CA2040363A1 - Surface-treated metal oxides and process for producing same - Google Patents
Surface-treated metal oxides and process for producing sameInfo
- Publication number
- CA2040363A1 CA2040363A1 CA002040363A CA2040363A CA2040363A1 CA 2040363 A1 CA2040363 A1 CA 2040363A1 CA 002040363 A CA002040363 A CA 002040363A CA 2040363 A CA2040363 A CA 2040363A CA 2040363 A1 CA2040363 A1 CA 2040363A1
- Authority
- CA
- Canada
- Prior art keywords
- reactive
- metal oxide
- resin
- process according
- oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 35
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000011248 coating agent Substances 0.000 claims abstract description 27
- 238000000576 coating method Methods 0.000 claims abstract description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 10
- 238000004381 surface treatment Methods 0.000 claims description 9
- 239000011787 zinc oxide Substances 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 4
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 239000000344 soap Substances 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims 2
- 239000012188 paraffin wax Substances 0.000 claims 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims 1
- 239000008187 granular material Substances 0.000 description 9
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 235000014692 zinc oxide Nutrition 0.000 description 9
- 239000000654 additive Substances 0.000 description 5
- 230000009969 flowable effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 238000005204 segregation Methods 0.000 description 4
- 239000011324 bead Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000003979 granulating agent Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 102400000830 Saposin-B Human genes 0.000 description 1
- 101800001697 Saposin-B Proteins 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- -1 for example Chemical compound 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000001665 trituration Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- ZUBNXRHITOZMOO-UHFFFAOYSA-N zinc;octadecanoic acid;oxygen(2-) Chemical compound [O-2].[Zn+2].CCCCCCCCCCCCCCCCCC(O)=O ZUBNXRHITOZMOO-UHFFFAOYSA-N 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3692—Combinations of treatments provided for in groups C09C1/3615 - C09C1/3684
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/04—Compounds of zinc
- C09C1/043—Zinc oxide
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
- C09C3/045—Agglomeration, granulation, pelleting
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/10—Treatment with macromolecular organic compounds
Abstract
Abstract of the Disclosure The invention relates to metal oxides which have been coated with reactive and/or non-reactive coating agents and to a process for producing same, wherein microwave-excitable metal oxides are surface-treated with coating agents and wherein the energy during the coating procedure is supplied by microwaves.
Description
2~4~3~
SURFACE-TREATED METAL OXIDES
I~ND PROCESS FOR PRODUCING SAME
Background of the Inven~-ion The present invention relates to metal oxides which have been coated wi-th reactive and/or non-reactive coating agents and to a process for producing same.
The surface treatment of metal oxides with suitable coating agents by melting the coating agent, optionally with the use of additives, at elevated temperatures in mixers and rotar~r means is known.
Thus, the German Published Unexamined Patent Application (DE-OS) 16 42 990 describes a process for the surface treatment of metal oxides by granulation (pelletization) at an elevated temperature, wherein the granulating agents, mostly polar organic substances in the solid state, are added to and mixed with the metal oxide present in a heatable and coolable fluid mixer equipped with a high-speed rotor. The granulating agent is melted at temperatures between 50~C and 120C with rapid stirring within 10 to ~5 minutes. Then, further aggregates, consis-ting o~ solid or liquid substances, may be added. The mixture is then cooled with further stirring to about ~0C. I'here are obtained granules (pellets) having a particle size of from 0.5 to 5 mm, depending on the mode of operation.
The granulating a~ents in the molten state display -their granulating action as bin~ers, and at room temperature -they act as parting agents which prevent the granules from s-ticking together.
20~03~.~
The granulation above all ensures an improved mixing of the granules in various material. In contrast to the use of powders, the use of granules results in the elimination of dust, and the granules can be metered more readily and more continuously. The electrostatic charge caused by the grinding processes and other processes of motion is reduced, and an adjustment or trituration with binders is rendered unnecessary. Furthermore, granules and/or pellets when stored are largely protected from light and moisture.
Melting binders and additives onto inorganic metal oxides or pigments has been widely described in the literature. However, in the heatable rotary-drum granulators/pelletizers used therein the mixture obtained of the material to be pelletized and the granulating agent is not highly homogeneous. Thus, the surface-treated metal oxide may undergo segregation, when the resulting coated material is subjected to further mechanical processing, e.g.
in the course of the rotation of the granulator drum or granulator pan. Further, there is a risk in that a non-uniform heat distribution arises from the ini-tial heating staye of the granulator drum, also resulting in a segregation of the initially homogeneous granules due to partial melt-off of the coating agent.
Then, an inhomogeneous distribution of the meltable additive in the granules results from the following heating and granulating process. When the mixture is heated in a vessel, molten coating agent will become deposited on the walls of the melting reac-tor vessel.
2~403~
Thus, it is an object of the invention to provide surface-treated metal oxides and a process for producing same, which, on the one hand, retain the appllcation-technological advantages of known surface-treated rnetal oxides such as an improved meterability, flowability, absence of dust and improved incorporation in rubbers, synthetic materials and binders but which, on the other hand, evade the drawbac~s as already mentioned, and especially the segregation of the granules upon heating and the undesirable deposits of molten additives on the walls of the reactor vessel and achieve a highly homogeneous distribution and strong adhesion of the coating agent to the metal oxide.
This object is attained by a metal oxide which has been coated with reactive and/or non-reactive coating agents and is obtainable by a surface treatment of microwave-excitable metal oxides with liquid or solid reactive and/or non-reactive coating a~ents, wherein the energy during the coating procedure has been supplied by microwaves.
This object is further attained by a process for the surface treatment of metal oxides wherein the metal oxides are at leas-t in part excitable by microwaves and the energy supply during the surface treatment is effected by means of microwaves.
Descriptioll o~ Preferrcd Embodiments As the microwave-excitable me-tal oxides there may be employed 2~41~13~
zinc oxide, titanium dioxide, aluminum oxide, cobal-t oxide or mixtures thereof.
As the reactive or non-reactive coating agents there mav be employed ground gum rosins, xylene-indene resins, styrene resins, coumarone-indeneresins, phenol-formaldehyde resins, terpene-phenol resins, solid paraffins, alcohols, fatty alcohols, organic long-chain acids, aromatic polyethers, fatty acid amides, anhydrides of higher carboxylic acids, and solid higher metal soaps. In a particular embodiment the surface-treated metal oxides are granulated or pelletized during or immediately after the coating procedure.
The process according to the invention results in the production of low-dust flowable and readily dispersible metal oxides which, due to a particularly strong adhesion of the surface-treatment agen-t homogeneously applied upon melting, eliminate the drawbacks mentioned of prior art. The direct application of heat by means of microwave energy to a metal oxide contained in the mixture in the absence of a simultaneous mechanical agitation prevents any segregation of the components when heated and any coagulation of the mixturcs as well as a build-up of the binder or coating agent on the rcactor wall.
Namely, the microwave irradiation causes the temperature of the metal oxide to increase in such a way that the coating agent on the reactor walls and withill the mixture is caused to ~omogeneously melt. Also the surface of the metal oxidc is activa-ted by the 2~03~
microwaves in such a way that the coating formed is strongly adhering. In the course of the procedure the temperature distribution within the vessel is homogeneous and, thus, is largely distinguished from a temperature profile obtained upon an external heat supply which results in that the -temperatures within the mixture are lower than those in the outer portion thereof. Upon melting, the metal oxides and coating agent coagulate to form micro-beads and become coated with the organic comDonent.
The temperatures attainable by microwave irradiation of the metal oxide will be even sufficient for causing the oxides to sinter or melt.
In the practice of the process, a rnetal oxide or a mixture of metal oxides is first mixed with the organic additives which preferably are in the powdered state. Then the resulting mixture is exposed to microwaves. Thereupon, the oxide is heated, transferring part of the absorbed heat to the organic components which are not excitable by microwaves and finally causing the organic component(s) to melt and become bonded to the oxide. The irradiation times required are extremely low and are within the range of from 1 to 1~ minutes, and preferably around 5 minutes.
A homogeneous product is thereby ob-tained, the properties of which are only dependent on the degree of homogeneity of the dry premix and, thus, on the grain si~e of the two componen-ts and on the intensity of mixing. The inorganic metal oxide component has been homogeneously covered throughout its surface in this process.
20~363 The surface-treated metal oxide thus produced may be subsecIuently granulated or pelletized without further heat supply be means of conventional procedures to obtain a better flowable and less dust containing product.
The range of applications for surface-treated metal oxides is very wide, especially for zinc oxide.
Thus, resin- or alcohol-treated zinc oxides may be very well incorporated in rubber mixes free from specks. The organic component melts in the admixing step and then is highly viscous and, as a carrier, entrains the oxide into the mixture and homogeneously distributes the oxide therein.
Furthermore, a zinc oxide surface treated with light-protective waxes or other UV-stabilizing organic components synergistically enhances the UV stability of a plastic material such as PVC.
Surface reactions between reactive organic compounds and surface-treated zinc oxide such as, for example, the formation of zinc stearate in the mixture of stearic acid-zinc oxide, result in material combinations which positively affect the vulcanization kinetics. A further application form is the use of surface-treated zinc oxide in numerous dispersin~ operations, wherein the additive added to the oxide ma~ be utilized as a dispersing aid and dispersion stabilizer.
The following Examples serve to illustrate the invention in greater de-tail.
~)403~
Example I:
500 g of zinc oxide were mixed with 5% by weight of finely ground gum rosin in a Lodige mixer (10 minutes), and the mi;ture was transferred into an 800 ml beaker. The beaker was placed into a conventional household microwave apDliance and heated to the melting point of the resin (about 100C) with a radia-tion power of 90 W for 5 minutes. Upon cooling a homogeneous flo~able powder composed of micro-fine beads was obtained. Subse~uen~ drum granulation (residence time 1 hour) led to iurther grain enlargement; then the product was in the form of microqranules.
Example II:
500 g of zinc oxide were mixed with 5% by weight of finely ground l-octadecanol {CH3-(CH2)170H} in a Lodige mixer, and the mixture was transferred into an 800 ml beaker. The beaker was placed into a conventional household microwave appliance and heated to the melting point of the alcohol (about 58-60~C) with a radiation power of 90 W for 5 minutes. Upon cooling a hornogeneous flowable powder composed of micro-fine beads was obtained. Also, with this product a subse(luellt grain enlargelllent ~as achievable by drum granulation.
Example III:
500 g of zinc oxide were mi.ied with 25-o- by weiyht of finely ground gum rosin in a Lodiqe mixer (10 minutes), and the mixture 204~3~i~
was transferred into an 800 ml beaker. The beaker was placed into a conventional household microwave appliance and heated to the melting point of the resin (about 100C) wi-h a radiation power of 90 W for 5 minutes. Upon cooling, a product was obtained which in part consisted of coarse lumps. However, the bigger lumpy pieces could be readily powdered by applying a low mechanical pressure, so that here again a powdery flowable final product was obtained.
Example IV:
250 g of titanium dioxide (rutile) were mixed with 10 -~ by weight of coumarone-indene resin. The mixture was transferred into a beaker and heated in a microwave oven to the melting point of the resin (about 90C) with a radiation power of 600 W for 4 minutes.
A flowable powder composed of micro-fine beads was ob-tained.
SURFACE-TREATED METAL OXIDES
I~ND PROCESS FOR PRODUCING SAME
Background of the Inven~-ion The present invention relates to metal oxides which have been coated wi-th reactive and/or non-reactive coating agents and to a process for producing same.
The surface treatment of metal oxides with suitable coating agents by melting the coating agent, optionally with the use of additives, at elevated temperatures in mixers and rotar~r means is known.
Thus, the German Published Unexamined Patent Application (DE-OS) 16 42 990 describes a process for the surface treatment of metal oxides by granulation (pelletization) at an elevated temperature, wherein the granulating agents, mostly polar organic substances in the solid state, are added to and mixed with the metal oxide present in a heatable and coolable fluid mixer equipped with a high-speed rotor. The granulating agent is melted at temperatures between 50~C and 120C with rapid stirring within 10 to ~5 minutes. Then, further aggregates, consis-ting o~ solid or liquid substances, may be added. The mixture is then cooled with further stirring to about ~0C. I'here are obtained granules (pellets) having a particle size of from 0.5 to 5 mm, depending on the mode of operation.
The granulating a~ents in the molten state display -their granulating action as bin~ers, and at room temperature -they act as parting agents which prevent the granules from s-ticking together.
20~03~.~
The granulation above all ensures an improved mixing of the granules in various material. In contrast to the use of powders, the use of granules results in the elimination of dust, and the granules can be metered more readily and more continuously. The electrostatic charge caused by the grinding processes and other processes of motion is reduced, and an adjustment or trituration with binders is rendered unnecessary. Furthermore, granules and/or pellets when stored are largely protected from light and moisture.
Melting binders and additives onto inorganic metal oxides or pigments has been widely described in the literature. However, in the heatable rotary-drum granulators/pelletizers used therein the mixture obtained of the material to be pelletized and the granulating agent is not highly homogeneous. Thus, the surface-treated metal oxide may undergo segregation, when the resulting coated material is subjected to further mechanical processing, e.g.
in the course of the rotation of the granulator drum or granulator pan. Further, there is a risk in that a non-uniform heat distribution arises from the ini-tial heating staye of the granulator drum, also resulting in a segregation of the initially homogeneous granules due to partial melt-off of the coating agent.
Then, an inhomogeneous distribution of the meltable additive in the granules results from the following heating and granulating process. When the mixture is heated in a vessel, molten coating agent will become deposited on the walls of the melting reac-tor vessel.
2~403~
Thus, it is an object of the invention to provide surface-treated metal oxides and a process for producing same, which, on the one hand, retain the appllcation-technological advantages of known surface-treated rnetal oxides such as an improved meterability, flowability, absence of dust and improved incorporation in rubbers, synthetic materials and binders but which, on the other hand, evade the drawbac~s as already mentioned, and especially the segregation of the granules upon heating and the undesirable deposits of molten additives on the walls of the reactor vessel and achieve a highly homogeneous distribution and strong adhesion of the coating agent to the metal oxide.
This object is attained by a metal oxide which has been coated with reactive and/or non-reactive coating agents and is obtainable by a surface treatment of microwave-excitable metal oxides with liquid or solid reactive and/or non-reactive coating a~ents, wherein the energy during the coating procedure has been supplied by microwaves.
This object is further attained by a process for the surface treatment of metal oxides wherein the metal oxides are at leas-t in part excitable by microwaves and the energy supply during the surface treatment is effected by means of microwaves.
Descriptioll o~ Preferrcd Embodiments As the microwave-excitable me-tal oxides there may be employed 2~41~13~
zinc oxide, titanium dioxide, aluminum oxide, cobal-t oxide or mixtures thereof.
As the reactive or non-reactive coating agents there mav be employed ground gum rosins, xylene-indene resins, styrene resins, coumarone-indeneresins, phenol-formaldehyde resins, terpene-phenol resins, solid paraffins, alcohols, fatty alcohols, organic long-chain acids, aromatic polyethers, fatty acid amides, anhydrides of higher carboxylic acids, and solid higher metal soaps. In a particular embodiment the surface-treated metal oxides are granulated or pelletized during or immediately after the coating procedure.
The process according to the invention results in the production of low-dust flowable and readily dispersible metal oxides which, due to a particularly strong adhesion of the surface-treatment agen-t homogeneously applied upon melting, eliminate the drawbacks mentioned of prior art. The direct application of heat by means of microwave energy to a metal oxide contained in the mixture in the absence of a simultaneous mechanical agitation prevents any segregation of the components when heated and any coagulation of the mixturcs as well as a build-up of the binder or coating agent on the rcactor wall.
Namely, the microwave irradiation causes the temperature of the metal oxide to increase in such a way that the coating agent on the reactor walls and withill the mixture is caused to ~omogeneously melt. Also the surface of the metal oxidc is activa-ted by the 2~03~
microwaves in such a way that the coating formed is strongly adhering. In the course of the procedure the temperature distribution within the vessel is homogeneous and, thus, is largely distinguished from a temperature profile obtained upon an external heat supply which results in that the -temperatures within the mixture are lower than those in the outer portion thereof. Upon melting, the metal oxides and coating agent coagulate to form micro-beads and become coated with the organic comDonent.
The temperatures attainable by microwave irradiation of the metal oxide will be even sufficient for causing the oxides to sinter or melt.
In the practice of the process, a rnetal oxide or a mixture of metal oxides is first mixed with the organic additives which preferably are in the powdered state. Then the resulting mixture is exposed to microwaves. Thereupon, the oxide is heated, transferring part of the absorbed heat to the organic components which are not excitable by microwaves and finally causing the organic component(s) to melt and become bonded to the oxide. The irradiation times required are extremely low and are within the range of from 1 to 1~ minutes, and preferably around 5 minutes.
A homogeneous product is thereby ob-tained, the properties of which are only dependent on the degree of homogeneity of the dry premix and, thus, on the grain si~e of the two componen-ts and on the intensity of mixing. The inorganic metal oxide component has been homogeneously covered throughout its surface in this process.
20~363 The surface-treated metal oxide thus produced may be subsecIuently granulated or pelletized without further heat supply be means of conventional procedures to obtain a better flowable and less dust containing product.
The range of applications for surface-treated metal oxides is very wide, especially for zinc oxide.
Thus, resin- or alcohol-treated zinc oxides may be very well incorporated in rubber mixes free from specks. The organic component melts in the admixing step and then is highly viscous and, as a carrier, entrains the oxide into the mixture and homogeneously distributes the oxide therein.
Furthermore, a zinc oxide surface treated with light-protective waxes or other UV-stabilizing organic components synergistically enhances the UV stability of a plastic material such as PVC.
Surface reactions between reactive organic compounds and surface-treated zinc oxide such as, for example, the formation of zinc stearate in the mixture of stearic acid-zinc oxide, result in material combinations which positively affect the vulcanization kinetics. A further application form is the use of surface-treated zinc oxide in numerous dispersin~ operations, wherein the additive added to the oxide ma~ be utilized as a dispersing aid and dispersion stabilizer.
The following Examples serve to illustrate the invention in greater de-tail.
~)403~
Example I:
500 g of zinc oxide were mixed with 5% by weight of finely ground gum rosin in a Lodige mixer (10 minutes), and the mi;ture was transferred into an 800 ml beaker. The beaker was placed into a conventional household microwave apDliance and heated to the melting point of the resin (about 100C) with a radia-tion power of 90 W for 5 minutes. Upon cooling a homogeneous flo~able powder composed of micro-fine beads was obtained. Subse~uen~ drum granulation (residence time 1 hour) led to iurther grain enlargement; then the product was in the form of microqranules.
Example II:
500 g of zinc oxide were mixed with 5% by weight of finely ground l-octadecanol {CH3-(CH2)170H} in a Lodige mixer, and the mixture was transferred into an 800 ml beaker. The beaker was placed into a conventional household microwave appliance and heated to the melting point of the alcohol (about 58-60~C) with a radiation power of 90 W for 5 minutes. Upon cooling a hornogeneous flowable powder composed of micro-fine beads was obtained. Also, with this product a subse(luellt grain enlargelllent ~as achievable by drum granulation.
Example III:
500 g of zinc oxide were mi.ied with 25-o- by weiyht of finely ground gum rosin in a Lodiqe mixer (10 minutes), and the mixture 204~3~i~
was transferred into an 800 ml beaker. The beaker was placed into a conventional household microwave appliance and heated to the melting point of the resin (about 100C) wi-h a radiation power of 90 W for 5 minutes. Upon cooling, a product was obtained which in part consisted of coarse lumps. However, the bigger lumpy pieces could be readily powdered by applying a low mechanical pressure, so that here again a powdery flowable final product was obtained.
Example IV:
250 g of titanium dioxide (rutile) were mixed with 10 -~ by weight of coumarone-indene resin. The mixture was transferred into a beaker and heated in a microwave oven to the melting point of the resin (about 90C) with a radiation power of 600 W for 4 minutes.
A flowable powder composed of micro-fine beads was ob-tained.
Claims (8)
1. Metal oxide which has been coated with a reactive or non-reactive coating agent, obtained by a surface treatment of microwave-excitable metal oxide with liquid or solid reactive or non-reactive coating agent, wherein the energy during the coating procedure has been supplied by microwaves.
2. A process for the surface treatment of metal oxide with a reactive or non-reactive coating agent, wherein the metal oxide includes a microwave-excitable metal oxide and the energy supply during the surface treatment is effected by means of microwaves.
3. The process according to claim 2, wherein zinc oxide, titanium dioxide, aluminum oxide, cobalt oxide or a mixture thereof is employed as the microwave-excitable metal oxide.
4. The process according to claim 2, wherein the reactive or non-reactive coating agent includes a ground gum rosin, xylene-indene resin, styrene resin, coumarone-indene resin, phenol-formaldehyde resin, terpene-phenol resin, solid paraffin, alcohol, fatty alcohol, organic long-chain acid, aromatic polyether, fatty acid amide, anhydride of higher carboxylic acid, or solid higher metal soap.
5. The process according to claim 3, wherein the reactive or non-reactive coating agent includes a ground gum rosin, xylene-indene resin, styrene resin, coumarone-indene resin, phenol-formaldehyde resin, terpene-phenol resin, solid paraffin, alcohol, fatty alcohol, organic long-chain acid, aromatic polyether, fatty acid amide, anhydride of higher carboxylic acid, or solid higher metal soap.
6. The process according to claim 2, wherein the surface-treated metal oxide is granulated or pelletized during or after the coating procedure.
7. The process according to claim 3, wherein the surface-treated metal oxide is granulated or pelletized during or after the coating procedure.
8. The process according to claim 4, wherein the surface-treated metal oxide is granulated or pelletized during or after the coating procedure.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4012457A DE4012457C2 (en) | 1990-04-19 | 1990-04-19 | Surface treated zinc oxide and process for its manufacture |
| DEP4012457.6 | 1990-04-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2040363A1 true CA2040363A1 (en) | 1991-10-20 |
Family
ID=6404648
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002040363A Abandoned CA2040363A1 (en) | 1990-04-19 | 1991-04-12 | Surface-treated metal oxides and process for producing same |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0452711A3 (en) |
| JP (1) | JPH04227667A (en) |
| CA (1) | CA2040363A1 (en) |
| DE (1) | DE4012457C2 (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06329948A (en) * | 1993-05-21 | 1994-11-29 | Nara Kikai Seisakusho:Kk | Surface modification of powder |
| AU8010494A (en) * | 1993-09-29 | 1995-04-18 | E.I. Du Pont De Nemours And Company | Melt granulation with dielectric heating |
| US5594180A (en) * | 1994-08-12 | 1997-01-14 | Micro Motion, Inc. | Method and apparatus for fault detection and correction in Coriolis effect mass flowmeters |
| FR2734834B1 (en) * | 1995-05-31 | 1997-07-25 | Zschimmer Schwarz France | METHOD FOR MODIFYING THE SURFACE PROPERTIES OF AQUEOUS SUSPENSION PARTICLES AND APPLICATIONS THEREOF |
| US6287374B1 (en) | 1998-09-11 | 2001-09-11 | Shozo Yanagida | Pigment and process for producing the same, water base ink and process for producing the same |
| JP3506942B2 (en) * | 1998-09-11 | 2004-03-15 | 祥三 柳田 | Surface-modified pigment and method for producing the same, aqueous ink and method for producing the same |
| DE10041038B4 (en) * | 2000-08-22 | 2005-05-04 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Spherical metal oxide particles with particulate surface elevations and process for its preparation and their use |
| DE10315185A1 (en) * | 2003-04-03 | 2004-10-14 | Cognis Deutschland Gmbh & Co. Kg | Use of compositions containing basic metal oxides and / or hydroxides for stabilizing halogen-containing organic plastics |
| US8206827B2 (en) * | 2007-03-15 | 2012-06-26 | Nanovere Technologies, Llc | Dendritic polyurethane coating |
| JP5150826B2 (en) * | 2007-05-11 | 2013-02-27 | 国立大学法人宇都宮大学 | Method for producing silica-coated zinc oxide fine particles and silica-coated zinc oxide fine particles obtained by the method |
| JP2008284501A (en) * | 2007-05-18 | 2008-11-27 | Noritake Co Ltd | Granulation method, zirconia granulated powder and zirconia porous body |
| EP2265669B1 (en) | 2008-03-28 | 2018-02-21 | 3M Innovative Properties Company | Filled resins and method for making filled resins |
| CN102037083B (en) | 2008-03-28 | 2014-02-05 | 3M创新有限公司 | Method for surface modification of particles |
| KR20110015572A (en) | 2008-04-25 | 2011-02-16 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | Process for the surface modification of particles |
| EP2298694A4 (en) * | 2008-06-03 | 2011-06-01 | Asahi Glass Co Ltd | Method for producing core-shell particle, core-shell particle, method for producing hollow particle, paint composition and article |
| RU2494045C1 (en) * | 2012-04-27 | 2013-09-27 | Федеральное государственное бюджетное учреждение науки Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук | Method of producing titanium dioxide |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5745335A (en) * | 1980-09-02 | 1982-03-15 | Mitsui Eng & Shipbuild Co Ltd | Heating fluidized bed reactor |
| US4518031A (en) * | 1981-02-24 | 1985-05-21 | Kabushiki Kaisha Komatsu Seisakusho | Method for making molds |
| CA1327769C (en) * | 1986-06-20 | 1994-03-15 | Shoji Ikeda | Powder treating method and apparatus used therefor |
| US5002826A (en) * | 1988-09-01 | 1991-03-26 | James River Corporation Of Virginia | Heaters for use in microwave ovens |
-
1990
- 1990-04-19 DE DE4012457A patent/DE4012457C2/en not_active Expired - Lifetime
-
1991
- 1991-03-26 EP EP19910104721 patent/EP0452711A3/en not_active Withdrawn
- 1991-04-12 CA CA002040363A patent/CA2040363A1/en not_active Abandoned
- 1991-04-19 JP JP3115401A patent/JPH04227667A/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04227667A (en) | 1992-08-17 |
| DE4012457C2 (en) | 2003-12-04 |
| EP0452711A2 (en) | 1991-10-23 |
| DE4012457A1 (en) | 1991-10-24 |
| EP0452711A3 (en) | 1992-08-19 |
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