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    • 专利摘要:
    polyimide membranes made from polymerization solutions the present invention relates to polyimide membranes and a phase inversion method for producing the membranes. polyimide membranes can be used to separate different mixtures of gases.
    公开号:BR112012001481B1
    申请号:R112012001481
    申请日:2010-07-22
    公开日:2020-02-04
    发明作者:Baumgarten Goetz；Ungerank Markus
    申请人:Evonik Fibres Gmbh；
    IPC主号:
    专利说明:

    Descriptive Report of the Invention Patent for POLY-IMIDA MEMBRANES, AND ITS PREPARATION PROCESS. Field of technique [001] The invention relates to polyimide membranes, produced directly from a polyimide polymerization solution without the polyimide having been isolated in the form of solid material, especially not in dry solid material and, most especially, not dry powder and then again dissolved. The polyimide membranes which refer to the invention can be flat plate membranes or hollow fiber membranes. Polyimide membranes can be not only porous membranes in the form of micro, ultra or nanofiltration membranes, but also non-porous membranes for gas separation. All membranes are integrally asymmetric membranes and are produced by a phase inversion process.
    Object of the invention [002] The object of the present invention is to provide a production process for polyimides which does not make use of any substances that have a harmful influence on the subsequent membrane production process. It is yet another object that the process provided by the invention makes it possible to produce membranes having sufficient mechanical properties.
    [003] Additional objects, not explicitly mentioned, will become evident from the general context of the description, examples and claims that follow.
    Background of the invention [004] The production of membranes by phase inversion generally requires that the polymers be soluble in conventional water-miscible solvents. This process is currently being used to produce thousands of metric tons of membranes.
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    2/38 li (ether-sulfone). Possible solvents include, but are not limited to, dimethylformamide (DMF), dimethylacetamide or Nmethylpyrrolidone. Many additives, such as cosolvents, non-solvents, pore builders, hydrophilic agents, etc., are mixed in order to influence the properties of the membranes. The starting point of this process is usually a material in the form of pellets, the casting solution being produced by bonding with solvents and additives. Success in membrane production, as elsewhere, depends decisively on the molar mass and the distribution of the polymer used.
    [005] P84 is a polymer that is well known in the literature and used for the production of flat plate membranes and hollow fiber membranes (US 2006/0156920, WO 04050223, US 7018445, US 5635067, EP 1457253, US 7169885, US 20040177753, US 7025804). P84 is sold in 2 forms (P84 type 70 and P84 HT) in powder form by HP Polimer from Lenzing in Austria. Customers then dissolve this powder again in aprotic dipolar solvents and mix it with additives. The membranes can then be produced from this. However, several customers (for example, Air Liquide Medal, US 2006/156920) have reported that the films and membranes derived from this powder are very friable and, only when mixed with other polymers, result in stable films and fiber membranes the CA. The powder needs to be subjected to a special treatment to have sufficiently high molar masses (Air Liquide WO 2006/092677). For that, the treatment time and the method are very important. The result is powders with slightly different properties, but which produce casting solutions exhibiting different viscosities. Therefore, the production of uniform polymeric membranes is only possible with great difficulty.
    [006] P84 is also transformed into a mixture with other
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    3/38 polymers (US 2006/156920), so that the resulting derived membranes have sufficiently high stability. However, the disadvantage in this process is that very good gas separation properties, stability in CO2 plastification and chemical stability in many solvents are, in part, unfavorably influenced, or even destroyed, by mixing with other polymers. [007] The cause for low molar mass lies in the process of producing powdered P84. It is at this stage that the polymer loses molar mass. The molar masses obtained directly after polymerization and after the production of the powder are shown in Table 1.
    Table 1: Molar masses after polymerization and after production of
    P84 type 70 and P84 HAT powder
    TypeDirectly after solution polymerization (g.mol -1 ) After conversion to powder (g.mol -1 ) P84 type70 Mn 76 600 g 56 200 Mw 146 200 101 500 Mp 130 500 93 500 PDI 1.91 1.81 P84 HT Mn 75 500 52 200 Mw 150 900 84 200 Mp 122 200 84 100 PDI 2.00 1.61
    [008] It is clearly evident that the polymer loses molar mass in the conversion cycle from the polymerization solution to the powder by a precipitation process.
    [009] P84 powder is also used for the production of flat plate membranes (WO 2007/125367, WO 2000/06293). In this process, the same problems occurred as in the production of hollow fiber membranes.
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    Measuring technique
    Determination of viscosity [0010] The dynamic viscosity η is verified by shearing the polymeric solution in a cylindrical space (gap) at a constant temperature of 25 ° C, once, exerting several rotation rates Ω (or shear gradients γ) and, then, exerting several shear stresses τ.
    [0011] The instrument used for measurement is HAAKE RS 600, equipped with receiver in cup for measuring liquid that can be heated TEF / Z28, cylindrical rotor Z25DIN53019 / ISO3219 and disposable aluminum cup for measurement Z25E / D = 28 mm.
    [0012] Shear stress τ is measured in a given shear gradient. The dynamic viscosity η is computed from the formulas below and is reported at a 10 s -1 shear gradient in Pa.s.
    T 2
    Proper viscosity function Y
    Shear gradient γ = M * Ω τ = Shear stress η = Dynamic viscosity
    M = Rotor shear factor: 12350 rad / s
    Ω = angular velocity
    Molar mass determination [0013] Molar mass is determined using a gel permeation chromatography system. The system is calibrated with polystyrene standards. The reported molar masses should therefore be understood as relative molar masses.
    [0014] The components and configurations used were as follows:
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    HPLC WATERS 600 pump, 717 auto-injector, 2487 UV detector Pre-column PSS SDV column Columns PSS SDV 10 μm 1000, 105 and 106 A Eluent 0.01 M LiBr + 0.03 M H3PO4 in DMF(sterile filtrate, 0.45 μm) Flow 1.0 mL / minute Running time 45 minutes Pressure ~ 1,550 psi (10.69 kPa) Wave-length 270 nm (using UV detector) Injected volume 50 μl or 20 μl (for solutions c> 1 g / L) Standards PS (Polystyrene) standards (narrow distribution, 300-3n10 6 , PSS)
    Permeabilities [0015] Gas permeabilities for films are reported in barrers (10 -10 cm 3 .cm -2 .cm.s -1 .cmHg -1 ). The permeability to gases of hollow fibers or flat plate membranes are reported in GPU (Gas Permeation Unit, 10 -6 cm 3 .cm -2 .s -1 .cmHg -1 ). The flows of nano and ultrafiltration membranes are reported at 1 .m 2 .h -1 .bar- 1 .
    Gas permeabilities [0016] Gas permeabilities are measured using the pressure rise method. To a flat plate film between 10 and 70 μ thick, a gas or gas mixture is applied on one side. On the other side, the permeate side, there is a vacuum (about 10 -2 mbar [1 P]) at the beginning of the test. Then, the pressure rise on the permeate side is reported over time.
    [0017] The polymer's permeability can be computed by the formula below:
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    P = Permeability in barriers (10 -10 cm 3 .cm ' 2 .cm.s' 1 .cmHg · 1 )
    Vdead = Volume of the permeate side in cm 3
    MWg as = Molar mass of gas in g.mol -1 l = Film layer thickness in cm p = Gas density in g.cm -3
    R = Gas constant in cm 3 .cmHg.K ' 1 .mol' 1
    T = Temperature in kelvins
    A = Film area in cm 2
    Ap = Pressure difference between feed and the permeate side in cmHg dp / dt = Pressure rise over time on the permeate side in cmHg.s - [0018] The permeability of hollow fibers is measured using the same pressure elevation method.
    [0019] Permeation is computed by the following formula:
    P = GPU permeability (Gas permeation units. 10 -6 cm 3 .cm -2 .cm.s' 1 .cmHg · 1 )
    Vdead = Volume of the permeate side in cm 3
    MWgas = Molar mass of the gas in g.mol -1 p = Density of the gas in g.cm -3
    R = Gas constant in cm 3 .cmHg.K ' 1 .mol' 1
    T = Temperature in kelvins
    A = External area of hollow fiber in cm 2
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    Δρ = Pressure difference between supply and the permeate side in cmHg dp / dt = Pressure rise per time on the permeate side in cmHg.s - [0020] The selectivities of several gas pairs refer to selectivities for pure gas. The selectivity between two gases is computed from the selectivity ratio:
    P,
    S = optimal gas selectivity
    Pi = gas permeability or permeability 1
    P2 = gas permeability or permeability 2
    Liquid permeations [0021] Flat plate membrane permeations are determined using a stirred and pressurized Milipore cell with 5 to 6 bar (500 to 600 kPa) of nitrogen. What is measured is the flow permeated per unit of time at a defined pressure. Permeation is provided by:
    V
    P Δρ.Α
    P = Permeation at 1.m -2 .h -1 .bar -1 v = Tidal volume at 1 .h -1
    Δp = Pressure difference between feed and permeate side in bar A = Filtration area in m 2 [0022] Retention R is obtained from the following formula:
    7 = (1 - ^). 100
    R = Retention in%
    Cp = Concentration of the dissolved product in the permeate
    Cf = Concentration of the product dissolved in the feed [0023] When the retention is 100%, the whole product is retained by
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    8/38 membrane. When the retention is 0%, the membrane allows all dissolved product to pass through.
    Solution to the problem [0024] The problem of molar mass degradation in the production of powdered P84 is bypassed by the polymer after polymerization in aprotic dipolar solvent is not isolated in the form of solid material, especially not in dry solid material, and more especially , not in dry powder, but instead the polymerization solution is used directly to produce the membranes.
    [0025] The membrane production process involves the following subsidiary steps:
    a) polymerization
    b) production of the casting solution
    c) membrane production
    Polymerization [0026] Polyimides are produced by polycondensing an aromatic tetracarboxylic anhydride with an aromatic diisocyanate by releasing carbon dioxide. Substances and combinations of these preferably used are described below:
    Dianhydrides:
    [0027] 3,4,3 ’, 4’-benzophenonatetracarboxylic dianhydride, dianhydride
    1.2.4.5- benzenotetracarboxylic, 3,4,3 'dianhydride, 4'- biphenyltetracarboxylic, oxidiftalic dianhydride, phenyldiptyl dianhydride, dianhydride 1, 1,1,3,3,3-hexafluor-2,2-propylidenodiftalic Di-isocyanates:
    [0028] 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'methylenediphenyl diisocyanate, 2,4,6-trimethyl-1,3-phenylene diisocyanate,
    2.3.4.5- tetramethyl-1,4-phenylene diisocyanate [0029] Polymerization takes place in an aprotic dipolar solvent. Dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone and
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    9/38 sulfolane are used preferably, but not exclusively, alone or in mixtures.
    [0030] This involves the aromatic dianhydride or mixtures of aromatic dianhydrides being dissolved, in concentrations of 10% by weight to 40% by weight, preferably between 18% by weight and 32% by weight and more preferably between 22% by weight and 28% by weight, in aprotic dipolar solvent and heated to 50 ° C to 150 ° C, preferably from 70 ° C to 120 ° C and more preferably to 80 ° C to 100 ° C. This solution is mixed with 0.01% by weight to 5% by weight, preferably with 0.05% by weight to 1% by weight and more preferably with 0.1% by weight to 0.3% by weight of a basic catalyst. Useful catalysts include:
    • Alkali or alkaline earth metal hydroxides, methoxides, ethoxides, carbonates and phosphates such as, for example, sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium carbonate, bicarbonate sodium, potassium carbonate, potassium bicarbonate, potassium phosphate, potassium hydrogen phosphate, potassium dihydrogen phosphate;
    • Tertiary amines such as, but not limited to, trimethylamine, triethylamine, tripropylamine, diazabicycloundecane, diazabicyclooctane, dimethylaminopyridine.
    [0031] The diisocyanate is then added over a period of 1 to 25 hours, preferably 3 to 15 hours and more preferably 5 to 10 hours.
    [0032] Special preference is given to produce the following polyimides:
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    R is selected from the group consisting of:
    x, y: molar fraction with 0 <x <0.5 and 1> y> 0.5.
    [0033] The result is a clear polymeric solution of gold yellow to dark brown color with viscosity between 1 and 300 Pa.s, preferably from 20 to 150 Pa.s and more preferably from 40 to 90 Pa.s. Mp molar masses are greater than 100,000 g.mol -1 and therefore differ distinctly from powdered polyimide polymers, especially from powdered P84 polymers.
    [0034] The polyimide polymer of the present invention is obtained after the reaction as a solute in an aprotic dipolar solvent. There are no concurrent products or harmful by-products in the polymeric solution. The viscosity is very high and suitable for membrane production. For this reason, it is also economically advantageous in that the polymer does not precipitate and then is dissolved again in the same solvent. The solutions are therefore used directly without isolating the polymer, and preferably also without any additional treatment - to produce the solution for casting.
    Production of the casting solution [0035] The polymeric solutions obtained from the polymer condensation have a solids content between 22% by weight and 28% by weight and can be used to produce the casting solution without further treatment.
    [0036] The casting solution of the present invention is notable for the following properties:
    • It has sufficiently high viscosity for the production of flat-plate or hollow fiber membranes;
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    11/38 • May contain additives to prevent the formation of large empty spaces (macrovazios) in the membranes;
    • May contain volatile solvents to produce a surface having the desired pore size.
    [0037] The viscosity of the casting solution is ideal when it corresponds to the entanglement point in the viscosity graph plotted according to the solids content. This point represents that in which the viscosity function against the solids content is no longer linear and becomes exponential. This point is also highly dependent on molar mass. The higher the molar mass, the lower the solids content at which entanglement occurs.
    [0038] With respect to viscosity, molar mass and mass distribution, the casting solutions to be obtained by the process according to the present invention differ distinctly from the prior art casting solutions. It is only the process of the present invention that provides casting solutions combining high viscosity with high molar mass and narrow molar mass distribution for the polyimide. The processes of the present invention therefore make it possible to obtain membranes that have exceptional mechanical properties.
    [0039] With the prior art processes, that is, dissolving powdery polyimides with subsequent post-treatment to raise the molar mass, it is not possible to obtain solutions for casting that have comparable combinations of properties.
    [0040] The process of the present invention also makes it possible to add additives. Various amounts of additives result in different levels of solids, which in this case would shift the entanglement point. Again, the molar mass in the polymerization can be modulated to displace this entanglement point.
    [0041] As the composition of the casting solution becomes
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    12/38 distance from the concentration at which the phase separation occurs, the gradient between solvent and non-solvent increases too much in the production of membranes by phase inversion, and results in large voids in the membranes. These voids, which are also known as macrovazios, are responsible for the reduced stability of the membranes under pressure when used and limit their usefulness, for example, for cleaning natural gas. The formation of macrovazios can be prevented by the addition of non-solvents. Suitable for this are the following water-miscible solvents or mixtures thereof.
    [0042] The list below is illustrative only and will not prevent the technician skilled in the art from quickly considering yet other solvents:
    • Alcohols such as, for example, methanol, ethanol, isopropanol, propanol, butanol, butanediol, glycerol, • water, • ketones such as, for example, acetone or butanone.
    [0043] In order to produce a defined surface on the membrane, several methods can be used in principle. In addition to the method of late component separation (demixing), the evaporative removal of volatile co-solvents will also lead to very thin selective layers, not only in the gas separation membrane sector, but also in the nano and ultrafiltration membranes sector. . The degree of evaporation removal and, consequently, the pore size is influenced by the type of volatile solvent, its concentration, the evaporation time, the temperature of the melting solution, the quantity and temperature of the ambient gas in the removal zone. by evaporation.
    [0044] Useful volatile solvents include those listed below. The solvents must be miscible in water, for example, acetone, tetrahydrofuran, methanol, ethanol, propanol, isopropanol, dioxane, diethyl ether.
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    13/38 [0045] The production of the casting solution is preferably carried out by adding additives by addition by measuring the mixture of additives or separately from one another in succession. The additives are gradually introduced by measurements into the mixture with stirring. The measurement addition takes between 10 minutes and 3 hours, preferably, and between 30 minutes and 2 hours, especially. Adding the cosolvents causes partial precipitation of polyimide at the drop entry point. But, the solids dissolve again after a few minutes without leaving residue. The clear solution is additionally filtered, and followed through a 15 μ steel mesh sieve to remove destructive concomitants that would lead to imperfections on the membrane surface.
    [0046] After filtration, the solution is left to rest in a sealed container at 50 ° C for 2 days to remove air bubbles and, consequently, devolatilization.
    Production of hollow fibers [0047] The polymeric polyimide solution, devolatilized, filtered and additive, is thermostable - preferably from 20 to 100 ° C and more preferably from 30 to 70 ° C. The solution is driven by a gear pump through the outside of a two-material mold. The outside diameter of the mold of two materials is 600 i.im, the inside diameter is 160 μm and the pumping rate is between 1.3 and
    13.5 ml / min. A liquid mixture of water and one or more aprotic dipolar solvents is pumped inside the mold of two materials.
    [0048] Useful solvents include, but are not limited to, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, Netylpyrrolidone, sulfolane or dimethyl sulfoxide.
    [0049] The composition is between solvent and water and formed between 10% by weight and 95% by weight of solvent and 90% by weight and 5% in
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    14/38 weight of water, preferably between 30% by weight and 90% by weight of solvent and between 70% by weight and 10% by weight of water and more preferably between 50% by weight and 80% by weight of solvent and between 50% by weight and 20% by weight of water. The pumping rate is between 0.2 mL / min. and 10 ml / min.
    [0050] The resulting hollow fiber then enters a tube flooded with dry thermostable gas. Useful gases include: nitrogen, air, argon, helium, carbon dioxide, methane or other inert industrial gases. The gas temperature is adjusted by means of a heat exchanger and is preferably between 20 and 250 ° C, more preferably between 30 and 150 ° C and even more preferably between 40 and 120 ° C.
    [0051] The velocity of the gas in the pipe is preferably between 0.1 and 10 m / min, more preferably between 0.5 and 5 m / min and even more preferably between 1 and 3 m / min. The distance and, consequently, the length of the tube is preferably between 5 cm and one meter and more preferably between 10 and 50 cm. The fiber thus conditioned then drips in a water bath to coagulate the polymeric mass and thus form the membrane. The temperature of the water bath is preferably between 1 and 60 ° C, more preferably between 5 and 30 ° C and still preferably between 8 and 16 ° C.
    [0052] The concentration of aprotic dipolar solvent and other solvents such as, for example, but not limited to, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, sulfolane, dimethyl sulfoxide, tetrahydrofuran, dioxane, isopropanol , ethanol or glycerol in the coagulation bath is between 0.01% by weight and 20% by weight, preferably between 0.1% by weight and 10% by weight and more preferably between 0.2% by weight and 1% by weight.
    [0053] The hollow fibers are dragged out at a rate between 2 and 100 m / min, preferably between 10 and 50 m / min and more preferably between 20 and 40 m / min. The fibers are coiled and washed
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    15/38 with water until the residual solvent content is below 1%. Then, treatment is carried out in ethanol and hexane. The fibers are then dried - preferably between room temperature and 150 ° C and more preferably between 50 and 100 ° C. The fibers are obtained with external diameters from 100 to 1000 qm, preferably between 200 and 700 qm and more preferably between 250 and 400 μ.
    [0054] The process of the present invention thus provides hollow fiber polyimide membranes that exhibit high performances for separation of various gases. A statement for various polymers and gases is summarized in Table 2.
    Table 2: Permeability of several hollow polyimide fibers of the invention in measurements with a single gas
    Hollow fiber polyimide polymer Internal diameter[qm] Outside diameter [qm] Gas Transmembrane pressure [bar] (MPa) Permeability[GPU] selectivelydade P84type 70 250 412 O2 5 (0.5) 1.45 8.8250 412 N2 5 (0.5) 0.165 250 412 CO2 5 (0.5) 6.0 72250 412 CH4 5 (0.5) 0.084 250 412 CO2 40 (4) 9.0 88250 412 CH4 40 (4) 0.101P84 T100 339 189 O2 10 (1) 0.56 7.8339 189 N2 10 (1) 0.072
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    Continuation...
    339 189 CO2 10 (1) 1.68 72339 189 CH4 10 (1) 0.023 P84 HT 174 300 O2 9 (0.9) 0.65 8.4174 300 N2 10 (1) 0.078245 397 CO2 10 (1) 2.60 58245 397 CH4 9 (0.9) 0.044
    [0055] It is still notable that membranes, even when under high partial pressures of CO2, rarely exhibit an increase in permeation to methane, selectively retain and therefore rarely plasticize. This property is necessary to process sour gases with high levels of CO2 and high pressures, as is the case, for example, with the development of crude natural gas or crude biogas.
    [0056] Hollow fiber membranes can also be cross-linked with amines. When the hollow fiber is cross-linked, cross-linking is carried out subsequent to the washing step. For this purpose, the hollow fiber passes through a bath containing an amine with 2 or more amino groups per molecule such as, for example, diamine, triamine, tetramine or polyamine. The amine can be primary or secondary or consist of mixtures of primary, secondary and tertiary amines in a single molecule. Useful amines include aliphatic aromatic amines and mixed aliphatic-aromatic amines. Silicone-based amines are also possible. Examples of aliphatic diamines include, but are not limited to: diaminoethane, diaminopropane, diaminobutane, diaminopentane, diaminohexane, diaminoheptane, diaminooctane, diaminodecane or diamino compounds of branched or cyclic aliphatic compounds (for example, cis and trans-1,4-cycle hexane) and longer chain.
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    17/38 [0057] Useful aromatic compounds include, but are not limited to: p-phenylenediamines, m-phenylenediamines, 2,4-tolylenediamines, 2,6-tolylenediamines, 4,4'-diaminediphenyl ether.
    [0058] Examples of mixed aliphatic-aromatic amines include, but are not limited to: substituted aminalalkyl aromatics such as, for example, p-bis (aminomethyl) -benzene.
    [0059] Useful amines based on silicone include, but are not limited to: bis (aminoalkyl) siloxanes of different chain lengths.
    [0060] Useful representatives of polyfunctional amines include, but are not limited to, the following compounds: oligo or polyethyleneimines having various molar masses (400 to 200 000 g / mol), N, N ', N ”-trimethylbis (hexamethylene) triamine, bis (6-aminohexyl) amine.
    [0061] The cross-linking is carried out by internal placement or continuous dragging of the entire hollow fiber through a solution of the diamine in particular in water or mixture of water and water-miscible solvents or other solvents without influence on the membrane structure and which dissolve the amines in particular. Possibilities for these are, for example, but not exclusively:
    • Alcohols such as, for example, methanol, ethanol, isopropanol, propanol, butanol, butanediol, glycerol;
    • Ethers such as, for example, diethyl ether, tetrahydrofuran, dioxane or polyethylene glycols or polyethylene glycol ethers;
    • Dipolar aprotic solvents such as, for example, dimethylformamide, dimethylacetamide, N-methyl-pyrrolidone, N-ethylpyrrolidone, tetramethylurea, dimethyl sulfoxide or sulfolane;
    • Ketones such as, for example, acetone or methyl ethyl ketone;
    • Others such as ethyl acetate, dichloromethane, chloroform, toluene, xylene, aliphatic and cycloaliphatic compounds such as hexane, heptane or cyclohexane.
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    18/38 [0062] The concentration of diamines is between 0.01% by weight and 10% by weight, but preferably between 0.05% by weight and 5% by weight and more preferably between 0.1% by weight and 1 % by weight.
    [0063] The temperature of the cross-linking solution is between 1 and 100 ° C, preferably between 10 and 70 ° C and more preferably between 20 and 50 ° C.
    [0064] The residence time is between 10 seconds and 10 hours, preferably between 1 minute and 60 minutes and more preferably between 2 and 10 minutes.
    [0065] In order to remove the residual amine, the membrane is washed with water. The temperature of the wash bath is between 10 and 90 ° C and preferably between 20 and 60 ° C. The residence time of the wash bath is 1 to 200 minutes, preferably between 2 and 50 minutes and more preferably between 3 and 10 minutes.
    [0066] Hollow fibers are obtained that are no longer soluble in traditional organic solvents, such as, but not limited to, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, Netylpyrrolidone, tetramethylurea, dimethyl or sulfolane, acetone, methyl ethyl ketone, ether diethyl, tetrahydrofuran, dioxane, ethyl acetate, dichloromethane, chloroform, toluene, xylene, hexane, heptane or cyclohexane. These can therefore be used in nano-, ultra- or microfiltration in organic solvents.
    Production of flat plate membranes [0067] The devolatilized additive solution is poured without bubbles in the equipment applicator to melt flat plate membranes. The width of the applicator can be up to 1.2 m. A calendered support fleece, preferably, but not exclusively, made of polyimide, polypropylene, polyamide, polyester or polyphenylene sulfide, passes under the applicator at a speed of 0.1 to 10 m / min and preferably 1 at 5 m / min. The thickness of the fleece is between 30 and 300 μ and, preferably
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    19/38, between 100 and 200 μ. The weight is between 20 and 300 g / m 2 and preferably between 50 and 150 g / m 2 . The width of the space between the applicator and the fleece is between 100 and 800 μ and preferably between 200 and 400 μ. The coated fleece enters a channel flooded with a gas flow in the opposite direction. Useful gases include, but are not limited to, dry air, nitrogen, argon or helium. The gas flow over the coated fleece moves at a speed in the range of 100 to 5000 m / h and preferably between 200 and 1000 m / h, the gas temperatures can be between 10 and 150 ° C and preferably between 15 and 90 ° C. The coated fleece then enters a coagulation bath, the polymer coagulates and forms the desired membrane. The coagulation bath consists of water or mixtures of water and one or more solvents that are miscible in water.
    [0068] The possibilities for this solvent include:
    • Alcohols such as, for example, methanol, ethanol, isopropanol, propanol, butanol, butanediol, glycerol;
    • Ethers such as, for example, diethyl ether, tetrahydrofuran, dioxane or polyethylene glycols or polyethylene glycol ethers;
    • Dipolar aprotic solvents such as, for example, dimethylformamide, dimethylacetamide, N-methyl-pyrrolidone, N-ethylpyrrolidone, tetramethylurea, dimethyl sulfoxide or sulfolane;
    • Ketones such as, for example, acetone or metal ethyl ketone. [0069] The temperature of the coagulation bath is between 1 and 90 ° C and preferably between 10 and 50 ° C. After a short residence time of 10 seconds to 10 minutes and preferably 1 to 5 minutes, the membrane is rolled up in the wet state.
    [0070] In order to remove the residual solvent, the membrane is washed with water. The temperature of the wash bath is between 10 and 90 ° C and preferably between 20 and 60 ° C. The residence time in the wash bath is 1 to 200 minutes, preferably between 2 and 50 minutes and
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    20/38 more preferably between 3 and 10 minutes.
    [0071] When the membrane is cross-linked, cross-linking is carried out subsequent to the washing step. For this, the membrane is passed through a bath containing an amine with 2 or more amino groups per molecule such as, for example, diamine, triamine, tetraamine or polyamine. The amine can be primary or secondary or consist of mixtures of primary, secondary and tertiary amines in a single molecule. Useful amines include aliphatic amines, aromatic amines and mixed aliphatic-aromatic amines. Silicone-based amines are also possible.
    [0072] Examples of aliphatic diamines include, but are not limited to: diaminoethane, diaminopropane, diaminobutane, diaminopentane, diaminohexane, diaminoheptane, diaminooctane, diaminodecane or diamino compounds of branched or cyclic aliphatic compounds (for example, cis and trans-1, 4-cyclohexane) and longer chain.
    [0073] Useful aromatic compounds include, but are not limited to: p-phenylenediamines, m-phenylenediamines, 2,4-tolylenediamines, 2,6-tolylenediamines, 4,4'-diaminediphenyl ether.
    [0074] Examples of mixed aliphatic-aromatic amines include, but are not limited to: substituted aminoalkyl aromatics such as, for example, p-bis (aminomethyl) -benzene.
    [0075] Useful amines based on silicone include, but are not limited to: bis (aminoalkyl) siloxanes of different chain length. Useful representatives of polyfunctional amines include, but are not limited to, the following compounds: oligo or polyethyleneimines with various molar masses (400 to 200,000 g / mol), N, N ', N ”-trimethylbis (hexamethylene) triamine, bis ( 6aminohexyl) amine.
    [0076] Cross-linking is carried out by placing the entire membrane
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    21/38 in a solution of the diamine in particular in water or a mixture of water and water-miscible solvents or other solvents without influence on the membrane structure and which dissolve the amines in particular.
    [0077] Possibilities for these are, for example, but not exclusively:
    • Alcohols such as, for example, methanol, ethanol, isopropanol, propanol, butanol, butanediol, glycerol;
    • Ethers such as, for example, diethyl ether, tetrahydrofuran, dioxane or polyethylene glycols or polyethylene glycol ethers;
    • Dipolar aprotic solvents such as, for example, dimethylformamide, dimethylacetamide, N-methyl-pyrrolidone, N-ethylpyrrolidone, tetramethylurea, dimethyl sulfoxide or sulfolane;
    • Ketones such as, for example, acetone or methyl ethyl ketone;
    [0078] Others such as ethyl acetate, dichloromethane, chloroform, toluene, xylene, aliphatic and cycloaliphatic compounds such as hexane, heptane or cyclohexane.
    [0079] The concentration of diamines, the temperature of the crosslinking solution, the residence time and the manner in which the washing step is carried out correspond to the values and procedures, respectively, indicated above to crosslink the hollow fibers.
    [0080] After washing / cross-linking operations, the membrane is impregnated to ensure that the pores are preserved during subsequent drying. This is done by immersing the membrane in a mixture of water and water-miscible high-boiling compound.
    [0081] The possibilities for this are, for example, but not exclusively: glycerol, polyethylene glycols of different chain lengths in mixture or alone, dialkyl polyethylene glycol ethers of different chain lengths mixed or alone as
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    22/38 methyl or ethyl ether, mono- or diols with a boiling point above 200 ° C such as, for example, decanol, 1,4-butanediol, 1,6-hexanediol.
    [0082] The concentration of the high boiling compound in water is between 5% and 95%, but preferably between 25% by weight and 75% by weight. The temperature of the impregnation solution is between 1 and 100 ° C, preferably between 10 and 70 ° C and more preferably between 20 and 50 ° C.
    [0083] The residence time is between 10 seconds and 10 hours, preferably between 1 minute and 60 minutes and more preferably between 2 and 10 minutes.
    [0084] After impregnation, the membrane is dried. Drying is carried out in room air or continuous mode in a convective dryer. The drying temperature ranges from 20 to 200 ° C and preferably between 50 and 120 ° C. The drying time is between 10 seconds and 10 hours, preferably between 1 minute and 60 minutes and more preferably between 2 and 10 minutes. After drying, the final membrane is rolled up and can be further processed into spiral-wound elements or small modules.
    [0085] The flat and hollow fiber membranes of the present invention therefore comprise a polyimide having Mp> 100,000 g.mol -1 , preferably 110,000 to 200,000 g.mol -1 and more preferably 120,000 to 170,000 g.mol -1 and PDI in the range of 1.7 to 2.3 and preferably in the range of 1.8 to 2.1. Mp, in this specification, corresponds to the maximum peak molar mass distribution in calibration against polystyrene standards in 0.01 mol / L lithium bromide in dimethylformamide.
    [0086] The high molar mass has the effect of improving the mechanical properties related to the strength and toughness of the membrane. This characteristic is most especially necessary in high pressure applications. Flat plate membranes must support at least
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    23/38 minus 4 MPa (40 bar) when in operation and certain hollow fiber membranes, above 10 MPa (100 bar) in natural gas enrichment.
    [0087] High molar mass is also advantageous so that the viscosity is sufficiently high even at moderate solids contents. Foundry solutions require a certain viscosity for stable processing in hollow membranes and fibers and for dense and selective layers on the surface to be produced with them.
    Production examples [0088] The examples that follow serve to offer more specific elucidation and a better understanding of the present invention, but not to limit it in any way.
    Production of polyimide solutions
    Example 1: Production of P84 type 70 polyimide solution in dimethylacetamide [0089] A 3 L glass reactor equipped with a stirrer and reflux condenser is initially charged with 1622 g of anhydrous dimethylacetamide. An amount of 456.4 g of 3.3 'dianhydride, 4.4' benzophenonatetracarboxylic acid is dissolved in the reactor, and the solution is heated to 90 ° C. To this solution, 0.45 g of sodium hydroxide is added. Under nitrogen, 266.8 g of a mixture of 64% 2,4tolylene diisocyanate, 16% 2,6-tolylene diisocyanate and 20% of 4,4'di-isocyanatodiphenylmethane are measured over several hours. In the process, CO2 escapes as a by-product and a polyimide results directly in solution.
    [0090] The highly viscous solution obtained is golden in color and has a solids content of 25% and a viscosity of 49 Pa.s.
    [0091] Molar masses are determined by gel permeation chromatography as follows: Mn = 80 600 g.mol -1 , Mp = 139 600
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    g.mol -1 , Mw = 170 000 g.mol -1 , PDI = 2.11.
    Example 2: Production of P84 type 70 polyimide solution in dimethylformamide [0092] A 3 L glass reactor equipped with stirrer and reflux condenser is initially charged with 1622 g of anhydrous dimethylformamide. An amount of 456.4 g of 3.3 'dianhydride, 4.4' benzophenonatetracarboxylic acid is dissolved in the reactor, and the solution is heated to 90 ° C. To this solution, 0.45 g of sodium hydroxide is added. Under nitrogen, 266.8 g of a mixture of 64% 2,4-tolylene diisocyanate, 16% 2,6-tolylene diisocyanate and 20% 4,4'di-isocyanatodiphenylmethane are measured over several hours. In the process, CO2 escapes as a by-product and a polyimide results directly in solution.
    [0093] The highly viscous solution obtained is golden in color and has a solids content of 27% and a viscosity of 48 Pa.s.
    [0094] Molar masses are determined by gel permeation chromatography as follows: Mn = 76 600 g.mol -1 , Mp = 130 500 g.mol -1 , Mw = 146 200 g.mol -1 , PDI = 1 , 91.
    Example 3: Production of P84 type 70 polyimide solution in Nmethylpyrrolidone [0095] A 3 L glass reactor equipped with a stirrer and reflux condenser is initially charged with 1800 g of anhydrous Nmethylpyrrolidone. An amount of 456.4 g of 3.3 ', 4,4'-benzophenonatetracarboxylic dianhydride is dissolved in the reactor and the solution is heated to 90 ° C. To this solution, 0.45 g of sodium hydroxide is added. Under nitrogen, 266.8 g of a mixture of 64% 2,4-tolylene diisocyanate, 16% 2,6-tolylene diisocyanate and 20% 4,4'di-isocyanatodiphenylmethane are measured over several hours. In the process, CO2 escapes as a by-product and a polyimide results directly in solution.
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    25/38 [0096] The highly viscous solution obtained is golden in color and has a solids content of 25% and a viscosity of 45 Pa.s.
    [0097] Molar masses are determined by gel permeation chromatography as follows: Mn = 65 700 g.mol -1 , Mp = 107 200 g.mol -1 , Mw = 147 000 g.mol -1 , PDI = 2 , 24.
    Example 4: Production of P84 type 70 polyimide solution in Netylpyrrolidone [0098] A 3 L glass reactor equipped with stirrer and reflux condenser is initially loaded with 1622 g of anhydrous Netylpyrrolidone. An amount of 456.4 g of 3,3 ', 4,4'-benzophenonatetracarboxylic dianhydride is dissolved in the reactor and the solution is heated to 90 ° C. To this solution, 0.45 g of sodium hydroxide is added. Under nitrogen, 266.8 g of a mixture of 64% 2,4-tolylene diisocyanate, 16% 2,6-tolylene diisocyanate and 20% 4,4'di-isocyanatodiphenylmethane are measured over several hours. In the process, CO2 escapes as a by-product and a polyimide results directly in solution.
    [0099] The highly viscous solution obtained is golden in color and has a solids content of 27% and a viscosity of 87 Pa.s.
    [00100] Molar masses are determined by gel permeation chromatography as follows: Mn = 64 600 g.mol -1 , Mp = 105 200 g.mol -1 , Mw = 144 700 g.mol -1 , PDI = 2 , 24.
    Example 5: Production of P84 T100 polyimide solution in dimethylformamide [00101] A 3 L glass reactor equipped with a stirrer and reflux condenser is initially charged with 1800 g of anhydrous dimethylformamide. A quantity of 473.6 g of 3.3 'dianhydride, 4.4' benzophenonatetracarboxylic acid is dissolved in the reactor and the solution is heated to 90 ° C. To this solution, 1.8 g of diazabicyclooctane are added. Under nitrogen, 254.4 g of a mixture of 2,4-tolylene di
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    26/38 isocyanates are measured over several hours. In the process, CO2 escapes as a by-product and a polyimide results directly in solution. [00102] The highly viscous solution obtained is golden in color and has a solids content of 25% and a viscosity of 59 Pa.s.
    [00103] Molar masses are determined by gel permeation chromatography as follows: Mn = 82 100 g.mol -1 , Mp = 151 500 g.mol -1 , Mw = 181 900 g.mol -1 , PDI = 2 , 21.
    Example 6: Production of P84 T80 polyimide solution in dimethylformamide [00104] A 3 L glass reactor equipped with a stirrer and reflux condenser is initially charged with 1622 g of anhydrous dimethylformamide. An amount of 473.6 g of 3.3 'dianhydride, 4.4' benzophenonatetracarboxylic dianhydride is dissolved in the reactor and the solution is heated to 90 ° C. To this solution, 1.8 g of diazabicyclooctane are added. Under nitrogen, 254.4 g of a mixture of 80% 2,4-tolylene diisocyanate and 20% 2,6-tolylene diisocyanate are measured over several hours. In the process, CO2 escapes as a by-product and a polyimide results directly in solution.
    [00105] The highly viscous solution obtained is golden in color and has a solids content of 27% and a viscosity of 108 Pa.s.
    [00106] Molar masses are determined by gel permeation chromatography as follows: Mn = 83 800 g.mol -1 , Mp = 152 300 g.mol -1 , Mw = 173 800 g.mol -1 , PDI = 2 , 07.
    Example 7: Production of P84 HT polyimide solution in dimethylformamide [00107] A 3 L glass reactor equipped with a stirrer and reflux condenser is initially charged with 1800 g of anhydrous dimethylformamide. An amount of 316.4 g of 3.3 'dianhydride, 4.4' benzophenonatetracarboxylic acid and 142.8 g of pyromelitic dianhydride is dissolved in the reactor and the solution is heated to 90 ° C. This solution is
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    27/38 1.8 g of diazabicyclooctane added. Under nitrogen, 283.4 g of a mixture of 80% 2,4-tolylene diisocyanate and 20% 2,6-tolylene diisocyanate are measured over several hours. In the process, CO2 escapes as a by-product and a polyimide results directly in solution.
    [00108] The highly viscous solution obtained is golden in color and has a solids content of 27% and a viscosity of 70 Pa.s.
    [00109] Molar masses are determined by gel permeation chromatography as follows: Mn = 75 500 g.mol -1 , Mp = 122 200 g.mol -1 , Mw = 150 900 g.mol -1 , PDI = 2 , 00.
    Example 8: Production of P84 MDI polyimide solution in dimethylformamide [00110] A 3 L glass reactor equipped with a stirrer and reflux condenser is initially charged with 1500 g of anhydrous dimethylformamide. An amount of 369.2 g of 3.3 'dianhydride, 4.4' benzophenonatetracarboxylic acid is dissolved in the reactor and the solution is heated to 90 ° C. To this solution, 1.5 g of diazabicyclooctane are added. Under nitrogen, 222.3 g of 2,4,6-trimethyl-1,3-phenylene diisocyanate are measured over several hours. In the process, CO2 escapes as a by-product and the polyimide results directly in solution.
    [00111] The highly viscous solution obtained is light yellow in color and has a solids content of 25% and a viscosity of 5 Pa.s.
    [00112] Molar masses are determined by gel permeation chromatography as follows: Mn = 55 200 g.mol -1 , Mp = 95 000 g.mol -1 , Mw = 112 000 g.mol -1 , PDI = 2 , 03.
    Film production and intrinsic gas permeability [00113] The polymerization solutions are filtered pure through a 15 μ metal sieve. Films are produced using an Elcometer instrument (Elcometer 4340) with applicator. Glass plates are coated with polymeric solutions, using an application
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    28/38 pain and gap size of 250 μ. The solvent is subsequently separated by evaporation in a circulating air drying cabinet at 70 ° C (0.5 h), 150 ° C (2 h) and 250 ° C (12 h). The films are then virtually solvent free (content <0.1%) and are detached from the glass plates. The thickness of the films obtained is around 30 to 40 μm. None of the films were friable and all exhibited good mechanical properties. These films were then examined under the microscope to find places free of imperfections, and round samples in circles with diameters of 46 mm are cut. These samples are then placed in the built-in apparatus for gas permeation, and the permeability of various gases is determined by the vacuum method.
    [00114] The method involves pressing the films with a single gas (for example, nitrogen, oxygen, methane or carbon dioxide) at various pressures and recording the increase in pressure on the permeate side. In this way, the permeability in barriers (10-6 cm 3 .cm -2 .s -1 .cmHg -1 ) is calculated. Some examples are shown below.
    Example 9: Gas permeabilities of various polymers from the examples above
    Polymer Thickness (μίΌ) Gas Transmembrane pressure (bar) MPa Permeability * (Barrer) Selectivity Example 2 (P84 type70)O20.182 10.0N20.018CO20.571 67.2CH40.008 Example 5 (P84 T100) 37.9 O2 1.09 (10.9) 0.250 30.9 37.9 N2 1.10 (11.0) 0.008 37.9 CO2 2.52 (25.2) 0.622 124 37.9 CH4 1.75 (17.5) 0.005 Example 6 36.0 O2 1.07 (10.7) 0.280 21.2
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    Polymer Thickness (μ ™) Gas Transmembrane pressure (bar) MPa Permeability * (Barrer) Selectivity (P84 T80) 36.0 N2 1.11 (11.1) 0.01336.0 CO2 2.84 (28.4) 0.696 237 36.0 CH4 3.15 (31.5) 0.003 Example 7 (P84 HT) 41.2 O2 1.20 (12.0) 0.53 13.2 41.2 N2 1.23 (12.3) 0.04 41.6 CO2 3.68 (36.8) 1.69 169 41.6 CH4 3.64 (36.4) 0.01
    Adding the polymerization solution
    Example 10: Production of casting solution from P84 type 70 for the production of hollow polyimide fibers [00115] In a 3 liter glass stirred tank with a powerful stirrer, 1168 g of a solution of P84 type 70 in dimethylformamide of Example 2 are mixed with a mixture of 94.1 g of tetrahydrofuran and 40.3 g of isopropanol added in drops at room temperature. As the addition proceeds, the polymer precipitates briefly at the drop entry point, but quickly dissolves again. Stirring is continued until a homogeneous solution is produced. This homogeneous solution is then filtered through a 15 μ mesh size sieve and left to stand for 2 days without stirring. The foundry solution obtained has a solids content of 23.5%, a dimethylformamide content of 66.5%, a tetrahydrofuran content of 7% and an isopropanol content of 3%.
    Example 11: Production of casting solution from P84 type 70 for the production of hollow polyimide fibers [00116] In a stirred glass tank of 3 liters with powerful stirrer, 1034 g of solution of P84 type 70 in dimethylformamide from Example 2 are mixed with a mixture of 58.6 g of tetrahydrofuran and 46.9 g of isopropanol added in drops to the temperature.
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    30/38 r environment. As the addition proceeds, the polymer precipitates briefly at the drop entry point, but quickly dissolves again. Stirring is continued until a homogeneous solution is produced. This homogeneous solution is then filtered through a 15 μ mesh size sieve and left to stand for 2 days without stirring. The foundry solution obtained has a solids content of 23.8%, a dimethylformamide content of 67.2%, a tetrahydrofuran content of 5% and an isopropanol content of 4%.
    Example 12: Production of a casting solution from P84 type HT for the production of hollow polyimide fibers [00117] In a stirred 3 liter glass tank with a powerful stirrer, 1034 g of solution of P84 type HT in dimethylformamide from Example 7 are mixed with a mixture of 47 g of tetrahydrofuran and 65 g of isopropanol added in drops at room temperature. As the addition proceeds, the polymer precipitates briefly at the drop entry point, but quickly dissolves again. Stirring is continued until a homogeneous solution is produced. This homogeneous solution is then filtered through a 15 μ mesh size sieve and left to stand for 2 days without stirring. The foundry solution obtained has a solids content of 23.6%, a dimethylformamide content of 66.9%, a tetrahydrofuran content of 4% and an isopropanol content of 5.5%.
    Example 13: Production of casting solution from P84 T100 for the production of hollow polyimide fibers [00118] In a stirred 3 liter glass tank with a powerful stirrer, 1034 g of P84 T100 solution in dimethylformamide from Example 5 are mixed with a mixture of 46.8 g of tetrahydrofuran and
    58.5 g of isopropanol added in drops at room temperature. As the addition proceeds, the polymer precipitates briefly at the drop entry point, but quickly dissolves again. The unrest
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    31/38 continues until a homogeneous solution is produced. This homogeneous solution is then filtered through a 15 μ mesh size sieve and left to stand for 2 days without stirring. The foundry solution obtained has a solids content of 22.1%, a dimethylformamide content of 68.9%, a tetrahydrofuran content of 5% and an isopropanol content of 4%.
    Example 14: Production of casting solution from P84 type 70 for production of flat plate membranes for organophilic nanofiltration [00119] In a stirred 3 liter glass tank with powerful stirrer, 1034 g of P84 type 70 solution in dimethylformamide of Example 2 are mixed with 258.5 g of tetrahydrofuran added in drops at room temperature. Stirring is continued until a homogeneous solution is produced. This homogeneous solution is then filtered through a 15 μ mesh size sieve and left to stand for 2 days without stirring. The foundry solution obtained has a solids content of 21.6%, a dimethylformamide content of 58.4% and a tetrahydrofuran content of 20%.
    Hollow fiber production
    Example 15: Production of hollow fiber from a solution for casting with P84 type 70 in dimethylformamide of Example 10 [00120] The devolatilized, filtered and additive solution of P84 type 70 in dimethylformamide of Example 10 is thermally stabilized to 50 ° C and pulsed by gear pump through a mold of two materials. The flow is 162 g / h. While the polymeric solution is transported in the outermost region of the two-material mold, a mixture of 70% dimethylformamide and 30% water is transported in the innermost region in order to produce a hole in the hollow fiber. The flow is 58 mL / h. After a distance of 40 cm, the hollow fiber enters cold water at 10 ° C. The hollow fiber is enveloped at this point with a tube.
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    This tube is flooded with a stream of nitrogen at 2 L / min, the internal temperature of the tube being 41 ° C. The fiber is then dragged through a water wash bath and finally wound at a speed of 15 m / min. After extraction with water for several hours, the hollow fibers are first immersed in ethanol and then in heptane and subsequently air-dried to obtain hollow fibers having an external diameter of 412 μ, orifice diameter of 250 μ and wall thickness of 81 μ.
    [00121] Measurements of isolated gases provided the following permeability for hollow fibers at a transmembrane pressure of 0.5 MPa (5 bar):
    Oxygen: 1,450 GPU
    Nitrogen: 0.165 GPU
    Carbon dioxide: 6.03 GPU
    Methane: 0.084 GPU [00122] The selectivities of isolated gases are, therefore, 8.8, between oxygen and nitrogen, and 71.9 between carbon dioxide and methane.
    [00123] Measurements of isolated gases provided the following permeations for hollow fibers at a transmembrane pressure of 4 MPa (40 bar):
    Carbon dioxide: 8.99 GPU
    Methane: 0.101 GPU [00124] The selectivity of isolated gases is 88.5 between carbon dioxide and methane.
    Example 16: Production of hollow fiber from a solution for casting with P84 type 70 in dimethylformamide of Example 11 [00125] The devolatized, filtered and additive solution of P84 type 70 in dimethylformamide of Example 11 is thermally stabilized to 50 ° C and boosted with gear pump through a mold of two materials. The flow is 162 g / h. While the polymeric solution is
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    33/38 carried in the outermost region of the mold of two materials, a mixture of 70% of dimethylformamide and 30% of water is transported in the innermost region in order to produce the hole in the hollow fiber. The flow is 58 mL / h. After a distance of 42 cm, the hollow fiber enters cold water at 10 ° C. The hollow fiber is enveloped at this point with a tube. This tube is flooded with nitrogen stream at 2 L / min, the internal temperature of the tube being 46 ° C. The fiber is then dragged through a water wash bath and finally wound at a speed of 24 m / min. After extraction with water for several hours, the hollow fibers are first immersed in ethanol and then in heptane and subsequently air-dried to obtain hollow fibers having an outer diameter of 310 μ, orifice diameter of 188 μ and wall thickness of 61 μ.
    [00126] Measurements of isolated gases provided the following permeability for hollow fibers at a transmembrane pressure of 0.9 MPa (9 bar):
    Oxygen: 1,463 GPU Nitrogen: 0.164 GPU [00127] The selectivities of isolated gases are therefore 8.9 between oxygen and nitrogen.
    Example 17: Production of hollow fiber from a solution for casting with P84 T100 in dimethylformamide of Example 13 [00128] The devolatized, filtered and additive solution of P84 T100 in dimethylformamide of Example 13 is thermostated to 50 ° C and driven by pump of gear through a mold of two materials. The flow is 162 g / h. While the polymeric solution is transported in the outermost region of the two-material mold, a mixture of 70% dimethylformamide and 30% water is transported in the innermost region in order to produce the hole in the hollow fiber. The flow is 58 mL / h. After a distance of 42 cm, the hollow fiber comes into contact
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    34/38 cold water at 10 ° C. The hollow fiber is enveloped at this point with a tube. This tube is flooded with nitrogen stream at 2 L / min, the internal temperature of the tube being 46 ° C. The fiber is then dragged through a water wash bath and finally wound at a speed of 20 m / min. After extraction with water for several hours, the hollow fibers are first immersed in ethanol and then in heptane and subsequently dried in air to obtain hollow fibers having an outer diameter of 339 μ, orifice diameter of 189 μ and wall thickness of 75 μ.
    [00129] Measurements of isolated gases provided the following permeations for hollow fibers at a transmembrane pressure of 0.9 MPa (9 bar):
    Oxygen: 0.564 GPU Nitrogen: 0.072 GPU
    Carbon dioxide: 1,679
    Methane: 0.023 [00130] The selectivities of isolated gases are, therefore, 7.8 between oxygen and nitrogen and 71.6 between carbon dioxide and methane.
    Example 18: Production of hollow fiber from a solution for casting with P84 HT in dimethylformamide [00131] The devolatized, filtered and additive solution of P84 HT in dimethylformamide of Example 12 is thermostated to 50 ° C and driven with a gear pump through of a mold of two materials. The flow is 162 g / h. While the polymeric solution is transported in the outermost region of the two-material mold, a mixture of 70% dimethylformamide and 30% water is transported in the innermost region in order to produce the hole in the hollow fiber. The flow is 58 mL / h. After a distance of 15 cm, the hollow fiber enters cold water at 10 ° C. The hollow fiber is enveloped at this point with a tube. This tube is flooded with nitrogen stream at 1 L / min, the temperature
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    35/38 internal tube thickness being 40 ° C. The fiber is then dragged through a water wash bath and finally wound at a speed of 24 m / min. After extraction with water for several hours, the hollow fibers are first immersed in ethanol and then in heptane and subsequently air-dried to obtain hollow fibers having an external diameter of 306 μ, orifice diameter of 180 μ and wall thickness of 63 μ.
    [00132] Measurements of isolated gases provided the following permeations for hollow fibers at a transmembrane pressure of 1 MPa (10 bar):
    Carbon dioxide: 6.0 GPU
    Methane: 0.2 GPU [00133] The selectivities of isolated gases are therefore 30 between carbon dioxide and methane.
    Example 19: Production of hollow fiber from a polymerisation solution with P84 HT in dimethylformamide of Example 7 [00134] The filtered devolatilized solution of P84 HT in dimethylformamide of Example 7 is thermally stabilized to 50 ° C and driven with a gear pump through of a mold of two materials. The flow is 162 g / h. While the polymeric solution is transported in the outermost region of the two-material mold, a mixture of 70% dimethylformamide and 30% water is transported in the innermost region in order to produce the hole in the hollow fiber. The flow is 58 mL / h. After a distance of 15 cm, the hollow fiber enters cold water at 10 ° C. The hollow fiber is enveloped at this point with a tube. This tube is flooded with nitrogen stream at 1 L / min, the internal temperature of the tube being 70 ° C. The fiber is then dragged through a water wash bath and finally wound at a speed of 24 m / min. After extraction with water for several hours, the hollow fibers are first immersed in ethanol and then in heptane and subsequently
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    36/38 air-dried to obtain hollow fibers having an outer diameter of 307 μ, an orifice diameter of 189 μ and a wall thickness of 59 μ.
    [00135] Measurements of isolated gases provided the following permeability for hollow fibers at a transmembrane pressure of 1 MPa (10 bar):
    Carbon dioxide: 3.37 GPU
    Methane: 0.051 GPU [00136] The selectivities of isolated gases are therefore 66 between carbon dioxide and methane.
    [00137] The fiber was additionally measured at higher pressures in order to measure the characteristics of plasticization and pressure stability.
    Pressure [bar](MPa) Permeability toCO2[GPU] Methane permeation [GPU] Selectivity 1 (10) 3,365 0.051 66 2 (20) 3,199 0.045 72 3 (30) 3,535 0.034 103 4 (40) 4.025 0.042 96 5 (50) 4,376 0.033 131 6 (60) 4,300 0.026 165 7 (70) - 0.027 - 9 (90) - 0.014 -
    Flat plate membrane production
    Example 20: Production of flat plate membrane from P84 type 70.
    [00138] A flat plate membrane equipment is used to produce 35 cm wide membranes from the solution
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    37/38 for casting described in Example 14. For this purpose, the casting solution is coated with an application and gap for casting of 200 μ on a calendered polyester fleece, having a weight of 100 g / m2 and at a speed of 5 m / min. The polyester-coated fleece then crosses an axis through which nitrogen is flooded. The flow speed is 339 m / h. The residence time thus achieved is 3 seconds. The coated fleece then immerses in cold water at 10 ° C. The raw membrane is then wound wet.
    [00139] Subsequently, the membrane is extracted from water at 70 ° C and impregnated with conditioning agent (25% polyethylene glycol dimethyl ether (Clariant PGDME 250) in water). Drying is carried out in a pulley dryer at a temperature of 60 ° C. [00140] The membrane is characterized in a Milipore cell stirred at a pressure of 0.5 MPa (5 bar). The solvent used is heptane, in which hexafenylbenzene is dissolved in a concentration of 12 mg / L. The measurement revealed a flow of 1.7 Lm -2 .h -1 .bar -1 associated with 94% retention.
    [00141] The membrane is subsequently also tested at a pressure of 3 MPa (30 bar) and 30 ° C in toluene. Oligostyrenes are used as test molecules. The flow in this test with toluene was 90 Lm -2 .h -1 . The membrane exhibits very high retention over the entire range of molar mass and has an abrupt cut in the region between 200 and 300 Daltons (see figure 3).
    Crosslinking of membranes with diamines
    Example 21: Crosslinking of flat plate membrane with amines [00142] The flat plate membrane of Example 20 was placed for 16 hours in 0.1% ethanolic solution of oligoethyleneimine (ref. 468533, Aldrich, typical molecular weight 423, contains 5 - 20% and tetraethylene-pentamine). The membrane cross-links and does not show solubility in hexane, heptane, toluene, xylene, acetone, butanone, methanol, ethanol,
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    38/38 isopropanol, tetrahydrofuran, dichloromethane, chloroform, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and ethyl acetate.
    [00143] The membrane is characterized in a Milipore cell stirred at a pressure of 5 bar (0.5 MPa). The solvent used is dimethylformamide in which hexafenylbenzene is dissolved in a concentration of 2.2 mg / L. The measurement revealed a flow of 1.3 Lm -2 .h -1 .bar -1 associated with 89% retention.
    Example 22: Crosslinking of hollow fiber membrane with amines [00144] The hollow fiber membrane of Example 19 was placed for 16 hours in a solution of hexamethylenediamine 0.1% in ethanol. The membrane cross-links and does not show solubility in hexane, heptane, toluene, xylene, acetone, butanone, methanol, ethanol, isopropanol, tetrahydrofuran, dichloromethane, chloroform, dimethylformamide, dimethylacetamide, N-methyl-pyrrolidone, dimethoxyl acetate and dimethoxyl acetate ethyl. Description of illustrations
    Figure 1: Influence of concentrations of P84 type 70 in DMF on the viscosity of the solution: comparison of a polymerization solution of P84 and a solution of P84, prepared from a precipitated polymer and again dissolved at 25 ° C.
    Figure 2: Cross sections of hollow fiber membranes with macrovazios (image on the left) and without macrovazios (image on the right)
    Figure 3: Example 20 membrane application test.
    Petition 870180166221, of 12/21/2018, p. 41/51
    权利要求:
    Claims (16)
    [1]
    1. Process for the production of polyimide membranes, which comprises the steps of:
    (a) production of the polyimide from aromatic dianhydrides or mixtures thereof and aromatic diisocyanates or mixtures thereof;
    (b) producing a casting solution comprising the polyimide;
    (c) production of a polyimide membrane from the foundry solution, the membrane being produced by a phase inversion process, the said process being characterized by the fact that the polyimide between these steps ( a) and (b) is not isolated as a solid material, particularly not as a dry solid material, and, more particularly, not as a dry powder, and redissolved.
    [2]
    2. Process, according to claim 1, characterized by the fact that, in step (a):
    (a) the polyimide is produced by reacting an aromatic dianhydride or a mixture of aromatic dianhydrides with an aromatic diisocyanate or a mixture of aromatic diisocyanates in an aprotic dipolar solvent or a mixture of aprotic dipolar solvents in the presence of 0.01 to 5% by weight of a basic catalyst, calculated on the combined amount of aromatic dianhydride, to generate a polyimide solution.
    [3]
    3. Process according to claim 1 or 2, characterized by the fact that the step to produce the polyimides in step (a) uses:
    aromatic dianhydrides or mixtures thereof, selected from 3,4,3 ’, 4’-benzophenonatetracarboxylic dianhydride, piPetition 870190047727, from 5/22/2019, p. 6/16
    2/7 romelitic, 3,4,3 ', 4'-biphenyltetracarboxylic dianhydride; and / or aromatic diisocyanates or mixtures thereof, selected from 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'methylenediphenyl diisocyanate, 2,4,6-trimethyl-1, 3-phenylene diisocyanate,
    2,3,5,6-tetramethyl-1,4-phenylene diisocyanate; and / or aprotic dipolar solvents or mixtures thereof, preferably dimethylformamide, dimethylacetamide, N-methylpyrrolidinone, Netylpyrrolidinone, sulfolane, tetrahydrofuran, dioxane.
    [4]
    Process according to any one of claims 1 to 3, characterized in that the polyimide is a polyimide with the structure below:

    R is selected from the group consisting of:
    n

    where x, y: molar fraction with 0 <x <0.5 and 1> y> 0.5.
    [5]
    5. Process according to any one of claims 1 to 4, characterized by the fact that the casting solution is produced in step (b) in the presence of water-soluble additives, the additives used being preferably :
    water-miscible volatile solvents such as diethyl ether, tetrahydrofuran, dioxane or acetone, or mixtures thereof; and / or
    Petition 870190047727, of 05/22/2019, p. 7/16
    3/7 non-solvents such as water, methanol, ethanol, n-propanol, isopropanol, butanol, butanediol, ethylene glycol, glycerol, gamma butyrolactone or mixtures thereof; and / or pore builders, preferably polyvinylpyrrolidinone; and / or water miscible solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidinone, N-ethylpyrrolidinone, sulfolane, dimethyl sulfoxide or mixtures thereof.
    [6]
    Process according to any one of claims 1 to 5, characterized in that step (c) comprises coating a support fleece with polyimide casting solution, preferably after coating the fleece of support with a polymeric solution for casting, part of the solvent is evaporated with a dry thermostable stream of nitrogen or air in order to adjust the separation limits of the membrane.
    [7]
    Process according to any one of claims 1 to 6, characterized in that the polyimide membrane is cross-linked with aliphatic or polyethyleneimines, preferably with aliphatic diamines, such as diaminoethane, diaminopropane, diaminobutane , diaminopentane, diaminohexane, diaminooctane, diaminodecane, diaminododecane, bis-4-4 '- (aminomethyl) benzene, oligoethyleneimines, polyethyleneimines or mixtures thereof are used; and / or cross-linking is carried out by immersion in a solution of diamine in water or alcohols, such as methanol or ethanol or isopropanol or mixtures thereof; and / or cross-linking occurs at temperatures between 0 and 90 ° C, preferably between 10 and 60 ° C, and, more preferably, between 15 and 30 ° C; and / or the crosslinking time is between 10 seconds and 16 hours, from
    Petition 870190047727, of 05/22/2019, p. 8/16
    4/7 preferably between 30 seconds and 30 minutes, and more preferably between 1 and 5 minutes; and / or the concentration of diamine is between 0.01% by weight to 50% by weight, preferably between 0.1% by weight and 10% by weight, and more preferably between 0.2% by weight and 1% by weight.
    [8]
    Process according to any one of claims 1 to 5, characterized in that step (c) comprises producing an integrally asymmetric hollow fiber membrane, the hollow fiber being preferably spun using a mold of two materials, from a polyimide casting solution as defined in claim 4, and from a solution to the orifice in a continuous process.
    [9]
    9. Process according to claim 8, characterized by the fact that the solution used for the orifice is a mixture of water and alcohols with dimethylformamide, dimethylacetamide, Nmethylpyrrolidinone, N-ethylpyrrolidinone, sulfolane, dimethyl sulfoxide or combinations thereof; and / or where the spinning mold is at a distance of 1 to 60 cm from a spinning water bath in which the hollow fiber is spun, and by precipitation of the polymer, an integrally asymmetric hollow fiber membrane is formed; and / or in the course of the spinning process, the hollow wire before entering the spinning bath is subjected to the flow of thermostable dry current of nitrogen or air in order to adjust the separation properties of the membrane; and / or the polyimide polymer being cross-linked with aliphatic or polyethyleneimines, where more preferably, as aliphatic diamines, diaminoethane, diaminopropane, diaminobutane, diaminopentane, diaminohexane, diaminooctane, diaminodecane, diaminododecane, diaminododecane 4 '- (aminomethyl) benzene, oligoethyl
    Petition 870190047727, of 05/22/2019, p. 9/16
    5/7 noimines, polyethyleneimines or mixtures; and / or cross-linking is carried out by immersion in a solution of diamine in water or alcohols, such as methanol or ethanol or isopropanol or mixtures thereof; and / or cross-linking occurs at temperatures between 0 and 90 ° C, preferably between 10 and 60 ° C and, more preferably, between 15 and 30 ° C; and / or the cross-linking time is between 10 seconds and 16 hours, preferably between 30 seconds and 30 minutes, and, more preferably, between 1 and 5 minutes; and / or the concentration of diamine is between 0.01% by weight to 50% by weight, preferably between 0.1% by weight and 10% by weight and, more preferably, between 0.2% by weight and 1 % by weight.
    [10]
    10. Process according to claim 8 or 9, characterized by the fact that it comprises:
    (a) forming a polyimide solution comprising an aprotic dipolar solvent and a polyimide;
    (b) filtering and devolatizing the polyimide solution to obtain a melt solution;
    (c1) pumping the casting solution through a matrix of two materials together with a solution for the orifice to produce a hollow polyimide fiber by phase inversion;
    (c2) treating the polyimide hollow fibers with a dry thermostated gas before entering an aqueous coagulation bath rotation to produce hollow fibers;
    (c3) dipping the hollow fibers treated in the aqueous coagulation bath to produce the hollow polyimide fiber membrane;
    the polyimide being obtained by polymerizing an aromatic dianhydride and an aromatic diisocyanate from a reaction mixture comprising the aprotic dipolar solvent and 0.01 to 5%
    Petition 870190047727, of 05/22/2019, p. 10/16
    6/7 by weight of a basic catalyst, calculated on the combined amount of aromatic dianhydride and aprotic dipolar solvent, and was not isolated as a solid material and then redissolved before the formation of said polyimide solution.
    [11]
    11. Polyimide membrane, characterized by the fact that it is obtained by the process, as defined in any one of claims 1 to 8, and which comprises a polyamide having Mp> 100 000 g.mol -1 (Mp = maximum peak of molar mass distribution, calibration against polystyrene standards in 0.01 mol / L lithium bromide in dimethylformamide) and PDI in the range of 1.7 to 2.3 (PDI = Mw / Mn; Mw = average weight of distribution of molar mass; Mn = numerical mean of molar mass distribution).
    [12]
    12. Polyimide membrane according to claim 11, characterized by the fact that it has an IDP in the range of 1.8 to 2.1.
    [13]
    13. Polyimide membrane according to claim 11 or 12, characterized in that the polyimide is a polyimide with the structure below:

    R is selected from the group consisting of:

    where x, y: molar fraction with 0 <x <0.5 and 1> y> 0.5.
    [14]
    14. Polyimide membrane according to one of claims 11 to 13, characterized in that they are membranes
    Petition 870190047727, of 05/22/2019, p. 11/16
    7/7 micro, ultra or nanofiltration, useful for separating dissolved or particulate homogeneous products from organic solvents or water, or because they are non-porous membranes useful for gas separation.
    [15]
    15. Polyimide membrane according to any one of claims 11 to 14, characterized in that the polyimide membranes are flat plate membranes, integrally asymmetric, on a support fleece, preferably a fleece of polyphenylene sulfide support, polyethylene terephthalate or polypropylene, or hollow fiber membranes, entirely asymmetric.
    [16]
    16. Polyimide membrane according to claim 15, characterized in that it is a hollow fiber polyimide membrane useful for separating a wide variety of gas mixtures, preferably for separating methane and carbon dioxide; and / or to separate oxygen and nitrogen; and / or to separate hydrogen from process gases; and / or to separate water vapor from gases or gas mixtures of various types.
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    同族专利:
    公开号 | 公开日
    KR101896721B1|2018-09-07|
    US20160310912A1|2016-10-27|
    MY160267A|2017-02-28|
    RU2566769C9|2016-07-10|
    CN102470329B|2015-06-24|
    CN102470329A|2012-05-23|
    CA2769033A1|2011-01-27|
    HK1169075A1|2013-01-18|
    WO2011009919A1|2011-01-27|
    RU2012106081A|2013-08-27|
    JP6125229B2|2017-05-10|
    JP2012533671A|2012-12-27|
    KR20120075454A|2012-07-06|
    EP2456546A1|2012-05-30|
    US20120123079A1|2012-05-17|
    CA2769033C|2019-09-03|
    JP2015193852A|2015-11-05|
    US10118136B2|2018-11-06|
    RU2566769C2|2015-10-27|
    BR112012001481A2|2016-03-15|
    EP2456546B1|2015-04-22|
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    法律状态:
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
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    申请号 | 申请日 | 专利标题
    AT11642009|2009-07-23|
    PCT/EP2010/060648|WO2011009919A1|2009-07-23|2010-07-22|Polyimide membranes made of polymerization solutions|
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