h-Boron nitride and polycyclic olefin polymers containing olefin functional groups to form low-loss films with improved dielectric and thermal properties

Abstract

Embodiments of the present invention include compositions comprising polymers formed from various polycycloolefin monomers, including at least one monomer containing additional unpolymerized ethylene bonds, 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 unachievable low dielectric constants, low loss characteristics, and very high thermal properties. The compositions of the present invention can further include one or more organic or inorganic fillers, which provide improved thermal and mechanical properties in addition to very low dielectric properties. The compositions of the present invention are useful in a variety of applications, including as insulating materials for millimeter-wave radar antennas.

Description

[Technical Field]

[0001] Cross-reference to related applications This application claims the benefit of U.S. Provisional Application No. 63 / 404,355, 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 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 polycycloolefin 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 for low-loss thermosets and copper-clad laminate prepregs, which exhibit not only low dielectric constants and low loss characteristics but also very high thermal 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 0.001 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 a high glass transition temperature (T g High-performance thermosets are needed that combine low CTE, low Dk / Df, high peel strength to copper, and excellent high-temperature storage reliability. The ability to form prepregs (composites with glass cloth), B-stage (producing layers of uncrosslinked or partially crosslinked material), and film-fusing capabilities to create multilayer structures are also important. Most commercial materials available in the art do not 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 or 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] Although certain polymers such as fluorinated polyethylene, polyethylene, and polystyrene have low Dk / Df as reported in the literature, all of these polymers exhibit very low glass transition temperatures (which can be much lower than 150°C), making them unsuitable as organic insulating materials. Furthermore, the literature also reports that certain substituted norbornene combinations, typically substituted with polar groups such as ester or alcohol groups, generally exhibit low CTE and T g However, the combination of such groups increases both Dk and Df due to polarizability under electromagnetic fields, especially at high frequencies. Therefore, norbornenes substituted with such polar groups are not suitable for forming insulating materials as intended in this application.

[0008] WO2020 / 072566A1 discloses an embodiment comprising a polymer matrix, a plurality of coated boron nitride particles, and a crosslinker such as 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (also known as triallyl isocyanurate (TAIC)). However, the embodiment reported therein exhibits a high Dk of about 3.5 and a Df of about 0.003.

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

[0010] Additionally, there is a need to develop materials that can form thermosets rather than thermoplastics, 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] Accordingly, it is an object of the present invention to provide polymers comprising two or more substituted norbornene monomers, one of which contains at least one olefinic functionality and hexagonal boron nitride, and to provide compositions derived therefrom which can be formed into insulating materials having heretofore unattainable properties. Other objects and scope of applicability of the present invention will become apparent from the following detailed description. [Means for solving the problem]

[0012] Surprisingly, it has been found that when using compositions comprising polymers having two or more polycyclic olefin monomers of formulas (I) and (II) as described herein, comprising at least 4 mole percent or more of a monomer of formula (II) and 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. 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]

[0013] 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. [Figure 1] FIG. 1 shows a graphical plot of a dielectric reliability study at a storage temperature of 125° C. over a period of 1,000 hours for several exemplary films formed from compositions of the present invention, compared to comparative compositions available in the art as described herein. DETAILED DESCRIPTION OF THE INVENTION

[0014] The terms used in this application have the following meanings:

[0015] In this application, the articles "a," "an," and "the" include plural referents unless otherwise expressly and unambiguously limited to one referent.

[0016] 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."

[0017] 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.

[0018] 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 hydrocarbon group in which all hydrogens have been replaced with halogens.

[0019] 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.

[0020] 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.

[0021] As used herein, the term "perhaloalkyl" refers to an alkyl 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, and the like. Derived expressions such as "perhaloalkoxy" should be construed 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 construed accordingly.

[0022] 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.

[0023] 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.

[0024] 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.

[0025] 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.

[0026] 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.

[0027] 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.

[0028] "Halogen" or "halo" means chlorine, fluorine, bromine, or iodine.

[0029] 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.

[0030] 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.

[0031] It is understood that, herein, the terms "dielectric" and "insulating" are used interchangeably. Thus, a reference to an insulating material or layer includes a dielectric material or layer, and vice versa. Also, 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.

[0032] 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.

[0033] 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.

[0034] 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.

[0035] 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.

[0036] 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]

[0037] 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.

[0038] Thus, in accordance with the practice of the present invention a) a polymer, the polymer comprising: 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) comprising 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, linear 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 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, forms 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 of 10 mole % or more, 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) hexagonal boron nitride having a particle size ranging from about 0.05 μm to about 50 μm; d) containing an adhesive; and e) a composition comprising one or more additives selected from the group consisting of a free radical initiator, an antioxidant, a synergist, and mixtures of any combination thereof.

[0039] 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 on the monomers of formula (II) do not react during the vinyl addition polymerization, and such olefinic functional groups may be used in other applications. 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, such as copper-clad laminates. Even small amounts of the monomer of formula (II) can be incorporated to form polymers according to the present invention, and these polymers have been found to be highly effective in forming crosslinkable compositions of the present invention, as described in more detail below.

[0040] 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).

[0041] 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.

[0042] 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.

[0043] 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).

[0044] 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.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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:

[0050] [ka]

[0051] Similarly, any monomer of formula (II) that is 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 (II) may be selected from the group consisting of:

[0052] [ka]

[0053] 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).

[0054] 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:

[0055] 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.

[0056] 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:

[0057] 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).

[0058] 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.

[0059] Any temperature condition that will result in 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.

[0060] 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.

[0061] 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.

[0062] 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 6-8 N / cm, making them suitable for use in many applications, such as copper-clad laminates.

[0063] 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.

[0064] 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.

[0065] 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. Advantageously, it has been observed that various other crosslinkers 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.

[0066] As mentioned above, the composition of the present invention further comprises hexagonal boron nitride (h-BN). Advantageously, it has been found that the use of h-BN with a suitable particle size not only improves the high thermal properties required for various applications, but also improves peel strength when applied to metal substrates such as copper, providing exceptional benefits in various applications where copper-clad laminates are used, such as printed circuit boards and mm-wave radar antennas.

[0067] 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 can generally exhibit a lower dielectric constant (Dk) and a lower dissipation factor (Df) when an appropriate amount of h-BN is 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, plates, 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, can 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.

[0068] 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 stacked in an aligned fashion, matching the hexagonal rings of the layers. The positions of the N and B atoms alternate from layer to layer. h-BN particles can be obtained from a variety of commercial sources. The 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.

[0069] Generally, the particle size distribution of h-BN varies considerably, and further reduction in particle size is preferred to form the uniform compositions 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 other embodiments, 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; 0.1 μm to about 10 μm, etc.

[0070] 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. Furthermore, h-BN not only serves as an insulating material in various electronic applications, but also provides excellent thermal conductivity, allowing heat to dissipate more quickly than traditional insulating materials. Therefore, the compositions of the present invention are particularly suitable for the manufacture of microelectronic devices (e.g., mm-wave radar antennas) that generate heat and require its dissipation. In general, boron nitride exhibits good thermal conductivity, and certain forms have been shown to have the highest thermal conductivity coefficient (up to 751 W / mK at room temperature) among semiconductors and electrical insulators. Thinner thicknesses result in fewer interlayer bonds, increasing thermal conductivity. 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 according to methods known in the art, such as the procedure set forth in ASTM D5470-17.

[0071] In one embodiment, the amount of h-BN used in the compositions of the present invention is at least 20% by weight 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 25% to about 120% by weight based on the amount of polymer. In still other embodiments, such amounts may vary from about 30% to about 100% by weight, from about 40% to about 80% by weight, from about 50% to about 70% by weight, etc., based on the amount of polymer used in the composition. However, it should be noted that amounts of h-BN less than 20% by weight or greater than 120% by weight based on the amount of polymer used can also be used in the compositions of the present invention if needed to produce suitable devices.

[0072] 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 gallium 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; and carbides such as carbides. inorganic borides such as boron, titanium boride, borohydrium 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 phosphates such as aluminum phosphate, calcium phosphate, iron phosphate, nickel phosphate, and iron-nickel phosphate; montmorillonite (SiO2 / Al2O 10 Aluminum silicate (SiO2 / Al2O5), available as kaolinite (Al2Si2O5(OH)4) 10), inorganic silicates such as lithium aluminum silicate, available from Lithafrax of St. Gobain; inorganic molybdates such as zinc molybdate, available from Chemguard; inorganic stannates such as zinc stannate, available from Fremtado; inorganic sulfates such as calcium sulfate, barium sulfate, ammonium sulfate; and calcium sulfite; talc, mica; clay; glass cloth; 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 are available as SC2300-SVJ from Adamatech Co. Ltd., and the ceramic filler Lithafrax-2121 is available from St. Gobain, among other filler materials suitable for use with the compositions of the present invention.

[0073] 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.

[0074] 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 an alkoxysilyl group and an organic functional group such as an alkyl group, an epoxy group, a vinyl group, a phenyl group, and a styryl group in one 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(β-methoxyethoxy)silane, β-(3,4-epoxycyclohexyl)ethyltris-methoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, N-β(aminoethyl)γ-aminopropyl Examples of suitable silanes include, but are not limited to, propylmethyldimethoxysilane, N-β(amino-ethyl)γ-aminopropyltrimethoxysilane, bis(trimethoxysilylethyl)benzene, bis(triethoxysilyl)-ethylene, triethoxysilyl-modified butadiene, styrylethyltrimethyloxysilane, N-β(aminoethyl)γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, trimethoxyphenylsilane, perfluorooctyltriethoxysilane, and γ-mercaptopropyltrimethoxysilane.

[0075] 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 + 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 of up to 8 carbon atoms, and A is an anion such as a halogen atom.

[0076] 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.

[0077] As described herein, it has been observed that the incorporation of h-BN and various other inorganic fillers can reduce the coefficient of thermal expansion (CTE) of the compositions of the present invention. Furthermore, heat resistance can also be improved. Thus, 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 dielectric loss (Df) to less than about 0.002. In another embodiment, the Dk ranges from about 2.4 to about 2.7, and the dielectric dissipation factor (Df) is between about 0.0005 and 0.002 at a frequency of 10 GHz.

[0078] 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 can generally be crosslinked 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 also 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.

[0079] Non-limiting examples of tackifiers suitable for these compositions include: [ka]

[0080] As mentioned 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, ranging from about 1 pphr to 6 pphr of free radical initiator.

[0081] Non-limiting examples of free radical generators that can be used in the compositions of the present invention are: [ka]

[0082] 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.

[0083] Non-limiting examples of compositions according to the present invention are 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 solution 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 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 solution containing a mixture of 1,3,5-triallyl-1,3,5-trianane-2,4,6-trione (TAIC), 1,2-butadiene rubber (B1000), a polyaryl ether crosslinker end-capped with methacrylate groups (SA9000), and dicumyl peroxide (DCP), and hexagonal boron nitride (h-BN); a 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); a solution containing a mixture of 1,3,5-triallyl-1,3,5-trianane-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 hexagonal boron nitride (h-BN); and A 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); a solution containing a mixture of 1,3,5-triallyl-1,3,5-trianane-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 hexagonal boron nitride (h-BN).

[0084] Generally, compositions according to the present invention comprise polymers comprising one or more separate monomers of formula (I) as described herein and a minor amount of at least one monomer of formula (II). As described below, various composition embodiments can be tailored to a variety of specific applications, as selected to provide properties suitable and preferred for the intended use of such embodiments. 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).

[0085] For example, as already 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. Furthermore, as will be 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.

[0086] Further 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., higher glass transition temperatures than those observed for uncrosslinked polymers of similar composition. Furthermore, such crosslinked polymers are more stable at elevated 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 ranges from about 360°C to about 400°C.

[0087] 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) (IRGANOX® by BASF). 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. For example, didodecyl 3,3'-thiodipropionate has the following structure: [ka]

[0088] Therefore, the compositions of the present invention can be easily formed into films by conventional film casting techniques, such as doctor blade, drum roll, 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 applied to a suitable substrate, such as a glass plate, by doctor blade coating. The coated plate is then heated to a suitable temperature in an inert atmosphere to remove residual solvent. Such temperatures may range from about 80°C to 150°C or 120°C to 140°C. Suitable inert atmospheres include nitrogen and argon. Heating at this temperature for a sufficient time will remove all residual solvent. For example, a time period of about 45 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. B-staged films can be heated to higher temperatures, such as 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.

[0089] The films formed according to the present invention exhibit very low dielectric constants, low loss, low coefficients of thermal expansion (CTE), and high glass transition temperatures. In one embodiment, the 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. g may be greater than 150° C., greater than 200° C., or greater than 250° C. In yet another embodiment, the film according to the present invention exhibits 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.

[0090] In one embodiment, films formed in accordance with the present invention exhibit a dielectric constant (Dk) of less than 2.7 and a dielectric dissipation factor (Df) of less than 0.002 at a frequency of 10 GHz. In another embodiment, films formed in accordance with the present invention exhibit a dielectric constant (Dk) in the range of about 2.4 to about 2.7 and a dielectric dissipation factor (Df) of about 0.0005 to 0.002 at a frequency of 10 GHz.

[0091] 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.

[0092] 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 described herein.

[0093] 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.

[0094] Non-limiting examples of flame retardants include phosphorus-based flame retardants such as triacylenyl phosphate, disylenyl phosphate, and 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10phosphapenanthrene-10-oxide; halogen-based flame retardants such as brominated epoxy resins; and inorganic flame retardants such as aluminum hydroxide and magnesium hydroxide.

[0095] 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.

[0096] 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, resulting in 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 (T d5 ) can be increased. g Such an increase in T can be substantial and may 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 a thermal free radical initiator. g increases from 20 to 40°C. Similarly, the T d5 The temperature may also increase by about 3°C ​​to 10°C.

[0097] 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. Accordingly, 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 considering its application as a dielectric material, it 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 may be provided on an optional carrier layer or alone. Examples of carrier layers include polyimide films and glass sheets. Any other known peelable film substrates can be used as the carrier layer.

[0098] As described above, the films / sheets formed by the present invention have excellent dielectric properties and 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 films / sheets is approximately 2.4 to 2.7 at frequencies between 10 GHz and 80 GHz. The dielectric loss tangent (Df) is approximately 0.0004 to 0.0008 at frequencies between 10 GHz and 80 GHz. As can be seen from these properties, the compositions of the present invention 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, JP 2018-109090 A and JP 2003-216823 A. Antennas are generally composed 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 an insulator. Antennas using the compositions or sheets of the present invention as part or all of an 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 Cu, 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.

[0099] 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 metals with conductivity, 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.

[0100] Advantageously, the compositions of the present invention fill a gap not previously available with prior art materials: as previously noted above, the compositions of the present invention not only exhibit the much-needed low Dk / Df properties, but also, as previously noted, exhibit very high T g and very high T d5 As evidenced by the properties, it provides a very high thermal stability material.

[0101] More importantly, the compositions of the present invention can be formed into films / sheets of thicknesses suitable for forming various prepregs using glass cloth to produce copper-clad laminates. 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.

[0102] 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 1,000 hours or more at temperatures ranging from about 120°C to 150°C or higher.

[0103] 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.

[0104] In yet another aspect of the present invention, a kit for forming a film is provided. The kit includes a composition of the present invention. Thus, in one embodiment, the kit includes 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) each in combination with at least one of a crosslinking agent, h-BN, a tackifier, a free radical generator, and an optional additive to achieve a desired result and / or objective.

[0105] 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.

[0106] Typically, as noted above, these crosslinking steps are performed by first heating the film 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.

[0107] To ensure the flatness of the sheet and prevent unintended shrinkage during sheet production, various heating methods known 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, etc., there is a method of heating the sheet while pressing it with a flat plate (metal plate) or the like before heating, and / or a method of heating it while pressing it with a flat plate. The pressure used for such pressing may be, for example, 0.1 to 8 MPa, and in some other embodiments, may be in the range of about 0.3 to 5 MPa.

[0108] In one embodiment, the kits described herein include various exemplary compositions described above.

[0109] 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: forming a homogeneous, transparent composition comprising a polymer as described herein; a suitable amount of hBN; 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 a suitable temperature so that a B-stageable film and a cured film are formed.

[0110] Coating the desired substrate from the composition of the present invention to form a film can be accomplished 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 blading, meniscus coating, inkjet coating, and slot coating. The mixture can also be poured onto the substrate to form a film. Suitable substrates include suitable substrates that can be used as is or in electrical, electronic, or optoelectronic devices, such as semiconductor substrates, ceramic substrates, and glass substrates.

[0111] The coated substrate is then baked. That is, it is heated to facilitate solvent removal and crosslinking, for example, at a temperature of 50°C to 150°C for about 1 to 180 minutes, although other suitable temperatures and times can be used. That is, a film is first formed through a B-stage process, which removes any existing solvent and partially cures it, and then in a subsequent step, it 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 at a temperature greater than about 150°C to fully cure the film.

[0112] 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 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 thermomechanical analyzer (Seiko Instruments Inc., SS6000) with a sample size of approximately 4 mm (width) x 40 mm (length) x 0.1 mm (thickness), a 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.

[0113] 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.

[0114] 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, and stainless steel. 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 B-staged to form a prepreg, as described herein. The prepreg thus formed can then be sandwiched between layers of copper or other metal foil and cured at temperatures above 150°C to form a copper-clad laminate.

[0115] 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. A further advantage has been surprisingly found to be that peel strength can be increased by using an optimal level of free radical initiator. 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.

[0116] Thus, in one embodiment, a glass cloth composite film / fabric (i.e., prepreg) formed from the polymer of the present invention is provided, which exhibits a dielectric constant (Dk) of less than 2.8 at a frequency of 10 GHz, a dielectric dissipation factor (Df) of less than 0.002, a glass transition temperature greater than 250°C, 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) in the range of about 2.6 to about 2.75 and a dielectric dissipation factor (Df) of about 0.001 to 0.0016 at a frequency of 10 GHz.

[0117] 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 can then be cured at a higher temperature to form a fully cured insulating layer that firmly bonds 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.

[0118] 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.

[0119] The following examples provide detailed descriptions of the preparation and use of specific 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, the ratio of monomer to catalyst is on a mole-to-mole basis.

[0120] 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.

[0121] NB···bicyclo[2.2.1]hept-2-ene; HexNB···5-hexylbicyclo[2.2.1]hept-2-ene; BuNB···5-butylbicyclo[2.2.1]hept-2-ene; CyHexeneNB···5-(cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene; HexenylNB···5-(hex-5-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; h-BN···Hexagonal boron nitride; TAIC···1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione; TAC···2,4,6-tris(allyloxy)-1,3,5-triazine; DCP···dicumyl peroxide; B1000···1,2-butadiene rubber; T67···Ethylene-propylene-ethylidenenorbornene terpolymer; SC2300-SVJ···Silica nanoparticles; 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; MCH···methylcyclohexane; 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, as specifically described below.

[0122] 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.

[0123] [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 heated at 80 °C with stirring 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 of 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): M w =153,450, M n =31,600, 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.

[0124] [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), BCO (3.24 g, 30 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 stirred and heated at 80 °C 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, approximately 560 g each, into excess methanol (approximately 2,700 g each), and the polymer was precipitated with rapid stirring. 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 (231 g, 91% yield). GPC (THF): M w =166,600, M n =34,000, PDI=4.8). 13 By C-NMR (CDCl3) analysis, the monomer composition of the terpolymer (NB / HexNB / CyHexeneNB) was calculated to be 64 / 19 / 17.

[0125] [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 (974 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 stirred and heated at 80 °C for 6 hours. THF (427 g) was 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 2,850 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 (231 g, 91% yield). GPC (THF): M w =92,500, M n =27,300, PDI=3.4). 13 By C-NMR (CDCl3) analysis, the monomer composition of the terpolymer (NB / HexNB / CyHexeneNB) was calculated to be 63 / 19 / 18.

[0126] [Example 4] Terpolymer of NB / HexNB / HexenylNB (molar ratio 60 / 20 / 20) A mixture of NB (113 g, 1,200 mmol), HexNB (71.3 g, 400 mmol), HexenylNB (70.5 g, 400 mmol), BCO (1.62 g, 15 mmol), and LiFABA (0.26 g, 0.30 mmol) dissolved in anhydrous toluene (976 g) was placed in a glass reactor and 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 heated at 80 °C with stirring for 6 h. 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 of approximately 570 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 a purified polymer. 13 By C-NMR (CDCl3) analysis, the monomer composition of the terpolymer (NB / HexNB / HexenylNB) was calculated to be 60 / 20 / 20.

[0127] [Example 5] 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 (2.05 g, 17.6 mmol), ethanol (9.2 g, 200 mmol), and LiFABA (0.26 g, 0.3 mmol) dissolved in anhydrous toluene (972 g) was placed in a glass reactor and 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 h. To the reaction mixture was then added toluene (1,280 g). The diluted polymerization mixture was cooled to room temperature and poured into three portions of approximately 570 g each into excess isopropanol (approximately 1,400 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. GPC (THF):M w =146,150,M n =58,750, PDI=2.5). 13 By C-NMR (CDCl3) analysis, the monomer composition of the terpolymer (NB / HexNB / CyHexeneNB) was calculated to be 63 / 19 / 18.

[0128] Example 5A Terpolymer of NB / HexNB / CyHexeneNB (molar ratio 60 / 20 / 20) The title terpolymer was prepared essentially according to the procedure specified in Example 5. GPC (THF):M w =174,250,M n =57,350, PDI=3. 13 By C-NMR (CDCl3) analysis, the monomer composition of the terpolymer (NB / HexNB / CyHexeneNB) was calculated to be 62 / 20 / 18.

[0129] [Example 6] Evaluation of h-BN with various particle sizes The terpolymer of Example 1 (NB / HexNB / CyHexeneNB, molar ratio 60 / 20 / 20) was dissolved in decalin to prepare a 20 wt. % solution. To one portion of this solution, B1000 (20 pphr), T67 (15 pphr), TAIC (10 pphr), DCP (0.75 pphr), Irganox-1076 (1.75 pphr), and Irgafos-168 (0.60 pphr) were added. The composition was rolled overnight to thoroughly mix. Various portions of this composition were mixed with h-BN of various particle sizes, as shown in Table 1, using a high-speed mixer to achieve a good dispersion. Each of these compositions was doctor-bladed onto a glass substrate to remove the solvent and heated to 130°C for 1 hour in an oven under nitrogen. These B-staged films were cured at 190°C for 1.5 hours under vacuum to yield films with thicknesses ranging from approximately 75 to 140 μm, as shown in Table 1. The dielectric constant (Dk) and dielectric dissipation factor (Df) at 10 GHz were measured for each cured film. Table 1 summarizes the Dk and Df for each film obtained in Example 6 and compares them with Comparative Example 1, which lacked h-BN. As is evident from the data summarized in Table 1, platelet-shaped h-BN with a particle size distribution ranging from less than 100 nm to 33 μm produced excellent quality films with film thicknesses (FT) ranging from 75 to 125 μm. The data also reveal that the dielectric constant (Dk) remained below 2.7, while the dielectric dissipation factor (Df) decreased slightly with the addition of various amounts of h-BN (25 pphr to 75 pphr) and various particle size distributions of h-BN (0.7 μm to 30 μm). It is also noteworthy that the Dk values ​​remained relatively constant regardless of the h-BN loading level, and increased slightly with increasing h-BN loading levels. However, agglomerated h-BN and h-BN with a particle size distribution of 33 μm produced films with rough quality. Most importantly, it should be noted that both Dk and Df are much lower than those reported in the literature for compositions containing h-BN.

[0130] [Table 1]

[0131] [Example 7] Evaluation of low-loss film characteristics at various frequencies The terpolymer of Example 2 (NB / HexNB / CyHexeneNB, molar ratio 60 / 20 / 20) was dissolved in decalin to prepare a 20 wt. % solution. To a portion of this solution, B1000 (20 pphr), T67 (15 pphr), TAIC (10 pphr), DCP (0.75 pphr), Irganox-1076 (1.75 pphr), and Irgafos-168 (0.60 pphr) were added. The composition was mixed by rolling overnight. To a portion of this composition, 50 pphr, 30 μm of St. Gobain h-BN was added and mixed using a high-speed mixer to achieve a good dispersion. The composition was doctor-bladed onto a glass substrate and heated to 130°C in an oven under nitrogen for 1 hour to remove the solvent. The B-staged film was cured under vacuum at 190°C for 1.5 hours to yield a film thickness of approximately 93 μm. The dielectric constant (Dk) and dielectric dissipation factor (Df) of the cured films were measured at 10 GHz, 35 GHz, and 80 GHz. The results are summarized in Table 2, along with the Dk and Df of the film formed from the composition of Comparative Example 2. As can be clearly seen from the data presented in Table 2, the Df of the film of Example 7 is lower than that observed for the film of Comparative Example 2, which does not contain h-BN filler. It should also be noted that Df varies significantly depending on the frequency at which the measurements are made. That is, not only does the film of Example 7, which contains h-BN, exhibit a lower Df than the film of Comparative Example 2, which does not contain h-BN, but the difference increases as the measurement frequency increases, for example, from 10 GHz to 35 GHz. When the ceramic filler Lithafrax 2121 (50 pphr, Comparative Example 6) was used, Df significantly increased to 0.0024 at 10 GHz. Similarly, when silica (71 pphr, Comparative Example 7) was used, Df also increased to 0.0009 at 10 GHz.

[0132] [Table 2]

[0133] [Example 8] Evaluation of low loss and thermal properties of glass cloth impregnated films The terpolymer of Example 5A (NB / HexNB / CyHexeneNB, molar ratio 60 / 20 / 20) was dissolved in decalin to prepare a 15 wt. % solution. To one 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. The composition was mixed by rolling overnight. h-BN with an average particle size of 0.7 μm, manufactured by Showa Denko, was added to three separate portions of this composition in different amounts as summarized in Table 3, and then the mixture was thoroughly dispersed using a high-speed mixer. Low Df glass cloth (NE glass cloth, style #1280, 50 μm) was thoroughly wetted with these compositions to impregnate the glass cloth with the low-loss compositions. The treated glass cloth was heated to 130°C for 1 hour in an oven under nitrogen to remove the solvent. These B-staged prepregs were cured under vacuum at 190°C for 1.5 hours to yield glass cloth composites with thicknesses of approximately 140 μm (Example 8A), 155 μm (Example 8B), and 170 μm (Example 8C). The Dk and Df of the composites were measured at 10 GHz. Table 3 summarizes the Dk and Df of the composites. For comparison, the Dk and Df obtained for the film of Comparative Example 3 are also shown in Table 3. The glass transition temperatures (T g The thermal expansion coefficient (CTE) was measured by DMA and the decomposition temperature (T d5) were measured by TGA. As is evident from the data presented in Table 3, the Dk and Df of the compositions containing h-BN are lower than the composition of Comparative Example 3, which does not contain h-BN. Superior properties were observed for the composites produced in accordance with the present invention, which are suitable for producing copper clad laminates for printed circuit boards that can be used in a variety of applications, including, for example, low Dk and Df, high T useful for high temperature processing, and the like. g and the high decomposition temperature (T d5 ) and other devices such as mm-wave radar antennas that require low loss characteristics.

[0134] [Table 3]

[0135] [Example 9] Evaluation of low loss and thermal properties of films The terpolymer of Example 2 (NB / HexNB / CyHexeneNB, 60 / 20 / 20 molar ratio) was dissolved in mesitylene to form a 15 wt. % solution. To this solution were added B1000 (20 pphr), T67 (15 pphr), TAC (20 pphr), DCP (0.87 pphr), h-BN (25 pphr, 30 μm platelets from St. Gobain), Irganox-1076 (1.75 pphr), and Irgafos-168 (0.50 pphr). An additional amount of mesitylene (50 pphr) was added to facilitate solubility of all components. The composition was mixed by rolling overnight. Low Df glass cloth (NE glass cloth, style #1280, 50 μm) was thoroughly wetted with the composition, and the glass cloth was impregnated with the low-loss composition. The treated glass cloth was heated to 130°C in an oven under nitrogen for 1 hour to remove the solvent. The B-staged prepreg was cured in vacuum at 190°C for 1.5 hours to yield a composite approximately 100 μm thick. The Dk and Df of the composite were measured at 10 GHz. The glass transition temperature (T gThe thermal expansion coefficient (CTE) was measured by DMA and the decomposition temperature (T d5 ) were measured by TGA. Table 4 summarizes the results, including those obtained for the composite in Comparative Example 4. The data presented in Table 4 demonstrate that the glass cloth produced in accordance with the present invention has low Dk and Df, and high T useful for high temperature processing. g and the high decomposition temperatures (T d5 This further demonstrates that the copper clad laminate exhibits excellent properties suitable for manufacturing copper clad laminates for use in printed circuit boards used in devices such as mm-Wave radar antennas, which require low loss characteristics such as:

[0136] Example 10 The terpolymer (NB / HexNB / CyHexeneNB, molar ratio 60 / 20 / 20) from Example 2 was dissolved in mesitylene to form a 15 wt % solution. To this solution were added B1000 (20 pphr), T67 (15 pphr), TAIC (10 pphr), DCP (0.6 pphr), h-BN (25 pphr from St. Gobain, 30 μm platelets), Irganox-1076 (1.75 pphr), and Irgafos-168 (0.60 pphr). To facilitate solubility of all components in the composition, an additional amount of decalin (50 pphr) was also added to form a homogeneous solution. The composition was mixed by rolling overnight. Two layers of low Df glass cloth (NE glass cloth, style #1280, 50 μm) were thoroughly wetted with this composition to form a low-loss composition impregnated into the glass cloth. The treated glass cloth was heated to 130°C for 1 hour in an oven under nitrogen to remove the solvent. The B-staged prepreg was cured in a vacuum at 190°C for 1.5 hours to yield a glass cloth composite approximately 240 μm thick. The Dk and Df of the composite were measured at 10 GHz. The glass transition temperature (T g The thermal expansion coefficient (CTE) was measured by DMA and the decomposition temperature (T d5) were measured by TGA. Table 4 summarizes the results, including similar results obtained for the composite formed in Comparative Example 5. Composites produced according to the present invention exhibit low Dk and Df, high T useful for high temperature processing. g and the high decomposition temperature (T d5 It is again clear that the excellent properties obtained make the laminate suitable for forming copper clad laminates for use in printed circuit boards used in devices such as mm-Wave radar antennas which require low loss characteristics such as

[0137] [Table 4]

[0138] [Example 11] Study on film reliability after storage at 125℃ The cured films obtained in Example 6B (Example 11A), Example 10 (Example 11B), and Comparative Example 5 (Example 11C) were stored in an oven at 125°C in air, and their Dk and Df were measured periodically for up to 1,080 hours to confirm the reliability of such low-loss films containing h-BN during high-temperature storage. The Dk of the film of Example 11A changed slightly from 2.56 to 2.53 over 1,080 hours, while that of Example 11B changed from 2.54 to 2.50 over 1,008 hours, and that of Example 11c changed from 2.56 to 2.60 over 1,008 hours. The change in Dk was less than 2%, indicating excellent reliability of the dielectric constant during storage at 125°C in air. Figure 1 graphically illustrates the excellent reliability of the dielectric dissipation factor (Df) of these compositions over a period of more than 1,000 hours. Although both films showed minor variations that could be attributed to changes in Df measurements, the excellent stability of the dielectric properties was again evident. Therefore, the compositions of the present invention can be used in a variety of applications, such as mm-wave radar antenna layers that require operation under harsh conditions, as described herein. The cured film of Example 11C (Comparative Example 5) also exhibited good reliability, but had an even higher dielectric dissipation factor (Df).

[0139] [Example 12] Comparison of crosslinking ability A 20 wt% solution of NB / HexNB / CyclohexeneNB (feed ratio 70 / 10 / 20) prepared using a procedure similar to Examples 1-5 was dissolved in xylene. DCP (4 pphr) was added to this solution to prepare the composition of Example 12A. T67 (15 pphr), TAIC (10 pphr), DCP (3 pphr), Irganox-1076 (1.75 pphr), and Irgafos-168 (0.75 pphr) were added to the polymer solution to prepare the composition of Example 12B. Similarly, norbornene / ethylene copolymer (TOPAS) was dissolved in xylene to prepare the composition of Comparative Example 8A (4 pphr DCP), and Comparative Example 8B, as in Example 12B, contained T67 (15 pphr), TAIC (10 pphr), DCP (3 pphr), Irganox-1076 (1.75 pphr), and Irgafos-168 (0.75 pphr). Hexagonal boron nitride (h-BN) from Showa Denko with a particle size of 0.7 μm was dispersed in these solutions at a loading of 50 pphr. These compositions were applied to glass substrates with a doctor blade and heated to 130°C in an oven under nitrogen for 1 hour to remove the solvent. These B-staged films were cured at 200°C for 1 hour under nitrogen to yield films with a thickness of approximately 150 μm. The glass transition temperatures of some films were measured by TMA in compression mode. Approximately 0.25-0.35 g of these films were mixed with THF (approximately 6-7 g) and sonicated at 30°C for 1 hour. The dissolved portion was removed, and the films were dried at 150°C for 1 hour. The percentage of the dissolved film was calculated from the initial and final weights of the films and is summarized in Table 5. Because the h-BN additive is insoluble, the initial and final weights of the films were corrected for the presence of h-BN. The results in Table 5 demonstrate that the compositions prepared in this invention are more suitable for applications requiring resins that can be formed into thermosets with higher glass transition temperatures than NB / ethylene copolymers, which cannot form thermosets via a free-radical initiation process.

[0140] [Table 5]

[0141] [Comparative Example 1] The terpolymer of Example 2 (NB / HexNB / CyHexeneNB, molar ratio 60 / 20 / 20) was dissolved in decalin to prepare a 20 wt. % solution. To a portion of this solution, B1000 (20 pphr), T67 (15 pphr), TAIC (10 pphr), DCP (0.75 pphr), Irganox-1076 (1.75 pphr), and Irgafos-168 (0.60 pphr) were added. The composition was mixed by rolling overnight. The composition was applied to a glass substrate with a doctor blade and heated to 130°C in an oven under nitrogen for 1 hour to remove the solvent. The B-staged film was cured under vacuum at 190°C for 1.5 hours to yield a film with a thickness of 90 μm. The dielectric constant (Dk) and dielectric dissipation factor (Df) of the cured film were measured at 10 GHz and are listed in Table 1.

[0142] Comparative Example 2 The terpolymer of Example 2 (NB / HexNB / CyHexeneNB, molar ratio 60 / 20 / 20) was dissolved in decalin to prepare a 20 wt. % solution. To a portion of this solution, B1000 (20 pphr), T67 (15 pphr), TAIC (10 pphr), DCP (0.75 pphr), Irganox-1076 (1.75 pphr), and Irgafos-168 (0.60 pphr) were added. The composition was mixed by rolling overnight. The composition was applied to a glass substrate with a doctor blade and heated to 130°C in an oven under nitrogen for 1 hour to remove the solvent. The B-staged film was cured under vacuum at 190°C for 1.5 hours to yield a film thickness of approximately 83 μm. The dielectric constant (Dk) and dielectric dissipation factor (Df) of the cured film were measured at 10 GHz and 35 GHz and are listed in Table 2.

[0143] Comparative Example 3 The terpolymer of Example 5A (NB / HexNB / CyHexeneNB, molar ratio 60 / 20 / 20) 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 (2.0 pphr), Irganox-1076 (1.75 pphr), and Irgafos-168 (0.60 pphr) were added. To facilitate the solubility of all components, an additional amount of decalin (50 pphr) was added to form a homogeneous solution. The composition was mixed overnight by rolling. A low Df glass cloth (NE glass cloth, style #1280, 50 μm) was completely wetted with the composition to obtain a composite impregnated with the glass cloth. The treated glass cloth was heated to 130°C in an oven under a nitrogen atmosphere for 1 hour to remove the solvent. The B-staged prepreg was cured under vacuum at 190°C for 1.5 hours to yield a 90 μm thick composite. The Dk and Df of the composite were measured at 10 GHz. Table 3 summarizes the Dk and Df of the composite obtained in Comparative Example 3 and compares them with the composite of Example 8.

[0144] Comparative Example 4 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), TAC (20 pphr), DCP (0.87 pphr), Irganox-1076 (1.75 pphr), and Irgafos-168 (0.50 pphr) were added. An additional amount of mesitylene (50 pphr) was added to facilitate solubility of all components. The composition was mixed by rolling overnight. A layer of low Df glass cloth (NE glass cloth, style #1280, 50 μm) was thoroughly wetted with the composition, impregnating the glass cloth with the low-loss composition. The treated glass cloth was heated to 130°C in an oven under nitrogen for 1 hour to remove the solvent. The B-staged prepreg was cured at 190°C for 1.5 hours under vacuum to yield a composite approximately 100 μm thick. The Dk and Df of the composite were measured at 10 GHz. The glass transition temperature (T gThe thermal expansion coefficient (CTE) was measured by DMA and the decomposition temperature (T d5 ) was measured by TGA. The results are summarized in Table 4.

[0145] Comparative Example 5 The terpolymer of Example 2 (NB / HexNB / CyHexeneNB, molar ratio 60 / 20 / 20) 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 (0.6 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. The composition was mixed by rolling overnight. Two layers of low Df glass cloth (NE glass cloth, style #1280, 50 μm) were thoroughly wetted with the composition, impregnating the glass cloth with the low-loss composition. The treated glass cloth was heated to 130°C in an oven under nitrogen for 1 hour to remove the solvent. The B-staged prepreg was cured under vacuum at 190°C for 1.5 hours to yield a composite with a thickness of 210 μm. The Dk and Df of the composite were measured at 10 GHz. The results are summarized in Table 4. This prepreg sample was used in a reliability study as described in Example 11, and the results are shown in Figure 1.

[0146] Comparative Example 6 The terpolymer of Example 2 (NB / HexNB / CyHexeneNB, 60 / 20 / 20 molar ratio) was dissolved in decalin to prepare a 20 wt. % solution. To a portion of this solution, B1000 (20 pphr), T67 (15 pphr), TAIC (10 pphr), DCP (0.6 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. Ceramic filler Lithafrax 2121 (50 pphr) was dispersed in this portion of the composition. These compositions were applied to glass substrates with a doctor blade and heated to 130°C in an oven under nitrogen for 1 hour to remove the solvent. These B-staged films were cured under vacuum at 190°C for 1.5 hours to yield films with thicknesses of approximately 90-120 μm. Dk and Df were measured at 10 GHz. The results are summarized in Table 2.

[0147] Comparative Example 7 The terpolymer of Example 5 (NB / HexNB / CyHexeneNB, molar ratio 60 / 20 / 20) was dissolved in decalin to prepare a 20 wt. % solution. To a portion of this solution, B1000 (20 pphr), T67 (15 pphr), TAIC (15 pphr), DCP (0.7 pphr in the case of Example 27a), Irganox-1076 (1.50 pphr), Irgafos-168 (0.38 pphr), and silica nanoparticles (71 pphr of SC2300-SVJ) were added. An additional amount of decalin (100 pphr) was added to facilitate solubility of all components. The composition was doctor-bladed onto a glass substrate and heated to 130°C in an oven under a nitrogen atmosphere for 1 hour to remove the solvent. These B-staged films were cured under vacuum at 190°C-195°C for 1.5 hours to yield films approximately 105 μm thick. For Comparative Example 7, a Dk of 2.24 and a Df of 0.0009 were measured at 10 GHz, which are also summarized in Table 2 and compared with the film of Example 7.

[0148] [Comparative Example 8] TOPAS (GPC (THF:Mw =84,650,M n A commercially available NB / ethylene copolymer with a pH of 50, 150, and PDI of 1.7 was dissolved in xylene to prepare a 27 wt. % solution. DCP (4 pphr) was added to this solution to produce the composition of Comparative Example 8A. T67 (15 pphr), TAIC (10 pphr), DCP (3 pphr), Irganox-1076 (1.75 pphr), and Irgafos-168 (0.75 pphr) were added to the polymer solution to form the composition of Comparative Example 8B. Showa Denko's hexagonal boron nitride (h-BN) with a particle size of 0.7 μm was dispersed in these solutions at a 50 pphr loading. These compositions were doctor blade coated onto glass substrates and heated to 130°C in an oven under nitrogen for 1 hour to remove the solvent. These B-staged films were cured at 200°C under nitrogen for 1 hour to yield films approximately 150 μm thick. Approximately 0.25–0.35 g of these films were mixed with approximately 6–7 g of THF and sonicated for 1 h at 30° C. The dissolved portion was removed, and the films were dried at 150° C. for 1 h. The percentage of dissolved film was calculated from the initial and final weights of the films and is shown in Table 5.

[0149] 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 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 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 of 10 mole % or more, 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) hexagonal boron nitride having a particle size ranging from about 0.05 μm to about 50 μm; d) 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; A composition comprising:

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 6】

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 7】

4. 10. The composition of claim 1, wherein the polymer is selected from the group consisting of: 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).

5. 10. The composition of claim 1, wherein the hexagonal boron nitride is in platelet morphology and has a particle size ranging from about 0.1 μm to about 30 μm.

6. 10. The composition of claim 1, wherein the hexagonal boron nitride is present in an amount of at least 20% by weight based on the amount of polymer.

7. 10. The composition of claim 1, wherein the hexagonal boron nitride is present in an amount ranging from about 25% 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 8】

11. 10. The composition of claim 1, wherein the free radical generator is selected from the group consisting of: 【Chemistry 9】

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 solution 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 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 solution containing a mixture of 1,3,5-triallyl-1,3,5-trianane-2,4,6-trione (TAIC), 1,2-butadiene rubber (B1000), a polyarylether crosslinker end-capped with methacrylate groups (SA9000), and dicumyl peroxide (DCP), 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-trianane-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 solution containing a mixture of dicumyl peroxide (DCP), and hexagonal boron nitride (h-BN); and 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); 1,3,5-triallyl-1,3,5-trianane-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 solution containing a mixture of dicumyl peroxide (DCP), and hexagonal boron nitride (h-BN).

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

14. 14. The film of claim 13, having a dielectric constant (Dk) of less than 2.7 and a dielectric dissipation factor (Df) of less than 0.002 at a frequency of 10 GHz.

15. 14. The film of claim 13, having a dielectric constant (Dk) in the range of about 2.4 to about 2.7 and a dielectric dissipation factor (Df) of about 0.0005 to 0.002 at a frequency of 10 GHz.

16. 14. The film of claim 13 formed from a composition 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 solution 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 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 solution containing a mixture of 1,3,5-triallyl-1,3,5-trianane-2,4,6-trione (TAIC), 1,2-butadiene rubber (B1000), a polyarylether crosslinker end-capped with methacrylate groups (SA9000), and dicumyl peroxide (DCP), 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-trianane-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 solution containing a mixture of dicumyl peroxide (DCP), and hexagonal boron nitride (h-BN); and 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); 1,3,5-triallyl-1,3,5-trianane-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 solution containing a mixture of dicumyl peroxide (DCP), and hexagonal boron nitride (h-BN).

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

18. 18. The glass cloth composite of claim 17, having a dielectric constant (Dk) of less than 2.8, a dielectric dissipation factor (Df) of less than 0.002, a glass transition temperature greater than 250°C, and a temperature at which 5% weight loss occurs greater than 380°C.

19. 18. The glass cloth composite of claim 17, having a dielectric constant (Dk) in the range of about 2.6 to about 2.75 and a dielectric dissipation factor (Df) of about 0.001 to 0.0016 at a frequency of 10 GHz.

20. 18. The glass cloth composite of claim 17 formed from a composition 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 solution 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 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 solution containing a mixture of 1,3,5-triallyl-1,3,5-trianane-2,4,6-trione (TAIC), 1,2-butadiene rubber (B1000), a polyarylether crosslinker end-capped with methacrylate groups (SA9000), and dicumyl peroxide (DCP), 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-trianane-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 solution containing a mixture of dicumyl peroxide (DCP), and hexagonal boron nitride (h-BN); and 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); 1,3,5-triallyl-1,3,5-trianane-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 solution containing a mixture of dicumyl peroxide (DCP), and hexagonal boron nitride (h-BN).

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