DE19846608B4 - Production of semipermeable membranes, useful for separation processes, from liquid prepared hydrolytic condensation of specified organosilanes - Google Patents

Abstract

Process for producing a semipermeable membrane comprises preparing a low-viscosity to resin-like liquid by hydrolytic condensation of one or more specified organosilanes, forming the liquid into a membrane, optionally drying the membrane and then curing the membrane by thermal, radiation and/or chemical means. - The liquid is prepared by hydrolytic condensation of one or more compounds of formula (I)-(IV) and/or precondensates derived from (I)-(IV) and optionally one or more compounds of formula (V) and/or precondensates derived from (V), provided that the molar ratio of (I)+(II)+(III) to (IV) is 1:0-20, in the presence of water or humidity and optionally a solvent and/or a condensation catalyst, optionally with addition of one or more copolymerizable and/or (poly)additionable monomers and/or oligomers and/or one or more curing catalysts and/or one or more soluble and/or volatile pore-forming additives: - R = 1-15C alkyl, alkenyl, aryl, alkaryl or aralkyl, optionally containing O and/or S atoms and/or ester, carbonyl, carboxyl, amide and/or amino groups; - R1, R2 = 0-15C alkylene, arylene or arylenealkylene, optionally containing O and/or S atoms and/or ester, carbonyl, carboxyl, amide and/or amino groups; - R3 = H, R2-R1-R4-SiXxR3-x, COOH or R; - R4 = (CHR6-CHR6)n, CHR6-CHR6-S-R5, CO-S-R5, CHR6-CHR6-NR6-R5, Y-CS-NH-R5, S-R5, Y-CO-NH-R5, CO-O-R5, Y-CO-C2H3(COOH)-R5, Y-CO-C2H3(OH)-R5 or CO-NR6-R5; - n = 0 or 1; - R5 = 1-15C alkylene, arylene or arylenealkylene, optionally containing O and/or S atoms and/or ester, carbonyl, carboxyl, amide and/or amino groups; - R6 = H or 1-10C alkyl or aryl; - R7 = H or R; - Y = O, S or NR6; - Z = O or (CHR6)m; - m = 1 or 2; - a, b = 1-3, but not both 1; - c = 1-6; - x = 1-3; - x = 1-3; - a+x = 2-4. - B(A-(Z)d-R1(R2)-R3-SiXaRb)c (II) - B = a 4-50C linear or branched organic group containing at least one C=C double bond; - R = 1-15C alkyl, alkenyl, aryl, alkaryl or aralkyl, optionally containing O and/or S atoms and/or ester, carbonyl, carboxyl, amide and/or amino groups; - R3 = 0-15C alkylene, arylene, arylenealkylene or alkylenearylene, optionally containing O and/or S atoms and/or ester, carbonyl, carboxyl, amide and/or amino groups; - X = H, halogen, OH, alkoxy, acyloxy, alkanoyl, alkoxycarbonyl or NR2; - R = H, alkyl, aryl or alkaryl; - A = O, S, NH or COO; - d = 0 or 1; - Z = CO or CHR'; - R' = H, alkyl, aryl or alkaryl; - R1 = Q or N; - Q = 1-10C alkylene, arylene or alkylenearylene, optionally interrupted by O and/or S atoms and/or amino groups; - R2 = H, COOH or OH; - a = 1-3; - b = 0-2; - a+b = 3; - c = 1-4; - provided that: (a) A = O, S or NH when d = 1, Z = CO, R1 = Q and R2 = H or COOH; (b) A = O, S, NH or COO when d = 1, Z = CHR', R1 = Q and R2 = OH; (c) A = O, S, NH or COO when d = 0, R1 = Q and R2 = OH; and (d) A = S when d = 1, Z = CO, R1 = N and R2 = H. - (XaRbSi((R'A)c)(4-a-b)xB (III) - A = O, S, PR, POR, NHC(O)O or NHC(O)NR; - B = a linear or branched group derived from a compound B' containing 5-50 C atoms and at least one (when c = 1 and A = NHC(O)O or NHC(O)NR) or at least two C=C double bonds; - R = 1-15C alkyl, alkenyl, aryl, alkaryl or aralkyl, optionally containing O and/or S atoms and/or ester, carbonyl, carboxyl, amide and/or amino groups; - R' = alkylene, arylene or alkylenearylene; - R = H, alkyl, aryl or alkaryl; - X = H, halogen, OH, alkoxy, acyloxy, alkanoyl, alkoxycarbonyl or NR2; - a = 1-3; - b = 0-2; - c = 0 or 1; - x = an integer whose maximum value corresponds to the number of double bonds in B' minus 1 or is equal to the number of double bonds in B' when c = 1 and A = NHC(O)O or NHC(O)NR; - alkyl = optionally substituted 1-20C linear, branched or cyclic alkyl; - alkenyl = optionally substituted 2-20C linear, branched or cyclic alkenyl; - aryl = optionally substituted phenyl, naphthyl or biphenylyl; - alkoxy, acyloxy, alkanoyl, alkoxycarbonyl, alkaryl, aralkyl, arylene, alkylene and alkylenearylene are derived from alkyl and aryl groups as defined above. - YaSiXxR4-a-x (IV) - R = 1-15C alkyl, alkenyl, aryl, alkaryl or aralkyl,

Description

The The invention relates to semipermeable membranes based on organic modified silicic acid polycondensates, a process for their preparation and their use in gas exchange and in separation processes, in particular in the gas separation, in the Dialysis, in pervaporation, as well as in micro-, ultra- and hyperfiltration. The membranes of the invention represent flat membranes or tubular membranes.

to Separation of mixtures are the most diverse membrane materials known, all in terms of their technical operational capability and their profitability can be improved. So are known Membrane materials, such as e.g. Cellulose acetate, low temperature and pressure resistant and swell in organic solvents strong. The low temperature, pressure and solvent resistance has the consequence that the pore size in the technical Use constantly changes and This results in non-reproducible results as well as short service lives lead the membranes can.

ultrafiltration e.g. become prevalent in aqueous systems carried out, so that on the mechanical and thermal stability (sterilizability up to 140 ° C) of the used for this Membranes whose durability across from acids and alkalis and their specifically adjustable hydrophilic / hydrophobic Properties are placed particularly high demands. The Previously used for membrane production polymers, these can Do not meet requirements simultaneously and show e.g. at relative good thermal resistance up to about 140 ° C no adequate mechanical stability.

For different Applications often necessary surface modifications (setting the porosity, the adsorption behavior, etc.) require further subsequent processes. Furthermore, such modified materials have the disadvantage that they only have a modified monolayer on the surface so that they are extraordinary sensitive to mechanical and chemical influences.

Commercially available polymers such as polyethylenes, polypropylenes, polysulfones, polyimides, polymethacrylates etc. have only a low gas permeability (for example to O ₂ , CO _2, etc.). A permeation increase based on these types of polymers is possible only by incorporation of a porosity. For example, provided with a defined, continuous porosity polymer hollow fibers directly accessible only by very complicated spinning processes or by subsequent and thus additional process steps. If such modified polymers are used, for example, for gas exchange in fluid systems, there is the danger of passage of the fluid phase. For example, in the O ₂ / CO ₂ exchange in the blood in oxygenators during open chest surgery, the pores pose a significant risk potential. Especially during longer operations, a passage of blood through the pores is often observed.

Very high gas permeation values without porosity are only very specific Polymers (silicones, substituted polysilylpropines, etc.) can be realized. The high gas permeability However, this is only due to extreme losses in mechanical properties reached. With increasing permeability, the strength and decreases E modulus decreases, i. The material is getting softer. Unsupported thin films and stable hollow fibers with a small wall thickness are therefore not possible. films and hollow fibers with an over Wide ranges of adjustable permeability are only very basic different types of polymers in connection with different production processes possible.

membranes on the basis of silicic acid heteropolycondensates show excellent resistance against acids and organic solvents and are also quite stable in the pH range up to about 10.

From the DE 2758415 C2 It is known to process silicic acid heteropolycondensates into porous membranes by mechanically cutting the polycondensates obtained in compact blocks into very thin slices, which are then used directly or after previous grinding as membranes. However, since the silicic acid heteropolycondensates are generally not elastic enough, the membrane discs break during cutting, and also the necessary membrane area is usually not reached by this method.

In the DE 2925969 C2 Another method for the preparation of porous membranes based on silicic acid heteropolycondensates at the interface of an organic and an aqueous phase is described. However, since the resulting membranes are very watery due to contact with an aqueous phase, there is a risk of excessive shrinkage and cracking associated with drying. The hydrolytic polycondensation of the starting components to silicic acid heteropoly Condensates runs under substance leakage, so that inevitably comes to a shrinkage of the polycondensates.

In the in the DE 2758415 C2 and in the DE 2925969 C2 Membranes described the shaping of the membrane and the curing of the membrane by an inorganic condensation, ie by the construction of a Si-O-Si network. These membranes show very poor mechanical properties, the mechanical stabilities rarely meet the demands placed on them. In addition, these membranes are brittle and not flexible.

From the EP 0094060 B1 Another method for the preparation of membranes based on silicic acid heteropolycondensates is known. The polycondensation is carried out on the surface of a support which supports the membrane. The shaping of the membrane and the hardening of the membrane also takes place here by inorganic condensation, ie by the construction of an inorganic network. The resulting membranes are carrier supported and not self-supporting.

task It is the object of the present invention to provide semipermeable membranes for gas exchange and for substance separations provide their exchange capacity varies over a wide range and adapted to the requirements of the particular application. Furthermore, the membranes should not only support supported, but also self-supporting be, and they should be as tubular Membrane or as flat membranes. The permeability and flexibility of the membranes should over wide ranges and the requirements of the particular application customized be. Furthermore, the membranes should show high permeability with high mechanical stability, in particular also opposite Gases, hence these membranes also for gas exchange and for substance separations can be used without that Risk of passage of the fluid phase exists. Even at high Permeationswerten the membranes are still self-supporting. The membranes should be toxicologically safe and therefore in the medical field be applicable.

Further It is an object of the present invention to provide a method be able to be made with the semi-permeable membranes whose Property profile can be varied within wide ranges. By simple Variation of the process steps should be the chemical and physical Characteristics of the membrane in a wide range of requirements be adapted to the particular application. The procedure should be simple, fast and inexpensive feasible be. The process should be able to produce membranes that meet the above requirements. Furthermore, the method should also for the endless production of hollow fibers and flat membranes suitable be. Furthermore should the for various applications often require surface modifications, e.g. to avoid blood coagulation, to adjust the polarity, the adsorption behavior etc., both during the material synthesis, i. realized in situ, as well as subsequently can be.

Is solved this object by membranes, which are obtainable by having a slightly viscous to resinous liquid according to usual Processes methods to membranes and these optionally dried. The hardening the resulting membranes can e.g. thermally and / or radiation-induced and / or chemically induced.

• a) durch hydrolytische Polykondensation von
• • einer oder mehreren Verbindungen der allgemeinen Formel I, und/oder
• • einer oder mehreren Verbindungen der allgemeinen Formel II, und/oder
• • einer oder mehreren Verbindungen der allgemeinen Formel III, und/oder
• • einer oder mehreren Verbindungen der allgemeinen Formel IV, und/oder
• • von den Verbindungen der Formeln I bis IV abgeleiteten Vorkondensaten und gegebenenfalls
• • einer oder mehreren Verbindungen der allgemeinen Formel V, und/oder von diesen abgeleiteten Vorkondensaten, und gegebenenfalls
• b) durch Zugabe von
• • einem oder mehreren copolymerisierbaren und/oder (poly)addierbaren Monomeren und/oder Oligomeren,
• • und/oder von einem oder mehreren Härtungskatalysatoren,
• • und/oder von einem oder mehreren, löslichen und/oder flüchtigen, Poren erzeugenden Additiven.

The liquid or resin from which (m) the membranes are made is obtained

• a) by hydrolytic polycondensation of
• One or more compounds of general formula I, and / or
• • one or more compounds of general formula II, and / or
• • one or more compounds of general formula III, and / or
• • one or more compounds of general formula IV, and / or
• • precondensates derived from the compounds of the formulas I to IV and, if appropriate,
• One or more compounds of general formula V, and / or precondensates derived therefrom, and optionally
• b) by adding
• One or more copolymerizable and / or (poly) addable monomers and / or oligomers,
• • and / or one or more curing catalysts,
• • and / or one or more, soluble and / or volatile, pore-forming additives.

The hydrolytic polycondensation is carried out by adding water or moisture and optionally in the presence of a solvent and / or a condensation catalyst. Based on the monomers, the molar ratio of the sum of the compounds of the formulas I, II, III and IV to compounds of formula V between 1: 0 and 1:20.

The Liquid used for the preparation of the membranes according to the invention or the resin used so make a polycondensate from hydrolytic condensed silicon compounds of the formulas I and / or II and / or III and / or IV and optionally V, wherein the polycondensate optionally also water and / or solvent and / or the above receives said additives. Dependent on from the viscosity The polycondensate can be of a more or less viscous liquid or talk about a resin.

R = Alkyl, Alkenyl, Aryl, Alkylaryl oder Arylalkyl mit jeweils 1 bis 15 Kohlenstoff-Atomen, wobei diese Reste Sauerstoff- und/oder Schwefel-Atome und/oder Ester- und/oder Carbonyl- und/oder Carboxyl- und/oder Amid- und/oder Amino-Gruppen enthalten können.
R¹ = Alkylen, Arylen, Arylenalkylen oder Arylenalkylen mit jeweils 0 bis 15 Kohlenstoff-Atomen, wobei diese Reste Sauerstoff- und/oder Schwefel-Atome und/oder Ester- und/oder Carbonyl- und/oder Carboxyl- und/oder Amid- und/oder Amino-Gruppen enthalten können.
R² = Alkylen, Arylen, Arylenalkylen oder Arylenalkylen mit jeweils 0 bis 15 Kohlenstoff-Atomen, wobei diese Reste Sauerstoff- und/oder Schwefel-Atome und/oder Ester- und/oder Carbonyl- und/oder Carboxyl- und/oder Amid- und/oder Amino-Gruppen enthalten können.
R³ = Wasserstoff, R²-R¹-R⁴-SiX_xR_3-x, Carboxyl-, Alkyl, Alkenyl, Aryl, Alkylaryl oder Arylalkyl mit jeweils 1 bis 15 Kohlenstoff-Atomen, wobei diese Reste Sauerstoff- und/oder Schwefel-Atome und/oder Ester- und/oder Carbonyl- und/oder Carboxyl- und/oder Amid- und/oder Amino-Gruppen enthalten können.
R⁴ = -(CHR⁶-CHR⁶)_n-, mit n = 0 oder 1, -CHR⁶-CHR⁶-S-R⁵-, -CO-S-R⁵-, -CHR⁶-CHR⁶-NR⁶-R⁵-, -Y-CS-NH-R⁵-, -S-R⁵,-Y-CO-NH-R⁵-, -CO-O-R⁵-, -Y-CO-C₂H₃(COOH)-R⁵-, -Y-CO-C₂H₃(OH)-R⁵- oder -CO-NR⁶-R⁵-.
R⁵ = Alkylen, Arylen, Arylenalkylen oder Arylenalkylen mit jeweils 1 bis 15 Kohlenstoff-Atomen, wobei diese Reste Sauerstoff- und/oder Schwefel-Atome und/oder Ester- und/oder Carbonyl- und/oder Carboxyl- und/oder Amid- und/oder Amino-Gruppen enthalten können.
R⁶ = Wasserstoff, Alkyl oder Aryl mit 1 bis 10 Kohlenstoff-Atomen.
R⁷ = Wasserstoff, Alkyl, Alkenyl, Aryl, Alkylaryl oder Arylalkyl mit jeweils 1 bis 15 Kohlenstoff-Atomen, wobei diese Reste Sauerstoff- und/oder Schwefel-Atome und/oder Ester- und/oder Carbonyl- und/oder Carboxyl- und/oder Amid- und/oder Amino-Gruppen enthalten können.
X = Wasserstoff, Halogen, Hydroxy, Alkoxy, Acyloxy, Alkylcarbonyl, Alkoxycarbonyl oder NR''₂, mit R'' = Wasserstoff, Alkyl, Alkylaryl oder Aryl.
Y = -O-, -S- oder -NR⁶-.
Z = -O- oder -(CHR⁶)_m, mit m = 1 oder 2.
a = 1, 2 oder 3, mit b = 1 für a = 2 oder 3.
b = 1, 2 oder 3, mit a = 1 für b = 2 oder 3.
c = 1 bis 6.
x = 1, 2 oder 3, mit a+x = 2, 3 oder 4.In the general formula I, the radicals and indices have the following meaning, wherein for indices> 2, the relevant radicals are the same or different.

R = alkyl, alkenyl, aryl, alkylaryl or arylalkyl having in each case 1 to 15 carbon atoms, these radicals being oxygen and / or sulfur atoms and / or ester and / or carbonyl and / or carboxyl and / or amide - And / or amino groups may contain.
R ¹ = alkylene, arylene, arylenealkylene or arylenealkylene each having 0 to 15 carbon atoms, these radicals being oxygen and / or sulfur atoms and / or ester and / or carbonyl and / or carboxyl and / or amide and / or amino groups.
R ² = alkylene, arylene, arylenealkylene or arylenealkylene each having 0 to 15 carbon atoms, these radicals being oxygen and / or sulfur atoms and / or ester and / or carbonyl and / or carboxyl and / or amide and / or amino groups.
R ³ = hydrogen, R ² -R ¹ -R ⁴ -SiX _x R _3-x , carboxyl, alkyl, alkenyl, aryl, alkylaryl or arylalkyl having in each case 1 to 15 carbon atoms, where these radicals oxygen and / or Sulfur atoms and / or ester and / or carbonyl and / or carboxyl and / or amide and / or amino groups may contain.
R ⁴ = - (CHR ⁶ -CHR ⁶ ) _n -, with n = 0 or 1, -CHR ⁶ -CHR ⁶ -SR ⁵ -, -CO-SR ⁵ -, -CHR ⁶ -CHR ⁶ -NR ⁶ -R ⁵ -, -Y-CS-NH-R ⁵ -, -SR ⁵ , -Y-CO-NH-R ⁵ -, -CO-OR ⁵ -, -Y-CO-C ₂ H ₃ (COOH) -R ⁵ -, -Y-CO-C ₂ H ₃ (OH) -R ⁵ - or -CO-NR ⁶ -R ⁵ -.
R ⁵ = alkylene, arylene, arylenealkylene or arylenealkylene each having 1 to 15 carbon atoms, these radicals being oxygen and / or sulfur atoms and / or ester and / or carbonyl and / or carboxyl and / or amide and / or amino groups.
R ⁶ = hydrogen, alkyl or aryl having 1 to 10 carbon atoms.
R ⁷ = hydrogen, alkyl, alkenyl, aryl, alkylaryl or arylalkyl having in each case 1 to 15 carbon atoms, these radicals being oxygen and / or sulfur atoms and / or ester and / or carbonyl and / or carboxyl and or amide and / or amino groups.
X = hydrogen, halogen, hydroxy, alkoxy, acyloxy, alkylcarbonyl, alkoxycarbonyl or NR " ₂ , with R" = hydrogen, alkyl, alkylaryl or aryl.
Y = -O-, -S- or -NR ⁶ -.
Z = -O- or - (CHR ⁶ ) _m , where m = 1 or 2.
a = 1, 2 or 3, with b = 1 for a = 2 or 3.
b = 1, 2 or 3, with a = 1 for b = 2 or 3.
c = 1 to 6.
x = 1, 2 or 3, with a + x = 2, 3 or 4.

Organically modified silanes of the general formula I, their preparation and concrete examples are in the DE 19627198 C2 described in detail. On the revelation of DE 19627198 C2 is hereby incorporated by reference. In preferred embodiments of the membranes according to the invention, organically modified silanes of the general formula I and / or precondensates derived therefrom are used, in which the indices a and / or b and / or c assume the value 1.

B = ein geradkettiger oder verzweigter organischer Rest mit mindestens einer C=C-Doppelbindung und 4 bis 50 Kohlenstoff-Atomen.
R = Alkyl, Alkenyl, Aryl, Alkylaryl oder Arylalkyl mit jeweils 1 bis 15 Kohlenstoff-Atomen, wobei diese Reste Sauerstoff- und/oder Schwefel-Atome und/oder Ester- und/oder Carbonyl- und/oder Carboxyl- und/oder Amid- und/oder Amino-Gruppen enthalten können.
R³ = Alkylen, Arylen, Arylenalkylen oder Alkylenarylen mit jeweils 0 bis 10 Kohlenstoff-Atomen, wobei diese Reste durch Sauerstoff- und/oder durch Schwefel-Atome und/oder durch Amino-Gruppen unterbrochen sein können.
X = Wasserstoff, Halogen, Hydroxy, Alkoxy, Acyloxy, Alkylcarbonyl, Alkoxycarbonyl oder NR''₂, mit R''= Wasserstoff, Alkyl, Aryl oder Alkylaryl.
A = O, S oder NH für d = 1 und Z = CO und
R¹ = Alkylen, Arylen oder Alkylenarylen mit jeweils 1 bis 10 Kohlenstoff-Atomen, wobei diese Reste durch Sauerstoff- und/oder durch Schwefel-Atome und/oder durch Amino-Gruppen unterbrochen sein können, und
R2 = COOH oder H.
oder
A = O, S, NH oder COO für d = 1 und Z = CHR', mit R' = H, Alkyl, Aryl oder Alkylaryl, und
R¹ = Alkylen, Arylen oder Alkylenarylen mit jeweils 1 bis 10 Kohlenstoff-Atomen, wobei diese Reste durch Sauerstoff- und/oder durch Schwefel-Atome und/oder durch Amino-Gruppen unterbrochen sein können, und
R2 = OH.
oder
A = O, S, NH oder COO für d = 0 und
R¹ = Alkylen, Arylen oder Alkylenarylen mit jeweils 1 bis 10 Kohlenstoff-Atomen, wobei diese Reste durch Sauerstoff- und/oder durch Schwefel-Atome und/oder durch Amino-Gruppen unterbrochen sein können, und
R2 = OH.
oder
A = S für d = 1 und Z = CO und
R¹ = N und
R² = H.
a = 1, 2 oder 3.
b = 0, 1 oder 2, mit a+b = 3.
c = 1, 2, 3 oder 4.In the general formula II, the radicals and indices have the following meaning, wherein for indices> 2, the relevant radicals are the same or different.

B = a straight-chain or branched organic radical having at least one C =C double bond and 4 to 50 carbon atoms.
R = alkyl, alkenyl, aryl, alkylaryl or arylalkyl having in each case 1 to 15 carbon atoms, these radicals being oxygen and / or sulfur atoms and / or ester and / or carbonyl and / or carboxyl and / or amide - And / or amino groups may contain.
R ³ = alkylene, arylene, arylenealkylene or alkylenearylene each having 0 to 10 carbon atoms, where these radicals may be interrupted by oxygen and / or by sulfur atoms and / or by amino groups.
X = hydrogen, halogen, hydroxy, alkoxy, acyloxy, alkylcarbonyl, alkoxycarbonyl or NR " ₂ , with R" = hydrogen, alkyl, aryl or alkylaryl.
A = O, S or NH for d = 1 and Z = CO and
R ¹ = alkylene, arylene or Alkylenarylen each having 1 to 10 carbon atoms, where these radicals may be interrupted by oxygen and / or by sulfur atoms and / or by amino groups, and
R2 = COOH or H.
or
A = O, S, NH or COO for d = 1 and Z = CHR ', where R' = H, alkyl, aryl or alkylaryl, and
R ¹ = alkylene, arylene or Alkylenarylen each having 1 to 10 carbon atoms, where these radicals may be interrupted by oxygen and / or by sulfur atoms and / or by amino groups, and
R2 = OH.
or
A = O, S, NH or COO for d = 0 and
R ¹ = alkylene, arylene or Alkylenarylen each having 1 to 10 carbon atoms, where these radicals may be interrupted by oxygen and / or by sulfur atoms and / or by amino groups, and
R2 = OH.
or
A = S for d = 1 and Z = CO and
R ¹ = N and
R ² = H.
a = 1, 2 or 3.
b = 0, 1 or 2, with a + b = 3.
c = 1, 2, 3 or 4.

Organically modified silanes of the general formula II, their preparation and concrete examples are given in US Pat DE 4416857 C1 described in detail. On the revelation of DE 4416857 C1 is hereby incorporated by reference. In preferred embodiments of the membranes according to the invention, organically modified silanes of the general formula II and / or precondensates derived therefrom are used, in which the alkyl and / or alkylene and / or alkoxy groups have 1 to 4 carbon atoms. In further preferred embodiments, the radical B of the general formula II has one or more acrylate and / or methacrylate groups.

In the general formula III, the radicals and indices have the following meaning, wherein for indices> 2, the relevant radicals are the same or different. {X _a R _b Si [(R'A) _c ] _(4-ab) } _x B (III) A = O, S, PR ", POR", NHC (O) O or NHC (O) NR ".
B = straight-chain or branched organic radical which is derived from a compound B 'having at least one (for c = 1 and A = NHC (O) O or NHC (O) NR'') or at least two C = C double bonds and 5 to 50 carbon atoms derived.
R = alkyl, alkenyl, aryl, alkylaryl or arylalkyl having in each case 1 to 15 carbon atoms, these radicals being oxygen and / or sulfur atoms and / or ester and / or carbonyl and / or carboxyl and / or amide - And / or amino groups may contain.
R '= alkylene, arylene or alkylenearylene.
R '' = hydrogen, alkyl, aryl or alkylaryl.
X = hydrogen, halogen, hydroxy, alkoxy, acyloxy, alkylcarbonyl, alkoxycarbonyl or NR " ₂ .
a = 1, 2 or 3.
b = 0, 1 or 2.
c = 0 or 1.
x = an integer whose maximum value corresponds to the number of double bonds in the compound B 'minus 1, or equal to the number of double bonds in the compound B', if c = 1 and A is NHC (O) O or NHC ( O) NR "stands.

The The above alkyl or alkenyl radicals are optionally substituted straight-chain, branched or cyclic radicals having 1 or 2 to 20 Carbon atoms. Aryl stands for optionally substituted phenyl, naphthyl or biphenyl, and the above alkoxy, acyloxy, alkylcarbonyl, alkoxycarbonyl, alkylaryl, Arylalkyl, arylene, alkylene and alkylenearyl radicals are derived from the above-defined alkyl and Aryl residues from.

Organically modified silanes of the general formula III, their preparation and concrete examples are described in US Pat DE 4011044 C2 described in detail. On the revelation of DE 401 1044 C2 is hereby incorporated by reference. In preferred embodiments of the membranes according to the invention, silanes of the general formula III and / or precondensates derived therefrom are used in which the radical B has one or more acrylate and / or methacrylate groups.

In the general formula IV, the radicals and indices have the following meaning, wherein for indices> 2, the relevant radicals are the same or different. Y _a SiX _x R ₄ -ax (IV) R = alkyl, alkenyl, aryl, alkylaryl or arylalkyl having in each case 1 to 15 carbon atoms, these radicals being oxygen and / or sulfur atoms and / or ester and / or carbonyl and / or carboxyl and / or amide - And / or amino groups may contain.
X = hydrogen, halogen, hydroxy, alkoxy, acyloxy, alkylcarbonyl, alkoxycarbonyl or NR " ₂ , with R" = hydrogen, alkyl, aryl or alkylaryl.
Y = organic radical having 1 to 30, preferably having 1 to 20 carbon atoms and having 1 to 5, preferably having 1 to 4 mercapto groups.
a = 1, 2 or 3.
x = 1, 2 or 3, with a + x = 2, 3 or 4.

The Alkyl radicals are e.g. straight-chain, branched or cyclic radicals with 1 to 20, in particular with 1 to 10 carbon atoms and preferably lower alkyl radicals having 1 to 6, particularly preferably 1 to 4 Carbon atoms. Specific examples are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl, Cyclohexyl, 2-ethylhexyl, dodecyl and octadecyl. The alkenyl radicals are e.g. straight-chain, branched or cyclic radicals having 2 to 20, preferably with 2 to 10 carbon atoms, and preferably lower Alkenyl radicals having 2 to 6 carbon atoms, such as e.g. Vinyl, allyl and 2-butenyl. Preferred aryl radicals are phenyl, biphenyl and naphthyl.

The Alkoxy, acyloxy, alkylamino, dialkylamino, alkylcarbonyl, alkoxycarbonyl, Arylaklyl-, alkylaryl, alkylene and Alkylenarylen radicals lead preferably from the abovementioned alkyl and aryl radicals from. Specific examples are methoxy, ethoxy, n- and i-propoxy, n-, i-, s- and t-butoxy, monomethylamino, monoethylamino, dimethylamino, Diethylamino, N-ethylanilino, acetyloxy, propionyloxy, methylcarbonyl, ethylcarbonyl, Methoxycarbonyl, ethoxycarbonyl, benzyl, 2-phenylethyl and tolyl.

The radicals mentioned may optionally bear one or more substituents, for example halogen, alkyl, hydroxyalkyl, alkoxy, aryl, aryloxy, alkylcarbonyl, alkoxycarbonyl, furfuryl, tetrahydrofurfuryl, amino, monoalkylamino, dialkylamino, trialkylammonium, amido, hydroxy, formyl, carboxy, mercapto, Cyano, isocyanato, nitro, epoxy, SO ₃ H or PO ₄ H ₂ . Among the halogens, fluorine, chlorine and bromine, and especially chlorine, are preferred.

In particular embodiments of the membranes according to the invention, silanes of the general formula IV 'are used. [(HS-R ⁵ ) _n R ⁶ -SER ⁵ ] _a SiX _x R ₄ -ax (IV ') in which the radicals and indices have the following meanings:
E = -CO-NH-, -CS-NH-, -CH ₂ -CH ₂ - or -CH ₂ -CH (OH) -
R = as defined in the case of general formula IV;
R ⁵ = alkylene, arylene, arylenealkylene or arylenealkylene having in each case 1 to 15 carbon atoms, where these radicals are represented by oxygen and / or by sulfur atoms and / or by ester and / or by carbonyl and / or by carboxyl and / or may be interrupted by amide and / or by amino groups;
R ⁶ = alkylene, arylene, arylenealkylene or arylenealkylene each having 1 to 15 carbon atoms, where these radicals are represented by oxygen and / or by sulfur atoms and / or by ester and / or by carbonyl and / or by carboxyl and / or may be interrupted by amide and / or by amino groups;
X = as defined in the case of general formula IV;
a = as defined in the case of general formula IV;
n = 2, 3, 4 or 5;
x = as defined in the case of general formula IV.

Organically modified silanes of the general formula IV ', their preparation and concrete examples are in the DE 19627220 C2 described in detail. On the revelation of DE 19627220 C2 is hereby incorporated by reference.

In the general formula V, the radicals and indices have the following meaning, wherein for indices> 2, the relevant radicals are the same or different. X _a SiR _4-a (V) R = alkyl, alkenyl, aryl, alkylaryl or arylalkyl having in each case 1 to 15 carbon atoms, these radicals being oxygen and / or sulfur atoms and / or ester and / or carbonyl and / or carboxyl and / or amide - And / or amino groups may contain.
X = hydrogen, halogen, hydroxy, alkoxy, acyloxy, alkylcarbonyl, alkoxycarbonyl or NR " ₂ , with R" = hydrogen, alkyl, aryl or alkylaryl.
a = 1, 2 or 3.

The Alkyl radicals are e.g. straight-chain, branched or cyclic radicals with 1 to 20, in particular with 1 to 10 carbon atoms and preferably lower alkyl radicals having 1 to 6, particularly preferably 1 to 4 Carbon atoms. Specific examples are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl, Cyclohexyl, 2-ethylhexyl, dodecyl and octadecyl. The alkenyl radicals are e.g. straight-chain, branched or cyclic radicals having 2 to 20, preferably with 2 to 10 carbon atoms, and preferably lower Alkenyl radicals having 2 to 6 carbon atoms, such as e.g. Vinyl, allyl and 2-butenyl. Preferred aryl radicals are phenyl, biphenyl and naphthyl.

The Alkoxy, acyloxy, alkylamino, dialkylamino, alkylcarbonyl, alkoxycarbonyl, Arylaklyl-, alkylaryl, alkylene and Alkylenarylen radicals lead preferably from the abovementioned alkyl and aryl radicals from. Specific examples are methoxy, ethoxy, n- and i-propoxy, n-, i-, s- and t-butoxy, monomethylamino, monoethylamino, dimethylamino, Diethylamino, N-ethylanilino, acetyloxy, propionyloxy, methylcarbonyl, ethylcarbonyl, Methoxycarbonyl, ethoxycarbonyl, benzyl, 2-phenylethyl and tolyl.

The radicals mentioned may optionally bear one or more substituents, for example halogen, alkyl, hydroxyalkyl, alkoxy, aryl, aryloxy, alkylcarbonyl, alkoxycarbonyl, furfuryl, tetrahydrofurfuryl, amino, monoalkylamino, dialkylamino, trialkylammonium, amido, hydroxy, formula, carboxy, mercapto, Cyano, isocyanato, nitro, epoxy, SO ₃ H or PO ₄ H ₂ . Among the halogens, fluorine, chlorine and bromine, and especially chlorine, are preferred.

silanes of general formula V are either commercially available or can be prepared by known methods, e.g. in "Chemistry and Technology of Silicones ", W. Noll, Verlag Chemie GmbH, Weinheim / Bergstrasse (1968).

Without limiting the generality, concrete examples of silanes of the general formula V are:

The Silanes of the general formulas I, II, III, IV, IV 'and V are above the Residues X hydrolyzable and polycondensable, and by the hydrolytic Polykondensati on an inorganic network is built with Si-O-Si bridges. The polycondensation is preferably carried out by the sol-gel method, as it is e.g. in DE-A1 2758414, 2758415, 301 1761, 3826715 and 3835968 is described. The polycondensation is in the on this Area usual Fashion performed, by e.g. the silicon compounds to be hydrolyzed, the either as such or solved in a solvent present, the required water at room temperature or below easier cooling directly added (preferably with stirring and in the presence of a Hydrolysis and condensation catalyst) and the resulting Mixture then stirs for some time (one to several hours). at Presence of reactive compounds is usually recommended in stages Adding the water. Independently from the reactivity The compounds present in the hydrolysis is usually at Temperatures between -20 and 130 ° C or the boiling point of optionally used Solvent. As already indicated, depends the best way of adding water especially from the Reactivity of the starting compounds used. So you can, for example the dissolved starting compounds slowly to an excess of water drop or you give water in one portion or in portions the possibly dissolved Starting compounds too. It may also be useful, not the water as such, but with the help of hydrous organic or inorganic systems in the reaction system. In many cases, the entry of the amount of water has proven to be particularly suitable into the reaction mixture with the aid of moisture-laden adsorbents, e.g. molecular sieves, and hydrous organic solvents, e.g. of 80% ethanol. The addition of water can but also over a chemical reaction takes place during which water in the course of the reaction is released. Examples of this are esterifications.

If a solvent is used, in addition to the lower aliphatic alcohols (e.g., ethanol or i-propanol) also ketones, preferably lower ones Dialkyl ketones, such as acetone or methyl isobutyl ketone, ethers, preferably lower dialkyl ethers such as diethyl ether or dibutyl ether, THF, amides, Esters, in particular ethyl acetate, Dimethylformamide, amines, especially triethylamine, and mixtures thereof in question.

The Output connections must not necessarily already all at the beginning of the hydrolysis (polycondensation) be present, but it may even prove beneficial if only some of these compounds are initially in contact with water is brought and later the remaining compounds are added.

Around precipitations while hydrolysis and polycondensation as much as possible to avoid water addition in several stages, e.g. on three Stages, performed become. In this case, in the first stage, e.g. a tenth to one Twentieth of the amount of water required for the hydrolysis added become. After a short stir can the addition of a fifth up to a tenth of the required amount of water done and after further short stirring can finally the rest are added.

The Condensation time depends on the respective output components and their proportions, the optionally used catalyst, the reaction temperature, etc. In general, the polycondensation is carried out at normal pressure, but it can also be at elevated or at reduced Pressure performed become.

The polycondensate thus obtained can be processed either as such or after partial or almost complete removal of the solvent used to the membranes of the invention who the. In some cases, it may be advantageous to replace in the product obtained after the polycondensation, the excess water and the solvent formed and optionally additionally used by another solvent in order to stabilize the polycondensate. For this purpose, the reaction mixture can be so far thickened, for example, in vacuo at slightly elevated temperature that it can still be easily absorbed with another solvent.

The Polycondensate obtained in this way represents one more or less viscous liquid or a resin, and it is by conventional methods to flat membranes or too tubular Membranes processed. After shaping and one if necessary required drying, the resulting membrane by training hardened an organic network.

The Silanes of the formula I and resulting polycondensates can over the Bicyclic radicals, the silanes of the formulas II and III and their Polycondensates over the radicals B and the silanes of the formulas IV and IV 'and their polycondensates on the Mercapto groups of a polymerization and / or a polyaddition be subjected. By these polymerization or polyaddition reactions An organic network is being set up. That from the silanes of Formulas I to V resulting polycondensate or made thereof Membrane can thus by polymerization and / or by polyaddition hardened become. These curing reactions are thermally and / or radiation-induced and / or chemical induced. To hardening results in an inorganic-organic network, i. the membranes of the invention have a inorganic-organic network. By variation of the inorganic and / or the organic network, e.g. the network density, the chemical and physical properties of the membranes of the invention varies widely and the property profile of the membranes of the invention can be adapted to the requirements of the respective application.

The for the Preparation of the membranes of the invention used polycondensate may contain other additives. These Additives can before and / or during and / or after the polycondensation. In these Additives are e.g. to copolymerizable and / or addable and / or polyaddable monomers and / or oligomers. These monomers or oligomers are used in the course of curing resulting membrane over Polymerization and / or (poly) addition reactions in the organic Network of the membrane according to the invention built-in. Are hydrolyzable silicon compounds with SH- or-C = C or amino groups are used and these are before added hydrolytic polycondensation, so these compounds in the course of polycondensation in the inorganic and in the course of Polymerization or (poly) addition into the organic network of incorporated membranes of the invention.

Further Additives that are suitable for the preparation of the membranes of the invention used polycondensate may include, e.g. Curing catalysts. These are e.g. required if the resulting membrane is chemically induced hardened becomes.

The made of the polycondensate membranes are gas permeable and tight. Become porous membranes desired so can for the preparation of the membranes of the invention used polycondensate Additives are added which generate pores and thus the membranes of the invention a porosity to lend. Such additives are e.g. volatile and / or soluble additives, after curing the membrane e.g. removed by raising the temperature and / or by dissolution be so that cavities in the Membrane remain. Thus, e.g. in the membranes of the invention thereby a porosity be generated that one solvent (e.g., ethyl acetate, ethanol, isopropanol, etc.) to the polycondensate there and this after curing the membrane removed again. In the resin system no. 1, which is explained in more detail below, can e.g. up to 25% by weight of various solvents (e.g., ethyl acetate, Ethanol, isopropanol, etc.) are stirred without the Spinnability is lost. After curing this can still be done in the Membrane contained solvents gently by storage at room temperature or forced by heating about 100 ° C and evacuation are removed quantitatively. By adding oils and their Removal after curing the membrane becomes larger voids, i. larger pores generated. soluble Substances that can be added are e.g. Salts.

It but it is also possible To create pores in that one the blowing agent added to the polycondensate before hardening of Relieve membrane by thermal stress (e.g., between 150 and 250 ° C) gases. Such propellants are e.g. Azo compounds, such as azodicarbonamides. Other additives that can be added for pore generation are for example, hydrazine derivatives (e.g., 4.4-oxybis (benzenesulfohydrazide), Semicarbazides (e.g., p-toluenesulfonyl semicarbazide), tetrazoles (e.g. 5-phenyltetrazole) or benzoxazines (e.g., isatoic anhydride).

pore can in the membranes of the invention also be generated by that thermal cracking or by oxidation, e.g. by annealing at 650 ° C, the organic portion of the membrane changes or completely or partially Will get removed. This preserves you have a pore structure in the nanometer range.

The Pore-forming additives can also porous and thus give the membrane by their presence one Porosity. Without restriction the general public, such porous additives are e.g. porous glass particles, Perlites, zeolites, silica gel, kieselguhr, clay or aerosils in spherical or ground form.

to Production of e.g. Endless flat membranes are preferably solvent-free Systems used, - solvent-containing are, however, also processable, - which continuously on one rotating roller are applied. After the film formation by means of Splitting blade takes the cure, e.g. a radiation-induced curing, the replacement and winding the membranes.

to Production of e.g. Endless hollow fibers are preferably solvent-free Systems used, - solvent-containing however, are also processable, - from which hollow fibers as follows be made. First becomes the resinous one Polycondensate through an annular Extruded nozzle, wherein the cavity is produced by a gas or liquid-conducting inner nozzle becomes. The dimension of the resin thread is by conventional methods by the Variation of spinning parameters, e.g. the withdrawal speed, the temperature, pressure, etc., set. Subsequently, will through an annular Vorhärtungskomponente, e.g. a radiation source just below the spinneret of the resin thread Pre-crosslinked and thus preserves the shape. By means of one underneath mounted round radiator, the final curing is performed. The resulting endless fiber is wound up and rewound. For precuring and / or for final curing In addition to radiation-induced curing, it can also be a self-induced one or a chemically induced cure carried out become. A combination of different curing principles is also possible.

The curing of the membranes according to the invention can be carried out according to different curing principles, ie thermally, radiation- and / or chemically induced, and according to customary methods. Optionally, the addition of conventional curing catalysts is required. The curing principles and methods are eg in the DE 401 1044 C2 . DE 4310733 A1 . DE 4405261 A1 . DE 4416857 C1 . DE 19627198 C2 and the DE 19627220 C2 described.

The membranes according to the invention are in single-phase as well as in two-phase design with and without porosity produced. The single-phase version finds its application especially where transparency is an important one Role play.

biphasic Membranes are obtained from systems that are immiscible, but form emulsions. Such systems can be used as fibers as well into films, e.g. by stirring one Made emulsion of immiscible components, this emulsion according to usual Methods are processed into membranes and in the curing of the resulting membrane hardens the immiscible components together. Another variant is to process systems in which it during the Synthesis for phase separation comes. Through these two-phase variants can membranes of the invention made of a stable organic-inorganic network, in a continuous, highly permeable second phase is incorporated.

The Production process of the membranes according to the invention is simple, economical and in a small space feasible. It is for the continuous production of hollow fibers and films are suitable and they are all common curing principles applicable. Due to the toxicological safety of the materials are the membranes of the invention Easily applicable in the medical field. The for different Applications often necessary surface modifications, e.g. to Prevention of blood coagulation, adjustment of polarity, adsorption behavior etc., can either already during the material synthesis, i. be carried out in situ, or subsequently. Such surface modifications are e.g. Coatings with heparin, with hydrophilic or hydrophobic Silanes, with fluorosilanes or with biomolecules.

The membranes according to the invention show high permeation values with high mechanical stability, too without porosity. Thus, self-supporting foils are still at high permeation values and hollow fibers can be produced without e.g. the danger of passage the fluid phase exists.

• • Variation der anorganischen und der organischen Strukturdichte
• • Variation des Gehalts an Dimethylsilan-Einheiten
• • Chemischer und physikalischer Einbau von anorganischen oder organischen vorgefertigten, hochpermeablen Monomeren, Oligomeren oder Polymeren
• • Silanisierung freier SiOH-Gruppen mit Trimethylsilyl-Einheiten

By the following exemplary modifications, the permeability of the membrane can be adapted to the requirements of the particular application.

• • Variation of inorganic and organic structure density
• Variation of the content of dimethylsilane units
• Chemical and physical incorporation of inorganic or organic preformed, highly permeable monomers, oligomers or polymers
• • Silanization of free SiOH groups with trimethylsilyl units

Variation of inorganic structural density

Without restricting the generality, the comparison of the following resin systems shows the influence of the inorganic structure density on O ₂ permeability, modulus of elasticity and strength of the resulting membranes. The results are summarized in tabular form. In general, it can be said that increasing the inorganic structure density leads to an increase in mechanical stability and a decrease in oxygen permeability.

At the Resin type 1 will be initially, according to the following Reaction scheme, glycerol-1,3-dimethacrylate and 3-Isocyanatopropyltriethoxysilane linked together.

The resulting silane becomes the structure of the inorganic network hydrolytically polycondensed, the 1,12-dodecanediol dimethacrylate before, while or after the polycondensation can be added. From the resulting Mixture be after usual Processes made membranes, when cured by polymerization the methacrylate groups from the polycondensate and the 1,12-dodecanediol dimethacrylate the organic network is built.

For resin type 2, first, according to the following reaction scheme, trimethylolpropane tri acrylate and the mercaptopropylmethyldimethoxysilane linked together.

The resulting silane becomes the structure of the inorganic network hydrolytically polycondensed. From the polycondensate are then according to usual Processes made membranes, when cured by polymerization the acrylate groups that organizes organic networks.

At the Resin Type 3 will be initially, according to the following Reaction scheme, the tris (2-hydroxyethyl) isocyanurate triacrylate and the mercaptopropylmethyldimethoxysilane linked together.

Subsequently, will to build up the inorganic network, the resulting silane hydrolytically polycondensed together with the tetraethoxysilane, and the membrane made therefrom by polymerization of Hardened acrylate groups.

At the Resin type 4 will be initially, in analogy to resin type 2, trimethylolpropane triacrylate and mercaptopropylmethyldimethoxysilane linked together. Subsequently the resulting silane, together with the dimethyldiethoxysilane, hydrolytically polycondensed, and the membrane made therefrom is cured by polymerization of the acrylate groups.

At the Resin type 5 will be initially, in analogy to resin type 2, trimethylolpropane triacrylate and mercaptopropylmethyldimethoxysilane linked together. Subsequently becomes the resulting silane, along with the dimethyldiethoxysilane and the methyltrimethoxysilane, hydrolytically polycondensed, and the membrane made therefrom by polymerization of the acrylate groups hardened.

In the resin type 6, first, in analogy to the resin type 2, the trimethylolpropane triacrylate and the mercaptopropylmethyldimethoxysilane are linked together. Subsequently, the resulting silane, too together with the Methyltri methoxysilane, hydrolytically polycondensed, and the membrane made therefrom is cured by polymerization of the acrylate groups.

At the same organic crosslinking potential, the high inorganic crosslinking potential of resin type 1 results in a higher modulus of elasticity compared to resin type 2, a higher bending strength and a reduced O ₂ permeation coefficient. Addition of the tetra-hydrolyzable and condensable tetraethoxysilane in the case of resin type 3 leads to an increase in the inorganic crosslinking density with respect to resin type 2, while at the same time reducing O ₂ permeability. The comparison of resin types 4, 5 and 6 shows that the replacement of methyl groups by the crosslinking potential-increasing alkoxy groups leads to a reduction of O ₂ permeability.

Variation of the organic Structure-dense silanization of SiOH groups and incorporation of permeation enhancing monomers

Without restricting the general public, the influence of the organic structure density on O ₂ permeability, modulus of elasticity and strength of the resulting membranes is shown by comparing other resin types. The results are summarized in tabular form. In general, it can be said that a reduction in the organic crosslinking potential causes a marked reduction in mechanical strength and an increase in O ₂ permeability. By silanization of SiOH groups and / or by the incorporation of reactive monomers, the O ₂ permeability of the membranes of the invention can be further increased.

As a rule, the polycondensates are not completely inorganically condensed, ie there are free ≡SiOH groups. These can be converted into ≡Si-O-Si (CH ₃ ) ₃ groups as part of a silanization, for example. This causes, on the one hand, a loosening of the overall structure of the membrane according to the invention and, on the other hand, an increase in the number of Si-O-Si groups which favor the O ₂ permeability. The silanization is monitored by recording the IR spectrum based on the disappearance of the remaining SiOH band.

The Preparation of resin type 2 membranes is under discussion of inorganic structure density.

At the Resin Type 7 will be initially, according to the following Reaction scheme, the 1.12-Dodecandioldimethacrylat and Mercaptopropylmethyldimethoxysilane linked with each other.

Subsequently, will the resulting silane hydrolytically polycondensed, and the resulting fabricated membrane is formed by polymerization of the methacrylate groups hardened.

At the Resin type 8 will be initially, according to the following Reaction scheme, after the polycondensation still existing SiOH groups of the resin type 7 silanized.

The made of membranes are obtained by polymerization of the methacrylate groups hardened.

at resin types 9 and 10 become the reactive monomers after silanization TRIS or TETRAKIS incorporated, and the resulting membranes are cured by polymerization of the methoxy groups.

With the same inorganic crosslinking of resin types 2 and 7, a reduction in the organic crosslinking potential of resin type 7 causes a marked reduction of the modulus of elasticity and an increase in permeation. Resin type 8 shows a further increase in O ₂ permeability as compared to resin type 7 as a result of silanization. Compared with the resin type 8, the addition of the reactive monomer TRIS in the resin type 9 causes the incorporation of O ₂ permeation-promoting end groups into the resulting membrane. Compared with the resin type 8, in the resin type 10, the addition of the crosslinking component TETRAKIS further increases the O ₂ permeability of the resulting membrane.

Incorporation of dimethylsiloxane structures

The O ₂ permeability of the resulting membrane is also increased, for example, by the incorporation of dimethylsiloxane structures. Without restriction of generality, the incorporation into the polycondensate takes place, for example, by co-condensation of, for example, dimethyldialkoxysilane, by addition of amino-terminated polydimethylsiloxane or by co-polymerization of acryloxy-terminated polydimethylsiloxane. The resulting range of variation of O ₂ permeation is three orders of magnitude.

at the following examples, whose results are tabulated, the incorporation of the dimethylsiloxane structures in the polycondensate by co-polymerization.

at resin types 11 to 15 are first, according to the following reaction scheme, Glycerol-1,3-dimethacrylate and 3-isocyanatopropyltriethoxysilane linked together.

The resulting silane then becomes the structure of the inorganic network either alone (resin type 11) or together with the dimethyldiethoxysilane (Resin type 12 to 15) hydrolytically polycondensed. From the polycondensate be after usual Methods manufactured membranes, when hardened by polymerization the methacrylate groups the organic network is built up.

• O₂-Permeabilität : x = cm³/cm·s·cmHg

In further embodiments, the incorporation of dimethylsiloxane units in the polycondensate is carried out by co-polycondensation with dimethyldiethoxysilane. The results are summarized in tabular form.

• O ₂ permeability: x = cm ³ / cm · s · cmHg

und anschließend mit dem Dimethyldiethoxysilan hydrolytisch polykondensiert. Das resultierende Polykondensat wird mit Trimethylpropan-tris(3-mercaptopropionat versetzt und zu Membranen verarbeitet, deren Härtung dann durch strahlungsinduzierte Polyaddition des Trimethylpropan-tris(3-mercaptopropionat an die C=C-Doppelbindungen der Norbornen-Reste erfolgt.First, the "norbornene silane" of resin types 16 to 19 is prepared according to the following reaction scheme.

and then polycondensed with the dimethyldiethoxysilane hydrolytically. The resulting polycondensate is treated with trimethylpropane tris (3-mercaptopropionate and processed into membranes, the curing then takes place by radiation-induced polyaddition of trimethylpropane tris (3-mercaptopropionate to the C = C double bonds of the norbornene radicals.

In the following examples, the incorporation of dimethylsiloxane units in the polycondensate by addition of aminopropyl-terminated polydimethylsiloxane with about 65 -Si (CH ₃ ) ₂ -O-segments (= DMS A 21). The results are summarized in tabular form.

At the Resin types 20 and 21 are first, according to the following Reaction scheme, the trimethylolpropane triacrylate and the mercaptopropylmethyldimethoxysilane linked together.

• • Das resultierende Silan wird zunächst zum Aufbau des anorganischen Netzwerkes hydrolytisch polykondensiert, und das Polykondensat wird dann mit dem Polydimethylsiloxan über die Addition von Acrylat- und Amino-Gruppen verknüpft.
• • Das resultierende Silan wird zunächst mit dem Polydimethylsiloxan über die Addition von Acrylat- und Amino-Gruppen verknüpft, und das Additionsprodukt wird dann zum Aufbau des anorganischen Netzwerkes hydrolytisch polykondensiert.

For the further processing of the resulting silane to the membranes of the invention, there are two variants:

• The resulting silane is first hydrolytically polycondensed to form the inorganic network, and the polycondensate is then linked to the polydimethylsiloxane via the addition of acrylate and amino groups.
• The resulting silane is first linked to the polydimethylsiloxane via the addition of acrylate and amino groups, and the addition product is then hydrolytically polycondensed to form the inorganic network.

The membrane made from the resulting polycondensate then becomes to build up the organic network by polymerizing the acrylate groups hardened, and the solvent is removed quantitatively.

• O₂-Permeabilität : x = cm³/cm·s·cmHg

In the following embodiment, dimethylsiloxane units are incorporated into the polycondensate by co-polymerization with a relatively short chain polydimethylsiloxane containing terminal acrylate groups and consisting of about 14 dimethylsiloxane units (PDMS U22 from ABCR). The results are shown in the following table.

• O ₂ permeability: x = cm ³ / cm · s · cmHg

First, in analogy to resin type 1, glycerol-1,3-dimethacrylate and 3-isocyanatopropyltriethoxysilane linked together. The resulting silane becomes the structure of the inorganic network hydrolytically polycondensed, the 1,12-dodecanediol dimethacrylate and / or the PDMS U22 before, during or can be added after the polycondensation. Then it will be through Co-polymerization of the acrylate and methacrylate groups the PDMS U22 chemically anchored in the polycondensate. From the resulting mixture be after usual Processes made membranes, when cured by polymerization the remaining methacrylate groups continue the organic network is built.

• O₂-Permeabilität : x = cm³/cm·s·cmHg

The following table summarizes the O ₂ permeabilities of silanized and non-silanized systems. It can be clearly seen that the silanization of free -OH units by, for example, trimethylsilyl units results in an increase in the O ₂ permeability.

• O ₂ permeability: x = cm ³ / cm · s · cmHg

reactants and preparation of resin types 2, 4 and 7 are in the variation of inorganic and organic structure density. The silanization of the polycondensates is carried out according to the following reaction scheme by reaction with trimethylchlorosilane.

Alternatively, the silanization can be carried out by adding hexamethyldisilazane (HMDS) to the tetrahydrofuran (THF) diluted batch under an argon atmosphere. As a result, free Si-OH groups are also converted to Si-CH ₃ groups.

The membranes made therefrom are by polymerization of the acrylate or methacrylate groups hardened. The silanization has no effect on the process parameters during spinning or film casting, provided it takes place immediately before further processing and thus does not affect the aging effect.

Exemplary embodiment of two-phase systems

At the Resin type 23 is first, as described for resin type 4, the trimethylolpropane triacrylate and the mercaptopropylmethyldimethoxysilane linked together. Subsequently, will the resulting silane, together with the dimethyldiethoxysilane, hydrolytically polycondensed. The resulting polycondensate is with immiscible with the amino-terminated polydimethylsiloxane, giving a biphasic Mixing system, which can be processed into milky-cloudy membranes whose hardening by polymerization of the acrylate groups.

The membranes according to the invention can be used for separation processes, for example in ultrafiltration or hyperfiltration technology, in dialysis, in gas separation, in gas permeation, in electrodialysis, in extracorporeal ventilation, as artificial blood vessels or in medical technology (eg as a replacement for PVC or Silicone hoses) can be used. The membranes according to the invention show an excellent permeation rate for O ₂ and CO ₂ , so that they are outstandingly suitable, for example, for use in oxygenators.

in the The following is the preparation of the membranes of the invention in concrete embodiments explained in more detail.

The embodiments 1 to 3 relate to the production of films and hollow fibers or Capillaries. These systems are highly cross-linked, non-porous and comparatively gas impermeable.

example 4 relates to a modification of one of the basic systems in the direction even lower gas permeability by the incorporation of tetraethoxysilane (TEOS).

Examples 5 to 10 relate to targeted modifications based on these systems towards increased gas permeability. As a measure of the gas permeability, the O ₂ permeability is indicated (unit Barrer = 10 ^-10 cm ³ (STP) / cm · s · cm Hg).

example 11 relates to the production of porous Structures and Examples 12 relates to pyrolysis of the membranes obtained microporous Systems.

• Example 1 starting materials: Glycerol-1,3-dimethacrylate 1 mol 3-isocyanatopropyltriethoxysilane 1 mol 1,12-dodecanediol 0.2 mol

The synthesis of the resin is carried out as in DE 195 36 498 A1 , Page 4, lines 15 to 62 described.

Hollow fiber production:

The resin mixed with a photoinitiator (eg 2% Irgacure 184, Ciba Geigy) (viscosity at processing temperature (10 ° C.) approx. 100 Pas) is extruded through an annular die (outer diameter approx. 1 mm, ring thickness approx. 0, 2 mm). By an N ₂ -purged second co-centric inner nozzle, the hollow fiber geometry is first stabilized until a combination of two UV radiation units (eg Blue-Point II, Fa. Hönle with an omnidirectional F 300, Fusion), the organic curing takes place spinning parameters Spinning temperature: 8 ° C Spinning pressure: 15 bar Withdrawal speed: 0.8 m / s

Subsequently, will the hollow fiber wound up. By varying the spinning parameters (spinning mass temperature, Pressure, take-off speed, gas flow rate through the inner channel) let yourself the fiber geometry vary widely. In the present Fall were the minimum fiber geometries achieved in continuous operation at about 50 microns outer diameter and about 10 microns Wall thickness. The biggest ones achieved Hollow fiber dimensions were about 2 mm outside diameter and 0.2 mm wall thickness.

film production

The with a photoinitiator (e.g., 1% Irgacure 184, Ciba Geigy) staggered resin is applied by means of a Spaltrakels on a highly polished Roll applied. After passing through a UV curing unit (eg UVAPRINT CM, Hönle) the foil detached and wound up. By varying the roller circulation speed, the roll temperature and gap height could in the present case set film thicknesses between about 30 microns and 200 microns become.

• properties O ₂ permeation coefficient [10 ^-10 cm ³ (STP) / cm • cm Hg]: 00:09 Modulus of elasticity [MPa]: 2640 Tensile strength [MPa]: 106 Example 2 starting materials: Trimethylolpropane triacrylate TMPTA) 1.2 (1) mol mercaptopropylmethyldimethoxysilane 1 mol

The synthesis of the resin is carried out as in DE 40 1 1 044 C2 in Example 1 on page 10, lines 28 to 50 described.

Fiber / film production:

The Fiber / film production takes place analogously to Example 1. The achieved minimum hollow fiber dimensions were about 350 microns outside diameter and 50 μm Wall thickness.

• properties O ₂ permeation coefficient [10 ^-10 cm ³ (STP) / cm • cm Hg]: 00:23 Modulus of elasticity [MPa]: 1520 Tensile strength [MPa]: 59 Example 3 starting materials: "Norbornene silane" 1 mol dimethyldiethoxysilane 2 mol Trimethylolpropane tris (3-mercaptopropionate) 0.47 mol

• The relationship SH groups: C = C double bonds is 0.71: 1

synthesis of the "norbornene silane"

As explained in the resin types 16 to 19 and as in the DE 196 27 198 C2 in Example 11 and 12 on page 34, line 42, to page 35, line 22 described.

Synthesis of the resin

After submission of 13.31 g (21.9 mmol) are weighed 6.49 (43.8 mmol) of dimethyldiethoxysilane and stirred at 30 ° C. For the hydrolysis and condensation, 2.76 g of water (corresponding to 2 H ₂ O per OR group) and catalyst are added. After about 28 h stirring at 30 ° C, the mixture is worked up after addition of ethyl acetate and shaking in water. The resulting resin exhibits a pronounced and controllable aging effect (increase in viscosity from 1000 to 3000 Pa · s within 20 days (25 ° C.) and good spinnability.) Shortly before being further processed into fibers / films, trimethylpropane tris (3-mercaptopropionate added.

fiber production

It were hollow tubes of approx. 1000 μm outer diameter and 100 μm Wall thickness and of high flexibility (80% elongation at break) produced.

Example 4

• With tetraethoxysilane (TEOS) -modified base systems starting materials: Tris (2-hydroxyethyl) isocyanurate triacrylate (SR 368) 1 mol mercaptopropylmethyldimethoxysilane 1 mol Tetraethoxysilane (TEOS) 0.5 mol Solvent: ethoxyethyl acetate 42.5% by weight

synthesis

to Submission of 155.6 g (0.37 mol) of SR 368 in 370 ml of ethoxyethyl acetate 66.34 g (0.37 mol) of mercaptopropylmethyldimethoxysilane under Protective atmosphere dropwise. Under cooling 23.95 g of an ethanolic KOH solution are slowly added dropwise. to Hydrolysis and condensation of the methoxy groups become 10.64 g of 0.5n HCl added dropwise. After 5 h stirring TEOS and 21.88g 0.12n HCl are added. After stirring for 20 h RT, the mixture is extracted by shaking with water, filtered and on a Solids content of 57.5 wt.% Rotated.

film production

In order to avoid cracking due to the shrinkage accompanying the polymerization, it was cured with very low radiation intensity (about 0.01 W / cm ² ). The solvent was removed as slowly as possible after curing.

properties

The Addition of the quadruple hydrolyzable and condensable TEOS causes across from the resin of Example 2 an increase the inorganic crosslinking potential with simultaneous reduction the oxygen permeability to a value of 0.07. Porosity due to solvent deprivation it could not be detected.

Example 5

Of the Exchange of a methyl group for one the networking potential increasing Alkoxy group leads to an increase the mechanical stability and simultaneous reduction of permeability.

• Resin A reactants: TMPTA 1 mol mercaptopropylmethyldimethoxysilane 1 mol dimethyldiethoxysilane 4 mol methyltrimethoxysilane O ₂ permeability [10 ^-10 cm ³ (STP) / cm • cm Hg] 11.5 Resin B starting materials: TMPTA 1 mol mercaptopropylmethyldimethoxysilane 1 mol dimethyldiethoxysilane 2 mol methyltrimethoxysilane 2 mol O ₂ permeability [10 ^-10 cm ³ (STP) / cm • cm Hg] 3.9 Resin C starting materials: TMPTA 1 mol mercaptopropylmethyldimethoxysilane 1 mol dimethyldiethoxysilane methyltrimethoxysilane 4 mol O ₂ permeability [10 ^-10 cm ³ (STP) / cm • cm Hg] 1.2

Synthesis of Resin A

to Presentation of 89.03 g (0.3 mol) trimethylpropane triacrylate (TMPTA) in 300 ml of ethyl acetate under argon atmosphere and ice cooling 54.15 g (0.3 mol) Mer captopropylmethyldimethoxysilan added. Subsequently are slowly added dropwise 19.55 g of an ethanolic KOH solution. After adding of 8.73 g of 0.5N HCl and stirring for 10 minutes 178.03 g (1.2 mol) of dimethyldiethoxysilane and 35.0 g of 0.12 n HCl added. After stirring for 23 h at RT, the mixture is extracted by shaking with water, filtered and on a Solids content of 89% evaporated.

The Synthesis of the resin variants B and C takes place completely analogously.

Example 6

Incorporation of O ₂ permeation-promoting crosslinkers (TETRAKIS).

The double-crosslinkable 1,3-bis (3-methacryloxypropyl) tetrakis (trimethylsiloxy) disiloxane (TETRAKIS) contributes to an increase in the organic crosslinking potential and at the same time increases O ₂ permeation, which is why it can also be combined with a low-crosslinking system.

• Resin A reactants: Dodecandiodimethacrylat 1 mol mercaptopropylmethyldimethoxysilane 1 mol O ₂ permeability [10 ^-10 cm ³ (STP) / cm • cm Hg]: 3 Resin B starting materials: Dodecandiodimethacrylat 1 mol mercaptopropylmethyldimethoxysilane 1 mol TETRAKIS 1/3 mol O ₂ permeability [10 ^-10 cm ³ (STP) / cm • cm Hg]: 20

Example 7

Installation of Dimethylsiloxane structures by condensation

The Integration of dimethylsiloxane structures by co-condensation of the precursor with dimethyldiethoxysilane is in wide ranges varriierbar. The resulting variation range of oxygen permeation is three orders of magnitude.

• Resin A reactants: Glycerol 1.3 dimethacrylate 1 mol isocyanatopropyltriethoxysilane 1 mol dimethyldiethoxysilane 0 mol O ₂ permeability [10 ^-10 cm ³ (STP) / cm • cm Hg]: 00:09 Resin B starting materials: Glycerol 1.3 dimethacrylate 1 mol isocyanatopropyltriethoxysilane 1 mol dimethyldiethoxysilane 4 mol O ₂ permeability [10 ^-10 cm ³ (STP) / cm • cm Hg]: 22 Resin C starting materials: Glycerol 1.3 dimethacrylate 1 mol isocyanatopropyltriethoxysilane 1 mol dimethyldiethoxysilane 6 mol O ₂ permeability [10 ^-10 cm ³ (STP) / cm • cm Hg]: 66 Resin D starting materials: Glycerol 1.3 dimethacrylate 1 mol isocyanatopropyltriethoxysilane 1 mol dimethyldiethoxysilane 8 mol O ₂ permeability [10 ^-10 cm ³ (STP) / cm • cm Hg]: 1 10 Resin E starting materials: Glycerol 1.3 dimethacrylate 1 mol isocyanatopropyltriethoxysilane 1 mol dimethyldiethoxysilane 10 mol O ₂ permeability [10 ^-10 cm ³ (STP) / cm • cm Hg]: 140

Synthesis of Resin C

to Initial charge of 66.4 g (0.29 mol glycerol-1,3-dimethacrylate and dibutyltin dilaurate (as the addition catalyst) under cooling 72.0 g (0.29 mol) of 3-Isocyanatopropyltriethoxysilan dropwise. After 21 h stirring 290 ml of ethyl acetate, 258.9 g (1.75 mol) of dimethyldiethoxysilane and 63. Added 3 g of water (including catalyst). After stirring for 6 d shaken with water, filtered, evaporated and the volatile Components on the oil pump Completely away. Solids content: 95.6%, viscosity after 1 h: 2.2 Pas (25 ° C).

The Synthesis of the resin variants A, B, D and E is completely analogous.

Example 8

installation of dimethylsiloxane structures by addition via amino-terminated amino-terminated polydimethylsiloxane DMS A 21 (Gelest) is by reaction of the amino groups with the Added acrylate groups of the system of Example 2.

• Resin A reactants: Resin system from example 2 1 mol DMS A 21 0.03 mol O ₂ permeability [10 ^-10 cm ³ (STP) / cm • cm Hg]: 19 Resin B starting materials: Resin system from example 2 1 mol DMS A 21 0.09 mol O ₂ permeability [10 ^-10 cm ³ (STP) / cm • cm Hg]: 160 Modulus of elasticity [MPa] 210 Bending strength [MPa] 25

The solvent n-butyl acetate was cured after curing removed quantitatively.

Example 9

• Edukte : System aus Beispiel 1 8 mol Acryloxy-terminiertes Polydimethylsiloxan PDMS U22 1 mol entsprechend 1.5 DMS-Einheiten pro Basiseinheit.

Incorporation of dimethylsiloxane structures by co-polymerization of acryloxy-terminated polydimethylsiloxane PDMS U22 (ABCR) The relatively short-chain, containing about 14 polydimethylsiloxane units PDMS U22 the company ABCR is in any mixing ratio z. B. miscible with system of Example 1. This system remained spinnable to a molar ratio of about 8: 1 to hollow fibers.

• Starting materials: System of Example 1 8 mol Acryloxy-terminated polydimethylsiloxane PDMS U22 1 mol corresponding to 1.5 DMS units per base unit.

Example 10

generation of porosities in hollow fibers

The Bifurcation of the organic curing process at the hollow fiber manufacturing in an initially incomplete, only Form preservative pre-hardening immediately below the spinneret exit and the subsequent one full curing in a UV omnidirectional provides a possibility of pore generation in UV-curing, solventborne Systems.

The System of Example 1 was diluted with 20% solvent (ethyl acetate), without adverse influence the spinnability. After addition of 2% of the UV starter Irgacure 184 the system became a hollow thread according to the method described extruded (spinning parameters: spinning pressure = 8 bar, filament temperature = 5 ° C, Withdrawal speed = 0.8 m / s). After pre-hardening with a UV lamp of low power (Blue Point II, Fa. Hönle) about 5 mm below the spinneret the hollow fiber is still sticky, but already dimensionally stable. By heating with an IR emitter becomes the solvent expelled before it is completely cured in the UV omnidirectional. The result is a porous one Hollow fiber.

Example 11

generation a microporous, silicate hollow fiber In the material of the membranes according to the invention are at the molecular level inorganic Si-O-Si units with organic combined polymerized carbon units. After the removal the organic portion, e.g. from an inorganic highly crosslinked hollow fiber according to the invention By pyrolysis and oxidation, a microporous hollow fiber with a narrow Pore radius distribution obtained.

• Starting materials: Glycerol 1.3dimethacrylat 1 mol 3-isocyanatopropyltriethoxysilane 1 mol Tetraethoxysilane (TEOS) 0.5 mol

The TEOS-modified resin system was prepared by the method described processed into hollow fibers.

• spinning parameters spinning pressure 18 bar Filament temperature 45 ° C off speed 0.3 m / s

Hollow fibers of 231 μm outside diameter and 36 μm wall thickness were obtained. These hollow fibers were pre-pyrolyzed in a tube furnace by slow heating to 650 ° C, first in a nitrogen atmosphere, then cooled and completely oxidized by reheating to 650 ° C in air. The result was hollow fiber structures of 126 μm outside diameter and 20 μm wall thickness. The determination of the porosity by nitrogen adsorption gave a BET surface area of 300 to 800 m ² / g and the micro pore analysis showed an average pore radius of <1 nm.

Claims (29)

Semipermeable membrane, obtainable by processing a slightly viscous to resinous liquid by conventional methods to form a membrane, that the membrane is optionally dried and then cured thermally and / or radiation-induced and / or chemically induced, wherein the liquid has been obtained a) by hydrolytic polycondensation of one or more compounds of general formula I,

in which the radicals and indices have the following meanings: R = alkyl, alkenyl, aryl, alkylaryl or arylalkyl having in each case 1 to 15 carbon atoms, these radicals being oxygen and / or sulfur atoms and / or ester and / or carbonyl and / or carboxyl and / or amide and / or amino groups, R ¹ = alkylene, arylene, arylenealkylene or arylenealkylene each having 0 to 15 carbon atoms, these radicals being oxygen and / or sulfur atoms and / or may contain ester and / or carbonyl and / or carboxyl and / or amide and / or amino groups, R ² = alkylene, arylene, arylenealkylene or arylenealkylene each having 0 to 15 carbon atoms, these being Radicals may contain oxygen and / or sulfur atoms and / or ester and / or carbonyl and / or carboxyl and / or amide and / or amino groups, R ³ = hydrogen, R ² -R ¹ -R ⁴ -SiX _x R _3-x , carboxyl, alkyl, alkenyl, aryl, alkylaryl or arylalkyl having in each case 1 to 15 carbon atoms, where these radicals May contain oxygen and / or sulfur atoms and / or ester and / or carbonyl and / or carboxyl and / or amide and / or amino groups, R ⁴ = - (CHR ⁶ -CHR ⁶ ) _n - , with n = 0 or 1, -CHR ⁶ -CHR ⁶ -SR ⁵ -, -CO-SR ⁵ -, -CHR ⁶ -CHR ⁶ -NR ⁶ -R ⁵ -, -Y-CS-NH-R ⁵ - , -SR ⁵ , -Y-CO-NH-R ⁵ -, -CO-OR ⁵ -, -Y-CO-C ₂ H ₃ (COOH) -R ⁵ -, -Y-CO-C ₂ H ₃ ( OH) -R ⁵ - or -CO-NR ⁶ -R ⁵ -, R ⁵ = alkylene, arylene, arylenealkylene or arylenealkylene each having 1 to 15 carbon atoms, where these radicals oxygen and / or sulfur atoms and / or May contain ester and / or carbonyl and / or carboxyl and / or amide and / or amino groups, R ⁶ = hydrogen, alkyl or aryl having 1 to 10 carbon atoms, R ⁷ = hydrogen, alkyl, alkenyl , Aryl, alkylaryl or arylalkyl having in each case 1 to 15 carbon atoms, these radicals being oxygen and / or sulfur atoms and / or ester and / or carbonyl and / or carboxyl and / or amide and / or amino Groups may contain, X = hydrogen f, halogen, hydroxy, alkoxy, acyloxy, alkylcarbonyl, alkoxycarbonyl or NR " ₂ , with R" = hydrogen, alkyl or aryl, Y = -O-, -S- or -NR ⁶ -, Z = -O- or - (CHR ⁶ ) _m -, where m = 1 or 2, a = 1, 2 or 3, where b = 1 for a = 2 or 3, b = 1, 2 or 3, where a = 1 for b = 2 or 3, c = 1 to 6, x = 1, 2 or 3, with a + x = 2, 3 or 4, and / or • one or more compounds of general formula II,

in which the radicals and indices have the following meaning: B = a straight-chain or branched organic radical having at least one C =C double bond and 4 to 50 carbon atoms, R =alkyl, alkenyl, aryl, alkylaryl or arylalkyl, each having 1 to 15 Carbon atoms, these radicals may contain oxygen and / or sulfur atoms and / or ester and / or carbonyl and / or carboxyl and / or amide and / or amino groups, R ³ = alkylene, arylene , Arylenalkylen or Alkylenarylen each having 0 to 10 carbon atoms, where these radicals may be interrupted by oxygen and / or by sulfur atoms and / or by amino groups, X = hydrogen, halogen, hydroxy, alkoxy, acyloxy, alkylcarbonyl , Alkoxycarbonyl or NR " ₂ , with R" = hydrogen, alkyl, aryl or alkylaryl, A = O, S or NH for d = 1 and Z = CO and R ¹ = alkylene, arylene or alkylenearylene each having 1 to 10 Carbon atoms, where these radicals are represented by oxygen and / or by sulfur atoms and / or may be interrupted by amino groups, and R ² = COOH or H, or A = O, S, NH or COO for d = 1 and Z = CHR ', where R' = H, alkyl, aryl or alkylaryl, and R ¹ = alkylene, arylene or Alkylenarylen each having 1 to 10 carbon atoms, where these radicals may be interrupted by oxygen and / or by sulfur atoms and / or by amino groups, and R ² = OH, or A = O, S, NH or COO for d = 0 and R ¹ = alkylene, arylene or alkylenearylene having in each case 1 to 10 carbon atoms, where these radicals are interrupted by oxygen and / or by sulfur atoms and / or by amino groups and R ² = OH, or A = S for d = 1 and Z = CO and R ¹ = N and R ² = H, a = 1, 2 or 3, b = 0, 1 or 2, with a + b = 3, c = 1, 2, 3 or 4, and / or • one or more compounds of general formula III, {X _a R _b Si (R'A) _c ] _(4-ab) } _x B (III) in which the radicals and indices have the following meaning: A = O, S, PR ", POR", NHC (O) O or NHC (O) NR ", B = straight-chain or branched organic radical which differs from a Compound B 'with at least one (for c = 1 and A = NHC (O) O or NHC (O) NR ") or at least two C = C double bonds and 5 to 50 carbon atoms derived, R = alkyl, Alkenyl, aryl, alkylaryl or arylalkyl having in each case 1 to 15 carbon atoms, these radicals being oxygen and / or sulfur atoms, and / or ester and / or carbonyl and / or carboxyl and / or amide and / or or amino groups, R '= alkylene, arylene or alkylenearylene, R "= hydrogen, alkyl, aryl or alkylaryl, X = hydrogen, halogen, hydroxy, alkoxy, acyloxy, alkylcarbonyl, alkoxycarbonyl or NR" ₂ , a = 1, 2 or 3, b = 0, 1 or 2, c = 0 or 1, x = an integer whose maximum value corresponds to the number of double bonds in the compound B 'minus 1, or equal to the number of double bonds in the compound B', if c = 1 and A is NHC (O) O or NHC ( O) NR '', wherein the above alkyl or alkenyl radicals are optionally substituted straight-chain, branched or cyclic radicals having 1 or 2 to 20 carbon atoms, aryl is optionally substituted phenyl, naphthyl or biphenyl and the above alkoxy, acyloxy, alkylcarbonyl, alkoxycarbonyl, alkylaryl, arylalkyl, arylene, alkylene and Alkylenaryl radicals derived from the above-defined alkyl and aryl radicals, and / or • one or more compounds of the general Formula IV, Y _a SIX _x R _4-ax (IV) in which the radicals and indices have the following meanings: R = alkyl, alkenyl, aryl, alkylaryl or arylalkyl having in each case 1 to 15 carbon atoms, these radicals being oxygen and / or sulfur atoms and / or ester and / or carbonyl and / or carboxyl and / or amide and / or amino groups, X is hydrogen, halogen, hydroxyl, alkoxy, acyloxy, alkylcarbonyl, alkoxycarbonyl or NR '' ₂ , with R '' = hydrogen, alkyl, Aryl or alkylaryl, Y = organic radical having 1 to 30, preferably having 1 to 20 carbon atoms, and having 1 to 5, preferably having 1 to 4 mercapto groups, a = 1, 2 or 3, x = 1, 2 or 3, with a + x = 2, 3 or 4, and / or • precondensates derived from the compounds of the formulas I to IV and, if appropriate, • one or more compounds of the general formula V, X _a SiR _4-a (V) in which the radicals and indices have the following meanings: R = alkyl, alkenyl, aryl, alkylaryl or arylalkyl having in each case 1 to 15 carbon atoms, these radicals being oxygen and / or sulfur atoms and / or ester and / or carbonyl and / or carboxyl and / or amide and / or amino groups, X is hydrogen, halogen, hydroxyl, alkoxy, acyloxy, alkylcarbonyl, alkoxycarbonyl or NR '' ₂ , with R '' = hydrogen, alkyl, Aryl or alkylaryl, a = 1, 2 or 3, and / or precondensates derived therefrom, wherein the hydrolytic polycondensation is carried out by adding water or moisture and optionally in the presence of a solvent and / or a condensation catalyst, and wherein, based on the Monomers, the molar ratio of the sum of the compounds of the formulas I, II, III and IV to compounds of the formula V is between 1: 0 and 1:20, and optionally b) by addition of one or more copolymerisable and / or (poly) adding barer monomers and / or oligomers, • and / or one or more curing catalysts, • and / or one or more pore-forming additives. Semipermeable membrane according to claim 1, obtainable thereby, that he the liquid to flat membranes or tubular Membranes processed. Semipermeable membrane according to claim 1 or 2, characterized characterized in that they yourself on a carrier located. Semipermeable membrane according to one or more of claims 1 to 3, characterized in that they consist of a liquid which contains polycondensates which differ from one or more derive several compounds of formula I, in which the indices a and / or b and / or c have the value = 1. Semipermeable membrane according to one or more of claims 1 to 4, characterized in that they consist of a liquid which contains polycondensates which differ from one or more derive several compounds of formulas II and / or III, in which the radical B is one or more acrylate and / or methacrylate groups having. Semipermeable membrane according to one or more of claims 1 to 5, characterized in that it has been obtained from a liquid containing polycondensates derived from one or more compounds of formula IV ', [(HS-R ⁵ ) _n R ⁶ -SER ⁵ ] _a SiX _x R ₄ -ax (IV ') in which the radicals and indices have the following meaning: E = -CO-NH-, -CS-NH-, -CH ₂ -CN ₂ - or -CN ₂ -CH (OH) -R = as defined in claim 1; R ⁵ = alkylene, arylene, arylenealkylene or arylenealkylene having in each case 1 to 15 carbon atoms, where these radicals are represented by oxygen and / or by sulfur atoms and / or by ester and / or by carbonyl and / or by carboxyl and / or may be interrupted by amide and / or by amino groups; R ⁶ = alkylene, arylene, arylenealkylene or arylenealkylene each having 1 to 15 carbon atoms, where these radicals are represented by oxygen and / or by sulfur atoms and / or by ester and / or by carbonyl and / or by carboxyl and / or may be interrupted by amide and / or by amino groups; X = as defined in claim 1; a = as defined in claim 1; n = 2, 3, 4 or 5; x = as defined in claim 1; Semipermeable membrane according to one or more of claims 1 to 6, characterized in that they consist of a liquid has been obtained containing one or more organic compounds with one or more mercapto groups contains. Semipermeable membrane according to one or more of claims 1 to 7, characterized in that they consist of a liquid has been obtained containing one or more organic compounds containing one or more C = C double bonds. Semipermeable membrane according to claim 8, characterized in that that she from a liquid has been obtained, the polycondensates and / or oligocondensates contains which have one or more C = C double bonds and which are of organically modified, hydrolytically condensable silanes derived. Semipermeable membrane according to one or more of claims 1 to 9, characterized in that they consist of a liquid has been obtained containing one or more organic compounds with one or more substituted and / or unsubstituted Contains amino groups. Semipermeable membrane according to claim 10, characterized characterized in that they obtained from a liquid containing polycondensates and / or oligocondensates which one or more substituted and / or unsubstituted amino groups which are different from organically modified, hydrolytic Derive condensable silanes. Semipermeable membrane according to one or more of claims 1 to 1 1, characterized in that they consist of a liquid has been obtained, the one or as pore-forming additives several salts and / or one or more liquids and / or one or a plurality of blowing agents and / or one or more porous fillers contains. Semipermeable membrane according to claim 12, characterized available, that after hardening the pore-forming additives dissolved out of the membrane and / or be removed by thermal treatment. Semipermeable membrane according to one or more of claims 1 to 13, obtainable thereby, that after hardening the organic components are removed by thermal cracking. Process for the preparation of semipermeable membranes according to one or more of Claims 1 to 14, characterized in that a) by hydrolytic condensation of one or more compounds of general formula I

in which the radicals and indices are defined as in claim 1, and / or • one or more compounds of general formula II

in which the radicals and indices are defined as in claim 1, and / or • one or more compounds of general formula III {X _a R _b Si [(R'A) _c )] _(4-ab) } _x B (III) in which the radicals and indices are as defined in claim 1, and / or • one or more compounds of general formula IV, Y _a Si _x R _{4 -ax} (IV) in which the radicals and indices are as defined in claim 1, and / or • precondensates derived from compounds of the formula I to IV and, if appropriate, • one or more compounds of the general formula V, X _a SiR _4-a (V) in which the radicals and indices are as defined in claim 1, by addition of water or moisture and optionally in the presence of a solvent and / or a condensation catalyst and wherein, based on the monomers, the molar ratio of the sum of the compounds of the formulas I, II and III to compounds of the formula IV is between 1: 0 and 1:20, and optionally b) by addition of • one or more copolymerizable and / or (poly) addable monomers and / or oligomers, • and / or one or more curing catalysts, • and / or one or more, soluble and / or volatile, pore-forming additives manufactures a low-viscosity to resinous liquid, that these are processed by conventional methods to a membrane that this membrane is optionally dried and then thermally and / or radiation-induced and / or chemically induced cures. Method according to claim 15, characterized in that that he the liquid to flat membranes or tubular Membranes processed. Method according to claim 15 or 16, characterized that he the membrane on a support manufactures. Method according to one or more of claims 15 to 17, characterized in that one liquid used, which contains polycondensates, which differ from one or derive several compounds of formula I, in which the indices a and / or b and / or c have the value = 1. Process according to one or more of claims 15 to 18, characterized in that one uses a liquid containing polycondensates derived from one or more compounds of the Derive formulas II and / or III, in which the radical B contains one or more acrylate and / or methacrylate groups. Process according to one or more of Claims 15 to 19, characterized in that a liquid is used which contains polycondensates which are derived from one or more compounds of the formula IV ', [(HS-R ⁵ ) _n R ⁶ -SER ⁵ ] _a SiX _x R ₄ -ax (IV ') in which the radicals and indices are defined as in claim 6. Method according to one or more of claims 15 to 20, characterized in that one has a liquid used one or more organic compounds with a or more mercapto groups. Method according to one or more of claims 15 to 21 characterized in that one a liquid used one or more organic compounds with a or more C = C double bonds. Method according to claim 22, characterized in that that he a liquid used, the polycondensates and / or oligocondensates containing a or have multiple C = C double bonds and are different from organic derived modified, hydrolytically condensable silanes. Method according to one or more of claims 15 to 23, characterized in that one has a liquid used one or more organic compounds with a or more substituted and / or unsubstituted amino groups contains. Method according to Claim 24, characterized that he a liquid used, which contains polycondensates and / or oligocondensates, the one or more substituted and / or unsubstituted amino groups which are different from organically modified, hydrolytic Derive condensable silanes. Method according to one or more of claims 15 to 25, characterized in that a liquid used as the pore-forming additives one or more salts and / or one or more liquids and / or one or more propellants and / or one or more porous fillers contains. Method according to claim 26, characterized in that that after hardening the pore-forming additives dissolved out of the membrane and / or be removed by thermal treatment. Method according to one or more of claims 15 to 27, characterized in that after hardening the organic components are removed by thermal cracking. Use of the membranes according to one or more the claims 1 to 15 for Separation processes, in particular for the gas separation, for the reverse osmosis, for electrodialysis, for Dialysis, for the pervaporation, for the micro, ultra and Hyperfiltration.