Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C267/00—Carbodiimides
• • 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
  • C07F9/6568—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 atoms as the only ring hetero atoms
• • 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

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 other isocyanates or for the preparation of isocyanate-containing prepolymers and of polyurethane plastics, preferably polyurethane foams.
• CD storage-stable carbodiimide
• UI uretonimine
• CD and / or UI groups containing isocyanate mixtures can be easily with the highly effective catalysts from the phospholine series, in particular the phospholine oxide series, by the method according to US-A-2,853,473, US-A-6, 120,699 and EP -A-515,933.
• 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
• CD / UI-containing isocyanates prepared in this way are only of limited use for the preparation of prepolymers, ie reaction products of these CD / UI-containing isocyanates with polyols.
• the correspondingly prepared reaction products of polyols and the CD / UI-modified isocyanates tend for outgassing, which can lead to a pressure build-up in the transport containers or foaming in the handling of such products.
• 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 groups-containing isocyanate mixtures which does not have the mentioned defects and liquid, storage-stable isocyanate mixtures with low color numbers leads.
• 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 an orthoester. As a result, the required reaction time can be lowered or kept low and / or the required amount of catalyst can be reduced.
• Orthoester is preferably used in substance, ie without dilution, or as a masterbatch, for example, as a solution of the orthoester in the starting isocyanate or already carbodiimidized isocyanate 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 also relates to the use of the organic isocyanates containing carbodiimide and / or uretonimine groups according to the invention and of the isocyanate blends and / or prepolymers prepared therefrom having an 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, for example, aromatic, araliphatic, aliphatic and / or cycloaliphatic diisocyanates and / or polyisocyanates. - A -
• AIs representatives of the aliphatic and / or cycloaliphatic diisocyanate are exemplified by isophorone diisocyanate, hexamethylene diisocyanate and dicyclohexylmethane diisocyanate (in each case the pure isomers and any isomer mixtures).
• araliphatic diisocyanate are, for example, the various isomers of xylidene diisocyanate.
• 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
• 2,2'- 2,4'- preferred organic isocyanates are especially aromatic diisocyanates such as 2,4- and / or 2,6-diisocyanatotoluene (TDI), and / or 4,4 '-Diiso- cyanatodiphenylmethan (MDI ) or any mixtures of such aromatic diisocyanates.
• aromatic diisocyanates such as 2,4- and / or 2,6-diisocyanatotoluene (TDI), and / or 4,4 '-Diiso- cyanatodiphenylmethan (MDI ) or any mixtures of such aromatic diisocyanates.
• 2,2'-, 2,4'- and / or 4,4'-diisocyanatodiphenylmethane or any mixtures of such aromatic diisocyanates, wherein the sum of 2,2'-, 2,4'- and or 4,4'-diisocyanatodiphenylmethane in the starting material (organic isocyanate) is at least 85 wt .-%, and wherein the diisocyanatodiphenylmethane isomers to 0 to 100 wt .-% of 4,4'-diisocyanatodiphenylmethane, 100 to 0 % By weight 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 4,4'-diisocyanatodiphenylmethane
• 2,2'-, 2,4'- and / or 4,4'-diisocyanatodiphenylmethane or any mixtures of aromatic diisocyanates, where the sum of 2,2'-, 2,4 ' and / or 4,4'-diisocyanatodiphenylmethane in the starting material (organic isocyanate) is at least 90% by weight, and where the diisocyanatodiphenylmethane isomers contain from 0 to 100% by weight of 4,4'-diisocyanatodiphenyl methane, 100 to 0 wt .-% of 2,4'-diisocyanatodiphenylmethane and to 0 to 8 wt .-% of 2,2'-diisocyanatodiphenylmethane composed, wherein said percentages to 100 wt .-% complement.
• MDI 2,2'-, 2,4'- and / or 4,4'-diisocyanatodiphen
• 2,2'-, 2,4'- and / or 4,4'-diisocyanatodiphenylmethane MDI or any mixtures of aromatic diisocyanates
• the sum of 2,2'-, 2,4'- and / or 4,4'-diisocyanatodiphenylmethane in the starting material (organic isocyanate) is at least 99 wt .-%
• 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.
• orthoesters ensures that the reactivity of the starting isocyanate is increased. This can e.g. causally done by counteracting the reactivity-reducing effect of potentially eliminating HCl secondary components in the starting isocyanate. But other mechanisms of action are possible.
• Suitable orthoesters are, for example, orthoesters of a carboxylic acid.
• Suitable orthoesters of the carboxylic acids have the general structure R 1 - (C (OR 2 ) (OR 3 ) (OR 4 )) n , where
• R 1 is an aliphatic, cycloaliphatic, aromatic or araliphatic radical which may contain heteroatoms and / or further functional groups,
• R 2 to R 4 denote an aliphatic, cycloaliphatic, aromatic or araliphatic radical which may contain heteroatoms and / or further functional groups,
• R 2 to R 4 may either be the same or different, or two of R 2 to R 4 may be the same. It is also possible that two or three of the radicals R 2 to R 4 are parts of a single molecule and thus present cyclic or bicyclic orthoester structures.
• Suitable orthoesters of the carboxylic acids are e.g. Orthoester of formic acid, such as. Trimethyl orthoformate, triethyl orthoformate, orthoesters of acetic acid, e.g. Trimethyl orthoacetate, triethyl orthoacetate, orthoester of propionic acid, e.g. Trimethyl orthopropionate, triethyl orthopropionate or mixtures thereof.
• Orthoester of formic acid such as. Trimethyl orthoformate, triethyl orthoformate, orthoesters of acetic acid, e.g. Trimethyl orthoacetate, triethyl orthoacetate, orthoester of propionic acid, e.g. Trimethyl orthopropionate, triethyl orthopropionate or mixtures thereof.
• Suitable orthoesters are, for example, the orthoesters of carbonic acid.
• Suitable orthoesters of carbonic acid have the general structure C (OR 2 ) (OR 3 ) (OR 4 ) (OR 5 ), where
• R 2 to R 5 denote an aliphatic, cycloaliphatic, aromatic or araliphatic radical which may contain heteroatoms and / or further functional groups.
• Jl3_bis-R ⁇ can-either-all-or-don ⁇ t immediately all -versehieden Being-or-two of the radicals R 2 ⁇ to ⁇ 5 ⁇ R may be the same, or two or three of the radicals R 2 to R 5 can be the same. It is also possible that two or two or three of the radicals R 2 to R 5 are parts of a single molecule and thus cyclic or bicyclic orthoester structures are present.
• Suitable orthoesters of carbonic acid are e.g. Tetramethyl orthocarbbnate and tetraethyl orthocarbonate or mixtures thereof.
• the compounds mentioned are considered as examples only; suitable orthoesters of carbonic acid are not limited to the compounds mentioned.
• Suitable orthoesters are, for example, the orthoesters of silicic acid.
• Suitable orthoesters of silicic acid have the general structure Si (OR 2 ) (OR 3 ) (OR 4 ) (OR 5 ), where
• R 2 to R 5 denote an aliphatic, cycloaliphatic, aromatic or araliphatic radical which may contain heteroatoms and / or further functional groups.
• R 2 to R 5 may either be the same or different, or two of R 2 to R 5 may each be the same, or two or three of R 2 to R 5 may be the same. It is also possible that two or two or three of the radicals R 2 to R are parts of a single molecule and thus cyclic or bicyclic orthoester structures are present.
• Suitable orthoesters of silicic acid include Tetramethylorthosüicat and tetraethyl orthosilicate or mixtures thereof. The compounds mentioned are considered as examples only; suitable orthoesters of silicic acid are not limited to the compounds mentioned.
• the orthoester or the mixture of several different orthoesters can be added immediately before, simultaneously with or even after the addition of the catalyst.
• the orthoester only becomes active after the addition of the catalyst, i. during carbodiimidization.
• the best time of addition can be determined in a simple preliminary test and is preferably before reaching 50%, more preferably before reaching 30% and most preferably before reaching 20% of the total desired conversion of isocyanate.
• the optimum amount of the orthoester can also be determined in a simple preliminary test and is preferably ⁇ 1000 ppm, more preferably ⁇ 250 ppm and very particularly preferably ⁇ 100 ppm, based on the weight of the isocyanate used.
• the addition of the orthoester can thus be carried out to the starting isocyanate or to the reaction mixture during the carbodiimidization.
• the orthoester is preferably used in substance, i. without dilution, or as a masterbatch, for example as a solution of the orthoester in the starting isocyanate or already carbodiimidis faced isocyanate added.
• the carbodiimidization reaction is usually carried out in the temperature range between 50 to 150 ° 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%.
• a degree of carbodiimidization is the percentage of carbodiimidized isocyanate groups based on the total amount of isocyanate groups present in starting isocyanate
• 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 mid-infrared analysis.
• the degree of carbodiimidization can likewise be recognized during the performance of the process according to the invention, for example, by the amount of carbon dioxide escaping in the reactor mixture. 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.
• the time of addition is not critical.
• the color stabilizers can either be added to the isocyanate used as starting material before the carbodiimidization, or the reaction product after completion of the reaction. It is also possible to add color stabilizers to both the starting material and the reaction product.
• Such stabilizers are generally known to those skilled in the art and include e.g. Substances from the group of sterically hindered phenols, the Phosphorigklaer 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 the color stabilizers used are in the order of magnitude known to the person skilled in the art, usually in the range from 100 ppm to 10000 ppm for the individual substance or the mixture, based on the isocyanate used as the starting material or the reaction product of the carbodiimidization.
• Isocyanate group-containing prepolymers are obtained by reacting the carbodiimide and / or uretonimine-containing organic isocyanates prepared by the process according to the invention with polyols customary in polyurethane chemistry.
• 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 butanediol 1-2,3, hexanediol , Octanediol, dodecanediol and / or octadecanediol, but in particular higher molecular weight polyether polyols and / or polyester polyols known from polyurethane chemistry with molecular weights of 600 to 8000 g / mol, preferably 800 to
• Phospholoxide 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
• 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.
• Comparative Examples 1 and 2 illustrate the negative influence of the increased value of hydrolyzable chlorine on the reactivity or the reaction time.
• an improved reactivity with respect to Comparative Example 2 is achieved with the same content of hydrolyzable chlorine; After 360 minutes, in Comparative Example 2, the NCO value had dropped from originally about 33.6% to only 31.6%, compared to 29.5% in the example according to the invention.
• Comparative Example 1 shows that the addition of the orthoester with a double content of hydrolyzable chlorine again achieves comparable reactivity, ie. H. to achieve the same NCO value, a comparable reaction time is made possible.

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• 2006
  • 2006-01-05 DE DE102006000825A patent/DE102006000825A1/de not_active Withdrawn
  • 2006-12-27 JP JP2008548948A patent/JP2009522418A/ja not_active Withdrawn
  • 2006-12-27 WO PCT/EP2006/012552 patent/WO2007076999A1/de active Application Filing
  • 2006-12-27 EP EP06841178A patent/EP1973870A1/de not_active Withdrawn
  • 2006-12-27 CN CNA2006800505438A patent/CN101356154A/zh active Pending
  • 2006-12-27 KR KR1020087019154A patent/KR20080090500A/ko not_active Application Discontinuation
• 2007
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