The present invention relates to a method for preparing an inorganic crystalline ceramic material having an organized structure.
Object of the present invention is to provide a coating of an inorganic ceramic material having excellent barrier and/or antifouling properties. Surprisingly, it has been found that this can be established when nanoparticles of an inorganic ceramic material are modified using a chemical compound having reactive moieties.
Accordingly, the present invention relates to a method for preparing an inorganic crystalline ceramic material having an organized structure, comprising the steps of:
In this way, the nanoparticles of the inorganic ceramic material can advantageously be coupled thereby creating an organized structure which displays excellent barrier and/or antifouling activities.
The molecules of the chemical compound to be used in accordance with the present invention comprise at least a first and a second reactive moiety. Such molecules may, however, each comprise one or more additional reactive moieties.
The first reactive moieties of the molecules of the chemical compound can suitably be selected from the group consisting of halogens (Cl, Br, I) alcohols or alkoxides (OR) (R═H, Na, K, Li) esters or activated esters (O—C═OR), cyanates, isocyanates (NCO), isothiocyanates (NCS), acid chlorides (C(═O)Cl), epoxies, amines (NRR′), carboxylic acids and carboxylates (COOX, with X═Na, H, Li, or K), aldehydes, ketones (C(═O)C), thiols (SH), sulfides (SS) anhydrides and polysulfides (SSSS).
Preferably, the first reactive moiety of the chemical compound is selected from the group consisting of epoxy, amines, and (iso)cyanates. More preferably, the first reactive moieties of the molecules of the chemical compound comprise an epoxy or an isocyanate.
The second reactive moieties of the molecules of the chemical compound can suitably be selected from the group consisting of halogens (Cl, Br, I) alcohols or alkoxides (OR) (R═H, Na, K, Li) esters or activated esters (O—C═OR), cyanates, isocyanates (NCO), isothiocyanates (NCS), acid chlorides (C(═O)Cl), alkenes, epoxies, amines (NRR′), carboxylic acids and carboxylates (COOX(X═Na, H, Li, K)), aldehydes, ketones (C(═O)C), thiols (SH), sulfides (SS) anhydrides and polysulfides (SSSS).
Preferably, the second reactive moieties of the molecules of the chemical compound are selected from the group consisting of amines and (iso)cyanates. More preferably, the second reactive moieties of the molecules of the chemical compound comprise an epoxy or an isocyanate.
In accordance with the present invention, the first reactive moieties of the molecules of the chemical compound and second reactive moieties of the molecule of the chemical compound may either be the same or they may differ from each other.
Preferably, the first reactive moieties of the molecules of the chemical compound and second reactive moieties of the molecules of the chemical compound differ from each other.
In a particular embodiment of the present invention, the present method comprises the steps of
In this way, a bond can be directly or indirectly formed between nanoparticles of a first inorganic ceramic material and nanoparticles of a second inorganic ceramic material.
The molecules of the first and second chemical compound to be used in accordance with the present invention comprise at least a first and a second reactive moiety. Such molecules may, however, each comprise one or more additional reactive moieties.
In step (c), the nanoparticles obtained in step (b) are subjected to a treatment which enables the formation of a direct or indirect bond. Such a chelate or direct bond can be a covalent bond, whereas such an indirect bond can be an ionic bond or metal bridge complexation bond. Suitable treatments to enable the formation of such a direct bond include, for instance, mechano-chemical activation and water absorption. Suitable treatments to enable the formation of such an indirect bond include, for instance, treatment to increase or decrease pH, bead milling and metal salts.
The first reactive moieties of the molecules of the first chemical compound and the first reactive moieties of the molecules of the second chemical compound can suitably be selected from the group consisting of halogens (Cl, Br, I) alcohols or alkoxides (OR) (R═H, Na, K, Li) esters or activated esters (O—C═OR), cyanates, isocyanates (NCO), isothiocyanates (NCS), acid chlorides (C(═O)Cl), epoxies, amines (NRR′), carboxylic acids and carboxylates (COOX(X═Na, H, Li, K)), aldehydes, ketones (C(═O)C), thiols (SH), sulfides (SS) and polysulfides (SSSS).
Preferably, the first reactive moieties of the molecules of the first chemical compound and the first reactive moieties of the molecules of the second chemical compound are selected from the group consisting of amines, epoxies and (iso)cyanates. More preferably, the first reactive moieties of the molecules of the first chemical compound and the first reactive moieties of the molecules of the second chemical compound comprise an epoxy or an isocyanate.
In accordance with the present invention, the first reactive moieties of the molecules of the first chemical compound and the second reactive moieties of the molecules of the first chemical compound may either be the same or they may differ from each other.
Preferably, the first reactive moieties of the molecules of the first chemical compound and the second reactive moieties of the molecules of the first chemical compound differ from each other.
In accordance with the present invention, the first reactive moieties of the molecules of the second chemical compound and the second reactive moieties of the molecules of the second chemical compound may either be the same or they may differ from each other.
Preferably, the first reactive moieties of the molecules of the second chemical compound and the second reactive moieties of the molecules of the second chemical compound differ from each other.
The second reactive moieties of the molecules of the first chemical compound and the second reactive moieties of the molecules of the second chemical compound can suitably be selected from the group consisting of halogens (Cl, Br, I) alcohols or alkoxides (OR) (R═H, Na, K, Li) esters or activated esters (O—C═OR), cyanates, isocyanates (NCO), isothiocyanates (NCS), acid chlorides (C(═O)Cl), epoxies, amines (NRR′), carboxylic acids and carboxylates (COOX(X═Na, H, Li, K)), aldehydes, ketones (C(═O)C), thiols (SH), sulfides (SS) and polysulfides (SSSS).
Preferably, the second reactive moieties of the molecules of the first chemical compound and the second reactive moieties of the molecules of the second chemical compound are selected from the group consisting of alcohols, amines, epoxies and (iso)cyanates.
More preferably, the second reactive moieties of the molecules of the first chemical compound and the second reactive moieties of the molecules of the second chemical compound comprise an amine or an alcohol.
In accordance with the present invention, the first reactive moieties of the molecules of the first chemical compound and the first reactive moieties of the molecules of the second chemical compound may be the same or they may differ from each other. Preferably, the first reactive moieties of the molecules of the first chemical compound and the first reactive moieties of the molecules of the second chemical compound are different.
In accordance with the present invention, the second reactive moieties of the molecules of the first chemical compound and the second reactive moieties of the molecules of the second chemical compound may be the same or they may differ from each other. Preferably, the second reactive moieties of the molecules of the first chemical compound and the second reactive moieties of the second chemical compound are different.
The nanoparticles of the one or more inorganic crystalline ceramic materials in accordance with the present invention suitably have an aspect ratio in the range of from 4 to 1000.
Preferably, the nanoparticles of the one or more inorganic crystalline ceramic materials have an aspect ratio in the range of from 50 to 1000.
Suitably, the nanoparticles to be used in accordance with the present invention have an average particle size in the range of from 20 nm to 800 nm preferably in the range of from 50 nm to 500 nm. In accordance with the present invention, the one or more inorganic crystalline ceramic materials comprise a clay having a layered structure and an exchange capacity of from 5 to 250 milliequivalents per 100 gram.
Suitably, such a clay can be selected from the group consisting of a sepiolite, attapulgite, palygorskite, montmorillonite, saponite, hectoraite, fluorohectorite, beidellite, nontronite, vermiculite, halloysite and stevensite. Preferably, such a clay comprises montmorillonite or hectorite.
Suitably, the metal hydroxide groups of the one or more inorganic ceramic materials comprise Si—OH and/or Al—OH and/or Mg—OH groups.
In a particular embodiment of the present invention, the bond between the second reactive moieties of the molecules of the first or second chemical compound that are present on the respective nanoparticles is formed indirectly by means of molecules of a third chemical compound which molecules each comprise a first and a second reactive moiety, whereby the first and second reactive moieties of the molecules of the third chemical compound form direct bonds with the second reactive moieties of the molecules of the first chemical compound that are covalently bonded to metal hydroxide groups present on the respective nanoparticles and the second moieties of the molecules of the second chemical compound that are covalently bonded to metal hydroxide groups present on the respective nanoparticles.
In such an embodiment the first and second reactive moieties of the molecules of the third chemical compound may be different or the same. Preferably, the first and second reactive moieties of the molecules of the third chemical compound are different. The molecules of the third chemical compound may comprise any of the reactive moieties which have been described hereinbefore. In addition to the first and second moieties the molecules of the third chemical compound may comprise one or more other reactive moieties.
The present invention also relates to a nanocomposite material comprising one or more inorganic crystalline ceramic materials having an organized structure as prepared with the present method, a polymeric matrix and a block copolymer or a graft copolymer.
The inorganic ceramic material having an organized structure as prepared in accordance with the present invention can attractively be used in barrier coatings, antifouling paints or fouling-release paints. Other suitable applications include mechanically improved surface properties, surface finishes, improved barrier properties, formation of a network and percolation.
In addition, the present invention provides a shaped article which comprises an inorganic crystalline ceramic material having an organized structure prepared in accordance with the present invention or a nanocomposite material according to the present invention.
Suitably, the shaped article according to the present invention comprises a coating, which coating comprises an inorganic crystalline ceramic material having an organized structure prepared in accordance with the present invention or the nanocomposite material in accordance with the present invention.
Metal Hydroxides of the Clay Edges were Reacted with an Epoxy-silane Using the Following Procedure:
16.6 g of montmorillonite (clay) were dried at 100° C. in a circulation-oven for 16 hours. The remaining clay (14.62 g) was quickly placed under a nitrogen atmosphere. Next to that, 250 ml of toluene were added, followed by 10.64 g (45 mmol) of (MeO)3Si(CH2)3OCH2CH(cy-O)CH2 and 1 ml of triethylamine (Et3N). This mixture was stirred at room temperature for 1 hour. While stirring, the temperature was risen to 90° C. Stirring was continued for 2 hours, after which time another 5.32 g (22.5 mmol) of (MeO)3Si(CH2)3OCH2CH(cy-O)CH2 was added. Stirring at 90° C. was then continued for 18 hours. After cooling to room temperature, the product was isolated by filtration and washed with 100 ml of toluene (6 times). Finally, the product was dried in vacuum (1 mm Hg) at 40° C. for 16 hours. Yield: 15.3 g of a beige-brown solid. XRD: very broad first reflection at ca. 7.66°2θ with d-spacing 11.5 Å. TGA/DTA: volatiles (<200° C.) 1.9% and the residue at 800° C. was 87.42%.
Metal Hydroxides of the Clay Edges were Reacted with an Amino-silane Using the Following procedure:
This product was prepared as described above in Example 1, now, however, with 9.96 g (45 mmol) and 4.98 g (22.5 mmol) of (EtO)3Si(CH2)3NH2, respectively. Yield: 15.35 g of a beige-brown solid. XRD: very broad first reflection at ca. 8.12° 2θ with d-spacing 10.9 Å. TGA/DTA: volatiles (<200° C.) 2.8% and the residue at 800° C. was 89.05%.
Metal Hydroxides of the Clay Edges were Reacted with an Epoxy-silane Using the Following procedure:
5 g of organically modified Hectorite with Cetyltributylphosphonium (CeBu3P) were dispersed in 75 ml of toluene under nitrogen atmosphere. Then 6.55 g (30 mmol) of EtOSi(Me)2(CH2)3OCH2CH(cy-O)CH2 and 1 ml of Et3N were added while stirring. Stirring was continued for 1 hour at room temperature and 24 hours at 100° C. After cooling to room temperature, the solid product was isolated by centrifugation at 4000 rpm for 30 minutes. Next to that, the product was washed with (by stirring for 15 minutes) 75 ml of toluene (3 times), 75 ml of 96% ethanol (2 times) and 75 ml of water (2 times), each time followed by isolation of the product by centrifugation at 4000 rpm for 15 minutes. Finally, the product was isolated by freeze-drying with 100 g of water. Yield: 3.75 g of a white solid, which was characterized by XRD and TGA/DTA. XRD: broad first reflection at 4.71° 2θ with d-spacing 18.75 Å. TGA/DTA: residue at 800° C. was 68.93%.
Metal Hydroxides of the Clay Edges were Reacted with an Epoxy-silane Using the Following Procedure:
This product was prepared as described above in Example 3, now, however, with 5 g of montmorillonite clay modified with dimethyldioctadecylammonium and 4.37 g (20 mmol) of EtOSi(Me)2(CH2)3OCH2CH(cy-O)CH2. Yield: 4.5 g of a off-white solid.
Metal Hydroxides of the Clay Edges were Reacted with an Epoxy-silane Using the Following Procedure:
5 g of organically modified hectorite with cetyltributylphosphonium (CeBu3P) were dispersed in 75 ml of toluene under nitrogen atmosphere. Then 6.55 g (30 mmol) of EtOSi(Me)2(CH2)3OCH2CH(cy-O)CH2 and 1 ml of Et3N were added while stirring. Stirring was continued for 1 hour at room temperature and 24 hours at 100° C. After cooling to room temperature, the solid product was isolated by centrifugation at 4000 rpm for 30 minutes. Next to that, the product was washed with (by stirring for 15 minutes) 75 ml of toluene (3 times), 75 ml of 96% ethanol (2 times) and 75 ml of water (2 times), each time followed by isolation of the product by centrifugation at 4000 rpm for 15 minutes. Finally, the product was isolated by freeze-drying with 100 g of water. Yield: 3.75 g of a white solid, which was characterized by XRD and TGA/DTA. XRD: broad first reflection at 4.71° 2θ with d-spacing 18.75 Å. TGA/DTA: residue at 800° C. was 68.93%.
Metal Hydroxides of the Clay Edges were Reacted with an Epoxy-silane Using the Following Procedure:
This product was prepared as described above in Example 5, now, however, with 4.84 g (30 mmol) of EtOSi(Me)2(CH2)3NH2. Yield: 2.2 g of a white solid. XRD: broad first reflection at 4.77° 2θ with d-spacing 18.53 Å. TGA/DTA: residue at 800° C. is 71.59%.
Metal Hydroxides of the Clay Edges were Reacted with an Epoxy-silane Using the Following Procedure:
This product was prepared as described above in Example 5, now, however, with 1.95 g of a modified hectorite clay with dimethyldioctadecylammonium and 1.94 g (12 mmol) of EtOSi(Me)2(CH2)3NH2. Yield: 1.21 g of a white solid.
These Samples were Reacted Together to Obtain Self Organized Particles in the Following Way:
0.5 g of clay edged with Si(CH2)3OCH2CH(cy-O)CH2 and 0.5 g of clay edged with Si(CH2)3NH2 were combined and 10 ml of THF are then added. The suspension was stirred at room temperature for 1 hour, followed by stirring at reflux temperature for 1.5 hours. After cooling to room temperature, the mixture was evaporated to dryness. The residue was dried in vacuo (1 mm Hg) at room temperature for 24 hours. Yield: 1 g of an off-white solid.
These Samples were Reacted Together to Obtain Self Organized Particles in the Following Way:
This reaction is performed as described above in Example 8, now, however, in 10 ml of diglyme. After stirring at room temperature for 1 hour, stirring was now continued for 1.5 hours at 90° C. After cooling down to room temperature, the solid(s) were isolated by filtration and washed with 20 ml of THF (4 times). Finally, the product was dried in vacuo (1 mm Hg) at room temperature for 24 hours. Yield: 0.96 g of an off-white solid.
These Samples were Reacted Together to Obtain Self Organized Particles in the Following Way:
0.5 g of clay edged with Si(CH2)3OCH2CH(cy-O)CH2 was stirred in 75 ml of water for 1 hour. Likewise, 0.5 g of clay edged with Si(CH2)3NH2 was stirred in 75 ml of water for 1 hour. Both suspensions were then combined, with the aid of an additionally 50 ml of water. The resulting mixture was placed under an atmosphere of nitrogen and stirred at room temperature for 1 hour, followed by stirring at 75° C. for 2 hours. After cooling to room temperature, the solid(s) were isolated by centrifugation (0.5 hour at 4000 rpm). Finally, the residue was dried in a circulation-oven at 70° C. for 16 hours. Yield: 1.0 g of a very compact, rigid solid.
Number | Date | Country | Kind |
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07118958.3 | Oct 2007 | EP | regional |
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/NL08/50663 | 10/22/2008 | WO | 00 | 6/22/2010 |