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    • 专利摘要:
    silicone composite membranes with high separation effect - the present invention relates to a composite membrane with an active membrane layer for separation, characterized by the fact that an active membrane layer for separation is produced by hardening acrylates laterally modified silicone tubes of the general formula i.
    公开号:BR112012013130B1
    申请号:R112012013130-3
    申请日:2010-11-02
    公开日:2020-02-11
    发明作者:Rene Haensel；Hardi Doehler；Peter Schwab；Peter Seidensticker；Michael Ferenz；Goetz Baumgarten；Marina Lazar；Markus Ungerank
    申请人:Evonik Degussa Gmbh；
    IPC主号:
    专利说明:

    Descriptive Report of the Invention Patent for SILICON COMPOUND MEMBRANES WITH HIGH SEPARATION EFFECT, THEIR USE AND THE PRODUCTION PROCESS. STATE OF THE TECHNIQUE [001] Silicone membranes are suitable for a large number of separation processes. An advantage of silicone membranes is, in particular, that they are resistant against a series of organic solvents and, therefore, in most cases, they can be used without problems in solvent-based membrane processes, for example, in organophilic nanofiltration or in gas separation. In the case of solvent-based nanofiltration it is a pressure-driven separation process based on membranes, which separates molecules dissolved in organic solvents at the molecular level. Currently, solvent-resistant membranes are especially used in the food industry, in the petrochemical industry, in the chemical industry and for the production of pharmaceutically active substances in the pharmaceutical industry.
    [002] In addition, silicone membranes are used for gas separation (GS). Typical gas separation processes are nitrogen separation from the atmosphere, hydrogen recycling, air drying, hydrocarbon separation processes and the removal of volatile organic components. Compared to other polymers, which are used in gas separation processes, silicone membranes generally have markedly greater permeability, however, in most cases, they have less selectivity. Various applications in the area of gas separation are described in detail in the following literature sites: Ind. Eng. Chem. Res., Vol. 41, No. 6, 2002.
    [003] An example of a solvent-based nanofiltration, for which silicone membranes are suitable, is the recycling of he
    Petition 870190095404, of 09/24/2019, p. 4/32
    2/19 xane in the production of vegetable oils. Through the use of membranes to recycle hexane, it is possible to save significant amounts of energy.
    [004] The first stage of oil production is oil extraction.
    In the extraction, the raw materials containing oil are mixed with hexane. A solution of the oil in hexane is obtained, which is also called miscella. The dissolved oil contains over 95% of triacyl glycerides and as secondary components phospholipids, free fatty acids (FFA), pigments, sterols, carbohydrates, proteins and their degradation products.
    [005] The miscella consists of 70 to 75% hexane. The separation of oil and hexane can be carried out, for example, by means of a multi-stage distillation separation. This requires a comparatively high energy expenditure for the evaporation of hexane. If, on the other hand, a membrane is used to separate at least a large part of the hexane, then it is possible to save a considerable amount of energy.
    [006] A problem, which can occur when using silicone membranes, is insufficient long-term stability in systems containing hexane, as well as the unwanted accumulation of substances on the membrane surface.
    [007] The use of silicone composite membranes or also called silicone composite membranes in the vegetable oil industry is well known. The research, which was carried out in this field, is described, for example, in the following literary reference: Fett. Lipid 98 (1996), page 10-14, JAOCS 79 (2002) page 937-942. The connection between superficial hydrophobia and the accumulation of components on the membrane surface in soybean-miscella oil solutions, has been described in the following literary reference: in Colloids and Surfaces, A: Physicochemical and Engineering Aspects 204 (2002) 31-41.
    Petition 870190095404, of 09/24/2019, p. 5/32
    3/19 [008] Another example of solvent-based nanofiltration applications for which, in principle, silicone membranes are suitable, is the separation of homogeneous catalysts, for example, hydroformylation reaction mixtures: Elements, DegussaScienceNewsletter, 18, (2007) 30-35, EP-A1-931.472; of metathesis reaction mixtures: Recovery of Enlarged Olefin Metathesis Catalysts by Nanofiltration in an Eco-Friendly Solvent, A. Keraani, T. Renouard, C. Fischermeister, C. Bruneau, M. Rabiller-Baudry, ChemSusChem 2008, 1, 927 , EP 1817097; of Suzuki copulation reaction mixtures: Solvent-Resistant Nanofiltration of Enlarged (NHC) Pd (allyl) Cl Complexes for Cross-Coupling Reactions, Dirk Schoeps, Volodymyr Sashuk, Katrin Ebeert, Herber Plenio, Organometallics 2009, 28, 3922 or de US2009 telomerization reaction mixes 0032465A1.
    [009] A broad overview of various solvent-based nanofiltration processes (Organic Solvent Nanofiltration, OSN) is provided by the literary reference: Chem. Soc. Claims., 2008, 37, 365-405. Here it is also described that the silicone membranes, according to the state of the art, retained at best 90% of the triglycerides in a hexane solution in the membrane. The triglycerides described there are distinguished by molar masses of 900 g / mol (+/- 10%).
    [0010] A manufacturer of silicone membranes available on the market is GMT Membrantechnik GmbH (Germany). The silicone separating layer of its membranes is produced, for example, using the process described in the DE 19507584 patent report. In this case, the silicone coatings are additionally crosslinked by means of radiation. Thus, the swelling of the separation layer in systems containing solvent must be reduced. Despite this, the membranes swell clearly in hydrophobic media, such as, for example, in low molecular weight n-alkanes and clearly lose
    Petition 870190095404, of 09/24/2019, p. 6/32
    4/19 in performance and retention. In addition, the membranes are very hydrophobic, which means that, for example, in a miscella or in the concentration of pharmaceutically active substance or in the concentration of homogeneous catalyst systems or in the concentration of dyes, there is a clear accumulation of hydrophobic components in the membrane surface.
    [0011] In U.S. patent applications 2007 0007195, EP 1,741,481 and EP 0.979,851, membranes are described, in which an active separating layer is produced by hardening silicone acrylates. In this case, silicone acrylates are used, which are exclusively modified at the ends of the chains. There, there are also references to production methods, with all methods being common, which also uses a solvent, which needs to be evaporated during production. This is disadvantageous, since solvent vapors must be discarded.
    [0012] Furthermore, it is shown, that such membranes do not have any improved selectivity compared to DE19507584 or other membranes according to the state of the art. A satisfactory selectivity for the technical separation objectives is only present, as a rule, when clearly more than 95% of the component is retained in the membrane. All known silicone-based or silicone acrylate membranes do not have such a satisfactory retention for the mentioned applications.
    [0013] Given this foundation, the objectives of the invention were to provide membranes based on silicones, which can separate at least 95% of components with a molecular weight less than 800 g / mol from an organic solvent with a molar mass <200 g / mol, preferably <150 g / mol, particularly preferably <120 g / mol. Examples of such solvents are tetrahydrofuran, hexane, heptane, isopropanol, toluene, dichloromethane,
    Petition 870190095404, of 09/24/2019, p. 7/32
    5/19 acetone and ethyl ester of acetic acid.
    [0014] In addition, the objective was to reduce the high tendency for swelling of silicone membranes known so far, in particular, for example, in aliphatic solvents, such as, for example, hexane and heptane through an appropriate crosslinking.
    [0015] The efficient reduction of swelling in the solvents mentioned above is shown in obtaining separation properties over time. Membranes according to the state of the art show, for example, in the exchange of the solvent toluene for the solvent of strong hexane swelling, a doubling of the molecular exclusion limit (90% retention of a polystyrene of the respective molecular weight, MWCO) in further conditions equals. This applies also expressly to membranes, which are produced by EP 1,741,481, although it is stated here, that a reduced tendency to swelling has been created. The examples published in EP 1,741,481 show, that the retention power changes, which confirms, that a swelling is very well performed. Short-term consideration is not sufficient for the intended effect = no swelling.
    [0016] In addition, the objective was to reduce the very hydrophobic properties of silicone membranes known until now by incorporating hydrophilic components in the membrane polymer in favor of hydrophilia.
    [0017] It was surprisingly found that membranes composed of silicone, which have one or more layers of active membrane for separation, have particularly advantageous properties in the sense of equating the objectives.
    [0018] The objective of the invention is therefore solved by membranes composed of silicone, which have one or more layers of active membranes for separation, when at least one layer of active membrane for separation has been prepared by means of
    Petition 870190095404, of 09/24/2019, p. 8/32
    6/19 hardening of modified General Formula I silicone acrylates in lateral position.
    R 1
    R 2 Si-0
    R 1
    R 1
    Si-0
    R 1
    R 1
    -Si-0
    R 3 to L
    R 1
    Si-0
    I
    R 1
    --Si-R 2
    R 1 c Formula I where:
    a = 25 - 500, preferably
    - 200, b = 1 - 25, preferably 1-15, especially 1 - 8, c = 0 - 20, preferably 0-10, especially 0,
    R 1 , independently of one another, represents the same or different alkyl or aryl radicals with 1 to 30 carbon atoms, which optionally carry ether and / or ester and / or epoxy and / or alcohol functions, preferably equal or aryl radicals or different with 1 to 30 carbon atoms, especially methyl or phenyl,
    R 2 , independent of each other, represents the same or different radicals of the group: R 1 , R 3 and R 4 ,
    R 3 represents the same or different organic radicals that carry one or more acrylate groups, preferably substituents of General Formula II or III,
    - 300, especially
    O - CH 2 CH 2 CH 2 OCH 2 CH (OH) CH 2 -OCCH = CH 2
    Formula II o
    - (CH 2 ) d - {O) e - (CR%) rCR 6 gíR 7 OCCH = CH 2 ) h
    Formula III d = 0 to 12, e = 0 or 1, f = 0-12, g = 0-2, h = 1 -3, where: g + h = 3,
    R 6 , independently of each other, represents the same or different radicals with 1 to 30 carbon atoms or H,
    R 7 represents bivalent hydrocarbon radicals equal to or
    Petition 870190095404, of 09/24/2019, p. 9/32
    7/19 different, preferably -CR 6 2-, especially -CH2R 4 represents the same or different polyether radicals, preferably the same or different polyether radicals of General Formula IV
    - (CH2) iO- (CH2CH2O) j- (CH2CH (CH3) O) k- (CH2CHR8O) lR 9 Formula IV i = 0 - 12, preferably 3 - 7, especially 3, j = 0 - 50, k = 0 - 50, l = 0 - 50,
    R 8 represents alkyl or aryl radicals, the same or different, with 2 - 30 carbon atoms, preferably ethyl and phenyl,
    R 9 represents the same or different alkyl or aryl radicals with 2 - 30 carbon atoms, or H or alkanoyl radicals, preferably methyl, H or acetyl.
    [0019] Another object of the invention are also composite membranes produced by hardening silicone acrylates of Formula I, which are structured in several layers of different silicone acrylates.
    [0020] In addition, it has been shown that it is possible to produce a particularly advantageous family of silicone membranes, if this is done by hardening a mixture of different silicone acrylates. Through the choice of the mixture, the limit properties of separation, degree of crosslinking and hydrophilicity can be adjusted almost without graduation in scales hitherto unknown.
    [0021] Therefore, other objectives of these inventions are membranes composed of silicone, which have one or more layers of active membranes for separation, which were produced by hardening a mixture of various silicone acrylates.
    [0022] Particularly advantageously, the mixture of the various silicone acrylates consists of at least the following components:
    Petition 870190095404, of 09/24/2019, p. 10/32
    8/19
    a) one or more silicone acrylates with an average silicon content of> 29% by weight, preferably in one or more silicone acrylates with an average silicon content of> 29% by weight, of General Formula I, especially in one or more silicone acrylates with a silicon content of> 29% by weight, of General Formula I with b = c = 0,
    Formula I in which it applies for the component to:
    a = 25 - 500, preferably 25 - 300, especially 30 - 200, b = 0 - 15, preferably 0-8, especially 0 c = 0 - 20, preferably 0-10, especially 0 with the condition, that with b = 0, R 2 = R 3 ,
    b) one or more silicone acrylates with an average silicon content of 27.5% by weight, preferably one or more silicone acrylates with a silicon content of 27.5% by weight, of General Formula I, especially one or more silicone acrylates with a silicon content of <27.5% by weight, of General Formula I with c> 3, where for component b) it applies:
    a is 1 - 24, preferably 5 - 20, particularly preferably 10 - 20 and especially 10, 11, 12, 13, 14, 15, 16 or 17, especially b is 0 - 25, preferably 3 - 10, particularly preferably 3, 4, 5, 6, 7 or 8, c is 0 - 20, preferably 0 - 10, particularly preferably 0 or 1, 2, 3 or 4, with the proviso that with b is 0, R 2 is R 3 .
    [0023] Preferably, components a) and b) are present
    Petition 870190095404, of 09/24/2019, p. 11/32
    9/19 in mixtures in a mass ratio of 10 to 1 to 1 to 10, especially in the ratio of 2 to 8 to 8 to 2.
    [0024] In the case of the indicated formulas, these are polymers with a molar weight distribution. The indices a, b, c, j, k and l therefore represent average values and are not optionally integers.
    [0025] The different monomer units of the composition elements indicated in the Formulas (siloxane chains or polyoxyalkylene chain) can be structured together with blocks with an arbitrary number of blocks and subjected to an arbitrary sequence or to a statistical distribution. The indices used in the Formulas are considered as average statistical values.
    [0026] The silicon content of silicone acrylates is influenced by the degree of organic modification. The more organic binders are attached to the siloxane structure, the lower the silicon content. It has been demonstrated that silicone composite membranes with advantageous properties are obtained, if they have an active layer for separation, which is produced by hardening a mixture of various silicone acrylates. In that case, one or more relatively highly modified silicone acrylates with a Si content of less than 27.5% by weight (component b) is (are) hardened with one or more relatively little modified silicone acrylates with a Si> 29% by weight (component a) as a mixture.
    [0027] The properties of the membranes, which are obtained with a mixture of silicone acrylates according to the invention, preferably have properties, as shown below.
    [0028] Particularly advantageous properties result, when silicone acrylates are used as component a), which are merely modified at the ends of the chain, the so-called α, ω-modified silicone acrylates. In addition, properties are shown
    Petition 870190095404, of 09/24/2019, p. 12/32
    10/19 disadvantageous, when laterally modified silicone acrylates are used.
    [0029] In addition to silicone acrylates, it may be convenient to add a series of other substances to the mixture, such as, for example, fillers, stabilizers, colors or organic acrylates. This listing should not be considered as being restrictive.
    [0030] The present invention describes modern composite membranes, which have at least one active layer for separation, which are produced by means of special silicone acrylates or by a mixture of silicone acrylates.
    [0031] In order to produce the composite membranes according to the invention, porous three-dimensional structures resistant to solvents, which can serve as support material, such as, for example, non-woven fleece or micro or ultrafiltration membranes, are generally used as substructure. or separators, such as, for example, battery separators, such as Separion ® (registered trademark of Evonik Degussa GmbH) or Solupor®.
    [0032] Fundamentally, all the structures provided for filtrations and / or phase separations are provided, which through the special silicone acrylates according to the invention can be modified to form composite membranes.
    [0033] Another object of the invention are also composite membranes, which are obtained by hardening the silicone acrylates of Formula I according to the invention with a photoinitiator through electromagnetic radiation with a wavelength, which is less than 800 nm and / or through electronic rays. Hardening is especially carried out using UV radiation with wavelengths below 400 nm.
    [0034] Another objective of the invention is also the membranes
    Petition 870190095404, of 09/24/2019, p. 13/32
    11/19 compounds containing the silicone acrylates hardened according to Formula I, which feature an ultrafiltration membrane as support membranes.
    [0035] Especially the use of mixtures of different silicone acrylates allows to adjust the properties of the membrane in a specific way. By adjusting a certain mixing ratio, it is possible to adapt the membrane to certain requirements and address special separation problems.
    [0036] Evonik Goldschmidt GmbH offers a series of commercially available silicone acrylates, which are suitable for the production of membranes according to the invention.
    [0037] Typical products from Evonik Goldschmidt GmbH are TEGO®
    RC 902, TEGO® RC 715. TEGO® RC 902 and TEGO® RC 715 are linear polymers, which are merely modified at the ends of the chain. TEGO ® RC 902 has a silicon fraction of, for example, 34% by weight and TEGO® RC 715 has a silicon fraction of, for example, 32% by weight, these are comparatively low modification products. Laterally modified siloxanes are also available, which have a silicon fraction of, for example, 24% by weight. The fraction of organic components / groups is relatively high compared to the silicon oxide structure. TEGO ® RC 902 and TEGO ® RC 715 correspond, for example, to the modified linear polymers at the ends of the chain of component a), when mixtures of different silicone acrylates are used, whereas the laterally modified polymers correspond to component b).
    [0038] The silicone composite membranes described above are produced by coating porous support materials, for example, based on micro- or ultrafiltration membranes or separators. In principle, as material for such support layers, in principle, all macroporous materials can be used
    Petition 870190095404, of 09/24/2019, p. 14/32
    12/19 known: K.-V. Peinemann et al. Nunes, Membrane Technology in the Chemical Industry, Wiley-VCH Verlag GmbH, 2006. As porous support material, membranes selected from the group of the following materials are particularly suitable: polyacrylonitrile (PAN), polyimide (PI), polyether ketone (PEEK), polyvinylidene fluoride (PVD), polyamide (PA), polyamidimide (PAI), polyether sulfone (PES), polybenzimidazole (PBI), sulfonated polyether ketone (SPEEK), polyethylene (PE), polypropylene (PP), as well as materials porous inorganics and / or ceramic membranes or polymeric ceramic membranes produced using aluminum oxide, titanium dioxide, zirconium dioxide, silicon oxide and / or titanium nitrite, as well as mixtures, modifications or compounds of the different materials support membranes mentioned above.
    [0039] The silicone composite membranes described above are suitable for separation purposes in organic solvents. Depending on the execution, they are able to separate or retain dissolved molecules with a molecular weight less than 2000 g / mol, preferably molecules with a molecular weight less than 1000 g / mol and particularly preferably molecules with a molecular weight less than 500 g / mol in a retention quota of at least 90% by weight, preferably> 95% by weight, particularly preferably> 98% by weight and especially> 99% by weight.
    [0040] In a particularly preferred embodiment of the invention, through membranes according to the invention of components of different molecular masses dissolved in an organic solvent, at least 95% of components with a molecular weight less than 800 g / mol, preferably with a molar mass <200 g / mol, particularly preferably, <150 g / mol and especially <120 g / mol can be separated. Examples of such separable solvents are tetrahydrofuran, hexane, heptane, isopropanol, tolue
    Petition 870190095404, of 09/24/2019, p. 15/32
    13/19 no, dichloromethane, acetone and ethyl ester of acetic acid, preferably hexane or heptane.
    [0041] In the case of dissolved molecules, in principle, it can be all molecules soluble in the respective solvent. Therefore, another objective of the invention is the use of silicone composite membranes according to the invention, for example, to separate homogeneous catalyst systems from reaction mixtures, to separate triglycerides from solvents, such as, for example, hexane, heptane, ethanol or acetone, to separate oligomers from monomeric solutions or to separate active (pharmacological) substances or their precursors from reaction mixtures or solutions.
    [0042] Thus, another objective of the invention is also the use of membranes composed of silicone acrylate to separate homogeneous catalyst systems from reaction mixtures, to separate triglycerides from solvents with a molecular weight less than 200 g / mol, to separate oligomers monomeric solutions or to separate active substances (pharmaceutically) or their precursors from reaction mixtures or solutions.
    [0043] Preferably, these processes use hydrocarbon solvents with 1-8 carbon atoms, preferably hexane or heptane, their isomers or also their mixtures or also CO2.
    [0044] To purify substances, the membranes composed according to the invention are especially suitable, since, for example, in the case of fixed separation parameters, such as temperature, pressure and solvents, the molecular weight fractions can be specifically separated of solutions below the fixed ranges. Under typical system conditions, such as, for example, 30 o C, 3000 kPa (30 bar) pressure (TMP - Trans Membrane Pressure), molecular weight fractions less than 1000 g / mol, preferably
    Petition 870190095404, of 09/24/2019, p. 16/32
    14/19 less than 600 g / mol and especially less than 300 g / mol can be separated from n-heptane solutions.
    [0045] Starting from a mixture of laterally modified and α, ω-modified silicone acrylates at the end, the membrane separation performance (in wide limits) can be specifically adjusted for different solvent systems (see also Figure 1 or Figure 2).
    [0046] Another object of the invention is a process for the production of a composite membrane, in which a support membrane is coated with at least one silicone acrylate of Formula I and / or mixtures of different silicone acrylates and then , it is hardened by electromagnetic radiation and / or electron radiation at room temperature.
    [0047] The silicone acrylate or optionally the mixture of silicone acrylate is placed in a lamination system optionally with the coutilization of a solvent, as is conventionally applied, for example, for the coating of non-stick coatings of support materials, for example, for labels, particularly advantageously, no other solvent is used for that purpose. Through the lamination system, silicone acrylate is applied over the membrane material in layer thicknesses between 0.3 - 2 micrometers and hardened by radicals by means of UV radiation or electron radiation. No other thermal energy is required. The silicone acrylate is immediately hardened after going through the reaction chamber. In the reaction chamber the free radical spots are abruptly cooled by means of oxygen, which is why it is essential to inert the reaction chamber with nitrogen. EXAMPLES [0048] In the examples presented below, the present invention is described for the elucidation of the invention, without the invention, whose
    Petition 870190095404, of 09/24/2019, p. 17/32
    15/19 extension of application results from the entire description and the claims, be limited to the forms of execution mentioned in the examples. If, below, ranges, general formulas or classes of compounds are indicated, then these should not only comprise the corresponding ranges or groups of compounds, which are explicitly mentioned, but also all partial ranges and partial groups of compounds, which can be obtained by removing some values (ranges) or compounds. If documents are cited in the context of this described report, then their content must belong entirely to the published content of the present invention. If compounds, such as, for example, organomodified silicone acrylates, are described in the context of the present invention, which can have the different monomer units several times, then these can occur statistically distributed (statistical oligomer) or ordered (block oligomer) in these compounds . Data on the number of units in these compounds should be understood as mean statistical values, divided by all the respective compounds. PRODUCTION OF MEMBRANES [0049] Based on polyacrylonitrile ultrafiltration membranes available on the market, to be mentioned, for example, by GMT, Rheinfelden or GE-Osmonics, Vista, USA, sold by Desalogics, Ratzeburg, coatings were made with TEGO silicone acrylates from Evonik Goldschmidt GmbH. The coatings were made in layers with a 5-roller smooth roller applicator mechanism. The coatings were made with an application weight of 0.6 to 1.5 g / m 2 . The coatings were cross-linked in an atmosphere of inert nitrogen over a UV lamp. For this purpose, a suitable photoinitiator is added to the silicone acrylates, such as, for example, a hydroxyl ketone in an amount of 1/100 in relation to the silicone mass. In this way, they are produced
    Petition 870190095404, of 09/24/2019, p. 18/32
    16/19 composite membranes were made based on the aforementioned ultrafiltration membranes, which presented different mixtures and sequences of layers of silicone acrylates according to component a) and component b). The following coatings were produced, with different mass proportions of component a) and component b), respectively in relation to the total amount of silicone acrylate:
    • 90% by weight, from a) & 10% by weight, from b);
    • 80% by weight, from a) & 20% by weight, from b), with 3% by weight, additional inorganic filler in relation to the total amount of silicone acrylate;
    • 70% by weight, from a) & 30% by weight, from b), with 3% by weight, additional inorganic fillers in relation to the total amount of silicone acrylate and without inorganic fillers, as well as • 100% by weight of b).
    [0050] Components a) and b) used in the examples are formed according to Formula I, as follows: component a) a = 83, b = 0, c = 0, R 1 = CH3,
    R 2 = (CH2) 3-O-CH2-C (C2H6) (CH2O-C (O) -CH = CH2) 2 Si content = 34.2% component b) a = 13, b = 5, c = 0, R 2 = CH3
    R 3 = substituent according to Formula II Si content = 23.8% [0051] The components are produced using methods according to the state of the art, such as, for example, described in DE 3820294 C1 (US 4978726) .
    [0052] Silicic acid was used as the inorganic filler.
    [0053] As a comparative sample of a membrane according to the state of the art, a membrane that was produced was examined.
    Petition 870190095404, of 09/24/2019, p. 19/32
    17/19 made exclusively on the basis of TEGO® 902 according to component a).
    [0054] The membrane produced was characterized using the so-called MWCO method (Molecular Weight Cut-Off) in n-heptane. The MWCO method is described, for example, in the following literature: Journal of Membrane Science 291 (2007) 120-125. The method is based on measuring the retention of different styrene oligomers as a function of their molar weight (MWCO curve).
    [0055] With the aid of the MWCO method it is possible to assess how much a dissolved material with a certain molar value can be separated. In Figure 1 and Figure 2, the molar mass (Mw) of the dissolved materials, here polystyrenes against the retention of the membrane examined respectively is shown in% by weight, derived from mass concentrations.
    [0056] The stability of the active layer for separation was determined, in which the MWCO curve and the permeability of the membrane were determined over a long period in n-heptane.
    [0057] The membranes were tested using axial circulation filtration. The operating temperature imported at 30 o C and the transmembrane pressure (TMP), 3000 kPa (30 bar). In the long-term tests a pressure of 1000 kPa (10 bar) was applied. The membranes were conditioned with pure solvents until a steady flow was obtained. Then, the pure solvent was replaced by a mixture of solvent and oligo-styrene indicator. After obtaining a steady flow again, samples of permeate and feed were taken and the proportion of styrene oligomer was determined in analogy with the MWCO method.
    [0058] Figures 1 and 2 show the results of the holding power for polystyrenes with different molecular weights, as well as the solvent flows of the silicone acrylate membranes
    Petition 870190095404, of 09/24/2019, p. 20/32
    18/19 in a different way. The permeate liquid is n-heptane.
    [0059] The results in Figure 1 confirm that the properties of the layers of active membranes for separation can be specifically adjusted by mixing the different TEGO RC products, by a membrane with an excellent separation effect, however, with a low flow, even a membrane with a high flow, but with less separation effect. In this way, by mixing the different silicone acrylates, the properties profile of the membrane can be specifically adjusted for an application.
    [0060] From the MWCO curves it is possible to deduce that the membrane with the largest fraction of components a) of 90% has relatively lower retention and shows the highest permeate flow. On the other hand, a membrane, consisting of 100% of component b), shows almost no flow of permeate to nheptane and very high retention. The results presented for mixtures 20/80 and 30/70 with and without fillers show that the properties are adjustable almost without graduation.
    [0061] The comparative test of the membranes according to the invention with a composition of 30% of b) & 70% of a) with silicone membranes according to the state of the art (100% of a)) was carried out, as as described above, in n-heptane. After a permanent operation of the membranes for another 11 days at 1000 kPa (10 bar) and 30 o C in hexane, the MWCO test was performed again.
    [0062] The results shown in Figure 2 show, that the membrane according to the invention has a separation limit clearly shifted to lower molecular weights.
    [0063] The clear displacement of the membrane separation curve according to the state of the art to higher molecular weights and the increase in permeate flow results, which is not stable in heptane. The membrane according to the invention
    Petition 870190095404, of 09/24/2019, p. 21/32
    19/19 does not show any relevant changes in the permeate flow capacity and separation properties as a function of the operating time, which confirms the stability of the membrane in nheptane.
    权利要求:
    Claims (16)
    [1]
    1. Composite membrane with a layer of active membrane for separation and a support membrane, which have one or more layers of active membranes for separation, characterized by the fact that at least one layer of active membrane for separation is produced through the hardening of laterally modified silicone acrylates of General Formula I

    where a = 25 - 500, b = 1 - 25, c = 0 - 20,
    R 1 , independently of one another, represents the same or different alkyl or aryl radicals with 1 to 30 carbon atoms, which optionally carry functions of ether and / or ester and / or epoxy and / or alcohol,
    R 2 , independent of each other, represents the same or different radicals of the group: R 1 , R 3 and R 4 ,
    R 3 , independent of each other, represents the same or different radicals that carry one or more acrylate groups, and
    R 4 represents the same or different polyether radicals.
    [2]
    2. Composite membrane according to claim 1, characterized by the fact that radicals of General Formula II or III are preferably used as R 3 substituent
    O - CH 2 CH 2 CH 2 OCH 2 CH (OH) CH 2 -OCCH = CH 2
    Formula II
    O - (CH 2 ) d - (O) e - (CR 6 2) rCR% (R 7 OCCH = CH 2 ) h
    Formula III
    Petition 870190095404, of 09/24/2019, p. 23/32
    2/5 where d = 0 to 12, e = 0 or 1, f = 0-12, g = 0-2, h = 1 -3, where: g + h = 3,
    R 6 , independently of each other, represents the same or different alkyl or aryl radicals with 1 to 30 carbon atoms or H, and
    R 7 represents the same or different bivalent hydrocarbon radicals, preferably -CR 6 2, especially -CH2-.
    [3]
    3. Composite membrane, according to claim 1 or 2, characterized by the fact that as radical R 4 , in Formula I, polyether radicals equal to or different from General Formula IV - (CHsJj-O-fCHsCHsOjj-ÍCHaCHÍCHsJOJk-ÍCHíCHR ^ OJrR 9
    Formula IV in which i = 0 - 12, preferably 3-7, especially 3, j = 0 - 50, k = 0 - 50, I = 0 - 50, and
    R 8 represents the same or different alkyl or aryl radicals with 2-30 carbon atoms, preferably ethyl and phenyl; and
    R 9 represents alkyl or aryl radicals, the same or different, with 2-30 carbon atoms, or H or alkanoyl radicals, preferably methyl, H or acetyl.
    [4]
    Composite membrane according to any one of claims 1 to 3, characterized by the fact that it is structured by several layers of different silicone acrylates.
    [5]
    5. Composite membrane, according to claim 4, characterized by the fact that this is structure by mixtures of different silicone acrylates.
    [6]
    6. Composite membrane, according to claim 5, characterized by the fact that two different silicone acrylates are used, where as component (a) α, ω-modified terminal silicone acrylates are used and as component (b), sili acrylates
    Petition 870190095404, of 09/24/2019, p. 24/32
    3/5 cone laterally modified according to Formula I.
    [7]
    7. Composite membrane according to claim 4 or 6, characterized by the fact that it contains at least one of the following components:
    (a) one or more silicone acrylates with an average silicon content of> 29% by weight, of General Formula I

    and for component (a):
    a = 25 - 500, b = 0 - 15, c = 0 - 20, with the proviso that with b = 0, R 2 = R 3 ;
    (b) one or more silicone acrylates with a silicon content of <27.5% by weight, of the General Formula I, and, for component (b):
    a = 1 - 24, b = 0 - 25, c = 0 - 20, with the proviso that with b = 0, R 2 = R 3 .
    [8]
    8. Composite silicone membrane according to claim 7, characterized in that the components (a) and (b) in the mixture are present in a mass ratio of 10 to 1 to 1 to 10.
    [9]
    9. Composite membrane according to any one of claims 1 to 8, characterized by the fact that the hardening of the silicone acrylates with a photoinitiator is obtained through electromagnetic radiation with a wavelength, which is less
    Petition 870190095404, of 09/24/2019, p. 25/32
    4/5 at 800 nm and / or through electron radiation.
    [10]
    10. Composite membrane according to any one of claims 1 to 9, characterized in that the support membrane is a three-dimensional porous solvent-resistant support structure, selected from the group of non-woven fleece or microfiltration membranes or ultrafiltration or separators.
    [11]
    11. Composite membrane according to any one of claims 1 to 10, characterized by the fact that the porous support material is produced from the group of the following materials: polyacrylonitrile (PAN), poly-inide (PI), ketone of polyether (PEEK), polyvinylidene fluoride (PVDF), polyamide (PA), polyamidimide (PAI), polyether sulfone (PES), polybenzimidazole (PBI), sulfonated polyether ketone (SPEEK), polyethylene (PE), polypropylene (PP) ) or porous inorganic materials and / or ceramic membranes or polymeric ceramic membranes, using aluminum oxide, titanium dioxide, zirconium dioxide, silicon oxide and / or titanium nitrite, as well as mixtures, modifications or composites of different support membrane materials mentioned above.
    [12]
    12. Use of the composite membrane, as defined in claim 1, characterized by the fact that it is for retaining dissolved molecules with a molecular weight less than 2000 g / mol with a retention quota of at least 90% by weight.
    [13]
    13. Use according to claim 12, characterized by the fact that it is for the separation of homogeneous catalyst systems from reaction mixtures, for the separation of triglycerides from solvents with a molecular weight less than 200 g / mol, for the separation of oligomers of monomeric solutions or for the separation of active substances (pharmaceuticals) or their precursors to reaction mixtures or solutions.
    Petition 870190095404, of 09/24/2019, p. 26/32
    5/5
    [14]
    14. Use, according to claim 13, characterized by the fact that as a solvent hydrocarbons with 1-8 carbon atoms are used, whose isomers or also their mixtures or also CO2 are used.
    [15]
    15. Use according to any one of claims 12 to 14, characterized by the fact that at 30 o C, 3000 kPa (30 bar) of pressure, fractions of molecular weight less than 1000 g / mol are separated from solutions in n-heptane.
    [16]
    16. Process for the production of a composite membrane, as defined in any one of claims 1 to 11, characterized by the fact that it comprises:
    coating a support membrane with at least one Formula I silicone acrylate and mixtures of different silicone acrylates, and hardening said coated support membrane by means of electromagnetic radiation and / or electron beam radiation.
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    同族专利:
    公开号 | 公开日
    BR112012013130A2|2017-04-04|
    MY169960A|2019-06-19|
    WO2011067054A1|2011-06-09|
    HK1175735A1|2013-07-12|
    CA2782798C|2017-06-20|
    CN102665879A|2012-09-12|
    AU2010327002A1|2012-07-19|
    US20120279922A1|2012-11-08|
    CN102665879B|2016-06-08|
    KR101725575B1|2017-04-26|
    PL2506957T3|2016-01-29|
    DK2506957T3|2015-12-14|
    TWI511778B|2015-12-11|
    JP5923447B2|2016-05-25|
    RU2012127210A|2014-01-10|
    PT2506957E|2015-12-16|
    KR20120114244A|2012-10-16|
    ES2553765T3|2015-12-11|
    HUE026270T2|2016-06-28|
    CA2782798A1|2011-06-09|
    DE102009047351A1|2011-06-09|
    EP2506957B1|2015-09-02|
    AU2010327002B2|2014-06-26|
    JP2013512100A|2013-04-11|
    US9539549B2|2017-01-10|
    EP2506957A1|2012-10-10|
    TW201130557A|2011-09-16|
    AR079039A1|2011-12-21|
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    法律状态:
    2017-08-15| B25A| Requested transfer of rights approved|Owner name: EVONIK DEGUSSA GMBH (DE) |
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-12-04| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|Free format text: O DEPOSITANTE DEVE RESPONDER A EXIGENCIA FORMULADA NESTE PARECER POR MEIO DO SERVICO DE CODIGO 206 EM ATE 60 (SESSENTA) DIAS, A PARTIR DA DATA DE PUBLICACAO NA RPI, SOB PENA DO ARQUIVAMENTO DO PEDIDO, DE ACORDO COM O ART. 34 DA LPI.PUBLIQUE-SE A EXIGENCIA (6.20). |
    2019-07-16| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2019-12-31| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-02-11| 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 02/11/2010, OBSERVADAS AS CONDICOES LEGAIS. |
    2020-05-12| B25D| Requested change of name of applicant approved|Owner name: EVONIK OPERATIONS GMBH (DE) |
    优先权:
    申请号 | 申请日 | 专利标题
    DE102009047351A|DE102009047351A1|2009-12-01|2009-12-01|Composite silicone membranes with high separation efficiency|
    DE102009047351.3|2009-12-01|
    PCT/EP2010/066604|WO2011067054A1|2009-12-01|2010-11-02|Composite silicone membranes with high separating action|
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