Patent Application
20220119635
Rubber and latex are produced via the polymerization of petrochemical monomers. For example, polybutadiene is a synthetic rubber polymer formed from the polymerization of butadiene monomer. Polybutadiene has a high resistance to wear and a high electrical resistivity. Polybutadiene can be used in the manufacture of tires and can also be used as an additive to improve the impact resistance of plastics, for example, polystyrene and acrylonitrile-butadiene-styrene (ABS). Polybutadiene rubber accounted for approximately 25% of total global consumption of synthetic rubbers in 2012. Polybutadiene can also be used to manufacture golf balls, elastic objects, and electronic assembly coatings.
ABS copolymer resins in particular are engineering thermoplastics used in electronics, appliances, business equipment, and automobile parts. Many ABS production processes involve the emulsion polymerization of butadiene monomer. During the emulsion polymerization process, formation of over crosslinked polybutadiene gels, rubber particle agglomerates, degraded rubber particles, fibrous materials, coagulates, and other contaminates, can lead to downstream defects in final ABS products. These defects degrade product quality in applications requiring low contaminant levels, for example, in film, laminating, painting, and electroplating.
DE 10016011 A1 includes a system for separating the particulate products of a suspension polymerisation from the liquid medium and any by-products, unreacted starting materials and/or catalyst, wherein the liquid suspension medium passes through screen(s) and/or filter(s). U.S. Pat. No. 4,064,093 A includes a process for preparing a latex comprising grafted rubber particles for ABS blends, the process comprising preparing said latex and passing it through a porous filter bed means comprising agglomerated particles of said latex, removing coagulum, and producing a filtered latex.
Accordingly, it would be desirable to discover improved rubber and latex production processes, for example, improved polybutadiene and ABS production processes, which result in reduced crosslinking gels, degraded rubber particles, fibrous materials, coagulates, and other agglomerate contaminates. It would be further desirable if such a process also resulted in reduced fouling, corrosion, and final product defect formation. It would be further beneficial still if such a process could reduce the need for butadiene washing, butadiene distillation, styrene cleaning, and/or other cleaning of inert and/or retarding components.
Disclosed, in various embodiments, are a method of forming articles from acrylonitrile-butadiene-styrene.
A method of forming articles from acrylonitrile-butadiene-styrene, the method comprising: feeding a monomer stream comprising a petrochemical monomer into a reactor; contacting the petrochemical monomer with a polymerization activator within the reactor to produce a polymerized stream comprising rubber, latex, or a combination thereof and withdrawing the polymerized stream from the reactor; passing the polymerized stream through a filter to produce a filtered product stream, wherein the filter is a continuously self-cleaning filter; passing the filtered product stream through a grafting unit comprising acrylonitrile and styrene to produce acrylonitrile-butadiene-styrene; and forming an article from the acrylonitrile-butadiene-styrene, wherein the article is an extruded sheet, a molded part, or a combination thereof.
A system for forming articles from acrylonitrile-butadiene-styrene, the system comprising: a monomer stream comprising a petrochemical monomer; a reactor, wherein the petrochemical monomer is contacted with a polymerization activator within the reactor to produce a polymerized stream comprising rubber, latex, or a combination thereof; a filter, wherein the polymerized stream is passed through the filter to produce a filtered product stream, wherein the filter is a continuously self-cleaning filter; a grafting unit, wherein the filtered product stream is passed through the grafting unit comprising acrylonitrile and styrene to produce acrylonitrile-butadiene-styrene; and an extrusion unit, a molding unit, or a combination thereof, wherein an article is formed from the acrylonitrile-butadiene-styrene, wherein the article is an extruded sheet, a molded part, or a combination thereof.
These and other features and characteristics are more particularly described below.
The following is a brief description of the drawing wherein like elements are numbered alike and which is presented for the purposes of illustrating the exemplary embodiments disclosed herein and not for the purposes of limiting the same.
The method disclosed herein can reduce crosslinking gels, coagulates, and agglomerate contaminates, reduce fouling and corrosion, reduce final product defect formation, and reduce need for butadiene washing, butadiene distillation, styrene cleaning, and/or other cleaning of inert and/or retarding components. The method disclosed herein can provide a product with no substantial detectable amounts of gel, for example, less than about 25 parts per million by weight (ppm). The method disclosed herein can also provide a product wherein a substantial amount of the polymer has not been exposed to a crosslinking treatment and therefore does not suffer from restricted molecular mobility which may tend to limit the extension of the polymer under loading.
The method disclosed herein for forming articled from acrylonitrile-butadiene-styrene can include feeding a monomer stream comprising petrochemical monomer into a reactor. For example, the method and filter disclosed herein can be used for the production of polybutadiene, styrene-butadiene, nitrile rubber, acrylics, for example, polymethyl acrylate, or a combination comprising at least one of the foregoing. The method and filter disclosed herein can be used for any rubber or latex production process that involves the removal of coagulate and/or agglomerated particles. For example, the petrochemical monomer can comprise butadiene. The butadiene monomer in the monomer stream can be contacted with an emulsion mixture within the reactor to produce a polymerized stream comprising polybutadiene. For example, a polymerization reaction can take place within the reactor. In the continuous production of polymers by free-radical polymerization, different types of reactors, including continuous-flow stirred tank reactors, tower reactors, horizontal linear flow reactors, tubular reactors, and screw-type reactors, are commonly used.
The reactor can comprise a gas distributor, reflux liquid distributor, feed tray, packing tray, vacuum jacket, inner thermocouples located along a height of the reactor, spiral-prismatic packing, automated flow rate control, automated temperature control, automated pressure control, automated level control, automated composition control, or a combination comprising at least one of the foregoing. The reactor can comprise computer-controlled pumps/compressors. These pumps can control the reactor parameters, for example, flowrates of streams entering and exiting the reactor. The reactor and related streams can be heated using heat exchangers, for example, a Proportional-Integral-Derivative (PID) controlled electronic heater.
A stirred tank reactor can be an agitated, jacketed pressure vessel, with a provision for an overhead condenser for solvent or monomer reflux. Reactors other than stirred tanks may be functionally equivalent to stirred tanks. For example, loop reactors can be used for solution and slurry-phase catalytic olefin polymerizations. In a loop reactor, the agitator in the stirred tank is replaced by a circulation pump. The loop reactor can consist of a jacketed pipe and can include several tube sections connected in series. Due to the very high circulation rate of the reaction mixture, the operation (design equation) of a loop reactor can be approximated by that of a well-stirred tank vessel.
A fixed bed reactor can be a reactor in which the catalyst remains stationary in the reactor and the catalyst particles are arranged in a vessel, generally a vertical cylinder, with the reactants and products passing through the stationary bed. In a fixed bed reactor, the catalyst particles can be held in place, stationary, with respect to a fixed reference frame. The fixed bed reactor may be an adiabatic single bed, a multi-tube surrounded with heat exchange fluid or an adiabatic multi-bed with internal heat exchange, among others. Fixed bed reactors can also be referred to as packed bed reactors. Fixed bed reactors can provide gas solids contacting.
In a moving bed catalytic reactor, gravity can cause the catalyst particles to flow while maintaining their relative positions to one another. The bed can move with respect to the reactor in which it is contained. The reactants can move through this bed with concurrent, countercurrent or crossflow. The moving bed can allow withdrawal of catalyst particles continuously or intermittently so they can be regenerated outside the reactor and reintroduced later on. A moving bed reactor may comprise at least one tray as well as supporting means for one or more catalyst beds. The supporting means can be permeable to gas and impermeable to catalyst particles.
A fluidized bed reactor can be used to carry out a variety of multiphase chemical reactions. In this type of a reactor, a gas can be passed through the catalyst at high enough velocities to suspend the solid and cause it to behave as though it were a fluid. The catalyst particles can be supported by a porous plate. The gas can be forced through the porous plate up through the solid material. At lower gas velocities the solids can remain in place as the gas passes through the voids in the material. As the gas velocity is increased, the reactor can reach a stage where the force of the fluid on the solids is enough to balance the weight of the solid material and above this velocity the contents of the reactor bed can begin to expand and swirl around much like an agitated tank or boiling pot of water. A fluidized bed reactor can provide uniform particle mixing, uniform temperature gradients, and the ability to operate the reactor in a continuous state. The catalyst can leave the reaction zone with the reaction products and can be separated therefrom in order to be regenerated before being recycled to the reaction zone.
A conjugated di-olefin and optionally a copolymerizable olefin can be polymerized within the reactor. Examples of conjugated di-olefin monomers include butadiene-1,3,2-chlorobutadiene-1,3, isoprene, piperylene, chloroprene, cyclobutadiene-1,3,2-phenylbutadiene, 2,3-dimethylbutadiene-1,3 and the like. Representative examples of the copolymerizable olefin monomers include aryl olefins such as styrene, vinyl naphthylene, alpha-methylstyrene, parachlorostyrene and the like; alpha-methylenecarboxylic acids and their esters, amides and nitriles such as acrylic acid, methacrylic acid, acrylonitrile, methacrylamide, and the like, and vinyl halides such as vinylidene chloride, vinyl bromide and the like.
A temperature of the polymerization reaction within the reactor can be from 0 to 50° C. preferably from 0 to 25° C., more preferably from 5 to 20° C. more preferably from 0 to 15° C. A pressure within the reactor can be from 0 kiloPascals to 200 kiloPascals, preferably from 50 kiloPascals to 150 kiloPascals, more preferably from 75 kiloPascals to 125 kiloPascals.
The emulsion mixture can comprise water, a surfactant, and a polymerization activator composition. For example, the emulsion mixture can comprise styrene, butadiene, fatty acid soap, rosin acid soap, electrolyte, chelated iron complex, sodium formaldehyde sulfoxylate, ter-dodecyl mercaptane, di-isopropylbenzene hydroperoxide, p-methanehydroperoxide, or a combination comprising at least one of the foregoing.
The polymerized stream comprising polymerized petrochemical monomer, for example, polybutadiene can be withdrawn from the reactor and can then be passed through a filter. A volumetric flow rate of the polymerized stream through the filter can be from 0.1 cubic meters per second to 5 cubic meters per second, for example, 0.5 cubic meters per second to 1.5 cubic meters per second.
The filter can comprise a shell and a body. For example, the body can be a cylindrical body. The shell and the body can comprise a corrosion resistant material, preferably stainless steel. The body can comprise an inner surface, an outer surface, and openings. For example, the openings can be slits. The polymerized stream can be passed from the inner surface to the outer surface via the openings to remove a particulate contaminate from the polymerized stream. The cylindrical body can allow the polymerized stream to pass through the openings while trapping unwanted particulate contaminates, thus removing particulate contaminates from the polymerized stream. For example, the particular contaminants can comprise crosslinked gel, for example, crosslinked polybutadiene gel, agglomerated rubber particles, degraded rubber particles, fibrous material, coagulate, dirt, rust, or a combination comprising at least one of the foregoing. The openings can be from 1 micrometer to 500 micrometers in diameter, for example, 30 micrometers to 70 micrometers in diameter. For example, the openings can be from 40 micrometers to 60 micrometers in diameter, preferably from 45 micrometers to 55 micrometers in diameter.
The filter can further comprise a mechanized scrubber which contacts the inner surface of the body at a timed interval, thus removing any accumulated particulate contaminate from the body. For example, the mechanized scrubber can scrape particulate contaminate from the inner surface of the body, pushing particulate contaminate downward toward one end of the body. The timed interval for the mechanized scrubber can be from 0.5 hours to 2.5 hours, preferably 1 hour to 1.5 hours. In order to facilitate movement of the mechanized scrubber, the mechanized scrubber can comprise a solenoid mechanism, a spring loaded mechanism, a magnetic drive mechanism, or a combination comprising at least one of the foregoing.
The filter can further comprise a mechanized valve which opens at a timed interval and is located at an end of the body, allowing particulate contaminate to be removed from the filter. The timed interval for the mechanized valve can be longer than the timed interval for the mechanized scrubber, thus allowing accumulation of particulate contaminate before release from the filter via the mechanized valve. The timed interval for the mechanized valve can be from 1 hour to 5 hours, preferably from 3 hours to 4 hours. In order to facilitate movement of the mechanized valve, the mechanized valve can comprise a solenoid mechanism, a spring loaded mechanism, a magnetic drive mechanism, or a combination comprising at least one of the foregoing. The mechanized valve and mechanized scrubber described herein can allow the filter to be “self-cleaning” and to operate continuously without clogs or maintenance.
The filtered product stream can comprise greater than or equal to 99% or a polymerized petrochemical monomer by weight after passing through the filter. For example, the filtered product stream can comprise greater than or equal to 99% polybutadiene by weight after passing through the filter, preferably greater than or equal to 99.9% polybutadiene by weight. The filtered product stream can also comprise less than or equal to 25 ppm of a particulate contaminant after passing through the filter, preferably less than or equal to 10 ppm, more preferably less than or equal to 5 ppm, more preferably less than or equal to 4 ppm. A diameter of a particulate contaminant particle can be less than or equal to 10 micrometers, for example, less than or equal to 5 micrometers, for example, less than or equal to 1 micrometer. Particle diameter can be measured by any suitable method for, for example, in accordance with ISO 13320:2020.
A volume of the filtered product stream can be further passed through a screen after passing through the filter. For example, the screen can be a mesh screen. The volume of the filtered product stream passed through the screen can be from 5 cubic decimeters to 30 cubic decimeters, preferably from 10 cubic decimeters to 20 cubic decimeters, more preferably from 14 cubic decimeters to 16 cubic decimeters, more preferably 15 cubic decimeters. This process can allow for assessment of the upstream filter. For example, the upstream filter is functioning better if less particulate contaminate is trapped by the screen. The screen can comprise stainless steel and openings in the stainless steel, wherein the openings are from 1 micrometer to 500 micrometers in diameter, for example, 40 micrometers to 60 micrometers in diameter, preferably from 40 micrometers to 50 micrometers, more preferably from 40 micrometers to 45 micrometers, more preferably 43 micrometers.
A portion of the filtered product stream can be further passed through a grafting unit comprising acrylonitrile and styrene to produce acrylonitrile-butadiene-styrene. An article can further be formed from the acrylonitrile-butadiene-styrene, via an extrusion unit, a molding unit, or a combination thereof, for example, the article can be an extruded sheet, a molded part, or a combination thereof. For example, the article can be an electronic device, an automotive part, or a combination thereof.
The article can also be substantially free from visible surface defects (e.g., bumps, bubbles, and lumps). For example, a surface of the article can have no visible surface defects as determined by an unaided eye having 20/20 vision in accordance with a Snellen chart. A surface of the article can have an average surface roughness value (Ra) of less than or equal to about 10 micrometers, for example, less than or equal to about 1 micrometer, for example, less than or equal to about 0.5 micrometers. The average surface roughness value (Ra) can be measured by any suitable method, for example, a method in accordance with ISO 4287:1997.
The monomer stream, the polymerized stream, the filtered product stream, the acrylonitrile-butadiene-styrene, or a combination thereof, can be stored in a storage vessel in between any of the method steps described herein. For example, the filtered product stream can be stored in a storage vessel for a period of time prior to being passed through the grafting unit.
A more complete understanding of the components, processes, and apparatuses disclosed herein can be obtained by reference to the accompanying drawings. These figures (also referred to herein as “FIG.”) are merely schematic representations based on convenience and the ease of demonstrating the present disclosure, and are, therefore, not intended to indicate relative size and dimensions of the devices or components thereof and/or to define or limit the scope of the exemplary embodiments. Although specific terms are used in the following description for the sake of clarity, these terms are intended to refer only to the particular structure of the embodiments selected for illustration in the drawings, and are not intended to define or limit the scope of the disclosure. In the drawings and the following description below, it is to be understood that like numeric designations refer to components of like function.
Referring now to
Referring now to
The following examples are merely illustrative of the method and system described herein for forming articles from acrylonitrile-butadiene-styrene and are not intended to limit the scope hereof.
Experimental trials were conducted using a method and system described herein for forming articles from acrylonitrile-butadiene-styrene as shown in
Particulate contaminate levels in polybutadiene latex were evaluated. Polybutadiene product was passed through a filter (as shown in
A sample size of 15.1 liters was shown to be most repeatable due to the low level of contaminate in the polybutadiene product. A mesh opening size of 43 micrometers was shown to be most effective in filtering out particulate contaminates.
Samples of both filtered and unfiltered polybutadiene latex were evaluated. Samples were filtered through a stainless steel mesh screen with 43 micrometer openings. The contaminate levels are shown in Table 3. As shown, the filtration process significantly reduced particulate contaminant levels in the polybutadiene latex samples.
A self-cleaning filter unit (as shown in
In the case of the self-cleaning filter unit (as shown in
Furthermore, a reduction in visible surface defects (e.g., bumps, bubbles, and lumps) of over 95% was surprisingly achieved in downstream formed acrylonitrile-butadiene-styrene articles as determined by a composition analysis of customer-identified defects. The articles can be substantially free from visible surface defects. A surface of the article can have an average surface roughness value (Ra) of less than or equal to about 10 micrometers, for example, less than or equal to about 1 micrometer, for example, less than or equal to about 0.5 micrometers. The average surface roughness value (Ra) can be measured by any suitable method, for example, a method in accordance with ISO 4287:1997.
As demonstrated the method and system disclosed herein can provide a product with reduced crosslinking gels, coagulates, and agglomerate contaminates, higher monomer conversion, less fouling, corrosiveness, and final product defects, and reduced need for employing a short stop agent, monomer recycling, butadiene washing, butadiene distillation, styrene cleaning, and/or other cleaning of inert and/or retarding components. The method disclosed herein can provide a product with no substantial detectable amounts of gel, for example, less than 25 ppm. The method and system disclosed herein can provide a product wherein a substantial amount of the polymer has not been exposed to a crosslinking treatment and therefore does not suffer from restricted molecular mobility which may tend to limit the extension of the polymer under loading.
The methods disclosed herein include(s) at least the following aspects:
Aspect 1: A method of forming articles from acrylonitrile-butadiene-styrene, the method comprising: feeding a monomer stream comprising a petrochemical monomer into a reactor; contacting the petrochemical monomer with a polymerization activator within the reactor to produce a polymerized stream comprising rubber, latex, or a combination thereof and withdrawing the polymerized stream from the reactor; passing the polymerized stream through a filter to produce a filtered product stream, wherein the filter is a continuously self-cleaning filter; passing the filtered product stream through a grafting unit comprising acrylonitrile and styrene to produce acrylonitrile-butadiene-styrene; and forming an article from the acrylonitrile-butadiene-styrene, wherein the article is an extruded sheet, a molded part, or a combination thereof.
Aspect 2: The method of Aspect 1, wherein a volumetric flow rate of the polymerized stream through the filter is from 0.5 cubic meters per second to 1.5 cubic meters per second.
Aspect 3: The method of any of the preceding aspects, further comprising storing the monomer stream, the polymerized stream, the filtered product stream, the acrylonitrile-butadiene-styrene, or a combination thereof, in a storage vessel.
Aspect 4: The method of any of the preceding aspects, wherein the filter comprises: a body, preferably corrosion resistant and cylindrical, comprising an inner surface, an outer surface, and openings having a diameter from 1 micrometer to 500 micrometers, wherein the polymerized stream is passed from the inner surface to the outer surface via the openings to remove a particulate contaminate from the polymerized stream; a mechanized scrubber which contacts the inner surface of the body at a timed interval: and a mechanized valve which opens at a timed interval and is located at an end of the body.
Aspect 5: The method of Aspect 4, wherein the mechanized scrubber, the mechanized valve, or a combination thereof, comprises a solenoid mechanism, a spring loaded mechanism, a magnetic drive mechanism, or a combination comprising at least one of the foregoing.
Aspect 6: The method of any of Aspects 4-5, where the timed interval for the mechanized scrubber is from 0.5 hours to 2.5 hours, preferably from 1 hour to 1.5 hours.
Aspect 7: The method of any of Aspects 4-6, where the timed interval for the mechanized valve is from 1 hour to 5 hours, preferably from 3 hours to 4 hours.
Aspect 8: The method of any of Aspects 4-7, wherein the openings are from 30 micrometers to 70 micrometers in diameter, preferably 40 micrometers to 60 micrometers, more preferably from 45 micrometers to 55 micrometers.
Aspect 9: The method of any of the preceding aspects, wherein the petrochemical monomer comprises butadiene and the filtered product stream comprises greater than or equal to 99% polybutadiene by weight after passing through the filter, preferably greater than or equal to 99.9% polybutadiene by weight.
Aspect 10: The method of any of the preceding aspects, wherein the filtered product stream comprises less than or equal to 25 parts per million of a particulate contaminant by weight after passing through the filter, preferably less than or equal to 10 parts per million by weight, more preferably less than or equal to 5 parts per million by weight, more preferably less than or equal to 4 parts per million by weight.
Aspect 11: The method of Aspect 10, wherein the particulate contaminant comprises crosslinked gel, agglomerated rubber particles, degraded rubber particles, fibrous material, coagulate, dirt, rust, or a combination comprising at least one of the foregoing, and wherein a diameter of a particulate contaminant particle is less than or equal to 10 micrometers, preferably less than or equal to 5 micrometers, preferably less than or equal to 1 micrometer as measured in accordance with accordance with ISO 13320:2020.
Aspect 12: The method of any of the preceding aspects, further comprising passing a volume of the filtered product stream through a screen to provide a secondary filtered product stream, wherein the volume of the filtered product stream is from 5 cubic decimeters to 30 cubic decimeters, preferably from 10 cubic decimeters to 20 cubic decimeters, more preferably from 14 cubic decimeters to 16 cubic decimeters.
Aspect 13: The method of any of the preceding aspects, wherein the article formed from the acrylonitrile-butadiene-styrene is an electronic device, an automotive part, or a combination thereof.
Aspect 14: The method of any of the preceding aspects, wherein the article is substantially free from visible surface defects, wherein a surface of the article has an average surface roughness value (Ra) of less than or equal to about 10 micrometers, preferably, less than or equal to about 1 micrometer, preferably, less than or equal to about 0.5 micrometers, wherein the average surface roughness value (Ra) is measured in accordance with ISO 4287:1997.
Aspect 15: A system for forming articles from acrylonitrile-butadiene-styrene, the system comprising: a monomer stream comprising a petrochemical monomer; a reactor, wherein the petrochemical monomer is contacted with a polymerization activator within the reactor to produce a polymerized stream comprising rubber, latex, or a combination thereof; a filter, wherein the polymerized stream is passed through the filter to produce a filtered product stream, wherein the filter is a continuously self-cleaning filter; a grafting unit, wherein the filtered product stream is passed through the grafting unit comprising acrylonitrile and styrene to produce acrylonitrile-butadiene-styrene; and an extrusion unit, a molding unit, or a combination thereof, wherein an article is formed from the acrylonitrile-butadiene-styrene, wherein the article is an extruded sheet, a molded part, or a combination thereof.
In general, the invention may alternately comprise, consist of, or consist essentially of, any appropriate components herein disclosed. The invention may additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any components, materials, ingredients, adjuvants or species used in the prior art compositions or that are otherwise not necessary to the achievement of the function and/or objectives of the present invention. The endpoints of all ranges directed to the same component or property are inclusive and independently combinable (e.g., ranges of “less than or equal to 25 wt %, or 5 wt % to 20 wt %.” is inclusive of the endpoints and all intermediate values of the ranges of “5 wt % to 25 wt %,” etc.). Disclosure of a narrower range or more specific group in addition to a broader range is not a disclaimer of the broader range or larger group. “Combination” is inclusive of blends, mixtures, alloys, reaction products, and the like. Furthermore, the terms “first,” “second,” and the like, herein do not denote any order, quantity, or importance, but rather are used to denote one element from another. The terms “a” and “an” and “the” herein do not denote a limitation of quantity, and are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. “Or” means “and/or.” The suffix “(s)” as used herein is intended to include both the singular and the plural of the term that it modifies, thereby including one or more of that term (e.g., the film(s) includes one or more films). Reference throughout the specification to “one embodiment”, “another embodiment”, “an embodiment”, and so forth, means that a particular element (e.g., feature, structure, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments.
The modifier “about” used in connection with a quantity is inclusive of the stated value and has the meaning dictated by the context (e.g., includes the degree of error associated with measurement of the particular quantity). The notation “+10%” means that the indicated measurement can be from an amount that is minus 10% to an amount that is plus 10% of the stated value. The terms “front”. “back”, “bottom”, and/or “top” are used herein, unless otherwise noted, merely for convenience of description, and are not limited to any one position or spatial orientation. “Optional” or “optionally” means that the subsequently described event or circumstance can or cannot occur, and that the description includes instances where the event occurs and instances where it does not. Unless defined otherwise, technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art to which this invention belongs. A “combination” is inclusive of blends, mixtures, alloys, reaction products, and the like.
All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if a term in the present application contradicts or conflicts with a term in the incorporated reference, the term from the present application takes precedence over the conflicting term from the incorporated reference.
While particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are or may be presently unforeseen may arise to applicants or others skilled in the art. Accordingly, the appended claims as filed and as they may be amended are intended to embrace all such alternatives, modifications variations, improvements, and substantial equivalents.
| Number | Date | Country | Kind |
|---|---|---|---|
| 19157070.4 | Feb 2019 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/US2020/018275 | 2/14/2020 | WO | 00 |
