MATERIALS FOR USE AS ADHESIVE AND FOR SURFACE SEALING

Abstract

Materials from the group consisting of

a) one or more hybrid materials containing an organic polymer from the group of the polyamides, polyimides and epoxy resins and an inorganic oligo- or polymer from the group of the oligo- and polysiloxanes and heterocondensates of Si with Ti, Zr and/or Al, wherein the organic and the inorganic component are covalently bound to one another, in combination with one or more inorganic sols based on silyl alkoxylates and/or titanium alkoxylates, wherein hybrid material and inorganic sol are crosslinked,
b) one or more hybrid materials containing an organic polymer from the group of the polyamides, polyimides and epoxy resins and an inorganic oligo- or polymer from the group of the oligo- and polysiloxanes and heterocondensates of Si with Ti, Zr and/or Al, wherein the organic and the inorganic component are covalently bound to one another,
c) one or more inorganic sols based on silyl alkoxylates and/or titanium alkoxylates and
d) one or more polyamides, polyimides and/or epoxy resins mixed with oxidic and/or non-oxidic metal and/or metalloid particles, preferably from the group of the oxides, nitrides, carbides and mixtures thereof,
are suitable as adhesive for the bonding of metals, plastics, concrete and/or ceramics.

Claims

1. The use of one or more materials from the group consisting of a) one or more hybrid materials containing an organic polymer from the group of the polyamides, polyimides and epoxy resins and an inorganic oligo- or polymer from the group of the oligo- and polysiloxanes and heterocondensates of Si with Ti, Zr and/or Al, wherein the organic and the inorganic component are covalently bound to one another, in combination with one or more inorganic sols based on silyl alkoxylates and/or titanium alkoxylates, wherein hybrid material and inorganic sol are crosslinked, b) one or more hybrid materials containing an organic polymer from the group of the polyamides, polyimides and epoxy resins and an inorganic oligo- or polymer from the group of the oligo- and polysiloxanes and heterocondensates of Si with Ti, Zr and/or Al, wherein the organic and the inorganic component are covalently bound to one another, c) one or more inorganic sols based on silyl alkoxylates and/or titanium alkoxylates and d) one or more polyamides, polyimides and/or epoxy resins mixed with oxidic and/or non-oxidic metal and/or metalloid particles, preferably from the group of the oxides, nitrides, carbides and mixtures thereof, as adhesive for the bonding of metals, plastics, concrete and/or ceramics.

2. The use according to claim 1, wherein one or more materials from the group a) are used.

3. The use according to claim 1, wherein one or more materials from the group b) are used.

4. The use according to claim 1, wherein one or more materials from the group c) are used.

5. The use according to claim 1, wherein one or more materials from the group d) are used.

6. The use according to claim 1, wherein the adhesive contains encapsulated curing accelerators, preferably selected from the group consisting of water, Lewis acids, Lewis bases and mixtures of these components.

7. The use according to claim 1, wherein the adhesive is doped with magnetic nanoparticles, preferably nanoscale magnetite, wherein the doping serves to detect flaws or defects of the adhesive layer.

8. The use according to claim 1, wherein the adhesive contains one or more fluorine-containing additives.

9. The use according to claim 1, wherein the adhesive contains conduction sensors, which after the application enable detection of flaws.

10. The use according to claim 1, wherein the adhesive contains encapsulated polymerization initiators and encapsulated alkoxysilane precursors, which on the occurrence of defects after the application serve for self-healing.

11. The use according to claim 1, wherein the adhesive is applied in media-carrying pipe systems of steel, stainless steel or inconel, preferably in tank systems in which chemical products are stored or transported.

12. The use according to claim 1, wherein the adhesive serves to line metal or plastic pipes, concrete pipes or tanks with a corrosion-protected metal film.

13. A method for the bonding of two substrates with metal, plastic, concrete and/or ceramic surfaces, wherein one or more adhesives according to claim 1 from the group consisting of a) one or more hybrid materials containing an organic polymer from the group of the polyamides, polyimides and epoxy resins and an inorganic oligo- or polymer from the group of the oligo- and polysiloxanes and heterocondensates of Si with Ti, Zr and/or Al, wherein the organic and the inorganic component are covalently bound to one another, in combination with one or more inorganic sols based on silyl alkoxylates and/or titanium alkoxylates, wherein hybrid material and inorganic sol are crosslinked, b) one or more hybrid materials containing an organic polymer from the group of the polyamides, polyimides and epoxy resins and an inorganic oligo- or polymer from the group of the oligo- and polysiloxanes and heterocondensates of Si with Ti, Zr and/or Al, wherein the organic and the inorganic component are covalently bound to one another, c) one or more inorganic sols based on silyl alkoxylates and/or titanium alkoxylates and d) one or more polyamides, polyimides and/or epoxy resins mixed with oxidic and/or non-oxidic metal and/or metalloid particles, preferably from the group of the oxides, nitrides, carbides and mixtures thereof, are applied onto at least one metal, concrete or ceramic surface of at least one substrate and the two substrates are thereafter joined together.

14. The method according to claim 13, wherein a metal surface is bonded with a metal or plastic surface, preferably metal surface.

15. The method according to claim 13, wherein the adhesive develops its adhesive action through pressing and cures dimensionally stably through pressure.

16. A composition containing ca) a hybrid material, containing an organic polymer from the group of the polyamides, polyimides and epoxy resins and, covalently bound thereto, an inorganic oligo- or polymer from the group of the oligo- or polysiloxanes or corresponding heterocondensates of Si with Ti, Zr and/or Al, and cb) an inorganic sol based on silyl alkoxylates and/or titanium alkoxylates, wherein hybrid material and sol are crosslinked.

17. The composition according to claim 16, containing fluorine-containing additives for the establishment of an antiadhesive surface.

18. The composition according to claim 16, containing titanium dioxide, preferably anatase and/or rutile, particularly preferably anatase, for obtention of a self-cleaning effect under UV irradiation.

19. The use of a composition according to claim 16 as sealing material and/or corrosion protection layer.

Description

EXAMPLES

Materials Used:

[0103] Fluorolink DH 10=perfluoropolyether, OH-terminated
L20: epoxy resin based on bisphenol A with a viscosity of 900+200 mPA*s and an epoxide equivalent of 179+10 g/equiv.
VE 3261: curing agent based on amino group-containing prepolymers (polyethers, silicones, polyaniline) or di-tri-functional amines
SiC UF-10: silicon carbide (d50=0.7 m)
Si.sub.3N.sub.4 (silicon nitride)
Boron nitride

[0104] Aerosil R 202: pyrolytically produced SiO.sub.2 particles with a hydrophobized surface.

Synthetic Procedure A-1:

[0105] 31.14 g of 4,4bis(3-aminophenoxy)diphenylsulphone were placed in a suitable reaction vessel and then treated with 2-methylpyrrolidone (NMP). Next, a 4,4-benzophenone-tetracarboxylic dianhydride suspension (25.78 g) mixed to a paste with NMP was added slowly dropwise. The reaction mixture was stirred for 6 to 8 hrs at room temperature and then treated with 11.2 g of perfluoropolyether (OH terminated) for hydrophobization. In the last synthesis step, 45.41 g of silicon carbide (d.sub.50=0.7 m) in combination with 0.21 g of SiO.sub.2 (d.sub.50=8 nm) were added to the mixture. In order to obtain a homogeneous solution, the polymer dispersion produced was dispersed at 1500 rpm. As a dispersion aid, 10 to 15 g of glass beads were used.

[0106] After dispersion, the material can be used for coating purposes. For application, the viscosity can be adjusted by dilution with NMP. It is preferable to perform a brief ultrasound treatment after each dilution.

Synthetic Procedure B-1:

[0107] 20 g of epoxy resin with a viscosity of 900+200 mPA*s and an epoxide equivalent of 179+10 g/equiv. were placed in a reaction vessel and treated with 5 g of isopropoxyethanol. Next, 0.8 g of HDPE and 0.23 g of a hydroxyl group terminated perfluoropolyether were added for hydrophobization. Next, to improve the corrosion protection, 1.6 g of a zinc phosphate pigment and 3.2 g of zinc oxide as filler were added. For further hydrophobization of the layers and to stabilize the corrosion protection pigments, 0.25 g of hydrophobic silicon dioxide (d.sub.50=8 nm) were added to the reaction solution.

[0108] Directly before application, 5 g of polyetheramine were added for the curing. The mixture was dispersed at 15 C. for 60 min and a speed of 2000 rpm, with the aid of glass beads.

[0109] To adjust the viscosity, NMP, dioxan or isopropoxyethanol can be used.

Synthetic Procedure B-2:

[0110] 20 g of epoxy resin with a viscosity of 900+200 mPA*s and an epoxide equivalent of 179+10 g/equiv were placed in a suitable reaction vessel and treated with NMP. The solution was then cooled to 5 to 10 C. Next, 7.4 g of aminopropyldiethoxysilane were added dropwise. After the full quantity of aminopropyldiethoxysilane had been added dropwise and a stable temperature had been reached, 3.4 g of aminopropyltriethoxysilane were added to the system. For formation of the polysilsesquioxane network, 5.8 ml of a 0.1 molar HCl were slowly added dropwise. The rate at which the hydrochloric acid required was added dropwise was set such that the temperature did not exceed 35 C.

[0111] The material can then be used for coating purposes. For application, the viscosity can be adjusted by dilution with short-chain alcohols, xylene, DMF or dioxan.

Synthetic Procedure B-2:

[0112] 20 g of epoxy resin were placed in a reaction vessel, treated with NMP and cooled to 5 to 10 C. Next, 7.4 g of aminopropyldiethoxysilane were added dropwise. After the complete quantity of aminopropyldiethoxysilane had been added dropwise and a stable temperature had been reached, 3.4 g of aminopropyltriethoxysilane were added to the system. To form the polysilsesquioxane network, 3.2 ml of a 0.1 molar HCl is slowly added dropwise. The rate at which the hydrochloric acid required was added dropwise was adjusted such that the temperature did not exceed 35 C.

[0113] In a second preparation, 20 ml of methyltriethoxysilane and 6 ml of tetraethoxysilane were placed in a reaction vessel and treated with 2.5 ml of a 1 N hydrochloric acid with stirring at room temperature. After addition of the hydrochloric acid, within 5 minutes a clear sol was formed with strong heat evolution. After the reaction mixture had cooled to room temperature, the sol created in preparation 2 was slowly blended with the alkoxysilane-modified epoxy resin.

[0114] The material can then be used for coating purposes. For application the viscosity can be adjusted by dilution with short-chain alcohols, xylene, DMF or dioxan.

Synthetic Procedure C-1:

[0115] 1.5 mol of pyromellitic dianhydride were placed in a suitable reaction vessel and made into a paste with 80 g of ethanol. Next, the heterogeneous solution was cooled to ca. 5 C. 1.5 mol of aminopropyltrieethoxysilane were slowly added dropwise to the mixture. After ca. 30 minutes, a clear solution resulted. Next, the reaction solution was slowly warmed to room temperature.

[0116] The material can then be used for coating purposes. For application the viscosity can be adjusted by dilution with short-chain alcohols, xylene, DMF, dioxan etc.

Synthetic Procedure C-2

[0117] 1.5 mol of pyromellitic dianhydride were placed in a suitable reaction vessel and made into a paste with 80 g of ethanol. Next, the heterogeneous solution was cooled to ca. 5 C. A mixture of 0.70 mol of aminopropyltriethoxysilane and 0.8 mol of aminopropyldiethoxysilane was slowly added dropwise to the mixture. After ca. 30 minutes a clear solution was formed. Next, the reaction solution was slowly warmed to room temperature. The reaction mixture was stirred at room temperature for 6 to 8 hrs and then treated with 5.8 g of alkoxysilane modified perfluoropolyether for the hydrophobization. In the last synthesis step, 15 g of silicon carbide were added to the mixture. In order to obtain a homogenous solution, the polymer dispersion obtained was dispersed at 1500 rpm. 10 to 15 g of glass beads were used as a dispersion aid.

[0118] The material can then be used for coating purposes. For application the viscosity can be adjusted by dilution with short-chain alcohols, xylene, DMF or dioxan.

Synthetic Procedure D-1

[0119] 20 ml of the coating solution produced according to DE 102004001097 B4 were placed in a round-bottomed flask. 30 ml of the materials synthesized on the basis of C1-C2 were slowly added dropwise to this. After a stirring phase of two hours at room temperature, the system could be used as hybrid material for coating and bonding purposes.