Resumen
[0001] The present invention relates to the field porous crystalline materials, more particularly to metal organic frameworks (MOFs) and covalent organic frameworks (COFs). According to this invention, micelles are used as nanoreactors for the synthesis and stabilisation of porous crystalline materials in aqueous dispersions. Disclosed are dispersions comprising such porous crystalline materials, the synthesis and use of such dispersions. Further disclosed are novel porous crystalline materials, the synthesis and use of such crystalline materials. Further disclosed are novel inks comprising the dispersions and non-solvent, the synthesis and use of such inks for direct printing, 2D printing and 3D printing.
Reivindicaciones
1. Claims 1. A colloidal dispersion comprising a continuous phase and micelles dispersed therein, characterized in that • said continuous phase comprising water and optionally one or more additives, ® said micelles comprising surfactants and porous crystalline materials (PCMs) selected from the group consisting of metal organic frameworks (MOFs) and covalent organic frameworks (COFs); • said micelles are between 10 - 1000 nm; • the concentration of said surfactants in said dispersion is above the CMC. 2. The dispersion of claim 1 characterized in that • said dispersion having a micellar size between 15 - 200 nm; and / or • said continuous phase comprises at least 90wt%, preferably at least 95 wt%, water; and / or • said surfactants are selected from the group consisting of cationic surfactants, anionic surfactants and non-ionic surfactants; and/or • said additives, if present, are selected from the group consisting of pH modifiers, ionic strength modifiers, viscosity modifiers, and catalysts; and/or • said micelles are monodisperse in size. 3. An ink comprising a continuous phase and micelles dispersed therein, characterized in that • said continuous phase comprising water, one or more non-solvents and optionally one or more further additives , • said micelles comprising surfactants and porous crystalline materials (PCMs) selected from the group consisting of metal organic frameworks (MOFs) and covalent organic frameworks (COFs); * said micelles are between 10 - 1000 nm; and « the concentration of said surfactants in said dispersion is above the CMC; and • the non-solvent is selected from the group of organic solvents miscible with water and having a dielectric constant in the range of 2 - 50. The ink according to claim 3 characterized in that • the non-solvent is selected from the group consisting of C1-C4 alcohols, C1-C4 aldehydes, C3- C5 ketones, C1-C6 carboxylic acids, C1-C6 carboxylic acid C1-C2 esters, C1-C2 nitriles, and THF; • the ink has a viscosity in the range of 1 - 10<6>cP; and / or • the ink is adapted to 3D printing. A method for manufacturing a dispersion according to claim 1 or 2, said method comprising the steps of: • providing a micellar solution (a) and a micellar solution (b) , whereby o micellar solution (a) comprises a first building block of said porous crystalline material, water, a first surfactant and optionally additives, o micellar solution (b) comprises a second building block of said porous crystalline material, water, a second surfactant and optionally additives ("step i") • combining said micellar solutions (a) and (b) , thereby obtaining said dispersion ("step ii") . 6. The method of claim 5, characterized in that • said step (ii) takes place at temperatures between 10-100°C, preferably 20 - 30°C; • said step (ii) takes place for 0.1-20 hrs; • said step (ii) is effected by providing micellar solution (a) first and adding micellar solution (b) afterwards . 7. A method for manufacturing an ink according to claim 3 or 4, said method comprising the steps of: • providing a colloidal dispersion according to claim 1 or 2 and a non-solvent; • combining said colloidal dispersion with said non solvent, thereby obtaining said ink ("step ix"). 8. Use of a dispersion according to claim 1 or 2 • for the manufacturing of an ink, particularly an ink adapted to 3D printing; ® for manufacturing PCMs in the form of bulk material ; • for manufacturing thin films of PCMs; • for the treatment of water; • as a vehicle for drug delivery; or « as catalyst material in homogeneous catalysis. 9. A method for manufacturing PCMs, as a solid bulk material or in the form of a thin film, said method comprising the steps of: • providing a dispersion according to claim 1 or 2 and • isolating said porous crystalline material ("step iii") . 10. The method according to claim 9, where step (iii) is selected from • solvent precipitation ( iii-a ) , • ph-adj ustment (iii-b) , • centrifugation (iii-c), • osmosis ( iii-d) , coating • printing (iii-e) and combinations thereof. 11. An isolated porous crystalline material, obtainable by or obtained by a method according to claim 9 or 10. 12. A porous crystalline material, said material having the following characteristics: • COF from the class of imines with particle size below 16 nm as isolated bulk material, as a thin film on a support, or in the form of a suspension; • MOF from the class of Catechols with particle size below 20 nm as isolated bulk material, as a thin film on a support, or in the form of a suspension; • TCPP-Cu MOF free of metal in the porphyrin core as isolated bulk material, as a thin film on a support, or in the form of a suspension; • ZIF-8 of square nanoparticles of 30 nm<2>as a nano- dipersion; • MIL 100 (Fe) with particle size below 16nm as isolated bulk material as a thin film on a support, or in the form of a suspension • MOF or COF, particularly RT-COF-1, as a free standing film with a thickness below 500 nm. 13. A method for the treatment of water, said method comprising the steps of: « providing a dispersion according to claim 1 or 2 and • contacting said dispersion with untreated water ("step iv") and • removing dissolved pollutant to thereby obtain treated water ("step v"), particularly wherein said pollutant being selected from the group consisting of heavy metals, organic dyes, active ingredients, and micro pollutants. 14. A method for manufacturing a pharmaceutical product, said method comprising the steps of: • providing a dispersion according to claim 1 or 2 and * contacting said dispersion with an active ingredient ("step vi") particularly wherein said active ingredient is selected from the group consisting of Biomolecules and small molecules. 15. A homogenous catalytic process, said process comprising the steps of: • providing a dispersion according to claim 1 or 2; • optionally contacting said dispersion with a catalytically active component ("step vii") to thereby obtain a modified dispersion; • contacting said modified dispersion with starting materials of said catalytic process ("step viii").
