EP1973869A1 - Procede de production d'isocyanates organiques presentant des groupes de carbodiimides et/ou d'uretonimines, stables au stockage et liquides - Google Patents

Procede de production d'isocyanates organiques presentant des groupes de carbodiimides et/ou d'uretonimines, stables au stockage et liquides

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Publication number
EP1973869A1
EP1973869A1 EP06829880A EP06829880A EP1973869A1 EP 1973869 A1 EP1973869 A1 EP 1973869A1 EP 06829880 A EP06829880 A EP 06829880A EP 06829880 A EP06829880 A EP 06829880A EP 1973869 A1 EP1973869 A1 EP 1973869A1
Authority
EP
European Patent Office
Prior art keywords
cycloaliphatic
aliphatic
araliphatic
radicals
tertiary amine
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.)
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Application number
EP06829880A
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German (de)
English (en)
Inventor
Stefan Wershofen
Marcus Steinwegs
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.)
Bayer Intellectual Property GmbH
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Bayer MaterialScience AG
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Filing date
Publication date
Application filed by Bayer MaterialScience AG filed Critical Bayer MaterialScience AG
Publication of EP1973869A1 publication Critical patent/EP1973869A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C263/00—Preparation of derivatives of isocyanic acid
    • C07C263/16—Preparation of derivatives of isocyanic acid by reactions not involving the formation of isocyanate groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C265/00—Derivatives of isocyanic acid
    • C07C265/14—Derivatives of isocyanic acid containing at least two isocyanate groups bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C267/00—Carbodiimides
    • 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
    • C08G18/09—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture
    • C08G18/095—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture oligomerisation to carbodiimide or uretone-imine groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes

Definitions

  • the invention relates to a process for the preparation of liquid, storage-stable carbodiimide (CD) and / or uretonimine (UI) groups containing isocyanate mixtures having a low color number, the isocyanate mixtures obtainable by this process and their use for the preparation of mixtures with further Isocyanates or for the production of isocyanate-containing prepolymers and of polyurethane plastics, preferably polyurethane foams.
  • CD storage-stable carbodiimide
  • UI uretonimine
  • CD- and / or UI group-containing isocyanate mixtures can in a simple manner with the highly effective catalysts from the phospholine series, in particular the phospholine oxide series, according to the method according to US-A-2,853,473, US-A-6,120,699 and EP-A -515 933 are made.
  • the high catalytic activity of the phospholine catalysts is desirable in order to initiate the carbodiimidization reaction under mild temperature conditions, but on the other hand no process is known which effectively eliminates phospholine catalysis or phospholine oxide catalysis without restriction guaranteed.
  • the carbodiimidized isocyanates tend to post-reaction, ie they gase due to CO 2 evolution. This then leads to pressure build-up, for example in the storage containers, especially at higher temperatures.
  • stoppers are e.g. in the patents DE-A-25 37 685, EP-A-515 933, EP-A-609 698 and US-A-6, 120,699 and include e.g. Acids, acid chlorides, chloroformates, silylated acids and halides of main group elements. Stopping the catalyst with acids, e.g. may also be present as acid chlorides is not sufficiently effective.
  • CD / UI-containing isocyanate mixtures prepared by means of phospholine catalysis are stopped with, for example, trimethylsilyl trifluoromethanesulphonate (TMST) with at least the equimolar amount, preferably 1 to 2 times the molar amount, based on the catalyst used.
  • TMST trimethylsilyl trifluoromethanesulphonate
  • the object of the present invention was therefore to provide a simple and economical process for the preparation of liquid, storage-stable and light carbodiimide and / or uretonimine containing Isocyanatmischept available, which does not have the mentioned shortcomings and leads to liquid, storage stable isocyanate mixtures with low color numbers.
  • the invention relates to a process for preparing carbodiimide and / or uretonimine containing organic isocyanates, in which one or more organic isocyanates having a Hazen color number of ⁇ 100 APHA, preferably ⁇ 50 APHA, partially carbodiimidized with phospholine-type catalysts, and Subsequently, the carbodiimidization reaction is stopped, characterized in that the carbodiimidization is carried out in the presence of a secondary or tertiary amine which contains at least one aliphatic or cycloaliphatic or araliphatic, optionally substituted and optionally heteroatom-containing, hydrocarbon radical.
  • a secondary or tertiary amine which contains at least one aliphatic or cycloaliphatic or araliphatic, optionally substituted and optionally heteroatom-containing, hydrocarbon radical.
  • a sterically hindered, secondary or tertiary amine which contains at least one aliphatic or cycloaliphatic or araliphatic, optionally substituted and optionally heteroatom-containing, hydrocarbon radical is used.
  • a sterically hindered, secondary or tertiary amine is thereby a secondary or tertiary one Amine to understand, which carries at least two non-hydrogen radicals / substituents on the carbon atoms bonded directly to nitrogen.
  • a secondary or tertiary amine which contains at least one aliphatic or cycloaliphatic or araliphatic, optionally substituted and optionally heteroatom-containing, hydrocarbon radical, or a mixture of several different such secondary or tertiary amines can be used.
  • the addition of the secondary or tertiary amine, which contains at least one aliphatic or cycloaliphatic or araliphatic, optionally substituted and optionally heteroatom-containing, hydrocarbon radical can be carried out to the starting isocyanate or to the reaction mixture during the carbodiimidization.
  • the secondary or tertiary amine which contains at least one aliphatic or cycloaliphatic or araliphatic, optionally substituted and optionally heteroatom-containing, hydrocarbon radical is preferably used in substance, i. without dilution, or as a masterbatch, for example as a solution of secondary or tertiary amine, which contains at least one aliphatic or cycloaliphatic or araliphatic, optionally substituted and optionally heteroatom-containing, hydrocarbon radical, in the starting isocyanate or already carbodiimidized isocyanate or as a solution in a suitable solvent added.
  • the measurement of the Hazen color number can be carried out in accordance with DIN / EN / ISO 6271-2 (draft September 2002) in substance against water as a reference at a layer thickness of 5 cm.
  • a measuring device z. B. a photometer Long LICO 300 can be used.
  • organic isocyanates having a higher color number can also be used as starting materials. In this case, however, the advantages in terms of favorable color values can not be fully exploited.
  • the invention also relates to the carbodiimide and / or uretonimine containing organic isocyanates obtainable by the above-mentioned process.
  • These carbodiimide and / or uretonimine having organic isocyanates are liquid at room temperature and depending on the CD / UI content and / or the isocyanate used up to low temperatures (eg 0 0 C).
  • the invention also provides for the use of the organic isocyanates having carbodiimide and / or uretonimine groups according to the invention for the preparation of mixtures with further isocyanates or for the preparation of isocyanate group-containing prepolymers having an improved color number.
  • the invention finally also relates to the use of the carbodiimide and / or uretonimine group-containing organic isocyanates according to the invention and of the isocyanate blends and / or prepolymers prepared therefrom with improved color number for the production of polyurethane plastics.
  • the process according to the invention it is possible to use any organic isocyanates having a Hazen color number of ⁇ 100 APHA, preferably ⁇ 50 APHA.
  • the process according to the invention is preferably used for the carbodiimidization of organic diisocyanates which can be used in polyurethane chemistry.
  • organic isocyanates having a higher color number can also be used as starting materials. In this case, however, the advantages in terms of favorable color values can not be fully exploited.
  • Suitable isocyanates are e.g. aromatic, araliphatic, aliphatic and / or cycloaliphatic diisocyanates and / or polyisocyanates.
  • isophorone diisocyanate hexamethylene diisocyanate and dicyclohexylmethane diisocyanate (in each case the pure isomers and any isomer mixtures).
  • aromatic di- and polyisocyanates such as tolylene diisocyanate and di- and polyisocyanates of the diphenylmethane series.
  • Aromatic diisocyanates such as 2,4- and / or 2,6-diisocyanatotoluene (TDI), 2,2'-, 2,4'- and / or 4,4'-diisocyanatodiphenylmethane (MDI) or any desired mixtures of such aromatic diisocyanates .
  • TDI 2,4- and / or 2,6-diisocyanatotoluene
  • MDI 4,4'-diisocyanatodiphenylmethane
  • Preferred starting materials are organic isocyanates, in particular aromatic diisocyanates, such as 2,4- and / or 2,6-diisocyanatotoluene (TDI), 2,2'-, 2,4'- and / or 4,4'-diisocyanatodiphenylmethane (MDI) or any mixtures of such aromatic diisocyanates.
  • aromatic diisocyanates such as 2,4- and / or 2,6-diisocyanatotoluene (TDI), 2,2'-, 2,4'- and / or 4,4'-diisocyanatodiphenylmethane (MDI) or any mixtures of such aromatic diisocyanates.
  • 2,2'-, 2,4 '- and / or 4,4-diisocyanatodiphenylmethane MDI
  • MDI 4,4-diisocyanatodiphenylmethane
  • the sum of 2,2'-, 2,4'- and or 4,4'-diisocyanatodiphenylmethane in the starting material (organic isocyanate) is at least 85 wt .-%
  • 2,4'-diisocyanatodiphenylmethane % of 2,4'-diisocyanatodiphenylmethane and from 0 to 8% by weight of 2,2'-diisocyanatodiphenylmethane, the said percentages being equal to 100% by weight.
  • MDI 2,2'-, 2,4'- and / or 4,4'-diisocyanatodiphenylmethane
  • MDI 4,4'-diisocyanatodiphenylmethane
  • the sum of 2,2'-, 2,4'- and or 4,4'-diisocyanatodiphenylmethane in the starting material (organic isocyanate) is at least 90 wt .-%, and wherein the diisocyanatodiphenyl methane isomers to 0 to 100 wt .-% of 4,4'-diisocyanatodiphenylmethane, 100 to 0 % By weight
  • 2,2'-, 2,4'- and / or 4,4'-diisocyanatodiphenyl methane or any mixtures of aromatic diisocyanates, wherein the sum of 2,2'-, 2,4 '- and / or 4,4'-diisocyanatodiphenylmethane in the starting material (organic isocyanate) is at least 99 wt .-%, and wherein the diisocyanatodiphenylmethane isomers to 0 to 100 wt .-% of 4,4'-diisocyanatodiphenylmethane, 100 to 0 wt .-% of 2,4'-diisocyanato-diphenylmethane and 0 to 8 wt .-% of 2,2'-diisocyanatodiphenylmethane composed, wherein said percentages to 100 wt .-% complement.
  • MDI 2,2'-, 2,4'- and / or 4,
  • the process according to the invention is carried out in the presence of phospholine-type catalysts.
  • the phospholine-type catalysts are known, for example, from EP-A-515 933 and US-A-6, 120,699. Typical examples of these catalysts are, for example, the mixtures of the phospholine oxides of the formula ## STR1 ## known from the prior art:
  • the amount of catalyst used depends on the quality and / or the reactivity of the starting isocyanates. The amount of catalyst necessary in each case can therefore be determined most simply in a preliminary experiment.
  • a secondary or tertiary amine which contains at least one aliphatic or cycloaliphatic or araliphatic, optionally substituted and optionally heteroatom-containing, hydrocarbon radical, it is achieved that the reactivity of the starting isocyanate is increased. This can be done, for example, causally by counteracting the reactivity-reducing effect of potentially HCl-eliminating secondary components in the starting isocyanate by acting as bases and binding HCl as the hydrochloride. But other mechanisms of action are possible.
  • Suitable secondary or tertiary amines which contain at least one aliphatic or cycloaliphatic or araliphatic, optionally substituted and optionally heteroatom-containing, hydrocarbon radical, in a particular embodiment sterically hindered, secondary or tertiary amines, are e.g. Amines of the general structure (I), as well as cyclic amines such as pyrrolidine-derived amines of the general structure (II) or piperidine-derived amines of the general structure (III).
  • R 1 , R 2 and / or R 3 independently of one another denote a hydrogen atom, an aliphatic, cycloaliphatic, aromatic or araliphatic radical containing heteroatoms and / or additional functional groups, such as, for example, hydroxyl groups and / or Amino groups, may contain.
  • R 1 , R 2 and R 3 may either be the same or different, or two of R 1 , R 2 and R 3 may be the same. It is also possible that two or three of the radicals R 1 , R 2 and R 3 are bonded together and thus present cyclic or bicyclic structures.
  • At least one of the radicals R 1 to R 3 is selected from the group of aliphatic, cycloaliphatic or araliphatic hydrocarbon radicals which may contain heteroatoms and / or additional functional groups (substituents), such as hydroxyl groups and / or amino groups.
  • R 4 represents a hydrogen atom or an aliphatic, cycloaliphatic, aromatic or araliphatic radical which may contain heteroatoms and / or additional functional groups, such as hydroxyl groups and / or amino groups.
  • R 5 to R 12 independently of one another Hydroxyl group, an amino group or an aliphatic, cycloaliphatic, aromatic or araliphatic radical which may contain heteroatoms and / or additional functional groups, such as hydroxyl groups and / or amino groups.
  • the radicals R 5 to R 12 can either all be the same or different, or two or more of the radicals R 5 to R 12 can each be identical.
  • radicals R 5 to R 12 are bonded together and thus present cyclic, bicyclic or polycyclic (partial) structures.
  • at least one of the radicals R 4 to R 12 is selected from the group of aliphatic, cycloaliphatic or araliphatic hydrocarbon radicals which may contain heteroatoms and / or additional functional groups (substituents), such as hydroxyl groups and / or amino groups.
  • R 4 represents a hydrogen atom or an aliphatic, cycloaliphatic, aromatic or araliphatic radical which may contain heteroatoms and / or additional functional groups, such as hydroxyl groups and / or amino groups.
  • R 5 to R 14 independently of one another represent a hydroxyl group, an amino group or an aliphatic, cycloaliphatic, aromatic or araliphatic radical which may contain heteroatoms and / or additional functional groups, such as, for example, hydroxyl groups and / or amino groups.
  • the radicals R 5 to R 14 may either all be the same or different, or two or more of the radicals R 5 to R 14 may each be the same.
  • radicals R 5 to R 14 are bonded together and thus present cyclic, bicyclic or polycyclic (partial) structures.
  • at least one of the radicals R 4 to R 14 is selected from the group of aliphatic, cycloaliphatic or araliphatic hydrocarbon radicals which may contain heteroatoms and / or additional functional groups (substituents), such as hydroxyl groups and / or amino groups.
  • aliphatic radicals are e.g. Methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, higher optionally indicated n, iso, sec-or tert-alkyl groups, where the aliphatic radicals may contain heteroatoms and / or others functional groups, such as Can carry hydroxyl groups and / or amino groups.
  • cycloaliphatic radicals are e.g. Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, higher optionally branched cycloalkyl groups, wherein the cycloaliphatic radicals may contain heteroatoms and / or further functional groups, such as. Can carry hydroxyl groups and / or amino groups.
  • aromatic radicals are, for example, phenyl, tolyl, ethylphenyl, other mono- or polysubstituted phenyl groups, naphthyl, other monosubstituted or polysubstituted Naphthyl groups, other unsubstituted or mono- or polysubstituted and / or optionally fused aromatic radicals, wherein the aromatic radicals may contain heteroatoms and / or other functional groups, such as hydroxyl groups and / or amino groups, may carry.
  • araliphatic radicals are e.g. Benzyl, singly or multiply substituted benzyl groups, 1-phenylethyl, mono- or poly-substituted 1-phenylethyl groups, 2-phenylethyl, mono- or polysubstituted 2-phenylethyl groups, other unsubstituted or mono- or polysubstituted and / or optionally anneli faced araliphatic radicals, wherein the araliphatic radicals may contain heteroatoms, and / or further functional groups, such as Can carry hydroxyl groups and / or amino groups.
  • Suitable secondary or tertiary amines comprising at least one aliphatic or cycloaliphatic or araliphatic, optionally substituted and optionally containing hetero atoms containing hydrocarbon radical, for example, are the well known as a color stabilizer Sanol LS 2626 ® ⁇ 4- [3- (3,5- Di- or he-butyl-4-hydroxyphenyl) propionyloxy] -1- [2- [3- (3,5-di- / he / butyl-4-hydroxyphenyl) propionyloxy] ethyl] -2,2, 6,6-tetramethylpiperidine ⁇ , alkylpiperidines such as 1,2,2,6,6-pentamethyl-4-piperidinol or 2,2,6,6-tetramethyl-4-piperidinol.
  • suitable secondary or tertiary amines which contain at least one aliphatic or cycloaliphatic or araliphatic, optionally substituted and optionally heteroatom-containing, hydrocarbon radical are not limited to the compounds mentioned.
  • the secondary or tertiary amine which contains at least one aliphatic or cycloaliphatic or araliphatic, optionally substituted, and optionally heteroatom-containing, hydrocarbon radical, or the mixture of several different secondary or tertiary amines, which at least one aliphatic or cycloaliphatic or araliphatic, optionally substituted and optionally containing heteroatom-containing hydrocarbon radical may be added immediately before, simultaneously with or after addition of the catalyst.
  • the secondary or tertiary amine which contains at least one aliphatic or cycloaliphatic or araliphatic, optionally substituted and optionally heteroatom-containing, hydrocarbon radical is added before the addition of the catalyst.
  • the secondary or tertiary amine which contains at least one aliphatic or cycloaliphatic or araliphatic, optionally substituted and optionally heteroatom-containing, hydrocarbon radical is added only after the addition of the catalyst, ie during the carbodiimidization.
  • the best time to add can be achieved in a simple can be determined and is preferably before reaching 90%, more preferably before reaching 70% of the total desired conversion of isocyanate.
  • the optimum amount of secondary or tertiary amine which contains at least one aliphatic or cycloaliphatic, optionally substituted and optionally heteroatom-containing, hydrocarbon radical can likewise be determined in a simple preliminary test and is preferably ⁇ 1000 ppm, more preferably ⁇ 250 ppm and most preferably ⁇ 100 ppm, based on the weight of the isocyanate used.
  • the addition of the secondary or tertiary amine which contains at least one aliphatic or cycloaliphatic or araliphatic, optionally substituted, and optionally heteroatom-containing, hydrocarbon radical can thus be carried out to the starting isocyanate or to the reaction mixture during the carbodiimidization.
  • the secondary or tertiary amine which contains at least one aliphatic or cycloaliphatic or araliphatic, optionally substituted and optionally heteroatom-containing, hydrocarbon radical is preferably used in substance, i.
  • the use of the secondary or tertiary amine which contains at least one aliphatic or cycloaliphatic or araliphatic, optionally substituted, and optionally heteroatom-containing, hydrocarbon radical results in a higher reactivity with respect to the carbodiimization reaction, resulting in either the required reaction time and / or the required Catalyst can be reduced.
  • the carbodiimidization reaction is usually carried out in the temperature range between 50 to 150 0 C, preferably from 60 to 100 0 C, performed. However, significantly higher reaction temperatures are possible (up to about 280 0 C). The optimum reaction temperature depends on the nature of the starting isocyanates and / or the catalyst used and can be determined in a simple preliminary experiment.
  • the carbodiimidization reaction is generally terminated upon reaching a degree of carbodiimidization (carbodiimidization degree is the percentage of carbodiimidized isocyanate groups based on the total amount of isocyanate groups present in starting isocyanate) of from 3 to 50%, preferably from 5 to 30%.
  • the degree of carbodiimidization can be determined during the performance of the method according to the invention by determining the NCO value, for example by means of titration known per se to the person skilled in the art or by means of an online method.
  • a suitable online method is, for example, near-infrared or medium-infrared analysis.
  • the degree of carbodiimidization may also be adjusted during the performance of the process of the invention, e.g. be recognized by the amount of escaping in the reactor mixture carbon dioxide. This volumetrically determinable amount of carbon dioxide is thus at any time information about the reached Carbodiimidmaschinesgrad.
  • a stopper preferably Trimethylsilyltrifluormethansulfonat (TMST) or an alkylating agent or a Mixture of said stopper used.
  • TMST Trimethylsilyltrifluormethansulfonat
  • An alkylating agent or trimethylsilyl trifluoromethanesulfonate (TMST) is preferably used as the sole stopper.
  • Preferred alkylating agents are esters of trifluoromethanesulfonic acid, esters of inorganic acids (preferably strong inorganic acids) or trialkyloxonium compounds.
  • the reaction product of the carbodiimidization may contain color stabilizers, such as are commonly added to isocyanates.
  • color stabilizers such as are commonly added to isocyanates.
  • the time of addition is not critical.
  • Color stabilizers can either the isocyanate used as starting material before
  • Carbodiimidmaschine be added, or the reaction product after completion of the reaction.
  • Such stabilizers are generally known to those skilled in the art and include e.g. Substances from the group of sterically hindered phenols, the Phosphorigklareester or sterically hindered amines.
  • the color stabilizers can each be used alone or in admixture with other representatives of the same or different substance groups. The amounts of color stabilizers used move in the
  • Isocyanate group-containing prepolymers are obtained by reaction of the carbodiimide and / or uretonimine groups prepared by the process according to the invention having organic isocyanates customary in polyurethane chemistry polyols.
  • Suitable polyols are both simple polyhydric alcohols of the molecular weight range 62 to 599 g / mol, preferably 62 to 300 g / mol, such as ethylene glycol, trimethylolpropane, 1,2-propanediol, 1,2-butanediol or 2,3-butanediol, hexanediol, Octanediol, dodecanediol and / or octadecanediol, but in particular higher molecular weight polyether polyols and / or polyester polyols known in polyurethane chemistry with molecular weights of 600 to 8000 g / mol, preferably 800 to 4000 g / mol, the at least two, as a rule to 8, preferably 2 to 4 primary and / or secondary hydroxyl groups. Examples of such polyols are described in US-PS 4,218,843, column 7, line 29 to column 9, line 32.
  • the advantages of the process according to the invention are obvious:
  • the reactivity of the reaction mixture is determined by the presence of a secondary or tertiary amine which contains at least one aliphatic or cycloaliphatic or araliphatic, optionally substituted and optionally heteroatom-containing, hydrocarbon radical increased and / or unified.
  • the required reaction time can be lowered or kept low and / or the required amount of catalyst can be reduced.
  • Both the carbodiimide and / or uretonimine-containing isocyanates and the prepolymers prepared therefrom furthermore have good storage stability and a light color.
  • Phospholinoxide type catalyst technical mixture of 1-methyl-1-oxo-1-phosphacyclopent-2-ene and 1-methyl-1-oxo-1-phosphacyclopent-3-ene, 1% by weight in toluene
  • Catalyst solution added to achieve the desired amount of catalyst.
  • Reaction mixture prior to catalyst addition with the corresponding amount of a secondary or tertiary amine (substance and offset amount see Table;
  • reaction mixture is heated to about 95 ° C. under N 2 / stirring until the desired NCO content has been reached.
  • the carbodiimidization is then stopped by addition of the respective stoppers (trifluoromethanesulfonic acid ethyl ester (TFMSEE) or trimethylsilyl trifluoromethanesulfonate (TMST), see Table) and stirred for 1 hour.
  • TFMSEE trifluoromethanesulfonic acid ethyl ester
  • TMST trimethylsilyl trifluoromethanesulfonate
  • amines A, B and C belong to the group of amines used according to the invention, which contain at least one aliphatic or cycloaliphatic or araliphatic, optionally substituted and optionally heteroatom-containing, hydrocarbon radical.
  • amine D contains only aromatic hydrocarbon radicals.
  • the Hazen color number is measured in accordance with DIN / EN / ISO 6271-2 (draft September 2002) in substance against water as reference at a layer thickness of 5 cm.
  • a measuring device z. B. a photometer Long LICO 300 can be used.
  • Example 1 shows that, despite the same catalyst concentration and approximately the same concentration of hydrolyzable chlorine, the addition of the secondary or tertiary amine which contains at least one aliphatic or cycloaliphatic or araliphatic, optionally substituted and optionally heteroatom-containing, hydrocarbon radical , causes a shortened reaction time in Example 1 according to the invention. This is true even if in the examples according to the invention the concentration of catalyst was reduced.
  • Example 1 shows that the shortening of the reaction time upon addition of a secondary or tertiary amine, which contains at least one aliphatic or cycloaliphatic or araliphatic, optionally substituted and optionally heteroatom-containing hydrocarbon radical contains much larger precipitates than with the addition of a substituted exclusively with aromatic hydrocarbon radicals tertiary amine.

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

Abstract

L'invention concerne un procédé de production de mélanges d'isocyanates présentant des groupes de carbodiimides (CD) et/ou d'urétonimines (UI), stables au stockage, liquides et ayant un indice de couleur faible. L'invention concerne également les mélanges d'isocyanates ainsi obtenus et leur utilisation pour produire des mélanges avec d'autres isocyanates, notamment pour la production de prépolymères contenant des groupes d'isocyanates ainsi que de matières synthétiques de polyuréthane, de préférence, les mousses de polyuréthane.
EP06829880A 2006-01-05 2006-12-27 Procede de production d'isocyanates organiques presentant des groupes de carbodiimides et/ou d'uretonimines, stables au stockage et liquides Withdrawn EP1973869A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006000833A DE102006000833A1 (de) 2006-01-05 2006-01-05 Verfahren zur Herstellung flüssiger, lagerstabiler Carbodiimid- und/oder Uretonimingruppen aufweisender organischer Isocyanate
PCT/EP2006/012551 WO2007076998A1 (fr) 2006-01-05 2006-12-27 Procede de production d'isocyanates organiques presentant des groupes de carbodiimides et/ou d'uretonimines, stables au stockage et liquides

Publications (1)

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EP1973869A1 true EP1973869A1 (fr) 2008-10-01

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EP06829880A Withdrawn EP1973869A1 (fr) 2006-01-05 2006-12-27 Procede de production d'isocyanates organiques presentant des groupes de carbodiimides et/ou d'uretonimines, stables au stockage et liquides

Country Status (8)

Country Link
US (1) US7825276B2 (fr)
EP (1) EP1973869A1 (fr)
JP (1) JP5227184B2 (fr)
KR (1) KR20080081017A (fr)
CN (1) CN101356153B (fr)
DE (1) DE102006000833A1 (fr)
TW (1) TWI391368B (fr)
WO (1) WO2007076998A1 (fr)

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Publication number Priority date Publication date Assignee Title
DE102006000822A1 (de) * 2006-01-05 2007-07-12 Bayer Materialscience Ag Verfahren zur Herstellung flüssiger, lagerstabiler Carbodiimid- und/oder Uretonimingruppen aufweisender organischer Isocyanate
DE102006000825A1 (de) * 2006-01-05 2007-07-12 Bayer Materialscience Ag Verfahren zur Herstellung flüssiger, lagerstabiler Carbodiimidgruppen aufweisender organischer Isocyanate
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WO2007076998A1 (fr) 2007-07-12
CN101356153A (zh) 2009-01-28
CN101356153B (zh) 2013-06-19
DE102006000833A1 (de) 2007-07-12
US7825276B2 (en) 2010-11-02
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