WO2009077795A1 - Procédé pour la préparation de polyisocyanates de la série diphénylméthane - Google Patents

Procédé pour la préparation de polyisocyanates de la série diphénylméthane Download PDF

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Publication number
WO2009077795A1
WO2009077795A1 PCT/HU2008/000045 HU2008000045W WO2009077795A1 WO 2009077795 A1 WO2009077795 A1 WO 2009077795A1 HU 2008000045 W HU2008000045 W HU 2008000045W WO 2009077795 A1 WO2009077795 A1 WO 2009077795A1
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WIPO (PCT)
Prior art keywords
pmdi
phosgene
colour
reaction
solvent
Prior art date
Application number
PCT/HU2008/000045
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English (en)
Inventor
José Trujillo Vilaboy
Szilvia SZILÁGYINÉ DICZHÁZI
Zoltán KOZÁR
József RÉTI
Tibor Klement
Tamás PURZSA
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Borsodchem Zrt
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Publication date
Application filed by Borsodchem Zrt filed Critical Borsodchem Zrt
Publication of WO2009077795A1 publication Critical patent/WO2009077795A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C263/00—Preparation of derivatives of isocyanic acid
    • C07C263/10—Preparation of derivatives of isocyanic acid by reaction of amines with carbonyl halides, e.g. with phosgene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C263/00—Preparation of derivatives of isocyanic acid
    • C07C263/18—Separation; Purification; Stabilisation; Use of additives
    • C07C263/20—Separation; Purification

Definitions

  • the present invention relates to a process for preparing mixtures of diphenylmethane diisocyanates and polyphenylpolymethylene polyiso- cyanates, known as PMDI, having a higher HunterLab colour (L) number by reaction of the corresponding mixtures of diphenylmethanediamines and polyphenylpolymethylenepolyamines, known as PMDA, with phosgene in the presence of at least one inert organic solvent.
  • PMDI polyphenylpolymethylene polyiso- cyanates
  • the colour of the plastics does not have an adverse effect on their mechanical properties, light-coloured products are preferred because of their good versatility in the production process of the processor, e.g. the ability of light to pass through thin covering layers and the ability to produce a variety of colours.
  • Such added compounds can be characterised by the presence of functional groups (especially -OH, -NH, -NH2) which react readily with phosgene and include water (US 4465639), low molecular weight monohydric or polyhydric alcohols (BP 445602), polyether polyols or alkane polyols (US 4507464), water and alcohols (US 6229043), phenol derivatives (DE 4300774), amines and/or ureas (DE 4232769), polyoxyalkylene polyalcohols (DE 4021712), hydrazine or derivatives (US 5942151).
  • functional groups especially -OH, -NH, -NH2
  • BP 445602 low molecular weight monohydric or polyhydric alcohols
  • polyether polyols or alkane polyols US 4507464
  • water and alcohols US 6229043
  • phenol derivatives DE 4300774
  • amines and/or ureas DE 4232
  • the present invention accordingly provides a process for preparing mixtures comprising diphenylmethane diisocyanates and polyphenylpolymethylene polyisocyanates having a higher HunterLab colour (L) number by reaction of the corresponding mixtures comprising diphenylmethane- diamines and polyphenylpolymethylenepolyamines with phosgene in the presence of at least one solvent, where the reaction mixture at the end of phosgenation is subjected to a staged work-up by removal of phosgene, HCl and solvent, and halogenated impurities are removed, and in said work-up the product streams are not subjected to temperatures greater than 160 0 C, and preferably not greater than 140 °C, before the acidity level and hydrolysable chlorine level of the isocyanate are reduced to specific levels, namely acidity less than 1 10 ppm (m/m), preferably less than 30 ppm (m/m), and hydroly
  • the level of chlorine-containing impurities is measured in various ways. Here we refer to the "acidity” and “hydrolysable chlorine” content of the product. Acidity is measured according to the ASTM method D6099. Hydrolysable chlorine is measured according to the ASTM method D4663.
  • Acidity is measured according to the ASTM method D6099.
  • Hydrolysable chlorine is measured according to the ASTM method D4663.
  • the phosgenation of primary amines in a mixing reactor as first stage of the phosgenation has been described a number of times. Thus, for example, US 354461 1 and EP 150435 report the phosgenation in a pressure mixing circuit. Furthermore, EP 291819 discloses carrying out this reaction in a reaction pump.
  • the corresponding carbamoyl chlorides and amine hydrochlorides formed in the first stage of the phosgenation can be run through many types of residence time apparatus in which the amine hydrochlorides are phosgenated to form the corresponding carbamoyl chlorides and the carbamoyl chlorides are dissociated into the corresponding isocyanates and hydrogen chloride.
  • the mixture from a previous stage of the phosgenation can be fed to a series of stirred tank reactors, tubular or column reactors or thin film devices (such as in WO 2004031 132) or combinations of different types of reactors. Batch, continuous, semi- continuous processes and combinations of these, operating at atmospheric pressure or above, are all known in the art.
  • Acid catalysts which have been found to be useful are proton donors such as acid ion exchange resins or strong organic and preferably inorganic acids.
  • strong acids are those having a pKa of less than 1.5; in the case of polybasic acids, this value is that for the first hydrogen dissociation.
  • hydrochloric acid, sulfuric acid, phosphoric acid, fluorosulfonic acid and oxalic acid examples which may be mentioned are hydrochloric acid, sulfuric acid, phosphoric acid, fluorosulfonic acid and oxalic acid.
  • Hydrogen chloride in gaseous form can also be used. Preference is given to using aqueous hydrochloric acid in concentrations of from about 25 to 33% by mass.
  • Suitable solvents are compounds in which the crude PMDA and the phosgene are at least partially soluble.
  • Solvents which have been found to be useful are chlorinated aromatic hydrocarbons, for example mono- chlorobenzene, dichlorobenzenes such as o-dichlorobenzene and p-dichloro- benzene, trichlorobenzenes, the corresponding toluenes and xylenes, chloro- ethylbenzene, monochlorobiphenyl, alpha- or beta-naphthyl chloride and dialkyl phthalates such as diethyl isophthalate.
  • Isocyanate compounds or mixtures other than MDI's or, preferably, crude or purified PMDI or other MDI material can also be used to replace some or all of the non-isocyanate solvent after the crude PMDA has been initially reacted with the phosgene.
  • Excess phosgene can also be used to take the role of the solvent.
  • MMB monochlorobenzene
  • the solvents can be used individually or as mixtures. It is advantageous to use a solvent which has a boiling point lower than that of the MDI isomers so that the solvent can easily be separated from the crude PMDI by distillation.
  • the amount of solvent is advantageously selected such that the reaction mixture has an isocyanate content of from 2 to 40% by mass, preferably from 10 to 30% by mass, based on the total weight of the reaction mixture.
  • the crude PMDA can be employed as such or as a solution in organic solvents.
  • crude PMDA solutions having an amine content of from 2 to 45% by mass, preferably from 25 to 44% by mass, based on the total weight of the amine solution.
  • amine content of from 2 to 45% by mass, preferably from 25 to 44% by mass, based on the total weight of the amine solution.
  • varying proportions of phosgene, hydrogen chloride, solvent and other components of the complex reaction mixture will be partitioned between vapor, solution and solids phases.
  • the vapor phase may be largely or partially separated from or may be kept in direct contact with the solution and solids during different stages of the phosgenation.
  • the manner in which the acidity and hydrolysable chlorine levels are reduced below the target levels is not critical, so long as the target maximum temperatures are not exceeded.
  • the severity of the dechlorination procedure will depend upon the levels of chlorinated impurities created in the preceding MDA preparation and phosgenation stages.
  • the procedure may be carried out in one or more stirred tanks, optionally with inert gas stripping, or in one or more packed columns, optionally with countercurrent inert gas flow, or a combination of such equipment.
  • Aryl phosphites which have been found to be useful are tri( alkylphenyl)- phosphites having from 1 to 10 carbon atoms in the alkyl radical, e.g. tri(methylphenyl)phosphite, tri(ethylphenyl)phosphite, tri(n-propylphenyl)- phosphite, tri(isopropylphenyl)phosphite, tri(n-butylphenyl)phosphite, tri(sec- butylphenyl)phosphite, tri(tert-butylphenyl)phosphite, tri(pentylphenyl)- phosphite, tri(hexylphenyl)phosphite, tri(2-ethylhexylphenyl)phosphite, tri(octylphenyl)phosphite, tri(2-ethyloctylphenyl)
  • PMDI having lighter colour, typically having a HunterLab colour (L) number of greater than 10, preferably greater than 25, more preferably greater than 40 and, typically, in the range 20 to 50.
  • L HunterLab colour
  • Colour can be determined using laboratory instruments on samples of final product or crude PMDI or by on-line instrumentation.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de préparation de mélanges composés de diisocyanates de diphényl-méthane et de polyisocyanates de polyphénylpolyméthylène présentant un numéro de couleur HunterLab (L) plus élevé en faisant réagir les mélanges correspondants incluant des diphénylméthanediamines et des poly-phénylpoly-méthylène-poly-amines avec du phosgène en présence d'au moins un solvant, procédé au cours duquel, dans le traitement conclusif étagé consécutif à la réaction de phosgénation, le niveau des impuretés contenant du chlore est réduit par ce que l'on appelle le processus de traitement thermique/de déchloration à un niveau spécifiquement défini avant que le mélange de réaction ne soit soumis à des températures supérieures à une température spécifiquement définie. Dans la mesure où ce niveau d'impuretés n'est pas dépassé, une détérioration de couleur très faible, voire nulle, se produit lorsque l'on chauffe le flux de produit à des températures supérieures dans les étapes de traitement ultérieures.
PCT/HU2008/000045 2007-12-17 2008-05-14 Procédé pour la préparation de polyisocyanates de la série diphénylméthane WO2009077795A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
HUP0700818 2007-12-17
HU0700818A HU227245B1 (en) 2007-12-17 2007-12-17 Process for the preparation of polyirocyanates of the diphenylmethane series

Publications (1)

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WO2009077795A1 true WO2009077795A1 (fr) 2009-06-25

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HU (1) HU227245B1 (fr)
WO (1) WO2009077795A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011138245A1 (fr) * 2010-05-05 2011-11-10 Bayer Materialscience Ag Procédé de préparation d'isocyanates en phase gazeuse
WO2017174765A1 (fr) * 2016-04-07 2017-10-12 Vencorex France Procédé de préparation des xylylène diisocyanates xdi
WO2017194293A1 (fr) * 2016-05-10 2017-11-16 Huntsman International Llc Procédé de production d'isocyanates et/ou de polycarbonates
WO2021042251A1 (fr) * 2019-09-02 2021-03-11 万华化学集团股份有限公司 Procédé de préparation de polyisocyanate par réaction photochimique et procédé de préparation de résine polyuréthane à l'eau

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5364958A (en) * 1992-06-23 1994-11-15 Mitsui Toatsu Chemicals, Incorporated Process for the production of methylene-crosslinked polyphenylene polyisocyanate
JPH07233136A (ja) * 1994-02-23 1995-09-05 Mitsui Toatsu Chem Inc メチレン架橋ポリフェニレンポリイソシアネートの製造方法
JPH07316122A (ja) * 1994-05-26 1995-12-05 Mitsui Toatsu Chem Inc メチレン架橋ポリフェニレンポリイソシアネートの製造方法
US6576788B1 (en) * 1998-04-21 2003-06-10 Basf Aktiengesellschaft Method for producing mixtures consisting of diphenylmethane diisocyanates and polyphenylene-polymethylene-polyisocyanates containing a reduced amount of chlorinated secondary products and with a reduced iodine color index
EP1440990A1 (fr) * 2003-01-27 2004-07-28 BorsodChem Rt. Procédé pour diminuer l'acidité de mélanges de polyéthyléne-polyphényl-polyisocyanates

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5364958A (en) * 1992-06-23 1994-11-15 Mitsui Toatsu Chemicals, Incorporated Process for the production of methylene-crosslinked polyphenylene polyisocyanate
JPH07233136A (ja) * 1994-02-23 1995-09-05 Mitsui Toatsu Chem Inc メチレン架橋ポリフェニレンポリイソシアネートの製造方法
JPH07316122A (ja) * 1994-05-26 1995-12-05 Mitsui Toatsu Chem Inc メチレン架橋ポリフェニレンポリイソシアネートの製造方法
US6576788B1 (en) * 1998-04-21 2003-06-10 Basf Aktiengesellschaft Method for producing mixtures consisting of diphenylmethane diisocyanates and polyphenylene-polymethylene-polyisocyanates containing a reduced amount of chlorinated secondary products and with a reduced iodine color index
EP1440990A1 (fr) * 2003-01-27 2004-07-28 BorsodChem Rt. Procédé pour diminuer l'acidité de mélanges de polyéthyléne-polyphényl-polyisocyanates

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011138245A1 (fr) * 2010-05-05 2011-11-10 Bayer Materialscience Ag Procédé de préparation d'isocyanates en phase gazeuse
US9102594B2 (en) 2010-05-05 2015-08-11 Bayer Intellectual Property Gmbh Method for producing isocyanates in the gas phase
US9328064B2 (en) 2010-05-05 2016-05-03 Bayer Materialscience Ag Method for producing isocyanates in the gas phase
WO2017174765A1 (fr) * 2016-04-07 2017-10-12 Vencorex France Procédé de préparation des xylylène diisocyanates xdi
FR3049950A1 (fr) * 2016-04-07 2017-10-13 Vencorex France Procede de preparation des xylylene diisocyanates xdi
CN108884024A (zh) * 2016-04-07 2018-11-23 温科莱斯法国公司 苯二亚甲基二异氰酸酯xdi的制备流程
RU2740907C2 (ru) * 2016-04-07 2021-01-21 Венкорекс Франс Способ получения ксилилендиизоцианатов (xdi)
CN108884024B (zh) * 2016-04-07 2021-09-03 温科莱斯法国公司 苯二亚甲基二异氰酸酯xdi的制备流程
WO2017194293A1 (fr) * 2016-05-10 2017-11-16 Huntsman International Llc Procédé de production d'isocyanates et/ou de polycarbonates
WO2021042251A1 (fr) * 2019-09-02 2021-03-11 万华化学集团股份有限公司 Procédé de préparation de polyisocyanate par réaction photochimique et procédé de préparation de résine polyuréthane à l'eau

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Publication number Publication date
HU227245B1 (en) 2010-12-28
HU0700818D0 (en) 2008-02-28
HUP0700818A2 (en) 2009-10-28

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