Flame retardant compositions containing polycyclic olefin polymers having olefinic functional groups to form low loss films with improved dielectric and thermal properties - Patent Application 20070122999

Abstract

Embodiments of the present invention include compositions comprising polymers formed from various polycyclic olefin monomers, optionally containing at least one monomer containing additional unpolymerized ethylene bonds, an organophosphate compound, optionally hexagonal boron nitride, a crosslinker, a free-radical initiator, a tackifier, and one or more suitable additives. The compositions of the present invention can be formed into various three-dimensional insulating materials, such as films, upon exposure to suitable elevated temperatures. Objects formed from the compositions of the present invention exhibit previously unattainable low dielectric constants, low loss characteristics, flame retardancy, and exceptionally high thermal properties. The compositions of the present invention can further comprise one or more organic or inorganic filler materials, which provide improved thermal and mechanical properties in addition to excellent thermal and dielectric properties. The compositions of the present invention are useful in a variety of applications, including insulating materials for millimeter-wave radar antennas. Films formed from the compositions of the present invention have a UL-94 rating of V-0, a dielectric constant (Dk) of less than 2.7, and a dielectric dissipation factor (Df) of less than 0.0009.

Description

[Technical Field]

[0001] Cross-reference to related applications This application claims the benefit of U.S. Provisional Application No. 63 / 404,374, filed September 7, 2022, which is incorporated herein.

[0002] Embodiments of the present invention generally relate to compositions comprising polymers containing olefinic functional groups in combination with a flame-retardant organophosphate compound, hexagonal boron nitride, a tackifier, a crosslinker, a free-radical initiator, and one or more additives. More specifically, the polymers used herein are formed from two or more polycyclic olefinic monomers, such as norbornene-type monomers, at least one of which contains free olefinic functional groups. The compositions of the present invention can be readily formed into films useful as prepregs for low-loss thermosets and copper-clad laminates, which exhibit not only low dielectric constants and low loss characteristics, but also very high thermal and flame-retardant properties. For example, films formed from the compositions of the present invention typically exhibit high glass transition temperatures in the range of about 250°C to 280°C, low dielectric constants (about 2.4 to 2.8 at 10 GHz) and low dielectric dissipation factors (about 0.0008 to 0.002 at 10 GHz). Thus, the polymers and compositions of the present invention find use as insulating materials in a variety of applications, including electromechanical device applications in the manufacture of automotive parts. [Background technology]

[0003] It is well known in the art that insulating materials with low dielectric constant (Dk) and low loss (also known as dielectric dissipation factor (Df)) are important for printed circuit boards used in electrical appliances and automotive components, as well as other applications. Generally, insulating materials suitable for most such devices should have a dielectric constant below 3 and exhibit low loss, e.g., below 0.002 at high frequencies above 10 GHz. Furthermore, ease of fabrication, among other advantages, has led to increased interest in the development of organic dielectric materials.

[0004] However, for such materials to be used in copper clad laminates for printed circuit boards, they require high glass transition temperatures (T g High-performance thermosets with low Dk / Df, low CTE, low Dk / Df, high peel strength to copper, and excellent high-temperature storage reliability are needed. The ability to form prepregs (composites with glass cloth), B-stage (producing layers of uncrosslinked or partially crosslinked material), and film fusion to create multilayer structures are also important. Most commercial materials available in the art fail to achieve these properties, particularly low Dk / Df and high glass transition temperatures above 250°C.

[0005] Furthermore, the development of such insulating materials that meet all the requirements presents considerable technical challenges. Yet another challenge is that such materials have very high glass transition temperatures (T g This temperature is preferably greater than 150°C, and even greater than 250°C, due to the process conditions used in manufacturing printed circuit boards and the harsh conditions that devices may face, such as millimeter wave radar antennas used in automobiles and other terminal devices in 5G devices.

[0006] For example, films made by addition polymerization of norbornene derivatives containing long side chains, such as 5-hexylnorbornene (HexNB) and 5-decylnorbornene (DecNB), are known to have low Dk and Df due to their hydrophobic properties, but these films also have high CTE (>200 ppm / K) and low T g For example, see Japanese Patent Application Laid-Open No. 2016-037577 and Japanese Patent Application Laid-Open No. 2012-121956.

[0007] According to the literature, certain polymers such as fluorinated polyethylene, polyethylene, and polystyrene have low Dk / Df, but all of these polymers exhibit very low glass transition temperatures (possibly much lower than 150°C), making them unsuitable as organic insulating materials. Furthermore, the literature also indicates that certain substituted norbornene combinations, typically substituted with polar groups such as ester or alcohol groups, generally result in low CTE and T g However, the combination of such groups increases both Dk and Df due to polarizability, especially under high-frequency electromagnetic fields. Therefore, norbornenes substituted with such polar groups are not suitable for forming insulating materials as intended in this application. Furthermore, the high heat generated in many applications increases the need to ensure that materials used in these applications are flame-retardant.

[0008] U.S. Patent No. 10,104,769 B2 discloses embodiments of circuit subassemblies including a thermosetting resin composition containing a low polarity resin, an oxaphosphorine oxide-containing aromatic compound, which has a UL-94 rating of at least V-1. However, the embodiments reported herein exhibit a high Dk of about 3.8 and a Df of about 0.006.

[0009] Therefore, there remains a need to develop new insulating materials that not only exhibit low dielectric properties but also very high thermal properties and good flame retardant properties.

[0010] Additionally, there is a need to develop materials that can form thermoset films rather than thermoplastic films, which are generally cross-linked, more stable at high temperatures, and do not exhibit thermal mobility like thermoplastics. Summary of the Invention [Problem to be solved by the invention]

[0011] It is therefore an object of the present invention to provide a flame retardant composition exhibiting a UL-94 rating of V-0 and excellent dielectric and thermal properties, which comprises a polymer having one or more substituted norbornene monomers, one of which may contain a free olefin functional group, an organophosphate compound, and optionally hexagonal boron nitride, which can be formed into an insulating material with heretofore unattainable properties.

[0012] Other objects and scope of applicability of the present invention will become apparent from the following detailed description. [Means for solving the problem]

[0013] Surprisingly, it has been discovered that when a composition comprising one or more polycyclic olefin monomers of formula (I) and optionally a monomer of formula (II) as described herein, one or more organophosphate compounds of formulas (III) and (IV) as described herein, and optionally a polymer comprising hexagonal boron nitride, in combination with certain other components as described herein, it is possible to form a variety of three-dimensional objects, including films, which provide heretofore unattainable dielectric and thermal properties.

[0014] In yet another embodiment, there is provided a film-forming composition comprising two or more polycyclic olefin monomers of formula (I) and (II), one or more organophosphate compounds of formula (III) or (IV), and optionally a polymer having hexagonal boron nitride, as described herein, in combination with certain other ingredients as described herein, which can form a film suitable for insulating materials that exhibits excellent flame retardant properties. In yet another aspect of the present invention, there are provided films, composites, and prepregs comprising the compositions of the present invention. [Brief explanation of the drawings]

[0015] Embodiments in accordance with the present invention will now be described with reference to the following accompanying drawings and / or images. Where drawings are provided, they are simplified portions of various embodiments of the present invention and are provided for illustrative purposes only.

[0016] [Figure 1] FIG. 1 shows a graphical plot of a dielectric reliability study conducted at a storage temperature of 125° C. over a period of over 1,000 hours of exemplary films formed from compositions of the present invention, compared to comparative compositions.

[0017] [Figure 2] FIG. 2 shows a graphical plot of a dielectric reliability study of exemplary films formed from compositions of the present invention at a storage temperature of 125° C. over a period of over 1,000 hours, compared to other films formed from the same compositions stored at 85° C. and 85% relative humidity.

[0018] [Figure 3] FIG. 3 shows a graphical plot of a dielectric reliability study conducted at a storage temperature of 85° C. and 85% relative humidity for a period of over 1,000 hours on several exemplary films formed from various composition embodiments of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0019] The terms used in this application have the following meanings:

[0020] In this application, the articles "a," "an," and "the" include plural referents unless otherwise expressly and unambiguously limited to one referent.

[0021] In this specification and the claims appended hereto, all numbers, values, and / or expressions setting forth quantities of ingredients, reaction conditions, and the like are subject to various measurement uncertainties arising in obtaining such values, and therefore, unless expressly stated otherwise, should be understood as all being modified in all instances by the term "about."

[0022] When numerical ranges are disclosed herein, such ranges are continuous and include both the minimum and maximum values ​​of the range, as well as all values ​​between such minimum and maximum values. Furthermore, when a range refers to integers, all integers between the minimum and maximum values ​​of such range are included. Furthermore, when multiple ranges are provided to describe a single feature or characteristic, such ranges are combinable. In other words, unless otherwise expressly stated, all ranges disclosed herein should be understood to include all subranges subsumed therein. For example, a range stated as "1 to 10" should be considered to include all subranges between the minimum value of 1 and the maximum value of 10. Exemplary subranges of the 1 to 10 range include, but are not limited to, 1 to 6.1, 3.5 to 7.8, and 5.5 to 10.

[0023] As used herein, "hydrocarbyl" refers to a group containing carbon and hydrogen atoms, including, but not limited to, alkyl, cycloalkyl, aryl, aralkyl, alkaryl, and alkenyl. The term "halohydrocarbyl" refers to a hydrocarbyl group in which at least one hydrogen has been replaced with a halogen. The term perhalocarbyl refers to a hydrocarbyl group in which all hydrogens have been replaced with halogens.

[0024] As used herein, the term "alkyl" means a saturated, straight- or branched-chain hydrocarbon substituent having the specified number of carbon atoms. Particular alkyl groups include methyl, ethyl, n-propyl, isopropyl, tert-butyl, and the like. Derived expressions such as "alkoxy," "thioalkyl," "alkoxyalkyl," "hydroxyalkyl," "alkylcarbonyl," "alkoxycarbonylalkyl," "alkoxycarbonyl," "diphenylalkyl," "phenylalkyl," "phenylcarboxyalkyl," and "phenoxyalkyl" should be construed accordingly.

[0025] As used herein, the term "cycloalkyl" includes all known cyclic groups. Representative examples of "cycloalkyl" include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like. Derived expressions such as "cycloalkoxy," "cycloalkylalkyl," "cycloalkylaryl," and "cycloalkylcarbonyl" should be construed accordingly.

[0026] As used herein, the term "perhaloalkyl" refers to an alkyl group as defined above, wherein all hydrogen atoms of the alkyl group are replaced with halogen atoms selected from fluorine, chlorine, bromine, or iodine. Illustrative examples include trifluoromethyl, trichloromethyl, tribromomethyl, triiodomethyl, pentafluoroethyl, pentachloroethyl, pentabromoethyl, pentaiodoethyl, and linear or branched heptafluoropropyl, heptachloropropyl, heptabromopropyl, nonafluorobutyl, nonachlorobutyl, undecafluoropentyl, undecachloropentyl, tridecafluorohexyl, tridecachlorohexyl, etc. Derived expressions such as "perhaloalkoxy" should also be interpreted accordingly. It should also be noted that certain alkyl groups described herein may be partially fluorinated. That is, only a portion of the hydrogen atoms of the alkyl group are replaced with fluorine atoms, and should be interpreted accordingly.

[0027] As used herein, the term "acyl" is synonymous with "alkanoyl," which may be structurally represented as "R-CO-," where R is "alkyl" having the specified number of carbon atoms, as defined herein. Also, "alkylcarbonyl" is synonymous with "acyl," as defined herein. Specifically, "(C1-C4)acyl" refers to formyl, acetyl, or ethanoyl, propanoyl, n-butanoyl, etc. Derived expressions such as "acyloxy" and "acyloxyalkyl" should be construed accordingly.

[0028] As used herein, the term "aryl" refers to substituted or unsubstituted phenyl or naphthyl. Specific examples of substituted phenyl or naphthyl include o-, p-, m-tolyl, 1,2-, 1,3-, 1,4-xylyl, 1-methylnaphthyl, 2-methylnaphthyl, and the like. "Substituted phenyl" or "substituted naphthyl" includes substituents that may be further defined herein or that are known in the art.

[0029] As used herein, the term "arylalkyl" refers to an aryl, as defined herein, further attached to an alkyl, as defined herein. Representative examples include benzyl, phenylethyl, 2-phenylpropyl, 1-naphthylmethyl, 2-naphthylmethyl, and the like.

[0030] As used herein, the term "alkenyl" refers to an acyclic, straight-chained or branched hydrocarbon chain having the specified number of carbon atoms and containing at least one carbon-carbon double bond, and includes ethenyl and straight-chained or branched propenyl, butenyl, pentenyl, hexenyl, and the like. Derived expressions "arylalkenyl" and 5- or 6-membered "heteroarylalkenyl" are to be construed accordingly. Examples of such derived expressions include furan-2-ethenyl, phenylethenyl, 4-methoxyphenylethenyl, and the like.

[0031] As used herein, the term "heteroaryl" includes all known heteroatoms, including aromatic radicals. Representative 5-membered heteroaryl radicals include furanyl, thienyl, or thiophenyl, pyrrolyl, isopyrrolyl, pyrazolyl, imidazolyl, oxazolyl, thiazolyl, isothiazolyl, and the like. Representative 6-membered heteroaryl radicals include pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, and the like. Representative examples of bicyclic heteroaryl radicals include benzofuranyl, benzothiophenyl, indolyl, quinolinyl, isoquinolinyl, cinnolyl, benzimidazolyl, indazolyl, pyridofuranyl, pyridothienyl, and the like.

[0032] As used herein, the term "heterocycle" includes all known reduced heteroatom-containing ring radicals. Representative 5-membered heterocycle radicals include tetrahydrofuranyl, tetrahydrothiophenyl, pyrrolidinyl, 2-thiazolinyl, tetrahydrothiazolyl, tetrahydrooxazolyl, and the like. Representative 6-membered heterocycle radicals include piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, and the like. Miscellaneous heterocycle radicals include, but are not limited to, aziridinyl, azepanyl, diazepanyl, diazabicyclo[2.2.1]hept-2-yl, triazocanyl, and the like.

[0033] "Halogen" or "halo" means chlorine, fluorine, bromine, or iodine.

[0034] In its broadest sense, the term "substituted" is contemplated to include all permissible substituents of organic compounds. In certain specific embodiments disclosed herein, the term "substituted" means substituted with one or more substituents independently selected from the group consisting of (C-C) alkyl, (C-C) alkenyl, (C-C) perfluoroalkyl, phenyl, hydroxy, -COH, ester, amide, (C-C) alkoxy, (C-C) thioalkyl, and (C-C) perfluoroalkoxy. However, any other suitable substituent known to one of ordinary skill in the art can be used in such embodiments.

[0035] It should be noted that in this text, equations, examples, and tables, all atoms with unsatisfied valences are assumed to have the appropriate number of hydrogen atoms necessary to satisfy such valences.

[0036] It is understood that the terms "dielectric" and "insulating" are used interchangeably herein. Thus, a reference to an insulating material or layer includes a dielectric material or layer, and vice versa. Also, as used herein, the term "organic electronic device" is understood to include "organic semiconductor device" and various specific implementations of such devices used, for example, in the automotive industry.

[0037] As used herein, the dielectric constant (Dk) of a material is the ratio of the charge stored in an insulating material placed between two metal plates to the charge stored when the insulating material is replaced by a vacuum or air. It is also called the electrical permittivity or simply the dielectric constant. It is also sometimes called the relative permittivity because it is measured relative to the permittivity of free space.

[0038] In this application, "low loss" refers to the dissipation factor (Df), which measures the rate at which a vibration mode (mechanical, electrical, or electromechanical) loses energy in a dissipative system. It is the inverse of the quality factor, which indicates the "quality" or durability of the vibration.

[0039] As used herein, "B-stage" refers to a material in which the reaction between the base polymer and the curing agent / hardener is not complete. That is, such "B-staged" materials are in a partially cured state and are generally free of the solvent used to prepare compositions containing the base polymer and the curing agent / hardener. Typically, such "B-staged" materials can be reheated at elevated temperatures to complete crosslinking and fully cure the material.

[0040] As used herein, "prepreg" refers to a material that has been pre-impregnated with a polymeric material, which may be a thermoplastic or thermosetting resin. Typically, a fibrous material, such as glass cloth, is pre-impregnated with the polymeric material to form a prepreg, which is formed in a "B-stage" process and then cured by heating again at an elevated temperature.

[0041] The term "derived" means that the polymerized repeat unit is polymerized (formed) from a polycyclic norbornene-type monomer, for example, according to formula (I) or (II), and the resulting polymer is formed by 2,3-chaining of the norbornene-type monomer, as shown below. [ka]

[0042] Such polymerizations are also commonly known as vinyl addition polymerizations, which are generally carried out in the presence of organometallic compounds such as organopalladium compounds or organonickel compounds, as will be explained in more detail below.

[0043] Thus, in accordance with the practice of the present invention a) comprises a polymer; i) comprising at least one first repeat unit represented by formula (IA), said first repeat unit being derived from a monomer of formula (I): [ka] In the above formula: [ka] represents the position of bonding to other repeating units; m is an integer of 0, 1, or 2; R1, R2, R3, and R4 are the same or different and each is hydrogen, methyl, ethyl, straight-chain or branched (C3-C 16 ) alkyl, (C3-C 10 ) cycloalkyl, (C6-C 12 )bicycloalkyl, (C6-C 12 ) aryl, and (C6-C 12 )aryl(C1-C6)alkyl; or One of R1 and R2, together with one of R3 and R4 and the carbon atom to which they are attached, may form a substituted or unsubstituted (C5-C 14 )monocyclic ring, (C5-C 14 ) bicyclic ring, or (C5-C 14) forming a tricyclic ring; and ii) at least one second repeat unit of formula (IIA), said second repeat unit being derived from a monomer of formula (II): [ka] In the above formula: [ka] represents the position of bonding to other repeating units; n is an integer of 0, 1, or 2; At least one of R5, R6, R7, and R8 is methylidene, ethylidene, vinyl, straight-chain or branched (C3-C 16 ) alkenyl, (C3-C 10 ) cycloalkenyl, (C6-C 12 ) bicycloalkenyl, and (C6-C 12 )Aryl(C2-C 16 ) alkenyl, and the remaining R5, R6, R7, and R8 are the same or different and each is selected from the group consisting of hydrogen, methyl, ethyl, straight or branched (C3-C 16 ) alkyl, (C3-C 10 ) cycloalkyl, (C6-C 12 )bicycloalkyl, (C6-C 12 ) aryl, and (C6-C 12 )aryl(C1-C6)alkyl; or One of R5 and R6, together with one of R7 and R8 and the carbon atom to which they are attached, is a substituted or unsubstituted (C5-C 14 )monocyclic ring, (C5-C 14 ) bicyclic ring, or (C5-C 14 ) forming a tricyclic ring; and the second repeat unit is present in an amount ranging from about 0 mol % to about 40 mol %, based on the total number of moles of the first and second repeat units; b) comprising a cross-linking agent selected from the group consisting of: [ka] c) comprising an organophosphate compound selected from the group consisting of: Compounds of formula (III): [ka] In the above formula: a and b are each independently an integer from 0 to 5; c is an integer from 2 to 4; Q is a divalent or trivalent (C2-C 24 ) alkyl, divalent NH(C2-C6) alkylNH, and divalent O(C2-C6) alkylNH, wherein the alkyl is optionally methyl, ethyl, straight or branched (C3-C6) alkyl, (C6-C 12 ) aryl, and (C5-C 12 ) substituted with one or more groups selected from the group consisting of heteroaryl; R9 and R 10 are each independently selected from the group consisting of hydrogen, methyl, ethyl, and straight-chain or branched (C3-C6) alkyl; and Compounds of formula (IV): [ka] In the above formula: R 11 and R 12 are each independently selected from the group consisting of methyl, ethyl, straight or branched (C-C) alkyl, phenyl, methoxy, ethoxy, straight or branched (C-C) alkoxy, phenoxy, and 6H-phosphanthridine 5-oxide-(C-C) alkyl; d) containing a tackifier; and e) one or more additives selected from the group consisting of free radical initiators, antioxidants, synergists, and mixtures of any combination thereof.

[0044] It should be noted that when the one or more organophosphate compounds of formula (III) or (IV) are present in an amount greater than 70% by weight based on the amount of polymer, the composition when formed into a film has a UL-94 rating of at least V-1, a dissipation factor (Df) of less than 0.001 at 10 GHz, and a dielectric constant (Dk) of less than 2.5 at 10 GHz.

[0045] Polymers such as those described herein can be prepared by vinyl addition polymerization, as known in the art. It has been found that copolymerization of one or more monomers of formula (I) with one or more monomers of formula (II) can form polymers according to the present invention, where additional olefinic functional groups present in the monomers of formula (II) do not react during the vinyl addition polymerization, and such olefinic functional groups may be used in other applications of the polymer. Thus, for example, the polymers of the present invention can be used in a variety of applications where they can be further crosslinked with other materials. Such methods include forming prepregs suitable for the manufacture of printed circuit boards in which copper-clad laminates are used. It has been found that even small amounts of the monomers of formula (II) can be incorporated to form polymers according to the present invention, which are highly effective in forming crosslinkable compositions of the present invention, as described in more detail below.

[0046] Advantageously, it has been found that the additional olefinic functional groups present in the monomer of formula (II) are unreactive with vinyl addition polymerization catalysts and therefore remain present after the formation of the polymers of the present invention. That is, one of the olefinic groups present at R5, R6, R7, and R8 of the monomer of formula (II) remains available in the polymers formed by the present invention. Thus, the polymers of the present invention are useful in a variety of applications requiring additional reactions involving the olefinic functional groups, such as crosslinking with other materials. Furthermore, it has been observed that the amount of monomer of formula (II) used to observe the crosslinking ability of the polymers of the present invention when used in the compositions of the present invention can be as little as 10 mol % of the total amount of monomers of formulas (I) and (II).

[0047] Thus, in one embodiment, the amount of repeat units of the monomer of formula (IIA) present in the polymer is at least 10 mol % based on the total number of moles of the first and second repeat units of formulae (IA) and (IIA). In another embodiment, the amount of repeat units of the monomer of formula (IIA) present in the polymer is from about 10 mol % to about 40 mol %, from about 15 mol % to about 30 mol %, from about 18 mol % to about 25 mol %, etc., based on the total number of moles of the first and second repeat units of formulae (IA) and (IIA). In yet another embodiment, the amount of repeat units of the monomer of formula (IIA) present in the polymer can be less than 10 mol % depending on the intended crosslink density, or can exceed 40 mol % based on the total number of moles of the first and second repeat units of formulae (IA) and (IIA) when particularly high crosslink densities are desired.

[0048] As noted above, one or more monomers of formula (I) with at least one monomer of formula (II) can be used to form the polymers of the present invention. It has been found advantageous to use at least two separate monomers of formula (I) with one monomer of formula (II). Furthermore, as described herein, preferred amounts of separate monomers of formula (I) can be used in combination with a monomer of formula (II). In one embodiment, the molar ratio of such separate monomers of formula (I) can be 10:90, 20:80, 30:70, 40:60, 50:50, etc.

[0049] In one embodiment, the polymer used in the composition of the present invention has a repeating unit of formula (IA) where m is 0 or 1. In another embodiment, the polymer used in the composition of the present invention has a repeating unit of formula (IA) where m is 0. That is, the repeating unit of formula (IA) is derived from a monomer of formula (I), which is a derivative of norbornene. Furthermore, one or more separate monomers of formula (I) can be used to form the polymer of the present invention. In another embodiment, the monomer of formula (I) used has m=1. That is, the monomer used in this embodiment includes a dimeric norbornene monomer unit, also known as tetracyclodecene (TD). However, it should be noted that a combination of monomers of formula (I) having m=0 and m=1 can also be used to form the polymer of the present invention. That is, a mixture of norbornene derivatives of formula (I) as described herein can be used with a suitable tetracyclodecene derivative of formula (I) as described herein to form the polymer of the present invention. In other words, any suitable amount of these separate monomers of formula (I) that can provide the intended benefits can be used to form the polymer of the present invention. Thus, in one embodiment, a polymer according to the present invention comprises a first repeat unit derived from two separate monomers of formula (I).

[0050] Similarly, in another embodiment, the polymer used in the composition of the present invention has a repeating unit of formula (IIA) where n is 0 or 1. In another embodiment, the polymer of the present invention has a repeating unit of formula (IIA) where n is 0. That is, the repeating unit of formula (IIA) is derived from a monomer of formula (II), which is a derivative of norbornene. Furthermore, one or more separate monomers of formula (II) can be used to form the polymer of the present invention. In another embodiment, the monomer of formula (II) used has n=1. That is, the monomer used in this embodiment includes a dimeric norbornene monomer unit, also known as tetracyclodecene (TD). However, it should be noted that combinations of monomers of formula (II) having n=0 and n=1 can also be used to form the polymer of the present invention. That is, a mixture of norbornene derivatives of formula (II) as described herein can be used with a suitable tetracyclodecene derivative of formula (II) to form the polymer of the present invention. In other words, suitable amounts of these separate monomers that provide the intended benefits can be used to form the polymer of the present invention.

[0051] In one embodiment, R1, R2, R3, and R4 are the same or different and each is independently selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, n-butyl, n-hexyl, cyclopentyl, cyclohexyl, and norbornyl.

[0052] In another embodiment, one of R1 and R2 together with one of R3 and R4 and the carbon atom to which they are attached form a cyclopentyl, cyclohexyl, cycloheptyl, bicycloheptyl, bicyclooctyl, or adamantyl ring.

[0053] In yet another embodiment, at least one of R5, R6, R7, and R8 is selected from the group consisting of ethylidene, vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, cyclopentenyl, and cyclohexenyl, and the remaining R5, R6, R7, and R8 are the same or different and each independently selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, n-butyl, n-hexyl, cyclopentyl, cyclohexyl, and norbornyl.

[0054] In one embodiment, one of R5 and R6 together with one of R7 and R8 and the carbon atom to which they are attached form a cyclopentenyl, cyclohexenyl, cycloheptenyl, bicycloheptenyl, or bicyclooctenyl ring.

[0055] Additionally, any monomer of formula (I) within the scope of the present invention may be used to form the polymers of the present invention. Non-limiting examples of such monomers of formula (I) may be selected from the group consisting of:

[0056] [ka]

[0057] Similarly, any monomer of formula (II) that is within the scope of the present invention can be used to form the polymers of the present invention. Non-limiting examples of such monomers of formula (II) can be selected from the group consisting of:

[0058] [ka]

[0059] Illustrative, non-limiting examples of polymers according to the present invention include: Copolymer of norbornene (NB) and 5-vinylbicyclo[2.2.1]hept-2-ene (VNB); Copolymer of norbornene (NB) and 5-ethylidenebicyclo[2.2.1]hept-2-ene (ENB); Copolymer of norbornene (NB) and 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB); Copolymer of norbornene (NB) and 5-(hex-5-en-1-yl)bicyclo[2.2.1]hept-2-ene (HexenylNB); and Copolymer of norbornene (NB) and 5-(cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyclohexeneNB); Terpolymer of norbornene (NB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), and 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB); Terpolymer of norbornene (NB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB) and 5-(cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyclohexeneNB); Terpolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB) and 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB); Terpolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB) and 5-(hex-5-en-1-yl)bicyclo[2.2.1]hept-2-ene (HexenylNB); and Terpolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB) and 5-(cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyclohexeneNB).

[0060] In yet another aspect of the present invention, the polymers used in the compositions of the present invention contain only repeat units of formula (IA) derived from monomers of formula (I). That is, the polymers used in this embodiment of the present invention do not contain repeat units of formula (IIA) containing free olefin functional groups. Therefore, such polymers cannot be crosslinked to form thermoset compositions. Therefore, where such compositions are desired, thermoplastic compositions containing only repeat units of formula (IA) are also provided. In such composition aspects of the present invention, one or more monomers of formula (I) capable of forming homopolymers, copolymers, or terpolymers can be used.

[0061] Illustrative, non-limiting examples of polymers according to this aspect of the invention include: norbornene (NB) homopolymer; Homopolymer of 5-(butyl)bicyclo[2.2.1]hept-2-ene (BuNB); Homopolymer of 5-(hexyl)bicyclo[2.2.1]hept-2-ene (HexNB); Homopolymer of 5-(decyl)bicyclo[2.2.1]hept-2-ene (DecNB); Copolymer of norbornene (NB) and 5-(butyl)bicyclo[2.2.1]hept-2-ene (BuNB); Copolymer of norbornene (NB) and 5-(hexyl)bicyclo[2.2.1]hept-2-ene (HexNB); and Copolymer of norbornene (NB) and 5-(cyclohexyl)bicyclo[2.2.1]hept-2-ene (CyclohexaneNB); Terpolymer of norbornene (NB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), and 5-(hexyl)bicyclo[2.2.1]hept-2-ene (HexNB); Terpolymer of norbornene (NB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), and 5-(cyclohexyl)bicyclo[2.2.1]hept-2-ene (CyclohexaneNB); and Terpolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), and 5-(decyl)bicyclo[2.2.1]hept-2-ene (DecylNB).

[0062] As noted above, monomers of formulas (I) and (II) undergo vinyl addition polymerization using suitable catalysts known in the art. For example, various palladium compounds, platinum compounds, and various nickel compounds have been used to form polymers of the type described herein. In one embodiment of the present invention, the polymers of the present invention are formed using a palladium compound. Various palladium compounds known in the art can be used. Non-limiting examples of such palladium compounds include several platinum compounds, such as:

[0063] Palladium(II) bis(triphenylphosphine) dichloride; Palladium(II) bis(triphenylphosphine) dibromide; Palladium(II) bis(triphenylphosphine) diacetate; Palladium(II) bis(triphenylphosphine)bis(trifluoroacetate); Palladium(II) bis(tricyclohexylphosphine) dichloride; Palladium(II) bis(tricyclohexylphosphine) dibromide; Palladium(II) bis(tricyclohexylphosphine) diacetate (Pd785); Palladium(II) bis(tricyclohexylphosphine)bis(trifluoroacetate); Palladium(II) bis(tri-p-tolylphosphine) dichloride; Palladium(II) bis(tri-p-tolylphosphine) dibromide Palladium(II) bis(tri-p-tolylphosphine) diacetate; Palladium(II) bis(tri-p-tolylphosphine)bis(trifluoroacetate); Palladium(II) ethylhexanoate; Bis(acetonato)palladium(II); Dichlorobis(benzonitrile)palladium(II); n-Butyldi-1-adamantylphosphinepalladium diacetate(H2O)(Pd601); n-Butyldi-tert-butylphosphinepalladium diacetate(H2O)(Pd445); Bis(n-butyl-di-1-adamantylphosphine)palladium acetate(acetonitrile)tetrakis(pentafluorophenyl)borate (Pd1602); (Acetonitrile)bis(triisopropylphosphine)palladium(acetate)tetrakis(pentafluorophenyl)borate (Pd1206); [(allyl)palladium(trinaphthylphosphine)(trifluoroacetate)]; [(allyl)palladium(trinaphthylphosphine)(trifluoromethanesulfonate)]; Platinum(II) chloride; Platinum(II) bromide; and Platinum bis(triphenylphosphine) dichloride.

[0064] It is also well known in the art that such palladium compounds can be further activated using a variety of activator compounds. Non-limiting examples of such activators can be selected from the group consisting of: Lithium tetrafluoroborate; Lithium triflate; Lithium tetrakis(pentafluorophenyl)borate; Lithium tetrakis(pentafluorophenyl)borate etherate (LiFABA); sodium tetrakis(pentafluorophenyl)borate etherate (NaFABA); Trityl tetrakis(pentafluorophenyl)borate etherate (trityl FABA); Tropylium tetrakis(pentafluorophenyl)borate etherate (tropylium FABA); Lithium tetrakis(pentafluorophenyl)borate isopropanolate; Lithium tetraphenylborate; Lithium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate; Lithium tetrakis(2-fluorophenyl)borate; Lithium tetrakis(3-fluorophenyl)borate; Lithium tetrakis(4-fluorophenyl)borate; Lithium tetrakis(3,5-difluorophenyl)borate; Lithium hexafluorophosphate; Lithium hexaphenyl phosphate; Lithium hexakis(pentafluorophenyl)phosphate; Lithium hexafluoroarsenate; Lithium hexaphenylarsenate; Lithium hexakis(pentafluorophenyl)arsenate; Lithium hexakis(3,5-bis(trifluoromethyl)phenyl)arsenate; Lithium hexafluoroantimonate; Lithium hexaphenylantimonate; Lithium hexakis(pentafluorophenyl)antimonate; Lithium hexakis(3,5-bis(trifluoromethyl)phenyl)antimonate; Lithium tetrakis(pentafluorophenyl)aluminate; Lithium tris(nonafluorobiphenyl)fluoroaluminate; Lithium (octyloxy)tris(pentafluorophenyl)aluminate; Lithium tetrakis(3,5-bis(trifluoromethyl)phenyl)aluminate; Lithium methyltris(pentafluorophenyl)aluminate; and Dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA).

[0065] In general, the polymerization is carried out in a suitable solvent at a suitable temperature. For this purpose, any solvent can be used that is capable of dissolving the palladium compound and the monomers used or that is miscible with the liquid monomers. Suitable polymerization solvents include, but are not limited to, alkane and cycloalkane solvents such as pentane, hexane, heptane, decalin, cyclohexane, and methylcyclohexane; halogenated alkane solvents such as dichloromethane, chloroform, carbon tetrachloride, ethyl chloride, 1,1-dichloroethane, 1,2-dichloroethane, 1-chloropropane, 2-chloropropane, 1-chlorobutane, 2-chlorobutane, 1-chloro-2-methylpropane, and 1-chloropentane; ethers such as THF and diethyl ether; aromatic solvents such as benzene, xylene, toluene, mesitylene, chlorobenzene, and o-dichlorobenzene; halocarbon solvents such as Freon™ 112; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, and amyl acetate; and mixtures of any combination thereof.

[0066] Any temperature conditions that will cause such polymerization can be used herein. In one embodiment, the polymer of the present invention is formed by heating a mixture containing suitable amounts of monomers of formula (I) and (II) in the presence of a palladium compound and an activator, as described herein, at a temperature ranging from about 60°C to about 150°C for a sufficient period of time, e.g., about 1 hour to 8 hours. In another embodiment, the polymer of the present invention is formed by heating the catalyst-added monomer mixture at a temperature ranging from about 90°C to about 130°C for a sufficient period of time, e.g., about 1 hour to 4 hours. Alternatively, solution polymerization can be carried out using an anhydrous solvent under an inert atmosphere, e.g., nitrogen, helium, or argon atmosphere.

[0067] Advantageously, vinyl addition polymers can be formed from palladium compounds and monomers of formulas (I) and (II) at very high conversions at low catalyst loadings (e.g., 20,000-25,000:1), where the molecular weight of the polymer is controlled using a chain transfer agent, such as triethylsilane (TES). As described herein, various other chain transfer agents can also be used to control the molecular weight of the resulting polymer, including, for example, bicyclo[4.2.0]oct-7-ene (BCO), formic acid, various other silanes, and the like, including mixtures of any combination thereof. The use of various CTAs in vinyl addition polymerizations to control the properties of the resulting polymer is well known in the art. See, for example, U.S. Pat. No. 9,771,443 B2 and related portions incorporated herein by reference.

[0068] The polymers formed by the present invention generally have a weight average molecular weight (M) of at least about 1,000. w In still other embodiments, the polymers of the present invention have an M of at least about 3,000, 5,000, 10,000, or 20,000. w In yet other embodiments, the polymers of the present invention have an M of at least about 50,000. w In yet other embodiments, the polymers of the present invention have an M of at least about 60,000. w In yet other embodiments, the polymers of the present invention have an M of at least about 70,000. w In yet other embodiments, the polymers of the present invention have an M of at least about 80,000. w In another embodiment, the polymers of the present invention have an M of at least about 100,000. w In yet other embodiments, the polymers of the present invention have an M of 150,000 or greater. w With over 200,000 M w and in some other embodiments, an M of 500,000 or greater. w The weight average molecular weight (M wThe polydispersity index (PDI) of the polymers of the present invention can be determined through known techniques such as gel permeation chromatography (GPC) with a suitable detector and calibration standards, such as a differential refractive index detector calibrated with narrow distribution polystyrene standards or polybutadiene (PBD) standards. The polymers of the present invention generally exhibit a polydispersity index (PDI) of 3 or greater, which is indicative of the weight average molecular weight (M w ) and number average molecular weight (M n ) is the ratio of the PDI to the PDI. Generally, the PDI of the polymers of the present invention ranges from 3 to 5. In one embodiment, the PDI may be 3.5 or greater, 4 or greater, 4.5 or greater, or 5 or greater. However, it should be noted that in one embodiment, the PDI may be lower than 3, for example, 2.5.

[0069] The polymers thus formed can be used to make compositions, as described herein, which can be used to produce composite materials with previously unattainable properties, such as very low coefficients of thermal expansion (CTE). This property can be as low as 100 ppm / K, or less than 90 ppm / K, 80 ppm / K, 50 ppm / K, or even less than 40 ppm / K. The polymers of the present invention exhibit very low dielectric constants and low loss properties. For example, the dielectric constant (Dk) of the polymers of the present invention can be as low as 2.8 or in the range of about 2.2 to about 3.2 at a frequency of 10 GHz. The low loss (Df) of the polymers can be less than 0.0015 or in the range of about 0.001 to 0.002. Furthermore, the polymers of the present invention exhibit very high glass transition temperatures (T g ), which is greater than 250°C, typically in the range of about 250°C to 350°C. More importantly, the polymers of the present invention readily bond with other crosslinkable materials in various compositions made according to the present invention, as described in more detail below. The compositions thus formed typically exhibit excellent peel strengths in the range of 2 to 8 N / cm, making them suitable for use in many applications, such as copper-clad laminates.

[0070] The polymers described herein can be used in the compositions of the present invention in any amount to provide the intended benefits. Generally, such amounts may range from about 20% to about 80% by weight, based on the total weight of the composition. However, it should be noted that in one embodiment, the amount of polymer used can be less than 20% by weight or more than 80% by weight, and all such acceptable combinations are within the scope of the present invention.

[0071] As mentioned above, the composition according to the present invention comprises at least one cross-linking agent, which can be TAIC or TAC. In one embodiment, the composition according to the present invention can comprise a mixture of TAIC and TAC.

[0072] The crosslinking agents TAIC and TAC can be used in the compositions of the present invention in any amount, alone or in combination, to provide the intended benefits. Thus, in one embodiment, the composition contains only TAIC as the crosslinking agent. In another embodiment, the composition contains only TAC as the crosslinking agent. In yet another embodiment, the composition contains a mixture of TAIC and TAC as crosslinkers. Generally, the amount of TAIC or TAC used alone in the compositions of the present invention can range from about 5 to 20 parts per hundred parts of polymer (pphr), 8 to 18 pphr, 10 to 16 pphr, etc. When TAIC and TAC are used in combination in the composition, the amounts of each can be the same or different. The total amount of TAIC and TAC can be about 10 to 30 pphr, 15 to 25 pphr, etc. In other words, it should be noted that such amounts may be higher or lower depending on the intended use of the composition.

[0073] Advantageously, it has been observed that various other crosslinking agents that can provide similar effects to TAIC or TAC can also be used in the compositions of the present invention, including, but not limited to, 1,2,4-trivinylcyclohexane, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, and the like.

[0074] As mentioned above, the composition according to the invention further comprises at least one organophosphate compound of formula (III) or an organophosphate compound of formula (IV) or a phosphazene.

[0075] In one embodiment, the composition of the present invention comprises at least one compound of formula (III), wherein a and b are each independently 0, 1, 2, 3, 4, or 5. Typically, c is 2, but can be 3 or 4. Q is typically a divalent linking group selected from the group consisting of ethylene, propylene, butylene, pentalene, hexalene, 1,2-diaminoethylene, 1,3-diamino-propylene, -OCH2NH-, and -OCH2CH2NH-. One of these methylenes can optionally be replaced with methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, phenyl, biphenyl, naphthyl, furanyl, pyrrolyl, imidazolyl, and pyridinyl. Additionally, R9 and R 10 may be selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, and n-hexyl.

[0076] Non-limiting examples of such monomers of formula (III) may be selected from the group consisting of: [ka] [ka] [ka]

[0077] In one embodiment, the composition of the present invention comprises at least one compound of formula (IV), where R 11 and R 12can be selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, n-hexyl, phenyl, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, tert-butoxy, n-pentyloxy, n-hexyloxy, phenoxy, 6H-phosphanthridine 5-oxide-methyl, 6H-phosphanthridine 5-oxide-ethyl, and 6H-phosphanthridine 5-oxide-propyl.

[0078] Non-limiting examples of such monomers of formula (IV) can be selected from the group consisting of: [ka]

[0079] In yet another embodiment, the composition of the present invention comprises a phosphazene as the organophosphate compound.

[0080] The organophosphate compound can be used in any amount that provides the intended benefits and will vary depending on the end use of the composition. For example, by combining a suitable amount of organophosphate compound with the compositions of the present invention, it is possible to achieve excellent flame retardant properties, e.g., a UL-94 V-0 rating, as well as excellent dielectric properties and storage stability at temperatures ranging from about 80°C to 150°C and up to 85% relative humidity.

[0081] Thus, in one embodiment, the amount of organophosphate compound used in the compositions of the present invention is at least 60 wt. % based on the amount of polymer used in the composition. That is, 60 parts of organophosphate compound per 100 parts of polymer used in the compositions of the present invention, which is referred to herein as 60 parts per hundred parts of resin (pphr). In another embodiment, the amount of organophosphate compound present in the compositions of the present invention ranges from about 60 pphr to about 120 pphr. In still other embodiments, such amounts can vary from about 65 pphr to about 110 pphr, from about 70 pphr to about 100 pphr, from about 80 pphr to about 90 pphr, etc. However, it should be noted that amounts less than 60 pphr or greater than 120 pphr of organophosphate compound can be used in the compositions of the present invention if necessary to produce a suitable device. The amount of organophosphate compound used will also vary depending on the various other components present in the composition that provide the intended benefits, particularly flame retardant properties.

[0082] Surprisingly, it has been found that the use of hexagonal boron nitride (h-BN) in compositions according to the present invention provides such synergistic benefits: the use of h-BN with suitable particle size not only improves the high thermal properties required for various applications, but also improves flame retardant properties, e.g., peel strength when applied to metal substrates such as copper, providing exceptional benefits in various applications where copper-clad laminates are used, e.g., printed circuit boards, mm-wave radar antennas, etc.

[0083] Advantageously, it has been found that the low dielectric properties of films formed from the compositions of the present invention can be improved by incorporating h-BN. That is, the compositions of the present invention generally exhibit a lower dielectric constant (Dk) and a lower dissipation factor (Df) when moderate amounts of h-BN are used in the compositions of the present invention. Generally, the boron nitride used in the compositions of the present invention is in the form of a hexagonal crystal structure. It is well known in the art that h-BN is available in powder form, including flakes, platelets, and other shapes. In one embodiment, the h-BN used in the compositions of the present invention is in platelet form. The exact shape of the platelets is not critical. In this regard, h-BN platelets can have irregular shapes. In this application, the term "platelets" is generally used to describe thin, flat particles, including flakes. However, other forms of h-BN, including fibers, rods, whiskers, sheets, nanosheets, aggregates, or boron nitride nanotubes, may also be used, which may vary by crystal type, shape, or size, and may include distributions of the foregoing. The h-BN particles may have an average aspect ratio (ratio of particle width or diameter to length) of 1:2 to 1:100,000, or 1:5 to 1:1,000, or 1:10 to 1:300. Representative particle shapes with particularly high aspect ratios include plate-like and rod-like particles, fibers, whiskers, and the like. The plate-like particles may have an average aspect ratio (ratio of particle width to length) of 4:5 to 1:300, or 1:2 to 1:300, or 1:2 to 1:200, or 3:5 to 1:100, or 1:25 to 1:100.

[0084] The compositions of the present invention contain hexagonal boron nitride. Other forms of boron nitride may also be used in the compositions of the present invention, including cubic, wurtzite, rhombohedral, or other composite structures. h-BN has a layered structure similar to graphite, with the layers aligned so that the hexagonal rings within the layers coincide. The positions of N and B atoms alternate from layer to layer. h-BN particles can be obtained from a variety of commercial sources. Boron nitride particles can be crystalline or semi-crystalline and can be produced through processes known in the art. For example, these include boron nitride powders produced by the compaction process disclosed in U.S. Patent Nos. 5,898,009 and 6,048,511 and the boron nitride agglomerated powder disclosed in U.S. Patent Publication No. 2005 / 0041373. Various boron nitride powders are commercially available, for example, from St. Gobain.

[0085] Generally, the particle size distribution of h-BN varies considerably, and further reduction in particle size is preferred to form the uniform composition of the present invention. Thus, in one embodiment, the average particle size of the h-BN used is less than 0.05 μm (i.e., less than 50 nm). In another embodiment, the average particle size of the h-BN used is in the range of about 0.05 μm to about 70 μm. In yet another embodiment, the average particle size of the h-BN used is in the range of about 0.1 μm to about 30 μm, 0.1 μm to about 20 μm, or 0.1 μm to about 10 μm, etc.

[0086] h-BN can be used in any desired amount, depending on the intended benefit and the end use of the composition. For example, incorporating an appropriate amount of h-BN into the compositions of the present invention can provide excellent dielectric and low-loss properties, as well as very high thermal properties, including excellent flame retardancy. Furthermore, h-BN not only acts as an insulating material in various electronic applications, but also provides excellent thermal conductivity, allowing heat to dissipate faster than traditional insulating materials. Therefore, the compositions of the present invention are particularly suitable for manufacturing microelectronic devices, such as mm-wave radar antennas, where heat is generated and must be dissipated. Boron nitride has one of the highest thermal conductivity coefficients among semiconductors and electrical insulators (751 W / mK at room temperature), and it is well known in the art that its thermal conductivity increases with fewer interlayer bonds and reduced thickness. By comparison, the thermal conductivity of silica particles is approximately 1.3 W / mK at room temperature. Therefore, depending on the type and amount of h-BN used in the compositions of the present invention, compositions with very high thermal conductivity can be tailored. Thermal conductivity can be measured using a TIM Tester 1300 via methods known in the art, such as the procedures set forth in ASTM D5470-17.

[0087] In one embodiment in which h-BN is used in the compositions of the present invention, the amount of h-BN is at least 10 wt. % based on the amount of polymer used in the composition. In another embodiment, the amount of h-BN present in the compositions of the present invention ranges from about 15 wt. % to about 120 wt. % based on the amount of polymer used. In yet other embodiments, such amounts may vary from about 20 wt. % to about 100 wt. %, from about 30 wt. % to about 80 wt. %, from about 40 wt. % to about 70 wt. %, etc., based on the amount of polymer used in the composition. However, it should be noted that amounts of h-BN less than 10 wt. % or greater than 120 wt. % based on the amount of polymer used can also be used in the compositions of the present invention if needed to produce suitable devices.

[0088] Furthermore, it has been found that when using the organophosphate compounds of formula (IV), it is advantageous to use certain piperidine compounds as synergistic additives to enhance the flame retardant properties. Thus, in one embodiment, a compound selected from the group consisting of: Compounds of formula (V): [ka] In the above formula, d is an integer from 6 to 16; R 13 , R 14 , R 16 , and R 17 are the same or different, and each represents hydrogen, methyl, ethyl, and straight-chain or branched (C3-C 20 ) alkyl; R 15 is hydrogen, hydroxy, methyl, ethyl, straight or branched chain (C3-C 20 ) alkyl, methoxy, ethoxy, straight or branched (C3-C 20 ) alkoxy, and (C3-C 10 ) cycloalkyl; and Compounds of formula (VI): [ka] In the above formula, R 18 , R 19 , R 20 , and R 21 are the same or different, and each represents hydrogen, methyl, ethyl, and straight-chain or branched (C3-C 20 ) alkyl; R 23 is methyl, ethyl, straight chain or branched (C3-C 20 ) alkyl, methoxy, ethoxy, straight or branched (C3-C 20 )alkoxy, (C3-C 10 ) cycloalkyl, substituted or unsubstituted (C3-C 10 ) heterocycle, and substituted urea; R 22 is methyl, ethyl, straight chain or branched (C3-C20 ) alkyl, methoxy, ethoxy, straight or branched (C3-C 20 ) alkoxy, and (C3-C 10 ) cycloalkyl.

[0089] Exemplary compounds of formula (V) include, but are not limited to, the following: [ka] [ka]

[0090] Exemplary compounds of formula (VI) include, but are not limited to, the following: [ka]

[0091] It should be noted that other inorganic and organic fillers can also be used in combination with h-BN. Accordingly, in one embodiment, the film-forming composition according to the present invention includes an inorganic filler. Suitable inorganic fillers have a lower coefficient of thermal expansion (CTE) than the film formed from the composition of the present invention. Non-limiting examples of such inorganic fillers include inorganic oxides such as silicon dioxide (silica), aluminum oxide (alumina), diatomaceous earth, titanium oxide, iron oxide, zinc oxide, magnesium oxide, metal ferrites, germanium oxide, molybdenum oxide, tungsten oxide, zirconium dioxide, and yttrium oxide; inorganic carbides such as silicon carbide, boron carbide, aluminum carbide, and titanium carbide; inorganic nitrides such as aluminum nitride, silicon nitride, titanium nitride, gallium nitride, and boron nitride carbide; silicon borides. inorganic borides such as boron, titanium boride, yttrium boride, and iron boride; inorganic sulfides such as gallium sulfide, molybdenum sulfide, and tungsten disulfide; inorganic hydroxides such as aluminum hydroxide, zinc hydroxide, silicon hydroxide, and magnesium hydroxide; inorganic carbonates such as calcium carbonate (hard and heavy), magnesium carbonate, and dolomite; inorganic phosphides such as aluminum phosphide, calcium phosphide, iron phosphide, nickel phosphide, and iron-nickel phosphide; montmorillonite (SiO2 / Al2O 10 Aluminum silicate (SiO2 / Al2O5), available as kaolinite (Al2Si2O5(OH)4) 10), inorganic silicates such as lithium aluminum silicate, available as Lithafrax from St. Gobain; inorganic molybdates such as zinc molybdate, available from Kemguard; inorganic stannates such as zinc stannate, available from Flamtard; inorganic sulfates such as calcium sulfate, barium sulfate, ammonium sulfate; and calcium sulfite; talc, mica; clay; glass fiber; montmorillonite; silicates such as calcium silicate and bentonite; borates such as zinc borate, barium metaborate, aluminum borate, calcium borate, and sodium borate; carbon black; carbon such as carbon fiber; iron powder; copper powder; aluminum powder; boron fiber; potassium titanate; and lead zirconate. Various inorganic filler materials are commercially available, for example, silica nanoparticles available from Adamatech Co. Ltd. as SC2300-SVJ, and the ceramic filler Lithafrax-2121 available from St. Gobain, among other filler materials suitable for use with the compositions of the present invention.

[0092] In another embodiment, the film-forming composition according to the present invention further comprises an organic filler, typically a powdered synthetic resin or other suitable form or polymer. Examples of such polymeric fillers include, but are not limited to, poly(alpha-methylstyrene), poly(vinyltoluene), copolymers of alpha-methylstyrene and vinyltoluene, and the like. Further examples of such synthetic resin powders include powders of various thermosetting or thermoplastic resins, such as alkyd resins, epoxy resins, silicone resins, phenolic resins, polyesters, acrylic and methacrylic resins, acetal resins, polyethylene, polyethers, polycarbonates, polyamides, polysulfones, polystyrenes, polyvinyl chlorides, fluororesins, polypropylene, ethylene-vinyl acetate copolymers, and copolymer powders of such resins. Other examples of organic fillers include aromatic or aliphatic polyamide fibers, polypropylene fibers, polyester fibers, aramid fibers, and the like.

[0093] In one embodiment, the h-BN is treated with a coupling agent such as a silane, zirconate, titanate, etc. Exemplary silanes include silane compounds having organic functional groups such as alkoxysilyl groups, alkyl groups, epoxy groups, vinyl groups, phenyl groups, and styryl groups within a molecule. Examples of such silane compounds include alkyl silanes such as ethyltriethoxysilane, propyltriethoxysilane, and butyltriethoxysilane (alkylsilanes); phenyl silanes such as phenyltriethoxysilane, benzyltriethoxysilane, and phenethyltriethoxysilane; styryl silanes such as styryltrimethoxysilane, butenyltriethoxysilane, propenyltriethoxysilane, and vinyltrimethoxysilane (vinylsilane); acrylic or methacrylic silanes such as γ-(methacryloxypropyl)trimethoxysilane; amino silanes such as γ-aminopropyltriethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, and N-phenyl-γ-aminopropyltrimethoxysilane; and epoxy silanes such as γ-(3,4-epoxycyclohexyl)ureidotriethoxysilane. Mercapto silanes such as γ-mercaptopropyltrimethoxysilane can also be used. It should also be noted that one or more of the above-mentioned silane compounds can be used in any combination.Other coupling agents include vinyltrichlorosilane, trivinylmethoxysilane, vinyltriethoxysilane, vinyltris(b-methoxyethoxy)silane, b-(3,4-epoxycyclohexyl)ethyltris-methoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropylmethyldiethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma-methacryloxypropylmethyldimethoxysilane, gamma-methacryl-oxypropyltrimethoxysilane, gamma-methacryloxypropylmethyldiethoxysilane, gamma-methacryloxypropyltriethoxysilane, Nb(aminoethyl)gamma-amino These include, but are not limited to, propylmethyldimethoxysilane, Nb(amino-ethyl) g-aminopropyltrimethoxysilane, bis(trimethoxysilylethyl)benzene, bis(triethoxysilyl)-ethylene, triethoxysilyl-modified butadiene, styrylethyltrimethyloxysilane, Nb(aminoethyl) g-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, N-phenyl-g-aminopropyltrimethoxysilane, trimethoxyphenylsilane, perfluorocothyltriethoxysilane, and g-mercaptopropyltrimethoxysilane.

[0094] It should also be noted that h-BN is generally treated with a "non-polar silane compound." This can improve the adhesion between the cyclic olefin polymer used in the composition of the present invention and h-BN. As a result, the mechanical properties of the molded article can be improved. Advantageously, it has been observed that treatment with a "non-polar silane compound" can eliminate or reduce adverse effects on the dielectric properties. In this application, "non-polar silane compound" refers to a silane compound that does not have a polar substituent. A polar substituent is a group that can hydrogen bond or ionically dissociate. Such polar substituents include -OH, -COOH, -COOM, NH3, NR4, and the like. + A -, -CONH2, etc., where M is a cation such as an alkali metal, alkaline earth metal, or quaternary ammonium salt, R is H or an alkyl group having 8 or fewer carbon atoms, and A is an anion such as a halogen atom.

[0095] In one embodiment, the surface of h-BN is modified with vinyl groups. Vinyl groups are advantageously used because they are non-polar substituents, providing much-needed low dielectric properties. For example, any of the specific vinyl silanes listed above can be used to modify the surface of h-BN with vinyl groups.

[0096] As described herein, it has been observed that the coefficient of thermal expansion (CTE) of the compositions of the present invention can be reduced by combining h-BN with various other inorganic fillers. Furthermore, the heat resistance can also be improved. Therefore, the dielectric properties can be improved and the coefficient of thermal expansion can be reduced. In one embodiment, the use of an appropriate amount of h-BN, between about 20 pphr and 80 pphr, can reduce the dielectric constant (Dk) of the composition to 2.4 or less and the loss factor (Df) to less than about 0.002. In another embodiment, the Dk is in the range of between about 2.4 and about 2.7, and the dielectric dissipation factor (Df) is between about 0.0005 and 0.002 at a frequency of 10 GHz.

[0097] As mentioned above, the compositions of the present invention contain a tackifier. Generally, the purpose of the tackifier is not only to enhance the adhesive strength of the composition but also to improve the flexibility of the composition, particularly during manufacturing at temperatures above 130°C, so that the composition has a slight flowability for impregnating glass cloth or fusing with other layers of the device. The compositions of the present invention are generally capable of crosslinking at temperatures above 130°C, and maintaining the composition's flexibility at these temperatures is beneficial. Therefore, any tackifier that provides such benefits can be used in the compositions of the present invention. The amount of tackifier used can also vary depending on the intended application. Typically, such amounts may be about 5-30 parts per hundred parts of polymer (pphr), 8-25 pphr, 10-20 pphr, etc. It should be noted that two or more tackifiers can be used in combination in the compositions of the present invention. In such situations, the combined amounts can be adjusted to provide the intended benefits.

[0098] Non-limiting examples of tackifiers suitable for these compositions include: [ka]

[0099] As noted above, the compositions of the present invention further comprise a free radical generator. Any free radical generator that undergoes a crosslinking reaction with the polymer and other components present in the composition, facilitating adhesion to other suitable substrates, such as copper and / or glass cloth, can be used in the compositions of the present invention. In other words, any desired amount of free radical generator can be used to provide the intended benefits. Such an amount can vary, for example, from about 1 pphr to 6 pphr of free radical initiator.

[0100] Non-limiting examples of free radical generators that can be used in the compositions of the present invention are: [ka]

[0101] As mentioned above, all of the polymers described herein can be used in the compositions of the present invention. Generally, the compositions of the present invention are dissolved in a suitable solvent to form a homogeneous solution. Such suitable solvents can be the same as those listed above for forming the polymers of the present invention. Generally, solvents for forming the compositions of the present invention include, for example, aromatic solvents such as toluene, mesitylene, and xylene; hydrocarbon solvents such as decalin, cyclohexane, and methylcyclohexane; ether solvents such as tetrahydrofuran (THF); ester solvents such as ethyl acetate; and mixtures of any combinations thereof.

[0102] Non-limiting examples of compositions according to the present invention are selected from the group consisting of: Terpolymer of norbornene (NB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), and 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB); dispersion containing a mixture of 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), 1,2-butadiene rubber (B1000), dicumyl peroxide (DCP), and 6,6'-(ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphinine 6-oxide) (DiDOPO); a terpolymer of norbornene (NB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), and 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB); a dispersion containing a mixture of 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), 1,2-butadiene rubber (B1000), a polyaryl ether crosslinker end-capped with methacrylate groups (SA9000), dicumyl peroxide (DCP), and 6,6'-(ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphinine 6-oxide) (DiDOPO); Terpolymer of norbornene (NB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), and 5-(hex-5-en-1-yl)bicyclo[2.2.1]hept-2-ene (HexenylNB); 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), 1,2-butadiene rubber (B1000), ethylene-propylene-ethylidene norbornene terpolymer (T67), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl ester benzenepropanoic acid (Irganox 1076), tris(2,4-ditert-butylphenyl)phosphite (Irgafos 168), a dispersion comprising a mixture of dicumyl peroxide (DCP), and 6,6'-(ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphinine 6-oxide) (DiDOPO); and Terpolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), and 5-(cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyclohexeneNB); 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), 1,2-butadiene rubber (B1000), ethylene-propylene-ethylidene norbornene terpolymer (T67), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl ester benzenepropanoic acid (Irganox 1076), tris(2,4-ditert-butylphenyl)phosphite (Irgafos 168), a dispersion containing a mixture of dicumyl peroxide (DCP), and 6,6′-(ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphinine 6-oxide) (DiDOPO).

[0103] In another embodiment, the composition of the present invention comprises h-BN in combination with an organophosphate compound as described herein. Non-limiting examples of compositions according to the present invention are selected from the group consisting of: Terpolymer of norbornene (NB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), and 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB); dispersion containing a mixture of 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), 1,2-butadiene rubber (B1000), dicumyl peroxide (DCP), 6,6'-(ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphinine 6-oxide) (DiDOPO), and hexagonal boron nitride (h-BN); a terpolymer of norbornene (NB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), and 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB); a dispersion containing a mixture of 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), 1,2-butadiene rubber (B1000), a polyaryl ether crosslinker end-capped with methacrylate groups (SA9000), dicumyl peroxide (DCP), and 6,6'-(ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphinine 6-oxide) (DiDOPO), and hexagonal boron nitride (h-BN); Terpolymer of norbornene (NB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), and 5-(hex-5-en-1-yl)bicyclo[2.2.1]hept-2-ene (HexenylNB); 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), 1,2-butadiene rubber (B1000), ethylene-propylene-ethylidene norbornene terpolymer (T67), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl ester benzenepropanoic acid (Irganox 1076), tris(2,4-ditert-butylphenyl)phosphite (Irgafos 168), a dispersion containing a mixture of dicumyl peroxide (DCP), 6,6′-(ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphinine 6-oxide) (DiDOPO), and hexagonal boron nitride (h-BN); and Terpolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), and 5-(cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyclohexeneNB); 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), 1,2-butadiene rubber (B1000), ethylene-propylene-ethylidene norbornene terpolymer (T67), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl ester benzenepropanoic acid (Irganox 1076), tris(2,4-ditert-butylphenyl)phosphite (Irgafos 168), a dispersion containing a mixture of dicumyl peroxide (DCP), 6,6′-(ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphinine 6-oxide) (DiDOPO), and hexagonal boron nitride (h-BN).

[0104] Generally, compositions according to the present invention comprise polymers comprising one or more separate monomers of formula (I), as described herein, and optionally a minor amount of at least one monomer of formula (II); as described below, various composition embodiments are selected to provide such embodiments with properties appropriate and preferred for the intended use, and thus such embodiments can be customized for various specific applications. Thus, in one embodiment, a composition of the present invention comprises a polymer comprising a preferred amount of a monomer of formula (II), as described above, which may be 4 mole percent or less, along with two or more separate monomers of formula (I), such as, for example, three different monomers of formula (I) or four different monomers of formula (I). Furthermore, as noted in one embodiment, only one or more monomers of formula (I) are used.

[0105] For example, as discussed above, by appropriately combining various monomers of formula (I), it is possible to tailor compositions having, among other properties, particularly desirable low dielectric and thermal-mechanical properties. Additionally, as discussed in more detail below, depending on the intended end use, it may be desirable to include other polymeric or monomeric materials that are compatible in providing desirable low loss and low dielectric properties.

[0106] Even more advantageously, it has been found that the use of at least one monomer of formula (II) surprisingly allows for the formation of crosslinked structures within the polymerization framework, even in small amounts, with a crosslinking agent as described herein. That is, crosslinking can occur intermolecularly (i.e., between two crosslinking sites on different polymer chains) or intramolecularly (i.e., between two crosslinking sites on the same polymer chain). Statistically, this is possible, and all such combinations are part of the present invention. By forming such intermolecular or intramolecular crosslinks, polymers formed from the compositions of the present invention provide previously unobtainable properties. These may include, for example, improved thermal properties, i.e., glass transition temperatures higher than those observed for uncrosslinked polymers of similar composition. Furthermore, such crosslinked polymers are more stable at high temperatures, above 350°C. High temperature stability can also be measured through thermogravimetric analysis (TGA) methods well known in the art. One such measurement is the temperature at which a polymer loses 5% of its weight (T d5 The polymer formed from the composition of the present invention contains d5 Generally, the T of the polymer formed from the composition of the present invention is in the range of about 330°C to about 420°C or more, as will be seen from the specific examples below. d5 The temperature is in the range of about 360°C to about 400°C.

[0107] The compositions of the present invention may further comprise optional additives useful for improving the properties of the compositions and the resulting products produced therefrom. For example, such optional additives may include antioxidants and synergists. Any antioxidant capable of providing the intended benefits may be used in the compositions of the present invention. Non-limiting examples of such antioxidants include pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (BASF's IRGANOX TM 1010), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl ester benzenepropanoic acid (BASF IRGANOX TM1076), and thiodiethylene bis[3-(3,5-di-tert.-butyl-4-hydroxy-phenyl)propionate] (BASF IRGANOX TM 1035). Non-limiting examples of such synergists include certain secondary antioxidants which may provide additional benefits such as preventing autoxidation and degradation of the compositions of the present invention, extending the performance of the primary antioxidant, etc. Examples of such synergists include tris(2,4-ditert-butylphenyl)phosphite, commercially available from BASF as IRGAFOS 168, and various other diamine synergists (e.g., N,N'-di-2-naphthyl-1,4-phenylenediamine). Other synergists which may be suitable as additives in the composition include certain diesters, such as didodecyl 3,3'-thiodipropionate, whose structure is as follows: [ka]

[0108] The compositions of the present invention can be easily formed into films by conventional film casting techniques, including, for example, doctor blading, drum rolling, extrusion, and / or spin coating. Films formed from the compositions of the present invention are also provided. For example, the compositions of the present invention can be doctor bladed onto a suitable substrate, such as a glass plate. The coated plate is then heated to a suitable temperature in an inert atmosphere to remove residual solvent. Such a temperature may range from about 80°C to 150°C or 120°C to 140°C. A suitable inert atmosphere may be nitrogen or argon. Heating at this temperature for a sufficient time will remove all residual solvent. For example, a time period of about 45 minutes to about 75 minutes is required. This initial film formation stage is generally referred to as a B-staged film. Under these conditions, the film is still dissolved in a suitable solvent, such as THF, and is not fully crosslinked. The B-staged film can be heated to a higher temperature in the range of about 150°C to 220°C or 160°C to 190°C in an inert atmosphere for a sufficient time to effect crosslinking of the film. Typically, such heating is carried out for about 90 to 150 minutes to ensure complete crosslinking of the composition, as evidenced by the insolubility of the polymer film.

[0109] Thus, films formed according to the present invention typically exhibit very low dielectric constants, low loss, low coefficients of thermal expansion (CTE), high glass transition temperatures, and more importantly, flame retardant properties. In one embodiment, films formed according to the present invention have a dielectric constant (Dk) of less than 3, less than 2.8, less than 2.6, less than 2.5, less than 2.4, less than 2.3, or less than 2.2 at a frequency of 10 GHz, and a glass transition temperature (T g ) is in the range of about 150°C to 280°C or more. gThe flame retardancy temperature may be greater than 150°C, greater than 200°C, or even greater than 250°C. In yet another embodiment, films according to the present invention exhibit a coefficient of thermal expansion (CTE) in the range of about 80 ppm / K to 120 ppm / K, and when combined with glass cloth, the CTE is less than 50 ppm / K. The compositions of the present invention also exhibit excellent flame retardancy properties. For example, in one embodiment, films formed from the compositions of the present invention exhibit a UL-94 rating of at least V-1.

[0110] In one embodiment, a film formed from a composition of the present invention comprises 6,6'-(ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphinine 6-oxide) (DiDOPO) in an amount greater than 80%, 90%, or greater than 100% by weight of polymer, and has a dielectric constant (Dk) of less than 2.5 at a frequency of 10 GHz, a dielectric dissipation factor (Df) of less than 0.001, and a UL-94 rating of at least V-1. In another embodiment, a film formed by the present invention exhibits a dielectric constant (Dk) in the range of about 2.4 to about 2.5 at a frequency of 10 GHz, a dielectric dissipation factor (Df) of about 0.0004 to 0.002, and a UL-94 rating of at least V-0. In yet another embodiment, a film formed from the composition of the present invention comprises 6,6'-(ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphinine 6-oxide) (DiDOPO) in an amount greater than 100% by weight of polymer, and hexagonal boron nitride in an amount ranging from about 10% to about 75% by weight of polymer, and has a dielectric constant (Dk) of less than 2.7 at a frequency of 10 GHz, a dielectric dissipation factor (Df) of less than 0.0009, and a UL-94 rating of at least V-0.

[0111] Films according to the present invention can be formed from any of the specific embodiments of the compositions listed above. In yet another aspect of the present invention, films formed from the compositions of the present invention are also provided.

[0112] It should also be noted that the crosslinked polymers formed from the compositions of the present invention can form thermosets, which can provide additional advantages in certain applications where thermoplastic resins are not preferred. For example, thermoplastic polymers are not preferred in all applications where the temperatures above are relevant, as such polymeric materials can flow and are not suitable for such high temperature applications. Such applications include millimeter wave radar antennas, as discussed herein, among other applications.

[0113] The composition of the present invention may contain components other than those described above. These components include coupling agents, flame retardants, release agents, antioxidants, etc. Non-limiting examples of coupling agents include silane coupling agents, such as vinyl silanes, acrylic and methacrylic silanes, styryl silanes, and isocyanato silanes. The adhesive strength between the composition of the present invention and a substrate can be improved by using a silane coupling agent.

[0114] As described herein, various other flame retardant materials can also be used in combination with the organophosphate compounds. Non-limiting examples of such flame retardants include various other phosphate-based flame retardants such as trixylenyl phosphate, dixylenyl phosphate, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10 phosphaphenanthrene-10-oxide, halogen-based flame retardants such as brominated epoxy resins, and inorganic flame retardants such as aluminum hydroxide and magnesium hydroxide.

[0115] The compositions of the present invention may further comprise one or more compounds or additives used as adhesion promoters, surface levelers, synergists, plasticizers, cure accelerators, and the like.

[0116] Surprisingly, it has been discovered that the use of one or more thermal free radical initiators described herein can accelerate the crosslinking of polymers formed from the compositions of the present invention to yield crosslinked polymers that exhibit significantly improved thermal properties. For example, the glass transition temperature (T g ) and the temperature at which 5 wt% weight loss occurs (Td5 ) can be increased. g The increase in T can be significant and range from about 10°C to 50°C. In one embodiment, the T of the polymer can be increased by using a suitable amount of thermal free radical initiator. g increases from 20 to 40°C. Similarly, the T d5 The temperature can also be increased by approximately 3°C to 10°C.

[0117] It should be noted that the composition of the present invention can be formed into any shape or form and is not particularly limited to a film. Thus, in one embodiment, the composition of the present invention can be formed into a sheet. The thickness of the sheet is not particularly limited, but when considering application as a dielectric material, the thickness is, for example, 0.01 to 0.5 mm. In another embodiment, the thickness is about 0.02 to 0.2 mm. Sheets formed in this manner generally do not substantially flow at room temperature (25°C). The sheet can be provided on an optional carrier layer or alone. Examples of carrier layers include polyimide films and glass sheets. Any other known peelable film substrate can be used as the carrier layer.

[0118] As described above, the films / sheets formed by the present invention have excellent dielectric properties, which can be customized based on the types of components used in the compositions of the present invention, as described herein. Quantitatively, the relative dielectric constant (Dk) of the film / sheet is approximately 2.4 to 2.7 at frequencies between 10 GHz and 80 GHz. The dielectric loss tangent (Df) at frequencies between 10 GHz and 80 GHz is approximately 0.0004 to 0.0008. As can be seen from these properties, the compositions exhibit excellent dielectric properties even at very high frequencies where the change in Dk / Df is minimal. Therefore, the compositions of the present invention can be applied to various devices requiring such low dielectric materials. Examples include millimeter-wave radar antennas used in automotive applications and dielectric polymer layers used in various other terminal devices used in 5G devices. See, for example, Japanese Patent Application Laid-Open Nos. 2018-109090 and 2003-216823. Antennas generally consist of an insulator and a conductor layer (e.g., copper foil). The compositions or sheets of the present invention can be used as part or all of the insulator. Antennas using the compositions or sheets of the present invention as part or all of the insulator have good high-frequency characteristics and reliability (durability). The use of such materials in printed circuit boards, such as copper-clad laminates, requires high-performance thermosetting resins with high glass transition temperatures, low coefficients of thermal expansion (CTE), low Dk / Df, high peel strength to copper, and excellent reliability during high-temperature storage. The ability to form prepregs (composites with glass cloth), B-stage (producing uncrosslinked or partially crosslinked material layers), and film fusion to create multilayer structures are also important. Most commercially available materials available in this field have not achieved all of these properties, particularly low Dk / Df and high glass transition temperatures.

[0119] The conductor layer of the antenna is formed, for example, from a metal having a suitable electrical conductivity. Circuits are formed on the conductor layer using known circuit processing methods. Conductors forming the conductor layer include various conductive metals such as gold, silver, copper, iron, nickel, aluminum, or alloy metals thereof. Known methods can be used to form the conductor layer. Examples include vapor deposition, electroless plating, and electrolytic plating. Alternatively, a metal foil (e.g., copper foil) can be pressure-bonded by thermocompression bonding. The metal foil constituting the conductor layer is a metal foil generally used for electrical connections. In addition to copper foil, various metal foils such as gold, silver, nickel, and aluminum can be used. Furthermore, alloy foils substantially composed of these metals (e.g., 98% by weight or more) can also be included. Among such metal foils, copper foil is commonly used. The copper foil may be rolled copper foil or electrolytic copper foil.

[0120] Advantageously, the compositions of the present invention fill a gap heretofore unobtainable with prior art materials: as noted above, the compositions of the present invention not only exhibit the much-needed low Dk / Df properties, but also, as noted above, exhibit very high T g and very high T d5 As evidenced by the properties, it provides a very high thermal stability material.

[0121] More importantly, the compositions of the present invention can be formed into films / sheets of suitable thicknesses to form various prepregs for manufacturing copper-clad laminates using glass cloth. In one embodiment, the film thickness of the films formed from the compositions of the present invention may be in the range of about 75 to 150 microns, or 90 to 120 microns, suitable for forming metal-clad laminates. In one embodiment, the thickness may be less than 75 microns or greater than 150 microns.

[0122] It should also be noted that the various dielectric materials used in the applications described herein must withstand very severe temperature conditions and maintain their dielectric properties for extended periods of time. Surprisingly, films formed according to the present invention offer a further advantage by maintaining such low dielectric properties for extended periods of time, up to 1,000 hours or more, even when stored at elevated temperatures of about 125°C or higher. The change in Dk or Df is very low, and can be as low as 3%, or even as low as 1%. Thus, in one embodiment of the present invention, films formed according to the present invention substantially maintain their Dk / Df characteristics for periods of 1,000 hours or more at temperatures ranging from about 120°C to 150°C or higher.

[0123] As described above, the compositions of the present invention are typically used to form films or sheets. Furthermore, in certain applications, the compositions of the present invention can also be used as low-molecular-weight varnish-type materials. The weight-average molecular weight of the polymers used in these applications can be as low as 1,000, 2,000, or 3,000, or even less than 10,000. In these applications, a suitable amount of a suitable solvent can be added to maintain the solids content of the composition during polymerization at about 10 to 70% by weight. Furthermore, solvents suitable for forming such solutions can be used individually or in a mixture, as needed.

[0124] In yet another aspect of the present invention, a kit for forming a film is provided. The kit contains a composition of the present invention. Thus, in one embodiment, the kit contains a polymer as described herein, one or more crosslinking agents as described herein, an appropriate amount of h-BN, a tackifier, a free radical generator as described herein, and one or more optional additives as described herein. In one embodiment, the kit of the present invention includes a polymer having two separate monomers of formula (I) and a monomer of formula (II) in combination with a crosslinking agent, one of the flame retardant compounds of formula (III) or (IV) optionally combined with one or more compounds of formula (V) or (VI), a tackifier as described herein, a free radical generator, and at least one optional additive, respectively, to achieve a desired result and / or intended purpose.

[0125] In yet another aspect of this embodiment of the invention, the kits of the invention form a B-stageable film when exposed to a suitable temperature for a sufficient period of time, i.e., poured onto a surface or substrate that requires encapsulating and exposing the composition of the invention to a suitable heat treatment, such that the composition forms a crosslinked solid material that may be in the form of a film or sheet as described herein.

[0126] Typically, as noted above, such crosslinking is accomplished in stages, first by heating to temperatures below 150°C for a sufficient time, e.g., 5 minutes to 2 hours, at each temperature step to form a partially crosslinked, solvent-free, B-staged film / sheet. The B-staged film can be further heated to temperatures above 150°C, e.g., 190°C or higher, for various periods, e.g., 90 minutes to 150 minutes, to cure the film and form a fully crosslinked polymer network. By practicing the present invention, polymer films can be obtained on such substrates that are substantially uniform films. The film thickness can be as desired, particularly as noted above, typically ranging from 50 to 500 microns or more.

[0127] To ensure the flatness of the sheet and suppress unintended shrinkage during sheet production, various heating methods known in the art for producing sheet materials can be used. For example, it is possible to initially heat the sheet at a relatively low temperature and then gradually increase the temperature. To ensure flatness, the sheet can be heated by applying pressure with a flat plate (metal plate) or the like before heating and / or by applying pressure with a flat plate. The pressure used for such pressing can be, for example, 0.1 to 8 MPa, and in some other embodiments, can be in the range of about 0.3 to 5 MPa.

[0128] In one embodiment, a kit as described herein includes various exemplary compositions described above.

[0129] In yet another aspect of the present invention, there is further provided a method of forming a film for manufacturing various optoelectronic and / or automotive devices, comprising:

[0130] a polymer as described herein; an appropriate amount of one or more flame retardants of formula (III) or (IV); optionally one or more compounds of formula (V) or (VI) 、 forming a homogeneous, transparent composition comprising an appropriate amount of h-BN, if necessary; one or more crosslinking agents, as described herein; a tackifier, as described herein; a free radical initiator, as described herein; and, optionally, one or more additives, including a filler, as described herein; coating or pouring the composition onto a suitable substrate to form a film; and Stepwise heating the film to suitable temperatures to induce the formation of a B-stageable film and a cured film. Coating the desired substrate to form a film from the composition of the present invention can be performed by coating procedures described herein or known to those skilled in the art, such as spin coating. Other suitable coating methods include, but are not limited to, spraying, doctor blade, meniscus coating, inkjet coating, and slot coating. Depending on the type of material to be coated, other coating methods include chemical vapor deposition. The mixture can also be poured onto the substrate to form a film. Suitable substrates include any suitable substrate or substrates for use in electrical, electronic, or optoelectronic devices, such as semiconductor substrates, ceramic substrates, and glass substrates.

[0131] The coated substrate is then baked, i.e., heated to facilitate solvent removal and crosslinking. For example, the substrate is baked at a temperature of 50°C to 150°C for about 1 to 180 minutes, although other suitable temperatures and times may be used. That is, a film is first formed through a B-stage process, which removes any solvent and partially cures it, and then in a subsequent step, the film is fully cured at a higher temperature. In one embodiment, the substrate is baked at a temperature of about 100°C to about 120°C for 120 to 180 minutes. In another embodiment, the substrate is baked at a temperature of about 110°C to about 140°C for 60 to 120 minutes. This is a B-staged film. Finally, the B-staged film thus formed is further heated to a temperature greater than about 150°C to fully cure the film.

[0132] The electrical properties of the films thus formed were evaluated using methods known in the art. For example, the dielectric constant (Dk) or permittivity and dielectric loss tangent at a frequency of 10 GHz were measured using a device for measuring permittivity by the cavity resonator method (manufactured by AET, in accordance with JIS C 2565). The coefficient of thermal expansion (CTE) was measured using a thermal mechanical analyzer (e.g., Seiko Instruments Inc., SS6000 or Mettler Toledo, TMA / STDA 2+STAR system) with a sample size of approximately 4 mm (width) x 40 mm (length) x 0.1 mm (thickness), a measurement temperature range of 30 to 350°C, and a heating rate of 5°C / min. The linear expansion coefficient from 50°C to 100°C was used as the linear expansion coefficient. Generally, films formed according to the present invention exhibit excellent dielectric and thermal properties and can be customized to meet desired dielectric and thermal properties as described herein.

[0133] Thus, in one embodiment of the present invention, there is also provided a film or sheet obtained from the composition as described herein. In yet another embodiment, there is also provided an electronic device comprising the inventive film / sheet as described herein.

[0134] The compositions of the present invention can be formed into various composite structures, which can be used as prepreg materials in the manufacture of metal-clad laminates. Various metals may be used for this purpose, including copper, aluminum, stainless steel, and the like. Metal-clad lamination is well known in the art, where a metal layer is coated with an insulating material, such as the compositions of the present invention. For example, the compositions of the present invention can be impregnated into glass cloth, which can then be heated to a suitable temperature and formed into a prepreg in a B-stage process, as described herein. The prepreg thus formed is sandwiched between layers of copper or other metal foil and cured at temperatures above 150°C to form a copper-clad laminate. It should be noted, further, that various other materials known to those skilled in the art that can be used in place of glass cloth can also be used in the present invention. These commonly used materials are typically in the form of a fabric, including, but not limited to, polyimide fabrics, polybenzimidazole (PBI) fabrics, and the like.

[0135] Laminates formed according to the present invention have been found to exhibit excellent peel strength. That is, the cured films of the present invention bond so strongly to glass and metal surfaces that peeling the films from such substrates is difficult. Even more advantageously, it has been found that the use of optimal levels of free radical initiator can surprisingly increase peel strength. For example, using very low levels of free radical initiator, i.e., less than 0.5 pphr, can result in compositions with unacceptably low peel strengths. On the other hand, using free radical initiators in the range of about 2-3 pphr can provide surprisingly excellent peel strengths. Thus, in one embodiment, the peel strength of composites formed according to the present invention can be from about 5 N / cm to about 8 N / cm, or 9 N / cm, or 11 N / cm, or 13 N / cm, or even higher, depending on the optimal amount of free radical initiator used and the type of composite being produced.

[0136] Thus, in one embodiment, a glass cloth composite film / cloth (i.e., prepreg) formed from a composition of the present invention containing one or more organophosphate compounds of formula (III) or (IV) is provided, which exhibits a dielectric constant (Dk) of less than 2.8, typically in the range of about 2.4 to about 2.5 at a frequency of 10 GHz, a dielectric dissipation factor (Df) of less than 0.002, typically in the range of about 0.001 to 0.0009 at a frequency of 10 GHz and a UL-94 rating of at least V-0, a glass transition temperature greater than 250°C and a temperature at which 5% weight loss occurs greater than 380°C, a coefficient of thermal expansion (CTE) of less than 40 ppm / K, and excellent peel strength. In another embodiment, the glass cloth composite of the present invention exhibits a dielectric constant (Dk) of about 2.4 to about 2.45 and a dielectric dissipation factor (Df) of about 0.0009 at a frequency of 10 GHz.

[0137] In another embodiment, there is provided a glass cloth composite film / cloth (i.e., prepreg) formed from a composition of the present invention comprising one or more organophosphate compounds of formula (III) or (IV) and h-BN, which exhibits a dielectric constant (Dk) in the range of about 2.5 to about 2.7 and a dielectric dissipation factor (Df) of about 0.001 to 0.0008 at a frequency of 10 GHz and a UL-94 rating of at least V-0.

[0138] Advantageously, it has been further observed that the compositions of the present invention can be uniformly coated onto various glass or metal surfaces before being cured, completely covering any voids present on the surface of such materials. The coated surface is then cured at a higher temperature to form a fully cured insulating layer that is firmly bonded to the glass or metal surface. That is, it is possible to provide metal foils coated with the compositions of the present invention to produce, for example, printed wiring boards or metal-clad laminates with excellent adhesion between the insulating layer (i.e., a film formed from the composition of the present invention) and the metal layer, further reducing loss during signal transmission.

[0139] Even more advantageously, it has been found that the compositions of the present invention, when applied to a suitable surface, can still flow and fill voids before the two layers are fully bonded. This is particularly advantageous for producing metal-clad laminates, such as copper-clad laminates, where complete insulation of all voids is essential to minimize loss in signal transmission. Accordingly, one aspect of the present invention provides a method for producing prepregs or metal-clad laminates, which involves coating a suitable glass cloth or metal foil with the composition of the present invention and heating it to a suitable temperature in the range of about 80°C to 120°C to form an uncured film of the composition of the present invention on the glass cloth and / or metal foil. The composite thus formed is then cured at a higher temperature in the range of about 160°C to 180°C to form a fully cured laminate. It should be noted, in particular, that the polymers used in this aspect of the present invention may have very low molecular weights. That is, the weight average molecular weight (M w ) can be as low as 1,000 or in the range of about 1,000 to 5,000. The composition of the present invention exhibits excellent flow characteristics before fully curing, uniformly filling the surface of such glass cloth or metal foil, and provides an excellent insulating layer exhibiting a very low dielectric constant and low loss characteristics, as described herein.

[0140] The following examples provide detailed descriptions of the preparation and use of certain compounds / monomers, polymers, and compositions of the present invention. The detailed preparation processes fall within the scope of and serve to illustrate the more generally described preparation methods described above. Such examples are presented for illustrative purposes only and are not intended to limit the scope of the invention. As used in the examples and throughout the specification, ratios of monomer to catalyst are on a mole-to-mole basis.

[0141] Example (general) The following abbreviations have been used previously and hereinafter in some of the compounds, devices and / or methods used to describe certain embodiments of the present invention: NB···bicyclo[2.2.1]hept-2-ene; HexNB···5-hexylbicyclo[2.2.1]hept-2-ene; CyHexeneNB···5-(cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene; Pd601···palladium diacetate diadamantyl-(n-butyl)phosphine(H2O); Pd1602···[Pd(OAc)(MeCN)(PAd2-n-Bu)2]B(C6F5)4; LiFABA···lithium tetrakis(pentafluorophenyl)borate diethyl etherate; Red P···red phosphorus; DiDOPO···6,6′-(ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphinine 6-oxide); PCO-900···3,9-dimethyl-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane 3,9-dioxide; FCP-796···Mixture of 3,9-dimethyl-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide and substituted 2,2,6,6-tetramethylpiperidine derivatives; SPB-100···Phosphagen; h-BN···Hexagonal boron nitride; TAIC···1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione; DCP···dicumyl peroxide; B1000···1,2-butadiene rubber; T67···Ethylene-propylene-ethylidenenorbornene terpolymer; Irganox-1076···3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl ester benzenepropanoic acid; Irgafos-168···Tris(2,4-ditert-butylphenyl)phosphite; BCO···bicyclo[4.2.0]oct-7-ene; TES···triethylsilane; EA···ethyl acetate; THF···tetrahydrofuran; GPC···Gel Permeation Chromatography; M w ···Weight average molecular weight; M n ···Number average molecular weight; PDI···Polydispersity index; NMR...nuclear magnetic resonance spectroscopy; DSC···Differential scanning calorimetry; TGA...Thermogravimetric analysis; TMA...thermomechanical analysis; pphr··· parts per hundred parts of resin, i.e., polymer according to the present invention and as specifically described below.

[0142] The various monomers used herein are either commercially available or can be readily prepared according to the procedures described in US Pat. No. 9,944,818.

[0143] [Example 1] Terpolymer of NB / HexNB / CyHexeneNB (molar ratio 60 / 20 / 20) A mixture of NB (113 g, 1,200 mmol), HexNB (71.3 g, 400 mmol), CyHexeneNB (69.7 g, 400 mmol), BCO (1.62 g, 15 mmol), and LiFABA (0.26 g, 0.3 mmol) dissolved in anhydrous toluene (972 g) was placed in a suitable reactor flushed with nitrogen. The solution was heated to 80 °C under a nitrogen atmosphere. Pd601 (0.06 g, 0.1 mmol of a 1.3 wt% solution in THF) was added to the solution. The mixture was stirred and heated at 80 °C for 6 hours. Toluene (1,280 g) was then added to the reaction mixture. The diluted polymerization mixture was cooled to room temperature and poured into three portions, approximately 560 g each, into excess isopropanol (approximately 2,500 g each), with rapid stirring to precipitate the polymer. The liquid was filtered and the solid was dried in a vacuum oven at 80-90°C for 20-30 hours to obtain the purified polymer (238g, 94% yield). GPC (THF): Mw =153,470,M n =31,590, PDI=4.9. 13 By C-NMR (CDCl3) analysis, the monomer composition of the terpolymer (NB / HexNB / CyHexeneNB) was calculated to be 60 / 20 / 20.

[0144] [Example 2] Terpolymer of NB / HexNB / CyHexeneNB (molar ratio 60 / 20 / 20) A mixture of NB (113 g, 1,200 mmol), HexNB (71.3 g, 400 mmol), CyHexeneNB (69.7 g, 400 mmol), TES (1.63 g, 14 mmol), anhydrous ethanol (0.21 g, 200 mmol), and LiFABA (0.26 g, 0.3 mmol) dissolved in anhydrous toluene (969 g) was placed in a suitable reactor flushed with nitrogen. The solution was heated to 80°C under a nitrogen atmosphere. Pd601 (0.06 g, 0.1 mmol, 1.3 wt % solution in anhydrous THF) was added to the solution. The mixture was stirred and heated at 80°C for 6 hours. Toluene was added to the reaction mixture as in Example 1. The diluted polymerization mixture was cooled to room temperature and poured into excess isopropanol in three portions, each approximately 560 g, with rapid stirring to precipitate the polymer as specified in Example 1. The liquid was filtered and the solid was dried in a vacuum oven at 80-90°C for 20-30 hours to obtain the purified polymer. w =174,230,M n =57,360, PDI=3. 13 By C-NMR (CDCl3) analysis, the monomer composition of the terpolymer (NB / HexNB / CyHexeneNB) was calculated to be 62 / 20 / 18.

[0145] [Example 3] Terpolymer of NB / HexNB / CyHexeneNB (molar ratio 60 / 20 / 20) A mixture of NB (113 g, 1,200 mmol), HexNB (71.3 g, 400 mmol), CyHexeneNB (69.7 g, 400 mmol), BCO (1.08 g, 10 mmol), and LiFABA (0.26 mmol, 0.3 mmol) dissolved in anhydrous toluene (545 g) was placed in a suitable reactor flushed with nitrogen. The solution was heated to 80 °C under a nitrogen atmosphere. Pd1602 (0.16 g, 0.1 mmol of a 1.3 wt % solution in anhydrous EA) was added to the solution. The mixture was heated to 90 °C and stirring was continued for 6 h. THF (850 g) was added to the reaction mixture. The diluted polymerization mixture was cooled to room temperature and poured into three portions, each approximately 550 g, into excess isopropanol (approximately 2,800 g each), with rapid stirring to precipitate the polymer. The liquid was filtered and the solid was dried in a vacuum oven at 80-90°C for 20-30 hours to obtain the purified polymer (164g, 65% yield). GPC (THF): M w =140,600,M n =44,840, PDI=3.1. 13 By C-NMR (CDCl3) analysis, the monomer composition of the terpolymer (NB / HexNB / CyHexeneNB) was calculated to be 62 / 21 / 17.

[0146] [Example 4] Terpolymer of NB / HexNB / HexenylNB (molar ratio 60 / 20 / 20) Preparation of the preliminary composition The terpolymer of Example 1 (a terpolymer of NB / BuNB / CyHexeneNB in ​​a molar ratio of 60 / 20 / 20) was dissolved in mesitylene to prepare a 15 wt % solution. To a portion of this solution were added B1000 (20 pphr), T67 (15 pphr), TAIC (10 pphr), DCP (0.75 pphr), Irganox-1076 (1.75 pphr), and Irgafos-168 (0.6 pphr).

[0147] [Example 5] Preparation of the preliminary composition The terpolymer of Example 2 (NB / HexNB / CyHexeneNB, 60 / 20 / 20 molar ratio) was dissolved in mesitylene to prepare a 15 wt. % solution. To a portion of this solution, B1000 (20 pphr), T67 (15 pphr), TAIC (10 pphr), DCP (0.5 pphr), Irganox-1076 (1.75 pphr), and Irgafos-168 (0.6 pphr) were added. An additional amount of mesitylene (25 pphr) was added to facilitate dissolution of all components.

[0148] [Example 6] Preparation of the preliminary composition The terpolymer of Example 2 (NB / HexNB / CyHexeneNB, 60 / 20 / 20 molar ratio) was dissolved in decalin to prepare a 15 wt. % solution. To a portion of this solution, B1000 (20 pphr), T67 (15 pphr), TAIC (10 pphr), DCP (2 pphr), Irganox-1076 (1.75 pphr), and Irgafos-168 (0.6 pphr) were added. An additional amount of decalin (50 pphr) was added to facilitate solubility of all components.

[0149] [Example 7] Preparation of the preliminary composition The terpolymer of Example 3 (NB / HexNB / CyHexeneNB, 60 / 20 / 20 molar ratio) was dissolved in decalin to prepare a 15 wt. % solution. To a portion of this solution, B1000 (20 pphr), T67 (15 pphr), TAIC (10 pphr), DCP (2 pphr), Irganox-1076 (1.75 pphr), and Irgafos-168 (0.6 pphr) were added. An additional amount of decalin (50 pphr) was added to facilitate solubility of all components.

[0150] [Examples 8A-8B] Flame retardant composition The preliminary composition of Example 5 was separately mixed with DiDOPO (181 pphr) (Example 8A) and PCO-900 (181 pphr) (Example 8B) to form two compositions of the present invention, Examples 8A and 8B. Both compositions were rolled overnight to ensure good dispersion of the organophosphate compounds. Glass cloth composites of these two compositions were prepared as follows: Glass cloth (NE glass cloth, style #1280, 50 μm thick) composites were prepared by wetting approximately seven layers of rectangular glass cloth with the compositions of Examples 8A and 8B and then heating on a hot plate at 120°C for 1 hour to remove the solvent. The B-staged glass cloth composite laminate was cured in an oven under a nitrogen atmosphere at 190°C for 1 hour to produce a composite with a thickness of approximately 700-800 μm. The flammability of rectangular samples (approximately 13 mm wide and 125 mm long) was tested for flame flammability using a propane weight burner with a blue flame approximately 2 cm long and a cotton pad placed under a flame in an aluminum pan, using a procedure similar to ASTM D3801 (UL-94 flammability test). The aluminum pan was used to catch drips from a burning ampoule. The sample was held vertically and a metal clamp was used to contact one end of the sample with the flame for 10 seconds. After removing the sample from the flame, the afterburn time (the time it took for the burning sample to extinguish) was recorded. The sample was again exposed to the flame (the same end as the first contact) for 10 seconds, and the afterburn time was recorded. Afterglow was observed after the sample self-extinguished, as required by the UL-94 flammability test. However, no such afterglow was observed for the tested compositions. Drips sufficient to ignite the cotton pad and the sample burned violently, causing the flame to spread to the metal clamp. The results of this burn test are summarized in Table 1. By incorporating DiDOPO or PCO-900 into the pre-composition, samples cured under the conditions in which the burn test was conducted were able to achieve a UL-94 V-0 rating. However, PCO-900 did not exhibit good reliability characteristics, as summarized in Table 1. As shown in Examples 12 and 14, the reliability of PCO-900 containing films was poor when stored at 125°C or 85°C / 85% relative humidity.

[0151] [Table 1]

[0152] [Examples 9A to 9C] A portion of the preliminary composition from Example 4 was mixed with hexagonal boron nitride (h-BN, Showa Denko, average particle size 0.7 μm) and DiDOPO and rolled overnight to completely disperse the insoluble particles. The sample preparation and fire testing described in Example 8 was substantially repeated to produce cured glass cloth composite laminates. The results are summarized in Table 2. As can be seen from the data presented in Table 2, the combination of DiDOPO at 85 pphr provided a synergistic effect, with the h-BN providing a UL-94 V-0 rating for the cured samples under the conditions in which the fire tests were conducted.

[0153] [Table 2]

[0154] [Examples 10A to 10B] Portions of the precomposition from Example 6 were mixed with DiDOPO (80 pphr for Example 10A and 100 pphr for Example 10B) and h-BN (35 pphr with an average particle size of 30 μm, manufactured by St. Gobain), and the compositions were further mixed using a Thinky mixer to thoroughly disperse all components of the composition. Glass cloth (NE glass cloth, style #1280, 50 μm thick) composites were prepared by wetting approximately seven layers of rectangular glass cloth with the composition and then heating them in a nitrogen-filled oven at 130°C for 1 hour to remove the solvent. These B-staged glass cloth composite laminates were cured in a vacuum oven at 190°C for 1.5 hours to produce composites approximately 700-800 μm thick. The flammability of rectangular samples (approximately 13 mm wide and 125 mm long) was tested using the procedure described in Example 8. The results of the flammability tests are summarized in Table 3. Combining DiDOPO and h-BN in the composition allowed the cured samples to achieve a UL-94 V-0 rating under the conditions in which the flame test was conducted. When DiDOPO was replaced with the common flame retardant melamine in Comparative Examples 1A and 1B, the glass cloth composites failed to achieve a UL-94 V-0 rating.

[0155] [Table 3]

[0156] [Examples 11A to 11D] Portions of the precomposition from Example 6 were mixed with various amounts of h-BN (Showa Denko, average particle size 0.7 μm) and various amounts of DiDOPO, then rolled overnight to disperse the insoluble particles. Samples of these compositions were applied to glass substrates with a doctor blade and heated on a hot plate at 90°C for 1 hour to remove the solvent. These B-staged film strips were cut into rectangular pieces approximately 2 cm x 10 cm in size. The film strips were sandwiched between seven layers of glass cloth (NE glass cloth, style #1280, 50 μm thick), pressed together at a pressure of approximately 4-6 MPa, and then heated at 200°C for 1 hour. The cured composite laminate was vacuum dried at 190°C for 1.5 hours. The flammability of rectangular samples (approximately 13 mm wide and 125 mm long) was tested using the procedure described in Example 8. The results of these flammability tests are summarized in Table 4A. Combining DiDOPO and h-BN in the composition resulted in cured samples achieving a UL-94 V-0 rating under the conditions under which the burn test was conducted. It is important to note that combining h-BN alone, as in Example 11D, produced a cured sample that burned completely, as summarized in Table 4A. Similarly, B-staged films (without glass cloth) were heated in a vacuum oven at 190°C for 1.5 hours to crosslink the composition and produce a thermoset resin. The Dk and Df at 10 GHz, coefficient of thermal expansion (CTE), and glass transition temperature (T g ) were measured and the results are summarized in Table 4B.

[0157] [Table 4A]

[0158] [Table 4B]

[0159] [Examples 12A to 12B] Film reliability study after storage at 125℃ The precomposition from Example 7 was mixed with h-BN (Showa Denko, average particle size 0.7 μm, 25 pph) and DiDOPO (25 pph) for Example 12A, and with PCO-900 (25 pph) for Example 12B. The two compositions were rolled overnight to disperse insoluble particles. These compositions were then separately spread onto glass plates to wet rectangular glass cloth (NE glass cloth, style #1280, 50 μm thick) samples. The solvent was removed by heating at 130°C for 1 hour in an oven equipped with nitrogen inlet and outlet. These B-staged samples were cured in a vacuum oven at 190°C for 1.5 hours. The dielectric constant (Dk) and dielectric dissipation factor (Df) of the glass cloth composites were measured at 10 GHz. These samples were placed in an oven at 85°C and 85% relative humidity (RH), and the Dk and Df were periodically measured at 10 GHz to confirm the reliability of these low-loss compositions containing DiDOPO or PCO-900 flame retardants during high-temperature, high-humidity storage. Figure 1 shows that the Df of the composite of Example 12A remained constant, demonstrating excellent reliability, while the Df of Example 12B (demonstrating its ability to achieve a UL-94 V-0 rating as reported for Example 8B) increased sharply, resulting in poorer reliability during storage. Furthermore, the Dk at 10 GHz of Example 12A changed from 2.7 (initial) to 2.68 (1,130 hours), a decrease of less than 1%. The Dk at 10 GHz of Example 12B changed from 2.77 (initial) to 3.2 (125 hours), a decrease of approximately 16%. A comparison of the reliability of the glass cloth composites of Examples 12A and 12B suggests that while both DiDOPO and PCO-900 can impart flame retardancy to low-loss films while maintaining low Dk (<3 at 10 GHz) and Df (<0.0015 at 10 GHz), the DiDOPO-containing composition exhibits superior reliability under the storage conditions used. Figure 1 graphically illustrates the superior reliability of the dielectric dissipation factor (Df) of the composition of Example 12A over a period of more than 1,130 hours. Thus, the compositions of the present invention can be used in a variety of applications, such as those described herein, including mm-wave radar antenna layers that require operation under harsh conditions.

[0160] [Examples 13A to 13D] A portion of the precomposition from Example 6 was mixed with DiDOPO (85 pphr) and h-BN (35 pphr, St. Gobain average particle size 30 μm, or SS-nano particle size less than 200 nm) and mixed using a Thinky mixer to disperse the DiDOPO and h-BN and form a uniform composition. Glass cloth (NE glass cloth, style #1280, 50 μm thick) composites were prepared by wetting a rectangular piece of glass cloth with the composition and then heating it in a nitrogen oven at 130°C for 1 hour to remove the solvent. These B-staged glass cloth composites were cured in a vacuum oven at 190°C for 1.5 hours to produce composites with thicknesses of approximately 100–200 μm. The Dk and Df of these glass cloth composites were measured at 10 GHz. The results are summarized in Table 5A. For composites containing DiDOPO, the low Dk and Df values ​​were maintained or slightly decreased. The sample of Example 13B was placed in an oven at 85°C and 85% relative humidity (RH) in air, and after prolonged storage at 125°C in air, Dk and Df were measured at regular time intervals at 10 GHz. The results are shown in Figure 2. Good reliability was obtained after approximately 900 hours of high-temperature storage. Similarly, the B-staged films (without glass cloth) of Examples 13B and 13D were heated in a vacuum oven at 190°C for 1.5 hours to crosslink the composition and produce a thermoset resin. The coefficient of thermal expansion (CTE) and glass transition temperature (T g ) were measured and the results are summarized in Table 5B.

[0161] [Table 5A]

[0162] [Table 5B]

[0163] [Example 14] Copolymer, NB / HexNB (80 / 20, molar ratio; M w= 197,000, PDI = 1.8) (100.3 g) was dissolved in mesitylene (400 g) to prepare a 20 wt% solution. To various aliquots (13 g each) of this solution in vials, various flame retardant materials (DiDOPO (3 μm), DiDOPO (30 μm), red phosphorus, PCO-900, FCP-796, and SPB-100) were added at two concentrations (25 pphr and 100 pphr), as summarized in Table 6. The samples were rolled to mix the ingredients.

[0164] The solution was coated onto a glass substrate, dried overnight at room temperature, heated on a hot plate at 90°C for 2 hours, and then further dried overnight in a vacuum oven at 100°C. The film thickness of each of these samples was approximately 100 μm. The films were then lifted with a razor blade or a drop of water and cut to the appropriate sample size. One 3 x 5 cm film was used for Dk / Df measurement, and three 2 x 4 cm films were used for ion chromatography (IC) measurements. Dk / Df was measured against time 0, and one set of 2 x 4 cm samples was applied to ion chromatography.

[0165] [Table 6]

[0166] The Dk / Df films and remaining IC samples were placed in a temperature / humidity chamber at 85°C and 85% relative humidity (RH) for 1,000 hours. Dk / Df was measured over several hours. One set of 2 x 4 cm samples was removed after 500 hours for IC measurements. The remaining 2 x 4 cm samples were removed for IC measurements at 1,000 hours after the study was concluded. The ratio of Df values ​​to the initial values ​​is shown graphically in Figure 3. As is clearly evident from the data presented in Figure 3, the film samples of Examples 14A (control), 14B (DiDOPO, 3 μm, 25 pphr), 14C (DiDOPO, 30 μm, 25 pphr), 14G (SPB-100, 25 pphr), 14H (DiDOPO, 3 μm, 100 pphr), 14M (SPB-100, 100 pphr), and 14I (DiDOPO, 30 μm, 100 pphr) exhibited very stable D values ​​that increased by less than 150% over time. More specifically, the films of Examples 14A and 14C exhibited an initial increase over the first 48 hours, while the D values ​​of Examples 14B, 14G, 14H, 14M, and 14I remained essentially the same as their initial t=0 values. Examples 14K (PCO-900, 100 pph), 14E (PCO-900, 25 pph), 14F (FCP-796, 25 pph), 14L (FCP-796, 100 pph), and 14D (Red P, 25 pph) all significantly increased Df by over 1,000%. In the case of Red P, 25 pph, and Example 14D, it is known that red phosphorus decomposes in the presence of air and moisture to produce phosphate ions, which in turn increases the Df value. The phosphate (PO4 -3The nitrite concentration (in ppb) further confirmed this, being >700 ppm. For the FCP-796 and PCO-900 samples, Df increased significantly, as shown in Figure 3, but no significant phosphate concentrations were detected. This increase can be attributed to two different explanations. One is that these flame retardants dissolve in water. The increase in Df could be due to a sudden increase in water absorption. Another explanation is that the IC detected a large amount of nitrite ions at over 1,000 ppm. Such ion formation further increases Df. For Red P, 100 pphr, Example 14J, the film was rolled up, preventing Dk / Df measurements. The DiDOPO sample did not increase in phosphate or nitrite concentrations, indicating stability under these conditions. For stable samples, Dk values ​​were in the range of 2.2–2.5. For samples that failed the reliability study (i.e., Df increase >150%) and samples with a rapid increase in Df, such as PCO-900 and Red P, the Dk value increased to 3 or 4.

[0167] [Example 15] The compositions of Examples 14A (control), 14H (DiDOPO, 3 μm, 100 pphr), and 14J (Red P, 100 pphr) were each coated onto copper foil with the textured side facing up and allowed to dry overnight at room temperature. After drying, the foil was heated on a hot plate at 90°C for 2 hours and further dried in a vacuum oven at 100°C overnight. The samples were cut into three pieces. One sample was set aside for time 0 observation (t=0). The remaining two samples were placed in an 85°C / 85% relative humidity (RH) chamber. The samples were removed at 500 hours (t=500) and 1,000 hours (t=1000). Visual observations were recorded as summarized in Table 7. The DiDOPO and control films showed no visible signs of fading or corrosion. The red phosphorus sample, on the other hand, showed catastrophic abnormalities. At the bottom of the film, corrosion was only observed on the copper opposite the film.

[0168] [Table 7]

[0169] [Comparative Examples 1A~1B] Portions of the precomposition from Example 6 were mixed with melamine (80 pphr for Comparative Example 1A and 100 pphr for Comparative Example 1B) and h-BN (St. Gobain, average particle size 30 μm, 35 pphr) using a Thinky mixer to disperse the melamine and h-BN. Glass cloth (NE glass cloth, style #1280, 50 μm thick) composites were prepared by wetting approximately seven plies of rectangular glass cloth with the melamine and h-BN dispersion and then heating in a nitrogen oven at 130°C for 1 hour to remove the solvent. The B-staged glass cloth composite laminate was cured in a vacuum oven at 190°C for 1.5 hours to produce a composite approximately 700-800 μm thick. The flammability of rectangular samples (approximately 13 mm wide and 125 mm long) was tested using the procedure described in Example 8. The results of this flammability test are reported in Table 3. When melamine and h-BN were incorporated into the formulation, the cured samples failed to achieve a UL-94 V-0 rating under the conditions under which the flame test was conducted.

[0170] While the present invention has been described by the foregoing examples, it should not be construed as being limited thereto; rather, the present invention encompasses the general field disclosed above. Various modifications and embodiments can be made without departing from the spirit and scope of the present invention.

Claims

1. a) a polymer of: i) at least one first repeat unit derived from a monomer of formula (I) and represented by formula (IA): 【Chemical 1】 In the above formula: 【Chemistry 2】 represents the position of bonding to other repeating units; m is an integer of 0, 1, or 2; R １ , R ２ , R ３ , and R ４ are the same or different, and each represents hydrogen, methyl, ethyl, straight chain or branched (C ３ -C １６ ) alkyl, (C ３ -C １０ ) cycloalkyl, (C ６ -C １２ ) bicycloalkyl, (C ６ -C １２ ) aryl, and (C ６ -C １２ ) aryl (C １ -C ６ ) alkyl; or R １ and R ２ One of them is R ３ and R ４ and the carbon atom to which they are attached form a substituted or unsubstituted (C ５ -C １４ ) monocyclic ring, (C ５ -C １４ ) a bicyclic ring, or (C ５ -C １４ ) forming a tricyclic ring; and ii) at least one second repeat unit derived from a monomer of formula (II) and represented by formula (IIA): 【Chemistry 3】 In the above formula: 【Chemistry 4】 represents the position of bonding to other repeating units; n is an integer of 0, 1, or 2; R ５ , R ６ , R ７ , and R ８ At least one of is methylidene, ethylidene, vinyl, linear or branched (C ３ -C １６ ) alkenyl, (C ３ -C １０ ) cycloalkenyl, (C ６ -C １２ ) bicycloalkenyl, and (C ６ -C １２ ) aryl (C ２ -C １６ ) alkenyl, and the remaining R ５ , R ６ , R ７ , and R ８ are the same or different, and each is hydrogen, methyl, ethyl, straight chain or branched (C ３ -C １６ ) alkyl, (C ３ -C １０ ) cycloalkyl, (C ６ -C １２ ) bicycloalkyl, (C ６ -C １２ ) aryl, and (C ６ -C １２ ) aryl (C １ -C ６ ) alkyl; or R ５ and R ６ One of them is R ７ and R ８ and the carbon atom to which they are attached, together with at least one double bond. ５ -C １４ ) monocyclic ring, (C ５ -C １４ ) a bicyclic ring, or (C ５ -C １４ ) forming a tricyclic ring; Including, the second repeat unit is present in an amount ranging from about 0 mole % to about 40 mole %, based on the total number of moles of the first and second repeat units; b) a cross-linking agent selected from the group consisting of: 【Chemistry 5】 c) an organophosphate compound selected from the group consisting of: Compounds of formula (III): 【Chemistry 6】 In the above formula: a and b are each independently an integer from 0 to 5; c is an integer from 2 to 4; Q is a divalent or trivalent (C ２ -C ２４ ) alkyl, divalent NH(C ２ -C ６ ) alkylNH, and divalent O(C ２ -C ６ ) alkylNH, wherein the alkyl is optionally methyl, ethyl, straight or branched (C ３ -C ６ ) alkyl, (C ６ -C １２ ) aryl, and (C ５ -C １２ ) heteroaryl; R ９ and R １０ are each independently hydrogen, methyl, ethyl, and straight-chain or branched (C ３ -C ６ ) alkyl; and Compound of formula (IV): 【Chemistry 7】 In the above formula: R １１ and R １２ are each independently methyl, ethyl, straight-chain or branched (C ３ -C ６ ) alkyl, phenyl, methoxy, ethoxy, linear or branched (C ３ -C ６ ) alkoxy, phenoxy, and 6H-phosphanthridine 5-oxide-(C １ -C ３ ) alkyl; d) a tackifier; and e) one or more additives selected from the group consisting of free radical initiators, antioxidants, amino compounds, synergists, and mixtures of any combination thereof; Including, the organophosphate compound is present in an amount greater than 70% by weight based on the amount of polymer; A composition that, when formed into a film, has a UL-94 rating of at least V-1, a dissipation factor (Df) of less than 0.001 at 10 GHz, and a dielectric constant (Dk) of less than 2.5 at 10 GHz.

2. 10. The composition of claim 1, wherein the first repeat unit of the polymer is derived from a monomer of formula (I) selected from the group consisting of: 【Chemistry 8】

3. 10. The composition of claim 1, wherein the second repeat unit of the polymer is derived from a monomer of formula (II) selected from the group consisting of: 【Chemistry 9】

4. The composition of claim 1, wherein the compound of formula (III) is selected from the group consisting of: 【Chemistry 10-1】 【Chemistry 10-2】 【Chemistry 10-3】

5. The composition of claim 1, wherein the compound of formula (IV) is selected from the group consisting of: 【Chemistry 11】

6. 10. The composition of claim 1, further comprising hexagonal boron nitride having a particle size ranging from about 0.05 μm to about 50 μm, wherein the hexagonal boron nitride is plate-like.

7. 10. The composition of claim 1, wherein the hexagonal boron nitride is present in an amount ranging from about 10% to about 120% by weight based on the amount of polymer.

8. 10. The composition of claim 1, further comprising a compound selected from the group consisting of inorganic carbides, inorganic oxides, inorganic nitrides, inorganic sulfides, inorganic hydroxides, inorganic borates, inorganic silicates, inorganic molybdates, inorganic stannates, and inorganic phosphides.

9. Silicon carbide, boron carbide, silicon dioxide, aluminum oxide, aluminum silicate （ SiO ２ / Al ２ O １０ ), lithium aluminum silicate, zirconium dioxide, silicon nitride, aluminum nitride, aluminum hydroxide, titanium nitride, gallium nitride, boron nitride carbide, titanium boride, tungsten disulfide, zinc borate, zinc molybdate, zinc stannate, and mixtures of any combination thereof.

10. 10. The composition of claim 1, wherein the tackifier is selected from the group consisting of: 【Chemistry 12】

11. 10. The composition of claim 1, wherein the free radical generator is selected from the group consisting of: 【Chemistry 13】

12. 10. The composition of claim 1 selected from the group consisting of: a terpolymer of norbornene (NB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), and 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB); a dispersion comprising a mixture of 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), 1,2-butadiene rubber (B1000), dicumyl peroxide (DCP), and 6,6'-(ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphinine 6-oxide) (DiDOPO); a terpolymer of norbornene (NB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), and 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB); a dispersion comprising a mixture of 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), 1,2-butadiene rubber (B1000), a polyaryl ether crosslinker end-capped with methacrylate groups (SA9000), dicumyl peroxide (DCP), and 6,6'-(ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphinine 6-oxide) (DiDOPO); Terpolymer of norbornene (NB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), and 5-(hex-5-en-1-yl)bicyclo[2.2.1]hept-2-ene (HexenylNB); 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), 1,2-butadiene rubber (B1000), ethylene-propylene-ethylidene norbornene terpolymer (T67), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl ester benzenepropanoic acid (Irganox 1076), tris(2,4-ditert-butylphenyl)phosphite (Irgafos 168), dicumyl peroxide (DCP), and 6,6'-(ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphinine 6-oxide) (DiDOPO); and Terpolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), and 5-(cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyclohexeneNB); 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), 1,2-butadiene rubber (B1000), ethylene-propylene-ethylidene norbornene terpolymer (T67), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl ester benzenepropanoic acid (Irganox 1076), tris(2,4-ditert-butylphenyl)phosphite (Irgafos 168), a dispersion containing a mixture of dicumyl peroxide (DCP), and 6,6′-(ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphinine 6-oxide) (DiDOPO).

13. A film formed from the composition of claim 1.

14. 14. The film of claim 13, comprising at least 90% by weight of 6,6'-(ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphinine 6-oxide) (DiDOPO) based on polymer, and having a dielectric constant (Dk) of less than 2.5 at a frequency of 10 GHz, a dielectric dissipation factor (Df) of less than 0.001, and a UL-94 rating of at least V-0.

15. 7. The composition of claim 6, selected from the group consisting of: a terpolymer of norbornene (NB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), and 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB); a dispersion comprising a mixture of 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), 1,2-butadiene rubber (B1000), dicumyl peroxide (DCP), 6,6'-(ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphinine 6-oxide) (DiDOPO), and hexagonal boron nitride (h-BN); a terpolymer of norbornene (NB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), and 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB); a dispersion containing a mixture of 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), 1,2-butadiene rubber (B1000), a polyaryl ether crosslinker end-capped with methacrylate groups (SA9000), dicumyl peroxide (DCP), and 6,6'-(ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphinine 6-oxide) (DiDOPO), and hexagonal boron nitride (h-BN); Terpolymer of norbornene (NB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), and 5-(hex-5-en-1-yl)bicyclo[2.2.1]hept-2-ene (HexenylNB); 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), 1,2-butadiene rubber (B1000), ethylene-propylene-ethylidene norbornene terpolymer (T67), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl ester benzenepropanoic acid (Irganox 1076), tris(2,4-ditert-butylphenyl)phosphite (Irgafos 168), a dispersion comprising a mixture of dicumyl peroxide (DCP), 6,6′-(ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphinine 6-oxide) (DiDOPO), and hexagonal boron nitride (h-BN); and Terpolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), and 5-(cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyclohexeneNB); 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), 1,2-butadiene rubber (B1000), ethylene-propylene-ethylidene norbornene terpolymer (T67), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl ester benzenepropanoic acid (Irganox 1076), tris(2,4-ditert-butylphenyl)phosphite (Irgafos 168), a dispersion containing a mixture of dicumyl peroxide (DCP), 6,6′-(ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphinine 6-oxide) (DiDOPO), and hexagonal boron nitride (h-BN).

16. 16. The film of claim 15, comprising 6,6'-(ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphinine 6-oxide) (DiDOPO) in an amount of 100% or more by weight based on the polymer, and hexagonal boron nitride in an amount ranging from about 10% to about 75% by weight based on the polymer, and having a dielectric constant (Dk) of less than 2.7 at a frequency of 10 GHz, a dielectric dissipation factor (Df) of less than 0.0009, and a UL-94 rating of at least V-0.

17. A glass cloth composite formed from the composition of claim 1.

18. A glass cloth composite formed from the composition of claim 6.

19. 18. The glass cloth composite of claim 17, having a dielectric constant (Dk) in the range of about 2.4 to about 2.5 and a dielectric dissipation factor (Df) of about 0.001 to 0.0009 at a frequency of 10 GHz and a UL-94 rating of at least V-0.

20. 20. The glass cloth composite of claim 18, having a dielectric constant (Dk) in the range of about 2.5 to about 2.7 and a dielectric dissipation factor (Df) of about 0.001 to 0.0008 at a frequency of 10 GHz and a UL-94 rating of at least V-0.

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