DE102010040762A1 - Inorganic-organic polymer hybrid network, useful for preparing shape memory polymer, comprises hydroxyl group-containing thermoplastically processable polymer, nanoscale metal compounds, and reactive compounds - Google Patents

Abstract

Inorganic-organic polymer hybrid network comprises: (a) at least one hydroxyl group-containing thermoplastically processable polymer having at least two hydroxyl groups per molecule; (b) nanoscale metal compounds having a particle size of 1-300 nm, which exhibit at least two free hydroxyl groups on the particle surface; and (c) reactive compounds including di- and/or polyisocyanates or di- and/or polyepoxides, where the hydroxyl group-containing metal compounds are incorporated into the organic network via chemical bonds. An independent claim is also included for preparing inorganic-organic polymer hybrid networks, comprising reacting a hydroxyl group-containing polymer (a), a nanoscale metal compound (b) and a compound (c) including a di- and/or polyisocyanate or a di- and/or polyepoxide at temperatures of 40-300[deg] C and under intensively mixed reaction conditions optionally in the presence of catalysts and/or other additives, such that cross-linking reaction occurs by reacting the isocyanate or epoxy groups with the inorganic and organic hydroxyl group.

Description

The invention relates to new inorganic-organic polymeric hybrid networks and processes for their preparation and in particular hybrid networks based on nanoscale hydroxyl-containing metal compounds and monomeric and / or oligomeric hydroxyl-reactive compounds embedded in a hydroxyl-containing polymer matrix equipped with reactive groups.

• – die Zugabe von nanoskaligen Teilchen zu Polymeren, die das Kontinuum darstellen oder
• – die Umsetzung der nanoskaligen Partikel mit reaktiven Verbindungen, so dass die nanoskaligen Partikel auf ihrer Oberfläche reaktive Gruppen aufweisen und diese oberflächenmodifizierten Teilchen in Polymere eingebaut werden.

Hybrid networks are described in a number of publications and patents. At present, two strategies for incorporation of nanoscale particles into polymer networks are known:

• The addition of nanoscale particles to polymers which constitute the continuum or
• - The implementation of the nanoscale particles with reactive compounds, so that the nanoscale particles have on their surface reactive groups and these surface-modified particles are incorporated into polymers.

The production of composite materials from a polymer, which may be thermoplastic or crosslinked polymers, thus follows substantially the conventional process technologies. Such materials with a high degree of filling are z. B. from K. Shikinaka et al. in Langmuir 26 (15), 12493-5 (2010) described. In this work, flexible, transparent nanocomposite films with up to 57% inorganic components cast from solution are presented.

When cross-linked polymers are used as the continuous phase, other technologies are required. Thus, hard and flexible coatings are produced using nanoscale particles and hypercrosslinked polyesters with glass transition temperature increased by 9 to 16 K compared to the starting polymer, as well as an increased storage modulus of L. Fogelström et al. in ACS Applied Materials & Interfaces 2 (6), 1679-94 (2010) described. As in the case described above, these are also composite materials composed of a continuous polymer phase and nanoscale particles embedded therein.

The reaction of inorganic, hydroxyl-containing compounds with hydroxyl-reactive compounds is z. B. from Chen et al. described. After the apprenticeship of US-B2 7,662,983 modified inorganic, possibly nanoscale particles are prepared by surface modification by reacting hydroxyl groups present on the surface of the inorganic particles with isocyanates which have an unsaturated group in the molecule, so that the modification takes place via urethane groups. The thus modified inorganic-organic hybrids can, for. B. are polymerized in unsaturated polyester resins or acrylates, if z. B. acrylate groups are grafted onto the surface. The modification of the surface of the nanoscale particles is mainly to prevent agglomeration of the particles during processing due to their high polarity and the lower of the polymers, since the compatibility is poor at the interfaces and the polymer usually with the nanoscale metal hydroxide can not react. Such a process and such a material is z. B. in the WO 1995/27752 A1 as cellular polyester urethane with reinforcing particles therein, forming a complex network that can interact with other polymeric networks and ultimately yield building foams.

From Wei et al. describes electroactive, inorganic hybrid materials with homogeneous distribution of a conductive organic polymer in an inorganic matrix, see, for. B. US-A 6,066,269 , These hybrid materials are prepared from solutions of the components and evaporation of the solvent, thereby obtaining monolithic conductive materials having improved adhesion properties.

Another approach to the production of hybrid polymers is in the DE-A1 199 49 971 described. According to this teaching, hybrid dispersions of polyurethanes and other polymers, eg. Thermoplastic olefinic polymers, but not using inorganic particles.

Furthermore, microporous hybrid gels are after WO 2006/135882 A1 from interpenetrating polymer networks (IPN) of organic network and inorganic network. Although these networks penetrate the networks, they are not chemically linked to each other. In the US-A 6,120,905 describes hybrid networks prepared from polyurethanes by crosslinking at least one Cyclocarbonatoligomeren and an amino oligomer and optionally with 4 to 12% of free epoxy groups.

To WO 2009/005190 A1 modified clays are reacted with a hyperbranched organic modifier, which in turn consists of a polyamine alcohol and a compound which reacts therewith produced and reacted with the clay. In this way modified clays are obtained, which are used to reinforce polymers. A similar process for modifying fibers is discussed in WO 2010/081821 A1 described. Fibers are treated with a suspension of inorganic nanoscale particles, forming a continuous nanocomposite matrix around the fiber.

However, the use of nanoscale metal oxides or hydroxides is associated with a variety of problems, eg. B. due to the compatibility, which requires a surface modification, high viscosity of the starting materials, which dispersion or solvent are required, the tendency of nanoscale metal oxides for agglomeration, but also other problems, eg. As the drastic increase in brittleness or the large increase in the viscosity of oligomers, melts or added components.

Therefore, a method is desirable in which hybrid networks can be obtained, which on the one hand is easy to perform and on the other hand allows to set the advantageous properties of the hybrid networks or particular advantageous properties. The object of the invention is therefore to provide a method for producing new hybrid networks as well as hybrid networks produced therewith.

According to the invention, the object is achieved by reacting nanoscale hydroxyl-containing metal compounds having a particle size of 1 to 300 nm in a thermoplastically processable hydroxylgruppenhlatigen polymers with compounds having hydroxyl-functional groups and so the hydroxyl-containing metal hydroxides are incorporated into the organic network.

It has surprisingly been found that hydroxyl-containing metal hydroxides with reactive compounds selected from di- and / or polyisocyanates or di- and / or polyepoxides can be converted into hybrid networks under the conditions of the processing in thermoplastic polymers.

In particular, the invention relates to inorganic-organic polymeric hybrid networks, which are reacted by reaction of hydroxyl-containing metal oxides and hydroxyl-containing polymers with di- and / or polyisocyanates or di- and / or polyepoxides optionally in the presence of catalysts and other additives under the conditions of thermal processing ,

• a) mindestens ein hydroxylgruppenhaltiges thermoplastisch verarbeitbares Polymer mit mindestens zwei Hydroxylgruppen je Molekül,
• b) nanoskalige Metallverbindungen mit einer Teilchengröße von 1 bis 300 nm, die auf der Teilchenoberfläche mindestens zwei freie Hydroxylgruppen aufweisen,
• c) reaktive Verbindungen, ausgewählt aus der Gruppe der Di- und/oder Polyisocyanate oder aus der Gruppe der Di- und/oder Polyepoxide, wobei die hydroxylgruppenhaltigen Metallverbindungen über chemische Bindungen in das organische Netzwerk eingebaut vorliegen.

The invention accordingly provides inorganic-organic polymeric hybrid networks containing

• a) at least one hydroxyl-containing thermoplastically processable polymer having at least two hydroxyl groups per molecule,
• b) nanoscale metal compounds with a particle size of 1 to 300 nm, which have at least two free hydroxyl groups on the particle surface,
• c) reactive compounds selected from the group of di- and / or polyisocyanates or from the group of di- and / or polyepoxides, wherein the hydroxyl-containing metal compounds are incorporated via chemical bonds in the organic network.

• a) mindestens ein hydroxylgruppenhaltiges thermoplastisch verarbeitbares Polymer mit mindestens zwei Hydroxylgruppen je Molekül sowie mit einer Molmasse von mindestens 20.000, mit einem Schmelzpunkt von 0–270°C und mit einer OH-Zahl von 0,5 bis 200 mg KOH/g,
• b) nanoskalige Metallverbindungen mit einer Teilchengröße von 1 bis 300 nm, die auf der Teilchenoberfläche mindestens zwei freie Hydroxylgruppen aufweisen, wobei die Metallverbindungen synthetische oder natürlich vorkommende Metalloxide, Metalloxidhydroxide oder Metallhydroxide darstellen und das Metall ausgewählt ist aus der Gruppe umfassend Al, Mg, Zn, In, Si und/oder Ti oder deren Gemischen,
• c) reaktive Verbindungen, ausgewählt aus der Gruppe der Di- und/oder Polyisocyanate mit einer Viskosität von 5–13.000 mPas und mit einem Gehalt an freien isocyanatreaktiven Gruppen (berechnet als NCO, Molekulargewicht = 42) von 2 bis 26 Gew.-% oder aus der Gruppe der Di- und/oder Polyepoxide mit einem Schmelzpunkt von 20–140°C,
• d) gegebenenfalls Katalysatoren, Hilfs- und Zusatzstoffe,

wobei die Komponenten a), b) und c) in dem Verhältnis vorliegen, dass auf jede Hydroxylgruppe 0,1 bis 2 Isocyanat- oder Epoxidgruppen der Gruppe c) entfällt, so dass die hydroxylgruppenhaltigen Metallverbindungen über chemische Bindungen in das organische Netzwerk eingebaut vorliegen und damit Teil des Netzwerkes (Hybridnetzwerk) sind.In particular, the invention relates to inorganic-organic polymeric hybrid networks

• a) at least one hydroxyl-containing thermoplastically processable polymer having at least two hydroxyl groups per molecule and having a molecular weight of at least 20,000, with a melting point of 0-270 ° C and having an OH number of 0.5 to 200 mg KOH / g,
• b) nanoscale metal compounds having a particle size of 1 to 300 nm, having on the particle surface at least two free hydroxyl groups, wherein the metal compounds are synthetic or naturally occurring metal oxides, metal oxide or metal hydroxides and the metal is selected from the group comprising Al, Mg, Zn , In, Si and / or Ti or mixtures thereof,
• c) reactive compounds selected from the group of di- and / or polyisocyanates having a viscosity of 5-13,000 mPas and containing from free isocyanate-reactive groups (calculated as NCO, molecular weight = 42) from 2 to 26 wt .-% or from the group of di- and / or polyepoxides having a melting point of 20-140 ° C,
• d) if appropriate, catalysts, auxiliaries and additives,

wherein the components a), b) and c) are present in the ratio that 0.1 to 2 isocyanate or epoxide groups of group c) is omitted for each hydroxyl group, so that the hydroxyl-containing metal compounds are incorporated into the organic network via chemical bonds and so that they are part of the network (hybrid network).

• – 40 bis 95% des hydroxylgruppenhaltigen Polymeren a)
• – 0,5 bis 25% der nanoskaligen Metallverbindung b) und
• – 1 bis 25% des Di- und/oder Polyisocyanats oder des Di- und/oder Polyepoxids der Verbindung c).

In this case, the hybrid networks according to the invention preferably comprise

• 40 to 95% of the hydroxyl-containing polymer a)
• 0.5 to 25% of the nanoscale metal compound b) and
• - 1 to 25% of the di- and / or polyisocyanate or the di- and / or polyepoxide of the compound c).

• – 40 bis 95% eines hydroxylgruppenhaltigen Polymeren mit einer Molmasse von mindestens 20.000 und mindestens zwei Hydroxylgruppen je Molekül,
• – 0,5 bis 25% eines nanoskaligen Metalloxids, Metalloxidhydroxids und/oder Metallhydroxids mit einer Teilchengröße von 1 bis 300 nm mit mindestens zwei freien Hydroxylgruppen auf der Oberfläche und
• – 1 bis 25% eines Di- und/oder Polyisocyanats, das hergestellt wurde durch Umsetzung eines Di- und/oder Polyisocyanats mit einem Unterschuss an Hydroxyl- und/oder Aminverbindungen mit mindestens zwei isocyanatreaktiven Gruppen.

Preferably, the invention relates to inorganic-organic polymeric hybrid networks, which are prepared by reaction of hydroxyl-containing metal hydroxides and hydroxyl-containing polymers and consist of

• 40 to 95% of a hydroxyl-containing polymer having a molecular weight of at least 20,000 and at least two hydroxyl groups per molecule,
• From 0.5 to 25% of a nanoscale metal oxide, metal oxide hydroxide and / or metal hydroxide having a particle size of 1 to 300 nm with at least two free hydroxyl groups on the surface and
• From 1 to 25% of a diisocyanate and / or polyisocyanate which has been prepared by reacting a diisocyanate and / or polyisocyanate with a deficit of hydroxyl and / or amine compounds having at least two isocyanate-reactive groups.

• – 40 bis 95% eines hydroxylgruppenhaltigen Polymeren mit einer Molmasse von mindestens 20.000 und mindestens zwei Hydroxylgruppen je Molekül,
• – 0,5 bis 25% eines nanoskaligen Metalloxids, Metalloxidhydroxids und/oder Metallhydroxids mit einer Teilchengröße von 1 bis 300 nm mit mindestens zwei freien Hydroxylgruppen auf der Oberfläche und
• – 1 bis 25% eines Di- und/oder Polyepoxids.

Further preferably, the invention relates to inorganic-organic polymeric hybrid networks, which are prepared by reaction of hydroxyl-containing metal hydroxides and hydroxyl-containing polymers and consist of

• 40 to 95% of a hydroxyl-containing polymer having a molecular weight of at least 20,000 and at least two hydroxyl groups per molecule,
• From 0.5 to 25% of a nanoscale metal oxide, metal oxide hydroxide and / or metal hydroxide having a particle size of 1 to 300 nm with at least two free hydroxyl groups on the surface and
• - 1 to 25% of a di- and / or polyepoxide.

Suitable metal oxides are aluminum oxide, magnesium oxide, zinc oxide, indium oxide, zinc-indium mixed oxide, silicon dioxide, free hydroxyl titanium dioxide, but also naturally occurring metal oxides or metal oxide hydroxides such as bauxite, boehmite, laponite etc. Suitable metal hydroxides are aluminum hydroxide, magnesium hydroxide, zinc hydroxide, indium hydroxide, Zinc indium mixed hydroxide, etc., as well as naturally occurring metal hydroxides. Suitable metal oxide hydroxides are aluminum oxide hydroxide, magnesium oxide hydroxide, zinc oxide hydroxide, indium oxide hydroxide, zinc indium mixed oxide hydroxide or naturally occurring metal oxide hydroxides. Furthermore, metal silicates with free hydroxyl groups are suitable for preparing the hybrid networks according to the invention, for. As well as natural silicates such as montmorillonite, vermicullite, etc. The particle size of the nanoscale metal oxides, metal oxide and / or metal hydroxides should be in the range of 1 to 300 nm, preferably 2 to 250 nm and more preferably with the particle size maximum between 2 and 100.

Suitable hydroxyl-containing base polymers are preferably thermoplastically processable polymers having a melting point of 30-220 ° C. Particularly suitable polymers are polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyacrylates having free hydroxyl groups, polyesters such as PET, PBT, PTT or mixed esters thereof and hydroxyl-containing polyurethanes, polyureas, etc. In addition, there are also biologically produced or degradable polymers such as polylactic acid (PLA), polyhydroxyalkanoates (PHA ), Polyhydroxybutyrates (PHB), polyhydroxyvalerates (PHV) or their mixtures or copolymers but also cellulose or its esters or ethers. Particularly preferred is polyvinyl butyral.

Suitable diisocyanates are 4,4'-methylene bis (phenyl isocyanate) or other isomers or isomer mixtures, 2,4- and / or 2,6-toluene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, etc. Preferred Prepolymers based on said isocyanates with diols or polyether diols or di- and / or polyamines according to the invention used. Prepolymers based on said isocyanates with a deficit of hydroxyl and / or amine compounds and having at least two isocyanate-reactive groups by reaction with diols or polyether diols or di- and / or polyamines in a ratio of -OH or -HN: NCO = 1: 1.3 to 1:10 are particularly preferred.

Suitable Diepoxyde are z. Bis-2,2 '- [4- (2,3-epoxypropoxy) phenyl] propane or its oligomers (3-12 repeat units). Prepolymers based on these diepoxides with di- and / or polyamines are preferably used.

Tin, lead and / or bismuth compounds, in particular carboxylates and / or thiocarboxylates, may preferably be used as catalysts.

As auxiliaries and additives z. As fillers, light stabilizers, flame retardants, moisture stabilizers and / or pigments.

• – ein hydroxylgruppenhaltiges Polymer a)
• – eine nanoskalige Metallverbindung b) und
• – eine Verbindung c) ausgewählt aus einem Di- und/oder Polyisocyanat oder einem Di- und/oder Polyepoxids

bei Temperaturen zwischen 40 und 300°C, vorzugsweise bei Temperaturen bis 220°C und unter intensiv durchmischenden Reaktionsbedingungen ggf. in Gegenwart von Katalysatoren und/oder weiteren Zusatzstoffen umgesetzt, so dass eine Vernetzungsreaktion durch Umsetzung der Isocyanat- bzw. Epoxidgruppen mit den anorganischen und organischen Hydroxylgruppen eintritt.The hybrid networks according to the invention are produced by reacting the components in the desired mixing ratio under the conditions of thermoplastic processing. Advantageously

• A hydroxyl-containing polymer a)
• A nanoscale metal compound b) and
• A compound c) selected from a di- and / or polyisocyanate or a di- and / or polyepoxide

reacted at temperatures between 40 and 300 ° C, preferably at temperatures up to 220 ° C and under intensely mixing reaction conditions optionally in the presence of catalysts and / or other additives, so that a crosslinking reaction by reacting the isocyanate or epoxy groups with the inorganic and organic hydroxyl groups occurs.

Suitable methods may be extrusion, kneading, pressing, injection molding. Particularly suitable methods are extrusion and kneading in single or twin screw extruders or kneaders. Furthermore, combinations of these methods are suitable, for. As the combination of kneading into a granule or powder and its subsequent compression.

The metal oxides to be used have free hydroxyl groups on the particle surface. These are able to react with isocyanate groups or epoxy groups (oxiranes) and form inorganic-organic compounds:

Particular preference is given according to the invention nanoscale aluminas z. B. Aeroxide ^® Alu C (CAS Number: 1344-28-1) with the Teilchengrößenmaximum of 13 nm, Aeroxide ^® Alu C 805 with the Teilchengrößenmaximum of 13 nm, Aeroxide ^® Alu 65 with the Teilchengrößenmaximum of 17 nm, Aeroxide ^® TiO ₂ P 25 with the particle size maximum of 21 nm, indium-zinc oxides z. B. VP ITO IR5 with the particle size maximum of about 43 nm, VP ITO TC 8 with the particle size maximum of about 43 nm, the company Evonik, DE, silicon dioxides, z. B. AEROSIL EG 50 with the particle size maximum of about 40 nm, AEROSIL 380 with the particle size maximum of about 7 nm, the company Evonik, DE, or ACTILOX 400 SM ^® with the particle size maximum of about 200 nm from Nabaltec AG, DE used.

If di- or polyisocyanates and hydroxyl-containing polymers and metal oxide hydroxides with a plurality of hydroxyl groups are used, the hybrid networks are formed in the reaction. These are embedded in the matrix polymer; since the polymer used has hydroxyl groups (usually 0.1 to 13%), the isocyanate groups react with both the hydroxyl groups of the metal oxide hydroxides and the polymer to form a hydride permeation network which has very unique properties. Similarly, hybrid networks are formed when epoxy compounds are used in place of the isocyanate compounds.

The hybrid networks according to the invention have special properties, for. As a negative coefficient of thermal expansion, higher glass transition temperatures, higher hardness, etc., which can be adjusted by the components used, their nature and amount in the base polymer and the processing conditions.

The new inorganic-organic polymeric hybrid networks also exhibit a negative shrinkage on heating, which is the prerequisite for the production of shape memory polymers. Applications are z. As shrink tubing, cable sheaths, medical rails and bandages.

embodiments

example 1

An isocyanate prepolymer is first prepared. For this purpose, 1.6 kg Lupranol be ^® 1000 (polypropylene glycol, molecular weight 2000) with 410 g Desmodur ^® 44 M, and 0.2 g of dibutyltin bis (2-ethylhexyl thioglycolate) so mixed under protective gas, that the temperature does not exceed 60 ° C, and three Stirred for hours at a temperature of 70 ° C. A prepolymer with an isocyanate content of 7.5% is obtained.

183 g of PVB and 2 g of nanoscale aluminum hydroxide (ALU ^C® from Evonik Degussa AG) are introduced into a kneading chamber and homogenized at 140 ° C. for three hours. To this mixture, 15 g of the prepolymer are added and kneaded at a temperature rising from 140 to 180 ° C for 20 minutes.

Example 2

The procedure of Example 1 is repeated, except that subsequently the hybrid network polymer obtained from the kneader is pressed for 15 minutes at 180 ° C for 15 minutes under a pressure of 9.6 MPa to a 4 mm plate.

Example 3

The procedure of Example 1 is repeated with different mixtures, see table (W = thermal expansion in% / ° C). sample PVB prepolymer ALU ^C® Tg (° C) W [G] [G] [G] Example 3a 183 15 2 35 +0.05 Example 3b 181 15 4 Example 3c 179 15 6 Example 3d 177 15 8th Example 3e 175 15 10 38 -0.7 Example 3f 165 15 20 38 -1.07 Example 3g 145 15 40

The glass transition temperature of the PVB used in the experiments is 28 ° C.

Example 4

The procedure of Example 1 is repeated with different mixtures, see table. PVB prepolymer ALU ^C® Example 4a 170 20 10 Example 4b 160 20 20 Example 4c 160 30 10

Comparative Examples

The procedure of Example 1 is repeated without the addition of ALU ^C® . The glass transition temperature of this material is 30 ° C.

If instead of the ALU C ^® according to the invention used with a Teilchengrößenmaximum of 12 nm, an aluminum hydroxide used with a Teilchengrößenmaximum of 350 nm, then the location of the glass transition with respect to the cross-linked with prepolymer hybrid network does not change and is still at 30 ° C, ie the much larger particles act practically only as a filler without being involved in network formation.

Results

The glass transition temperature of the material obtained from the comparative example, determined by DMA (Automatic Torsion Pendulum ATM 3 from Myrenne GmbH), is 31 ° C., the thermal expansion is 0.16% / ° C. The glass transition temperature of the material of Example 1 is 33 ° C, the thermal expansion -0.1% / ° C. The glass transition temperature of the material according to Example 3f is 38 ° C, the thermal expansion is -1.07% / ° C. The glass transition temperature of the material according to Example 4b is 42 ° C, the thermal expansion -1.32% / ° C.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• US 7662983 B2 [0005]
• WO 1995/27752 A1 [0005]
• US 6066269 A [0006]
• DE 19949971 A1 [0007]
• WO 2006/135882 A1 [0008]
• US 6120905 A [0008]
• WO 2009/005190 A1 [0009]
• WO 2010/081821 A1 [0009]

Cited non-patent literature

• K. Shikinaka et al. in Langmuir 26 (15), 12493-5 (2010) [0003]
• L. Fogelström et al. in ACS Applied Materials & Interfaces 2 (6), 1679-94 (2010) [0004]
• Chen et al. [0005]
• Wei et al. [0006]

Claims (15)

Inorganic-organic polymeric hybrid networks containing a. at least one hydroxyl-containing thermoplastically processable polymer having at least two hydroxyl groups per molecule, b. nanoscale metal compounds with a particle size of 1 to 300 nm, which have at least two free hydroxyl groups on the particle surface, c. reactive compounds selected from the group of di- and / or polyisocyanates or from the group of di- and / or polyepoxides, wherein the hydroxyl-containing metal compounds are incorporated via chemical bonds in the organic network. Inorganic-organic polymeric hybrid networks according to claim 1 containing a. at least one hydroxyl-containing thermoplastically processable polymer having at least two hydroxyl groups per molecule and having a molecular weight of at least 20,000, a melting point of 0-270 ° C and an OH number of 0.5 to 200 mg KOH / g, b. nanoscale metal compounds having a particle size of 1 to 300 nm, having at least two free hydroxyl groups on the particle surface, wherein the metal compounds are synthetic or naturally occurring metal oxides, metal oxide or metal hydroxides and the metal is selected from the group comprising Al, Mg, Zn, In , Si and / or Ti, or mixtures thereof, c. reactive compounds selected from the group of di- and / or polyisocyanates having a viscosity of 5-13,000 mPas and containing from free isocyanate-reactive groups (calculated as NCO, molecular weight = 42) from 2 to 26 wt .-% or from Group of di- and / or polyepoxides having a melting point of 20-140 ° C, d. if appropriate, catalysts, auxiliaries and additives, wherein the components a), b) and c) are present in the ratio that 0.1 to 2 isocyanate or epoxide groups of group c) is omitted for each hydroxyl group, so that the hydroxyl-containing metal compounds are incorporated into the organic network via chemical bonds and so that they are part of the network (hybrid network). Hybrid network according to claim 1 or 2, characterized in that they contain a. 40 to 95% of the hydroxyl-containing polymer, b. 0.5 to 25% of the nanoscale metal compound and c. 1 to 25% of the di- and / or polyisocyanate or of the di- and / or polyepoxide. Hybrid network according to one of claims 1 to 3, characterized in that the compound a) is selected from polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyacrylates having free hydroxyl groups, polyesters, preferably PET, PBT, PTT or mixed esters thereof, as well as hydroxyl-containing polyurethanes, polyureas or biological polymers produced or degradable, preferably polylactic acid (PLA), polyhydroxyalkanoates (PHA), polyhydroxybutyrates (PHB), polyhydroxyvalerates (PHV) or mixtures thereof or copolymers or cellulose or esters or ethers thereof. Hybrid network according to one of claims 1 to 4, characterized in that the compound b) is selected from alumina, magnesium oxide, zinc oxide, indium oxide, zinc-indium mixed oxide, silica, titania with free hydroxyl groups, bauxite, boehmite, laponite, aluminum hydroxide, magnesium hydroxide , Zinc hydroxide, indium hydroxide, zinc indium mixed hydroxide, aluminum oxide hydroxide, magnesium oxide hydroxide, zinc oxide hydroxide, indium oxide hydroxide, zinc indium mixed oxide hydroxide or metal silicates having free hydroxyl groups and natural silicates. Hybrid network according to one of claims 1 to 5, characterized in that the compound c) is selected from diisocyanates, preferably 4,4'-methylene-bis (phenyl isocyanate), 2,4- and / or 2,6-toluene diisocyanate, 4, 4'-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate or prepolymers based on said isocyanates with a deficit of hydroxyl and / or amine compounds and having at least two isocyanate-reactive groups by reaction with diols or polyether diols or di- and / or polyamines in one Ratio of -OH and -HN: NCO = 1: 1.3 to 1:10. Hybrid network according to one of claims 1 to 5, characterized in that the compound c) is selected from diepoxides, preferably bis-2,2 '- [4- (2,3-epoxypropoxy) phenyl] propane or its Oligomers (3-12 repeat units) or prepolymers based on these diepoxides with di- and / or polyamines. Hybrid network according to one of claims 1 to 7, characterized in that as catalysts preferably tin, lead and / or bismuth compounds, in particular carboxylates and / or thiocarboxylates are used. Hybrid network according to one of claims 1 to 8, characterized in that as auxiliaries and additives fillers, light stabilizers, flame retardants, moisture stabilizers, pigments are included. Process for the preparation of inorganic-organic hybrid polymeric networks according to one of Claims 1 to 9, characterized in that A hydroxyl-containing polymer a) A nanoscale metal compound b) and A compound c) selected from a di- and / or polyisocyanate or a di- and / or polyepoxide be reacted at temperatures between 40 and 300 ° C and under intense mixing reaction conditions, if appropriate in the presence of catalysts and / or other additives, so that a crosslinking reaction by reaction of the isocyanate or epoxide groups with the inorganic and organic hydroxyl groups occurs. A method according to claim 10, characterized in that in a first step, compounds a) and b) are homogenized under heating and then compound c) is admixed with further heating. A method according to claim 10, characterized in that all compounds are mixed simultaneously with heating. Method according to one of claims 10 to 12, characterized in that the reaction takes place by extrusion, kneading, pressing and / or injection molding. Method according to one of claims 10 to 13, characterized in that the reaction takes place in a combination of kneading into a granulate or powder and its subsequent pressing. Use of the inorganic-organic polymeric hybrid networks according to any one of claims 1 to 9 for the production of shape memory polymers.