, dans l'état de la technique, sont connus depuis de nombreuses années. Ces composés sont utilisés de préférence comme additifs pour des polymères. L'utilisation de DOPO et de ses dérivés en tant qu'agents ignifuges pour des polymères, tels que les polyesters, les polyamides et les résines époxy, s'est révélée particulièrement avantageuse.
EP08840907A 2007-10-26 2008-10-16 Procédé pour la production continue d'un composé organophosphoré et utilisation de ce composé Withdrawn EP2205614A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08840907A EP2205614A1 (fr) 2007-10-26 2008-10-16 Procédé pour la production continue d'un composé organophosphoré et utilisation de ce composé

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP07021015A EP2053053A1 (fr) 2007-10-26 2007-10-26 Procédé de fabrication continue d'une liaison de phosphore organique et son utilisation
EP08840907A EP2205614A1 (fr) 2007-10-26 2008-10-16 Procédé pour la production continue d'un composé organophosphoré et utilisation de ce composé
PCT/EP2008/008782 WO2009052993A1 (fr) 2007-10-26 2008-10-16 Procédé pour la production continue d'un composé organophosphoré et utilisation de ce composé

Publications (1)

Publication Number Publication Date
EP2205614A1 true EP2205614A1 (fr) 2010-07-14

Family

ID=39046830

Family Applications (2)

Application Number Title Priority Date Filing Date
EP07021015A Withdrawn EP2053053A1 (fr) 2007-10-26 2007-10-26 Procédé de fabrication continue d'une liaison de phosphore organique et son utilisation
EP08840907A Withdrawn EP2205614A1 (fr) 2007-10-26 2008-10-16 Procédé pour la production continue d'un composé organophosphoré et utilisation de ce composé

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP07021015A Withdrawn EP2053053A1 (fr) 2007-10-26 2007-10-26 Procédé de fabrication continue d'une liaison de phosphore organique et son utilisation

Country Status (7)

Country Link
US (1) US20100298470A1 (fr)
EP (2) EP2053053A1 (fr)
JP (1) JP2011500739A (fr)
KR (1) KR20100091988A (fr)
CN (1) CN101835788A (fr)
MX (1) MX2010004317A (fr)
WO (1) WO2009052993A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101061602B1 (ko) 2009-05-21 2011-09-02 한국화학연구원 난연성 포스파펜안트렌 화합물 및 이의 제조방법
CN102219806B (zh) * 2011-05-07 2014-09-17 清远市普塞呋磷化学有限公司 一种高纯度环状膦酸脂9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物的制备方法
CN105906666A (zh) * 2016-05-24 2016-08-31 青岛和新精细化工有限公司 一种无卤阻燃剂的制备方法
KR102477271B1 (ko) 2020-12-18 2022-12-13 한국신발피혁연구원 고인성 및 난연성을 가지는 열경화성 수지 조성물
CN115838384A (zh) * 2022-11-18 2023-03-24 浙江万盛股份有限公司 一种6-氯-(6氢)-二苯[c,e][1,2]-磷杂菲的高效安全制备方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1547105A (en) * 1976-07-05 1979-06-06 Sanko Kaihatsu Kagaku Kenk Cyclic phosphinates and their use as flame-retardants
JPS59222496A (ja) 1983-06-01 1984-12-14 Sanko Kaihatsu Kagaku Kenkyusho:Kk 有機環状りん化合物の生成方法
JPS6267354A (ja) 1985-09-14 1987-03-27 Toyota Motor Corp 車両用自動変速機の変速制御装置
EP0703241B1 (fr) * 1994-09-19 2000-07-26 Bayer Ag Procédé de préparation de 6-oxo-(6H)-dibenz-(c,e)(1,2)-oxa-phosphorinen (ODOP)
DE19514946A1 (de) * 1995-04-24 1996-10-31 Bayer Ag Verfahren zur Herstellung von 6-Oxo-(6H)-dibenz-[c,e][1,2]-oxaphosphorinen
US6291627B1 (en) * 1999-03-03 2001-09-18 National Science Council Epoxy resin rendered flame retardant by reaction with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
BR0207577A (pt) * 2001-02-23 2004-07-27 Phat Cushion Llc Almofada de espuma, método para a fabricação de uma almofada de espuma, e, uso de uma almofada
DE102004044380A1 (de) * 2004-09-10 2006-03-30 Basf Ag Halogenfreie, flammgeschützte Polymerschaumstoffe

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2009052993A1 *

Also Published As

Publication number Publication date
KR20100091988A (ko) 2010-08-19
US20100298470A1 (en) 2010-11-25
CN101835788A (zh) 2010-09-15
JP2011500739A (ja) 2011-01-06
MX2010004317A (es) 2010-04-30
WO2009052993A1 (fr) 2009-04-30
EP2053053A1 (fr) 2009-04-29

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