Moisture-resistant polymer formulations containing phosphorus-based flame retardants

Abstract

A polymer composition is disclosed that includes a suitable polymer and a triazine metal phosphate compound, and the triazine metal phosphate compound has a d50 particle size of 0.1 to 45 μm and a d50 particle size of 0.5 to 30 μm. 2 The polymer composition may have a BET surface area of ​​100 / g. The polymer composition has improved moisture resistance and improved wet insulating properties compared to polymer compositions containing polymerized versions of triazine metal phosphate compounds. The polymer composition can be utilized in a variety of end uses, such as wire and cable applications.

Description

[Technical field]

[0001] [REFERENCE TO RELATED APPLICATIONS] This application was filed as a PCT international patent application on December 23, 2022, and claims the benefit of and priority to U.S. Provisional Patent Application No. 63 / 294,438, filed on December 29, 2021, the disclosure of which is incorporated herein by reference in its entirety. [Background technology]

[0002] The present invention relates generally to polymeric compositions containing flame retardant additives, and more particularly to polymeric compositions containing triazine metal phosphate flame retardants that impart improved moisture resistance. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] U.S. Patent No. 8,754,154 [Patent Document 2] U.S. Pat. No. 10,351,776 [Non-patent literature]

[0004] [Non-Patent Document 1] Chemical and Engineering News, 63(5), 27, 1985 [Non-Patent Document 2] J. Am. Chem. Soc., 60, 309 (1938) Summary of the Invention

[0005] This Summary is provided to introduce some concepts in a simplified form that are further described below in the Detailed Description. This Summary is not intended to identify essential or critical features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter.

[0006] Disclosed and described herein are polymer compositions or formulations that include triazine metal phosphate compounds. Exemplary compositions include those that include a suitable polymer and a compound of formula (I): (AH) a (+) [M b m+ (H2PO4) x1 (-) (HPO4) x2 2(-) ] (a-) * and a triazine metal phosphate compound having a pH of 2O. In formula (I), each M can independently be Cu, Mg, Ca, Zn, Mn, Fe, Co, Ni, B, Si, Al, Sb, La, Ti, Zr, Ce, V, or Sn, a can range from 1 to 6, b can range from 1 to 14, m can range from 1 to 6, x1 can range from 1 to 12, x2 can range from 0 to 12, p can range from 0 to 5, and a+mb=x1+2x2, and each (AH)(+) can independently be a triazine derivative having the following formula (II-1), (II-2), or (II-3): [ka]

[0007] The polymer composition provides flame retardancy and can be used in wire, cable and other end-use flame retardant polymer applications.

[0008] Both the foregoing summary and the following detailed description are exemplary and explanatory only. Thus, the foregoing summary and the following detailed description are not to be taken as limiting. Furthermore, features or variations may be provided in addition to those described herein. For example, particular aspects may be combinations and subcombinations of various features described in the detailed description. [Brief description of the drawings]

[0009] [Figure 1]1 is a bar graph showing the water absorption of the polymer compositions of Examples 1 to 4 at 90° C. for 14 days. [Diagram 2] 1 is a bar graph showing the water absorption rates of the polymer compositions of Examples 1 to 2 and 4 to 5 at 75° C. for 7 days. [Diagram 3] 1 is a bar graph of the dielectric constant (Dk) at 100 MHz for the polymer compositions of Examples 1 to 4 before and after aging in water at 90° C. for 14 days. [Figure 4] FIG. 4 is a bar graph of ΔDk based on Dk at 100 MHz before and after aging in water at 90° C. for 14 days for the polymer compositions of Examples 1 to 4 in FIG. [Diagram 5] 1 is a bar graph showing the dissipation factor (Df) at 100 MHz for the polymer compositions of Examples 1 to 4 before and after aging in water at 90° C. for 14 days. [Figure 6] FIG. 5 is a bar graph of ΔDf based on Df at 100 MHz before and after aging in water at 90° C. for 14 days for the polymer compositions of Examples 1 to 4. [Figure 7] 1 is a bar graph of the dielectric constant (Dk) at 100 MHz for the polymer compositions of Examples 1-2 and 4-6 before and after aging in water at 75° C. for 7 days. [Figure 8] FIG. 7 is a bar graph of ΔDk based on Dk at 100 MHz before and after aging in water at 75° C. for 7 days for the polymer compositions of Examples 1-2 and 4-6. [Figure 9] 1 is a bar graph showing the dissipation factor (Df) at 100 MHz before and after aging in water at 75° C. for 7 days for the polymer compositions of Examples 1-2 and 4-6. [Figure 10] FIG. 9 is a bar graph of ΔDf based on Df at 100 MHz before and after aging in water at 75° C. for 7 days for the polymer compositions of Examples 1-2 and 4-6. [Figure 11] 1 is a heat release rate (HRR) curve of the polymer compositions of Examples 1-2 and 4. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] In order to more clearly define the terms used herein, the following definitions are provided. Unless otherwise stated, the following definitions apply to this disclosure. If a term is used in this disclosure but is not specifically defined herein, the definition in the IUPAC Compendium of Chemical Terminology, Second Edition (1997) may be applied, unless that definition conflicts with other disclosures or definitions applied herein, or makes any claim in the patent to which it applies unclear 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 prevail.

[0011] The subject features are described herein such that within a particular embodiment, different combinations of features may be envisioned. For each embodiment and feature disclosed herein, all combinations that do not adversely affect the design, composition, process, or method described herein are envisioned and are interchangeable, regardless of whether or not a specific combination is explicitly described. Thus, unless expressly stated otherwise, any embodiment or feature disclosed herein may be described in combination with any inventive design, composition, process, or method consistent with this disclosure.

[0012] Although compositions and methods are described herein in terms "comprising" various components or steps, the compositions and methods can also "consist essentially of" or "consist of" various components or steps, unless otherwise specified. The terms "a," "an," and "the" are intended to include multiple alternatives, e.g., at least one, unless otherwise specified.

[0013] Groups of elements are generally designated using the numbering scheme set out in the version of the Periodic Table published in Chemical and Engineering News, 63(5), 27, 1985. In some cases, groups of elements may be designated using a common name assigned to the group, e.g., Group 1 elements are the alkali metals, Group 2 elements are the alkaline earth metals, etc.

[0014] As used herein, the term "contacting" is used to refer to materials or ingredients that can be blended, mixed, slurried, dissolved, reacted, processed, compounded, or otherwise brought into contact or combined in any suitable manner. The materials or ingredients can be contacted together in any order, in any manner, and for any length of time, unless otherwise specified.

[0015] Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, representative methods and materials are described herein.

[0016] All publications and patents mentioned herein are incorporated by reference in their entirety for the purpose of describing and disclosing, e.g., the constructs and methodologies described in the publications and patents that may be used in connection with the presently described invention.

[0017] In the present invention, several types of ranges are disclosed. When any type of range is disclosed or claimed, the intent is to individually disclose or claim each possible number that such range may reasonably encompass, including the endpoints of the range, and any subranges and combinations of subranges encompassed therein. As a representative example, the amount of triazine metal phosphate compound in a polymer composition or formulation may be in a particular range in various aspects of the present invention. By disclosing that the amount of triazine metal phosphate compound in a polymer composition or formulation may be in the range of 1-80 wt%, the intent is to state that the amount of triazine metal phosphate compound may be any amount within that range, such as any range or combination in the range of 1-80 wt%, such as 1-65 wt%, 1-40 wt%, 1-25 wt%, 1-15 wt%, 2-20 wt%, or 2-15 wt%, etc. Similarly, all other ranges disclosed herein should be interpreted in a similar manner to this example.

[0018] In general, any amount, size, formulation, parameter, range, or other quantity or characteristic is "about" or "approximate" whether or not expressly stated as such. Whether or not modified by the term "about" or "approximately," the claims include equivalents to that quantity or characteristic.

[0019] Detailed Description of the Invention Disclosed herein are flame retardant polymer formulations containing triazine metal phosphate compounds, and such polymer formulations have improved moisture resistance for use in wire and cable applications.

[0020] Safire® 200, Safire® 400, and Safire® 600 are melamine resin (aluminum phosphate), melamine resin (zinc phosphate), and melamine resin (magnesium phosphate) flame retardants, respectively. As one skilled in the art can readily recognize, such phosphorus-based flame retardants are not typically utilized in certain end uses where water or moisture may be present, because they absorb or pick up moisture. Therefore, one objective of the present invention is to produce polymeric formulations that have ASTM E1354 flame retardant performance equivalent to formulations containing these melamine resins (metal phosphates), but with improved moisture resistance.

[0021] A particular end use of flame retardant polymer formulations requiring moisture resistance is wire / cable applications. In wire / cable applications, flame retardant polymer formulations are often used as an insulating layer in multi-layer wire / cable structures. Thus, the flame retardant polymer formulation acts as an insulator. Insulation resistance can be defined as the resistance of alternating current between two conductors or two systems of conductors insulated by an insulating material or layer. Cable insulation resistance of a polymer formulation may depend on factors such as temperature, material purity, and humidity (amount of moisture present). The humidity of the environment in which an electric cable is used has a significant impact on the insulation performance of the cable, since when the humidity is high or the cable comes into contact with liquid water, the cable will absorb water and its resistance will change accordingly. Therefore, another object of the present invention is to refine a polymer formulation that is less susceptible to the effects of humidity (moisture) and improve the insulation performance of the polymer layer in wire / cable structures.

[0022] [Triazine metal phosphate compounds] In accordance with an aspect of the present invention, the polymeric compositions disclosed herein include a triazine metal phosphate compound having the formula (I): (AH) a (+) [M b m+ (H2PO4) x1 (-) (HPO4) x2 2(-) ](a-) * pH2O (I)

[0023] In formula (I), (AH), M, a, b, m, x1, x2, and p are independent elements of the triazine metal phosphate compound, where a, b, m, x1, and x2 are integers, and p can be a fraction. Thus, the triazine metal phosphate compound having formula (I) can be described using any combination of (AH), M, a, b, m, x1, x2, and p disclosed herein, subject to the overall charge balance of the compound. Unless otherwise stated, the above formula (I), other structural formulas disclosed herein, and any triazine metal phosphate compound disclosed herein are not designed to show the stereochemistry or isomeric positioning of different moieties (e.g., the formulas are not intended to show cis or trans isomers, or R or S diastereoisomers), but such compounds are contemplated and encompassed by these formulas and / or structures.

[0024] According to one embodiment of the present invention, each metal, M, in formula (I) is independently Cu, Mg, Ca, Zn, Mn, Fe, Co, Ni, B, Si, Al, Sb, La, Ti, Zr, Ce, V, or Sn. In another embodiment, each M is independently Ca, Mg, Zn, Al, or Sn, and in yet another embodiment, each M is Ca, or each M is Mg, or each M is Zn, or each M is Al, or each M is Sn. In formula (I), m is the oxidation state of the metal M, and depending on the metal and its respective oxidation state, m can range from 1 to 6. In some embodiments, m is 1 to 5 or 1 to 4, and in other embodiments, m ranges from 2 to 6, 2 to 4, or 2 to 3. In formula (I), b is the number of metals M in the triazine metal phosphate compound, and b can range from 1 to 14. This includes cases where there is only one metal ion or atom in the triazine metal phosphate compound, or where there is more than one metal ion or atom. Often, b ranges from, but is not limited to, 1 to 10, 1 to 8, 1 to 5, 1 to 3, 2 to 10, or 2 to 5. Even when there is only one metal in formula (I), b can be greater than 1 (e.g., 2, 3, 4, etc.) to properly balance the charges on the phosphate and triazine moieties.

[0025] The number of H2PO4 moieties in formula (I) is x1, and the number of HPO4 moieties in formula (I) is x2, where x1 ranges from 1 to 12 and x2 ranges from 0 to 12. For example, x1 can range from 1 to 8, 1 to 6, 1 to 5, 1 to 4, 1 to 3, or 1 to 2, while x2 can range from 0 to 8, 0 to 6, 0 to 4, or 0 to 2 (x2 equals 0, 1, or 2). In certain embodiments contemplated herein, x1 ranges from 1 to 6 (or 1 to 5, or 1 to 4, or 1 to 3), and x2 equals 0 or 1.

[0026] The presence of p in formula (I) encompasses hydrate versions of the triazine metal phosphate compounds, where p can range from 0 to 5, such as when p ranges from 0 to 3 or 0 to 2, where p is equal to 0, where p is equal to 1, where p is equal to 2, etc.

[0027] In formula (I), each (AH) is independently a triazine derivative having the following formula (II-1), (II-2) or (II-3): [ka]

[0028] Although the triazine metal phosphate compounds of formula (I) according to the present invention are not polymerized, depending on the conditions under which the triazine metal phosphate compound is formulated (including, for example, a drying step), it is possible for more than one of melamine, melam, and / or melem to be present. In formula (I), a is the number of triazine derivatives in the triazine metal phosphate compound, and a can range from 1 to 6. This includes situations where only one triazine derivative is present or more than one triazine derivative is present in the triazine metal phosphate compound. In many cases, a ranges from, but is not limited to, 1 to 5, 1 to 4, 1 to 3, or 1 to 2. Even when only one triazine derivative is present in formula (I), a can be greater than 1 (e.g., 2 or more) to properly balance the charges of the metal(s) and phosphate moieties. For the overall charge balance of the triazine metal phosphate compound, a+mb=x1+2x2 in formula (I).

[0029] In one embodiment of the present invention, the metal M is zinc, and therefore the triazine metal phosphate compound is a zinc triazine phosphate compound. Without being limited thereto, the zinc triazine phosphate compound has the following formula: (AH) (+) [Zn 2(+) (H2PO4) (-) (HPO4) 2(-) ] * pHO (AH) (+) [Zn 2(+) (H2PO4)3 (-) ] * pHO (AH)2 (+) [Zn 2(+) (H2PO4)2(-) (HPO4) 2(-) ] * pHO (AH)2 (+) [Zn 2(+) (H2PO4)4 (-) ] * pHO (AH)2 (+) [Zn 2(+) (HPO4)2 2(-) ] * pHO (AH) (+) [Zn2 2(+) (H2PO4) (-) (HPO4)2 2(-) ] * pHO (AH) (+) [Zn2 2(+) (H2PO4)3 (-) (HPO4) 2(-) ] * pHO (AH) (+) [Zn2 2(+) (H2PO4)5 (-) ] * pHO (AH)2 (+) [Zn2 2(+) (H2PO4)2 (-) (HPO4)2 2(-) ] * pHO (AH)2 (+) [Zn2 2(+) (H2PO4)4 (-) (HPO4) 2(-) ] * pHO (AH)2 (+) [Zn2 2(+) (HPO4)3 2(-) ] * pHO (AH)2 (+) [Zn2 2(+) (H2PO4)6 (-) ] * pHO, The present invention may have at least one of the following:

[0030] Thus, the zinc triazine phosphate compound may be a compound having any one of these formulas, or the zinc triazine phosphate compound may be a mixture of compounds having any two or more of these formulas. The presence of p in these formulas used to describe the zinc triazine phosphate compound has the same meaning as in formula (I), and thus includes hydrate versions of the zinc triazine phosphate compound. Thus, p can range from 0 to 5, for example, 0 to 3 or 0 to 2, and p can be equal to 0, 1, 2, etc.

[0031] The triazine metal phosphate compounds are not limited to those mentioned above in relation to formula (I). Other suitable triazine metal phosphate compounds encompassed by formula (I) are disclosed, for example, in U.S. Patent Nos. 8,754,154 and 10,351,776. General methods for preparing triazine metal phosphate compounds are also described in these patents.

[0032] The particle size of the triazine metal phosphate compound used in the polymer composition described herein is not particularly limited, but the triazine metal phosphate compound may often have a median particle size (d50) in the range of 0.1 to 45 μm. It may be advantageous for the triazine metal phosphate compound to have a smaller d50 particle, and thus suitable ranges of d50 particle size for the triazine metal phosphate compound include 0.5 to 20 μm, 0.5 to 10 μm, 1 to 6 μm, or 1 to 5 μm. Without wishing to be bound by theory, it is believed that if the particle size of the triazine metal phosphate compound is too coarse, the particles may act as failure points for both mechanical and electrical failure (e.g., sparks) when present in a flame retardant polymer formulation, for example, for wire / cable applications.

[0033] Similarly, the BET surface area of ​​the triazine metal phosphate compound is not particularly limited, but is generally in the range of 0.5 to 30 m 2 / g. A representative, but non-limiting, range for BET surface area is 0.5 to 10 m 2 / g, 1-15m 2 / g, 1-10m 2 / g, 2-8m 2 / g, or 2 to 5m 2 / g. Other suitable particle sizes and surface areas of the triazine metal phosphate compounds will be readily apparent from the present disclosure.

[0034] [Polymer composition] The present invention relates to and encompasses compositions, formulations, composites, and compositions comprising any of the triazine metal phosphate compounds (and their respective properties or characteristics, such as surface area, particle size, etc.). In certain aspects of the present invention, polymer compositions are disclosed, which can comprise any suitable polymer(s) and any of the triazine metal phosphate compounds having formula (I) disclosed herein. In some aspects, for example, the polymer in the polymer composition can comprise an elastomer, in other aspects the polymer can comprise a thermoplastic polymer, and in yet other aspects the polymer can comprise a thermoset polymer.

[0035] The polymers used in the polymer composition having the triazine metal phosphate compound can include any suitable rubber or elastomer, alone or in any combination, including, but not limited to, natural rubber (NR), epoxidized natural rubber (ENR), synthetic cis polyisoprene (IR), emulsion styrene butadiene rubber (ESBR), solution styrene butadiene rubber (SSBR), polybutadiene rubber (BR), butyl rubber (IIR / CIIR / BIR), chloroprene rubber (CR), nitrile rubber (NBR), hydrogenated nitrile rubber (HNBR), carboxylated nitrile elastomer (XNBR), ethylene propylene rubber (EPM / EPD), and the like. Examples include rubber, fluoroelastomer (FPM / FKM), and polyurethane rubber (AU / EU / PU).

[0036] In one embodiment, the polymer in the polymer composition can include a polyolefin. In another embodiment, the polymer can include, alone or in any combination, polyethylene (e.g., an ethylene homopolymer or an ethylene-based copolymer, such as an ethylene / α-olefin copolymer, which may often be referred to as LLDPE), polypropylene (e.g., a propylene homopolymer or a propylene-based copolymer), and / or ethylene / vinyl acetate (EVA) copolymer.

[0037] Optionally, any of these polymers can be crosslinked. For example, the polymer can include crosslinked polyethylene, and the technique for crosslinking can include any suitable methodology, such as peroxide initiated crosslinking.

[0038] In one embodiment, the polymer can include an epoxy resin. For example, the polymer can include, alone or in any combination, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type novolac epoxy resin, bisphenol F type novolac type epoxy resin, diphenylethylene type epoxy resin, epoxy resin having a triazine skeleton (e.g., bismaleimide triazine-epoxy, which is a mixture of epoxy resin and bismaleimide-triazine resin), epoxy resin having a fluorene skeleton, triphenylmethane type epoxy resin, biphenyl type epoxy resin, xylylene type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, and / or alicyclic epoxy resin. In general, any epoxy resin suitable for use in copper clad laminates or related applications can be used as the base polymer of the polymer composition encompassed herein.

[0039] Although not limited thereto, the amount of the triazine metal phosphate compound in the polymer composition can often range from 1 to 80 wt%. Thus, exemplary and non-limiting amounts of the triazine metal phosphate compound in the polymer composition can include the following ranges: 1 to 65 wt%, 1 to 40 wt%, 3 to 40 wt%, 10 to 40 wt%, or 3 to 25 wt%. Other suitable ranges for the amount of the triazine metal phosphate compound in the polymer composition are readily apparent from the present disclosure.

[0040] In many cases, the polymer composition further comprises an additional flame retardant compound (other than the triazine metal phosphate compound). Thus, the polymer composition can comprise a polymer, a triazine metal phosphate compound, and an additional flame retardant compound. Any suitable flame retardant compound can be used, examples of which are metal hydroxides such as aluminum trihydrate (ATH), magnesium hydroxide (MDH), and the like. A combination of a metal hydroxide and an additional flame retardant compound can be utilized in the polymer composition.

[0041] When present, the amount of additional flame retardant compound in the polymer composition can range from 10 to 80 wt% in some embodiments, from 20 to 70 wt% in other embodiments, from 30 to 65 wt% in still other embodiments, and from 40 to 60 wt% in still other embodiments. When additional flame retardant compounds are present in the polymer composition, typically the amount of triazine metal phosphate compound in the polymer composition is less than the amounts disclosed above, with typical ranges for the amount of triazine metal phosphate compound in the polymer composition (when additional flame retardants such as ATH and / or MDH are present) being 1 to 40 wt%, alternatively 1 to 25 wt%, alternatively 1 to 15 wt%, alternatively 2 to 20 wt%, or alternatively 5 to 15 wt%.

[0042] Optionally, the polymer composition may further comprise any suitable additive, non-limiting examples of which may include stabilizers or antioxidants, lubricants or processing aids, compatibilizers or coupling agents, fillers, colorants, rheology modifiers, or curing agents, and the like, and combinations thereof.

[0043] The polymer compositions disclosed herein that include any of the triazine metal phosphate compounds having formula (I) may also be characterized by beneficial features or properties of flame retardant compositions, such as low water absorption as quantified according to ASTM D570 at 90°C in water for 14 days. Under such test conditions, polymer compositions that include triazine metal phosphate compounds having formula (I) often have a water absorption of 6 wt% or less, and in some embodiments 5 wt% or less, 4 wt% or less, or 3 wt% or less.

[0044] This low water absorption is unexpected considering that the polymerized version of the triazine metal phosphate compound has a much higher water absorption. Surprisingly, the polymer composition containing the triazine metal phosphate compound having formula (I) has a lower water absorption by ASTM D570 at 90° C. and 14 days in water than the water absorption of an otherwise identical formulation containing the polymerized version of the triazine metal phosphate compound. The precursor polymerized version of the triazine metal phosphate compound can be formulated as generally described in U.S. Pat. No. 5,399,433 and U.S. Pat. No. 5,499,433. This polymerization step is believed to improve the thermal stability of the polymerized compound compared to the precursor, allowing the polymerized compound to be utilized in higher temperature applications. Here, the polymerized version is a (precursor) triazine metal phosphate compound polymerized at a temperature of 310° C. for 45 minutes.

[0045] Additionally or alternatively, the polymeric composition containing the triazine metal phosphate compound may also have a water absorption rate according to ASTM D570 that is less than the water absorption rate of an otherwise identical formulation containing a polymeric version of the triazine metal phosphate compound at 75° C. in water for 7 days.

[0046] Another unexpected advantage of the disclosed polymeric compositions is their excellent wet insulation properties. One parameter that can be used to quantify this advantage is the dielectric constant Dk, which increases with increasing moisture in the polymeric composition. Using ASTM D150 (100 MHz), the polymeric compositions containing the triazine metal phosphate compounds having formula (I) can be characterized by a ΔDk of 9% or less, more often 7% or less, 4% or less, or 2% or less. ΔDk is the percentage change from the initial Dk (unaged) to the Dk after aging in water at 90° C. for 14 days, as described in ASTM D150.

[0047] Similarly, another parameter that can be used to quantify beneficial wet insulation properties is the dissipation factor Df. The dissipation factor relates to the ability of a material to retain energy or to behave as an insulating material. The lower the dissipation factor, the more efficient the material is as an insulator. Most plastics have relatively low dissipation factors at room temperature. The dissipation factor can also be used to evaluate the properties or quality of insulating materials, such as moisture content, degradation, etc., in applications such as cables, terminations, and joints. It is therefore beneficial for the Df of insulating materials to only increase minimally upon exposure to moisture for extended periods of time.

[0048] Using ASTM D150 (100 MHz), polymer compositions including triazine metal phosphate compounds having formula (I) can be characterized as having a ΔDf of 500% or less, more often a ΔDf of 400% or less, 300% or less, or 200% or less, where ΔDf is the percent change from the initial Df (unaged) to Df after aging in water at 90° C. for 14 days, as described in ASTM D150.

[0049] These properties are a significant improvement over polymerized triazine metal phosphate compounds. In particular, a polymer composition comprising a triazine metal phosphate compound having formula (I) may have a smaller ΔDk (or ΔDf, or both) than an otherwise identical formulation comprising a polymerized version of a triazine metal phosphate compound, compared under the same conditions, i.e., 100 MHz, 90° C., 14 day water aging conditions according to ASTM D150.

[0050] The advantage of the polymer composition comprising the triazine metal phosphate compound having formula (I) can also be quantified using lower temperature and shorter aging time.For example, the polymer composition can be characterized by ΔDf of 250% or less, more often ΔDf of 225% or less, 200% or less, or 150% or less.This ΔDf is the percentage change from the initial Df (without aging) to the Df after aging in water at 75°C for 7 days, as described in ASTM D150 (at 100MHz).

[0051] Even when lower temperatures and shorter aging times are used, the improvement over polymerized triazine metal phosphate compounds is readily apparent. Thus, a polymer composition containing a triazine metal phosphate compound having formula (I) may have a smaller ΔDk (or ΔDf, or both) than an otherwise identical formulation containing a polymerized version of a triazine metal phosphate compound. This comparison uses the same test conditions, 75°C at 100 MHz and 7 days of water aging, according to ASTM D150.

[0052] The moisture resistance and wet insulation properties (e.g., water absorption, dielectric constant, dissipation factor) of the polymer compositions described above are applicable to polymer compositions containing any relative amount of polymer in the composition (compared to the amount of flame retardant and other non-polymeric additives). However, the moisture resistance and wet insulation properties are particularly beneficial for polymer compositions containing approximately 30-40 wt% polymer, such as 30-38 wt% polymer, 32-40 wt% polymer, 32-38 wt% polymer, etc. Thus, a polymer composition having any of the water absorption properties disclosed herein (per ASTM D570), any of the ΔDk properties disclosed herein (per ASTM D150), and any of the ΔDf properties disclosed herein (per ASTM D150) can be a polymer composition containing 30-40 wt% polymer, 30-38 wt% polymer, 32-40 wt% polymer, 32-38 wt% polymer, etc. While any suitable polymer, as described above, can be the polymer component of the polymer composition, polyolefins, such as ethylene homopolymers, ethylene / α-olefin copolymers, propylene homopolymers, propylene-based copolymers, ethylene / vinyl acetate (EVA) copolymers, either alone or in any mixture or combination, are often utilized in the polymer composition depending on the subsequent manufacture and end use.

[0053] An article of manufacture can be formed from and / or include any of the polymer compositions described herein. In one embodiment, the article of manufacture can include a wire or cable, and in another embodiment, the article can include a printed circuit board. Other suitable articles of manufacture and end uses will be readily apparent from this disclosure.

[0054] If desired, closed packing techniques can be applied to the triazine metal phosphate compounds, for example, a combination of larger particles of triazine metal phosphate compounds with smaller particles of triazine metal phosphate compounds (e.g., a bimodal particle size distribution) instead of a single particle size distribution, which can 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 are not to be construed as imposing limitations on the scope of the present invention. Various other embodiments, modifications, and equivalents may be suggested to those skilled in the art after reading the description herein, 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% of the sample by weight has a smaller particle size and 50% by weight has a larger particle size. Particle size measurements were performed using a Beckman Coulter LS 13 320 single wavelength laser diffraction particle size analyzer according to ISO 13320 laser diffraction method.

[0057] BET surface areas were measured using the BET nitrogen adsorption method of Brunauer et al., using a Micromeritics TriStar II surface area and porosity analyzer.

[0058] (Examples 1 to 6) Table I summarizes the EVA / LLDPE blends for Examples 1-6, with Examples 1-3 and 5-6 using 10 wt% FR synergist. Example 1 used a zinc triazine phosphate compound (formulated as described below) as the FR synergist, Example 2 used Safire® 400 as the FR synergist, Example 3 used silane surface treated Safire® 400 as the FR synergist, Example 5 used melamine polyphosphate as the FR synergist, and Example 6 used ammonium polyphosphate as the FR synergist. Example 4 used ATH (d50-2 μm, BET-4 m2 / g) without FR synergist, and in this example the amount of ATH was increased to 49.82-59.82 wt%.

[0059] The zinc triazine phosphate compound used as the FR synergist in Example 1 was formulated as follows: Water and melamine were combined in a main reaction vessel and stirred at 80-85°C to give a slurry with 10-15 wt% solids. Water and zinc oxide were added to a second reaction vessel and stirred at 80-85°C to give a slurry with 10-15 wt% solids. Phosphoric acid (75%) was added slowly with stirring to the zinc oxide slurry (approximate molar ratio of phosphoric acid to zinc oxide of 2:1), slowing the addition rate as necessary to control the exothermic reaction and produce zinc dihydrogen phosphate. After phosphoric acid addition was complete, the contents of the second reaction vessel were stirred at 95-99°C for at least 30 minutes until the zinc dihydrogen phosphate solution was clear and the pH was less than 1.7. The zinc dihydrogen phosphate solution in the second reaction vessel was then cooled to below about 85-88°C. The zinc dihydrogen phosphate solution in the second reactor was then transferred to the main reactor (containing the melamine slurry, with an approximate molar ratio of zinc to melamine of 1:2) and the contents of the main reactor were agitated for approximately 4-6 hours. The reaction product was dried at a temperature of 120°C for 24 hours to form a solid zinc triazine phosphate compound, which was then ground to a d50 particle size of 2.5 μm and a BET surface area of ​​3.5 m2 / g prior to use in the flame retardant polymer formulation of Example 1.

[0060] The Safire® 400 synergist used in the polymer composition of Example 2 was formulated by polymerizing the precursor zinc triazine phosphate compound of Example 1 at 310° C. for 45 minutes as generally described in U.S. Pat. Nos. 5,993,333 and 5,943,636.

[0061] The surface treated Safire® 400 synergist used in the polymer composition of Example 3 was prepared by compounding 3 pounds of Safire® 400 (from Example 2) into a 10 L high speed Henschel mixer with the mixing temperature set at 85-88°C. To achieve the hydrophobic surface treatment, the mixing speed was set at 1000 rpm for 1 minute and 1 wt% of Dynasilane 9116 (hexadecyltrimethoxysilane) was added to the Henschel mixer at 1000 rpm for 1 minute or more. The Henschel mixer was then increased to 3000 rpm and mixed for 10 minutes, after which the silane treated Safire® 400 was allowed to cool to room temperature.

[0062] The polymer formulations of Examples 1-6 were evaluated for water absorption performance (per ASTM D570) and wet insulation properties (per ASTM D150). Figure 1 compares the water absorption properties of the polymer compositions of Examples 1-4 after aging in water for 14 days at 90°C, and Figure 2 compares the water absorption properties of the polymer compositions of Examples 1-2 and Examples 4-5 after aging in water for 7 days at 75°C. As one skilled in the art can readily appreciate, phosphorus-based flame retardants absorb or pick up moisture and are therefore not typically utilized in end uses where water or moisture may be present. As expected, Example 2 in Figure 1 performed poorly (moisture absorption of 6 wt% or more) and Example 4 (ATH only) performed the best. Example 3 was also evaluated to reduce moisture absorption, but this time with a hydrophobic surface treatment. Surprisingly, moisture absorption was not affected by the surface treatment. Example 1, containing a zinc triazine phosphate compound as the FR synergist, had an unexpectedly low water absorption rate, 65-70% better (lower) than that of Examples 2-3. Similar results are shown in Figure 2, but the aging time was shortened to 7 days and the temperature was reduced to 75°C. Example 1, containing a zinc triazine phosphate compound as the FR synergist, showed an unexpectedly low water absorption rate, 42% better (lower) than that of Example 2 and 14% better (lower) than that of Example 5 (containing melamine polyphosphate as the FR synergist).

[0063] Referring now to the ASTM D150 test and A / C loss properties (wet insulation performance), Figure 3 compares the dielectric constant (Dk) at 100 MHz before and after aging in water at 90°C for 14 days for the polymer compositions of Examples 1 to 4, and Figure 4 compares the ΔDk based on the Dk at 100 MHz in Figure 3 before and after aging in water at 90°C for 14 days for the polymer compositions of Examples 1 to 4. These figures show that the initial Dk of each polymer composition was very similar, but after aging, Example 1 was surprisingly comparable to Example 4 with only ATH, with a ΔDk of only 1%, while the ΔDk values ​​for Examples 2 and 3 were 10 to 15%.

[0064] Figures 7-8 are similar to Figures 3-4, except that for the polymer compositions of Examples 1-2 and Examples 4-6, aging was performed in water at 75°C for 7 days. Figures 7-8 show that the initial Dk of each polymer composition was very similar, but after aging, Example 1 was superior to Example 2, and much superior to Examples 5-6 (melamine polyphosphate and ammonium polyphosphate), with Example 1 showing the lowest ΔDk other than Example 4.

[0065] Next, reference is made to Fig. 5, which compares the dissipation factor (Df) at 100 MHz before and after aging in water at 90°C for 14 days for the polymer compositions of Examples 1 to 4, and Fig. 6, which compares ΔDf, based on the Df at 100 MHz before and after aging in water at 90°C for 14 days in Fig. 5, for the polymer compositions of Examples 1 to 4. These figures show that the initial Df was very similar for each polymer composition, but after aging, Example 1 was surprisingly equivalent to Example 4, which contained only ATH, and the Df after aging was 70% lower than Examples 2 and 3.

[0066] Figures 9-10 are similar to Figures 5-6, except that for the polymer compositions of Examples 1-2 and 4-6, aging was performed in water for 7 days at 75° C. Figures 9-10 show that the initial Df was very similar for each polymer composition, but after aging, Example 1 was superior to Examples 2 and 5, and much superior to Example 6 (ammonium polyphosphate).

[0067] The polymer samples were tested for flame retardancy using a cone calorimeter (DEATAK CC-2) according to the procedure described in ASTM E1354. Test pieces measuring 100 mm × 100 mm × 0.635 mm were irradiated horizontally. The experiment was performed with a 50 kW / m 2An external heat flux of 1000 nm was used. Measured parameters included ignition duration, Peak Rate Release Rate (PHRR), average Rate of Heat release (RHR) over 300 seconds, Total Heat Released (THR), average available heat of combustion, average mass loss rate (10%-90%), and average SEA. Reported data is the average of three experiments. Numerical results are summarized in Table II (Table 2) for the polymer compositions of Examples 1-2 and 4, and Figure 11 provides the Heat Release Rate (HRR) curves for the polymer compositions of Examples 1-2 and 4. The use of FR synergist in the polymer compositions of Examples 1-2 significantly improved the flame retardant performance compared to the ATH-only polymer composition of Example 4. Importantly, in addition to the water absorption and wet insulation benefits discussed above, Example 1 had the same flame retardant performance benefits as Example 2.

[0068] [Table 1]

[0069] [Table 2]

[0070] The present invention has been described above with reference to numerous aspects and embodiments. Many modifications will be suggested to those skilled in the art in light of the above detailed description. All such obvious modifications are within the full intended scope of the appended claims. Other aspects of the present invention include, but are not limited to, the following (although aspects may be described as "comprising", they may alternatively be described as "consist essentially of" or "consist of"):

[0071] [Aspect 1] A polymer composition (or blend), comprising: (a) a polymer, and (b) a triazine metal phosphate compound having the following formula (I): (AH) a (+) [M b m+ (H2PO4) x1 (-) (HPO4) x2 2(-) ] (a-) * pH2O (I) and Equipped with Each (AH)(+) is independently a triazine derivative having the formula (II-1), (II-2) or (II-3), i.e. [ka] and M is independently Cu, Mg, Ca, Zn, Mn, Fe, Co, Ni, B, Si, Al, Sb, La, Ti, Zr, Ce, V, or Sn; a is 1 to 6; b is 1 to 14; m is 1 to 6; x1 is 1 to 12, x2 is 0 to 12, and p is 0 to 5; a+mb=x1+2x2, Polymer composition.

[0072] [Embodiment 2] The polymer composition defined in embodiment 1, wherein the amount of triazine metal phosphate compound in the polymer composition is any suitable amount or amount within any range disclosed herein, such as 1-80 wt%, 1-65 wt%, or 1-40 wt%.

[0073] [Embodiment 3] The polymer composition defined in embodiment 1 or 2, further comprising an additional flame retardant compound.

[0074] [Embodiment 4] The polymer composition defined in embodiment 3, wherein the additional flame retardant compound comprises a metal hydroxide.

[0075] [Embodiment 5] The polymer composition defined in embodiment 3, wherein the additional flame retardant compound comprises aluminum trihydrate and / or magnesium hydroxide.

[0076] [Embodiment 6] The polymer composition defined in any one of embodiments 3-5, wherein the amount of the additional flame retardant compound in the polymer composition is any suitable amount or amount within any range disclosed herein, e.g., 10-80 wt%, 20-70 wt%, or 30-65 wt%.

[0077] [Embodiment 7] The polymer composition defined in any one of embodiments 1-6, wherein the amount of triazine metal phosphate compound in the polymer composition is any suitable amount, or any amount within any range disclosed herein, e.g., 1-40 wt%, 1-25 wt%, or 1-15 wt%.

[0078] [Embodiment 8] The polymer composition defined in any one of embodiments 1 to 7, further comprising an additive, the additive comprising a stabilizer or antioxidant, a lubricant or processing aid, a compatibilizer or coupling agent, a filler, a colorant, a rheology modifier, or a curing agent, and any combination thereof.

[0079] [Embodiment 9] The polymer composition defined in any one of embodiments 1-8, wherein the polymer comprises any suitable polymer or any polymer disclosed herein, such as an elastomer, a thermoplastic, a thermoset, or a combination thereof.

[0080] [Aspect 10] The polymer composition defined in any one of aspects 1 to 9, wherein the polymer comprises a polyolefin.

[0081] [Aspect 11] The polymer composition defined in any one of aspects 1 to 10, wherein the polymer comprises an ethylene-based polymer, a propylene-based polymer, or a combination thereof.

[0082] [Aspect 12] The polymer composition defined in any one of aspects 1 to 11, wherein the polymer comprises a polyethylene (e.g., an ethylene-based copolymer such as an ethylene homopolymer or an ethylene / α-olefin copolymer).

[0083] [Embodiment 13] The polymer composition defined in any one of embodiments 1 to 11, wherein the polymer comprises polypropylene (e.g., a propylene homopolymer or a propylene-based copolymer).

[0084] [Aspect 14] The polymer composition defined in any one of aspects 1 to 11, wherein the polymer comprises an ethylene / vinyl acetate (EVA) copolymer.

[0085] [Aspect 15] The polymer composition defined in any one of aspects 1-9, wherein the polymer is selected from the group consisting of natural rubber (NR), epoxidized natural rubber (ENR), synthetic cis-polyisoprene (IR), emulsion styrene butadiene rubber (ESBR), solution styrene butadiene rubber (SSBR), polybutadiene rubber (BR), butyl rubber (IIR·CIIR / BIR), chloroprene rubber (CR), nitrile elastomer (NBR), hydrogenated nitrile elastomer (HNBR), carboxylated nitrile elastomer (XNBR), ethylene propylene rubber (EPM / EPDM), fluoroelastomer (FPM / FKM), polyurethane rubber (AU / EU / PU), or combinations thereof.

[0086] [Aspect 16] The polymer composition defined in any one of aspects 1 to 15, wherein the polymer is crosslinked.

[0087] [Aspect 17] The polymer composition defined in any one of aspects 1 to 9, wherein the polymer comprises an epoxy resin.

[0088] [Aspect 18] In the polymer composition defined in any one of Aspects 1-9, the polymer comprises a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a bisphenol A type novolac type epoxy resin, a bisphenol F type novolac type epoxy resin, a diphenylethylene type epoxy resin, an epoxy resin having a triazine skeleton, an epoxy resin having a fluorene skeleton, a triphenylmethane type epoxy resin, a biphenyl type epoxy resin, a xylylene type epoxy resin, a biphenyl aralkyl type epoxy resin, a naphthalene type epoxy resin, a dicyclopentadiene type epoxy resin, an alicyclic epoxy resin, or a combination thereof.

[0089] [Aspect 19] The polymer composition defined in any one of aspects 1-18, wherein the polymer composition has a water absorption rate within any suitable range, or any range disclosed herein, for example, 6 wt % or less, 5 wt % or less, 4 wt % or less, or 3 wt % or less in water at 90°C for 14 days according to ASTM D570.

[0090] [Embodiment 20] The polymer composition defined in any one of embodiments 1 to 19, wherein the polymer composition comprises a triazine metal phosphate compound, and wherein the polymer composition has a lower water absorption rate in water at 90°C for 14 days in ASTM D570 than an otherwise identical formulation comprising a polymerized version of the triazine metal phosphate compound.

[0091] [Embodiment 21] The polymer composition defined in any one of embodiments 1 to 20, wherein the polymer composition comprises a triazine metal phosphate compound, and wherein the polymer composition has a lower water absorption rate in water at 75°C for 7 days according to ASTM D570 than an otherwise identical formulation comprising a polymerized version of the triazine metal phosphate compound.

[0092] [EMBODIMENT 22] In the polymer composition defined in any one of Embodiments 1-21, the polymer composition has a ΔDk within any suitable range or within any range disclosed herein, e.g., 9% or less, 7% or less, 4% or less, or 2% or less, where ΔDk is the percentage change from the initial Dk to the Dk after aging in water at 90°C for 14 days according to ASTM D150 (100 MHz).

[0093] [EMBODIMENT 23] In the polymer composition defined in any one of Embodiments 1-22, the polymer composition has a ΔDf within any suitable range or within any range disclosed herein, e.g., 500% or less, 400% or less, 300% or less, or 200% or less, where ΔDf is the percentage change from the initial Df to Df after aging in water at 90°C for 14 days according to ASTM D150 (100 MHz).

[0094] [Embodiment 24] The polymer composition defined in any one of embodiments 1 to 23, wherein the polymer composition comprises a triazine metal phosphate compound and has a smaller ΔDk (or ΔDf, or both) than an otherwise identical formulation containing a polymerized version of the triazine metal phosphate compound (aged in water at 90°C for 14 days according to ASTM D150 (100 MHz)).

[0095] [EMBODIMENT 25] In the polymer composition defined in any one of Embodiments 1-24, the polymer composition has a ΔDf within any suitable range or within any range disclosed herein, e.g., 500% or less, 400% or less, 300% or less, or 200% or less, where ΔDf is the percentage change from the initial Df to Df after aging in water at 75°C for 7 days according to ASTM D150 (100 MHz).

[0096] [Embodiment 26] The polymer composition defined in any one of embodiments 1 to 24, wherein the polymer composition comprises a triazine metal phosphate compound and has a smaller ΔDk (or ΔDf, or both) than an otherwise identical formulation containing a polymerized version of the triazine metal phosphate compound (aged in water at 75°C for 7 days according to ASTM D150 (100 MHz)).

[0097] [Aspect 27] The polymer composition defined in any one of aspects 1 to 26, wherein each M is independently Ca, Mg, Zn, Al, or Sn.

[0098] [Embodiment 28] The polymer composition defined in any one of embodiments 1 to 26, wherein each M is Zn.

[0099] [Embodiment 29] In the polymer composition defined in any one of embodiments 1 to 26, the triazine metal phosphate compound is a triazine zinc phosphate compound having at least one of the following formulas: (AH) (+) [Zn 2(+) (H2PO4) (-) (HPO4) 2(-) ] * pHO (AH) (+) [Zn 2(+) (H2PO4)3 (-) ] * pHO (AH)2 (+) [Zn 2(+) (H2PO4)2 (-) (HPO4)2(-) ] * pHO (AH)2 (+) [Zn 2(+) (H2PO4)4 (-) ] * pHO (AH)2 (+) [Zn 2(+) (HPO4)2 2(-) ] * pHO (AH) (+) [Zn2 2(+) (H2PO4) (-) (HPO4)2 2(-) ] * pHO (AH) (+) [Zn2 2(+) (H2PO4)3 (-) (HPO4) 2(-) ] * pHO (AH) (+) [Zn2 2(+) (H2PO4)5 (-) ] * pHO (AH)2 (+) [Zn2 2(+) (H2PO4)2 (-) (HPO4)2 2(-) ] * pHO (AH)2 (+) [Zn2 2(+) (H2PO4)4 (-) (HPO4) 2(-) ] * pHO (AH)2 (+) [Zn2 2(+) (HPO4)3 2(-) ] * pHO (AH)2 (+) [Zn2 2(+) (H2PO4)6 (-) ] * pH2O; and p is 0 to 5.

[0100] [Embodiment 30] The polymer composition defined in any one of embodiments 1-29, wherein the triazine metal phosphate compound is characterized by any suitable d50 particle size, or any range of d50 particle size disclosed herein, such as 0.1-45 μm, 0.5-20 μm, 0.5-10 μm, 1-6 μm, or 1-5 μm.

[0101] [Embodiment 31] In the polymer composition defined in any one of embodiments 1 to 30, the triazine metal phosphate compound has any suitable BET surface area, or any range of BET surface areas disclosed herein, e.g., 0.5 to 30 m 2 / g, 0.5-10m 2 / g, 1-15m 2 / g, 2-8m 2 / g, or 2 to 5m 2 / g.

[0102] [Aspect 32] An article of manufacture comprising the polymer composition defined in any one of aspects 1 to 31.

[0103] [Embodiment 33] The article defined in embodiment 32, wherein the article comprises a wire or cable.

[0104] [Embodiment 34] The article defined in embodiment 32, wherein the article comprises a printed circuit board.

Claims

1. 1. A polymer composition comprising: (a) a polymer; and (b) triazine metal phosphate compounds having the following formula (I): (AH) a (+) [M b m+ (H 2 NIGHT 4 ) x1 (-) (HPO 4 ) x2 2(-) ] (a-) * pH 2 O (-) and, Equipped with Each (A-H)(+) is independently a triazine derivative having the following formula (II-1), (II-2) or (II-3): 【Chemistry 1】 M is independently Cu, Mg, Ca, Zn, Mn, Fe, Co, Ni, B, Si, Al, Sb, La, Ti, Zr, Ce, V, or Sn; a is 1 to 6; b is 1 to 14; m is 1 to 6; x １ is 1 to 12, and x ２ is 0 to 12, and p is 0 to 5; a + m b = x １ +2x ２ and (1) The polymer composition has a water absorption rate of 6 wt % or less in water at 90° C. for 14 days according to ASTM D570; or (2) The polymer composition has a ΔDk of 9% or less, measured after aging in water at 90° C. for 14 days according to ASTM D150 (100 MHz), or (3) The polymer composition has a ΔDf of 500% or less, in terms of the rate of change from the initial Df to Df after aging in water at 90° C. for 14 days according to ASTM D150 (100 MHz); or (4) The triazine metal phosphate compound is characterized in that the d50 particle size is in the range of 0.1 to 45 μm, or (5) any combination thereof; 1. A polymer composition comprising:

2. 10. The polymer composition of claim 1, wherein the absorption is 6 wt% or less, 5 wt% or less, 4 wt% or less, or 3 wt% or less.

3. 3. The polymer composition of claim 1 or 2, wherein the ΔDk is 9% or less, 7% or less, 4% or less, or 2% or less.

4. The polymer composition according to any one of claims 1 to 3, wherein the ΔDf is 500% or less, 400% or less, 300% or less, or 200% or less.

5. 5. The polymer composition according to any one of claims 1 to 4, wherein the d50 particle size is in the range of 0.1 to 45 μm, 0.5 to 20 μm, 0.5 to 10 μm, 1 to 6 μm, or 1 to 5 μm.

6. The polymer composition of any one of claims 1 to 5, wherein each M is independently Ca, Mg, Zn, Al, or Sn.

7. The polymer composition of any one of claims 1 to 5, wherein each M is Zn.

8. In the polymer composition according to any one of claims 1 to 5, the triazine metal phosphate compound has the following formula: (AH) (+) [Zn 2(+) (H 2 NIGHT 4 ) (-) (HPO 4 ) 2(-) ] * pH 2 O (A-H) (+) [Zn 2(+) (H 2 PO 4 ) 3 (-) ] * pH 2 O (AH) 2 (+) [Zn 2(+) (H 2 NIGHT 4 ) 2 (-) (HPO 4 ) 2(-) ] * pH 2 O (A-H) 2 (+) [Zn 2(+) (H 2 PO 4 ) 4 (-) ] * pH 2 O (AH) 2 (+) [Zn 2(+) (HPO 4 ) 2 2(-) ] * pH 2 O (AH) (+) [Zn 2 2(+) (H 2 NIGHT 4 ) (-) (HPO 4 ) 2 2(-) ] * pH 2 O (AH) (+) [Zn 2 2(+) (H 2 NIGHT 4 ) 3 (-) (HPO 4 ) 2(-) ] * pH 2 O (A-H) (+) [Zn 2 2(+) (H 2 PO 4 ) 5 (-) ] * pH 2 O (AH) 2 (+) [Zn 2 2(+) (H 2 NIGHT 4 ) 2 (-) (HPO 4 ) 2 2(-) ] * pH 2 O (AH) 2 (+) [Zn 2 2(+) (H 2 NIGHT 4 ) 4 (-) (HPO 4 ) 2(-) ] * pH 2 O (AH) 2 (+) [Zn 2 2(+) (HPO 4 ) 3 2(-) ] * pH 2 O (A-H) 2 (+) [Zn 2 2(+) (H 2 PO 4 ) 6 (-) ] * pH 2 O、 wherein p is 0 to 5.

9. In the polymer composition according to any one of claims 1 to 8, the triazine metal phosphate compound has a molecular weight of 0.5 to 30 m. ２ / g, 0.5-10m ２ / g, 1 to 15 m ２ / g, 1-10m ２ / g, 2-8m ２ / g, or 2 to 5 m ２ The polymer composition is characterized by a BET surface area in the range of 1 / g.

10. The polymer composition of any one of claims 1 to 9, wherein the polymer comprises a polyolefin.

11. The polymer composition of any one of claims 1 to 9, wherein the polymer comprises an ethylene / α-olefin copolymer, an ethylene / vinyl acetate (EVA) copolymer, or a combination thereof.

12. The polymer composition of any one of claims 1 to 9, wherein the polymer comprises an elastomer.

13. The polymer composition according to any one of claims 1 to 9, wherein the polymer comprises an epoxy resin.

14. 14. The polymer composition of claim 1, wherein the amount of the triazine metal phosphate compound in the polymer composition is in the range of 1 to 80 wt %, 1 to 65 wt %, 1 to 40 wt %, 3 to 40 wt %, 10 to 40 wt %, or 3 to 25 wt %.

15. The polymer composition according to any one of claims 1 to 13, further comprising an additional flame retardant compound.

16. 16. The polymer composition of claim 15, wherein the additional flame retardant compound comprises aluminum trihydrate and / or magnesium hydroxide.

17. 17. The polymer composition according to claim 15 or 16, wherein the amount of the additional flame retardant compound in the polymer composition is in the range of 10-80 wt%, 20-70 wt%, 30-65 wt%, or 40-60 wt%.

18. 18. The polymer composition of any one of claims 15 to 17, wherein the amount of the triazine metal phosphate compound in the polymer composition is in the range of 1 to 40 wt%, 1 to 25 wt%, 1 to 15 wt%, 2 to 20 wt%, or 5 to 15 wt%.

19. 19. The polymer composition of any one of claims 1 to 18, further comprising an additive, said additive comprising a stabilizer or antioxidant, a lubricant or processing aid, a compatibilizer or coupling agent, a filler, a colorant, a rheology modifier, a curing agent, or any combination thereof.

20. In the polymer composition according to any one of claims 1 to 19, the polymer composition containing the triazine metal phosphate compound is and / or the water absorption rate at 90° C. in water for 14 days according to ASTM D570 is less than the water absorption rate of an otherwise identical formulation containing a polymeric version of said triazine metal phosphate compound; The water absorption rate after 7 days at 75°C in water according to ASTM D570 is less than that of other identical formulations containing the polymerized variant of the triazine metal phosphate compound. Polymer composition.

21. The polymer composition according to any one of claims 1 to 20, comprising the triazine metal phosphate compound, a ΔDk smaller than the ΔDk of an otherwise identical formulation containing a polymerized version of said triazine metal phosphate compound, where ΔDk is the percent change from the initial Dk to Dk after aging in water at 90° C. for 14 days according to ASTM D150 at 100 MHz; and / or a ΔDf smaller than the ΔDf of an otherwise identical formulation containing a polymerized version of said triazine metal phosphate compound, where ΔDf is the percent change from initial Df to Df after aging for 14 days at 90° C. in water according to ASTM D150 at 100 MHz; 1. A polymer composition comprising:

22. The polymer composition according to any one of claims 1 to 21, wherein the polymer composition comprising the triazine metal phosphate compound is a ΔDk less than the ΔDk of an otherwise identical formulation containing a polymerized version of said triazine metal phosphate compound, where ΔDk is the percent change from the initial Dk to Dk after aging at 75° C. in water for 7 days according to ASTM D150 at 100 MHz; and / or a ΔDf less than the ΔDf of an otherwise identical formulation containing a polymerized version of said triazine metal phosphate compound, where ΔDf is the percent change from initial Df to Df after aging for 7 days at 75° C. in water according to ASTM D150 at 100 MHz; 1. A polymer composition comprising:

23. 23. The polymer composition of any one of claims 1 to 22, having a ΔDf of 250% or less, 225% or less, 200% or less, or 150% or less, where ΔDf is the percent change from initial Df to Df after aging at 75°C in water for 7 days according to ASTM D150 at 100 MHz.

24. An article of manufacture comprising the polymer composition of any one of claims 1 to 23.

25. 25. The article of manufacture of claim 24, comprising a wire or cable.

26. 25. The article of manufacture of claim 24, comprising a printed circuit board.

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