EP2780393A1 - Polymeres material, seine herstellung und verwendung - Google Patents

Polymeres material, seine herstellung und verwendung

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Publication number
EP2780393A1
EP2780393A1 EP12783983.5A EP12783983A EP2780393A1 EP 2780393 A1 EP2780393 A1 EP 2780393A1 EP 12783983 A EP12783983 A EP 12783983A EP 2780393 A1 EP2780393 A1 EP 2780393A1
Authority
EP
European Patent Office
Prior art keywords
polymeric material
material according
diisocyanate
mol
polyisocyanate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP12783983.5A
Other languages
German (de)
English (en)
French (fr)
Inventor
Anna MÜLLER-CRISTADORO
Helmut MÖHWALD
Jelan KUHN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP12783983.5A priority Critical patent/EP2780393A1/de
Publication of EP2780393A1 publication Critical patent/EP2780393A1/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1035—Preparatory processes from tetracarboxylic acids or derivatives and diisocyanates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
    • B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/343—Polycarboxylic acids having at least three carboxylic acid groups
    • C08G18/346—Polycarboxylic acids having at least three carboxylic acid groups having four carboxylic acid groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography

Definitions

  • the present invention relates to a polymeric material obtainable by reacting
  • (B) at least one diol or triol.
  • the present invention relates to the preparation of polymeric materials according to the invention and their use for substance separation, in particular as membranes, for example in membrane separation processes, for example ultrafiltration, nanofiltration, pervaporation, reverse osmosis and gas separation.
  • membrane separation processes for example for ultrafiltration, for nanofiltration, for pervaporation, for reverse osmosis and for gas separation, it is customary to use membranes to which demanding requirements are made. In many cases one uses inorganic membranes or polymeric membranes.
  • inorganic membranes examples include ⁇ 2 and ZrO2 membranes, and zeolite membranes. Inorganic membranes, however, often have the disadvantage that they have a certain brittleness and therefore can break under mechanical stress.
  • material separation materials are understood as meaning materials which, for example by adsorption-desorption processes or by different permeability properties, permit the separation or enrichment of individual components from mixtures of substances. Examples include membranes and stationary phases for chromatography columns.
  • materials such as selectivity, permeability and mechanical stability, in particular at high feed pressure, play a particular role for material separation materials.
  • materials for material separation in organic solvents should swell only slightly.
  • US 2010/0038306 describes membrane materials for nanofiltration, which can be obtained by reacting polyimides with diamines. However, diamines remaining in the material are questionable and can only be removed in a complicated way.
  • polyimide (A) at least one polyimide, also called polyimide (A), selected from condensation products of
  • polycarboxylic acid (b) at least one polycarboxylic acid having at least 3 COOH groups per molecule, called polycarboxylic acid (b) for short, or its anhydride, abbreviated to anhydride (b), and
  • diol at least one diol, hereinafter also called diol (B).
  • Polyimide (A) which is linear or branched and is selected from condensation products of
  • Polyimide (A) may have a molecular weight M w in the range of 500 to 200,000 g / mol, preferably at least 1, 000 g / mol. Polyimide (A) may have at least two imide groups per molecule, preferably at least 3 imide groups per molecule.
  • polyimide (A) may have up to 1,000 imide groups per molecule, preferably up to 660 per molecule.
  • polyimide (A) may be composed of structurally and molecularly uniform molecules. However, when polyimide (A) is a mixture of molecularly and structurally different molecules, for example, visible on the polydispersity M w / M n of at least 1.4, preferably M w / M n of 1.4 to 50, preferably 1, 5 to 10.
  • the polydispersity can be determined by known methods, in particular by gel permeation chromatography (GPC). Suitable standard is, for example, polymethyl methacrylate (PMMA).
  • polyimide (A) in addition to imide groups which form the polymer backbone, polyimide (A) furthermore has at least three, preferably at least six, more preferably at least ten terminal or pendant functional groups, also called branching.
  • Functional groups in polyimide (A) are preferably anhydride or acid groups and / or free or capped NCO groups.
  • Polyimides (A) preferably have not more than 500 terminal or pendant functional groups, preferably not more than 100.
  • alkyl groups such as methyl groups are not a branch of a molecule polyimide (A).
  • Polyisocyanate (a) can be selected from any polyisocyanates which have on average at least two isocyanate groups per molecule, which may be capped or preferably free.
  • Preferred polyisocyanates (a) are diisocyanates, for example hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, and mixtures of at least two of the aforementioned polyisocyanates (a).
  • Preferred mixtures are mixtures of 4,4'-
  • polyisocyanate (a) is selected from oligomeric hexamethylene diisocyanate, oligomeric tetramethylene diisocyanate, oligomeric isophorone diisocyanate, oligomeric diphenylmethane diisocyanate, trimeric tolylene diisocyanate and mixtures of at least two of the aforementioned polyisocyanates (a).
  • so-called trimeric hexamethylene diisocyanate is in many cases not present as pure trimeric diisocyanate, but as polyisocyanate having an average functionality of 3.6 to 4 NCO groups per molecule.
  • oligomeric tetramethylene diisocyanate and oligomeric isophorone diisocyanate are examples of the same.
  • polyisocyanate (a) is a mixture of at least one diisocyanate and at least one triisocyanate or a polyisocyanate having at least 4 isocyanate groups per molecule. In one embodiment of the present invention, polyisocyanate (a) has on average exactly 2.0 isocyanate groups per molecule. In another embodiment of the present invention, polyisocyanate (a) has on average at least 2.2, preferably at least 2.5, more preferably at least 3.0 isocyanate groups per molecule.
  • polyisocyanate (a) has on average up to 8, preferably up to 6 isocyanate groups per molecule.
  • polyisocyanate (a) is selected from oligomeric hexamethylene diisocyanate, oligomeric isophorone diisocyanate, oligomeric diphenylmethane diisocyanate and mixtures of the abovementioned polyisocyanates.
  • Polyisocyanate (a) may, in addition to urethane groups, also have one or more other functional groups, for example urea, allophanate, biuret, carbodiimide, amide, ester, ether, uretonimine, uretdione, isocyanurate or oxazolidine groups.
  • urethane groups also have one or more other functional groups, for example urea, allophanate, biuret, carbodiimide, amide, ester, ether, uretonimine, uretdione, isocyanurate or oxazolidine groups.
  • polycarboxylic acids (b) aliphatic or preferably aromatic polycarboxylic acids are selected which have at least three COOH groups per molecule, or the respective anhydrides, preferably if they are present in low molecular weight, ie non-polymeric form. Such polycarboxylic acids having three COOH groups are also included, in which two carboxylic acid groups are present as the anhydride and the third as the free carboxylic acid.
  • the polycarboxylic acid (b) used is a polycarboxylic acid having at least 4 COOH groups per molecule or the anhydride in question.
  • polycarboxylic acids (b) and their anhydrides are 1, 2,3-benzenetricarboxylic acid and
  • 1 .2.4-benzenetricarboxylic acid trimellitic acid
  • trimellitic anhydride 1, 2,4,5-benzenetetracarboxylic acid (pyromellitic acid) and 1, 2,4,5-benzenetetracarboxylic dianhydride (pyromellitic dianhydride)
  • pyromellitic acid 1, 2,4,5-benzenetetracarboxylic dianhydride
  • 3,3 ', 4,4'- Benzophenonetetracarboxylic acid, 3, 3 ', 4,4'-benzophenonetetracarboxylic dianhydride furthermore benzene hexacarboxylic acid (mellitic acid) and anhydrides of mellitic acid.
  • mellophanic acid and mellophanic 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 1,1,5,8-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-naphthalenetetracarboxylic dianhydride, 1, 4,5
  • polyisocyanate (a) and polycarboxylic acid (b) are allowed to condense with one another, preferably in the presence of a catalyst, an imide group is formed with elimination of CO 2 and H 2 O. If, instead of polycarboxylic acid (b), the corresponding anhydride is used, an imide group is formed with elimination of CO 2.
  • polyisocyanate (a) is used in admixture with at least one diisocyanate, for example with tolylene diisocyanate, hexamethylene diisocyanate or with isophorone diisocyanate.
  • polyisocyanate (a) is used in admixture with the corresponding diisocyanate, for example trimeric HDI with hexamethylene diisocyanate or trimeric isophorone diisocyanate with isophorone diisocyanate or polymeric diphenylmethane diisocyanate (polymer MDI) with diphenylmethane diisocyanate.
  • polycarboxylic acid (b) is used in combination with at least one dicarboxylic acid or with at least one dicarboxylic acid anhydride, for example with phthalic acid or phthalic anhydride.
  • Diol (B) or triol (B) may be low molecular weight or high molecular weight.
  • triols (B) are glycerol and 1,1,1- (trihydroxmethylene) methane, 1,1,1- (trihydroxmethylene) ethane and 1,1,1- (trihydroxmethylene) propane.
  • Diols (B) are preferred.
  • low molecular weight diols (B) in the context of the present invention, those having a molecular weight of up to 500 g / mol are to be mentioned by way of example: 1, 2-ethanediol, 1, 2-propanediol, 1, 3-propanediol, 1, 2 Butanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 4-but-2-endiol, 1, 4-but-2-indiol, 1, 5-pentanediol and its position 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 and especially 2,2-dimethylpropane-1, 3-diol (neopentyl glycol).
  • polymeric diols there may be mentioned dihydric or polyhydric polyester polyols and polyether polyols, the divalent ones being preferred.
  • Preferred polyetherpolyols are polyetherdiols, such as boron trifluoride-catalyzed linking of ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with themselves or with one another or by addition of these compounds, singly or in admixture, to starter components having reactive Hydrogen atoms such as water, polyhydric alcohols or amines such as 1, 2-ethanediol, propanediol (1, 3), 1, 2 or 2,2-bis (4-hydroxyphenyl) propane or aniline are available.
  • polyether-1, 3-diols for example, the trimethylolpropane alkoxylated on an OH group whose alkylene oxide chain is terminated with an alkyl radical containing 1 to 18 C atoms, are preferably used polymeric diols.
  • Preferred polymeric diols are: polyethylene glycol, polypropylene glycol and in particular polytetrahydrofuran (poly-THF).
  • polyether polyols selected from: polyethylene glycol having an average molecular weight (M n ) in the range from 200 to 9,000 g / mol, preferably in the range from 500 to 6,000 g / mol, poly-1,2-propylene glycol or poly-1,3 propanediol having an average molecular weight (M n ) in the range from 250 to 6,000, preferably 600 to 4,000 g / mol, poly-THF having an average molecular weight (M n ) in the range from above 250 to 5,000, preferably from 500 to 3,000 g / mol, more preferably in the range of 750 to 2,500 g / mol.
  • polyester polyols polyester diols
  • polycarbonate diols are preferred polymeric diols.
  • Particularly suitable polycarbonate diols are aliphatic polycarbonate diols, for example 1,4-butanediol polycarbonate and 1,6-hexanediol polycarbonate.
  • polyester diols are those mentioned by polycondensation of at least one primary diol, preferably at least one primary aliphatic diol, for example ethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol or more preferably 1, 4-dihydroxymethylcyclohexane (as Mixture of isomers) or mixtures of at least two of the aforementioned diols on the one hand and at least one, preferably at least two dicarboxylic acids or their anhydrides on the other hand.
  • Preferred dicarboxylic acids are aliphatic dicarboxylic acids such as adipic acid, glutaric acid, succinic acid and aromatic dicarboxylic acids such as phthalic acid and in particular isophthalic acid.
  • polyester diols and polycarbonate diols are selected from those having an average molecular weight (M n ) in the range of 500 to 9,000 g / mol, preferably in the range of 500 to 6,000 g / mol.
  • Very particularly preferred diols (B) are polytetrahydrofurans, for example having an average molecular weight M n in the range from 250 to 2,000 g / mol.
  • the polymeric material according to the invention has an acid number in the range from zero to 300 mg KOH / g, determined according to DIN 53402, preferably from zero to 200 mg KOH / g.
  • the polymeric material according to the invention has a hydroxyl number in the range from zero to 300 mg KOH / g, determined according to DIN 53240-2, preferably from zero to 200 mg KOH / g.
  • polymeric material according to the invention has a quotient M w / M n in the range from 1.2 to 10, preferably from 1.5 to 5, more preferably from 1.8 to 4.
  • M w and M are determined n preferably by gel permeation chromatography.
  • Another object of the present invention is the use of polymeric materials according to the invention as or for the production of materials for the separation of substances, for example as or for the preparation of stationary phases for chromatography, preferably as or for the production of membranes.
  • Another object of the present invention is a process for the preparation of materials for material separation, in particular for the production of stationary phases for chromatography or membranes, using at least one material according to the invention.
  • Another object of the present invention are materials for separation, for example, stationary phases for chromatography and in particular membranes, prepared using at least one polymeric material according to the invention.
  • Membranes of the invention may have an average thickness in the range of 0.01 to 100 ⁇ m, preferably 1 to 50 ⁇ m, particularly preferably 1 to 20 ⁇ m.
  • Membranes according to the invention can be formed as hollow-fiber membranes or flat membranes. Specific examples of flat membranes are wound membranes.
  • Membranes according to the invention are suitable for membrane separation processes, in particular for nanofiltration, gas separation, pervaporation, reverse osmosis, microfiltration and ultrafiltration, in particular nanofiltration and ultrafiltration with substances dissolved in organic solvents.
  • nanofiltration means a membrane separation process in which the membrane used in the case of non-porous membranes has a molecular weight cut-off (MWCO) of 100 to 1500 g / mol or in variants of porous membranes a maximum pore diameter of 1 nm.
  • MWCO molecular weight cut-off
  • substances can be separated which have an average molecular weight of less than 0.1 or less than 1.5 kg / mol, that is to say less than 100 or less than 1500 g / mol.
  • ultrafiltration is understood as meaning a membrane separation process in which the membrane has a separation limit in the range from 1, 500 to 1, 000 000 g / mol, or separates particles which have a maximum diameter in the range from 10 to 500 nm.
  • microfiltration is understood as meaning a membrane separation process in which the membrane has a separation limit above 1 000 000 g / mol, or has a pore diameter of 1 ⁇ m to 10 ⁇ m.
  • a polymeric material according to the invention In order to produce membranes of polymeric material according to the invention, it is possible, for example, to crosslink a polymeric material according to the invention with a precisely calculated amount of a crosslinker, for example a diisocyanate or polyisocyanate, on a solid surface.
  • a crosslinker for example a diisocyanate or polyisocyanate
  • the amount of crosslinker can be calculated, for example, on the basis of the OH number or acid number of polymeric material according to the invention on the one hand and the number of functional groups, for example NCO groups, of crosslinker on the other hand.
  • membranes according to the invention are produced by reacting a solution comprising at least one organic solvent, at least one crosslinker and at least one polymeric material according to the invention, in the form of a film, onto an article having a smooth surface, for example a plastic plate or on a glass plate, applies. Thereafter, the solvent or solvents are evaporated and treated thermally, for example in a range from 20 ° C to 400 ° C, preferably from 40 to 200 ° C, more preferably from 50 to 150 ° C. In this case, a crosslinking reaction takes place in situ. The desired crosslinking can be accelerated by adding a catalyst. Finally, according to the invention, after the thermal treatment, the membrane can be easily removed from the smooth-surfaced article.
  • the membrane according to the invention is combined with a further layer, preferably with a silicone layer, for example by lamination.
  • membranes of the invention can be spun as hollow fiber membranes. Such membranes of the invention are particularly well suited for gas separation, but also as protective layers. Membranes according to the invention can be embodied as integral asymmetric or composite membranes in which the actual separation layer effecting the separation and having a thickness of 0.01 to 100 ⁇ m, preferably 0.1 to 20 ⁇ m, is deposited on one or more meso membranes. and / or macroporous carrier (s) which consists of one or more organic, in particular polymeric and / or inorganic, material (s), for example ceramic, carbon, metal.
  • s macroporous carrier
  • Membranes according to the invention can be used in the form of flat, cushion, capillary, hollow fiber, mono-channel pipe or multi-channel pipe elements.
  • the geometries are known to the person skilled in the art from other membrane separation processes such as ultrafiltration or reverse osmosis (see, for example, R.
  • the separating layer can be on the inside
  • membranes according to the invention are surrounded by one or more housings of polymeric, metallic or ceramic material, the connection between the housing and the membrane being made by a sealing polymer (eg elastomer) or by an inorganic material
  • a sealing polymer eg elastomer
  • an inorganic material Another object of the present invention is a process for the separation of mixtures using polymeric material according to the invention, for example in the form of membranes according to the invention or of stationary phases according to the invention for chromatography Appropriate methods for the separation of mixtures using material for material separation according to the invention are also called separation method according to the invention below.
  • Material separation materials according to the invention for example membranes according to the invention or chromatography columns according to the invention, are suitable e.g. for the following separation tasks, i. for the separation of the following mixtures:
  • Polyalkylene glycols of various molecular weights for example polyethylene glycol / polypropylene glycol block copolymer 6,500 g / mol - polyethylene glycol 400 g / mol
  • Membranes according to the invention in many cases show no permeability to water, even after conditioning in THF. By contrast, membranes according to the invention show a good permeability to organic solvents, for example acetone, toluene, isopropanol and ethanol. Membranes of the invention are flexible and easy to cut. In many cases membranes of the invention are thermally stable, for example up to a temperature of 200 ° C.
  • a further subject of the present invention is a process for the preparation of polymeric materials according to the invention, also referred to in short as the production process according to the invention. To carry out the preparation process according to the invention, it is possible to proceed in such a way that a polyimide (A) obtainable by condensation of
  • polyimide (A) has a polydispersity M w / M n of at least 1.4.
  • Polyimide (A), polyisocyanate (a), polycarboxylic acid (b), anhydride (b) and diol (B) are described above.
  • the production process according to the invention is a two-stage process. It is possible after the production of polyimide (A) to isolate this and purify.
  • the preparation process according to the invention is carried out as a one-pot process and omits the purification and isolation of polyimide (A).
  • polyisocyanate (a) and polycarboxylic acid (b) or anhydride (b) in an amount such that the molar fraction of NCO groups to COOH groups is in the range from 1: 3 to 3: 1 , preferred are 1: 2 to 2: 1.
  • an anhydride group of the formula CO-O-CO counts as two COOH groups.
  • polyimide (A) and diol (B) are used in proportions such that the molar ratio of hydroxyl groups of diol (B) is related to the sum of NCO groups and COOH groups such as 1:10 to 10 : 1, preferably 1: 6 to 6: 1, more preferably 1: 4 to 4: 1.
  • the synthesis process according to the invention can be carried out at temperatures in the range from 50 to 140.degree. C., preferably from 50 to 100.degree.
  • the production process according to the invention can be carried out under atmospheric pressure. But the synthesis under pressure, for example at pressures in the range of 1, 1 to 10 bar, is possible.
  • the synthesis process according to the invention can be carried out in the presence of a solvent or solvent mixture.
  • suitable solvents are N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, dimethyl sulfone, xylene, phenol, cresol, ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), acetophenone, furthermore mono- and dichlorobenzene, ethylene glycol monoethyl ether acetate, and mixtures of two or more of the abovementioned solvents.
  • the solvent or solvents may be present during the entire duration of the synthesis or only during part of the synthesis.
  • NCO end groups of polyimide (A) with a secondary amine, for example with dimethylamine, di-n-butylamine or with diethylamine.
  • the preparation process according to the invention is carried out without addition of a catalyst.
  • the production process according to the invention is carried out with the aid of a catalyst, for example by admixing at least one catalyst customary in polyurethane chemistry.
  • catalysts are water and Br ⁇ nsted bases, for example alkali metal alkoxides, in particular alkoxides of sodium or potassium, for example sodium methoxide, sodium ethoxide, sodium phenolate, potassium methoxide, potassium ethanolate, potassium phenolate, lithium methoxide, lithium ethanolate and lithium phenolate.
  • alkali metal alkoxides for example sodium methoxide, sodium ethoxide, sodium phenolate, potassium methoxide, potassium ethanolate, potassium phenolate, lithium methoxide, lithium ethanolate and lithium phenolate.
  • tertiary amines are tertiary amines, amidines and / or organic metal compounds.
  • Examples are 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, tertiary amines such as triethylamine, tributylamine, dimethylbenzylamine, N-methyl-, N-ethyl-, N-cyclohexylmorpholine, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylethylenediamine, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyl-butanediamine, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyl hexanediamine, pentamethyldiethylenetriamine, tetramethyldiaminoethyl ether, bis (dimethylaminopropyl) urea, dimethylpiperazine, 1, 2-dimethylimidazole, 1-azabicyclo- (3,3,0)
  • metal compounds preferably tin compounds such as tin (II) salts of organic carboxylic acids, for example tin (II) acetate, tin (II) octoate, tin (II) ethylhexoate and tin ( II) -laurate and preferably organo-tin compounds, particularly preferably dialkyltin (IV) salts of organic carboxylic acids, in particular, in particular, di-n-C 1 -C 10 -alkyl-tin-alkanoates, eg.
  • tin compounds such as tin (II) salts of organic carboxylic acids, for example tin (II) acetate, tin (II) octoate, tin (II) ethylhexoate and tin ( II) -laurate and preferably organo-tin compounds, particularly preferably dialkyltin (IV) salts of organic carboxylic acids, in particular
  • Metal compounds or organometallic compounds can be used alone or in combination with basic amines.
  • Another preferred catalyst used is di-n-butyltin mercaptide or di-n-butyltin dioctanoate.
  • the synthesis process according to the invention is carried out under inert gas, for example under argon or under nitrogen.
  • Polyisocyanate (a.1) 4,4'-diphenylmethane diisocyanate
  • Anhydride (b.1) 1, 2,4,5-benzene tetracarboxylic dianhydride
  • the molecular weights were determined by gel permeation chromatography (GPC).
  • the standard was polystyrene (PS).
  • the solvent used was tetrahydrofuran (THF), unless expressly stated otherwise.
  • Detection was carried out with a differential refractometer Agilent 1 100, or a UV photometer Agilent 1 100 VWD.
  • the NCO content was determined by titrimetry according to DIN EN ISO 1 909 and stated in% by weight. The syntheses were carried out under nitrogen unless otherwise described.
  • Crosslinkers used (CL.1): Polymeric 4,4'-diphenylmethane diisocyanate with functionality of 2.7, NCO: 31, 5%

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
EP12783983.5A 2011-11-16 2012-11-07 Polymeres material, seine herstellung und verwendung Withdrawn EP2780393A1 (de)

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EP12783983.5A EP2780393A1 (de) 2011-11-16 2012-11-07 Polymeres material, seine herstellung und verwendung

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EP11189300 2011-11-16
PCT/EP2012/071955 WO2013072224A1 (de) 2011-11-16 2012-11-07 Polymeres material, seine herstellung und verwendung
EP12783983.5A EP2780393A1 (de) 2011-11-16 2012-11-07 Polymeres material, seine herstellung und verwendung

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JP (1) JP2014533750A (ko)
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CN105206793B (zh) 2009-08-24 2017-12-22 赛昂能源有限公司 用于电化学电池的剥离系统
KR20130105838A (ko) 2010-08-24 2013-09-26 바스프 에스이 전기화학 셀용 전해질 물질
US9676915B2 (en) 2012-12-17 2017-06-13 Basf Se Porous branched/highly branched polyimides
US9728768B2 (en) 2013-03-15 2017-08-08 Sion Power Corporation Protected electrode structures and methods
US10862105B2 (en) 2013-03-15 2020-12-08 Sion Power Corporation Protected electrode structures
JP6746062B2 (ja) 2014-02-19 2020-08-26 シオン・パワー・コーポレーション 電解質抑制イオン伝導体を使用する電極保護
US10490796B2 (en) 2014-02-19 2019-11-26 Sion Power Corporation Electrode protection using electrolyte-inhibiting ion conductor
KR20160084123A (ko) 2015-01-05 2016-07-13 김영기 회전식 빨래 건조대
WO2017178482A1 (en) * 2016-04-11 2017-10-19 Basf Se Porous thermoplastic membranes
KR102267821B1 (ko) * 2019-09-17 2021-06-21 도레이첨단소재 주식회사 나노분리막 및 이를 포함하는 분리막 모듈
CN112138638B (zh) * 2020-09-18 2021-08-13 北京理工大学 一种脂肪族聚碳酸酯的应用

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EP2716674A1 (en) * 2011-05-31 2014-04-09 Toyobo Co., Ltd. Carboxyl group-containing polyimide, heat-curable resin composition, and flexible metal-clad laminate

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KR20140089564A (ko) 2014-07-15
JP2014533750A (ja) 2014-12-15
CN103930469A (zh) 2014-07-16

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