EP4107199A1 - Procédé de carbodiimidation - Google Patents

Procédé de carbodiimidation

Info

Publication number
EP4107199A1
EP4107199A1 EP21704537.6A EP21704537A EP4107199A1 EP 4107199 A1 EP4107199 A1 EP 4107199A1 EP 21704537 A EP21704537 A EP 21704537A EP 4107199 A1 EP4107199 A1 EP 4107199A1
Authority
EP
European Patent Office
Prior art keywords
oxide
phosphetane
carbodiimidization
ppm
formula
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.)
Pending
Application number
EP21704537.6A
Other languages
German (de)
English (en)
Inventor
Igor POCHOROVSKI
Frank Richter
Kathleen FUCHS
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.)
Covestro Deutschland AG
Original Assignee
Covestro Deutschland 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 Covestro Deutschland AG filed Critical Covestro Deutschland AG
Publication of EP4107199A1 publication Critical patent/EP4107199A1/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
    • C08G18/025—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only the polymeric products containing carbodiimide groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/166—Catalysts not provided for in the groups C08G18/18 - C08G18/26
    • C08G18/168—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups

Definitions

  • the present invention relates to polycarbodiimides and a process for their preparation.
  • carbodiimide groups can be obtained in a simple manner from two isocyanate groups with the elimination of carbon dioxide:
  • oligomeric compounds with several carbodiimide groups and optionally isocyanate groups, in particular terminal isocyanate groups are thus obtainable, so-called polycarbodiimides.
  • the use of the stoppers known in the art e.g. EP-A-515 933, EP-A-609 698, US-A-6,120,699) in the required amounts often leads to discoloration of the product.
  • One object of the present invention was therefore to provide a simple process for the produc- tion of polycarbodiimides, the smallest possible residual amounts of carbodiimidization catalyst and thus do not have the stated disadvantages of the prior art.
  • the present invention relates to a process for the preparation of polyisocyanates containing carbodiimide groups, in which, in a first step, at least one monomeric diisocyanate and / or the polyisocyanate in the presence of at least one phosphetane-1 oxide of the general formula I
  • R stands for a monovalent organic radical with 1 to 6 carbon atoms, which can be saturated or unsaturated or aromatic and branched or unbranched and can have heteroatoms such as nitrogen or oxygen, and preferably a monovalent organic, saturated, aromatic, branched or unbranched radical with 1 to 6 carbon atoms, is subjected to a carbodiimidization reaction and in a second step the / the Phosphe tan-1 oxide (s) is / are removed from the reaction product of the first step, preferably by distillation.
  • the phosphethane-1 oxides to be used in the process according to the invention can be separated off and recovered from the reaction product in a simple manner by means of distillation. This possibility of recovering the catalyst makes the process extremely economical.
  • the catalysts to be used are significantly cheaper to produce than the phospholene oxides used in the prior art (the experimental part of the present document exemplifies an inexpensive production method for 1,2,2,3,4,4-hexamethylphosphetane-1-oxide and / or l-ethyl-2,2,3,4,4-pentamethyl-phosphetane-l-oxide.)
  • phosphetane oxides such as, for example, 1,2,2,3,4,4-hexamethylphosphetane-1-oxide or 1-ethyl-2, 2,3,4,4, which are particularly preferred in the process according to the invention -Pentamethyl-phosphetane-1-oxide, there is still an indication that phosphetane oxides can largely be removed from the reaction mixture obtained by distillation.
  • the phosphorus content determined according to elemental analysis is very particularly preferably ⁇ 100 ppm, furthermore preferably ⁇ 25 ppm and most preferably ⁇ 20 ppm.
  • the present invention also provides polyisocyanates containing carbodiimide groups and having a phosphorus content determined according to elemental analysis (ICP-OES, DIN ISO 17025) of preferably ⁇ 100 ppm, more preferably ⁇ 25 ppm, even more preferably ⁇ 20 ppm, obtainable by the process according to the invention .
  • ICP-OES elemental analysis
  • Examples include: methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (HDI), dipropylene diisocyanate, 2-methylpentane-1,5-diisocyanate, 2,2-dimethylpentane diisocyanate, 3-methoxyhexane diisocyanate, octamethylene diisocyanate , 4-trimethylpentane diisocyanate, 2,4,4-trimethyl-1,6-hexane diisocyanate, 2,2,4-trimethyl-1,6-hexane diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, 3-butoxyhexane diisocyanate, 1,4-butylene glycol dipropyl ether diisocyanate , Thiodihexyl diisocyanate, metax
  • Aliphatic and cycloaliphatic diisocyanates are preferred.
  • Isophorone diisocyanate (IPDI) hexamethylene diisocyanate (HDI), hydrogenated xylylene diisocyanate (H ( , XDI).
  • H ( , XDI) hydrogenated xylylene diisocyanate
  • H12MDI 4,4'-dicyclohexylmethane diisocyanate
  • H12MDI The cycloaliphatic polyisocyanate 4,4'-dicyclohexylmethane diisocyanate ( H12MDI).
  • the conversion of aromatic di- / polyisocyanates to polycarbodiimide takes place in the presence of up to 20 ppm by weight of carbodiimidization catalyst.
  • the conversion of aliphatic, cycloaliphatic and / or araliphatic di- / polyisocyanates to polycarbodiimide takes place in the presence of 0.1-3.0% by weight, preferably 0.1-2.0% by weight, of carbodiimidization catalyst.
  • the ppm and% figures relate in each case to the amount of di- / polyisocyanate used.
  • the 1-phosphetane oxides can be used in a mixture with other carbodiimidization catalysts, in which case the above quantitative data must be adhered to.
  • phosphane oxides, phospholane oxides and phospholene oxides, as well as their sulfo- and imino analogs can also be used.
  • their content based on the amount of phosphetane-1 oxides, should not exceed 80% by weight, preferably 50% by weight, particularly preferably 20% by weight.
  • the phosphetane-1 oxides are not used in admixture with these catalysts. That is, most preferably, only phosphetane-1-oxides are used as carbodiimidization catalysts in the process.
  • the conversion of di- / polyisocyanate to polycarbodiimide takes place at a temperature in the range from 130 to 230.degree. C., preferably in the range from 140 to 210.degree. C., particularly preferably in the range from 150 to 200.degree.
  • the conversion of di- / polyisocyanate to polycarbodiimide can be carried out in the presence or absence of solvents. It is preferably carried out in the presence of at least one solvent. It is preferred to use solvents which have a boiling point under normal pressure (1013 mbar) of> 120 ° C. These include, for example, monochlorobenzene (MCB), orthodichlorobenzene (OCB), chlorotoluenes (any isomer / mixture), trichlorobenzene, high-boiling ethers such as B. dibutyl ether, diphenyl ether, ditolyl ether.
  • the catalyst is removed from the reaction mixture obtained from step 1, preferably by distillation.
  • process step 1 is carried out in the presence of a solvent
  • the solvent and catalyst can be separated off from the reaction mixture obtained from process step 1 together in one distillation step or separately in several distillation steps.
  • the solvent and the catalyst are separated off at the same time.
  • the distillation is preferably carried out at reduced pressure, i.e. at a vacuum of ⁇ 250 mbar, particularly preferably ⁇ 100 mbar, very particularly preferably ⁇ 50 mbar, most preferably ⁇ 20 mbar.
  • the distillation is preferably carried out at temperatures up to 250.degree. C., particularly preferably at temperatures up to 200.degree.
  • the person skilled in the art is well aware of the dependence of the boiling point of a substance on the ambient pressure.
  • the distillation temperature to be set as a function of the pressure during the distillation is therefore determined by the person skilled in the art on the basis of his specialist knowledge.
  • distillation methods customary in industry are conceivable as distillation methods, such as, for example (continuously or discontinuously operated) bubble distillations and / or thin-film distillation optionally in the particular embodiment of short-path distillation.
  • the phosphetane oxide catalysts 1,2,2,3,4,4-hexamethylphosphetane-1-oxide and 1-ethyl-2,2,3,4,4-pentamethyl-phosphetane-1-oxide were according to literature [T. V. Nykaza, T. S. Harrison, A. Ghosh, R. A. Putnik and A. T. Radosevich, J Am Chem Soc 2017, 139, 6839-6842].
  • the reference catalyst phospholene oxide (present as a mixture of isomers 1-methyl -2 (and / or 3) -phospholene 1-oxide) was obtained from Clariant.
  • the phosphorus content was determined by elemental analysis (ICP-OES, DIN - ISO 17025). NCO values were determined volumetrically in accordance with DIN-EN ISO 11909.
  • Example 1 comparative example
  • Example 3 comparative example
  • Phospholene oxide (0.20 g) was added to H12MDI (20.0 g, 75.8 mmol, 1.0 eq) in chlorobenzene (2.22 g). The reaction mixture was heated to 200 ° C. for 8 h. A distillation bridge was then put in place and the mixture was distilled at 200 ° C. and 20 mbar. The residue was examined for P content by elemental analysis and a value of 480 mg / kg was found, which corresponds to 18% of the original amount of catalyst.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne des polycarbodiimides et un procédé pour leur préparation à l'aide de catalyseurs spéciaux.
EP21704537.6A 2020-02-18 2021-02-11 Procédé de carbodiimidation Pending EP4107199A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP20157825.9A EP3868803A1 (fr) 2020-02-18 2020-02-18 Procédé de carbodiimidation
PCT/EP2021/053266 WO2021165126A1 (fr) 2020-02-18 2021-02-11 Procédé de carbodiimidation

Publications (1)

Publication Number Publication Date
EP4107199A1 true EP4107199A1 (fr) 2022-12-28

Family

ID=69723774

Family Applications (2)

Application Number Title Priority Date Filing Date
EP20157825.9A Ceased EP3868803A1 (fr) 2020-02-18 2020-02-18 Procédé de carbodiimidation
EP21704537.6A Pending EP4107199A1 (fr) 2020-02-18 2021-02-11 Procédé de carbodiimidation

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP20157825.9A Ceased EP3868803A1 (fr) 2020-02-18 2020-02-18 Procédé de carbodiimidation

Country Status (5)

Country Link
US (1) US20230090655A1 (fr)
EP (2) EP3868803A1 (fr)
JP (1) JP2023513625A (fr)
CN (1) CN115066446A (fr)
WO (1) WO2021165126A1 (fr)

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2853473A (en) 1956-08-27 1958-09-23 Du Pont Production of carbodiimides
US2941966A (en) 1956-08-27 1960-06-21 Du Pont Carbodiimide polymers
US2840589A (en) 1957-06-14 1958-06-24 Du Pont Di(3-isocyanato-4-methylphenyl) carbodiimide
GB1215157A (en) * 1967-07-26 1970-12-09 Ici Ltd New phosphetane-1-oxide compounds, their manufacture and use
DE2342148A1 (de) 1973-08-21 1975-03-06 Bayer Ag Neue phosphorhaltige anlagerungsverbindungen und ihre verwendung als katalysatoren bei der herstellung von carbodiimidgruppen aufweisenden schaumstoffen
DE2504400A1 (de) 1975-02-01 1976-08-05 Bayer Ag Lagerstabile, carbodiimidgruppen enthaltende polyisocyanate
DE2552350A1 (de) 1975-11-21 1977-05-26 Bayer Ag Lagerstabile, carbodiimidgruppen enthaltende polyisocyanate
DE4117384A1 (de) 1991-05-28 1992-12-03 Bayer Ag Verfahren zur herstellung fluessiger, lagerstabiler carbodiimid- und/oder uretonimingruppen aufweisender organischer isocyanate und ihre verwendung zur herstellung von polyurethankunststoffen
DE4302697A1 (de) * 1993-02-01 1994-08-04 Bayer Ag Verfahren zur Herstellung organischer Carbodiimide und ihre Verwendung als Kunststoff-Stabilisatoren
DE4318979A1 (de) 1993-06-08 1994-12-15 Basf Ag Carbodiimide und/oder oligomere Polycarbodiimide auf Basis von 1,3-Bis-(1-methyl-1-isocyanato-ethyl)-benzol, ein Verfahren zu ihrer Herstellung und ihre Verwendung als Hydrolysestabilisator
US6120699A (en) 1998-09-21 2000-09-19 Basf Corporation Storage stable methylene bis(phenylisocyanate) compositions
DE102009027246A1 (de) * 2009-06-26 2010-12-30 Evonik Degussa Gmbh Katalysatorarme Carbodiimidgruppen und/oder Uretonimingruppen aufweisende Isocyanatmischungen

Also Published As

Publication number Publication date
US20230090655A1 (en) 2023-03-23
CN115066446A (zh) 2022-09-16
WO2021165126A1 (fr) 2021-08-26
EP3868803A1 (fr) 2021-08-25
JP2023513625A (ja) 2023-03-31

Similar Documents

Publication Publication Date Title
EP0792263B1 (fr) Procede de preparation d'isocyanates
EP1073628A1 (fr) Procede pour la preparation de melanges de diphenylmethane-diisocyanates et de polyisocyanates de polyphenylene-polymethylene a teneur reduite en sous-produits chlores et a indice colorimetrique d'iode reduit
EP3181548B1 (fr) Fabrication de di- et polyisocyanates de la série des diphénylméthanes ayant une teneur définie en chlore hydrolysable
EP3036217B1 (fr) Procédé de collecte d'isocyanates organiques à partir de résidus de distillation de la fabrication d'isocyanate
DE3739261A1 (de) Verfahren zur herstellung von urethangruppen aufweisenden polyisocyanaten und ihre verwendung
EP3024869B1 (fr) Procédé de fabrication de polyisocyanates et leur utilisation
DE102006000833A1 (de) Verfahren zur Herstellung flüssiger, lagerstabiler Carbodiimid- und/oder Uretonimingruppen aufweisender organischer Isocyanate
EP2970562B1 (fr) Procédé de fabrication de trimères de tdi d'une grande pureté
EP1671988B1 (fr) Procédé pour la préparation d'isocyanates organiques liquides, stables au stockage, contenant des groupes carbodiimido et/ou uretonimino et ayant un indice de couleur faible
DE1568017A1 (de) Verfahren zur Herstellung von stabilen Polyisocyanaten
EP1379569A1 (fr) Procede de production de mdi, en particulier de 2,4'-mdi
EP1973870A1 (fr) Procede de production d'isocyanates organiques presentant des groupes de carbodiimides et/ou d'uretonimines, liquides et stables au stockage
EP2445945A1 (fr) Mélanges d'isocyanate présentant des groupes carbodiimide et/ou des groupes urétonimine pauvres en catalyseur
EP0524507A1 (fr) Procédé de purification de polyisocyanates
EP1971623B1 (fr) Procede de production d'isocyanates organiques presentant des groupes de carbodiimides et/ou d'uretonimines, stables au stockage et liquides
EP1451239B1 (fr) Procede de production de prepolymeres contenant des groupes isocyanate et des groupes urethanne
EP4107199A1 (fr) Procédé de carbodiimidation
EP3262091B1 (fr) Procédé de fabrication d'une composition comprenant un polycarbodiimide présentant une stabilité au stockage améliorée
DE4232769A1 (de) Verfahren zur Herstellung von Mischungen aus Diphenylmethandiisocyanaten und Polyphenyl-polymethylen-polyisocyanaten mit einer verminderten Iodfarbzahl
DE2854940A1 (de) Verfahren zur auftrennung von polyurethanschaumstoff-hydrolysaten in polyol und diamin
DE19521800C2 (de) Verfahren zur Herstellung von Isocyanaten
EP3024863B1 (fr) Procédé de fabrication de polyisocyanates contenant des groupes iminooxadiazindione et leur utilisation
EP4038049A1 (fr) Procédé de distillation d'isocyanates
DE4215761A1 (de) Verfahren zur Herstellung von Mischungen aus Diphenylmethandiisocyanaten und Polyphenyl-polymethylen-polyisocyanaten mit einer verminderten Iodfarbzahl

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20220919

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)