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
  • C08G18/06—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
• • 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
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C267/00—Carbodiimides
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D229/00—Heterocyclic compounds containing rings of less than five members having two nitrogen 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
  • C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
• • 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
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/20—Compounding polymers with additives, e.g. colouring
  • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques

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 group-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 CC> 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 silylated acid amide. As a result, the required reaction time can be lowered or kept low and / or the required amount of catalyst can be reduced.
• silylated acid amide or else a mixture of a plurality of different silylated acid amides.
• the addition of the silylated acid amide can be carried out to the starting isocyanate or to the reaction mixture during the carbodiimidization.
• the silylated acid amide is preferably added in bulk, ie without dilution, or as a masterbatch, for example as a solution of the silylated acid amide in the starting isocyanate or already carbodiimidized isocyanate.
• 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 photometer can be used as a measuring device.
• 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 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 As representatives of the aliphatic and / or cycloaliphatic diisocyanates are exemplified isophorone diisocyanate, hexamethylene diisocyanate and dicyclohexylmethane diisocyanate (in each case the pure isomers and any isomer mixtures).
• AIs representative of the araliphatic diisocyanate are exemplified by 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
• organic isocyanates are in particular aromatic diisocyanates such as 2,4- and / or 2,6-diisocyanatotoluene (TDI), 2,2'-, 2,4'- and / or 4,4'-diiso cyanatodiphenylmethane (MDI ) or any mixtures of such aromatic diisocyanates.
• TDI 2,4- and / or 2,6-diisocyanatotoluene
• MDI 4,4'-diiso cyanatodiphenylmethane
• 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 wt.
• MDI 2,2'-, 2,4'- and / or 4,4'-diisocyanatodiphenylmethane
• 2,2'-, 2,4'- and / or 4,4'-diisocyanatodiphenylmethane 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 90 wt .-%, and wherein the diisocyanatodiphenylmethane isomers to 0 to 100 wt .-% of 4,4'-diisocyanatodiphenyl methane, 100 to 0 Wt .-% of 2,4'-diisocyanatodiphenylmethane and 0 to 8 wt .-% of 2,2'-diisocyanatodiphenylmethane composed, wherein said percentages to 100 wt .-% complement.
• MDI 4,4'-diisocyanatodiphenylmethane
• 2,2'-, 2,4'- and / or 4,4'-diisocyanatodiphenylmethane 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 diisocyanatodiphenyl methane isomers to 0 to 100 wt .-% of 4,4'-diisocyanatodiphenylmethane, from 100 to 0 wt .-% of 2,4'-diisocyanatodiphenylmethane and 0 to 8 wt .-% of 2,2 '-Diisocyanatodiphenyl- methane composed, whereby the said Percentages to 100% by weight.
• MDI 2,2'-, 2,4'- and / or 4,4
• 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.
• silylated acid amides ensures that the reactivity of the starting isocyanate is increased. This can e.g. caused by the fact that they counteract the reactivity-reducing effect of potentially eliminating HCl secondary components in the starting isocyanate. But other mechanisms of action are possible.
• Suitable silylated acid amides are e.g. silylated carboxylic acid amides or silylated carbamates, e.g. N-trimethylsilylacetamide, N, O-bis (trimethylsilyl) acetamide, or trimethylsilyl-N-trimethylsilylcarbamate or mixtures thereof.
• the compounds mentioned are considered as examples only; suitable silylated acid amides are not limited to the compounds mentioned.
• the silylated acid amide or the mixture of several different silylated acid amides can be added immediately before, simultaneously with or even after the addition of the catalyst.
• the silylated acid amide is added only after the addition of the catalyst, ie during the carbodimidization.
• the best time of addition can be determined in a simple preliminary experiment and is preferably before reaching 50%, especially preferably before reaching 30% and most preferably before reaching 20% of the total desired conversion of isocyanate.
• the optimum amount of silylated acid amide can likewise 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 silylated acid amide can thus be carried out to the starting isocyanate or to the reaction mixture during the carbodiimidization.
• the silylated acid amide is preferably used in substance, i. without dilution, or as a masterbatch, for example as a solution of the silylated acid amide in the starting isocyanate or already carbodiimidis studying isocyanate added.
• silylated acid amide results in a higher reactivity with respect to the carbodiimidization reaction, whereby either the required reaction time and / or the required amount of 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%.
• 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 may be determined during the performance of the process according to the invention by determining the NCO value, e.g. be determined by means of the titration known per se to the person skilled in the art or by means of online methods.
• a suitable online method is e.g. near-infrared or mid-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
• 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
• Stopper trifluoromethanesulfonic acid ethyl ester (TFMSEE) or trimethylsilyl trifluoromethanesulfonate (TMST)
• 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 influence of the increased content of hydrolyzable chlorine on the reactivity or the reaction time.
• Example 3 Despite a lower concentration of catalyst used in Example 3 according to the invention compared to Comparative Example 1 even shorter reaction time is required. This demonstrates the increased reactivity of the 4,4'-diphenylmethane diisocyanate used as the starting isocyanate by the addition of the silylated acid amide.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Polyurethanes Or Polyureas (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

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• 2006
  • 2006-01-05 DE DE102006000822A patent/DE102006000822A1/de not_active Withdrawn
  • 2006-12-27 KR KR1020087019153A patent/KR20080091472A/ko not_active Ceased
  • 2006-12-27 DE DE502006004896T patent/DE502006004896D1/de active Active
  • 2006-12-27 EP EP06841179A patent/EP1971623B1/de not_active Not-in-force
  • 2006-12-27 AT AT06841179T patent/ATE443090T1/de not_active IP Right Cessation
  • 2006-12-27 WO PCT/EP2006/012553 patent/WO2007077000A2/de not_active Ceased
  • 2006-12-27 PT PT06841179T patent/PT1971623E/pt unknown
  • 2006-12-27 CN CN2006800506337A patent/CN101356208B/zh not_active Expired - Fee Related
  • 2006-12-27 ES ES06841179T patent/ES2331380T3/es active Active
  • 2006-12-27 JP JP2008548949A patent/JP2009522419A/ja not_active Withdrawn
• 2007
  • 2007-01-03 US US11/649,001 patent/US7714148B2/en not_active Expired - Fee Related

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