Patent Application
20090226710
The present invention relates to mineral flame retardants. More particularly the present invention relates to novel magnesium hydroxide flame retardants, methods of making them, and their use.
Many processes for making magnesium hydroxide exist. For example, in conventional magnesium processes, it is known that magnesium hydroxide can be produced by hydration of magnesium oxide, which is obtained by spray roasting a magnesium chloride solution, see for example U.S. Pat. No. 5,286,285 and European Patent number EP 0427817. It is also known that a Mg source such as iron bitten, seawater or dolomite can be reacted with an alkali source such as lime or sodium hydroxide to form magnesium hydroxide particles, and it is also known that a Mg salt and ammonia can be allowed to react and form magnesium hydroxide crystals.
The industrial applicability of magnesium hydroxide has been known for some time. Magnesium hydroxide has been used in diverse applications from use as an antacid in the medical field to use as a flame retardant in industrial applications. In the flame retardant area, magnesium hydroxide is used in synthetic resins such as plastics and in wire and cable applications to impart flame retardant properties. The compounding performance and viscosity of the synthetic resin containing the magnesium hydroxide is a critical attribute that is linked to the magnesium hydroxide. In the synthetic resin industry, the demand for better compounding performance and viscosity has increased for obvious reasons, i.e. higher throughputs during compounding and extrusion, better flow into molds, etc. As this demand increases, the demand for higher quality magnesium hydroxide particles and methods for making the same also increases.
The present invention relates to magnesium hydroxide particles having:
The present invention also relates to a process comprising:
In another embodiment, the present invention relates to a process comprising:
The magnesium hydroxide particles of the present invention are characterized as having a d50 of less than about 3.5 μm. In one preferred embodiment, the magnesium hydroxide particles of the present invention are characterized as having a d50 in the range of from about 1.2 to about 3.5 μm, more preferably in the range of from about 1.45 to about 2.8 μm. In another preferred embodiment, the magnesium hydroxide particles of the present invention are characterized as having a d50 in the range of from about 0.9 to about 2.3 μm, more preferably in the range of from about 1.25 to about 1.65 μm. In another preferred embodiment, the magnesium hydroxide particles according to the present invention are characterized as having a d50 in the range of from about 0.5 to about 1.4 μm, more preferably in the range of from about 0.8 to about 1.1 μm. In still yet another preferred embodiment, the magnesium hydroxide particles are characterized as having a d50 in the range of from about 0.3 to about 1.3 μm, more preferably in the range of from about 0.65 to about 0.95 μm.
It should be noted that the d50 measurements reported herein were measured by laser diffraction according to ISO 9276 using a Malvern Mastersizer S laser diffraction machine. To this purpose, a 0.5% solution with EXTRAN MA02 from Merck/Germany is used and ultrasound is applied. EXTRAN MA02 is an additive to reduce the water surface tension and is used for cleaning of alkali-sensitive items. It contains anionic and non-ionic surfactants, phosphates, and small amounts of other substances. The ultrasound is used to de-agglomerate the particles.
The magnesium hydroxide particles according to the present invention are also characterized as having a BET specific surface area, as determined by DIN-66132, in the range of from about 1 to 15 m2/g. In one preferred embodiment, the magnesium hydroxide particles according to the present invention have a BET specific surface in the range of from about 1 to about 5 m2/g, more preferably in the range of from about 2.5 to about 4 m2/g. In another preferred embodiment, the magnesium hydroxide particles according to the present invention have a BET specific surface of in the range of from about 3 to about 7 m2/g, more preferably in the range of from about 4 to about 6 m2/g. In another preferred embodiment, the magnesium hydroxide particles according to the present invention have a BET specific surface in the range of from about 6 to about 10 m2/g, more preferably in the range of from about 7 to about 9 m2/g. In yet another preferred embodiment, the magnesium hydroxide particles according to the present invention have a BET specific surface area in the range of from about 8 to about 12 m2/g, more preferably in the range of from about 9 to about 11 m2/g.
The magnesium hydroxide particles of the present invention are also characterized as having a specific median average pore radius (r50). The r50 of the magnesium hydroxide particles according to the present invention can be derived from mercury porosimetry. The theory of mercury porosimetry is based on the physical principle that a non-reactive, non-wetting liquid will not penetrate pores until sufficient pressure is applied to force its entrance. Thus, the higher the pressure necessary for the liquid to enter the pores, the smaller the pore size. A smaller pore size was found to correlate to better wettability of the magnesium hydroxide particles. The pore size of the magnesium hydroxide particles of the present invention can be calculated from data derived from mercury porosimetry using a Porosimeter 2000 from Carlo Erba Strumentazione, Italy. According to the manual of the Porosimeter 2000, the following equation is used to calculate the pore radius r from the measured pressure p: r=−2γ cos(θ)/p; wherein θ is the wetting angle and y is the surface tension. The measurements taken herein used a value of 141.3° for θ and γ was set to 480 dyn/cm.
In order to improve the repeatability of the measurements, the pore size was calculated from the second magnesium hydroxide intrusion test run, as described in the manual of the Porosimeter 2000. The second test run was used because the inventors observed that an amount of mercury having the volume V0 remains in the sample of the magnesium hydroxide particles after extrusion, i.e. after release of the pressure to ambient pressure. Thus, the r50 can be derived from this data as explained below with reference to
In the first test run, a magnesium hydroxide sample was prepared as described in the manual of the Porosimeter 2000, and the pore volume was measured as a function of the applied intrusion pressure p using a maximum pressure of 2000 bar. The pressure was released and allowed to reach ambient pressure upon completion of the first test run. A second intrusion test run (according to the manual of the Porosimeter 2000) utilizing the same sample, unadulterated, from the first test run was performed, where the measurement of the specific pore volume V(p) of the second test run takes the volume V0 as a new starting volume, which is then set to zero for the second test run.
In the second intrusion test run, the measurement of the specific pore volume V(p) of the sample was again performed as a function of the applied intrusion pressure using a maximum pressure of 2000 bar.
From the second magnesium hydroxide intrusion test run, the pore radius r was calculated by the Porosimeter 2000 according to the formula r=−2γ cos(θ)/p; wherein θ is the wetting angle, γ is the surface tension and p the intrusion pressure. For all r measurements taken herein, a value of 141.3° for θ was used and y was set to 480 dyn/cm. The specific pore volume can thus be represented as a function of the pore radius r.
The procedure described above was repeated using a sample of the magnesium hydroxide particles according to the present invention, and the magnesium hydroxide particles were found to have an r50 in the range of from about 0.01 to about 0.5 μm. In a preferred embodiment of the present invention, the r50 of the magnesium hydroxide particles is in the range of from about 0.20 to about 0.4 μm, more preferably in the range of from about 0.23 to about 0.4 μm, most preferably in the range of from about 0.25 to about 0.35 μm. In another preferred embodiment, the r50 is in the range of from about 0.15 to about 0.25 μm, more preferably in the range of from about 0.16 to about 0.23 μm, most preferably in the range of from about 0.175 to about 0.22 μm. In yet another preferred embodiment, the r50 is in the range of from about 0.1 to about 0.2 μm, more preferably in the range of from about 0.1 to about 0.16 μm, most preferably in the range of from about 0.12 to about 0.15 μm. In still yet another preferred embodiment, the r50 is in the range of from about 0.05 to about 0.15 μm, more preferably in the range of from about 0.07 to about 0.13 μm, most preferably in the range of from about 0.1 to about 0.12 μm.
In some embodiments, the magnesium hydroxide particles of the present invention are further characterized as having a linseed oil absorption in the range of from about 15% to about 40%. In one preferred embodiment, the magnesium hydroxide particles according to the present invention can further be characterized as having a linseed oil absorption in the range of from about 16 m2/g to about 25%, more preferably in the range of from about 17% to about 25%, most preferably in the range of from about 19% to about 24%. In another preferred embodiment, the magnesium hydroxide particles according to the present invention can further be characterized as having a linseed oil absorption in the range of from about 20% to about 28%, more preferably in the range of from about 21% to about 27%, most preferably in the range of from about 22% to about 26%. In yet another preferred embodiment, the magnesium hydroxide particles according to the present invention can further be characterized as having a linseed oil absorption in the range of from about 24% to about 32%, more preferably in the range of from about 25% to about 31%, most preferably in the range of from about 26% to about 30%. In still yet another preferred embodiment, the magnesium hydroxide particles according to the present invention can further be characterized as having a linseed oil absorption in the range of from about 27% to about 34%, more preferably in the range of from about 28% to about 33%, most preferably in the range of from about 28% to about 32%.
The magnesium hydroxide particles according to the present invention can be made by mill drying a slurry comprising in the range of from 1 to about 45 wt. %, based on the total weight of the slurry, magnesium hydroxide. In preferred embodiments, the slurry comprises from about 10 to about 45 wt. %, more preferably from about 20 to about 40 wt. %, most preferably in the range of from about 25 to about 35 wt. %, magnesium hydroxide, based on the total weight of the slurry. In this embodiment, the remainder of the slurry is preferably water, more preferably desalted water.
In some embodiments, the slurry may also contain a dispersing agent. Non-limiting examples of dispersing agents include polyacrylates, organic acids, naphtalensulfonate/Formaldehydcondensat, fatty-alcohole-polyglycol-ether, polypropylene-ethylenoxid, polyglycol-ester, polyamine-ethylenoxid, phosphate, polyvinylalcohole. If the slurry comprises a dispersing agent, the magnesium hydroxide slurry that is subjected to mill drying may contain up to about 80 wt. % magnesium hydroxide, based on the total weight of the slurry, because of the effects of the dispersing agent. Thus, in this embodiment, the slurry typically comprises in the range of from 1 to about 80 wt. %, based on the total weight of the slurry, magnesium hydroxide. In preferred embodiments, the slurry comprises from about 30 to about 75 wt. %, more preferably from about 35 to about 70 wt. %, most preferably in the range of from about 45 to about 65 wt. %, magnesium hydroxide, based on the total weight of the slurry.
The slurry can be obtained from any process used to produce magnesium hydroxide particles. In an exemplary embodiment, the slurry is obtained from a process that comprises adding water to magnesium oxide, preferably obtained from spray roasting a magnesium chloride solution, to form a magnesium oxide water suspension. The suspension typically comprises from about 1 to about 85 wt. % magnesium oxide, based on the total weight of the suspension. However, the magnesium oxide concentration can be varied to fall within the ranges described above. The water and magnesium oxide suspension is then allowed to react under conditions that include temperatures ranging from about 50° C. to about 100° C. and constant stirring, thus obtaining a mixture or slurry comprising magnesium hydroxide particles and water. As described above, slurry can be directly mill dried, but in preferred embodiments, the slurry is filtered to remove any impurities solubilized in the water thus forming a filter cake, and the filter cake is re-slurried with water. Before the filter cake is re-slurried, it can be washed one, or in some embodiments more than one, times with de-salted water before re-slurrying.
By mill drying, it is meant that the slurry is dried in a turbulent hot air-stream in a mill drying unit. The mill drying unit comprises a rotor that is firmly mounted on a solid shaft that rotates at a high circumferential speed. The rotational movement in connection with a high air through-put converts the through-flowing hot air into extremely fast air vortices which take up the slurry to be dried, accelerate it, and distribute and dry the slurry to produce magnesium hydroxide particles that have a larger surface area, as determined by BET described above, then the starting magnesium hydroxide particles in the slurry. After having been dried completely, the magnesium hydroxide particles are transported via the turbulent air out of the mill and separated from the hot air and vapors by using conventional filter systems.
The throughput of the hot air used to dry the slurry is typically greater than about 3,000 Bm3/h, preferably greater than about to about 5,000 Bm3/h, more preferably from about 3,000 Bm3/h to about 40,000 Bm3/h, and most preferably from about 5,000 Bm3/h to about 30,000 Bm3/h.
In order to achieve throughputs this high, the rotor of the mill drying unit typically has a circumferential speed of greater than about 40 m/sec, preferably greater than about 60 m/sec, more preferably greater than 70 m/sec, and most preferably in a range of about 70 m/sec to about 140 m/sec. The high rotational speed of the motor and high throughput of hot air results in the hot air stream having a Reynolds number greater than about 3,000.
The temperature of the hot air stream used to mill dry the slurry is generally greater than about 150° C., preferably greater than about 270° C. In a more preferred embodiment, the temperature of the hot air stream is in the range of from about 150° C. to about 550° C., most preferably in the range of from about 270° C. to about 500° C.
As stated above, the mill drying of the slurry results in a magnesium hydroxide particle having a larger surface area, as determined by BET described above, then the starting magnesium hydroxide particles in the slurry. Typically, the BET of the mill-dried magnesium hydroxide is about 10% greater than the magnesium hydroxide particles in the slurry. Preferably the BET of the mill-dried magnesium hydroxide is from about 10% to about 40% greater than the magnesium hydroxide particles in the slurry. More preferably the BET of the mill-dried magnesium hydroxide is from about 10% to about 25% greater than the magnesium hydroxide particles in the slurry.
The magnesium hydroxide particles according to the present invention can be used as a flame retardant in a variety of synthetic resins. Non-limiting examples of thermoplastic resins where the magnesium hydroxide particles find use include polyethylene, polypropylene, ethylene-propylene copolymer, polymers and copolymers of C2 to C8 olefins (α-olefin) such as polybutene, poly(4-methylpentene-1) or the like, copolymers of these olefins and diene, ethylene-acrylate copolymer, polystyrene, ABS resin, AAS resin, AS resin, MBS resin, ethylene-vinyl chloride copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl chloride-vinyl acetate graft polymer resin, vinylidene chloride, polyvinyl chloride, chlorinated polyethylene, chlorinated polypropylene, vinyl chloride-propylene copolymer, vinyl acetate resin, phenoxy resin, polyacetal, polyamide, polyimide, polycarbonate, polysulfone, polyphenylene oxide, polyphenylene sulfide, polyethylene terephthalate, polybutylene terephthalate, methacrylic resin and the like. Further examples of suitable synthetic resins include thermosetting resins such as epoxy resin, phenol resin, melamine resin, unsaturated polyester resin, alkyd resin and urea resin and natural or synthetic rubbers such as EPDM, butyl rubber, isoprene rubber, SBR, NIR, urethane rubber, polybutadiene rubber, acrylic rubber, silicone rubber, fluoro-elastomer, NBR and chloro-sulfonated polyethylene are also included. Further included are polymeric suspensions (latices).
Preferably, the synthetic resin is a polypropylene-based resin such as polypropylene homopolymers and ethylene-propylene copolymers; polyethylene-based resins such as high-density polyethylene, low-density polyethylene, straight-chain low-density polyethylene, ultra low-density polyethylene, EVA (ethylene-vinyl acetate resin), EEA (ethylene-ethyl acrylate resin), EMA (ethylene-methyl acrylate copolymer resin), EAA (ethylene-acrylic acid copolymer resin) and ultra high molecular weight polyethylene; and polymers and copolymers of C2 to C8 olefins (a-olefin) such as polybutene and poly(4-methylpentene-1), polyamide, polyvinyl chloride and rubbers. In a more preferred embodiment, the synthetic resin is a polyethylene-based resin.
The inventors have discovered that by using the magnesium hydroxide particles according to the present invention as flame retardants in synthetic resins, better compounding performance and better viscosity performance, i.e. a lower viscosity, of the magnesium hydroxide containing synthetic resin can be achieved. The better compounding performance and better viscosity is highly desired by those compounders, manufactures, etc. producing final extruded or molded articles out of the magnesium hydroxide containing synthetic resin.
By better compounding performance, it is meant that variations in the amplitude of the energy level of compounding machines like Buss Ko-kneaders or twin screw extruders needed to mix a synthetic resin containing magnesium hydroxide particles according to the present invention are smaller than those of compounding machines mixing a synthetic resin containing conventional magnesium hydroxide particles. The smaller variations in the energy level allows for higher throughputs of the material to be mixed or extruded and/or a more uniform (homogenous) material.
By better viscosity performance, it is meant that the viscosity of a synthetic resin containing magnesium hydroxide particles according to the present invention is lower than that of a synthetic resin containing conventional magnesium hydroxide particles. This lower viscosity allows for faster extrusion and/or mold filling, less pressure necessary to extrude or to fill molds, etc., thus increasing extrusion speed and/or decreasing mold fill times and allowing for increased outputs.
Thus, in one embodiment, the present invention relates to a flame retarded polymer formulation comprising at least one synthetic resin, in some embodiments only one, as described above, and a flame retarding amount of magnesium hydroxide particles according to the present invention, and molded and/or extruded article made from the flame retarded polymer formulation.
By a flame retarding amount of the magnesium hydroxide, it is generally meant in the range of from about 5 wt % to about 90 wt %, based on the weight of the flame retarded polymer formulation, and more preferably from about 20 wt % to about 70 wt %, on the same basis. In a most preferred embodiment, a flame retarding amount is from about 30 wt % to about 65 wt % of the magnesium hydroxide particles, on the same basis.
The flame retarded polymer formulation can also contain other additives commonly used in the art. Non-limiting examples of other additives that are suitable for use in the flame retarded polymer formulations of the present invention include extrusion aids such as polyethylene waxes, Si-based extrusion aids, fatty acids; coupling agents such as amino-, vinyl- or alkyl silanes or maleic acid grafted polymers; barium stearate or calcium sterate; organoperoxides; dyes; pigments; fillers; blowing agents; deodorants; thermal stabilizers; antioxidants; antistatic agents; reinforcing agents; metal scavengers or deactivators; impact modifiers; processing aids; mold release aids, lubricants; anti-blocking agents; other flame retardants; UV stabilizers; plasticizers; flow aids; and the like. If desired, nucleating agents such as calcium silicate or indigo can be included in the flame retarded polymer formulations also. The proportions of the other optional additives are conventional and can be varied to suit the needs of any given situation.
The methods of incorporation and addition of the components of the flame-retarded polymer formulation and the method by which the molding is conducted is not critical to the present invention and can be any known in the art so long as the method selected involves uniform mixing and molding. For example, each of the above components, and optional additives if used, can be mixed using a Buss Ko-kneader, internal mixers, Farrel continuous mixers or twin screw extruders or in some cases also single screw extruders or two roll mills, and then the flame retarded polymer formulation molded in a subsequent processing step. Further, the molded article of the flame-retardant polymer formulation may be used after fabrication for applications such as stretch processing, emboss processing, coating, printing, plating, perforation or cutting. The molded article may also be affixed to a material other than the flame-retardant polymer formulation of the present invention, such as a plasterboard, wood, a block board, a metal material or stone. However, the kneaded mixture can also be inflation-molded, injection-molded, extrusion-molded, blow-molded, press-molded, rotation-molded or calender-molded.
In the case of an extruded article, any extrusion technique known to be effective with the synthetic resins mixture described above can be used. In one exemplary technique, the synthetic resin, magnesium hydroxide particles, and optional components, if chosen, are compounded in a compounding machine to form a flame-retardant resin formulation as described above. The flame-retardant resin formulation is then heated to a molten state in an extruder, and the molten flame-retardant resin formulation is then extruded through a selected die to form an extruded article or to coat for example a metal wire or a glass fiber used for data transmission.
The above description is directed to several embodiments of the present invention. Those skilled in the art will recognize that other means, which are equally effective, could be devised for carrying out the spirit of this invention. It should also be noted that preferred embodiments of the present invention contemplate that all ranges discussed herein include ranges from any lower amount to any higher amount. For example, when discussing the oil absorption of the magnesium hydroxide product particles, it is contemplated that ranges from about 15% to about 17%, about 15% to about 27%, etc. are within the scope of the present invention.
The r50 described in the examples below was derived from mercury porosimetry using a Porosimeter 2000, as described above. All d50, BET, oil absorption, etc., unless otherwise indicated, were measured according to the techniques described above.
200 l/ h of a magnesium hydroxide and water slurry with 33 wt. % solid content was fed to a drying mill. The magnesium hydroxide in the slurry, prior to dry milling, had a BET specific surface area of 4.5 m2/g and a median particle size of 1.5 μm. The mill was operated under conditions that included an air flow rate of between 3000-3500 Bm3/h at a temperature of 290-320° C. and a rotor speed of 100 m/s.
After milling, the mill-dried magnesium hydroxide particles were collected from the hot air stream via an air filter system. The product properties of the recovered magnesium hydroxide particles are contained in Table 1, below.
In this Example, the same magnesium hydroxide slurry used in Example 1 was spray dried instead of being subjected to mill drying. The product properties of the recovered magnesium hydroxide particles are contained in Table 1, below.
As can be seen in Table 1, the BET specific surface area of the magnesium hydroxide according to the present invention (Example 1) increased greater than 30% over the starting magnesium hydroxide particles in the slurry. Further, the oil absorption of the final magnesium hydroxide particles according to the present invention is about 23.6% lower than the magnesium hydroxide particles produced by conventional drying. Further, the r50 of the magnesium hydroxide particles according to the present invention is about 20% smaller than that of the conventionally dried magnesium hydroxide particles, indicating superior wettability characteristics.
The comparative magnesium hydroxide particles of Example 2 and the magnesium hydroxide particles according to the present invention of Example 1 were separately used to form a flame-retardant resin formulation. The synthetic resin used was a mixture of EVA Escorene® Ultra UL00328 from ExxonMobil together with a LLDPE grade Escorene® LL1001 XV from ExxonMobil, Ethanox® 310 antioxidant available commercially from the Albemarle® Corporation, and an amino silane Dynasylan AMEO from Degussa. The components were mixed on a 46 mm Buss Ko-kneader (L/D ratio=11) at a throughput of 22 kg/h with temperature settings and screw speed chosen in a usual manner familiar to a person skilled in the art. The amount of each component used in formulating the flame-retardant resin formulation is detailed in Table 2, below.
In forming the flame-retardant resin formulation, the AMEO silane and Ethanox® 310 were first blended with the total amount of synthetic resin in a drum prior to Buss compounding. By means of loss in weight feeders, the resin/silane/antioxidant blend was fed into the first inlet of the Buss kneader, together with 50% of the total amount of magnesium hydroxide, and the remaining 50% of the magnesium hydroxide was fed into the second feeding port of the Buss kneader. The discharge extruder was flanged perpendicular to the Buss Ko-kneader and had a screw size of 70 mm.
As demonstrated in
In order to determine the mechanical properties of the flame retardant resin formulations made in Example 2, each of the flame retardant resin formulations was extruded into 2 mm thick tapes using a Haake Polylab System with a Haake Rheomex extruder. Test bars according to DIN 53504 were punched out of the tape. The results of this experiment are contained in Table 3, below.
As illustrated in Table 3, the flame retardant resin formulation according to the present invention, i.e. containing the magnesium hydroxide particles according to the present invention, has a Melt Flow Index superior to the comparative flame retardant resin formulation, i.e. containing magnesium hydroxide particles that were produced using conventional methods. Further, the tensile strength and elongation at break of the flame retardant resin formulation according to the present invention is superior to the comparative flame retardant resin formulation.
It should be noted that the Melt Flow Index was measured according to DIN 53735. The tensile strength and elongation at break were measured according to DIN 53504, and the resistivity before and after water ageing was measured according to DIN 53482 on 100×100×2 mm3 pressed plates. The water pick-up in % is the difference in weight after water aging of a 100×100×2 mm3 pressed plate in a de-salted water bath after 7 days at 70° C. relative to the initial weight of the plate.
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/US07/63889 | 3/13/2007 | WO | 00 | 9/22/2008 |
| Number | Date | Country | |
|---|---|---|---|
| 60787844 | Mar 2006 | US |
