JP2014533750A - Polymer materials, their production and use - Google Patents

Abstract

The present invention comprises (A) (a) at least one polyisocyanate having an average of at least 2 isocyanate groups per molecule, and (b) at least one polycarboxylic acid having at least 3 COOH groups per molecule. It relates to a polymeric material obtainable by reaction of at least one polyimide selected from condensation products of acids or anhydrides with (B) at least one diol or triol.

Description

The present invention
(A) (a) at least one polyisocyanate having an average of at least two isocyanate groups per molecule, and (b) at least one polycarboxylic acid having at least three COOH groups per molecule or anhydrous At least one polyimide selected from product condensation products;
(B) relates to a polymeric material obtainable by reaction with at least one diol or triol.

  The invention further relates to the production of the polymer material according to the invention and its use for separating substances, for example in membrane separation processes, for example in ultrafiltration, nanofiltration, pervaporation, reverse osmosis, and gas separation, in particular as membranes. About use and.

  In the case of a membrane separation method, for example, in the case of ultrafiltration, in the case of nanofiltration, in the case of osmotic vaporization, in the case of reverse osmosis, and in the case of gas separation, membranes that are difficult to meet are usually used. Often inorganic or polymer membranes are used.

Inorganic membranes that can be mentioned are, for example, TiO ₂ and ZrO ₂ membranes in addition to zeolite membranes. However, inorganic membranes often have the drawback of exhibiting some brittleness and thus can be broken under mechanical loads.

  Hereinafter, a material for separating substances is taken to mean a material which causes the individual components to be separated or concentrated from a mixture of substances, for example by an adsorption / desorption process or via different permeation properties. Among the things that may be mentioned are membranes for stationary columns and stationary phases.

  In addition to the price of the material for separating the substances, factors such as selectivity, permeability, and mechanical stability, especially at high feed pressures, play a role. Furthermore, the material for separating substances in organic solvents should swell very little.

  Recently, it has often been suggested to use polymers as materials for separating substances. For example, certain polyimides bearing bis-trifluoromethyldiphenylidenemethane units have already been presented, see for example W.C. J. et al. Koros et al. Membr. Sci. 1988, 37, 45; Staudt-Bickel et al. Membr. Sci. See 1999, 155, 145 and the references cited therein. The polyimides described in the cited section can be used under certain conditions for separating olefin-alkane mixtures, but often severe swelling when separated under industrially interesting conditions. For example, adversely affecting the mechanical properties of the membrane. Furthermore, the presented material is laborious to produce and is therefore not preferred in terms of cost.

  US 2010/0038306 describes a membrane material for nanofiltration that can be obtained by reacting a polyimide with a diamine. However, the diamine remaining in the material is a material of concern and can only be removed by painstaking pathways.

US Patent Application Publication No. 2010/0038306

W. J. et al. Koros et al. Membr. Sci. 1988, 37, 45 C. Staudt-Bickel et al. Membr. Sci. 1999, 155, 145

  The aim is therefore to provide a material that is very suitable as a material for separating substances, has good mechanical properties, is not particularly brittle and does not further exhibit adverse swelling behavior.

Therefore, the first defined polymer material was found. The polymer material according to the invention is
(A) (a) abbreviated polyisocyanate (a), at least one polyisocyanate having an average of at least two isocyanate groups per molecule, and (b) abbreviated polycarboxylic acid (b) At least one polycarboxylic acid having at least three COOH groups per molecule, or at least one condensation product of its anhydride, referred to as anhydride (b) for short, also referred to as polyimide (A) Of polyimide,
(B) Thereafter, it can be obtained by reaction with at least one diol, also called diol (B).

The polyimide (A) is linear or branched,
(A) at least one polyisocyanate having an average of 3 or more isocyanate groups per molecule, and (b) at least one polycarboxylic acid having at least 3 COOH groups per molecule, or an anhydride thereof. Selected from condensation products.

The polyimide (A) can have a molecular weight _Mw in the range of 500 to 200000 g / mol, preferably at least 1000 g / mol.

  The polyimide (A) can have at least 2 imide groups per molecule, preferably at least 3 imide groups per molecule.

  In one embodiment of the invention, the polyimide (A) can have up to 1000 imide groups per molecule, preferably up to 660 per molecule.

  In one embodiment of the invention, the expression isocyanate groups or COOH groups per molecule in each case means an average value (number average).

The polyimide (A) can be composed of structurally and molecularly uniform molecules. However, the polyimide (A) is molecular, for example, with a polydispersity M _w / M _{n of} at least 1.4, preferably with a M _w / M _n of 1.4 to 50, preferably 1.5 to 10. And a mixture of structurally different molecules. The polydispersity can be determined by known methods, in particular by gel permeation chromatography (GPC). A suitable standard is, for example, polymethyl methacrylate (PMMA).

  In one embodiment of the present invention, the polyimide (A) has at least 3, preferably at least 6 and more preferably at least 10 branched chains as terminal or side chains in addition to the imide group forming the polymer main chain. It has terminal or side chain functional groups, also called. The functional groups of the polyimide (A) are preferably anhydride or acid groups and / or free or capped NCO groups. The polyimide (A) has preferably 500 or less, preferably 100 or less terminal or side chain functional groups.

  Therefore, for example, an alkyl group such as a methyl group is not a branched chain of the polyimide (A) molecule.

  The polyisocyanate (a) can be selected from any desired polyisocyanate having an average of at least two isocyanate groups per molecule, which can be present capped or preferably free. Preferred polyisocyanates (a) are diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, toluylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, and at least two of the aforementioned polyisocyanates (a). It is a mixture of A preferred mixture is a mixture of 4,4'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate, and a mixture of 2,4-toluylene diisocyanate and 2,6-toluylene diisocyanate.

  In another embodiment of the invention, the polyisocyanate (a) is oligomeric hexamethylene diisocyanate, oligomeric tetramethylene diisocyanate, oligomeric isophorone diisocyanate, oligomeric diphenylmethane diisocyanate, trimer toluylene diisocyanate, and at least two of the polyisocyanates (a) described above. Selected from a mixture of seeds. For example, what is referred to as trimer hexamethylene diisocyanate is often a polyisocyanate having an average functionality of 3.6 to 4 NCO groups per molecule, rather than pure trimed isocyanate. The same applies to oligomeric tetramethylene diisocyanate and oligomeric isophorone diisocyanate.

  In one embodiment of the invention, the polyisocyanate (a) is at least one diisocyanate and at least one triisocyanate or a mixture of polyisocyanates having at least 4 isocyanate groups per molecule.

  In one embodiment of the invention, the polyisocyanate (a) has an average of 2.0 isocyanate groups on average per molecule. In another embodiment of the invention, the polyisocyanate (a) has an average of at least 2.2, preferably at least 2.5, particularly preferably at least 3.0 isocyanate groups per molecule.

  In one embodiment of the invention, the polyisocyanate (a) has an average of up to 8, preferably up to 6, isocyanate groups per molecule.

  In one embodiment of the invention, the polyisocyanate (a) is selected from oligomeric hexamethylene diisocyanate, oligomeric isophorone diisocyanate, oligomeric diphenylmethane diisocyanate, and mixtures of the aforementioned polyisocyanates.

  In addition to the urethane group, the polyisocyanate (a) has one or more other functional groups such as urea, allophanate, biuret, carbodiimide, amide, ester, ether, uretonimine, uretdione, isocyanurate, or oxazolidine group You can also.

  When the polycarboxylic acid (b) is preferably in the low molecular weight form, i.e. in the non-polymeric form, it is an aliphatic or preferably aromatic polycarboxylic acid having at least 3 COOH groups per molecule or its Each anhydride is selected. Also included are those polycarboxylic acids having three COOH groups in which two carboxylic acid groups are present as anhydrides and the third is present as a free carboxylic acid.

  In a preferred embodiment of the invention, as polycarboxylic acid (b), a polycarboxylic acid having at least 4 COOH groups per molecule, or its respective anhydride, is selected.

  Examples of polycarboxylic acid (b) and its anhydride are 1,2,3-benzenetricarboxylic acid and 1,2,3-benzenetricarboxylic acid anhydride, 1,3,5-benzenetricarboxylic acid (trimesic acid), Preferably 1,2,4-benzenetricarboxylic acid (trimellitic acid), trimellitic anhydride, especially 1,2,4,5-benzenetetracarboxylic acid (pyromellitic acid) and 1,2,4,5- Benzenetetracarboxylic dianhydride (pyromellitic dianhydride), 3,3 ′, 4,4′-benzophenone tetracarboxylic acid, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, and Benzenehexacarboxylic acid (mellitic acid) and anhydride of merit acid.

  Other suitable polycarboxylic acids and anhydrides are melophanoic acid and melophanoic acid anhydride, 1,2,3,4-benzenetetracarboxylic acid and 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3,4,4-biphenyltetracarboxylic acid and 3,3,4,4-biphenyltetracarboxylic dianhydride, 2,2,3,3-biphenyltetracarboxylic acid and 2,2,3,3- Biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid and 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic acid and 1,2,4,5-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid and 2,3,6,7-naphthalenetetracar Acid dianhydride, 1,4,5,8-decahydronaphthalene tetracarboxylic acid and 1,4,5,8-decahydronaphthalene tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3 , 5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic acid and 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5 , 6-tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic acid and 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic acid and 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7- Tetrachloronaphthalene-1,4 5,8-tetracarboxylic acid and 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 1,3,9,10-phenanthrenetetracarboxylic acid and 1, 3,9,10-phenanthrenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic acid and 3,4,9,10-perylenetetracarboxylic dianhydride, bis (2,3-di Carboxyphenyl) methane and bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane and bis (3,4-dicarboxyphenyl) methane dianhydride, 1,1 -Bis (2,3-dicarboxyphenyl) ethane and 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dica Ruboxyphenyl) ethane and 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane and 2,2-bis (2,3 -Dicarboxyphenyl) propane dianhydride, 2,3-bis (3,4-dicarboxyphenyl) propane and 2,3-bis (3,4-dicarboxyphenyl) propane dianhydride, bis (3,4 -Carboxyphenyl) sulfone and bis (3,4-carboxyphenyl) sulfone dianhydride, bis (3,4-carboxyphenyl) ether and bis (3,4-carboxyphenyl) ether dianhydride, ethylenetetracarboxylic acid and Ethylenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic acid and 1,2,3,4-butanetetra Rubonic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid and 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,4,5-pyrrolidinetetracarboxylic acid and 2,3,4,5-pyrrolidinetetracarboxylic dianhydride, 2,3,5,6-pyrazinetetracarboxylic acid and 2,3,5,6-pyrazinetetracarboxylic dianhydride, 2,3,4 , 5-thiophenetetracarboxylic acid and 2,3,4,5-thiophenetetracarboxylic dianhydride.

  In one embodiment of the invention, an anhydride from US Pat. No. 2,155,687 or US Pat. No. 3,277,117 is used for the synthesis of polyimide (A).

When polyisocyanate (a) and polycarboxylic acid (b) are condensed together—preferably in the presence of a catalyst—imido groups are formed by eliminating CO ₂ and H ₂ O. When the corresponding anhydride is used instead of polycarboxylic acid (b), the imide group is formed by eliminating CO ₂ .

In this case, R ^* is a radical of polyisocyanate (a) not further specified in the above reaction formula, n is a number of 1 or more, for example, 1 in the case of tricarboxylic acid, and in the case of tetracarboxylic acid In which (HOOC) _n is one that can be replaced by an anhydride group of the formula C (═O) —O—C (═O).

  In one embodiment of the invention, the polyisocyanate (a) is used in a mixture with at least one diisocyanate, such as toluylene diisocyanate, hexamethylene diisocyanate, or isophorone diisocyanate. In a particular variant, the polyisocyanate (a) is mixed in a mixture with the corresponding diisocyanate, for example trimer HDI with hexamethylene diisocyanate, or trimer isophorone diisocyanate with isophorone diisocyanate, or polymer diphenylmethane diisocyanate with diphenylmethane diisocyanate (polymer). MDI).

  In one embodiment of the invention, the polycarboxylic acid (b) is used in a mixture with at least one dicarboxylic acid or at least one dicarboxylic anhydride, such as phthalic acid or phthalic anhydride.

  The diol (B) or triol (B) can be low molecular weight or high molecular weight. Examples of triols (B) are glycerol and 1,1,1- (trihydroxymethylene) methane, 1,1,1- (trihydroxymethylene) ethane, and 1,1,1- (trihydroxymethylene) propane It is.

  Diol (B) is preferred.

  As low molecular weight diols (B) in the context of the present invention, those having a molecular weight of up to 500 g / mol which can be mentioned by way of example are: 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,4-but-2-enediol, 1,4-but-2-ynediol, 1,5-pentanediol , And their positional isomers, 1,6-hexanediol, 1,8-octanediol, 1,4-bishydroxymethylcyclohexane, 2,2-bis- (4-hydroxycyclohexyl) propane, 2-methyl-1 , 3-propanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, especially 2,2-dimethyl Propane-1,3-diols (neopentyl glycol).

  Examples of the polymer diol include divalent or polyvalent polyester polyol and polyether polyol, and divalent is preferable. As polyether polyols, preferably polyether diols are considered, which are, for example, ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide, or epichlorohydrin per se or with each other by a boron trifluoride catalyst. By combining or individually or as a mixture of these compounds, starting components having reactive hydrogen atoms, such as water, polyhydric alcohols or amines, such as 1,2-ethanediol, propane- (1,3) It can be obtained by addition to diol, 1,2- or 2,2-bis- (4-hydroxyphenyl) propane or aniline. Furthermore, polyether-1,3-diols, such as trimethylolpropane alkoxylated with OH groups, the alkylene oxide chain of which is closed with an alkyl radical containing 1 to 18 carbon atoms, It is a polymer diol preferably used.

  Preferred polymer diols are: polyethylene glycol, polypropylene glycol, especially polytetrahydrofuran (poly-THF).

Particularly preferably, the polyether polyol is: polyethylene glycol having an average molecular weight (M _n ) in the range from 200 to 9000 g / mol, preferably in the range from 500 to 6000 g / mol, from 250 to 6000, preferably from 600 to 4000 g / mol. Poly-1,2-propylene glycol or poly-1,3-propanediol having an average molecular weight (M _n ) in the range, from more than 250 to 5000 g / mol, preferably from 500 to 3000 g / mol, particularly preferably from 750 Selected from poly-THF having an average molecular weight ( _Mn ) in the range of 2500 g / mol.

  Other preferred polymer diols are polyester polyols (polyester diols) and polycarbonate diols.

  As polycarbonate diols, mention may be made in particular of aliphatic polycarbonate diols, for example 1,4-butanediol polycarbonate and 1,6-hexanediol polycarbonate.

  As polyester diols, mention may be made on the one hand of at least one primary diol, preferably at least one primary aliphatic diol, such as ethylene glycol, 1,4-butanediol, 1,6. Hexanediol, neopentyl glycol, or particularly preferably 1,4-dihydroxymethylcyclohexane (as a mixture of isomers), or a mixture of at least two of the aforementioned diols, on the other hand at least one, preferably at least two Can be produced by polycondensation of the dicarboxylic acid or its anhydride. Preferred dicarboxylic acids are aliphatic dicarboxylic acids such as adipic acid, glutaric acid, succinic acid and aromatic dicarboxylic acids such as phthalic acid, especially isophthalic acid.

In one embodiment of the invention, the polyester diol and polycarbonate diol are selected from those having an average molecular weight ( _Mn ) in the range of 500 to 9000 g / mol, preferably in the range of 500 to 6000 g / mol.

A particularly highly preferred diol (B) is, for example, polytetrahydrofuran having an average molecular weight M _n in the range of 250 to 2000 g / mol.

  In one embodiment of the invention, the polymeric material according to the invention has an acid number ranging from zero to 300 mg KOH / g, preferably from zero to 200 mg KOH / g, determined as specified in DIN 53402.

  In one embodiment of the invention, the polymeric material according to the invention has a hydroxyl number in the range of zero to 300 mg KOH / g, preferably zero to 200 mg KOH / g, determined as specified in DIN 53240-2. .

In one embodiment of the invention, the polymeric material according to the invention has a quotient M _w / M _n in the range of 1.2 to 10, preferably 1.5 to 5, particularly preferably 1.8 to 4. In this case, M _w and M _n are preferably determined by gel permeation chromatography.

  The present invention further provides a material for separating substances or for producing this material, for example as a chromatographic stationary phase or for producing this stationary phase, preferably as a membrane or for producing this membrane. To the use of the polymeric material according to the invention. The invention further relates to a method for producing a material for separating substances, in particular for producing a chromatographic stationary phase or membrane, using at least one material according to the invention. The invention further relates to materials for separating substances, for example chromatographic stationary phases, in particular membranes, produced using at least one polymeric material according to the invention.

  The membrane according to the invention can have an average thickness in the range of 0.01 to 100 μm, preferably 1 to 50 μm, particularly preferably 1 to 20 μm.

  The membrane according to the invention can be configured as a hollow fiber membrane or a flat membrane. A specific example of a flat membrane is a coiled membrane.

  The membrane according to the invention is a membrane separation method, in particular nanofiltration, gas separation, pervaporation, reverse osmosis, microfiltration, and ultrafiltration, in particular nanofiltration and ultrafiltration, in which the substance is dissolved in an organic solvent. Suitable for things.

  In this case, nanofiltration in the context of the present invention has a separation limit (fractionated molecular weight, MWCO) of 100 to 1500 g / mol when the membrane used is a non-porous membrane-a variant of a porous membrane Is interpreted to mean a membrane separation method with a maximum pore size of 1 nm. When using nanofiltration, for example, substances with an average molecular weight of less than 0.1 kg / mol or less than 1.5 kg / mol, ie less than 100 g / mol or less than 1500 g / mol may be separated.

  Ultrafiltration is understood in the context of the present invention to mean a membrane separation method in which the membrane has a fractional molecular weight in the range of 1500 to 1000000 g / mol or separates particles in the maximum diameter range of 10 to 500 nm. Is done.

  Microfiltration is taken in the context of the present invention to mean a membrane separation method in which the membrane has a molecular weight cut-off greater than 1000000 g / mol or the pore size is from 1 μm to 10 μm.

  In order to produce a membrane from the polymer material according to the invention, the procedure is for example to crosslink the polymer material according to the invention, more precisely on a solid surface, with a strictly calculated amount of a crosslinking agent, such as a diisocyanate or polyisocyanate. To continue. As the polyisocyanate, those listed for the polyisocyanate (a) can be selected. The amount of crosslinking agent can be calculated, for example, on the one hand based on the OH number or acid number of the polymer material according to the invention and on the other hand based on the number of functional groups of the crosslinking agent, for example the number of NCO groups.

  In another embodiment of the invention, the membrane according to the invention is a smooth surface in the form of a film comprising a solution comprising at least one organic solvent, at least one cross-linking agent, and at least one polymer material according to the invention. For example, by attaching to a plastic plate or glass plate. Thereafter, the one or more solvents are vaporized and the plate is heat treated, for example in the range of 20 to 400 ° C., preferably 40 to 200 ° C., particularly preferably 50 to 150 ° C. In this method, the cross-linking reaction occurs in situ. The desired cross-linking can be accelerated by adding a catalyst. Finally, the membrane according to the invention can be easily removed from the article having a smooth surface after heat treatment.

  In one embodiment of the invention, the membrane according to the invention is joined to another layer, preferably a silicone layer, for example by laminating.

  In another embodiment, the membrane according to the invention can be spun as a hollow fiber membrane. Such a membrane according to the invention is particularly suitable for gas separation, but is also suitable as a protective layer.

  The membrane according to the invention can be configured as a completely asymmetric membrane or a composite membrane, with one kind of actual separation layer performing a separation having a thickness of 0.01 to 100 μm, preferably 0.1 to 20 μm. Or attached to one or more mesoporous and / or macroporous supports comprising a plurality of organic materials, in particular polymeric materials, and / or inorganic materials such as ceramics, carbon, metals.

  The membranes according to the invention can be used in the form of flat, cushion, capillary, hollow fiber, monochannel tubular or multichannel tubular elements. Geometries are known per se to those skilled in the art from other membrane separation methods such as ultrafiltration or reverse osmosis (eg R. Rautenbach, “Membranverfahren, Grandella der Modul-und Analogueslegung” [Membrande Ms. of Module and System Design], 1997, Springer Verlag). In the case of membrane elements having a tubular geometry, the separation layer can be placed inside or outside the tube.

  In another embodiment of the invention, the membrane according to the invention is surrounded by one or more housings made of a polymer, metal or ceramic material, and the connection between the housing and the membrane is a sealing polymer ( For example, an elastomer) or an inorganic material.

  The invention further relates to a method for separating a mixture of substances, for example using a polymeric material according to the invention in the form of a membrane according to the invention for chromatography or a stationary phase according to the invention. The method according to the invention for separating a mixture of substances using the material according to the invention for separating substances is hereinafter also referred to as separation method according to the invention.

A material according to the invention for separating substances, for example a membrane according to the invention or a chromatography column according to the invention, is suitable, for example, for separating the following separation tasks, ie the following mixtures of substances:
Polyalkylene glycols of various molecular weights such as polyethylene glycol / polypropylene glycol block copolymer 6500 g / mol-polyethylene glycol 400 g / mol
Separation of homogeneous or heterogeneous catalysts from organic solvents Monomer / dimer separation Decolorization of organic solutions Desalting

  Membranes according to the present invention are often not permeable to water, even after adjustment with THF. In contrast, the membrane according to the invention shows good permeability to organic solvents such as acetone, toluene, isopropanol and ethanol.

  The membrane according to the invention is flexible and easy to cut. In many cases, the membrane according to the invention is thermally stable, for example up to a temperature of 200 ° C.

The invention further relates to a method for producing a polymer material according to the invention, which is also abbreviated as the production method according to the invention. To carry out the production method according to the invention,
(A) (a) at least one polyisocyanate having an average of at least two isocyanate groups per molecule, and (b) at least one polycarboxylic acid having at least three COOH groups per molecule or anhydrous Polyimide that can be obtained by condensation of materials,
(B) A procedure can be followed such that it is reacted with at least one diol.

Preferably, the polyimide (A) has a polydispersity of M _w / M _n of at least 1.4.

  The polyimide (A), polyisocyanate (a), polycarboxylic acid (b), anhydride (b), and diol (B) have already been described.

  The production method according to the invention is a two-step method. In this case, after the polyimide (A) is produced, it can be isolated and purified. In another variant, the production method according to the invention is carried out as a one-pot method and the purification and isolation of the polyimide (A) is omitted.

  To carry out the synthesis process according to the invention, the polyisocyanate (a) and the polycarboxylic acid (b) or anhydride (b) have a molar fraction of NCO groups to COOH groups ranging from 1: 3 to 3: 1. The ratio is 1: 2 to 2: 1. In this case, one anhydride group of the formula CO—O—CO is counted as two COOH groups.

  In one embodiment of the invention, the polyimide (A) and diol (B) have a molar ratio of (hydroxyl groups from diol (B)) to (total of NCO groups and COOH groups) of 1:10 to 10: 1. , Preferably 1: 6 to 6: 1, particularly preferably 1: 4 to 4: 1.

  In one embodiment of the invention, the catalyst is 0.005 to 0.1 relative to the sum of polyisocyanate (a) and polycarboxylic acid (b), or the sum of polyisocyanate (a) and anhydride (b). It can be used in the mass% range. A catalyst of 0.01 to 0.05% by weight is preferred.

  In one embodiment of the invention, the synthesis method according to the invention can be carried out at a temperature in the range of 50 to 140 ° C; 50 to 100 ° C is preferred.

  In one embodiment of the invention, the production method according to the invention can be carried out at atmospheric pressure. However, synthesis under pressure, for example at a pressure in the range of 1.1 to 10 bar, is also possible.

  In one embodiment of the invention, the synthesis method according to the invention can be carried out in the presence of a solvent or solvent mixture. Examples of suitable solvents are N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, dimethylsulfone, xylene, phenol, cresol, ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK). ), Acetophenone, mono- and dichlorobenzene, ethylene glycol monoethyl ether acetate, and mixtures of two or more of the above-mentioned solvents. In this method, one or more solvents can be present during the entire synthesis period or only during a partial period of the synthesis.

  For example, the reaction can be carried out for 10 minutes to 24 hours.

  In a variant of the synthesis method according to the invention, the NCO end group of the polyimide (A) can be blocked with a secondary amine, for example with dimethylamine, di-n-butylamine or with diethylamine.

  In one embodiment of the invention, the production process according to the invention is carried out without the addition of a catalyst.

  In another embodiment of the invention, the production process according to the invention is carried out using a catalyst, for example by adding at least one catalyst which is common in polyurethane chemistry.

  Suitable catalysts are in particular water and Bronsted bases, such as alkali metal alcoholates, in particular sodium or potassium alkanolates, such as sodium methanolate, sodium ethanolate, sodium phenolate, potassium methanolate, potassium ethanolate, potassium. Phenolate, lithium methanolate, lithium ethanolate, and lithium phenolate.

  Further suitable catalysts are tertiary amines, amidines and / or organometallic compounds.

Examples are 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, tertiary amines such as triethylamine, tributylamine, dimethylbenzylamine, N-methyl-, N-ethyl-, N-cyclohexylmorpholine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylbutanediamine, N, N, N ′, N′-tetramethylhexanediamine, pentamethyldiethylenetriamine, tetramethyl Diaminoethyl ether, bis (dimethylaminopropyl) urea, dimethylpiperazine, 1,2-dimethylimidazole, 1-azabicyclo- (3,3,0) -octane, preferably 1,4-diazabicyclo- (2,2,2 ) -Octane, and alkanolamine compounds such as triethanolamine, tri Isopropanol amine, N- methyl - a and N- ethyl diethanolamine and dimethylethanolamine. Similarly, metal compounds are considered as catalysts, preferably tin compounds, such as tin (II) salts of organic carboxylic acids such as tin (II) acetate, tin (II) octoate, tin (II) ethylhexanoate, and tin laurate (II), preferably organic tin compounds, particularly preferably dialkyl tin (IV) salts of organic carboxylic acids, especially di _-n-C 1 _{~C 10} - alkyl tin alkanoate, such as di -n- Buchirusuzuji Acetate, di-n-butyltin dilaurate, di-n-butyltin maleate, and di-n-octyltin diacetate, plus bismuth carboxylates such as bismuth (III) neodecanoate, bismuth 2-ethylhexanoate, and octanoic acid Bismuth or a mixture thereof. The metal compound or organometallic compound can be used alone or in combination with a basic amine.

  As another preferred catalyst, di-n-butyltin mercaptide is used or di-n-butyltin dioctanoate.

  In a preferred embodiment of the invention, the synthesis method according to the invention is carried out in an inert gas, for example in argon or nitrogen.

  When a water sensitive Bronsted base is used as the catalyst, it is preferred to dry the inert gas and solvent. When water is used as the catalyst, drying of the solvent and inert gas can be omitted.

  The production process according to the invention—optionally after work-up, for example after removing the solvent—produces the polymer material according to the invention.

  The invention is illustrated by the examples.

General notes:
Polyisocyanate (a.1): 4,4′-diphenylmethane diisocyanate Anhydride (b.1): 1,2,4,5-benzenetetracarboxylic dianhydride Molecular weight was determined by gel permeation chromatography (GPC). . The standard used was polystyrene (PS). The solvent used was tetrahydrofuran (THF) unless otherwise stated. Detection was performed using an Agilent 1100 differential refractometer or an Agilent 1100 VWD UV photometer.

  The NCO content was determined by titration as specified in DIN EN ISO 11 909 and reported as units by weight.

  The synthesis was performed in nitrogen unless otherwise indicated.

Synthesis example:
I. Production of polymeric materials according to the invention 1 Synthesis of Polymer Material (PM.1) According to the Invention Anhydride (b.1) was placed in a 4 liter four-necked flask with a dropping funnel, reflux condenser, internal thermometer, and Teflon stirrer. ) 100 g (0.46 mol) was added and dissolved in 1400 ml of acetone which was not dried before the reaction and thus contained water. Subsequently, 173 g (0.69 mol) of polyisocyanate (a.1) was added dropwise at 20 ° C. The mixture was heated to 55 ° C. with stirring. The mixture was stirred for an additional 6 hours under reflux at 55 ° C. Thereafter, 600 g of poly-THF having an average molecular weight M _n of 1000 g / mol (0.6 mol) was added. The temperature was raised to 60 ° C. and acetone was distilled off at atmospheric pressure over 4 hours. The mixture was then heated to 125 ° C. and the pressure was reduced to 200 mbar. The residue was then stripped with nitrogen in the flask. This produced the polymer material (PM.1) according to the invention as a solid yellow mass.

M _n = 8360 g / mol, M _w = 21000 g / mol
M _w / M _n = 2.5
OH value: 22 mg KOH / g
Acid value: 88mg KOH / g

I. 2 Synthesis of Polymer Material (PM.2) According to the Invention Anhydride (b.1) was placed in a 4 liter four-necked flask with a dropping funnel, reflux condenser, internal thermometer, and Teflon stirrer. ) 100 g (0.46 mol) was added and dissolved in 1400 ml of acetone which was not dried before the reaction and thus contained water. Subsequently, 115 g (0.46 mol) of polyisocyanate (a.1) was added dropwise at 20 ° C. The mixture was heated to 55 ° C. with stirring. The mixture was stirred for an additional 6 hours under reflux at 55 ° C. Thereafter, 1000 g of poly-THF having an average molecular weight M _n of 1000 g / mol (1.0 mol) was added, and the mixture was stirred at 55 ° C. for 14 hours under reflux. The temperature was raised to 60 ° C. and acetone was distilled off at atmospheric pressure over 4 hours. The mixture was then heated to 125 ° C. and the pressure was reduced to 200 mbar. The residue was then stripped in the flask using nitrogen. This produced the polymer material (PM.2) according to the invention as a solid yellow mass.

M _n = 7250 g / mol, M _w = 16900 g / mol
M _w / M _n = 2.3
OH value: 26 mg KOH / g
Acid value: 40 mg KOH / g

I. 3 Synthesis of Polymer Material (PM.3) According to the Invention Anhydride (b.1) was placed in a 4 liter four-necked flask with a dropping funnel, reflux condenser, internal thermometer, and Teflon stirrer. ) 100 g (0.46 mol) was added and dissolved in 1400 ml of acetone which was not dried before the reaction and thus contained water. Subsequently, 115 g (0.69 mol) of polyisocyanate (a.1) was added dropwise at 20 ° C. The mixture was heated to 55 ° C. with stirring. The mixture was stirred for an additional 6 hours under reflux at 55 ° C. Thereafter, 300 g of poly-THF having an average molecular weight _Mn of 1000 g / mol (0.3 mol) was added. The mixture was stirred for an additional 6 hours under reflux at 55 ° C., after which the temperature was raised to 60 ° C. and acetone was distilled off at atmospheric pressure over 4 hours. The mixture was then heated to 125 ° C. and the pressure was reduced to 200 mbar. The residue was then stripped in the flask using nitrogen. This produced the polymer material (PM.3) according to the invention as a solid yellow mass.

M _n = 3670 g / mol, M _w = 11900 g / mol
M _w / M _n = 3.2
OH value: 37 mg KOH / g
Acid value: 144mg KOH / g

I. 4 Synthesis of Polymer Material (PM.4) According to the Invention Anhydride (b.1) was placed in a 4 liter four-necked flask with a dropping funnel, reflux condenser, internal thermometer, and Teflon stirrer. ) 100 g (0.46 mol) was added and dissolved in 1400 ml of acetone which was not dried before the reaction and thus contained water. Subsequently, 173 g (0.69 mol) of polyisocyanate (a.1) was added dropwise at 20 ° C. The mixture was heated to 55 ° C. with stirring. The mixture was stirred for an additional 5 hours under reflux at 55 ° C. Thereafter, 390 g of poly-THF having an average molecular weight M _n of 650 g / mol (0.6 mol) was added. The temperature was raised to 60 ° C. and acetone was distilled off at atmospheric pressure over 7 hours. The mixture was then heated to 80 ° C. and the pressure was reduced to 200 mbar. The residue was then stripped in the flask using nitrogen. This produced the polymer material (PM.4) according to the invention as a solid yellow mass.

M _n = 5900 g / mol, M _w = 14000 g / mol
M _w / M _n = 2.4
OH value: 14 mg KOH / g
Acid value: 107mg KOH / g

I. 5 Synthesis of Polymeric Material (PM.5) According to the Invention Anhydride (b.1) was placed in a 4 liter four-necked flask with a dropping funnel, reflux condenser, internal thermometer, and Teflon stirrer. ) 100 g (0.46 mol) was added and dissolved in 1400 ml of acetone which was not dried before the reaction and thus contained water. Subsequently, 173 g (0.69 mol) of polyisocyanate (a.1) was added dropwise at 20 ° C. The mixture was heated to 55 ° C. with stirring. The mixture was stirred for an additional 5 hours under reflux at 55 ° C. Thereafter, 173 g of poly-THF having an average molecular weight M _n of 250 g / mol (0.6 mol) was added. The temperature was raised to 60 ° C. and acetone was distilled off at atmospheric pressure over 7 hours. The mixture was then heated to 80 ° C. and the pressure was reduced to 200 mbar. The residue was then stripped in the flask using nitrogen. This produced the polymeric material (PM.5) according to the invention as a solid yellow mass.

M _n = 4360 g / mol, M _w = 8370 g / mol
M _w / M _n = 1.9
OH value: 12 mg KOH / g
Acid value: 151 mg KOH / g

II. Production of membranes according to the invention from (PM.1) or (PM.3), general method In a glass beaker, as shown in Table 1, the polymer material according to the invention is weighed and using 1,3-dioxolane as solvent Added. The mixture was stirred for 30 minutes using a magnetic stirrer, which produced a clear solution. The crosslinker (CL.1) according to Table 1 was then added and the mixture was stirred for a further 5 minutes.

  A membrane was then produced using a laboratory spreader. For this purpose, a spreader bench (Erichsen, Coatmaster 509 MC-1) was adjusted to 80 ° C. and the above solution was poured onto a glass plate with an undried film thickness of 100 μm. A film having an undried film thickness of 100 μm was then obtained from the solution on the glass plate. The undried film was dried in air for 15 minutes and then placed in a room temperature water bath for 24 hours. The product was then dried in a vacuum drying cabinet at 80 ° C. for 24 hours. This produced a membrane according to the invention.

  Crosslinker used: (CL.1): Polymer with 2.7 functionality, NCO, polymer 4,4'-diphenylmethane diisocyanate: 31.5%

Membrane MEMB. 1 and MEMB. The MWCO of 3 is determined by determining the retention of a 10 wt% solution of polyethylene glycol (M _w 400 g / mol) and polyethylene glycol / polypropylene glycol block copolymer (with M _w = 6500 g / mol) in THF. In this case, it was about 6.5 kg / mol.

Claims (17)

(A) (a) at least one polyisocyanate having an average of at least two isocyanate groups per molecule, and (b) at least one polycarboxylic acid having at least three COOH groups per molecule or anhydrous At least one polyimide selected from product condensation products;
(B) A polymeric material obtainable by reaction with at least one diol or triol. The polymer material according to claim 1, wherein the polyimide (A) is selected from polyimides having a molecular weight _Mw of at least 1000 g / mol.   Polymer material according to claim 1 or 2, wherein as the polycarboxylic acid (b) a polycarboxylic acid having at least 4 COOH groups per molecule or the respective anhydride is selected.   The polyisocyanate (a) is at least two of hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, toluylene diisocyanate, and the above-mentioned polyisocyanate (a). 4. The polymeric material according to any one of claims 1 to 3, selected from a mixture of:   The polyisocyanate (a) is selected from oligomeric hexamethylene diisocyanate, oligomeric tetramethylene diisocyanate, oligomeric isophorone diisocyanate, oligomeric diphenylmethane diisocyanate, trimer tolylene diisocyanate, and a mixture of at least two of the aforementioned polyisocyanates (a). Item 4. The polymer material according to any one of Items 1 to 3. 6. Polymeric material according to any one of claims 1 to 5, wherein the diol (B) is selected from diols having a molecular weight _Mw in the range of 250 to 5000 g / mol.   The polymer material according to any one of claims 1 to 6, wherein the diol (B) is selected from polyethylene glycol, polypropylene glycol, polyester diol, polycarbonate diol, and polytetrahydrofuran.   The polymeric material according to any one of the preceding claims, having an acid number in the range of zero to 300 mg KOH / g.   9. A polymeric material according to any one of the preceding claims having a hydroxyl number in the range of zero to 300 mg KOH / g.   Use of the polymeric material according to any one of claims 1 to 9 as a membrane or for the production of a membrane.   10. A method for producing a membrane using at least one polymeric material according to any one of claims 1-9.   10. A membrane containing or produced using at least one polymer material according to any one of claims 1-9.   Use of a membrane according to claim 12 in a membrane separation method.   Use of the polymeric material according to any one of claims 1 to 9 as a stationary phase for chromatography. (A) (a) at least one polyisocyanate having an average of at least two isocyanate groups per molecule, and (b) at least one polycarboxylic acid having at least three COOH groups per molecule or anhydrous Polyimide obtainable by condensation of the product,
10. A method for producing a polymeric material according to any one of claims 1 to 9, comprising reaction with (B) at least one diol or triol.   The process according to claim 15, wherein the polyimide (A) is reacted with the diol (B) using a catalyst. Wherein said catalyst is di _-n-C 1 _{~C 10} - is selected from alkyltin alkanoates The method of claim 16.