• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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    • 专利摘要:
    process for the production of mdi dimer The invention relates to a process for the preparation of 4,4'-methylene-bis(phenylisocyanate) dimer (mdi dimer) which is characterized in that an mdi dimer is obtained. of high purity. the mdi dimer prepared by the process according to the invention is characterized by being substantially free of mdi as well as urea derivatives. the invention further relates to a corresponding mdi dimer as well as its use as a crosslinking agent for polyurethanes.
    公开号:BR102013029100B1
    申请号:R102013029100-5
    申请日:2013-11-12
    公开日:2021-09-08
    发明作者:Kaplan Andreas
    申请人:Ems-Patent Ag；
    IPC主号:
    专利说明:

    The invention relates to a process for the preparation of 4,4'-methylene-bis(phenylisocyanate) dimer (MDI dimer) is characterized in that an MDI dimer is obtained which is of high purity. The MDI dimer produced by the process according to the invention is characterized in that it is substantially free of MDI and urea derivatives. The invention further concerns a corresponding MDI dimer, as well as their use as crosslinking agents for polyurethanes.
    4,4'-methylene-bis(phenylisocyanate) dimers (under other nomenclature also known as 4,4'-diphenylmethylene diisocyanate dimer) (MDI dimer) are known. The 4,4'-MDI dimer has the CAS number. 17589- 24-1.
    From JP 09-328474 of Nippon Polyurethane a process for the production of an MDI dimer is already known. In this process, MDI is first dissolved in ethyl acetate and treated with a catalyst. The MDI dimer is then removed by filtration after 24 hours. However, as is evident from JP 09-328474 (see Example 3), the reaction product is only 81% MDI dimer. The MDI dimer obtained according to the Japanese document thus still contains high levels of MDI monomer and urea derivatives. MDI dimers of this nature are therefore only limitedly suitable as crosslinking agents for polymers.
    For many applications, in particular for use as polymer crosslinkers, it is essential that the 4,4-MDI dimer be present in high purity. In particular for use as a crosslinking agent for polyurethanes it is a requirement to provide a 4,4'-MDI dimer that is available free of MDI monomer and urea derivatives. For such applications, it is also important that the MDI dimer is readily available and has a uniform grain size.
    Based on this, the object of the present invention is to make available a process for the preparation of a 4,4-MDI dimer that obtains a product with a high degree of purity. The goal here is for the 4,4-MDI dimer to be free of MDI monomer and urea derivatives. The invention further includes a corresponding 4,4-MDI dimer, as well as the use of said 4,4-MDI dimer as a crosslinking agent for polyurethanes.
    The invention is carried out in relation to the process by the features of claim 1 and with respect to the. MDI dimer by the features of claim 10. The dependent claims disclose advantageous developments. In claim 15 the uses of the invention are mentioned.
    The process according to the invention is characterized in that in a first process step (a) a solvent is provided, which already contains a catalyst, in which the solvent is selected from. so as to be suitable as a solvent for 4,4'-methylene-bis(phenylisocyanate). In this first step, it is also necessary to operate in an inert gas atmosphere, at the lowest possible temperature, ie >25°C to a maximum of 45°C.
    In the next step (b), 4,4'-methylene-bis(phenylisocyanate), i.e. MDI, melted and/or dissolved is added with stirring. Then then the product starts to precipitate.
    Subsequently, the reaction is terminated by adding a deactivator (step (c)) . At this stage, it is essential that, after stopping the reaction, the agitation is maintained for a certain amount of time. This period of time is in the range of 0.5 to 1.5 hours.
    After this process step, the MDI dimer is separated from the solvent (process step (d)) and purified in step (e).
    In the present process according to the invention, it is particularly important that the exact sequence of the above steps (a) to (e) is kept exactly. Special importance is attached to the control of the reaction, especially with regard to the temperature level. It is essential that, as indicated in step (a), the temperature is maintained, at > 25°C, is in the range up to 45°C.
    It is preferred that the temperature in step (a) is maintained at 30 to 40°C.
    For the addition of molten and/or dissolved MDI, a drip is preferred.
    The supply of the solvent contained in the catalyst is carried out under inert gas, wherein said inert gas is selected from nitrogen, argon and/or helium. It is preferred that the water content of these inert gases is set to . at most 0.01% by volume, preferably at most 0.005% by volume.
    Suitable catalysts that are contained in the solution according to the process in step (a) are selected from tertiary phosphines, amine substituted phosphines, imidazoles, guanidines, 3- or 4-substituted pyridines, 3- and 3-substituted pyridines 4-, cyclic amidines, antimony pentafluoride, boron trifluoride, or mixtures thereof.
    Preferred catalysts are tertiary, aliphatic or mixed aliphatic-aromatic phosphines, trialkylphosphines, tris-(N,N-dialkylamine)phosphine, dialkylimidazoliums, 4-N,N-dialkylaminopyridines, pyridines which are substituted at the 3- and 4-positions by atoms of N, which are linked together through carbon segments - preferably two-element saturated carbon segments, or mixtures thereof.
    As catalysts, tris-(N,N-dialkylamine)phosphine, 1,2-dialkylimidazolium, 4-N,N-dialkylaminopyridine or mixtures thereof are particularly preferred.
    Very particularly preferred are used as catalysts tris-(N,N-dimethylamine)phosphine, tris-(N,N-diethylamine)phosphine, 4-N,N-dimethylaminopyridine, 4-N,N-dimethylaminopyridine, 1,2 -dimethylimidazole, 1,2-diethylimidazole or mixtures thereof.
    Phosphines are also known as phosphanes or phosphorans.
    As deactivator for stopping the reaction (process step(c)) all deactivators common per se can be used. Examples include acids, acid chlorides, acid anhydrides or alkylating agents.
    Chloroacetic acid, trichloroacetic acid, trifluoroacetic acid, methanesulfonic acid, perfluoro butanol sulfonic acid, phosphoric acid, formic acid chloride, benzoyl chloride, dimethyl carbamide acid chloride, acetic anhydride, succinic acid anhydride, sulfate are preferably used as the deactivator of dimethyl, methyl iodide, toluenesulfonic acid methyl ester or mixtures thereof.
    Particularly preferred is the use of benzoyl chloride as a deactivator.
    The separation of the MDI dimer from the solvent (step (d)) is carried out with a mechanical separation process or a combination of several mechanical separation processes for solid-liquid separation. Preferably, the at least one mechanical separation process is selected from the group consisting of sedimentation, filtration, centrifugation, and precipitation with cyclones.
    In sedimentation, separation can be by gravity or by centrifugal force.
    In filtration, sedimentation can be caused by gravity, centrifugal force or pressure differences. Pressure differences can be either under-pressure (vacuum) or over-pressure.
    Filtration can be carried out by means of suction filters, disc filters, drum filters, sheet filters, plate filter, belt filter, shear gap filters, filter press, membrane filter press, filter presses. belt, or combinations thereof.
    Centrifugation can be performed by means of solid, closed-lid bowl centrifuges, dish centrifuges, disc centrifuges, peeling centrifuges, push centrifuges, cup centrifuges, decanters, separators or combinations.
    In cyclone separation, hydrocyclones are preferably used.
    Finally, in step (e) of the process, in principle it is possible to use a drying of MDI dimer already known in the state of the art, which is preferably carried out between 40°C and 60°C under vacuum or a current of inert gas for 12 to 24 hours. More preferably, drying is carried out between 40°C and 50°C under vacuum for 12 to 20 hours.
    Preferably, the MDI dimer is dried after step (e).
    Solvents which are suitable for the process according to the invention are those which are capable of completely dissolving the MDI monomer at the indicated reaction temperatures, i.e. at > 25°C to 45°C. The water content of the solvent should not exceed 0.04% by weight, preferably not more than 0.02% by weight, more preferably at most 0.01% by weight.
    Examples of solvents are acetone, N-methylpyrrolidone, benzene, ethyl acetate, acetonitrile, nitromethane, kerosene, octane or mixtures thereof.
    The inventors have shown here that ethyl acetate is particularly suitable as a solvent. In the process according to the invention, the purification of the MDI dimer is preferably carried out with the same solvent which is also used for the reaction. Preferably, ethyl acetate is thus used for both the MDI monomer and the purification step.
    The invention further relates to a 4,4'-methylene-bis(phenylisocyanate) dimer which is produced by a process as described above. The MDI dimer according to the invention is characterized in that it is substantially free of monomeric MDI. By substantially free of monomeric MDI is meant that the MDI dimer contains less than 1% by weight, preferably less than 0.5% by weight, more preferably less than 0.1% by weight, more preferably less than 0.08% by weight of monomeric MDI. The MDI dimer according to the invention also does not have percentages of products such as trimers, tetramers, pentamers, or even higher oligomers detectable by means of HPLC-MS (High Performance Liquid Chromatography - combination of mass spectrometry) with UV detector and mass detector. The inventive MDI dimer is also substantially free of urea derivatives. By substantially free of urea derivatives it will be understood that the MDI dimer contains percentages less than 10% by weight, preferably less than 7% by weight, more preferably less than 4% by weight, most preferably less than 2% by weight weight of urea derivatives.
    The high purity MDI dimer of the invention is preferably provided according to the invention in powder form. For this, the MDI dimer, after process step (d) (which separates the resulting MDI dimer from the solvent) and purification of the MDI dimer with the solvent (step (e)) is subjected to a milling process then so that the average particle size of the powder is in the range of 1 to 4 µm, preferably 2 µm.
    The highly pure MDI dimer according to the invention is particularly suitable as a crosslinking agent for polymers and in particular for the production of polyurethane foam and insulating materials, for example elastic materials such as soft, hard or integral foam, or solid non-foamed or elastic materials for technical articles such as seats, casting resins, coating resins, sealing resins, adhesive resins or coating compositions for artificial leather and textile auxiliary products. The inventive MDI dimer has been found to have an extremely high reaction capacity and provide the final products with excellent mechanical properties after crosslinking.
    The invention is explained with reference to an exemplary embodiment and an example embodiment, as well as with special reference to Figure 1.
    Figure 1 shows the particle size distribution of an MDI’ dimer according to the invention which, after step (e) was subjected to a milling. As can be seen from Figure 1, the MDI dimer in this case has a very narrow size distribution. An MDI dimer in highly purified form as described above in combination with a very fine particle size distribution is particularly suitable as a crosslinking agent for polyurethanes. Furthermore, a very high reactivity was observed which, on the one hand is due to the high degree of purity and, on the other hand, to the particle size distribution. Furthermore, an MDI dimer as described above has excellent shelf life and is therefore particularly suitable as crosslinking agents for polyurethanes.
    The production of. MDI dimer occurs in solution, in an inert atmosphere under anhydrous conditions between 30° and 40° C. The solvent containing the dissolved catalyst is introduced. MDI molten or dissolved is added dropwise with stirring within 0.5 to 3 hours. After about half the addition, the product starts to precipitate. After the dropwise addition, stirring still takes place for 1 to 4 hours at the reaction temperature. Subsequently, the reaction is terminated by adding the deactivator, stirring still remains after the addition for 0.5 to 1.5 hours at the reaction temperature. The mixture is filtered after cooling to room temperature through a glass or ceramic filter under vacuum and then washed at least twice with solvent. Drying takes place under vacuum or inert gas flow between 40 and 60°C for 12 to 24 hours.
    The MDI dimer thus produced does not contain trimers, tetramers, pentamers or higher oligomers, which are detectable by HPLC-MS with UV detector and a mass detector.
    Nitrogen, argon or helium can be used as inert gas, the maximum water content of which is 0.01% by volume.
    The solvent is dried to a water content of not more than 0.04% by weight. If molten MDI is used for the reaction, this is molten at maximum 60°C, preferably at 45 to 55°C. Determination of monomeric MDI in the MDI dimer
    Monomeric MDI is extracted from the MDI dimer and derived into an ethanol extract.
    The MDI dimer is extracted with 25 ml of ethyl acetate in a 50 ml round bottom flask for five hours at 23°C under stirring with a magnetic stirrer. The extract is filtered and the filtrate taken to a 50 ml measuring flask. Then, the extract is filled with ethanol to 50 ml, left to stand at 23°C for 30 minutes, filtered and transferred to a glass flask. This process is carried out from an initial weight (1 mg of MDI dimer per ml of ethyl acetate) and with a high initial weight (25 mg of MDI dimer per ml of ethyl acetate).
    The determination of the concentration of monomeric MDI in the extract is carried out by HPLC (High Performance Liquid Chromatography) using the external standard process.
    As HPLC device an ACQUITY UPLC from the company Waters Corp. is used, as a BEH C18 column from Waters Corp. (10.0 cm long, 2.1 mm internal diameter, 1.7 µm filler particle size). The eluent is used an acetonitrile/water gradient mixture with a flow rate of 0.4 ml/min. Detection is carried out with a UV detector with a wavelength of 254 nm < As an external standard, MDI is used. At least three weights are weighed, dissolved in 50 ml of 1/1 ethyl acetate/ethanol (vol/vol) and bottled. The calibration line is Waters Corp. Empower 2 software, created and must have a correlation coefficient of at least 0.999.
    The monomeric MDI content in % by weight is calculated according to the following formula: Monomeric MDI = ([(KA - KB) x V]: EA) x 100 KA concentration of monomeric MDI, in mg/ml, with a high initial weight 1® concentration of monomeric MDI, in mg/ml, with a low initial weight V is the volume in ml of ethyl acetate EA sample weight of MDI dimer with high sample weight in mg 20 Acetonitrile, ethanol and acetate of ethyl are used in purity (for analysis). In relation to water, it is double distilled water. The arithmetic mean of three measurements was established. 25 Determination of purity of MDI dimers
    The purity of the MDI dimer is determined by HPLC-MS (High Performance Liquid Chromatography-Combination of mass spectrometry) with UV detector and a mass detector, where the classification of the peaks occurs through the mass. The purity of the MDI dimers is given in % surface (Fl. -%) the total surface of all peaks corresponds to 100 Fl. . The values shown are the arithmetic mean of the three measurements. 35 10 mg of the MDI dimers are dissolved in a mixture of 5 ml of tetrahydrofuran and 5 ml of methanol at 23°C, for derivatization with methanol for a further 30 min and then left to stand, filtered and placed in a glass vial.
    As HPLC equipment an Acquity UPLC from Waters Corp. . As a column BEH C18 from Waters Corp. was used. (10.0 cm long, 2.1 mm internal diameter, 1.7 µm filler particle size). The eluent used is an acetonitrile/water gradient mixture. 0 UV detector operating at 254 nm and SQ mass detector in ESI mode (Electrospray Ionization Mode).
    Acetonitrile, methanol and tetrahydrofuran were used in purity (for analysis). In relation to water, it is double distilled water. Examples of preparation of 4,4'-methylene-bis(phenylisocyanate) dimer
    The reaction apparatus consists of a double-walled cylindrical reaction vessel (volume 11) with a bottom drain valve, stirrer, hermetic lid, three drip funnels, two of them double-walled, a G4 filter connected to the drain valve and a vacuum pump.
    The apparatus is rendered inert three times in the exchange of vacuum (30 mbar) and nitrogen. All MDI dimer production takes place under a stream of nitrogen.
    In a reaction vessel thermostated at 35°C, 500 ml of ethyl acetate in which 1.0 g of 4-N,N-dimethylaminopyridine is dissolved are submitted through a dropping funnel and in the reaction vessel thermostated to a temperature 35°C. 130.0 g of MDI melted in a convection oven at 50°C are added thermostated at 50°C in 45 minutes, with stirring. Care is taken that the temperature of the reaction mixture remains at 35°C. After about half of the addition, the product begins to precipitate.
    After addition of MDI stirring is maintained at 35°C for 2 hours. Then, 1.27 g of benzoyl chloride is dissolved in 5 ml of ethyl acetate by means of a dropping funnel thermostated at 35°C, in 10 minutes, with stirring, and further stirred for 15 min.
    Finally the mixture is then cooled to 23°C and filtered through a G4 filter at 550 mbar. The product is washed twice with 100 ml of ethyl acetate and dried at 50° 10 C and 30 mbar for 16 hours. Yield: 120.5 g, i.e. 92.7% by weight, based on the initial weight of MDI. The product contains: 0.07% by weight of monomeric MDI* 15 99.5 Fl -. % derivatized MDI dimer** 0.5 F1 -. % urea dimer, derivatized ** 1 Determined by extraction and subsequent HPLC 2 * Determined by HPLC-MS, indicated as % surface % (fl. -%).
    权利要求:
    Claims (15)
    [0001]
    1. Process for the production of 4,4'-methylene-bis(phenylisocyanate) dimer (MDI dimer), characterized by comprising the following steps in the following order: a) providing only one solvent for 4,4'-methylene- bis(phenylisocyanate) (MDI) in an inert gas atmosphere, said only one solvent and said inert gas being maintained at >25°C to 45°C, and said only one solvent comprising a dimerization catalyst; b) add a molten MDI and/or MDI dissolved in a solvent consisting of the same solvent as the only one solvent from step a) with stirring for a period of 0.5 to 3 hours, c) add a deactivator for cessation of dimerization, with the proviso that stirring takes place in addition over a period of 0.5 to 1.5 hours at a temperature of >25°C to 45°C, in which the deactivator is selected from the group consisting of strong acids, acid chlorides, and acid anhydrides, d) separating the resulting MDI dimer from only one solvent, and e) purifying the resulting MDI dimer, in which during purification of the MDI dimer, the solvent used consists of the same solvent as the only one solvent of step a), and the MDI is washed twice with the same solvent, in which the only one solvent of step a) is selected from the group consisting of acetone, N-methylpyrrolidone, benzene, ethylacetate, acetonitrile, nitromethane, kerosene, and octane; and the water content of only one solvent is maximum 0.04% by weight, and in which the MDI dimer produced by the process has a monomeric MDI content of less than 0.1% by weight.
    [0002]
    2. Process according to claim 1, characterized in that, in step (a), a temperature between 30° C and 40° C is maintained, and the molten and/or dissolved MDI is added in step b) by drip.
    [0003]
    3. Process according to claim 1, characterized in that the inert gas is selected from nitrogen, argon and/or helium.
    [0004]
    4. Process according to claim 3, characterized in that nitrogen, argon and/or helium has a maximum water content of 0.01% by volume.
    [0005]
    5. Process according to claim 1, characterized in that the dimerization catalyst is selected from the group consisting of tertiary phosphines, amino substituted phosphines, imidazoliums, guanidines, pyridines substituted in the 3- or 4- position, pyridines 3- and 4-substituted, cyclic amidines, antimony pentafluoride, boron trifluoride, and mixtures thereof.
    [0006]
    6. Process according to claim 5, characterized in that the dimerization catalyst is selected from the group consisting of tertiary or aliphatic phosphines or mixed aromatic-aliphatic phosphines, trialkylphosphines, tris-(N,N-dialkylamine) phosphines, dialkylimidazoliums, 4-N,N-dialkylaminopyridines, pyridines substituted at the 3- and 4-positions by N atoms, and which are linked together through carbon segments, and mixtures thereof.
    [0007]
    7. Process according to claim 6, characterized in that the dimerization catalyst is selected from the group consisting of tris-(N,N-dialkylamine)phosphines, 1,2-dialkylimidazoliums, 4-N,N - dialkylaminopyridines, and mixtures thereof.
    [0008]
    8. Process according to claim 7, characterized in that the dimerization catalyst is selected from the group consisting of tris-(N,N-dimethylamino)phosphine, tris(N,N-diethylamino)phosphine, 4 -N,N-dimethylaminopyridine, 4-N,N-diethylaminopyridine, 1,2-dimethylimidazolium, 1,2-diethylimidazolium, and mixtures thereof.
    [0009]
    9. Process according to claim 6, characterized in that the carbon segments are binary saturated carbon segments.
    [0010]
    10. Process according to claim 1, characterized in that the separation of the reaction product in step d) is carried out by one or a combination of a plurality of mechanical separation methods for solid-liquid separation.
    [0011]
    11. Process according to claim 1, characterized in that the deactivator is selected from the group consisting of chloroacetic acid, trichloroacetic acid, trifluoroacetic acid, methanesulfonic acid, perfluoro butane sulfonic acid, phosphoric acid, formic acid chloride , benzoyl chloride, dimethylcarbamide acid chloride, acetic acid anhydride, succinic acid anhydride, and mixtures thereof.
    [0012]
    12. Process according to claim 11, characterized in that the deactivator is benzoyl chloride.
    [0013]
    13. Process according to claim 1, characterized in that the only one solvent is ethyl acetate.
    [0014]
    14. Process for the production of 4,4'-methylene-bis(phenylisocyanate) dimer (MDI dimer), characterized by comprising the following steps in the following order: (a) providing only one solvent for 4,4'-methylene - bis(phenylisocyanate) (MDI) in an inert gas atmosphere, said only one solvent and said inert gas being maintained at >25°C to 45°C, and said only one solvent comprising a dimerization catalyst; subsequently (b) adding a molten MDI and/or MDI dissolved in a solvent consisting of the same solvent as the only one solvent from step a) with stirring for a period of 0.5 to 3 hours, subsequently (c) adding a deactivator for cessation of dimerization, with the proviso that agitation takes place in addition for a period of 0.5 to 1.5 hours at a temperature of >25°C to 45°C, in which the deactivator is selected from the group consisting of of strong acids, acid chlorides, and acid anhydrides, subsequently (d) separating the resulting MDI dimer from only one solvent, and subsequently (e) purifying the resulting MDI dimer by solvent washing, in which during purification of the dimer from MDI, the solvent used consists of the same solvent as the only one solvent from step a), in which the only one solvent is selected from the group consisting of acetone, N-methylpyrrolidone, benzene, ethylacetate, acetonitrile, nitromethane, kerosene, and octane; and the water content of only one solvent is maximum 0.04% by weight, and in which the MDI dimer produced by the process has a monomeric MDI content of less than 0.1%.
    [0015]
    15. Process according to claim 14, characterized in that the only one solvent is ethyl acetate.
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    法律状态:
    2014-10-29| B03A| Publication of a patent application or of a certificate of addition of invention [chapter 3.1 patent gazette]|
    2018-03-06| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-05-07| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2020-02-27| B06G| Technical and formal requirements: other requirements [chapter 6.7 patent gazette]|
    2021-04-06| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2021-08-10| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-09-08| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 12/11/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP12192416.1|2012-11-13|
    EP12192416.1A|EP2730563B1|2012-11-13|2012-11-13|Process for the preparation of MDI dimer|
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