Ammonium octamolybdate-metal hydroxide complexes and their use as smoke suppressants

Abstract

A method for making an ammonium octamolybdate / metal hydroxide complex includes pre-contacting ammonium dimolybdate with a metal hydroxide and then contacting with molybdenum trioxide to form an ammonium octamolybdate / metal hydroxide complex. The resulting complex contains a metal hydroxide and 1-95 wt% ammonium octamolybdate, generally at least 80 wt% of the ammonium octamolybdate in the complex is present in the orthorhombic crystal form. These ammonium octamolybdate / metal hydroxide complexes can be used as smoke suppressants in polymer compositions such as PVC-based and epoxy-based formulations.

Description

[Background technology]

[0001] (Reference to Related Application) This application was filed as a PCT international patent application on December 19, 2022, and claims the benefit of and priority to U.S. Provisional Patent Application No. 63 / 291,991, filed December 21, 2021, which is incorporated by reference in its entirety.

[0002] (Background technology) The present invention relates generally to smoke suppressants for use in polymer compositions, and more particularly to ammonium octamolybdate / metal hydroxide complexes that may be used as smoke suppressants in polymer compositions. Summary of the Invention

[0003] This Summary is provided to introduce a selection of concepts in a simplified form that are further described below in the Detailed Description. This Summary is not intended to identify required or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter.

[0004] Disclosed and described herein are methods for preparing ammonium octamolybdate / metal hydroxide complexes. One such method involves reacting ammonium dimolybdate (ADM), molybdenum trioxide (MoO3), and a metal hydroxide in any order in an aqueous system to form an ammonium octamolybdate / metal hydroxide complex. For example, the method may involve pre-contacting ammonium dimolybdate (ADM) with a metal hydroxide, and then contacting molybdenum trioxide (MoO3) to form an ammonium octamolybdate / metal hydroxide complex.

[0005] Ammonium octamolybdate / metal hydroxide complexes are also disclosed and described herein, which complexes may include (i) ammonium octamolybdate (AOM) and (ii) a metal hydroxide, and the amount of AOM present in the complex may range from 1 to 95% by weight, such as 5 to 80% by weight, 5 to 50% by weight, 10 to 60% by weight, or 10 to 30% by weight, etc. Generally, at least 80% by weight, and more often at least 85, 90, 95, 98, or 99% by weight, of the ammonium octamolybdate in the complex is present in the orthorhombic crystal form.

[0006] Polymer compositions are also provided herein, and such compositions may include a polymer and any of the ammonium octamolybdate / metal hydroxide complexes disclosed herein (e.g., produced by any of the methods disclosed herein). The relative amounts of polymer and ammonium octamolybdate / metal hydroxide complex in the composition are not particularly limited, nor is the type of polymer, although the ammonium octamolybdate / metal hydroxide complex is particularly well suited as a smoke suppressant for use in PVC and epoxy-based formulations.

[0007] Both the foregoing general description and the following detailed description provide examples and are for illustrative purposes only. As such, the foregoing general description and the following detailed description should not be considered as limiting. Furthermore, features or variations may be provided in addition to those described herein. For example, particular aspects may be directed to combinations and subcombinations of various features described in the detailed description. [Brief description of the drawings]

[0008] [Figure 1] 1 is an X-ray diffraction (XRD) plot of the powder composite produced in Example 1. [Diagram 2] 1 is an X-ray diffraction (XRD) plot of the powder composite produced in Example 2. [Diagram 3]1 is an X-ray diffraction (XRD) plot of the ammonium octamolybdate mixture produced in Example 9. [Figure 4] 1 is a bar graph of normalized total smoke for flexible PVC polymer composition Examples 1-2 and 8-9 and a control. [Diagram 5] 1 is a bar graph of normalized total smoke for flexible PVC polymer composition Examples 1A-1B and a control. [Figure 6] 1 is a bar graph of total smoke for flexible PVC polymer compositions Example 1C, Example 10, and a control. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] (definition) In order to more clearly define the terms used herein, the following definitions are provided. Unless otherwise stated, the definitions below apply to this disclosure. If a term is used in this disclosure but not specifically defined herein, the definition in the IUPAC Compendium of Chemical Terminology, Second Edition (1997) may apply, unless that definition conflicts with any other disclosure or definition applied herein or renders the claim to which it applies indefinite or invalid. To the extent that a definition or usage provided by a document incorporated herein by reference conflicts with a definition or usage provided herein, the definition or usage provided herein shall take precedence.

[0010] In this specification, the subject features are described so that in certain embodiments, different combinations of features can be envisioned.For any embodiment and any feature disclosed herein, all combinations that do not adversely affect the design, composition, process, or method described herein are contemplated and can be exchanged with or without the explicit description of a specific combination.Therefore, unless expressly stated otherwise, any embodiment or feature disclosed herein can be combined to describe the design, composition, process, or method of the invention consistent with this disclosure.

[0011] Although compositions and methods are described herein in terms of "comprising" various components or steps, unless otherwise indicated, the compositions and methods may also "consist essentially of" or "consist of" the various components or steps. The terms "a," "an," and "the" are intended to include plural options, e.g., at least one, unless otherwise specified.

[0012] Generally, groups of elements are designated using the numbering scheme set forth in the Periodic Table of the Elements, version published in Chemical and Engineering News, 63(5), 27, 1985. In some cases, groups of elements may be designated using the common name assigned to the group, e.g., alkali metals for Group 1 elements, alkaline earth metals for Group 2 elements, etc.

[0013] The term "contacting" is used herein to refer to materials or ingredients that may be contacted or combined by blending, mixing, slurried, dissolved, reacting, processing, compounding, or in any other manner or any suitable method. Unless otherwise specified, the materials or ingredients may be contacted (or reacted) together in any order, in any manner, and for any length of time.

[0014] Molybdenum trioxide (MoO3) may be referred to as molybdenum trioxide, molybdenum(VI) oxide, molybdenum anhydride (or molybdic acid anhydride). As one skilled in the art would readily recognize, in an (acidic) aqueous environment, molybdenum trioxide may form molybdic acid and other species such as hydrates and molybdates. Thus, when the use of molybdenum trioxide in an aqueous mixture or system is disclosed herein, this is meant to encompass any form of molybdenum species or complexes present in an aqueous environment, such as molybdic acid, hydrates, molybdates, etc., and combinations thereof.

[0015] Ammonium octamolybdate (AOM) has the CAS number 12411-64-2 and the chemical formula (NH4)4·Mo8O 26 and often 4(NH4) + ·(Mo8O 26 ) 4- This is expressed as:

[0016] Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, typical methods and materials are described herein.

[0017] All publications and patents mentioned herein are incorporated by reference in their entirety for the purpose of describing and disclosing, for example, the compositions and methodologies described in the publications and patents that may be used in connection with the presently described invention.

[0018] In the present invention, several types of ranges are disclosed. When any type of range is disclosed or claimed, the intent is to separately disclose or claim each possible value that the range may reasonably encompass, including the endpoints of the range, and any subranges and combinations of subranges included. As a representative example, the amount of ammonium octamolybdate / metal hydroxide complex in a polymer composition or formulation may be within a particular range in various embodiments of the present invention. By disclosing that the amount of complex in a polymer composition or formulation may range from 1 to 50 phr, the intent is to recite that the amount of complex may be any phr within the range, for example, 1 to 50 phr, such as 5 to 50 phr, 2 to 40 phr, 5 to 40 phr, 10 to 50 phr, 10 to 40 phr, 10 to 30 phr, or 15 to 40 phr, or any range or combination of ranges. Similarly, all other ranges disclosed herein should be interpreted in a similar manner to this example.

[0019] In general, amounts, sizes, formulations, parameters, ranges, or other quantities or characteristics are "about" or "approximately" whether or not expressly stated. Whether or not modified by the term "about" or "approximately," the claims include equivalents to the quantities or characteristics.

[0020] (Mode for carrying out the invention) The present invention discloses ammonium octamolybdate / metal hydroxide complexes containing metal hydroxide and ammonium octamolybdate (AOM) primarily in orthorhombic crystal form, methods for making the ammonium octamolybdate / metal hydroxide complexes, and polymer compositions and articles containing the ammonium octamolybdate / metal hydroxide complexes.

[0021] It is an object of the present invention to provide improved smoke suppression performance over that of zinc molybdate on borate core materials. Another object of the present invention is to provide improved smoke suppression performance over ammonium octamolybdate (AOM) on inert core materials. AOM is an effective smoke suppressant, especially in PVC-based compositions, but is expensive and has traditionally been used in small amounts (e.g., less than 50% by weight) relative to the inert core material.

[0022] (Method of Manufacturing the Composite) Various methods for producing ammonium octamolybdate / metal hydroxide complexes are provided herein. One such method can include (or consist essentially of, or consist of) reacting ammonium dimolybdate (ADM), molybdenum trioxide (MoO3), and a metal hydroxide in an aqueous system to form an ammonium octamolybdate / metal hydroxide complex. Generally, any feature of the methods disclosed herein (e.g., inter alia, ammonium dimolybdate, molybdenum trioxide, metal hydroxide, aqueous system, ammonium octamolybdate / metal hydroxide complex, and conditions under which the complex is formed) can be described independently herein, and these features can be described independently and any combination of these features can be used to further describe the disclosed methods. Additionally, unless otherwise noted, other method steps can be performed before, during, and / or after any of the steps recited in the disclosed methods. Additionally, any ammonium octamolybdate / metal hydroxide complex produced according to any of the disclosed methods is within the scope of the present disclosure and is encompassed herein.

[0023] The method for making the ammonium octamolybdate / metal hydroxide complex may be carried out at temperatures, typically within the range of 20°C to 98°C, such as, but not limited to, 50°C to 90°C, 75°C to 90°C, 80°C to 98°C, 80°C to 90°C, or 83°C to 93°C, to form the complex. In these and other embodiments, these temperature ranges are also meant to encompass the situation where the ammonium octamolybdate / metal hydroxide complex is formed at a series of different temperatures within each range, rather than at a single fixed temperature. The pressure at which the method is carried out and the complex is formed is not particularly limited, but may be high pressure (e.g., 5 psig to 100 psig), atmospheric pressure, or any suitable subatmospheric pressure. In some cases, the complex is formed at atmospheric pressure, thus eliminating the need for a pressurized vessel and the associated costs and complications. The method may be carried out and the complex formed over a wide range of times, such as, but not limited to, 15 minutes to 24 hours, 30 minutes to 12 hours, 90 minutes to 6 hours, or 2 hours to 10 hours. Other suitable temperature, pressure, and time ranges will be readily apparent from this disclosure.

[0024] In this method, ammonium dimolybdate (ADM), molybdenum trioxide (MoO3), and a metal hydroxide are contacted in an aqueous system to form an ammonium octamolybdate / metal hydroxide complex. Any suitable metal hydroxide compound may be used, such as alkali metal hydroxides, alkaline earth metal hydroxides, and combinations thereof. Generally, such metal hydroxides may function as inorganic flame retardants. In one aspect, the metal hydroxide may include aluminum trihydroxide (also referred to herein as Al(OH)3, aluminum hydroxide, alumina trihydrate, or ATH), in another aspect, the metal hydroxide may include magnesium dihydroxide (also referred to herein as Mg(OH)2, magnesium hydroxide, or MDH), and in yet another aspect, the metal hydroxide may include a mixture of ATH and MDH. Any suitable amount of metal hydroxide may be used, such as 1-99% by weight based on the total amount of reactants. Generally, however, the amount of metal hydroxide is from 20 to 90 weight percent, 50 to 90 weight percent, or 70 to 90 weight percent based on the total amount of reactants.

[0025] Molybdenum trioxide (MoO3) and ammonium dimolybdate (ADM) can be contacted or reacted in a molar ratio of MoO3:ADM that typically falls within the range of 1:1 to 3:1 based on the total amount of each reactant, regardless of the order of addition or contact of the reactants, or the method of addition used. For example, the method can be carried out by contacting ammonium dimolybdate (ADM), molybdenum trioxide (MoO3), and the metal hydroxide substantially simultaneously. Alternatively, the method can be carried out by pre-contacting ammonium dimolybdate (ADM) and the metal hydroxide, and then contacting molybdenum trioxide (MoO3). Molybdenum trioxide (e.g., a slurry in water) can be added slowly at any suitable addition rate and for any suitable time to a mixture of ADM and metal hydroxide in water. As one of ordinary skill in the art would readily recognize, the molar ratio of MoO3:ADM can change as the reaction proceeds. Thus, the disclosed molar ratio ranges encompass any molar ratio that occurs during the reaction and formation of the complex. In further embodiments of the invention, the molar ratio of MoO3:ADM can range from 1.2:1 to 2.8:1, 1.5:1 to 2.5:1, or 1.8:1 to 2.4:1 based on the total amount of each reactant. For example, the molar ratio of MoO3:ADM can range from 1.2:1 to 2.8:1, 1.5:1 to 2.5:1, or 1.8:1 to 2.4:1 based on the total amount of each reactant. 26 may be in a 2:1 (+ / -10%) stoichiometric ratio, reflecting the resulting ammonium octamolybdate having

[0026] The process for forming the ammonium octamolybdate / metal hydroxide complex is carried out in an aqueous system. The aqueous system can comprise (or consist essentially of, or consist of) water. The pH of the aqueous system is not particularly limited, and as one of ordinary skill in the art would readily appreciate, the pH of the aqueous system, and the pH at which the ammonium octamolybdate / metal hydroxide complex is formed, can change as the reaction progresses, particularly if one reactant is added slowly to the other. If desired, the aqueous system can include an acid or base to modify the pH during the process or to control the pH within a particular range. It is not uncommon for the pH to be in the range of 1.5-4 once all the molybdenum trioxide (MoO3) is present in the reaction mixture.

[0027] In some embodiments, the d50 particle size (median particle size) of the molybdenum trioxide can be in the range of 0.5 to 20 μm, e.g., 0.5 to 6 μm, 1 to 10 μm, 1 to 6 μm, 1.6 to 6 μm, or 1.6 to 4 μm. Additionally or alternatively, the d50 particle size (median particle size) of the metal hydroxide can be in the range of 0.5 to 5 μm, e.g., 0.5 to 3 μm, 0.75 to 2 μm, or 0.75 to 1.75 μm. Other suitable particle sizes of molybdenum trioxide and metal hydroxides (e.g., ATH) will be readily apparent from this disclosure.

[0028] Consistent with an embodiment of the present invention, the metal hydroxide may contain 29 ppm (by weight) or less of gallium as measured by ICP-OES. More often, the metal hydroxide (e.g., ATH, MDH, or a mixture of ATH and MDH) contains 27 ppm or less in one embodiment, 25 ppm or less in another embodiment, 23 ppm or less in another embodiment, 20 ppm or less in another embodiment, 15 ppm or less in yet another embodiment, or 10 ppm or less of gallium in yet another embodiment. The ppm by weight of gallium is measured by ICP-OES (inductively coupled plasma optical emission spectroscopy).

[0029] The metal hydroxide may have any suitable BET surface area, for example, in one embodiment, from 1 to 20 m 2 / g, in another embodiment 1 to 15 m 2 / g, and in yet another embodiment, 2 to 10 m 2 / g, and in yet another embodiment, 2 to 6 m 2 / g. The metal hydroxides are further characterized by a low content of soluble Na2O, generally encompassing the range of 0.001-0.035 wt.%. Other typical ranges for the amount of soluble Na2O in the metal hydroxide include 0.001-0.03 wt.%, 0.001-0.018 wt.%, 0.002-0.035 wt.%, 0.002-0.025 wt.%, or 0.002-0.02 wt.%, etc. Additionally, the metal hydroxides may be further characterized by a high TAPPI brightness of 95% or more, more often 97% or more, 98% or more, or 99% or more. In certain embodiments of the invention, the metal hydroxide comprises (or consists essentially of, or consists of) precipitated ATH.

[0030] Optionally, the method for producing the ammonium octamolybdate / metal hydroxide complex may further include removing the ammonium octamolybdate / metal hydroxide complex from the water (slurry) using any suitable separation technique, such as filtration or centrifugation, as well as combinations of these techniques.

[0031] Optionally, the method of making the ammonium octamolybdate / metal hydroxide complex may further include drying the ammonium octamolybdate / metal hydroxide complex using any suitable drying conditions, for example, drying temperatures ranging from 50° C. to 200° C., or from 100° C. to 150° C. may be used, and drying may be performed at atmospheric pressure or any suitable subatmospheric pressure, for example, less than 150 Torr, or less than 50 Torr.

[0032] If desired, the method of making the ammonium octamolybdate / metal hydroxide complex may further include a step of deagglomerating the ammonium octamolybdate / metal hydroxide complex, may further include a step of milling the ammonium octamolybdate / metal hydroxide complex (e.g., ACM milling), or may utilize both deagglomerating and milling steps.

[0033] (Ammonium Octamolybdate / Metal Hydroxide Complex) Consistent with embodiments of the present invention, the ammonium octamolybdate / metal hydroxide complexes described herein (or ammonium octamolybdate / metal hydroxide complexes produced according to any of the methods disclosed herein) may be used in a variety of polymer formulations having beneficial smoke suppression properties. In one embodiment, the ammonium octamolybdate / metal hydroxide complex may include (i) ammonium octamolybdate (AOM) and (ii) a metal hydroxide, and the complex may contain, in one embodiment, 1-95 wt. % AOM, in another embodiment, 5-80 wt. % AOM, in another embodiment, 5-50 wt. % AOM, in yet another embodiment, 10-60 wt. % AOM, and in yet another embodiment, 10-30 wt. % AOM. Other suitable ranges for the amount of AOM in the complex include 10-35 wt. %, 15-35 wt. %, 15-25 wt. %, and the like.

[0034] Typically, at least 80% by weight of the ammonium octamolybdate in the complex is in orthorhombic crystalline form. For example, in one embodiment, at least 85% by weight may be in orthorhombic crystalline form, while in another embodiment, at least 90% by weight may be in orthorhombic crystalline form, and in yet another embodiment, at least 95% by weight may be in orthorhombic crystalline form. In some embodiments consistent with the present invention, at least 98% by weight, or at least 99% by weight, of the ammonium octamolybdate in the complex is in orthorhombic crystalline form. Thus, substantially all (98-99+% by weight) or all (100% by weight) of the ammonium octamolybdate may be in orthorhombic crystalline form.

[0035] Consistent with embodiments of the present invention, the ammonium octamolybdate / metal hydroxide complex may often contain 29 ppm (by weight) or less of gallium as measured by ICP-OES (inductively coupled plasma optical emission spectroscopy). More often, the ammonium octamolybdate / metal hydroxide complex (e.g., AOM-ATH complex) contains gallium of 27 ppm or less in one embodiment, 25 ppm or less in another embodiment, 23 ppm or less in another embodiment, 20 ppm or less in another embodiment, 15 ppm or less in another embodiment, 10 ppm or less in yet another embodiment, or 5 ppm or less in yet another embodiment. The amount of gallium in the complex may vary widely based on the relative amounts of AOM and metal hydroxide (such as ATH) present in the complex. For example, when the composite is about 20% by weight AOM and 80% by weight ATH, typically the gallium content of the composite will be 23 ppm or less, often 20 ppm or less, 16 ppm or less, 12 ppm or less, or 8 ppm or less, or 4 ppm or less.

[0036] Without being limited thereto, the ammonium octamolybdate / metal hydroxide complex can often have a median particle size (d50) in the range of 0.5-10 μm, 0.5-4 μm, 1-10 μm, 1-6 μm, or 1-3 μm. Additionally or alternatively, the complex can have a median particle size (d50) in the range of 2-20 μm in one embodiment. 2 / g (or 2 to 12m 2 / g), in one embodiment 3 to 18 m 2 / g (or 3 to 10m 2 / g), in another embodiment, 4 to 15 m 2 / g (or 4 to 8m 2 / g), and in yet another embodiment, 5 to 12 m 2 / g (or 5-9m 2 The particle size may have any suitable BET surface area, such as 1 / 2 .0 μm / g. Other suitable particle sizes and surface areas will be readily apparent from this disclosure.

[0037] The metal hydroxide component of the ammonium octamolybdate / metal hydroxide complex (or complex) may be characterized by a low content of soluble Na2O, which, as noted above, generally encompasses the range of 0.001-0.035 wt.%. Similarly, other typical ranges for the amount of soluble Na2O in the metal hydroxide component (or complex) include 0.001-0.03 wt.%, 0.001-0.018 wt.%, 0.002-0.035 wt.%, 0.002-0.025 wt.%, or 0.002-0.02 wt.%, etc. Additionally, the metal hydroxide component (or complex) of the complex may be further characterized by a high TAPPI brightness of 95% or greater, more often 97% or greater, or 98% or greater, or 99% or greater.

[0038] Unlike a simple mixture of ammonium octamolybdate and a metal hydroxide, where the individual components can be easily separated, the ammonium octamolybdate / metal hydroxide complexes described herein generally contain AOM bound to the metal hydroxide. Thus, the ammonium octamolybdate and the metal hydroxide components are bound or entangled with each other to form a complex, and the individual components cannot be easily separated in this complex as in a simple mixture. The majority of the metal hydroxide may be present in the core of the complex, and the majority of the AOM may be present in the outer shell, but is not limited thereto.

[0039] Also, without limitation, in some embodiments of the present invention, the ammonium octamolybdate / metal hydroxide composite (or ammonium octamolybdate / metal hydroxide composite produced by any method described herein) may be spherical, i.e., have an average aspect ratio in the range of 1 to 1.5:1, and in some embodiments, the average aspect ratio may be 1:1 to 1.3:1 or 1:1 to 1.2:1. Aspect ratio is defined herein as the longest (measurable) particle dimension divided by the shortest dimension as viewed in a 2D SEM image. The average aspect ratio is the average of the aspect ratios of 10 (measurable) particles from the SEM image.

[0040] (Polymer Composition) The present invention also relates to and encompasses any compositions, formulations, compositions, and articles containing any of the ammonium octamolybdate / metal hydroxide complexes disclosed herein (and their respective properties or characteristics, e.g., surface area, particle size, soluble Na2O content, crystalline morphology, etc.). In certain aspects of the present invention, polymer compositions are disclosed, which may include any suitable polymer(s) and any of the ammonium octamolybdate / metal hydroxide complexes disclosed herein (or ammonium octamolybdate / metal hydroxide complexes produced by any of the methods described herein).

[0041] In one embodiment, the polymer in the polymer composition may comprise a thermoplastic polymer, and in another embodiment, the polymer may comprise a thermosetting polymer. In another embodiment, the polymer may comprise polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), chlorinated polyvinyl chloride (CPVC), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), and / or ethylene chlorotrifluoroethylene (ECTFE), either alone or in any combination. In yet another embodiment, the polymer may comprise plasticized PVC or unplasticized PVC. In yet another embodiment, the polymer may comprise rigid PVC, or the polymer may comprise flexible PVC. Generally, rigid PVC may be referred to as unplasticized PVC, and flexible PVC may be referred to as plasticized PVC.

[0042] As one of ordinary skill in the art would readily recognize, PVDC may be referred to as polyvinylidene chloride, but it may also be referred to as poly(vinylidene chloride). Similarly, PVC may be referred to as polyvinyl chloride, but it may also be referred to as poly(vinyl chloride).

[0043] In one embodiment, the polymer may include an epoxy resin. For example, the polymer may include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin, bisphenol F novolac type epoxy resin, diphenylethylene epoxy resin, epoxy resin with triazine skeleton, epoxy resin with fluorene skeleton, triphenylmethane type epoxy resin, biphenyl epoxy resin, xylylene epoxy resin, biphenyl aralkyl epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, and / or alicyclic epoxy resin, etc., either alone or in any combination.

[0044] Without being limited thereto, the amount of ammonium octamolybdate / metal hydroxide complex in the polymer composition can often range from 1 to 50 phr (parts by weight per 100 parts of resin). Thus, exemplary and non-limiting amounts of ammonium octamolybdate / metal hydroxide complex in the polymer composition can include ranges of 5 to 50 phr, 2 to 40 phr, 5 to 40 phr, 10 to 50 phr, 10 to 40 phr, 10 to 30 phr, or 15 to 40 phr. Other suitable ranges for the amount of ammonium octamolybdate / metal hydroxide complex in the polymer composition will be readily apparent from this disclosure.

[0045] Optionally, the polymer composition may further comprise any suitable additives, non-limiting examples of which may include stabilizers, lubricants, inorganic flame retardants (e.g., aluminum trihydrate or magnesium hydroxide), fillers, colorants, or curing agents, and the like, and combinations thereof.

[0046] The article may be formed from and / or include any of the polymer compositions described herein. In one embodiment, the article may include a wire or cable, and in another embodiment, the article may include a printed circuit board. Other suitable articles and end uses will be readily apparent from this disclosure.

[0047] For example, the ammonium octamolybdate / metal hydroxide composites can be used in at least three applications of industrial synthetic prepregs as well as in microelectronics manufacturing, benefiting from improved end product properties and improved manufacturing methods: the first is printed circuit boards (PCBs), the second is epoxy molding compounds (EMCs) such as microchip packaging, and the third is industrial synthetic prepregs such as aerospace and automotive end uses where flame retardancy and drilling are required.

[0048] Printed circuit boards (PCBs) are prevalent in electronics for consumer and industrial products such as televisions, cell phones, and computers. Manufacturers typically manufacture circuit boards using flame-retardant chemicals to ensure fire safety. Flame retardants may prevent fires from starting altogether or delay the onset of flashover, slowing the spread stage of a fire and extending the evacuation time window. In either case, flame retardants serve the primary purpose of reducing the risk of fatalities from fires. However, there are growing concerns about the fate and toxicity of some flame retardant chemicals if released into the environment. This is the case with Tetrabromobisphenol A or TBBPA. TBBPA is the most widely used flame retardant for PCBs. Here, a single composition offers several benefits such as halogen-free flame retardancy, improved drilling, thermal expansion control, and dimensional stability.

[0049] A basic PCB consists of flat sheets of insulating material and layers of copper foil laminated to a substrate. Chemical etching breaks the copper into features such as individual conductive lines called tracks or circuit traces, pads for connections, vias that pass connections between layers of copper, and solid conductive areas for electromagnetic shielding or other purposes. Printed circuit boards can have multiple copper layers. Two-layer boards have copper on both sides, and multi-layer boards sandwich additional copper layers between layers of insulating material. Conductors on different layers are connected with vias, which are copper-plated holes that act as electrical tunnels through the insulating substrate. Leads on through-hole components often also effectively function as vias. "Through-hole" components are attached by leads that pass through the substrate and are soldered to traces on the other side. Through-hole manufacturing increases the cost of the substrate because many holes must be precisely drilled. PCB holes larger than 76.2 micrometers in diameter are typically drilled using solid-coated tungsten carbide drill bits. Beneficially, the disclosed compositions have high thermal stability and are suitable for lead-free soldering.

[0050] Important properties are the level of flame retardancy of the laminate, the dielectric constant (er), loss factor (tδ), tensile strength, shear strength, glass transition temperature (Tg), and Z-axis expansion coefficient (how much thickness changes with temperature). Thermal expansion is an important consideration, especially in ball grid array (BGA) and naked die technologies, and glass fibers generally offer the best dimensional stability. As substrate sizes shrink and frequencies increase, small inhomogeneities such as uneven distribution of glass fibers or other fillers, thickness variations, and air bubbles within the resin matrix and the associated local variations in dielectric constant become important. The small particle size of the disclosed composites is consistent with these concerns.

[0051] The composites described herein can be used as fillers in epoxy molding compounds (EMCs). Epoxy molding compounds are widely used in encapsulating semiconductor devices due to their excellent properties, such as high mechanical strength and high productivity. Generally, a liquid epoxy polymer is injected onto the circuit and cured to a solid for protection. Here, the composites impart extremely low coefficient of thermal expansion (CTE), good dimensional stability, and flame retardancy to the packaging of semiconductor devices without significant increase in viscosity during the manufacturing process.

[0052] When referring to industrial synthetic prepreg applications, prepreg stands for "pre-impregnated" synthetic fibers. More specifically, prepreg is a composite material in which the reinforcing fibers are pre-compounded with a thermoplastic or thermosetting resin matrix. It is a synthetic material form that requires additional conversion or fabrication into a final fully cured part. Epoxy resin is the most common thermosetting polymer matrix material. The fibers are often in the form of a woven fabric, and the matrix is ​​used to glue them together or to other components during manufacturing. The thermosetting matrix is ​​easy to handle because it is only partially cured. This partially cured epoxy material is also called B-stage material. Synthetic prepregs are increasingly found to be used for high performance applications in various industrial sectors. Examples of the use of prepreg include aircraft interiors, aerospace parts, aircraft flooring, cargo liners, automotive parts and components, tools, bulletproof panels, electronic transmission applications, sporting goods, high rise flooring, high impact flooring, rotor blades in wind turbines, and orthopedic technology in orthotics and prosthetics. The composites described herein, when added as fillers, provide the necessary flame retardancy, very low coefficient of thermal expansion (CTE), and good dimensional stability.

[0053] The composite can also be used for high heat conductive materials due to its high thermal conductivity and low viscosity due to the spherical shape of the particles. The composite can also be surface treated with silanes and other surfactants, such as epoxy silanes, phenylamino silanes, methacryl silanes, isocyanate silanes, etc. After surface treatment, the properties of the compound can be improved. The advantages include lower viscosity of the resin compound, better compatibility with polymer resins, and less aggregation.

[0054] If desired, the complex may be subjected to close packing techniques, such as a combination of larger particles of the complex with smaller particles of the complex (e.g., a bimodal particle size distribution) rather than a single particle size distribution, which may improve the viscosity of the compound at very high loading levels (up to 80 wt. % or more). EXAMPLES

[0055] The present invention is further illustrated by the following examples, which should not be construed as imposing limitations on the scope of the invention in any way. After reading the description herein, various other embodiments, modifications, and equivalents thereof will occur to those skilled in the art without departing from the spirit of the invention or the scope of the appended claims.

[0056] The d50 particle size, or median particle size, refers to the particle size at which 50% by weight of the sample has a smaller size and 50% of the sample has a larger size. Particle size measurements were determined by laser diffraction according to ISO 13320 using a Beckman Coulter LS 13 320 single wavelength laser diffraction particle size analyzer.

[0057] BET surface areas were determined by Brunauer et al., J. Am. Chem. Soc., 60, 309 (1938) using a Micromeritics TriStar II surface area and porosity analyzer.

[0058] The soluble Na2O content (wt%) was measured by flame emission photometry and the TAPPI brightness was measured according to test method T452.

[0059] (Examples 1 to 9) In Example 1, 177.0 g (520.7 mmol) of ammonium dimolybdate (d50 of 20-25 μm, Climax Molybdenum Company) and 3.3 L of deionized water were placed in a reaction vessel equipped with an agitator and temperature controller and heated to 88° C. with stirring. Once the ammonium dimolybdate was completely dissolved, 1308.0 g of fine precipitated aluminum hydroxide (ATH, Hydral 710, Huber Engineered Materials, produced from ground aluminum hydroxide via digestion and recrystallization process, d50 of 1.1 μm, 4 mm diameter) was added. 2 A 100.0 g (1042.1 mmol) of molybdenum trioxide (Langeloth Metallurgical Company) was added to the ammonium dimolybdate solution (0.016 wt. % BET, 0.016 wt. % soluble Na2O, 99+% brightness, 13.4 μS / cm conductivity). The precipitated ATH contained gallium in the range of 20-22 ppm by weight as measured by ICP-OES (three tests). Separately, a slurry was made by adding 150.0 g (1042.1 mmol) of molybdenum trioxide (Langeloth Metallurgical Company) and 600.0 g of deionized water to a beaker at 88°C. Once both were well mixed, the molybdenum trioxide slurry was pumped at 8 mL / min using a peristaltic pump into the reaction vessel containing the ammonium dimolybdate solution with fine precipitated aluminum hydroxide particles. The reaction mixture was then stirred at 88°C for 8 hours. The resulting mixture was then poured into a glass pan and dried overnight in a 120°C oven. The dried product was deagglomerated in a Henschel at 1800 rpm for 3 min and subsequently hammer milled to a specific particle size distribution (d50 of approximately 2.5 μm and d50 of approximately 8 m 2 / g BET).

[0060] In Example 2, 177.0 g (520.7 mmol) of ammonium dimolybdate (d50 of 20-25 μm, Climax Molybdenum Company) and 3.3 L of deionized water were placed in a reaction vessel equipped with an agitator and temperature controller and heated to 88 °C with stirring. Once the ammonium dimolybdate was completely dissolved, 1308.0 g of ground aluminum hydroxide (ATH, Micral 932, Huber Engineered Materials, manufactured from bauxite ore using the Bayer process, d50 of 2 μm, 13 mmol) was added. 2 0.05 wt% soluble Na2O, 93% brightness, 93.2 μS / cm conductivity) was added to the ammonium dimolybdate solution. The ground ATH contained gallium in the range of 30-31 ppm by weight as measured by ICP-OES (three tests). Separately, a slurry was made by adding 150.0 g (1042.1 mmol) of molybdenum trioxide (Langeloth Metallurgical Company) and 600.0 g of deionized water to a beaker at 88 °C. Once both were well mixed, the molybdenum trioxide slurry was pumped at 8 mL / min using a peristaltic pump into the reaction vessel containing the ammonium dimolybdate solution with ground aluminum hydroxide particles. The reaction mixture was then stirred at 88 °C for 8 hours. The resulting mixture was then poured into a glass pan and dried overnight in a 120 °C oven. The dried product was deagglomerated in a Henschel at 1800 rpm for 3 min and subsequently hammer milled to a specific particle size distribution (d50 of approximately 2.5 μm and d50 of approximately 8 m 2 / g BET).

[0061] In Example 3, 81.7 g (567.6 mmol) of molybdenum trioxide (Langeloth Metallurgical Company) and 3.1 L of deionized water were placed in a reaction vessel equipped with an agitator and temperature controller and heated to 88°C with stirring. Once the molybdenum trioxide was completely dissolved, 704.0 g of fine precipitated aluminum hydroxide (ATH, Hydral 710) was added to the molybdenum trioxide solution. Separately, a slurry was made by adding 98.2 g (288.9 mmol) of ammonium dimolybdate (d50 of 20-25 μm, Climax Molybdenum Company) and 400.0 g of deionized water to a beaker at 88°C. Once both were well mixed, the ammonium dimolybdate solution was pumped at 8 mL / min using a peristaltic pump into the reaction vessel containing the molybdenum trioxide solution with fine precipitated aluminum hydroxide particles. The reaction mixture was then stirred for 8 hours at 88° C. The resulting mixture was then poured into a glass pan and dried overnight in an oven at 120° C. The dried product was deagglomerated in a Henschel at 1800 rpm for 3 minutes, followed by hammer milling to reduce the particle size distribution.

[0062] In Example 4, 81.7 g (567.6 mmol) of molybdenum trioxide (Langeloth Metallurgical Company) and 3.1 L of deionized water were placed in a reaction vessel equipped with an agitator and temperature controller and heated to 88°C with stirring. Once the molybdenum trioxide was completely dissolved, 704.0 g of ground aluminum hydroxide (ATH, Micral 932) was added to the molybdenum trioxide solution. Separately, a slurry was made by adding 98.2 g (288.9 mmol) of ammonium dimolybdate (d50 of 20-25 μm, Climax Molybdenum Company) and 400.0 g of deionized water to a beaker at 88°C. Once both were well mixed, the ammonium dimolybdate solution was pumped using a peristaltic pump at 8 mL / min into the reaction vessel containing the molybdenum trioxide solution with ground aluminum hydroxide particles. The reaction mixture was then stirred at 88°C for 8 hours. The resulting mixture was then poured into a glass pan and dried overnight in an oven at 120° C. The dried product was deagglomerated in a Henschel at 1800 rpm for 3 minutes and subsequently hammer milled to reduce the particle size distribution to a specific size.

[0063] In Example 5, 49.1 g (144.4 mmol) of ammonium dimolybdate (d50 of 20-25 μm, Climax Molybdenum Company) and 1.6 L of deionized water were placed in a reaction vessel equipped with an agitator and temperature controller and heated to 88 °C with stirring. Once the ammonium dimolybdate was completely dissolved, 352.1 g of zinc borate (Firebrake ZB Fine, USBorax) was added to the ammonium dimolybdate solution. Separately, a slurry was made by adding 40.9 g (284.1 mmol) of molybdenum trioxide (Langeloth Metallurgical Company) and 200.0 g of deionized water to a beaker at 88 °C. Once both were well mixed, the molybdenum trioxide slurry was pumped at 8 mL / min using a peristaltic pump into the reaction vessel containing the ammonium dimolybdate solution with zinc borate particles. The reaction mixture was then stirred for 8 hours at 88° C. The resulting mixture was then poured into a glass pan and dried overnight in an oven at 120° C. The dried product was deagglomerated in a Henschel at 1800 rpm for 3 minutes, followed by hammer milling to reduce the particle size distribution.

[0064] In Example 6, 80.0 g (555.8 mmol) of molybdenum trioxide (Langeloth Metallurgical Company) and 3.2 L of deionized water were placed in a reaction vessel equipped with an agitator and temperature controller and heated to 88°C with stirring. Once the molybdenum trioxide was completely dissolved, 700.0 g of zinc borate (Firebrake ZB Fine) was added to the molybdenum trioxide solution. Separately, a slurry was made by adding 96.0 g (282.4 mmol) of ammonium dimolybdate (d50 of 20-25 μm, Climax Molybdenum Company) and 400.0 g of deionized water to a beaker at 88°C. Once both were well mixed, the ammonium dimolybdate solution was pumped using a peristaltic pump at 8 mL / min into the reaction vessel containing the molybdenum trioxide solution with zinc borate particles. The reaction mixture was then stirred at 88°C for 8 hours. The resulting mixture was then poured into a glass pan and dried overnight in an oven at 120° C. The dried product was deagglomerated in a Henschel at 1800 rpm for 3 minutes and subsequently hammer milled to reduce the particle size distribution to a specific size.

[0065] In Example 7, 36.0 g (250.1 mmol) of molybdenum trioxide (Langeloth Metallurgical Company) and 8.0 L of deionized water were placed in a reaction vessel equipped with an agitator and temperature controller and heated to 88° C. with stirring. Once the molybdenum trioxide was completely dissolved, 160.0 g of talc (ABT 1000, Barretts Minerals Inc.) was added to the molybdenum trioxide solution. After mixing for 10 minutes, 15.0 g (128.4 mmol) of ammonium hydroxide solution (30 wt%) was pumped into the reactor vessel containing the molybdenum trioxide solution with talc particles at 2 mL / min for 1 minute every 10 minutes using a peristaltic pump until the entire amount of solution was transferred. The reaction mixture was then stirred at 88° C. for 8 hours. The resulting mixture was then poured into a glass pan and dried overnight in a 120° C. oven. The dried product was deagglomerated in a Henschel at 1800 rpm for 3 min and subsequently hammer milled to reduce the particle size distribution to a specific size.

[0066] In Example 8, 177.0 g (520.7 mmol) of ammonium dimolybdate (d50 of 20-25 μm, Climax Molybdenum Company) and 3.3 L of deionized water were placed in a reaction vessel equipped with an agitator and temperature controller and heated to 88°C with stirring. Separately, 150.0 g (1042.1 mmol) of molybdenum trioxide (Langeloth Metallurgical Company) and 600.0 g of deionized water were added to a beaker at 88°C to prepare a slurry. Once the ammonium dimolybdate was completely dissolved and the molybdenum trioxide slurry was well mixed, the slurry was pumped using a peristaltic pump at 8 mL / min into the reaction vessel containing the ammonium dimolybdate solution. Then, 1308.0 g of finely precipitated aluminum hydroxide (Hydral 710) was added to the reaction mixture, which was stirred at 88°C for 8 hours. The resulting mixture was then poured into a glass pan and dried overnight in an oven at 120° C. The dried product was deagglomerated in a Henschel at 1800 rpm for 3 minutes and subsequently hammer milled to reduce the particle size distribution to a specific size.

[0067] In Example 9, 40.0 g of ammonium octamolybdate (prepared from ADM and MoO) and 160.0 g of finely precipitated aluminum hydroxide (Hydral 710) were placed in a polypropylene bottle and the bottle was dried overnight at about 25° C. in a modified Blue M oven.

[0068] X-ray powder diffraction (XRD) is an analytical technique used primarily for phase identification of crystalline materials. The material to be analyzed is finely ground and homogenized. The basic principle of X-ray powder diffraction (XRD) was discovered by Max von Laue in 1912: crystalline materials act as a three-dimensional diffraction lattice with X-ray wavelengths similar to the interplanar spacing of the crystal lattice. X-ray diffraction is now a common technique for studying crystal structures and atomic spacing. X-ray diffraction is based on the constructive interference of monochromatic X-rays with a crystalline sample. These X-rays are generated by a cathode ray tube, filtered to produce monochromatic radiation, collimated, concentrated, and directed towards the sample. When conditions satisfy Bragg's law (nλ=2dsinθ), constructive interference (and diffracted rays) are produced by the interaction of the incident beam with the sample. This law relates the wavelength of electromagnetic radiation to the diffraction angle and lattice spacing of the crystalline sample. These diffracted X-rays are detected, processed, and counted. By scanning the sample over a range of 2θ angles, all possible diffraction directions of the lattice should be obtained due to the random orientation of the powder materials. Since each material has a unique set of d-spacings, converting the diffraction peaks to d-spacings makes it possible to identify the materials. The d-spacings of each peak are then obtained by the solution of the Bragg equation for the appropriate λ value. Once all d-spacings have been determined, an automated search / match routine compares the d of the sample to the d of known materials. Since each material has a unique set of d-spacings, samples are identified by matching these d-spacings. A systematic procedure is used by ordering the d-spacings in terms of intensity starting with the most intense peak. Files of d-spacings for hundreds of thousands of inorganic compounds are available as Powder Diffraction Files (PDF) from the International Diffraction Data Center.

[0069] Here, samples were loaded into a standard or background-zero sample holder and placed in a Panalytical X'pert MPD diffractometer using Cu radiation at 45 KV / 40 mA. Scans were performed in the range of 6°-80° with a step size of 0.0131° and an accumulated count time of 250 seconds per step. Once the diffraction patterns were obtained, phases were identified utilizing powder diffraction files or the Inorganic Crystal Structure Database published by the International Diffraction Data Center. The amount of crystalline phases was determined by Rietveld refinement.

[0070] FIG. 1 is an XRD plot of the powder composite produced in Example 1. FIG. 2 is an XRD plot of the powder composite produced in Example 2. FIG. 3 is an XRD plot of the ammonium octamolybdate mixture produced in Example 9. In addition to ATH (about 80 wt%) and about 1-3 wt% amorphous product, the composite of Example 1 (FIG. 1) contained about 17-19 wt% orthorhombic AOM, and surprisingly, substantially all (at least 99 wt% or more) of the AOM present in the composite was in orthorhombic crystalline form. In addition to ATH (about 80 wt%) and about 1-3 wt% amorphous product, the composite of Example 2 (FIG. 2) contained about 17-19 wt% chromium amine gallium molybdenum oxide hydroxide hydrate (Cr(NH3)6)(GaMo6O 18 (OH)6)·5H2O). Unexpectedly, no AOM was produced in Example 2, despite the fact that a type of ATH was used in both Examples 1 and 2. Without wishing to be bound by any particular theory, it is believed that the presence of high levels of gallium in the ATH of Example 2 may have prevented the formation of AOM. Example 9 was a dry mixture of 80 wt% ATH and 20 wt% AOM, and the AOM prepared in this manner was primarily (about 95 wt%) α-AOM (triclinic crystal form) with only about 2 wt% orthorhombic AOM, and about 3 wt% unreacted MoO3, as shown in Figure 3.

[0071] For the composites of Examples 1-2 and 8-9, the composites were incorporated into plasticized polyvinyl chloride using a two-stage melt blend compounding method. In the first step, PVC, plasticizer, stabilizer, lubricant, antimony trioxide, ATH, and MgOH2 were mixed using a Henschel mixer at a temperature of 90°C to form a PVC premix of the composition shown in Table I. In the second step, various amounts of the composites were added to the PVC premix and mixed for 5 minutes at 165°C and 45 rpm using a Brabender Intelli-Torque Plasti-Corder mixer equipped with roller blades. Samples for analysis were prepared by pressing the material using a Givin PHI hydraulic press at a pressure of 78.3 bar and a temperature of 196°C.

[0072] [Table 1]

[0073] Table II summarizes the PVC formulations containing the composites of Examples 1-2 and 8-9, as well as a control utilizing only a PVC premix, and Table III summarizes the PVC formulations containing different amounts of the composite of Example 1, as well as a control utilizing only a PVC premix.

[0074] [Table 2]

[0075] [Table 3]

[0076] A cone calorimeter (DEATAK CC-2) was used to test the flame retardancy of the samples according to the procedure described in ASTM E 1354. Specimens measuring 100mmx100mmx0.635mm were exposed in a horizontal orientation. The experiment was performed at 50kW / m 2 An external heat flux of 100 m was used. Measured parameters included total smoke production (m 2 / m 2) and normalized total smoke generation (m 2 / m 2 / g) were included. Data reported were the average of three experiments.

[0077] For the formulations shown in Table II, as shown in Figure 4, the normalized total smoke (m per gram of polymer composition sample) for the flexible PVC polymer compositions containing the composites of Examples 1-2 and 8-9 at 15 phr, as well as the control (which did not contain any smoke suppressant) was 1.0 phr. 2 / m 2 ) is a bar graph summarizing the smoke suppressant yield and smoke suppression performance of the formulations containing the smoke suppressant complexes. As expected, each formulation containing the smoke suppressant complexes reduced the total amount of smoke compared to the control. Unexpectedly, however, the formulation containing the complex of Example 1 had the lowest smoke yield and provided approximately 12-18% better smoke suppression performance than the formulations containing the complexes of Examples 8-9, and approximately 7% better smoke suppression performance than the formulation containing the milled ATH-based complex of Example 2. Surprisingly, the formulation containing the complex of Example 1 (AOM bound to ATH) had significantly better smoke suppression performance than the formulation containing the complex of Example 9 (a physical blend of AOM and ATH).

[0078] FIG. 5 shows the normalized total smoke (m per gram of polymer composition sample) for flexible PVC polymer compositions containing the composite of Example 1 at 15 phr (1A) and 25 phr (1B), as well as a control (containing no smoke suppressant) for the formulations shown in Table III. 2 / m 2 ) Increasing the smoke suppressant loading from 15 phr to 25 phr reduced the total smoke production of the control by nearly 50%.

[0079] For the composite of Example 1 and ammonium octamolybdate (AOM), these materials were incorporated into plasticized polyvinyl chloride using the methods described above. The PVC premixes had the compositions shown in Table IV. Example 1 at 15 phr (Example 1C) and AOM at 15 phr (Example 10) were tested in the formulations of Table IV and compared to a control example utilizing only the PVC premix.

[0080] [Table 4]

[0081] FIG. 6 shows the total smoke (m ) of a flexible PVC polymer composition containing the composite of Example 1 at 15 phr (Example 1C), AOM at 15 phr (Example 10), and a control (no smoke suppressant was included). 2 / m 2 ) is a bar graph summarizing the smoke suppressant composites used in the study. As expected, each formulation containing the smoke suppressant composite dramatically reduced the total amount of smoke compared to the control. Unexpectedly, however, the formulation of Example 1C (containing the composite of Example 1) produced less smoke and performed approximately 12% better in smoke suppression than the formulation containing 100% AOM. This is particularly beneficial because AOM is much more expensive than ATH, and Example 1 contained only about 20% AOM by weight, while Example 10 contained 100% AOM, and the performance of Example 1C (containing the composite of Example 1) was superior to that of Example 10.

[0082] The present invention has been described above with reference to numerous embodiments and specific examples. Numerous variations will occur to those skilled in the art in view of the above detailed description. All such obvious variations are included within the full intended scope of the appended claims. Other embodiments of the present invention include, but are not limited to, the following (embodiments may be described as "comprising" or alternatively may be "consisting essentially of" or "consisting of"):

[0083] Aspect 1. A method comprising reacting ammonium dimolybdate (ADM), molybdenum trioxide (MoO3), and a metal hydroxide in an aqueous system to form an ammonium octamolybdate / metal hydroxide complex.

[0084] Embodiment 2. The method of embodiment 1, wherein the metal hydroxide comprises aluminum trihydroxide.

[0085] Embodiment 3. The method of embodiment 1, wherein the metal hydroxide comprises magnesium dihydroxide.

[0086] 4. The method of any one of embodiments 1 to 3, comprising pre-contacting molybdenum trioxide (ADM) with a metal hydroxide and then contacting molybdenum trioxide (MoO3).

[0087] Embodiment 5. The method of any one of embodiments 1 to 3, comprising contacting ammonium dimolybdate (ADM), molybdenum trioxide (MoO3), and a metal hydroxide substantially simultaneously.

[0088] Embodiment 6. The method defined in any one of embodiments 1 to 5, wherein the method is carried out (or the complex is formed) at a temperature in any suitable range, or any range disclosed herein, e.g., 20°C to 98°C, 50°C to 90°C, 75°C to 90°C, or 80°C to 98°C.

[0089] Embodiment 7. The method defined in any one of embodiments 1 to 6, wherein molybdenum trioxide (MoO3) and ammonium dimolybdate (ADM) are reacted in a molar ratio of MoO3:ADM of 1:1 to 3:1, 1.2:1 to 2.8:1, 1.5:1 to 2.5:1, or 1.8:1 to 2.4:1, based on the total amount of each reactant, in any suitable range, or any range disclosed herein.

[0090] Embodiment 8. The method defined in any one of embodiments 1 to 7, wherein the method is carried out (or the complex is formed) at a pressure in any suitable range, or any range disclosed herein, e.g., from 5 psig to 100 psig, at atmospheric pressure, or at subatmospheric pressure.

[0091] Embodiment 9. The method of any one of embodiments 1 to 8, further comprising removing the complexes from the water using any suitable technique or any technique disclosed herein, such as filtration or centrifugation, and combinations thereof.

[0092] Embodiment 10. The method of any one of embodiments 1 to 9, further comprising drying the composite under any suitable drying conditions, or any drying conditions disclosed herein, e.g., a drying temperature in the range of 50° C. to 200° C., or 100° C. to 150° C., and drying at atmospheric or subatmospheric pressure, e.g., less than 150 Torr, or less than 50 Torr.

[0093] Example 11 The method of any one of examples 1 to 10, further comprising the step of deagglomerating the complex, comminuting the complex, or both.

[0094] Embodiment 12. The method of any one of embodiments 1 to 11, wherein the metal hydroxide has a soluble Na2O content in any suitable range, or any range disclosed herein, e.g., 0.001-0.035 wt%, 0.001-0.03 wt%, 0.001-0.018 wt%, 0.002-0.035 wt%, 0.002-0.025 wt%, or 0.002-0.02 wt%.

[0095] Embodiment 13. The method as defined in any one of embodiments 1 to 12, wherein the metal hydroxide is characterized by a TAPPI brightness in any suitable range, or any range disclosed herein, e.g., 95% or more, 97% or more, 98% or more, or 99% or more.

[0096] Embodiment 14. The method of any one of embodiments 1 to 13, wherein the metal hydroxide is characterized by any suitable median particle size (d50), or any range disclosed herein, such as a median particle size (d50) of 0.5-5 μm, 0.5-3 μm, 0.75-2 μm, or 0.75-1.75 μm.

[0097] Embodiment 15. The metal hydroxide can have any suitable BET surface area, or any range of BET surface areas disclosed herein, for example, 1-20 m 2 / g, 1-15m 2 / g, 2-10m 2 / g, or 2-6m 2 15. The method according to any one of the preceding aspects, characterized by:

[0098] Embodiment 16. The method of any one of embodiments 1 to 15, wherein the metal hydroxide contains any suitable amount of gallium (in ppm by weight), or any range of amounts disclosed herein, such as 29 ppm or less, 27 ppm or less, 25 ppm or less, 23 ppm or less, 20 ppm or less, 15 ppm or less, or 10 ppm or less of gallium.

[0099] Embodiment 17 The method of any one of embodiments 1 to 16, wherein the metal hydroxide comprises precipitated ATH.

[0100] Embodiment 18. The method of any one of embodiments 1 to 17, wherein the molybdenum trioxide is characterized by any suitable median particle size (d50), or any range disclosed herein, such as a median particle size (d50) of 0.5 to 20 μm, 1 to 10 μm, or 1.6 to 6 μm.

[0101] Embodiment 19. An ammonium octamolybdate / metal hydroxide complex produced by the method defined in any one of embodiments 1 to 18, wherein the complex comprises AOM in any suitable amount, or in any range of amounts disclosed herein, e.g., 1-95 wt%, 5-80 wt%, 5-50 wt%, 10-60 wt%, or 10-30 wt%.

[0102] Embodiment 20. An ammonium octamolybdate / metal hydroxide complex comprising ammonium octamolybdate and a metal hydroxide, the complex comprising any suitable amount or range of amounts disclosed herein, e.g., 1-95% by weight, 5-80% by weight, 5-50% by weight, 10-60% by weight, or 10-30% by weight, of AOM.

[0103] Embodiment 21. The method or complex of any one of embodiments 1 to 20, wherein any suitable amount or range of amounts disclosed herein, e.g., at least 80% by weight, at least 85% by weight, at least 90% by weight, at least 95% by weight, at least 98% by weight, or at least 99% by weight, of the ammonium octamolybdate is present in the orthorhombic crystal form.

[0104] Embodiment 22. The method or composite of any one of embodiments 1 to 21, wherein the composite comprises any suitable amount of gallium (in ppm by weight), or any range of amounts of gallium disclosed herein, such as 29 ppm or less, 27 ppm or less, 25 ppm or less, 23 ppm or less, 20 ppm or less, 15 ppm or less, 10 ppm or less, or 5 ppm or less.

[0105] Embodiment 23. The method or composite of any one of embodiments 1 to 22, wherein the composite is characterized by any suitable median particle size (d50), or any range disclosed herein, for example, a median particle size (d50) of 0.5-10 μm, 1-10 μm, or 1-6 μm.

[0106] Embodiment 24. The composite may have any suitable BET surface area, or any range of BET surface areas disclosed herein, for example, 2 to 20 m 2 / g, 3-18m 2 / g, 4~15m 2 / g, or 5 to 12 m 2 24. The method or complex of any one of the preceding embodiments, characterized by:

[0107] Embodiment 25. The method or composite of any one of embodiments 1 to 24, wherein the metal hydroxide in the composite (or composites) has a soluble Na2O content in any suitable range, or in any range disclosed herein, e.g., 0.001-0.035 wt%, 0.001-0.03 wt%, 0.001-0.018 wt%, 0.002-0.035 wt%, 0.002-0.025 wt%, or 0.002-0.02 wt%.

[0108] Embodiment 26. The method or composite of any one of embodiments 1 to 25, wherein the metal hydroxide in the composite (or composite) is characterized by a TAPPI brightness in any suitable range, or in any range disclosed herein, for example, 95% or more, 97% or more, 98% or more, or 99% or more.

[0109] Embodiment 27 The method or complex of any one of embodiments 1 to 26, wherein the complex comprises AOM bound to a metal hydroxide.

[0110] Embodiment 28 The method or complex according to any one of embodiments 1 to 27, wherein the complex is spherical.

[0111] Example 29. A polymer composition (or formulation) comprising: (a) a polymer; and (b) an ammonium octamolybdate / metal hydroxide complex as defined in any one of Examples 19 to 28.

[0112] Embodiment 30. The polymer composition according to embodiment 29, wherein the amount of the complex in the polymer composition is any suitable amount or range of amounts disclosed herein, for example, 1 to 50 phr, 5 to 50 phr, 2 to 40 phr, 5 to 40 phr, 10 to 50 phr, 10 to 40 phr, 10 to 30 phr, or 15 to 40 phr.

[0113] Embodiment 31. The polymer composition according to embodiment 29 or 30, wherein the polymer comprises any suitable polymer, or any polymer disclosed herein, such as a thermoplastic, thermosetting, or combination thereof.

[0114] Aspect 32. The polymer composition of aspect 29 or 30, wherein the polymer comprises polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), chlorinated polyvinyl chloride (CPVC), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), ethylene chlorotrifluoroethylene (ECTFE), or any combination thereof.

[0115] Embodiment 33. The polymer composition of embodiment 29 or 30, wherein the polymer comprises rigid PVC.

[0116] Embodiment 34. The polymer composition of embodiment 29 or 30, wherein the polymer comprises soft PVC.

[0117] Example 35. The polymer composition of example 29 or 30, wherein the polymer comprises plasticized or unplasticized PVC.

[0118] Example 36 The polymer composition of example 29 or 30, wherein the polymer comprises an epoxy resin.

[0119] Aspect 37. The polymer composition according to aspect 29 or 30, wherein the polymer comprises bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin, bisphenol F novolac type epoxy resin, diphenylethylene epoxy resin, epoxy resin having a triazine skeleton, epoxy resin having a fluorene skeleton, triphenylmethane type epoxy resin, biphenyl epoxy resin, xylylene epoxy resin, biphenyl aralkyl epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, alicyclic epoxy resin, or any combination thereof.

[0120] Aspect 38. The polymer composition according to any one of aspects 29 to 37, wherein the polymer composition further comprises an additive, the additive comprising a stabilizer, a lubricant, an inorganic flame retardant (e.g., aluminum trihydrate or magnesium hydroxide), a filler, a colorant, or a curing agent, as well as any combination thereof.

[0121] Example 39. An article comprising the polymer composition defined in any one of examples 29 to 38.

[0122] Example 40. The article of example 39, wherein the article comprises a wire or cable.

[0123] Example 41. The article of example 39, wherein the article comprises a printed circuit board.

Claims

1. Ammonium dimolybdate (ADM), molybdenum trioxide (MoO ３ ), and a metal hydroxide in an aqueous system to form an ammonium octamolybdate / metal hydroxide complex.

2. the complex is formed at a temperature ranging from 20°C to 98°C, 50°C to 90°C, 75°C to 90°C, 80°C to 98°C, 80°C to 90°C, or 83°C to 93°C; The molybdenum trioxide (MoO ３ ) and the ammonium dimolybdate (ADM) is MoO ３ 2. The method of claim 1, wherein the reactants are reacted in a molar ratio of 1:1 to 3:1, 1.2:1 to 2.8:1, 1.5:1 to 2.5:1, 1.8:1 to 2.4:1, or about 2:

1.

3. The step of pre-contacting the ammonium dimolybdate (ADM) with the metal hydroxide, and then the step of pre-contacting the molybdenum trioxide (MoO ３ 10. The method of claim 1, comprising contacting

4. The method of claim 1 further comprising removing the complex from the water.

5. drying the composite; deaggregating the complexes; grinding the composite; or The method of claim 1 further comprising any combination thereof.

6. Molybdenum trioxide (MoO ３ 2. The method of claim 1, wherein the granules have a d50 particle size of 0.5 to 20 μm, 0.5 to 6 μm, 1 to 10 μm, 1 to 6 μm, 1.6 to 6 μm, or 1.6 to 4 μm.

7. The metal hydroxide is 0.001 to 0.035 wt%, 0.001 to 0.03 wt%, 0.001 to 0.018 wt%, 0.002 to 0.035 wt%, 0.002 to 0.025 wt%, or 0.002 to 0.02 wt% of soluble Na ２ O content, or a Tappi brightness of 95% or more, 97% or more, 98% or more, or 99% or more; or a d50 particle size of 0.5 to 5 μm, 0.5 to 3 μm, 0.75 to 2 μm, or 0.75 to 1.75 μm; or 1 to 20 m ２ / g, 1-15m ２ / g, 2-10m ２ / g, or 2 to 6 m ２ / g BET surface area, or The method of claim 1 , comprising any combination thereof.

8. 10. The method of claim 1, wherein the metal hydroxide contains no more than 29 ppm (by weight), no more than 27 ppm, no more than 25 ppm, no more than 23 ppm, no more than 20 ppm, no more than 15 ppm, or no more than 10 ppm of gallium.

9. The method of claim 1 , wherein the metal hydroxide comprises magnesium dihydroxide.

10. The method of claim 1 , wherein the metal hydroxide comprises aluminum trihydroxide (ATH).

11. The method of claim 1 , wherein the metal hydroxide comprises precipitated ATH.

12. 10. The ammonium octamolybdate / metal hydroxide composite produced by the method of claim 1, wherein the composite comprises 1-95 wt%, 5-80 wt%, 5-50 wt%, 10-60 wt%, 10-35 wt%, 10-30 wt%, 15-35 wt%, or 15-25 wt% ammonium octamolybdate (AOM).

13. Ammonium octamolybdate (AOM), and metal hydroxide, 1. An ammonium octamolybdate / metal hydroxide complex comprising: the composite has 1 to 95 wt%, 5 to 80 wt%, 5 to 50 wt%, 10 to 60 wt%, 10 to 35 wt%, 10 to 30 wt%, 15 to 35 wt%, or 15 to 25 wt% AOM; Ammonium octamolybdate / metal hydroxide complex.

14. 14. The composite of claim 13, wherein the metal hydroxide comprises magnesium dihydroxide.

15. 14. The composite of claim 13, wherein the metal hydroxide comprises aluminum trihydroxide (ATH).

16. 14. The complex of claim 13, wherein the metal hydroxide comprises precipitated ATH.

17. 13. The method of claim 1 or the composite of claim 12, wherein at least 80%, at least 85%, at least 90%, or at least 95% by weight of the ammonium octamolybdate in the composite is present in the orthorhombic crystal form.

18. 13. The method of claim 1 or the complex of claim 12, wherein at least 98% or at least 99% by weight of the ammonium octamolybdate in the complex is in the orthorhombic crystal form.

19. 13. The method of claim 1 or the composite of claim 12, wherein the composite contains no more than 29 ppm (by weight), no more than 27 ppm, no more than 25 ppm, no more than 23 ppm, no more than 20 ppm, no more than 15 ppm, no more than 10 ppm, or no more than 5 ppm of gallium.

20. 13. The method of claim 1 or the composite of claim 12, wherein the composite contains no more than 23 ppm (by weight), no more than 20 ppm, no more than 16 ppm, no more than 12 ppm, no more than 8 ppm, or no more than 4 ppm of gallium.

21. The complex is 0.001 to 0.035 wt%, 0.001 to 0.03 wt%, 0.001 to 0.018 wt%, 0.002 to 0.035 wt%, 0.002 to 0.025 wt%, or 0.002 to 0.02 wt% of soluble Na ２ O content, or a Tappi brightness of 95% or more, 97% or more, 98% or more, or 99% or more; or a d50 particle size of 0.5 to 10 μm, 0.5 to 4 μm, 1 to 10 μm, 1 to 6 μm, or 1 to 3 μm; or 2 to 20 m ２ / g, 2-12m ２ / g, 3-18m ２ / g, 3-10m ２ / g, 4-15m ２ / g, 4-8m ２ / g, 5-12m ２ / g or 5 to 9 m ２ / g BET surface area, or The method of claim 1 or the complex of claim 12, having any combination thereof.

22. 13. The method of claim 1 or the complex of claim 12, wherein the complex comprises AOM bound to ATH.

23. The method of claim 1 or the complex of claim 12, wherein the complex is spherical.

24. (a) a polymer; (b) the ammonium octamolybdate / metal hydroxide composite of claim 12; and A polymer composition comprising:

25. 25. The polymer composition of claim 24, wherein the polymer comprises a thermoplastic polymer.

26. 25. The polymer composition of claim 24, wherein the polymer comprises a thermosetting polymer.

27. 25. The polymer composition of claim 24, wherein the polymer comprises rigid PVC or flexible PVC.

28. 25. The polymer composition of claim 24, wherein the polymer comprises an epoxy resin.

29. 25. The polymer composition of claim 24, wherein the amount of the ammonium octamolybdate / metal hydroxide complex in the polymer composition is in the range of 1 to 50 phr, 5 to 50 phr, 2 to 40 phr, 5 to 40 phr, 10 to 50 phr, 10 to 40 phr, 10 to 30 phr, or 15 to 40 phr.

30. 25. The polymer composition of claim 24, wherein the polymer composition further comprises an additive, the additive comprising a stabilizer, a lubricant, an inorganic flame retardant, a filler, a colorant, a curing agent, or any combination thereof.

31. 25. An article comprising the polymer composition of claim 24.

32. 32. The article of claim 31, wherein the article comprises a wire or cable.

33. 32. The article of claim 31, wherein the article comprises a printed circuit board.

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