EP1620383A1 - Initial compounds for producing polyurethanes - Google Patents

Initial compounds for producing polyurethanes

Info

Publication number
EP1620383A1
EP1620383A1 EP04727865A EP04727865A EP1620383A1 EP 1620383 A1 EP1620383 A1 EP 1620383A1 EP 04727865 A EP04727865 A EP 04727865A EP 04727865 A EP04727865 A EP 04727865A EP 1620383 A1 EP1620383 A1 EP 1620383A1
Authority
EP
European Patent Office
Prior art keywords
oligomers
formaldehyde
compounds
reaction
isocyanates
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.)
Withdrawn
Application number
EP04727865A
Other languages
German (de)
French (fr)
Inventor
Peter Groer
Regina Hendreich
Paul Ch. Kierkus
Thomas Ostrowski
Eckhard Stroefer
Kai Thiele
Christoph Schnorpfeil
Edward Michael Dexheimer
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Publication of EP1620383A1 publication Critical patent/EP1620383A1/en
Withdrawn legal-status Critical Current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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
    • C07C47/26—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms containing hydroxy groups
    • C07C47/263—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms containing hydroxy groups acyclic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/30—Compounds having groups
    • C07C43/315—Compounds having groups containing oxygen atoms singly bound to carbon atoms not being acetal carbon 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/54—Polycondensates of aldehydes
    • C08G18/546—Oxyalkylated polycondensates of aldehydes
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/56—Polyacetals
    • 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
    • C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
    • C08G2/30—Chemical modification by after-treatment
    • C08G2/34—Chemical modification by after-treatment by etherification
    • 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
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/34—Oligomeric, e.g. cyclic oligomeric

Definitions

  • the invention relates to new starting compounds for the production of polyurethanes and a process for their preparation.
  • Polyurethanes and their production have long been known and have been described many times in the literature. They are usually produced by reacting polyisocyanates with compounds having at least two hydrogen atoms reactive with isocyanate groups.
  • Polyols are mostly used as compounds with at least two hydrogen atoms reactive with isocyanate groups.
  • the greatest technical importance here are the polyether alcohols and the polyester alcohols.
  • Polyester alcohols are usually produced by reacting at least difunctional alcohols with at least difunctional carboxylic acids.
  • the polyether alcohols are generally obtained by adding alkylene oxides to OH- or NH-functional starter compounds.
  • the price of the usual polyols is determined by the starter compounds used and the alkylene oxides used, especially propylene oxide and ethylene oxide.
  • a much cheaper starting compound for the production of polyols would be formaldehyde.
  • formaldehyde reacts with itself to form oligomers that have terminal hydroxyl groups.
  • this reaction usually leads to a mixture of oligomers and polymers with different chain lengths, which are in equilibrium with formaldehyde.
  • compounds with such a broad molecular weight distribution are unusable for the production of polyurethanes.
  • Another disadvantage of these connections is their lack of stability. The oligomers and polymers are split back after a short time.
  • DD 247223 describes a process for the preparation of polyether alcohols in which a mixture of formaldehyde condensates, known as formose, and other compounds having active hydrogen atoms is reacted with alkylene oxides. In this process too, the formose has a broad molecular weight distribution.
  • EP 1 063221 describes a method for preparing formaldehyde oligomers of the general formula (I) with a narrow molecular weight distribution, starting from formaldehyde. The implementation follows the general equation
  • the resulting oligomer mixture of 2-9 formaldehyde units like polyoxymethylene, is unstable. In addition to higher molecular compounds (paraformaldehyde), water and monomolecular hydrated formaldehyde are formed within 2 hours.
  • the invention accordingly relates to starting compounds for the production of polyurethanes, hereinafter also referred to as polyurethane raw materials, which can be prepared by reacting oligomers of formaldehyde containing hydroxyl groups.
  • the invention further relates to a process for the production of polyurethane raw materials by reacting the hydroxyl groups of oligomers of formaldehyde.
  • the compounds of the general formula (I) can be prepared by known processes. It is thus possible to produce the oligomers by known polymerization of trioxane, a cyclic reaction product of the formaldehyde. This process is known from the literature. It is preferably used for the production of polyoxymethylene (POM) and is described, for example, in the Römpp Chemie Lexikon. However, this process is not preferred for the production of the polyurethane raw materials according to the invention, since high-molecular reaction products are preferably formed.
  • POM polyoxymethylene
  • the oligomers are prepared by the process described in EP 1 063221, the subsequent reaction of the oligomers with aniline described in this document being dispensed with.
  • the oligomers of formaldehyde are produced by removing certain fractions from a solution in which there is an equilibrium between formaldehyde and its oligomers. This separation is preferably carried out by distillation, mostly by means of a film evaporator, in particular by means of a thin-film evaporator. Suitable operating conditions for the film evaporator are generally a temperature between 10 and 230 ° C, preferably between 10 and 150 ° C, at an absolute pressure between 0.5 mbar and 2 bar. Temperatures between 20 and 100 ° C. at normal pressure are preferred for the separation of an aqueous formaldehyde solution.
  • fractions of oligomers of formaldehyde separated in this way usually have a very narrow molecular weight distribution. As stated above, they are stable in storage for a certain time and should be processed further during this time in order to avoid a change in their composition.
  • the terminal hydroxyl groups are reacted with alkylene oxides to form polyether alcohols.
  • the reaction is usually carried out as in the known production of polyether alcohols using the usual alcoholic starter substances.
  • the oligomers of formaldehyde are reacted with the alkylene oxides in the presence of catalysts.
  • basic compounds such as amines, basic metal oxides and metal hydroxides, in particular potassium hydroxide, can be used as catalysts.
  • Multimetal cyanide compounds also referred to as DMC catalysts
  • DMC catalysts are preferably used as catalysts. Such compounds have long been known and are described for example in EP 654302 or in EP 862947.
  • the advantage of using DMC catalysts is, on the one hand, that they can remain in the product after the reaction, and, on the other hand, that, unlike basic catalysts, they do not promote the cleavage of the oligomers.
  • the compounds known and customary for this purpose can be used as alkylene oxides.
  • the greatest technical importance has ethylene oxide and propylene oxide, which can be used individually or in any mixtures with one another.
  • the two alkylene oxides can be dosed together in a so-called statistic or in succession in so-called alkylene oxide blocks.
  • the type and amount of the metered alkylene oxides depends in particular on the use of the polyether alcohols.
  • the polyether alcohols have short chains for use in rigid foams.
  • the hydroxyl number of such polyether alcohols is usually in the range between 300 to 600, in particular between 400 and 500 mg KOH / g.
  • Propylene oxide is preferably used as the alkylene oxide.
  • Long-chain polyether alcohols are mostly used for use in flexible foams.
  • the hydroxyl number of these polyether alcohols is usually in the range between 30 and 120 mg KOH / g, preferably in the range between 30 and 60 mg KOH / g.
  • Mixtures of ethylene oxide and propylene oxide are mostly used as alkylene oxides.
  • a pure ethylene oxide block is added to the end of the polyether chain.
  • propylene oxide or statistical mixtures of propylene oxide and ethylene oxide are preferably used as alkylene oxide.
  • the ratio of the two alkylene oxides to one another in the mixture is changed in a statistical mixture of ethylene oxide and propylene oxide during the metering, as described in WO 01/44347.
  • the oligomers of formaldehyde can be reacted with the alkylene oxides alone or as a mixture with other H-functional starter substances.
  • At least two-functional alcohols such as glycerol, trimethylolpropane, ethylene glycol, propylene glycol and their higher homologs, are preferably used as additional starting substances.
  • the reaction of the starting substance with the alkylene oxides is generally carried out at the pressures customary for this in the range between 0.1 and 1.0 MPa and the customary temperatures in the range between 80 and 140 ° C.
  • the metering of the alkylene oxides is usually followed by a post-reaction phase for the complete reaction of the alkylene oxides.
  • catalyst in particular amine catalyst, is again added to the reaction mixture at the beginning of the post-reaction phase, preferably immediately after metering in of the alkylene oxides has ended.
  • the polyether alcohols are usually subjected to a short distillation treatment to remove volatile impurities.
  • the polyether alcohol can then be filtered to remove any solid contaminants.
  • the catalyst is removed after the addition of the alkylene oxides. This can be done by neutralization with acids or by using adsorbents. The salts or adsorbents are then removed by filtration.
  • the reaction of the oligomers of formaldehyde with the alkylene oxides can also be carried out continuously, in particular using DMC catalysts.
  • the separated oligomer mixture and the alkylene oxide and the catalyst are continuously fed to a reactor and the polyether alcohol formed is continuously removed from the reactor.
  • Such continuous processes are described for example in DD 203235 and WO 98/03571.
  • the continuous reaction can be carried out, for example, in tubular reactors, stirred tanks or loop reactors.
  • the continuous production of the polyether alcohols by reaction of the oligomers with alkylene oxides can be directly connected to the separation of the oligomers which is also carried out continuously
  • the polyether alcohols obtained in this way can be easily converted into polyurethanes using isocyanates by customary processes.
  • the polyether alcohols according to the invention can be used alone or preferably in a mixture with other compounds with additional alcohols, in particular short-chain polyfunctional alcohols, polyether and / or polyester alcohols, preferably polyether alcohols.
  • the short-chain alcohols used are usually two- or more-functional alcohols with a molecular weight in the range between 62 and 400 g / mol, such as ethylene glycol, propylene glycol and their higher homologues or glycerol.
  • the polyether alcohols and polyester alcohols which can be used are the compounds which are customary and known for this purpose. They usually have a molecular weight Mn of more than 400 g / mol, preferably in the range between 400 and 15000 g / mol.
  • These polyols are prepared by customary and known processes, in the case of polyester alcohols by reaction of polyfunctional alcohols with polyfunctional carboxylic acids, in the case of polyether alcohols by addition of alkylene oxides onto H-functional starter substances. Depending on the nature of the desired polyurethanes, the reaction is optionally carried out in the presence of catalysts, blowing agents and customary auxiliaries and / or additives.
  • the oligomers of formaldehyde are reacted with isocyanates to form prepolymers after their separation from the reaction mixture.
  • the terminal hydroxyl groups of the oligomers of the general formula (I) separated off as described above are reacted with isocyanates. Since the oligomers are only stable in storage for a limited time, here too the reaction must take place immediately after the oligomers have been separated off if a product with a narrow molar mass distribution is to be obtained.
  • the reaction of all hydroxyl groups of the oligomers completely suppresses their cleavage.
  • the prepolymers are stable on storage and can be processed like prepolymers from other polyols commonly used in polyurethane chemistry.
  • the reaction of the hydroxyl group-containing oligomers with the isocyanates is carried out according to the customary method of preparation for prepolymers containing isocyanate groups.
  • the oligomer is reacted with at least such an amount of isocyanate that is sufficient for complete conversion of the hydroxyl groups of the oligomers.
  • the reaction can be carried out in the presence of conventional urethane formation catalysts.
  • the isocyanate compound is usually initially introduced, optionally in the presence of a catalyst, at a temperature of 40 to 100 ° C., preferably 50 to 80 ° C.
  • the oligomer mixture is metered in with stirring, and the reaction mixture is then optionally allowed to after-react until complete conversion, usually up to 2 hours, at 60 to 140 ° C., preferably at 80 to 100 ° C.
  • the NCO content of the prepolymers depends on the molar mass of the oligomers, the excess of isocyanate used, the reaction time, the residence time, the reaction temperature and the catalysts used.
  • the NCO content of the prepolymers is usually in the range between 10 to 30% by weight, preferably 15 to 25% by weight.
  • the oligomers of formaldehyde can be reacted with the isocyanates individually or as a mixture with other compounds with at least two hydrogen atoms reactive with isocyanate groups.
  • the components which can be reacted with the oligomers of formaldehyde with isocyanates to form prepolymers are, in particular, alcohols.
  • different alcohols can be used in an amount of 0 to 90% by weight, preferably 0 to 60% by weight, based in each case on the sum of the oligomers of formaldehyde and the other compounds with at least two hydrogen atoms reactive with isocyanate groups be used.
  • short-chain polyfunctional alcohols polyether and / or polyester alcohols, preferably polyether alcohols, are used as additional alcohols.
  • the short-chain alcohols used are usually two- or more-functional alcohols with a molecular weight in the range between 62 and 400 g / mol, such as ethylene glycol, propylene glycol and their higher homologues or glycerol.
  • Polyether alcohols and polyester alcohols which can be used are those which are customary for this purpose and are described in more detail above. It is also possible to react the polyether alcohols which have been prepared by adding alkylene oxides to oligomers of the general formula (I) together with the oligomers of formaldehyde with isocyanates.
  • isocyanates with two or more isocyanate groups in the molecule are used as isocyanates for the process according to the invention.
  • Both aliphatic isocyanates such as hexamethylene diisocyanate (HDI) or isophorone diisocyanate (IPDI), or preferably aromatic isocyanates, such as tolylene diisocyanate (TDI), “ diphenylmethane diisocyanate (MDI) or mixtures of diphenylmethane diisocyanate and polymethylene polyphenylene MDI and polyisocyanates (P)
  • TDI tolylene diisocyanate
  • MDI diphenylmethane diisocyanate
  • P polymethylene polyphenylene MDI and polyisocyanates
  • isocyanates which have been modified by the incorporation of uretdione, isocyanurate, allophanate, uretonimine and other groups, and these compounds are often also referred to as modified isocyanates
  • the prepolymers produced in this way can be processed to give polyurethanes with compounds which have at least one, preferably at least two, hydrogen atoms reactive with isocyanate groups in the molecule.
  • the prepolymers can be processed into rigid foams, flexible foams, adhesives, coatings or elastomers.
  • a formalin solution with a formaldehyde content of 37% by weight was evaporated to a theoretical formaldehyde content of 73% by weight using a thin-layer evaporator apparatus at a wall temperature of 80 ° C. and 120 mbar.
  • the solution was stored at 80 ° C and processed within an hour. 961 g of this solution were mixed with 38.4 g of dimethylcyclohexylamine in a pilot plant autoclave and 1010 g of propylene oxide were metered in at 100 ° C. within 6 hours.
  • the reaction mixture was then left to react for 2 hours at the same temperature. Then volatile constituents were removed in vacuo.
  • the remaining liquid reaction product had a hydroxyl number of 685 mg KOH / g and a water content of 0.011% by weight.
  • a GPC investigation showed oligomeric products with a molecular weight in the range of 100-500 g / mol.
  • Investigations by gas chromatography and coupled mass spectroscopy (GC-MS) showed that adducts had formed from 2 molecules of propylene oxide and 2 molecules of formaldehyde.
  • a formalin solution with a formaldehyde content of 37% by weight was evaporated to a theoretical formaldehyde content of 73% by weight using a thin-layer evaporator apparatus at a wall temperature of 80 ° C. and 120 mbar.
  • the solution was stored at 80 ° C and processed within an hour. 1110 g of this solution was mixed with 70 g of potassium hydroxide in a pilot plant autoclave and 1600 g of propylene oxide were metered in over 9 hours.
  • the liquid reaction product had a hydroxyl number of 868 mg KOH / g and a water content of 0.014% by weight.
  • An investigation using gel permeation chromatography showed oligomeric products with a molar mass in the range of 100-500 g / mol.
  • GC-MS showed that adducts had formed from 2 molecules of propylene oxide and 2 molecules of formaldehyde.

Abstract

The invention relates to initial compounds for producing polyurethanes and is characterised in that said polyurethanes can be produced by reaction of hydroxyl group containing formaldehyde oligomers.

Description

Ausgangsverbindungen für die Herstellung von PolyurethanenStarting compounds for the production of polyurethanes
Beschreibungdescription
Gegenstand der Erfindung sind neue Ausgangsverbindungen für die Herstellung von Polyurethanen sowie ein Verfahren zu ihrer Herstellung.The invention relates to new starting compounds for the production of polyurethanes and a process for their preparation.
Polyurethane sowie ihre Herstellung sind seit langem bekannt und vielfach in der Literatur beschrieben. Ihre Herstellung erfolgt üblicherweise durch Umsetzung von Poly- isocyanaten mit Verbindungen mit mindestens zwei mit Isocyanatgruppen reaktiven Wasserstoffatomen.Polyurethanes and their production have long been known and have been described many times in the literature. They are usually produced by reacting polyisocyanates with compounds having at least two hydrogen atoms reactive with isocyanate groups.
Als Verbindungen mit mindestens zwei mit Isocyanatgruppen reaktiven Wasserstoffatomen werden zumeist Polyole eingesetzt. Die größte technische Bedeutung haben hierbei die Polyetheralkohole und die Polyesteralkohole.Polyols are mostly used as compounds with at least two hydrogen atoms reactive with isocyanate groups. The greatest technical importance here are the polyether alcohols and the polyester alcohols.
Polyesteralkohole werden üblicherweise durch Umsetzung von mindestens difunktio- nellen Alkoholen mit mindestens difunktionellen Carbonsäuren hergestellt.Polyester alcohols are usually produced by reacting at least difunctional alcohols with at least difunctional carboxylic acids.
Die Polyetheralkohole werden im allgemeinen durch Addition von Alkylenoxiden an OH- oder NH-funktionelle Starterverbindungen erhalten.The polyether alcohols are generally obtained by adding alkylene oxides to OH- or NH-functional starter compounds.
Dabei wird der Preis der bisher üblichen Polyole von den verwendeten Starterverbindungen und den eingesetzten Alkylenoxiden, vor allem Propylenoxid und Ethylenoxid, bestimmt.The price of the usual polyols is determined by the starter compounds used and the alkylene oxides used, especially propylene oxide and ethylene oxide.
Eine wesentlich kostengünstigere Ausgangsverbindung zur Herstellung von Polyolen wäre das Formaldehyd. Bekanntlich reagiert Formaldehyd mit sich selbst zu Oligome- ren, die endständige Hydroxylgruppen aufweisen. Diese Reaktion führt jedoch zumeist zu einem Gemisch aus Oligomeren und Polymeren mit unterschiedlichen Kettenlängen, die mit Formaldehyd im Gleichgewicht stehen. Verbindungen mit einer derart breiten Molekulargewichtsverteilung sind jedoch zur Herstellung von Polyurethanen unbrauchbar. Ein weiterer Nachteil dieser Verbindungen ist ihre mangelnde Stabilität. Bereits nach kurzer Zeit kommt es zu einer Rückspaltung der Oligomere und Poly- mere.A much cheaper starting compound for the production of polyols would be formaldehyde. As is known, formaldehyde reacts with itself to form oligomers that have terminal hydroxyl groups. However, this reaction usually leads to a mixture of oligomers and polymers with different chain lengths, which are in equilibrium with formaldehyde. However, compounds with such a broad molecular weight distribution are unusable for the production of polyurethanes. Another disadvantage of these connections is their lack of stability. The oligomers and polymers are split back after a short time.
In DD 247223 wird ein Verfahren zur Herstellung von Polyetheralkoholen beschrieben, bei dem ein Gemisch aus Formaldehydkondensaten, sogenannter Formose, und anderen Verbindungen mit aktiven Wasserstoffatomen mit Alkylenoxiden umgesetzt wird. Auch bei diesem Verfahren hat die Formose eine breite Molekulargewichtsverteilung. In EP 1 063221 wird eine Methode zur Darstellung von Formaldehydoligomeren der allgemeinen Formel (I) mit enger Molekulargewichtsverteilung, ausgehend von Formaldehyd beschrieben. Die Umsetzung verläuft nach der allgemeinen GleichungDD 247223 describes a process for the preparation of polyether alcohols in which a mixture of formaldehyde condensates, known as formose, and other compounds having active hydrogen atoms is reacted with alkylene oxides. In this process too, the formose has a broad molecular weight distribution. EP 1 063221 describes a method for preparing formaldehyde oligomers of the general formula (I) with a narrow molecular weight distribution, starting from formaldehyde. The implementation follows the general equation
n CH2O + H20 ** HO-f-C-O-jL-Hn CH 2 O + H 2 0 ** HO-fCO-jL-H
H2 H 2
(I) ab.(I) off.
Dabei können durch die Entwässerung von Formaldehydlösungen Formaldehyd- Oligomere der allgemeinen Formel (I) mit n= 2 bis 19, vorzugsweise 2-9, erhalten werden. Diese Lösungen können bis zu 80 % Oligo-Formaldehyd enthalten, freies Wasser liegt nicht vor. Es ist möglich, einzelne Fraktionen, d.h. Oligomere mit bestimmten Kettenlängen, mittels gezielt durchgeführter Verfahrensweise, insbesondere mittels Destillation, abzutrennen. Die Oligomere werden mit anderen Stoffen umgesetzt, wobei man hier die definierte Rückspaltung der Oligomere zu Formaldehyd ausnutzt.Formaldehyde oligomers of the general formula (I) with n = 2 to 19, preferably 2-9, can be obtained by dewatering formaldehyde solutions. These solutions can contain up to 80% oligo-formaldehyde, there is no free water. It is possible to separate single fractions, i.e. Separate oligomers with certain chain lengths by means of a specifically carried out procedure, in particular by means of distillation. The oligomers are reacted with other substances, using the defined cleavage of the oligomers to formaldehyde.
Das resultierende Oligomergemisch aus in der Regel 2-9 Formaldehydeinheiten ist, wie auch Polyoxymethylen, instabil. Binnen 2 Stunden bilden sich neben höhermolekulare Verbindungen (Paraformaldehyd), Wasser und monomolekularer hydratisierter Formaldehyd.The resulting oligomer mixture of 2-9 formaldehyde units, like polyoxymethylene, is unstable. In addition to higher molecular compounds (paraformaldehyde), water and monomolecular hydrated formaldehyde are formed within 2 hours.
Es ist wünschenswert, die Kosten der Ausgangsstoffe zur Herstellung von Polyurethanen, insbesondere der Polyole, zu senken.It is desirable to reduce the cost of the raw materials for making polyurethanes, particularly polyols.
Überraschenderweise wurde gefunden, daß Formaldehyd und seine Oligomeren in einfacher Weise als Ausgangssubstanz zur Herstellung von Polyurethan-Rohstoffen eingesetzt werden können.Surprisingly, it was found that formaldehyde and its oligomers can be used in a simple manner as a starting substance for the production of polyurethane raw materials.
Gegenstand der Erfindung sind demzufolge Ausgangsverbindungen zur Herstellung von Polyurethanen, im folgenden auch als Polyurethan-Rohstoffe bezeichnet, herstellbar durch Umsetzung von Hydroxylgruppen enthaltenden Oligomeren von Formaldehyd.The invention accordingly relates to starting compounds for the production of polyurethanes, hereinafter also referred to as polyurethane raw materials, which can be prepared by reacting oligomers of formaldehyde containing hydroxyl groups.
Gegenstand der Erfindung ist weiterhin ein Verfahren zur Herstellung von Polyurethan- Rohstoffen durch Umsetzung der Hydroxylgruppen von Oligomeren des Formaldehyds. Als Oligomere des Formaldehyds werden Gemische von Verbindungen der allgemeinen Formel (I), wobei n eine ganze Zahl von 2 bis 19, insbesondere von 2 bis 9 ist, eingesetzt.The invention further relates to a process for the production of polyurethane raw materials by reacting the hydroxyl groups of oligomers of formaldehyde. Mixtures of compounds of the general formula (I), where n is an integer from 2 to 19, in particular from 2 to 9, are used as oligomers of formaldehyde.
Die Herstellung der Verbindungen der allgemeinen Formel (I) kann nach bekannten Verfahren erfolgen. So ist es möglich, die Oligomere durch bekannte Polymerisation von Trioxan, einem cyclischen Umsetzungsprodukt des Formaldehyds, zu erzeugen. Dieses Verfahren ist literaturbekannt. Es wird vorzugsweise zur Herstellung von Poly- oxymethylen (POM) angewandt und ist beispielsweise im Römpp Chemie Lexikon beschrieben. Dieses Verfahren ist zur Herstellung der erfindungsgemäßen Polyurethan- Rohstoffe jedoch nicht bevorzugt, da bevorzugt hochmolekulare Umsetzungsprodukte entstehen.The compounds of the general formula (I) can be prepared by known processes. It is thus possible to produce the oligomers by known polymerization of trioxane, a cyclic reaction product of the formaldehyde. This process is known from the literature. It is preferably used for the production of polyoxymethylene (POM) and is described, for example, in the Römpp Chemie Lexikon. However, this process is not preferred for the production of the polyurethane raw materials according to the invention, since high-molecular reaction products are preferably formed.
In einer bevorzugten Ausführungsform der Erfindung werden die Oligomere nach dem in EP 1 063221 beschriebenen Verfahren hergestellt, wobei auf die in diesem Dokument beschriebene nachfolgende Umsetzung der Oligomere mit Anilin verzichtet wird.In a preferred embodiment of the invention, the oligomers are prepared by the process described in EP 1 063221, the subsequent reaction of the oligomers with aniline described in this document being dispensed with.
Die Herstellung der Oligomere des Formaldehyds erfolgt hierbei, indem aus einer Lösung, in der ein Gleichgewicht zwischen Formaldehyd und seinen Oligomeren herrscht, bestimmte Fraktionen abgetrennt werden. Diese Abtrennung erfolgt vorzugsweise destillativ, zumeist mittels eines Filmverdampfers, insbesondere mittels eines Dünnschichtverdampfers. Geeignete Betriebsbedingungen für den Filmverdampfer sind im allgemeinen eine Temperatur zwischen 10 und 230°C, bevorzugt zwischen 10 und 150°C, bei einem Absolutdruck zwischen 0,5 mbar und 2 bar. Für die Auftrennung einer wäßrigen Formaldehydlösung sind Temperaturen zwischen 20 und 100°C bei Normaldruck bevorzugt.The oligomers of formaldehyde are produced by removing certain fractions from a solution in which there is an equilibrium between formaldehyde and its oligomers. This separation is preferably carried out by distillation, mostly by means of a film evaporator, in particular by means of a thin-film evaporator. Suitable operating conditions for the film evaporator are generally a temperature between 10 and 230 ° C, preferably between 10 and 150 ° C, at an absolute pressure between 0.5 mbar and 2 bar. Temperatures between 20 and 100 ° C. at normal pressure are preferred for the separation of an aqueous formaldehyde solution.
Die so abgetrennten Fraktionen von Oligomeren des Formaldehyds weisen zumeist eine sehr enge Molekulargewichtsverteilung auf. Sie sind, wie oben ausgeführt, für eine bestimmte Zeit lagerstabil und sollten während dieser Zeit weiterverarbeitet werden, um eine Veränderung ihrer Zusammensetzung zu vermeiden.The fractions of oligomers of formaldehyde separated in this way usually have a very narrow molecular weight distribution. As stated above, they are stable in storage for a certain time and should be processed further during this time in order to avoid a change in their composition.
Prinzipiell könnte auf eine Abtrennung von bestimmten Oligomeren aus der Reaktionsmischung verzichtet und diese unmittelbar zur Herstellung der Ausgangsverbindungen zur Herstellung von Polyurethanen verwendet werden. Nachteilig hierbei ist jedoch, daß diese Mischung große Mengen freies Formaldehyd und Wasser enthält, wodurch es zu erheblichen Nebenreaktionen kommt. Die beschriebenen Oligomere der allgemeinen Formel (I) können prinzipiell auch ohne weitere Behandlung als Ausgangsverbindungen zur Herstellung von Polyurethanen verwendet werden. Wenn die Umsetzung sich unmittelbar an ihre Abtrennung anschließt, werden Abbaureaktionen, die zur Abspaltung von Formaldehyd führen, ver- mieden. Vorzugsweise erfolgt jedoch eine Umsetzung der endständigen Hydroxylgruppen der Oligomere.In principle, it would be possible to dispense with the separation of certain oligomers from the reaction mixture and these could be used directly for the production of the starting compounds for the production of polyurethanes. The disadvantage here, however, is that this mixture contains large amounts of free formaldehyde and water, which leads to considerable side reactions. The oligomers of the general formula (I) described can in principle also be used as starting compounds for the production of polyurethanes without further treatment. If the reaction immediately follows its separation, degradation reactions which lead to the elimination of formaldehyde are avoided. However, the terminal hydroxyl groups of the oligomers are preferably reacted.
Bei der Umsetzung der Oligomere zu Ausgangsverbindungen zur Herstellung von Polyurethanen werden deren endständige Hydroxylgruppen umgesetzt.When the oligomers are converted into starting compounds for the production of polyurethanes, their terminal hydroxyl groups are converted.
In einer Ausführungsform der Erfindung werden die endständigen Hydroxylgruppen mit Alkylenoxiden zu Polyetheralkoholen umgesetzt. Die Umsetzung erfolgt üblicherweise wie bei der bekannten Herstellung von Polyetheralkoholen unter Verwendung der üblichen alkoholischen Startsubstanzen.In one embodiment of the invention, the terminal hydroxyl groups are reacted with alkylene oxides to form polyether alcohols. The reaction is usually carried out as in the known production of polyether alcohols using the usual alcoholic starter substances.
Die Hydroxylzahl der Oligomere liegt je nach Zahl der Formaldehydeinheiten zwischen 1436 mg KOH/g bei n = 2 und 389 mg KOH/g bei n = 9. Da die Oligomere nach der Abtrennung wasserfrei sind, ist ein Trocknungsschritt zwischen der Abtrennung der Oligomere und deren Umsetzung mit den Alkylenoxiden nicht mehr notwendig.Depending on the number of formaldehyde units, the hydroxyl number of the oligomers is between 1436 mg KOH / g at n = 2 and 389 mg KOH / g at n = 9. Since the oligomers are anhydrous after the separation, there is a drying step between the separation of the oligomers and theirs Reaction with the alkylene oxides is no longer necessary.
Wie in der Technik üblich, erfolgt die Umsetzung der Oligomere des Formaldehyds mit den Alkylenoxiden in Anwesenheit von Katalysatoren. Als Katalysatoren können, wie üblich, basische Verbindungen, wie Amine, basische Metalloxide und Metallhydroxide, insbesondere Kaliumhydroxid, eingesetzt werden.As is customary in the art, the oligomers of formaldehyde are reacted with the alkylene oxides in the presence of catalysts. As usual, basic compounds such as amines, basic metal oxides and metal hydroxides, in particular potassium hydroxide, can be used as catalysts.
Bevorzugt als Katalysatoren eingesetzt werden Multimetallcyanidverbindungen, auch als DMC-Katalysatoren bezeichnet. Derartige Verbindungen sind seit langem bekannt und werden beispielsweise in EP 654302 oder in EP 862947 beschrieben. Der Vorteil der Verwendung von DMC-Katalysatoren liegt zum einen darin, daß sie nach der Um- setzung im Produkt verbleiben können, zum anderen darin, daß sie, im Gegensatz zu basischen Katalysatoren, die Rückspaltung der Oligomere nicht begünstigen.Multimetal cyanide compounds, also referred to as DMC catalysts, are preferably used as catalysts. Such compounds have long been known and are described for example in EP 654302 or in EP 862947. The advantage of using DMC catalysts is, on the one hand, that they can remain in the product after the reaction, and, on the other hand, that, unlike basic catalysts, they do not promote the cleavage of the oligomers.
Als Alkylenoxide können die hierfür üblichen und bekannten Verbindungen eingesetzt werden. Die größte technische Bedeutung haben Ethylenoxid und Propylenoxid, die einzeln oder in beliebigen Gemischen untereinander eingesetzt werden können. Beim Einsatz von Ethylenoxid und Propylenoxid können die beiden Alkylenoxide gemeinsam in einer sogenannten Statistik oder nacheinander in sogenannten Alkylenoxidblöcken dosiert werden. Die Art und Menge der dosierten Alkylenoxide hängt insbesondere von der Verwendung der Polyetheralkohole ab. Für den Einsatz in Hartschaumstoffen weisen die Polyetheralkohole kurze Ketten auf. Die Hydroxylzahl derartiger Polyetheralkohole liegt zumeist im Bereich zwischen 300 bis 600, insbesondere zwischen 400 und 500 mg KOH/g. Als Alkylenoxid wird vorzugsweise Propylenoxid eingesetzt.The compounds known and customary for this purpose can be used as alkylene oxides. The greatest technical importance has ethylene oxide and propylene oxide, which can be used individually or in any mixtures with one another. When using ethylene oxide and propylene oxide, the two alkylene oxides can be dosed together in a so-called statistic or in succession in so-called alkylene oxide blocks. The type and amount of the metered alkylene oxides depends in particular on the use of the polyether alcohols. The polyether alcohols have short chains for use in rigid foams. The hydroxyl number of such polyether alcohols is usually in the range between 300 to 600, in particular between 400 and 500 mg KOH / g. Propylene oxide is preferably used as the alkylene oxide.
Für den Einsatz in Weichschaumstoffen werden zumeist langkettige Polyetheralkohole eingesetzt. Die Hydroxylzahl dieser Polyetheralkohole liegt zumeist im Bereich zwischen 30 und 120 mg KOH/g, vorzugsweise im Bereich zwischen 30 und 60 mg KOH/g. Als Alkylenoxide werden zumeist Gemische aus Ethylenoxid und Propylenoxid eingesetzt. Für bestimmte Einsatzgebiete, beispielsweise für die Herstellung von Kaltformschäumen, wird am Ende der Polyetherkette ein reiner Ethylenoxidbiock angelagert.Long-chain polyether alcohols are mostly used for use in flexible foams. The hydroxyl number of these polyether alcohols is usually in the range between 30 and 120 mg KOH / g, preferably in the range between 30 and 60 mg KOH / g. Mixtures of ethylene oxide and propylene oxide are mostly used as alkylene oxides. For certain areas of application, for example for the production of cold-formed foams, a pure ethylene oxide block is added to the end of the polyether chain.
Bei der Verwendung von DMC-Katalysatoren zur Herstellung der Polyetheralkohole wird als Alkylenoxid vorzugsweise Propylenoxid oder statistische Mischungen aus Propylenoxid und Ethylenoxid eingesetzt. In einer besonderen Ausführungsform dieses Verfahrens wird in einer statistischen Mischung aus Ethylenoxid und Propylenoxid während der Dosierung das Verhältnis der beiden Alkylenoxide zueinander in der Mi- schung geändert, wie in WO 01/44347 beschrieben.When DMC catalysts are used to produce the polyether alcohols, propylene oxide or statistical mixtures of propylene oxide and ethylene oxide are preferably used as alkylene oxide. In a special embodiment of this method, the ratio of the two alkylene oxides to one another in the mixture is changed in a statistical mixture of ethylene oxide and propylene oxide during the metering, as described in WO 01/44347.
Durch diese Verfahrensvariante können, durch Verwendung von Oligomeren unterschiedlicher Molekulargewichte, auf einfache Weise Diole in weiten Molmassenbereichen hergestellt werden, die eine enge Molmassenverteilung aufweisen.With this process variant, by using oligomers of different molecular weights, diols in wide molar mass ranges can be easily produced, which have a narrow molar mass distribution.
Die Oligomere des Formaldehyds können allein oder im Gemisch mit anderen H- funktionellen Startsubstanzen mit den Alkylenoxiden umgesetzt werden. Als zusätzliche Startsubstanzen werden vorzugsweise mindestens zweifunktionelle Alkohole, wie Glyzerin, Trimethylolpropan, Ethylenglykol, Propylenglykol sowie deren höhere Homo- löge eingesetzt werden.The oligomers of formaldehyde can be reacted with the alkylene oxides alone or as a mixture with other H-functional starter substances. At least two-functional alcohols, such as glycerol, trimethylolpropane, ethylene glycol, propylene glycol and their higher homologs, are preferably used as additional starting substances.
Die Umsetzung der Startsubstanz mit den Alkylenoxiden wird im allgemeinen bei den hierfür üblichen Drücken im Bereich zwischen 0,1 und 1,0 MPa und den üblichen Temperaturen im Bereich zwischen 80 und 140°C durchgeführt. An die Dosierung der Alky- lenoxide schließt sich zumeist eine Nachreaktionsphase zum vollständigen Abreagieren der Alkylenoxide an. In einer vorteilhaften Ausführungsform des erfindungsgemäßen Verfahrens wird zu Beginn der Nachreaktionsphase, vorzugsweise unmittelbar nach Abschluß der Dosierung der Alkylenoxide, der Reaktionsmischung nochmals Katalysator, insbesondere Aminkatalysator, zugesetzt. Nach der Anlagerung der Alkylenoxide, werden die Polyetheralkohole zumeist einer kurzen destillativen Behandlung zur Abtrennung leichtflüchtiger Verunreinigungen unterzogen. Falls erforderlich, kann der Polyetheralkohol anschließend filtriert werden, um eventuell vorhandene feste Verunreinigungen zu entfernen. Falls als Katalysatoren basische Verbindungen eingesetzt werden, erfolgt im Anschluss an die Anlagerung der Alkylenoxide die Entfernung des Katalysators. Dies kann durch Neutralisation mit Säuren oder durch Einsatz von Adsorptionsmitteln erfolgen. Im Anschluss daran werden die Salze beziehungsweise die Adsorptionsmittel durch Filtration entfernt.The reaction of the starting substance with the alkylene oxides is generally carried out at the pressures customary for this in the range between 0.1 and 1.0 MPa and the customary temperatures in the range between 80 and 140 ° C. The metering of the alkylene oxides is usually followed by a post-reaction phase for the complete reaction of the alkylene oxides. In an advantageous embodiment of the process according to the invention, catalyst, in particular amine catalyst, is again added to the reaction mixture at the beginning of the post-reaction phase, preferably immediately after metering in of the alkylene oxides has ended. After the addition of the alkylene oxides, the polyether alcohols are usually subjected to a short distillation treatment to remove volatile impurities. If necessary, the polyether alcohol can then be filtered to remove any solid contaminants. If basic compounds are used as catalysts, the catalyst is removed after the addition of the alkylene oxides. This can be done by neutralization with acids or by using adsorbents. The salts or adsorbents are then removed by filtration.
In einer besonderen Ausführungsform des erfindungsgemäßen Verfahrens kann die Umsetzung der Oligomeren des Formaldehyds mit den Alkylenoxiden, insbesondere unter Verwendung von DMC-Katalysatoren, auch kontinuierlich durchgeführt werden. Dabei werden das abgetrennte Oligomerengemisch und das Alkylenoxid sowie der Katalysator kontinuierlich einem Reaktor zugeführt und der gebildete Polyetheralkohol kontinuierlich dem Reaktor entnommen. Solche kontinuierlichen Verfahren sind beispielsweise in DD 203235 und WO 98/03571 beschrieben. Die kontinuierliche Umsetzung kann beispielsweise in Rohrreaktoren, Rührkesseln oder Schlaufenreaktoren durchgeführt werden. Bei dieser Ausgestaltung des erfindungsgemäßen Verfahrens kann die kontinuierliche Herstellung der Polyetheralkohole durch Umsetzung der Oli- gomere mit Alkylenoxiden unmittelbar an die ebenfalls kontinuierlich durchgeführte Abtrennung der Oligomere angeschlossen seinIn a special embodiment of the process according to the invention, the reaction of the oligomers of formaldehyde with the alkylene oxides can also be carried out continuously, in particular using DMC catalysts. The separated oligomer mixture and the alkylene oxide and the catalyst are continuously fed to a reactor and the polyether alcohol formed is continuously removed from the reactor. Such continuous processes are described for example in DD 203235 and WO 98/03571. The continuous reaction can be carried out, for example, in tubular reactors, stirred tanks or loop reactors. In this embodiment of the process according to the invention, the continuous production of the polyether alcohols by reaction of the oligomers with alkylene oxides can be directly connected to the separation of the oligomers which is also carried out continuously
Die so erhaltenen Polyetheralkohole können problemlos nach üblichen Verfahren mit Isocyanaten zu Polyurethanen umgesetzt werden. Dabei können die erfindungsgemä- Ben Polyetheralkohole allein oder bevorzugt im Gemisch mit anderen Verbindungen mit zusätzlichen Alkoholen, insbesondere kurzkettigen mehrfunktionellen Alkoholen, Polyether- und/oder Polyesteralkoholen, vorzugsweise Polyetheralkoholen, eingesetzt werden. Als kurzkettige Alkohole werden zumeist zwei- oder mehrfunktionelle Alkohole mit einem Molekulargewicht im Bereich zwischen 62 und 400 g/mol, wie Ethlylenglykol, Propylenglykol und deren höhere Homologen oder Glycerin eingesetzt.The polyether alcohols obtained in this way can be easily converted into polyurethanes using isocyanates by customary processes. The polyether alcohols according to the invention can be used alone or preferably in a mixture with other compounds with additional alcohols, in particular short-chain polyfunctional alcohols, polyether and / or polyester alcohols, preferably polyether alcohols. The short-chain alcohols used are usually two- or more-functional alcohols with a molecular weight in the range between 62 and 400 g / mol, such as ethylene glycol, propylene glycol and their higher homologues or glycerol.
Als Polyetheralkohole und Polyesteralkohole können die für diesen Einsatzzweck üblichen und bekannten Verbindungen eingesetzt werden. Sie haben zumeist ein Molekulargewicht Mn von über 400 g/mol, vorzugsweise im Bereich zwischen 400 und 15000 g/mol. Die Herstellung dieser Polyole erfolgt nach üblichen und bekannten Verfahren, im Falle der Polyesteralkohole durch Umsetzung von mehrfunktionellen Alkoholen mit mehrfunktionellen Carbonsäuren, im Falle der Polyetheralkohole durch Anlagerung von Alkylenoxiden an H-funktionelle Startsubstanzen. Die Umsetzung erfolgt, je nach Art der gewünschten Polyurethane, gegebenenfalls in Anwesenheit von Katalysa- toren, Treibmitteln sowie üblichen Hilfs- und/oder Zusatzstoffen. In einerweiteren Ausführungsform der vorliegenden Erfindung werden die Oligomere des Formaldehyds nach ihrer Abtrennung aus der Reaktionsmischung mit Isocyanaten zu Prepolymeren umgesetzt.The polyether alcohols and polyester alcohols which can be used are the compounds which are customary and known for this purpose. They usually have a molecular weight Mn of more than 400 g / mol, preferably in the range between 400 and 15000 g / mol. These polyols are prepared by customary and known processes, in the case of polyester alcohols by reaction of polyfunctional alcohols with polyfunctional carboxylic acids, in the case of polyether alcohols by addition of alkylene oxides onto H-functional starter substances. Depending on the nature of the desired polyurethanes, the reaction is optionally carried out in the presence of catalysts, blowing agents and customary auxiliaries and / or additives. In a further embodiment of the present invention, the oligomers of formaldehyde are reacted with isocyanates to form prepolymers after their separation from the reaction mixture.
Hierzu werden die endständigen Hydroxylgruppen der wie oben beschrieben abgetrennten Oligomeren der allgemeinen Formel (I) mit Isocyanaten umgesetzt. Da die Oligomeren nur eine begrenzte Zeit lagerstabil sind, muß auch hier die Umsetzung unmittelbar im Anschluss an die Abtrennung der Oligomeren erfolgen, wenn ein Produkt mit einer engen Molmassenverteilung erhalten werden soll.For this purpose, the terminal hydroxyl groups of the oligomers of the general formula (I) separated off as described above are reacted with isocyanates. Since the oligomers are only stable in storage for a limited time, here too the reaction must take place immediately after the oligomers have been separated off if a product with a narrow molar mass distribution is to be obtained.
Bei einer zu langen Aufbewahrung der Oligomeren kommt es neben einer Verbreiterung der Molmassenverteilung auch zu einer Bildung von Formaldehyd und Wasser in der Oligomerenmischung. Dies ist, obwohl der gebildete Formaldehyd prinzipiell durch abstrippen entfernt werden kann, nachteilig für die Weiterverarbeitung der Oligomeren zu Prepolymeren, da es zu unerwünschten Nebenreaktionen führt.If the oligomers are stored for too long, in addition to broadening the molecular weight distribution, formaldehyde and water are also formed in the oligomer mixture. Although the formaldehyde formed can in principle be removed by stripping, this is disadvantageous for the further processing of the oligomers into prepolymers, since it leads to undesirable side reactions.
Durch die Reaktion aller Hydroxylgruppen der Oligomeren wird deren Rückspaltung völlig unterdrückt. Die Prepolymeren sind lagerstabil und können verarbeitet werden wie Prepolymere aus anderen, in der Polyurethanchemie gebräuchlichen Polyolen.The reaction of all hydroxyl groups of the oligomers completely suppresses their cleavage. The prepolymers are stable on storage and can be processed like prepolymers from other polyols commonly used in polyurethane chemistry.
Die Umsetzung der Hydroxylgruppen enthaltenden Oligomeren mit den Isocyanaten erfolgt nach der üblichen Herstellungsweise für Isocyanatgruppen enthaltende Prepolymere. Dazu wird das Oligomere mit mindestens einer solchen Menge an Isocyanat zur Reaktion gebracht, die für einen vollständigen Umsatz der Hydroxylgruppen der Oligomere ausreichend ist. Die Umsetzung kann im Beisein von üblichen Urethanbil- dungskatalysatoren erfolgen. Hierzu wird zumeist die Isocyanatverbindung, gegebenenfalls im Beisein eines Katalysators, bei einer Temperatur von 40 bis 100°C, bevorzugt 50 bis 80°C, vorgelegt. Unter Rühren wird das Oligomergemisch zudosiert, anschließend lässt man das Reaktionsgemisch gegebenenfalls bis zum vollständigen Umsatz, zumeist bis zu 2 Stunden, bei 60 bis 140 °C bevorzugt bei 80 bis 100°C nachreagieren.The reaction of the hydroxyl group-containing oligomers with the isocyanates is carried out according to the customary method of preparation for prepolymers containing isocyanate groups. For this purpose, the oligomer is reacted with at least such an amount of isocyanate that is sufficient for complete conversion of the hydroxyl groups of the oligomers. The reaction can be carried out in the presence of conventional urethane formation catalysts. For this purpose, the isocyanate compound is usually initially introduced, optionally in the presence of a catalyst, at a temperature of 40 to 100 ° C., preferably 50 to 80 ° C. The oligomer mixture is metered in with stirring, and the reaction mixture is then optionally allowed to after-react until complete conversion, usually up to 2 hours, at 60 to 140 ° C., preferably at 80 to 100 ° C.
Der NCO-Gehalt der Prepolymeren ist abhängig von der Molmasse der Oligomeren, dem verwendeten Überschuss an Isocyanat, der Reaktionszeit, der Verweilzeit, der Reaktionstemperatur und der verwendeten Katalysatoren.The NCO content of the prepolymers depends on the molar mass of the oligomers, the excess of isocyanate used, the reaction time, the residence time, the reaction temperature and the catalysts used.
Üblicherweise liegt der NCO-Gehalt der Prepolymere im Bereich zwischen 10 bis 30 Gew.-% bevorzugt 15 bis 25 Gew.-%. Die Oligomere des Formaldehyds können einzeln oder im Gemisch mit anderen Ver- , bindungen mit mindestens zwei mit Isocyanatgruppen reaktiven Wasserstoffatomen mit den Isocyanaten umgesetzt werden. Die Komponenten, die gemeinsam mit den Oligomeren des Formaldehyds mit Isocyanaten zu Prepolymeren umgesetzt werden kön- nen, sind insbesondere Alkohole. Je nach vorgesehener Verwendung der Prepolymere können unterschiedliche Alkohole in einer Menge von 0 bis 90 Gew.-%, bevorzugt 0 bis 60 Gew.-%, jeweils bezogen auf die Summe der Oligomere des Formaldehyds und der anderen Verbindungen mit mindestens zwei mit Isocyanatgruppen reaktiven Wasserstoffatomen eingesetzt werden.The NCO content of the prepolymers is usually in the range between 10 to 30% by weight, preferably 15 to 25% by weight. The oligomers of formaldehyde can be reacted with the isocyanates individually or as a mixture with other compounds with at least two hydrogen atoms reactive with isocyanate groups. The components which can be reacted with the oligomers of formaldehyde with isocyanates to form prepolymers are, in particular, alcohols. Depending on the intended use of the prepolymers, different alcohols can be used in an amount of 0 to 90% by weight, preferably 0 to 60% by weight, based in each case on the sum of the oligomers of formaldehyde and the other compounds with at least two hydrogen atoms reactive with isocyanate groups be used.
Für die meisten Anwendungen werden als zusätzliche Alkohole kurzkettige mehrfunkti- onelle Alkohole, Polyether- und/oder Polyesteralkohole, vorzugsweise Polyetheralkohole, eingesetzt. Als kurzkettige Alkohole werden zumeist zwei- oder mehrfunktionelle Alkohole mit einem Molekulargewicht im Bereich zwischen 62 und 400 g/mol, wie Ethlylenglykol, Propylenglykol und deren höhere Homologen oder Glycerin eingesetzt.For most applications, short-chain polyfunctional alcohols, polyether and / or polyester alcohols, preferably polyether alcohols, are used as additional alcohols. The short-chain alcohols used are usually two- or more-functional alcohols with a molecular weight in the range between 62 and 400 g / mol, such as ethylene glycol, propylene glycol and their higher homologues or glycerol.
Als Polyetheralkohole und Polyesteralkohole können die für diesen Einsatzzweck üblichen, oben näher beschriebenen eingesetzt werden. Es ist auch möglich, die Polyetheralkohole, die durch Anlagerung von Alkylenoxiden an Oligomere der allgemeinen Formel (I) hergestellt wurden, gemeinsam mit den Oligomeren des Formaldehyds mit Isocyanaten umzusetzen.Polyether alcohols and polyester alcohols which can be used are those which are customary for this purpose and are described in more detail above. It is also possible to react the polyether alcohols which have been prepared by adding alkylene oxides to oligomers of the general formula (I) together with the oligomers of formaldehyde with isocyanates.
Als Isocyanate kommen für das erfindungsgemäße Verfahren alle Isocyanate mit zwei oder mehr Isocyanatgruppen im Molekül zum Einsatz. Dabei können sowohl aliphati- sehe Isocyanate, wie Hexamethylendiisocyanat (HDI) oder Isophorondiisocyanat (IPDI), oder vorzugsweise aromatische Isocyanate, wie Toluylendiisocyanat (TDI), " Diphenylmethandiisocyanat (MDI) oder Mischungen aus Diphenylmethandiisocyanat und Polymethylenpolyphenylenpolyisocyanaten (P-MDI), vorzugsweise TDI und MDI, verwendet werden. Es ist auch möglich, Isocyanate einzusetzen, die durch den Einbau von Uretdion-, Isocyanurat-, Allophanat-, Uretonimin- und anderen Gruppen modifiziert wurden. Diese Verbindungen werden häufig auch als modifizierte Isocyanate bezeichnet.All isocyanates with two or more isocyanate groups in the molecule are used as isocyanates for the process according to the invention. Both aliphatic isocyanates, such as hexamethylene diisocyanate (HDI) or isophorone diisocyanate (IPDI), or preferably aromatic isocyanates, such as tolylene diisocyanate (TDI), “ diphenylmethane diisocyanate (MDI) or mixtures of diphenylmethane diisocyanate and polymethylene polyphenylene MDI and polyisocyanates (P) It is also possible to use isocyanates which have been modified by the incorporation of uretdione, isocyanurate, allophanate, uretonimine and other groups, and these compounds are often also referred to as modified isocyanates.
Die so hergestellten Prepolymere können mit Verbindungen, die mindestens ein, vor- zugsweise mindestens zwei mit Isocyanatgruppen reaktive Wasserstoffatome im Molekül aufweisen, zu Polyurethanen verarbeitet werden. Je nach Art der verwendeten Polyole und Isocyanate können die Prepolymere zu Hartschaumstoffen, Weichschaumstoffen, Klebern, Coatings oder Elastomeren verarbeitet werden.The prepolymers produced in this way can be processed to give polyurethanes with compounds which have at least one, preferably at least two, hydrogen atoms reactive with isocyanate groups in the molecule. Depending on the type of polyols and isocyanates used, the prepolymers can be processed into rigid foams, flexible foams, adhesives, coatings or elastomers.
Die Erfindung soll an den folgenden Beispielen näher erläutert werden. Beispiel 1The invention is illustrated by the following examples. example 1
Eine Formalinlosung mit einem Gehalt an Formaldehyd von 37 Gew.-% wurde mittels Dünnschichtverdampferapparatur bei 80°C Wandtemperatur und 120 mbar auf einen theoretischen Formaldehydgehalt von 73 Gew.-% eingedampft. Die Lösung wurde bei 80°C aufbewahrt und innerhalb einer Stunde weiterverarbeitet. 961 g dieser Lösung wurde in einem Technikumsautoklaven mit 38,4 g Dimethylcyclohexylamin versetzt und innerhalb von 6 Stunden 1010 g Propylenoxid bei 100°C zudosiert. Anschließend ließ man die Reaktionsmischung 2 Stunden bei derselben Temperatur nachreagieren. Da- nach wurden flüchtige Bestandteile im Vakuum entfernt. Das verbleibende flüssige Reaktionsprodukt hatte eine Hydroxylzahl von 685 mg KOH/g und einen Wassergehalt von 0,011 Gew.-%. Eine GPC Untersuchung zeigte oligomere Produkte mit einer Molmasse im Bereich von 100 - 500 g/mol. Mittels Untersuchungen durch eine Gaschromatographie und daran gekoppelter Massenspektroskopie (GC-MS) konnte gezeigt werden, dass sich Addukte aus 2 Molekülen Propylenoxid und 2 Molekülen Formaldehyd gebildet hatten.A formalin solution with a formaldehyde content of 37% by weight was evaporated to a theoretical formaldehyde content of 73% by weight using a thin-layer evaporator apparatus at a wall temperature of 80 ° C. and 120 mbar. The solution was stored at 80 ° C and processed within an hour. 961 g of this solution were mixed with 38.4 g of dimethylcyclohexylamine in a pilot plant autoclave and 1010 g of propylene oxide were metered in at 100 ° C. within 6 hours. The reaction mixture was then left to react for 2 hours at the same temperature. Then volatile constituents were removed in vacuo. The remaining liquid reaction product had a hydroxyl number of 685 mg KOH / g and a water content of 0.011% by weight. A GPC investigation showed oligomeric products with a molecular weight in the range of 100-500 g / mol. Investigations by gas chromatography and coupled mass spectroscopy (GC-MS) showed that adducts had formed from 2 molecules of propylene oxide and 2 molecules of formaldehyde.
Beispiel 2Example 2
Eine Formalinlosung mit einem Gehalt an Formaldehyd von 37 Gew.-% wurde mittels Dünnschichtverdampferapparatur bei 80°C Wandtemperatur und 120 mbar auf einen theoretischen Formaldehydgehalt von 73 Gew.-% eingedampft. Die Lösung wurde bei 80°C aufbewahrt und innerhalb einer Stunde weiterverarbeitet. 1110 g dieser Lösung wurde in einem Technikumsautoklaven mit 70 g Kaliumhydroxid versetzt und innerhalb von 9 h 1600 g Propylenoxid zudosiert. Das flüssige Reaktionsprodukt hatte eine Hydroxylzahl von 868 mg KOH/g und einen Wassergehalt von 0,014 Gew.-%. Eine Untersuchung mittels Gelpermeationschromographie zeigte oligomere Produkte mit der Molmasse im Bereich 100 - 500 g/mol. Mittels GC-MS konnte gezeigt werden, dass sich Addukte aus 2 Molekülen Propylenoxid und 2 Molekülen Formaldehyd gebildet hatten. A formalin solution with a formaldehyde content of 37% by weight was evaporated to a theoretical formaldehyde content of 73% by weight using a thin-layer evaporator apparatus at a wall temperature of 80 ° C. and 120 mbar. The solution was stored at 80 ° C and processed within an hour. 1110 g of this solution was mixed with 70 g of potassium hydroxide in a pilot plant autoclave and 1600 g of propylene oxide were metered in over 9 hours. The liquid reaction product had a hydroxyl number of 868 mg KOH / g and a water content of 0.014% by weight. An investigation using gel permeation chromatography showed oligomeric products with a molar mass in the range of 100-500 g / mol. GC-MS showed that adducts had formed from 2 molecules of propylene oxide and 2 molecules of formaldehyde.

Claims

Patentansprüche claims
1. Ausgangsverbindungen zur Herstellung von Polyurethanen, dadurch gekennzeichnet, dass sie durch Umsetzung von Hydroxylgruppen enthaltenden Oligo- meren von Formaldehyd herstellbar sind.1. Starting compounds for the production of polyurethanes, characterized in that they can be prepared by reacting oligomers of formaldehyde containing hydroxyl groups.
2. Verbindungen nach Anspruch 1 , dadurch gekennzeichnet, dass als Oligomere des Formaldehyds solche der allgemeinen Formel (I), wobei n eine ganze Zahl zwischen 2 und 19 ist, eingesetzt werden2. Compounds according to claim 1, characterized in that those of the general formula (I), where n is an integer between 2 and 19, are used as the oligomers of formaldehyde
3. Verbindungen nach Anspruch 1 , dadurch gekennzeichnet, dass sie durch Umsetzung der Hydroxylgruppen der Oligomeren von Formaldehyd mit Alkylenoxiden herstellbar sind.3. Compounds according to claim 1, characterized in that they can be prepared by reacting the hydroxyl groups of the oligomers of formaldehyde with alkylene oxides.
4. Verbindungen nach Anspruch 3, dadurch gekennzeichnet, dass als Alkylenoxide Ethylenoxid, Propylenoxid oder Gemische aus Ethylenoxid und Propylenoxid eingesetzt werden.4. Compounds according to claim 3, characterized in that ethylene oxide, propylene oxide or mixtures of ethylene oxide and propylene oxide are used as alkylene oxides.
5. Verbindungen nach Anspruch 1, dadurch gekennzeichnet, dass sie durch Umsetzung der Hydroxylgruppen der Oligomeren von Formaldehyd mit Isocyanaten hergestellt werden.5. Compounds according to claim 1, characterized in that they are prepared by reacting the hydroxyl groups of the oligomers of formaldehyde with isocyanates.
6. Verbindungen nach Anspruch 5, dadurch gekennzeichnet, dass sie einen NCO- Gehalt im Bereich von 10 bis 30 Gew.-% aufweisen.6. Compounds according to claim 5, characterized in that they have an NCO content in the range of 10 to 30 wt .-%.
7. Verbindungen nach Anspruch 5, dadurch gekennzeichnet, dass sie einen NCO- Gehalt im Bereich von 15 bis 25 Gew.-% aufweisen.7. Compounds according to claim 5, characterized in that they have an NCO content in the range of 15 to 25 wt .-%.
8. Verfahren zur Herstellung von Verbindungen nach Anspruch 1 , dadurch gekennzeichnet, dass die Hydroxylgruppen enthaltenden Oligomeren von Formaldehyd umgesetzt werden.8. A process for the preparation of compounds according to claim 1, characterized in that the hydroxyl-containing oligomers of formaldehyde are reacted.
9. Verfahren nach Anspruch 8, umfassend die Schritte a) Herstellung von Oligomeren von Formaldehyd mit der allgemeinen Formel (I) b) Umsetzung der Hydroxylgruppen der Oligomeren von Formaldehyd. 9. The method according to claim 8, comprising the steps a) preparation of oligomers of formaldehyde with the general formula (I) b) reaction of the hydroxyl groups of the oligomers of formaldehyde.
10. Verfahren nach Anspruch 9, dadurch gekennzeichnet, dass in Schritt a) die Oligomeren durch Destillation aus einer wässrigen Formaldehydlösung abgetrennt werden.10. The method according to claim 9, characterized in that in step a) the oligomers are separated by distillation from an aqueous formaldehyde solution.
11. Verfahren nach Anspruch 10, dadurch gekennzeichnet, dass die Destillation eine Dünnschichtdestillation ist.11. The method according to claim 10, characterized in that the distillation is a thin film distillation.
12. Verfahren nach Anspruch 9, dadurch gekennzeichnet, dass in Schritt b) eine Umsetzung mit Alkylenoxiden durchgeführt wird.12. The method according to claim 9, characterized in that in step b) a reaction with alkylene oxides is carried out.
13. Verfahren nach Anspruch 9, dadurch gekennzeichnet, dass in Schritt b) eine Umsetzung mit Isocyanaten durchgeführt wird.13. The method according to claim 9, characterized in that in step b) a reaction with isocyanates is carried out.
14. Verfahren nach Anspruch 9, dadurch gekennzeichnet, dass die Schritte a) und b) kontinuierlich durchgeführt werden.14. The method according to claim 9, characterized in that steps a) and b) are carried out continuously.
15. Verfahren zur Herstellung von Polyurethanen, dadurch gekennzeichnet, dass Verbindungen nach Anspruch 3 mit Isocyanaten umgesetzt werden.15. A process for the preparation of polyurethanes, characterized in that compounds according to claim 3 are reacted with isocyanates.
16. Verfahren zur Herstellung von Polyurethanen, dadurch gekennzeichnet, dass Verbindungen nach Anspruch 5 mit Verbindungen mit mindestens zwei mit Isocyanaten reaktiven Gruppen umgesetzt werden. 16. A process for the preparation of polyurethanes, characterized in that compounds according to claim 5 are reacted with compounds having at least two groups reactive with isocyanates.
EP04727865A 2003-04-28 2004-04-16 Initial compounds for producing polyurethanes Withdrawn EP1620383A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10319242A DE10319242A1 (en) 2003-04-28 2003-04-28 Starting compounds for the production of polyurethanes
PCT/EP2004/004036 WO2004096746A1 (en) 2003-04-28 2004-04-16 Initial compounds for producing polyurethanes

Publications (1)

Publication Number Publication Date
EP1620383A1 true EP1620383A1 (en) 2006-02-01

Family

ID=33305009

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04727865A Withdrawn EP1620383A1 (en) 2003-04-28 2004-04-16 Initial compounds for producing polyurethanes

Country Status (7)

Country Link
EP (1) EP1620383A1 (en)
JP (1) JP2006524648A (en)
KR (1) KR20060007398A (en)
CN (1) CN100349844C (en)
DE (1) DE10319242A1 (en)
MX (1) MXPA05011193A (en)
WO (1) WO2004096746A1 (en)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10435501B2 (en) 2014-04-07 2019-10-08 Covestro Deutschland Ag Thermoplastic polyurethanes, production and use thereof
ES2702327T3 (en) * 2014-04-07 2019-02-28 Covestro Deutschland Ag Process for the production of polyoxymethylene block copolymers
CN109890869A (en) 2016-08-12 2019-06-14 科思创德国股份有限公司 The method of preparation polymerization open-loop products
EP3533815A1 (en) 2018-02-28 2019-09-04 Covestro Deutschland AG Flexible polyurethane foams based on polyoxymethylene polyoxyalkylene block copolymers
EP3643730A1 (en) 2018-10-26 2020-04-29 Covestro Deutschland AG Method for the preparation of polyoxymethylene polyoxyalkylene block copolymers
EP3653657A1 (en) * 2018-11-16 2020-05-20 Covestro Deutschland AG Method for the preparation of prepolymers comprising a polyoxymethylene block
EP3656797A1 (en) 2018-11-22 2020-05-27 Covestro Deutschland AG Method for the preparation of polyoxymethylene polyoxyalkylene block copolymers
EP3656796A1 (en) 2018-11-22 2020-05-27 Covestro Deutschland AG Method for the preparation of polyoxymethylene polymers with medium chain length
EP3838938A1 (en) 2019-12-18 2021-06-23 Covestro Deutschland AG Method for the preparation of polyoxymethylene polyoxyalkylene copolymers
EP3960783A1 (en) 2020-09-01 2022-03-02 Covestro Deutschland AG Isocyanate-terminated prepolymers based on polyoxymethylene-polyoxyalkylene block copolymers, method for their preparation and their use
EP4015555A1 (en) 2020-12-18 2022-06-22 Covestro Deutschland AG Method for preparing a monol or polyol comprising a polyoxymethylene block
EP4201973A1 (en) 2021-12-21 2023-06-28 Covestro Deutschland AG Prepolymer comprising a polyoxymethylene block and method for producing the same

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2639083C2 (en) * 1976-08-31 1983-02-10 Bayer Ag, 5090 Leverkusen Process for the production of polyether polyols and their use as starting materials for polyurethane plastics
SU767122A1 (en) * 1978-04-10 1980-09-30 Предприятие П/Я А-3957 Method of preparing formose polyglycolic ethers
US4340719A (en) * 1980-08-25 1982-07-20 E. I. Du Pont De Nemours And Company Oligomeric formal diols of poly(tetramethylene ether) glycol and polyurethanes prepared therefrom
DD247223A1 (en) * 1986-03-06 1987-07-01 Schwarzheide Synthesewerk Veb PROCESS FOR THE PREPARATION OF POLYETHERAL COCOOLS
JP2695256B2 (en) * 1989-11-22 1997-12-24 日本化成株式会社 Formaldehyde-urea aqueous solution
DE19925870A1 (en) * 1999-06-07 2000-12-14 Basf Ag Process for converting a solution containing a mixture

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2004096746A1 *

Also Published As

Publication number Publication date
JP2006524648A (en) 2006-11-02
CN100349844C (en) 2007-11-21
DE10319242A1 (en) 2004-11-18
CN1780805A (en) 2006-05-31
KR20060007398A (en) 2006-01-24
MXPA05011193A (en) 2005-12-14
WO2004096746A1 (en) 2004-11-11

Similar Documents

Publication Publication Date Title
EP1797129B1 (en) Method for producing flexible polyurethane foams
EP1746117B1 (en) Prepolymers containing isocyanate groups
EP1620383A1 (en) Initial compounds for producing polyurethanes
WO2001044347A1 (en) Method for production of polyether alcohols
EP1379569A1 (en) Method for producing mdi, especially 2,4'-mdi
EP1448665A1 (en) Method for producing polyether alcohols
EP1451239B1 (en) Method for producing prepolymers containing isocyanate groups and urethane groups
EP0809663A1 (en) Process for producing polyisocyanates containing biuret groups
EP1869105B1 (en) Method for producing polyether alcohols
EP1443066A2 (en) Process for the preparation of oligomeric aliphatic diols, polycarbonatediols prepared using these oligomeric aliphatic diols and their prepolymers.
EP3880731A1 (en) Process for preparing prepolymers that comprise a polyoxymethylene block
US7705106B2 (en) Initial compounds for producing polyurethanes
EP3024862A1 (en) The use of succinonitrile in the production of polyisocyanates which contain iminooxadiazine dione groups
WO2004029131A1 (en) Method for producing polyether alcohols
EP1650242B1 (en) Crystallisation stable MDI allophanates obtained by a two step process
WO1998022519A1 (en) Two step procedure for the production of semi-hard solid polyurethane moulded bodies
EP3339340A1 (en) Method for producing a polyoxymethylene-block-copolymer having an increased proportion of built-in formaldehyde
DE2857586C2 (en) Storage-stable, activated NCO pre-adduct mixtures
WO2022128748A1 (en) Process for the production of a monol or polyol comprising a polyoxymethylene block
DD141525A1 (en) METHOD OF RECOVERING HYDROGEN-ACTIVE COMPOUNDS FROM POLYURETHANE WASTE
EP2411438B1 (en) Production of polyisocyanate prepolymers having allophanate structure units and use thereof in formulations for coatings, adhesives and sealants
WO2023083877A1 (en) Method for producing aromatic polymeric carbodiimides
DE1270810B (en) Process for the production of physiologically harmless urethane isocyanates
WO2001044340A1 (en) Polyurethane casting elastomers based on 2,5-toluylendiisocyanate
DE19700944A1 (en) Polyether-poly:ol mixture for polyurethane production

Legal Events

Date Code Title Description
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

17P Request for examination filed

Effective date: 20051128

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PL PT RO SE SI SK TR

DAX Request for extension of the european patent (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: BASF SE

17Q First examination report despatched

Effective date: 20111209

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

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20130723