DE19846608A1 - 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: [Image] 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 1>, R 2>0-15C alkylene, arylene or arylenealkylene, optionally containing O and/or S atoms and/or ester, carbonyl, carboxyl, amide and/or amino groups; R 3>H, R 2>-R 1>-R 4>-SiX xR 3-x, COOH or R; R 4>(CHR 6>-CHR 6>) n, CHR 6>-CHR 6>-S-R 5>, CO-S-R 5>, CHR 6>-CHR 6>-NR 6>-R 5>, Y-CS-NH-R 5>, S-R 5>, Y-CO-NH-R 5>, CO-O-R 5>, Y-CO-C 2H 3(COOH)-R 5>, Y-CO-C 2H 3(OH)-R 5>or CO-NR 6>-R 5>; n : 0 or 1; R 5>1-15C alkylene, arylene or arylenealkylene, optionally containing O and/or S atoms and/or ester, carbonyl, carboxyl, amide and/or amino groups; R 6>H or 1-10C alkyl or aryl; R 7>H or R; Y : O, S or NR 6>; Z : O or (CHR 6>) 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-R 1>(R 2>)-R 3>-SiX aR b] 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; R 3>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 NR 2; 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; R 1>Q or N; Q : 1-10C alkylene, arylene or alkylenearylene, optionally interrupted by O and/or S atoms and/or amino groups; R 2>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, R 1>= Q and R 2>= H or COOH; (b) A = O, S, NH or COO when d = 1, Z = CHR', R 1>= Q and R 2>= OH; (c) A = O, S, NH or COO when d = 0, R 1>= Q and R 2>= OH; and (d) A = S when d = 1, Z = CO, R 1>= N and R 2>= H. {X aR bSi[(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 NR 2; 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. Y aSiX xR 4-a-x(IV) 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; X : H, halogen, OH, alkoxy, acyloxy, alkanoyl, alkoxycarbonyl or NR 2; R : H, alkyl, aryl or alkaryl; Y : an organic group with 1-30 C atoms and 1-5 SH groups; a, x : 1-3; a+x : 2-4. X aSiR 4-a(V) 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; X : H, halogen, OH, alkoxy, acyloxy, alkanoyl, alkoxycarbonyl or NR 2; R : H, alkyl, aryl or alkaryl; a : 1-3. An independent claim is also included for a semipermeable membrane obtainable by such a process.

Description

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 gas separation, in dialysis, in pervaporation, as well as in micro-, and hyperfiltration. The membranes of the invention provide Flachmembra nen or tubular membranes.

For the separation of mixtures of substances are a variety of membrane materials known, all in terms of their technical operational capability and their host ability to improve. So are known membrane materials, such as z. As cellulose acetate, little temperature and pressure resistant and swell in or ganic solvents. The low temperature, pressure and Lösungsmit telbeständigkeit has the consequence that the pore size in technical use constantly changing and thus to non-reproducible results and too short zen life of the membranes can lead.

Ultrafiltration z. B. are mainly carried out in aqueous systems, so that the mechanical and thermal stability (Sterilisierbarkeit to 140 ° C) of the used for these membranes, whose resistance to acids and Alkalis and their specifically adjustable hydrophilic / hydrophobic properties particularly high demands are made. The previously to the membrane manufacturer The polymers used can not fulfill these requirements simultaneously len and show z. B. with relatively good thermal stability up to about 140 ° C. no adequate mechanical stability.

Often necessary surface modifications for different applications (Adjustment of porosity, the adsorption behavior, etc.) require more after sustainable processes. Furthermore, such modified materials have the disadvantage that  they have only a modified monolayer on the surface, so that they extremely sensitive to mechanical and chemical agents are.

Commercially available polymers such. As polyethylenes, polypropylenes, polysulfones, polyimides, polymethacrylates etc. have only a low gas permeability (eg, GE compared O ₂ , CO _2, etc.). A permeation increase based on these types of polymer is possible only by incorporation of a porosity. For example, provided with a defi ned, 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 z. B. used for gas exchange in fluid systems, there is a risk 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 hazard potential. Especially during longer operations, a passage of blood through the pores is often observed.

Very high gas permeation values without porosity are only possible with very specific Po lymeren (silicones, substituted Polysilylpropine etc.) feasible. The high gas permeability is however only by extreme losses with the mechani achieved properties. With increasing permeability, the strength decreases and the modulus of elasticity, d. H. The material is getting softer. Unsupported thin films and stable hollow fibers with low wall thickness are therefore not possible. Films and hollow fibers with a per over wide ranges adjustable Per Meability is only possible on the basis of very different types of polymers possible with different production methods.

Membranes based on silicic acid heteropolycondensates show a excellent resistance to acids and organic solvents and are also quite stable in the pH range up to about 10.

From DE 27 58 415 C2 it is known to porous zeolite polycondensates to Porö to process membranes by accumulating them in compact blocks mechanically cut the polycondensates to very thin slices, which then used directly or after previous grinding as membranes. Because the Silica heteropolycondensates, however, are generally not elastic enough,  The membrane discs break when cutting, and also the necessary Membrane surface is usually not reached by this method.

In DE 29 25 969 C2 another method for the preparation of porous meme based on silica hetero-polycondensates at the interface an organic and an aqueous phase described. As the resulting However, membranes are very watery due to contact with an aqueous phase are present, there is a risk of excessive shrinkage during drying and an associated cracking. The hydrolytic polycondensation of Starting components to silica heteropolycondensates is Sub punch exit, so that it inevitably leads to a shrinkage of the polycondensates comes.

In the described in DE 27 58 415 C2 and in DE 29 25 969 C2 Membra The shaping of the membrane and the hardening of the membrane take place an inorganic condensation, d. H. by building a Si-O-Si network. These membranes show very poor mechanical properties that me chanical stabilities seldom meet the demands placed on them. In addition, these membranes are brittle and not flexible.

From EP 0094060 B1 is another method for the production of membranes on the basis of silicic acid heteropolycondensates known. This is the Po lykondensation performed on the surface of a support, which is the membrane supports. The shaping of the membrane and the curing of the membrane also takes place here by inorganic condensation, d. H. by building a anorgani network. The resulting membranes are carrier supported and not self-supporting.

Object of the present invention is semipermeable membranes for the Gas exchange and provide for substance separations, their exchange capacity varies widely and the needs of the particular application case is adapted. Furthermore, the membranes should not only support supported, son They should also be cantilevered, and they should as a tubular membrane or as Flat membranes present. The permeability and flexibility of the membranes should varies over a wide range and the requirements of the respective user Be adapted case of application. Furthermore, the membranes at high mechanical  Stability show high permeabilities, especially with respect to gases, so that these membranes also for the gas exchange and for substance separations can be used without the risk of passage of the fluid phase consists. Even at high permeation levels, the membranes are still freitra be low. The membranes should be toxicologically safe and thus in me be applicable to the medical field.

It is another object of the present invention to provide a method, can be made with the semipermeable membranes whose own profile can be varied within a wide range. By simple variation of Ver The chemical and physical properties of the Membrane in wide ranges to the requirements of the respective application case can be adapted. The process should be simple, fast and cost be low feasible. With the method membranes are made who those who meet the above requirements. Furthermore, should the process also for the endless production of hollow fibers and Flachmembra be suitable. In addition, they are often used for various applications required surface modifications, eg. B. to avoid blood coagula tions, for adjusting the polarity, the adsorption behavior, etc., both elect during material synthesis, d. H. in situ, as well as subsequently realized can.

This object is achieved by membranes which are obtainable by that a low viscosity to resinous liquid by conventional methods Membranes processed and this dries if necessary. The hardening of the re sultierenden membranes can, for. B. thermally and / or radiation-induced and / or chemically induced.

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

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

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

The liquid used to prepare the membranes of the invention or the resin used so make a polycondensate of hydrolytic condenses silicon compounds of the formulas I and / or II and / or III and / or IV and optionally V, wherein the polycondensate optionally still What and / or solvents and / or the above-mentioned additives. In Depending on the viscosity of the polycondensate can be one more or less viscous liquid or talk of a resin.  

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 with in each case 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 may contain.
R ² = alkylene, arylene, arylenealkylene or arylenealkylene with in each case 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 may contain.
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, these radicals being oxygen and / or 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 with 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 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 -, with 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 described in detail in DE 196 27 198 C2. On the Revelation of DE 196 27 198 C2 is hereby incorporated by reference. In preferred embodiments of the membranes of the invention are organically modified silanes of the general formula I and / or derived therefrom used precondensates in which the indices a and / or b and / or c assume the value 1.

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 alkylenorylene having in each case 0 to 10 carbon atoms, these radicals being 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
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 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 = 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 described in detail in DE 44 16 857 C1. On the Revelation of DE 44 16 857 C1 is hereby incorporated by reference. In be Preferred embodiments of the membranes of the invention are or ganically modified silanes of the general formula II and / or derived therefrom te pre-condensates used in which the alkyl and / or alkylene and / or alk oxy groups have 1 to 4 carbon atoms. In another preferred embodiment In other 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 above alkyl or alkenyl radicals are optionally substituted straight chain ge, 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 alkylenearyl radicals are derived from the above-defined alkyl and aryl residues.

Organically modified silanes of the general formula III, their preparation and concrete examples are described in detail in DE 40 11 044 C2. On the Revelation of DE 40 11 044 C2 is hereby incorporated by reference. In be Preferred embodiments of the membranes according to the invention are sila ne of the general formula III and / or precondensates derived therefrom set in which the radical B one or more acrylate and / or methacrylate Has 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, for. B. straight-chain, branched or cyclic radicals having 1 to 20, in particular having 1 to 10 carbon atoms, and preferably lower alkyl Re ste with 1 to 6, particularly preferably with 1 to 4 carbon atoms. Special case 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 z. B. straight-chain, branched or cyclic radicals having 2 to 20, preferably 2 to 10 carbon atoms and preferably lower alkenyl radicals having 2 to 6 carbon atoms substance atoms, such as. 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 are preferably derived from the abovementioned alkyl and aryl radicals. Specific examples are methoxy, Ethoxy, n- and i-propoxy, n-, i-, s- and t-butoxy, monomethylamino, monoethyla mino, dimethylamino, diethylamino, N-ethylanilino, acetyloxy, propionyloxy, Me  thylcarbonyl, ethylcarbonyl, methoxycarbonyl, ethoxycarbonyl, benzyl, 2-phenyls methyl and tolyl.

The radicals mentioned may optionally bear one or more substituents, for. B. halogen, alkyl, hydroxyalkyl, alkoxy, aryl, aryloxy, alkylcarbonyl, alk oxycarbonyl, 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 with 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 with 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;
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 described in detail in DE 196 27 220 C2. On the Revelation of DE 196 27 220 C2 is hereby incorporated by reference.

In the general formula V, the radicals and indices have the following meaning, wherein in 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, for. B. straight-chain, branched or cyclic radicals having 1 to 20, in particular having 1 to 10 carbon atoms, and preferably lower alkyl Re ste with 1 to 6, particularly preferably with 1 to 4 carbon atoms. Special case 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 z. B. straight-chain, branched or cyclic radicals having 2 to 20, preferably 2 to 10 carbon atoms and preferably lower alkenyl radicals having 2 to 6 carbon atoms substance atoms, such as. 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 are preferably derived from  the abovementioned alkyl and aryl radicals. Specific examples are methoxy, Elhoxy, n- and i-propoxy, n-, i-, s- and t-butoxy, monomethylamino, monoethyla mino, dimethylamino, diethylamino, N-ethylanilino, acetyloxy, propionyloxy, Me thylcarbonyl, ethylcarbonyl, methoxycarbonyl, ethoxycarbonyl, benzyl, 2-phenyls methyl and tolyl.

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

Silanes of the general formula V are either available in the hand or leave can be prepared by known methods, the z. In "chemistry and technology the Silicone ", W. Noll, Verlag Chemie GmbH, Weinheim / Bergstrasse (1968), be are written.

Without restriction of generality, concrete examples of silanes of the general formula V are:
CH ₃ -Si-Cl ₃ , CH ₃ -Si (OC ₂ H ₅ ) ₃ , C ₂ H ₅ -Si-Cl ₃ , C ₂ H ₅ -Si (OC ₂ H ₅ ) ₃ , CH ₂ = CH -Si- (OC ₂ H ₅ ) ₃ ,
CH ₂ = CH-Si- (OC ₂ H ₄ OCH ₃ ) ₃ , (CH ₃ ) ₂ -Si-Cl ₂ , CH ₂ = CH-Si- (OOCCH ₃ ) ₃ , (CH ₃ ) ₂ -Si- ( OC ₂ H ₅ ) ₂ ,
(C ₂ H ₅ ) ₃ -Si-Cl, (C ₂ H ₅ ) -Si- (OC ₂ H ₅ ) ₂ , (CH ₃ ) ₂ (CH ₂ = CH) -Si-Cl ₂ , (CH ₃ ) ₃ -Si-Cl,
(tC ₄ H ₉ ) (CH ₃ ) ₂ -Si-Cl, (CH ₃ O) ₃ -Si-C ₃ H ₆ -NH-C ₂ H ₄ -NH-C ₂ H ₄ -NH ₂ , (CH ₃ O) ₃ -Si-C ₃ H ₆ -SH,
(CH ₃ O) ₃ -Si-C ₃ H ₆ -NH-C ₂ H ₄ -NH ₂ , (CH ₃ O) ₃ -Si-C ₃ H ₆ -Cl, (CH ₃ ) ₂ (CH ₂ = CH -CH ₂ ) -Si-Cl,
(CH ₃ O) ₃ -Si-C ₃ H ₆ -OC (O) -C (CH ₃ ) = CH ₂ , (C ₂ H ₅ O) ₃ -Si-C ₃ H ₆ -NH ₂ , (C ₂ H ₅ O) ₃ -Si-C ₃ H ₆ -CN,

The silanes of the general formulas I, II, III, IV, IV 'and V are hy above the radicals X. drolyzable and polycondensable, and by the hydrolytic polycondensation  On an inorganic network is built with Si-O-Si bridges. The Polykon Densification is preferably carried out by the sol-gel method, as z. Tie DE-A1 27 58 414, 27 58 415, 30 11 761, 38 26 715 and 38 35 968 is described. The poly condensation is carried out in the usual way in this field, by z. B. to be hydrolyzed silicon compounds, either as such or dissolved in a solvent, the required water at Room temperature or with gentle cooling directly (preferably below Stirring and in the presence of a hydrolysis and condensation catalyst) and The resulting mixture then stirs for some time (one to several hours). In the presence of reactive compounds is usually recommended a step wise adding the water. Regardless of the reactivity of the present Compounds are usually hydrolysed at temperatures between -20 and 130 ° C or the boiling point of the optionally used Lösungsmit means of. As already indicated, the best way to add something depends on what especially from the reactivity of the starting compounds used. So can you z. B. the dissolved starting compounds slowly to an excess dripping with water or you give water in one portion or in portions optionally dissolved starting compounds. It can also be useful to add the water not as such, but with the help of hydrous or ganic or inorganic systems in the reaction system. When In many cases, the registration of the amount of water in the reaction mixture with the aid of moisture-laden adsorbents, eg. B. of molecular sieves, and of hydrous organic solvents, e.g. B. of 80% ethanol. The addition of water can also have a chemical reaction occur, during which water is released during the course of the reaction becomes. Examples of this are esterifications.

If a solvent is used, in addition to the lower aliphati Alcohols (eg., Ethanol or i-propanol) and ketones, preferably low Re dialkyl ketones, such as acetone or methyl isobutyl ketone, ethers, preferably low dialkyl ethers such as diethyl ether or dibutyl ether, THF, amides, esters, in particular Ethyl acetate, dimethylformamide, amines, especially triethylamine, and their mixtures in question.

The output connections do not necessarily already have all at the beginning the hydrolysis (polycondensation) may be present, but it may even as  prove advantageous if only a part of these compounds first with water in Contact is brought and later added the remaining compounds who the.

To precipitation during hydrolysis and polycondensation as far as possible to avoid the addition of water in several stages, eg. B. in three Steps to be performed. It can in the first stage z. B. one-tenth to one Twentieth of the amount of water required for the hydrolysis is added.

After brief stirring, the addition can vary from one-fifth to one-tenth of the required amount of water and after further brief 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 Nor but it can also be at elevated or reduced pressure be performed.

The polycondensate thus obtained can be either as such or partially or almost complete removal of the solvent used Membranes according to the invention are processed. In some cases it can prove to be advantageous in the obtained after the polycondensation Pro Ducts the excess water and the formed and optionally in addition to replace the solvent used with another solvent to the Stabilize polycondensate. For this purpose, the reaction mixture z. B. in a vacuum at a slightly elevated temperature so far thickened that they still be easily absorbed with another solvent.

The polycondensate obtained in this way represents a more or less visko Liquid or a resin, and it is flat by conventional methods membranes or processed into tubular membranes. After the Formge and any drying required, the resulting Hardened membrane by forming 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  via the radicals B and the silanes of the formulas IV and IV 'and their polycondensates via the mercapto groups of a polymerization and / or a polyaddition un be withdrawn. By these polymerization or polyaddition reactions is built an organic network. From the silanes of the formulas I to V re sulting polycondensate or the membrane made therefrom can thus by Polymerization and / or cured by polyaddition. This cure re actions are thermally and / or radiation-induced and / or chemically in Duziert performed. After curing results in an inorganic-organic Network, d. H. the membranes of the invention have anorga niche-organic network. By variation of the inorganic and / or the organic network, z. As the network density, the chemical and physical properties of the membranes of the invention in wide Be rich varies and the property profile of the membranes of the invention can be adapted to the requirements of the respective application.

The poly used for the preparation of the membranes according to the invention condensate may contain other additives. These additives can be used before and / or during and / or after the polycondensation. at these additives are, for. B. to copolymerizable and / or add bare and / or polyaddierbare monomers and / or oligomers. This mono mers or oligomers are used in the course of curing the resulting membrane via polymerization and / or (poly) addition reactions in the organic Network built the membrane of the invention. Be hydrolyzable Silicon compounds with SH or -C = C or amino groups used and if these are added before the hydrolytic polycondensation, so be these compounds in the course of polycondensation in the inorganic and in As a result of the polymerization or (poly) addition into the organic network of the invention installed membranes according to the invention.

Further additives which are suitable for the preparation of the meme invention Branches used may contain polycondensate, z. B. curing catalyst ren. These are z. B. required when the resulting membrane chemically is induced hardened.

The membranes produced from the polycondensate are gas-permeable and tight. If porous membranes are desired, then that can be used for the production  added to the membranes of the invention used polycondensate additives are set, the pores and thus produce the invention Membra give a porosity. Such additives are for. B. volatile and / or lösli che additives after curing of the membrane z. B. by Temperaturerhö Hung and / or removed by dissolution, so that cavities in the Membrane remain. So z. B. in the membranes of the invention there be produced by a porosity that solvent (eg., Ethyl acetate, Etha nol, isopropanol, etc.) to the polycondensate and this after curing of the Membrane removed. In the resin system no. 1, which will be explained in more detail below is tert, z. B. up to 25 wt .-% of various solvents (eg., Ethyl acetate, Ethanol, isopropanol, etc.) are stirred without its spinnability get lost. After curing, the still contained in the membrane Lö gently by storage at room temperature or forced through Heating to about 100 ° C and evacuation be removed quantitatively. By Addition of oils and their removal after curing of the membrane larger cavities, d. H. produces larger pores. Soluble substances added can be, for. For example salts.

But it is also possible to create pores by the Polykon Densat added blowing agent, which prior to curing of the membrane by thermal Load (eg between 150 and 250 ° C) release gases. Such propellants are z. B. azo compounds, such as azodicarbonamides. Other additives that contribute to Pore production can be added are, for example, hydrazine derivatives (e.g., 4.4-oxybis (benzenesulfohydrazide), semicarbazides (e.g., p-toluenesulfonylsemi carbazide), tetrazoles (e.g., 5-phenyltetrazole) or benzoxazines (e.g., isatoic anhydryl drid).

Pores can also be produced in the membranes of the invention be that by thermal cracking or by oxidation, for. B. by Annealing at 650 ° C, the organic part of the membrane changed or completely or partially removed. This gives a pore structure in the nanome ter area.

The pore-forming additives may also themselves be porous and impart thus the membrane by their presence a porosity. Without restriction the general public are such porous additives z. B. porous glass particles, Perli  te, zeolites, silica gel, diatomaceous earth, clay or aerosils in spherical or ge ground mold.

For the production of z. B. endless flat membranes are preferred solvent free systems are used, but solvent-containing ones are also processable, - Which are applied continuously to a rotating roller. After Film formation by means of a doctor blade, the curing, z. B. a radiation-induced Hardening, the detachment and winding of the membranes.

For the production of z. B. endless hollow fibers are preferably solvent-free Sy However, solvents - containing are also processable, - from which hollow fibers are made as follows. First, the resinous poly condensate extruded through an annular nozzle, wherein the cavity through a gas or liquid-carrying inner nozzle is generated. The dimension of the Resin thread is made according to usual methods by the variation of the spinning parameter ter, such as As the withdrawal speed, the temperature, the pressure, etc., turned provides. Subsequently, by an annular precure component, for. B. a radiation source just below the spinneret of the resin thread networked and thus preserves the shape. By means of an attached below Round radiator, the final curing is performed. The resulting endless fiber is wound up and rewound. For pre-curing and / or final curing can in addition to a radiation-induced curing also a self-induced or a chemically induced curing can be performed. A combination of different ner hardening principles is also possible.

The curing of the membranes according to the invention may vary according to different Hardening principles, d. H. thermally, radiation and / or chemically induced, and be carried out by conventional methods. If necessary, the addition is required by conventional curing catalysts. The curing principles and me methods are z. B. in DE 40 11 044 C2, DE 43 10 733 A1, DE 44 05 261 A1, DE 44 16 857 C1, DE 196 27 198 C2 and DE 196 27 220 C2.

The membranes of the invention are in single-phase as well as in two-phase Version with and without porosity can be produced. The single-phase design finds their application especially where transparency plays an important role.  

Two-phase membranes are obtained from systems that are immiscible, but form emulsions. Such systems can be used as fibers as well are processed into films by z. B. by stirring together Emulsion of immiscible components made, this emulsion after übli methods are processed into membranes and result in the curing of the the membrane hardens the immiscible components together. One on dere variant is to process systems in which it during the Synthesis for phase separation comes. Leave through these two-phase variants produce membranes of the invention, which are made of a stable organic inorganic network, into which a continuous, highly permeable second phase is stored.

The production process of the membranes according to the invention is simple, ko low cost and feasible in the smallest space. It is for the endless production of hollow fibers and films and are all common curing principles applicable. Due to the toxicological safety of the materials are the membranes according to the invention in the medical field without problems reversible. Often necessary for various applications Oberflä chenmodifikationen, z. B. to avoid blood coagulation, to adjust the polarity, the adsorption behavior, etc., can either already during the material synthesis, d. H. be carried out in situ, or subsequently. Derar tige surface modifications are z. B. coatings with heparin, with hydro philen or hydrophobic silanes, with fluorosilanes or with biomolecules.

The membranes of the invention show high mechanical stability high permeation values, even without porosity. This is also at high perme Ations worth still self-supporting films and hollow fibers produced without z. B. the risk of passage of the fluid phase exists.

By the following exemplary modifications, the permeability of the mem 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 prefabricated, highly permeable monomers, oligomers or polymers
• - Silanization of free SiOH groups with trimethylsilyl units

Variation of the inorganic structure density

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

In resin type 1, glycerol-1,3-dimethacrylate and 3-isocyanatopropyltriethoxysilane are first linked together according to the following reaction scheme.

The resulting silane is used to build the inorganic network hydroly polycondensed table, wherein the 1,12-dodecanediol dimethacrylate before, during or after the polycondensation can be added. Out of the result the mixture membranes are manufactured by conventional methods in which Curing by polymerization of the methacrylate groups from the polycondensate and the 1,12-dodecanediol dimethacrylate built up the organic network becomes.

In resin type 2, first, according to the following reaction scheme, the tri methylolpropane triacrylate and the mercaptopropylmethyldimethoxysilane mitein other linked.

The resulting silane is used to build the inorganic network hydroly polycondensed. From the polycondensate are then after conventional Ver drive membranes, which cure by polymerization of the acrylate Groups that build organic networks.

In resin type 3, first, according to the following reaction scheme, the tris (2-hydroxyethyl / isocyanurate triacrylate and the mercaptopropylmethyldimethoxysilane are linked together.

Subsequently, the structure of the inorganic network is the resulting Silane together with the tetraethoxysilane hydrolytically polycondensed, and the made of membrane is ge by polymerization of the acrylate groups hardened.

In the resin type 4, first, in analogy to the resin type 2, the trimethylolpro pantriacrylate and the mercaptopropylmethyldimethoxysilane ver together ties. Subsequently, the resulting silane, together with the dimethyl diethoxysilane, hydrolytically polycondensed, and the membrane made therefrom is cured by polymerization of the acrylate groups.

In the resin type 5, first, in analogy to the resin type 2, the trimethylolpro pantriacrylate and the mercaptopropylmethyldimethoxysilane ver together ties. Subsequently, the resulting silane, together with the dimethyl diethoxysilane and methyltrimethoxysilane, hydrolytically polycondensed, and the membrane made therefrom by polymerization of the acrylate groups hardened.

When resin type 6 are first, in analogy to the resin type 2, the Trimethylolpro pantriacrylate and the mercaptopropylmethyldimethoxysilane ver together ties. Subsequently, the resulting silane, 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 is due to the higher inorganic crosslinking potential of resin type 1 compared to resin type 2 höher modulus E, a higher bending strength and a reduced O ₂ permea tion coefficient. The addition of the tetra-hydrolyzable and condensable tetra ethoxysilane causes in resin type 3 over resin type 2 an increase in the anor ganic crosslinking density while reducing the OtPermeabili ity. 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 Redu cation of O ₂ permeability.

Variation of organic structure density, silanization of SiOH groups and Ein Construction of Permeationssteiaernden 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 silanizing SiOH groups and / or incorporating reactive monomers, the O ₂ permeability of the membranes of the invention can be further increased.

The polycondensates are generally not completely inorganically condensed, ie there are free ~SiOH groups. These can be in the context of a sila nization z. B. to ~Si-O-Si (CH ₃ ) ₃ groups. 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 membranes of resin type 2 is in the discussion of described organic structure density.

In resin type 7, first, according to the following reaction scheme, 1.12-dodecanediol dimethacrylate and mercaptopropylmethyldimethoxysilane are linked together.

Subsequently, the resulting silane is hydrolytically polycondensed, and the made of membrane produced by polymerization of the methacrylate groups hardened.

In resin type 8, according to the following reaction scheme, after the polycondensation, residual SiOH groups of resin type 7 are first silanized.

The resulting membranes are made by polymerization of methacry hardened lat groups.

Resin grades 9 and 10 incorporate, after silanization, the reactive monomers TRIS and TETRAKIS, respectively, 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 brings about a significant reduction in the modulus of elasticity and an increase in permeation. Resin type 8 shows, in comparison to resin type 7, as a result of silanization a further increase in the O ₂ -Per meabilität. Compared to the resin type 8, the incorporation of the O ₂ permeation-promoting end groups is effected in the resulting membrane in the resin type 9 by the addition of the reactive monomer TRIS. 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 z. B. also increased by the incorporation of dimethylsiloxane structures. Without restricting the generality of the installation in the polycondensate z. B. by co-condensation of z. As 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.

In the following examples, the results of which are summarized in tabular form, the incorporation of the dimethylsiloxane structures into the polycondensate takes place by co-polymerization.

In the resin types 11 to 15, first glycerol-1,3-dimethacrylate and 3-isocyanatopropyltriethoxysilane mitein linked to one another according to the following reaction scheme.

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. Become from the polycondensate manufactured by conventional methods membranes, when hardened by polyme tion of the methacrylate groups, the organic network is built.

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.

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-mercaptopropio nat and processed into membranes, the curing then by strah treatment-induced polyaddition of trimethylpropane tris (3-mercaptopropionate to the C = C double bonds of the norbornene radicals takes place.  

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

For the resin types 20 and 21, first, according to the following reaction scheme, the trimethylolpropane triacrylate and the mercaptopropylmethyldimethoxysilane are linked together.

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

• - The resulting silane is first used to build the inorganic network kes hydrolytically polycondensed, and the polycondensate is then with the Polydimethylsiloxane via the addition of acrylate and amino groups ver ties.
• The resulting silane is first reacted with the polydimethylsiloxane over the Addition of acrylate and amino groups linked, and the addition product is then used to build the inorganic network hydrolytically polycon condenses.

The membrane made of the resulting polycondensate is then used for Construction of the organic network by polymerization of the acrylate groups hardened and the solvent is removed quantitatively.

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.

First, in analogy to resin type 1, glycerol-1,3-dimethacryiat and 3- Isocyanatopropyltriethoxysilane linked together. The resulting silane becomes to build up the inorganic network hydrolytically polycondensed, wherein the 1,12-dodecanediol dimethacrylate and / or the PDMS U22 before, during or can be added after the polycondensation. Then by co-poly polymerization of the acrylate and methacrylate groups the PDMS U22 in the polycon densat chemically anchored. From the resulting mixture are übli after übli chen process membranes produced in their curing by polymerization the remaining methacrylate groups further built up the organic network becomes.

In the following table, the O ₂ permeabilities of silanized and non-silanized systems are compiled. It can be clearly seen that the silanization tion of free -OH units by z. B. trimethylsilyl units has an increase in O ₂ - permeability result.

Starting materials and preparation of resin types 2, 4 and 7 are described in the variation of the anor ganic and the 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 produced therefrom by polymerization of the acrylate or Hardened methacrylate groups. On the process parameters when spinning or foli silanization has no effect, provided it is immediately before the Further processing takes place and thus does not affect the aging effect.

Exemplary embodiment of two-phase systems

In the resin type 23, first, as described in the resin type 4, the trimethylol propane triacrylate and the mercaptopropylmethyldimethoxysilane together ver ties. Subsequently, the resulting silane, together with the dimethyl diethoxysilane, hydrolytically polycondensed. The resulting polycondensate is immiscible with the amino-terminated polydimethylsiloxane, it gives a two-phase mixing system, which process into milky cloudy membranes whose curing is carried out by polymerization of Acryfat groups.

The membranes of the invention can be used for separation processes, for. As in ultrafiltration or hyperfiltration, in dialysis, in the gas separation, in the gas permeation, electrodialysis, in the extracorporeal ventilation, as artificial blood vessels or in medical technology (eg., As a replacement of PVC or Siliconschläu chen ) are used. The membranes of the invention show a marked permeation rate for O ₂ and CO ₂ , so that they z. B. are ideal for use in oxygenators.

In the following, the preparation of the membranes of the invention to kon Creten exemplary embodiments explained in more detail.

The embodiments 1 to 3 relate to the production of films and Hohlfa fibers or capillaries. These systems are highly cross-linked, non-porous and ver similarly gas impermeable.

Example 4 relates to a modification of one of the basic systems in the direction ge Lower gas permeability through 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 preparation of porous structures and Examples 12 relates to Pyrolysis of the membranes obtained microporous systems.

example 1

AL = L <reactants: 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 (for example 2% Irgacure 184, Ciba Geigy) (viscosity at processing temperature (10 ° C.) about 100 Pas) is extruded through a ring-shaped die (outer diameter about 1 mm, ring thickness about 0.2 mm). The hollow-fiber geometry is first stabilized by an N ₂ -purged second co-centric inner nozzle until it is thinned by a combination of two UV radiation units (eg Blue-Point II, Hönle with an omnidirectional F 300, Fusion ) the organic curing takes place.

AL = L <spinning parameters: Spinning temperature: 8 ° C Spinning pressure: 15 bar off speed 0.8 m / s

Subsequently, the hollow fiber is wound up. By variation of the spinning parameters (Spinning mass temperature, pressure, take-off speed, gas flow rate through the inner channel), the fiber geometry can be varied within wide limits. in the present case, the minimum amount of fibrous geome obtained in continuous operation lay triene at about 50 microns outside diameter and about 10 microns wall thickness. The biggest achieved hollow fiber dimensions were about 2 mm outside diameter and 0.2 mm wall thickness.

film production

The resin added with a photoinitiator (eg 1% Irgacure 184, Ciba Geigy) is applied by means of a Spaltrakels on a high-poled roller. To passing through a UV curing unit (eg UVAPRINT cm, Hönle)  The film is peeled off and wound up. By varying the roller Umlaufge speed, roll temperature and gap height could be present Case film thicknesses between about 30 microns and 200 microns can be adjusted.

AL = L <Features: O ₂ permeation coefficient [10 ^-10 cm ³ (STP) / cm.s cm Hg]: 12:09 Modulus of elasticity [MPa]: 2640 Tensile strength [MPa]: 106

Example 2

AL = L <reactants: Trimethylolpropane triacrylate TMPTA): 1.2 (1) mol mercaptopropylmethyldimethoxysilane: 1 mol

The synthesis of the resin is carried out as in DE 40 11 044 C2 in Example 1 on page 10, lines 28 to 50 described.

Fiber / film production

The fiber / film production is analogous to Example 1. The achieved minimum Hollow fiber dimensions were about 350 microns outside diameter and 50 microns Wall thickness.

AL = L <Features: O ₂ permeation coefficient [10 ^-10 cm ³ (STP) / cm.s cm Hg]: 12:23 Modulus of elasticity [MPa]: 1520 Tensile strength [MPa]: 59

Example 3

AL = L <reactants: "Norbornene silane": 1 mol dimethyldiethoxysilane: 2 mol Trimethylolpropane tris (3-mercaptopropionate): 0.47 mol

The ratio 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 DE 196 27 198 C2 in Bei game 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) Dimethyldieth oxysilane and stirred at 30 ° C. For the hydrolysis and condensation who sets the 2.76 g of water (corresponding to 2 H ₂ O per OR group) and catalyst 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 an embossed and controllable aging effect (viscosity increase from 1000 to 3000 Pa.s within 20 days (25 ° C.) and good spinnability.) Shortly before further processing into fibers / films, the trimethylpropane tris (3 -mercaptopropionate added.

fiber production

There were hollow tubes of about 1000 microns outside diameter and 100 microns Wall thickness and high flexibility (80% elongation at break) made.

Example 4 With tetraethoxysilane (TEOS) -modified base systems

AL = L <reactants: Tris (2-hydroxyethyl) isocyanurate triacrylate (SR 368): 1 mol mercaptopropylmethyldimethoxysilane: 1 mol Tetraethoxysilane (TEOS): 0.5 mol Solvent: ethoxyethyl: 42.5% by weight

synthesis

To prepare 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 gas atmosphere sphere dripped. While cooling 23.95 g of an ethanolic KOH solution slowly dropped. For the hydrolysis and condensation of the methoxy groups who the 10.64 g of 0.5N HCl added dropwise. After stirring for 5 h, TEOS and 21.88 g of 0.12 n HCl added. After stirring for 20 h at RT, the batch is extracted with water Telt, filtered and evaporated to a solids content of 57.5 wt .-%.

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 counteracts above the resin of Example 2, an increase in the inorganic crosslinking point tentials while reducing the oxygen permeability to a value from 0.07. Porosity due to solvent deprivation could not be determined become.

Example 5

Replacing a methyl group with an alkoxy group which raises the crosslinking potential leads to an increase in the mechanical stability and at the same time a reduction in the permeability.

Synthesis of Resin A

For the preparation of 89.03 g (0.3 mol) of trimethylpropane triacrylate (TMPTA) in 300 ml of Es sigester under argon atmosphere and ice cooling 54.15 g (0.3 mol) Mer  captopropylmethyldimethoxysilane added. Then slowly 19.55 g of an ethanolic KOH solution was added dropwise. After addition 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 0.12n HCl added. After stirring at RT for 23 h, the batch is extracted with water shaken, filtered and concentrated to a solids content of 89%. 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 (TETRAKlS) contributes to an increase in the organic crosslinking potential and at the same time increases the O ₂ permeation, which is why it can also be combined with a low-crosslinking system.

Example 7 Incorporation of dimethylsiloxane structures by condensation

The integration of dimethylsiloxane structures by co-condensation of Precur sors with dimethyldiethoxysilane is varrVerbar in a wide range. The resulting range of variation of oxygen permeation is three orders of magnitude.

Synthesis of Resin C

For the presentation of 66.4 g (0.29 mol glycerol-1,3-dimethacrylate and Dibutylzinndi laurate (as the addition catalyst) under cooling 72.0 g (0.29 mol) of 3-Isocya Natopropyltriethoxysilane added dropwise. After stirring for 21 hours, 290 ml of ethyl acetate, 258.9 g (1.75 mol) of dimethyldiethoxysilane and 63. 3 g of water (including catalyst) added. After stirring for 6d, it is shaken out with water, filtered, concentrated by rotary evaporation and completely remove the volatile components on the oil pump. Solids content: 95.6%, viscosity after 1 h: 2.2 Pas (25 ° C).

The synthesis of the resin variants A, B, D and E takes place quite analogously.

Example 8 Incorporation of dimethylsiloxane structures by addition via amino end groups

Amino-terminated polydimethylsiloxane DMS A 21 (Gelest) is added by reaction of the amino groups with the acrylate groups of the system of Example 2.

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

Example 9 Incorporation of dimethylsiloxane structures by co-polymerization of acryloxy-ter Polydimethylsiloxane PDMS U22 (ABCR)

The relatively short-chain, about 14 polydimethylsiloxane units containing PDMS U22 the company ABCR is in any mixing ratio z. B. with system of Example 1 miscible. This system remained up to a molar ratio of about 8: 1 to Hohlfa spun.

AL = L <reactants: System of Example 1: 8 mol Acryloxy-terminated polydimethylsiloxane PDMS U22: 1 mol

corresponding to 1.5 DMS units per base unit.

Example 10 Production of porosities in hollow fibers

The dichotomy of the organic curing process in hollow fiber manufacturing in an initially incomplete, only preservative pre-hardening unmit immediately below the spinneret outlet and the subsequent complete Curing in a UV omnidirectional provides a possibility of pore generation tion in UV-curing, solvent-containing systems.

The system of Example 1 was diluted with 20% solvent (ethyl acetate), without adverse effect on the spinnability. After adding 2% of the UV starter Irgacure 184, the system became one after the procedure described  Extruded hollow fiber (spinning parameters: spinning pressure = 8 bar, filament temperature = 5 ° C, take-off speed = 0.8 m / s). After precuring with a UV Spotlight low power (Blue Point II, Fo Hönle) about 5 mm below the spinning nozzle, the hollow fiber is still sticky, but already dimensionally stable. By heating with An IR emitter expels the solvent before it is in the UV round radiator is fully cured. The result is a porous hollow fiber.

Example 11 Generation of a microporous, silicate hollow fiber

In the material of the membranes of the invention are at the molecular level organic Si-O-Si units with organically polymerized carbon units combined. After removal of the organic portion, z. B. from anorga nisch highly crosslinked hollow fiber according to the invention by pyrolysis and Oxidati On, a microporous hollow fiber having a narrow pore radius distribution is obtained th.

AL = L <reactants: Glycerol 1.3dimethacrylat: 1 mol 3-isocyanatopropyltriethoxysilane: 1 mol Tetraethoxysilane (TEOS): 0.5 mol

The TEOS modified resin system was prepared according to the procedure described processed into hollow fibers.

AL = L <spinning parameters: Spinning pressure: 18 bar Filament temperature: 45 ° C Off speed: 0.3 m / s

There were hollow fibers of 231 microns outer diameter and 36 microns wall thickness he hold. 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)

1. Semipermeable membrane, obtainable by processing a slightly viscous to resinous liquid by conventional methods to form a membrane, that optionally dry the membrane and then cured thermally and / or radiation-induced and / or chemically induced, wherein the liquid has been obtained

• a) by hydrolytic polycondensation
  • 1. 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 or may contain amide and / or amino groups,
    R ¹ = alkylene, arylene, arylenealkylene or arylenealkylene with in each case 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 contain - and / or amino groups,
    R ² = alkylene, arylene, arylenealkylene or arylenealkylene with in each case 0 to 15 carbon atoms, where these radicals oxygen and / or sulfur atoms and / or ester and / or carbonyl and / or carboxyl and / or amide contain - 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 May contain 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 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 contain - 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 contain / or amide and / or amino groups,
    X = hydrogen, halogen, hydroxyl, 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, 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, and / or
  • 2. one or more compounds of general formula II,
    in which the radicals and indices have the following meanings:
    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 or may contain amide and / or amino groups,
    R ³ = alkylene, arylene, arylenealkylene or alkylenearylene having in each case 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, hydroxyl, 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, these radicals may be interrupted by oxygen and / or by sulfur atoms and / or by amino groups un, 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, these radicals may be interrupted by oxygen and / or by sulfur atoms and / or by amino groups un, and
    R ² = 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, these radicals may be interrupted by oxygen and / or by sulfur atoms and / or by amino groups un, 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
  • 3. 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 meanings:
    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 derives up 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 may contain amide and / 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 ge radkettige, branched or cyclic radicals having 1 or 2 to 20 carbon atoms, aryl is optionally substituted phenyl, naphthyl or bi phenyl and the above alkoxy, acyloxy -, alkylcarbonyl, alkoxy carbonyl, alkyiaryl, arylalkyl, arylene, alkylene and Alkylenaryl radicals derived from the above-defined alkyl and aryl radicals, and / or
  • 4. one or more compounds of 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 or may contain amide and / or amino groups,
    X = hydrogen, halogen, hydroxyl, alkoxy, acyloxy, alkylcarbonyl, alkoxycarbonyl or NR " ₂ ,
    with R "= hydrogen, alkyl, aryl or alkylaryl,
    Y = organic radical having from 1 to 30, preferably from 1 to 20 carbon atoms, and from 1 to 5, preferably from 1 to 4, mercapto groups,
    a = 1, 2 or 3,
    x = 1, 2 or 3, with a + x = 2, 3 or 4, and / or
  • 5. from the compounds of formulas I to IV derived precondensates and optionally
  • 6. one or more compounds of 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 or may contain amide and / or amino groups,
    X = hydrogen, halogen, hydroxyl, alkoxy, acyloxy, alkylcarbonyl, alkoxycarbonyl or NR " ₂ ,
    with R "= hydrogen, alkyl, aryl or alkylaryl,
    a = 1, 2 or 3,
    and / or derived precondensates,
  wherein the hydrolytic polycondensation is carried out 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 formulas I, II, III and IV to compounds of Formula V is between 1: 0 and 1:20, and optionally
• b) by addition
  • 1. one or more copolymerizable and / or (poly) adductable monomers and / or oligomers,
  • 2. and / or one or more curing catalysts,
  • 3. and / or one or more pore-forming additives.

2. Semipermeable membrane according to claim 1, obtainable by that the liquid is processed into flat membranes or tubular membranes. 3. Semipermeable membrane according to claim 1 or 2, characterized gekennzeich net, that she is on a carrier. 4. Semipermeable membrane according to one or more of claims 1 to 3, characterized in that it has been obtained from a liquid which Contains polycondensates derived from one or more compounds of For Derive mel I in which the indices a and / or b and / or c have the value = 1. 5. Semipermeable membrane according to one or more of claims 1 to 4, characterized in that it has been obtained from a liquid which Contains polycondensates derived from one or more compounds of For Derive II and / or III, in which the radical B one or more acrylate and / or or methacrylate groups. 6. 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 For mel 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 meanings:
E = -CO-NH-, -CS-NH-, -CH ₂ CH ₂ or -CH ₂ CH (OH) -
R = as defined in claim 1;
R ⁵ = alkylene, arylene, arylenealkylene or arylenealkylene with 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 with 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;
X = as defined in claim 1;
a = as defined in claim 1;
n = 2, 3, 4 or 5;
x = as defined in claim 1; 7. Semipermeable membrane according to one or more of claims 1 to 6, characterized in that it has been obtained from a liquid which one or more organic compounds containing one or more mercapto Contains groups. 8. Semipermeable membrane according to one or more of claims 1 to 7, characterized in that it has been obtained from a liquid which one or more organic compounds with one or more C = C-dop contains pelbindungen. 9. Semipermeable membrane according to claim 8, characterized in that it has been obtained from a liquid, the polycondensates and / or oligo contains condensates having one or more C = C double bonds  and those of organically modified, hydrolytically condensable silanes derived. 10. Semipermeable membrane according to one or more of claims 1 to 9, characterized in that it has been obtained from a liquid which one or more organic compounds having one or more substituents th and / or unsubstituted amino groups. 11. Semipermeable membrane according to claim 10, characterized that it has been obtained from a liquid containing polycondensates and / or ols gokondensate containing one or more substituted and / or unsubstituier te have amino groups and are derived from organically modified, hydroly derived table condensable silanes. 12. Semipermeable membrane according to one or more of claims 1 to 11, characterized in that it has been obtained from a liquid which as pore-forming additives one or more salts and / or one or more rere liquids and / or one or more blowing agents and / or one or more contains porous fillers. 13. Semipermeable membrane according to claim 12, obtainable by that curing the pore-forming additives dissolved out of the membrane and / or removed by thermal treatment. 14. Semipermeable membrane according to one or more of claims 1 to 13, obtainable in that, after curing, the organic components removed by thermal cracking. 15. A process for the preparation of semipermeable membranes according to one or more of claims 1 to 14, characterized in that

• a) by hydrolytic condensation
  • 1. one or more compounds of general formula I.
    in which the radicals and indices are defined as in claim 1, and / or
  • 2. one or more compounds of general formula II
    in which the radicals and indices are defined as in claim 1, and / or
  • 3. 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 defined as in claim 1, and / or
  • 4. one or more compounds of general formula IV,
    Y _a SiX _x R ₄ -ax (IV)
    in which the radicals and indices are defined as in claim 1, and / or
  • 5. precondensates derived from compounds of the formula I to IV and, if appropriate,
  • 6. one or more compounds of general formula V,
    X _a SiR _4-a (V)
    in which the radicals and indices are defined as in claim 1,
  by adding water or moisture and optionally in the presence of a solvent and / or a condensation catalyst and wherein, referred to the monomers, the molar ratio of the sum of the compounds of formulas I, II and III to compounds of formula IV between 1: 0 and 1: 20, and if necessary
• b) by addition
  • 1. one or more copolymerizable and / or (poly) addable monomers and / or oligomers,
  • 2. and / or one or more curing catalysts,
  • 3. and / or one or more, soluble and / or volatile, pore-forming additives
  a slightly viscous to resinous liquid manufactures that they are processed by conventional methods to a membrane that this membrane is dried if necessary and then cured thermally and / or radiation-induced and / or chemically induced.

16. The method according to claim 15, characterized in that the liquid to flat membranes or to tubular membranes.   17. The method according to claim 15 or 16, characterized in that one the membrane is made on a support. 18. The method according to one or more of claims 15 to 17, characterized ge indicates that a liquid containing polycondensates is used, which are derived from one or more compounds of formula I in which the Indices a and / or b and / or c have the value = 1. 19. The method according to one or more of claims 15 to 18, characterized ge indicates that a liquid containing polycondensates is used, which is derived from one or more compounds of the formulas II and / or III in which the radical B one or more acrylate and / or methacrylate Grup pen contains. 20. The method according to one or more of claims 15 to 19, characterized in that one uses a liquid containing polycondensates derived from one or more compounds of formula IV ',
[(HSR 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. 21. The method according to one or more of claims 15 to 20, characterized ge indicates that one uses a liquid containing one or more organi containing compounds with one or more mercapto groups. 22. The method according to one or more of claims 15 to 21, characterized ge indicates that one uses a liquid containing one or more organi contains compounds with one or more C = C double bonds. 23. The method according to claim 22, characterized in that one Flüs used, containing polycondensates and / or oligocondensates, the  have one or more C = C double bonds and are different from organic derived modified, hydrolytically condensable silanes. 24. The method according to one or more of claims 15 to 23, characterized ge indicates that one uses a liquid containing one or more organi compounds with one or more substituted and / or unsubstituier contains amino groups. 25. The method according to claim 24, characterized in that one Flüs used, containing polycondensates and / or oligocondensates, the one or more substituted and / or unsubstituted amino groups aufwei and the organically modified, hydrolytically condensable sila derive. 26. The method according to one or more of claims 15 to 25, characterized ge indicates that a liquid is used which acts as a pore-forming ad one or more salts and / or one or more liquids and / or contains one or more blowing agents and / or one or more porous fillers. 27. The method according to claim 26, characterized in that after the Här tion the pore-forming additives dissolved out of the membrane and / or be removed by thermal treatment. 28. The method according to one or more of claims 15 to 27, characterized ge indicates that after curing the organic components by ther mixed cracking be removed. 29. Use of the membranes according to one or more of claims 1 to 15 for separation processes, in particular for the gas separation, for the reverse osmosis for electrodialysis, for dialysis, for pervaporation, for the micro- and hyperfiltration.