Polycyclic olefin polymers containing acrylate functional groups with acrylate / maleimide crosslinkers as B-stageable compositions for low-loss applications

Abstract

Embodiments of the present invention include copolymers, terpolymers, and tetrapolymers of various polycycloolefin monomers, including at least one monomer containing unpolymerized acrylate groups. Another aspect of the present invention provides embodiments that include compositions containing the polymers of the present invention, a crosslinker, a free-radical initiator, a tackifier, and one or more suitable additives. Additionally, bulk polymerization compositions are provided that include one or more polycycloolefin monomers, optionally containing a crosslinker containing an acrylate group-containing monomer and / or a multifunctional acrylate. 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 exceptionally high thermal properties. The compositions of the present invention may further include one or more organic or inorganic fillers, which provide improved thermal and mechanical properties in addition to exceptionally low dielectric properties. The compositions of the present invention are useful in a variety of applications, such 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 / 404,342, filed September 7, 2022, which is incorporated herein.

[0002] Embodiments of the present invention generally relate to polymers formed from two or more polycycloolefin monomers, at least one of which contains an acrylate functional group. More specifically, the present invention relates to polymers containing two or more substituted norbornene derivatives, at least one of which contains at least one free acrylate functional group. Embodiments of the present invention further relate to compositions comprising such polymers in combination with a tackifier, a crosslinker, a free-radical initiator, and one or more additives. The compositions of the present invention can be easily formed into films useful for prepregs for low-loss thermosets and copper-clad laminates, which exhibit not only low dielectric constants and low loss characteristics but also very high thermal properties. For example, films formed from the compositions of the present invention typically exhibit high glass transition temperatures in the range of about 150°C to 280°C, low dielectric constants (about 2.2 to 3.0 at 10 GHz), low dielectric dissipation factors (about 0.001 to 0.002 at 10 GHz), and coefficients of thermal expansion (CTE) of at least 60 ppm / K. Thus, the polymers and compositions of the present invention find use as insulating materials in a variety of applications, including electromechanical device applications in the manufacture of automotive parts. [Background technology]

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

[0004] However, for such materials to be used in copper clad laminates for printed circuit boards, they require high glass transition temperatures (T g High-performance thermosets 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 commercially available materials available in the art fail to achieve these properties, particularly low Dk / Df and high glass transition temperatures above 150°C.

[0005] Furthermore, there are considerable technical challenges in developing such insulating materials that meet all the requirements. One such challenge is that such materials must exhibit a low coefficient of thermal expansion (CTE). This coefficient should preferably be less than 50 ppm / K due to concerns that they may delaminate from the copper layer. Yet another challenge is that such materials must exhibit a very high glass transition temperature (T g This temperature is preferably greater than 150°C, and even greater than 250°C, due to the process conditions used in manufacturing printed circuit boards and the harsh conditions that devices may face, such as millimeter wave radar antennas used in automobiles and other terminal devices in 5G devices.

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

[0007] According to the literature, certain polymers such as fluorinated polyethylene, polyethylene, and polystyrene have low Dk / Df, but all of these polymers exhibit very low glass transition temperatures (possibly much lower than 150°C), making them unsuitable as organic insulating materials. Furthermore, the literature also indicates that certain substituted norbornene combinations, typically substituted with polar groups such as ester or alcohol groups, generally result in low CTE and T g However, the combination of such groups increases both Dk and Df due to polarizability 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] US Patent No. 10,897,818B2 discloses a composition containing a modified polyphenylene ether containing vinylbenzyl end groups, a crosslinker such as 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (also known as triallyl isocyanurate (TAIC)), and an epoxy compound. However, although the composition reported therein exhibits a high Dk of about 3.7 and a Df of about 0.005, the T g is relatively high, ranging from about 200℃ to 230℃.

[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 acrylate functional group, and to provide compositions derived therefrom which can be formed into insulating materials having heretofore unattainable properties.

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

[0013] Surprisingly, when polymers comprising two or more polycyclic olefin monomers of formula (I) and (II), as described herein, are used, comprising at least 4 mole percent or more of the monomer of formula (II), as described herein, polymers can be formed that can be used to form a variety of three-dimensional objects, including films, that 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]

[0014] 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]1 shows a graphical plot of a dielectric reliability study at a storage temperature of 125° C. for 1,000 hours for several exemplary films formed from compositions of the present invention, as compared to comparative compositions available in the art as described herein. DETAILED DESCRIPTION OF THE INVENTION

[0015] The terms used in this application have the following meanings:

[0016] In this application, the articles "a," "an," and "the" include plural referents unless otherwise expressly and unambiguously limited to one referent.

[0017] 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."

[0018] 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.

[0019] 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.

[0020] 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.

[0021] 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.

[0022] 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.

[0023] 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.

[0024] 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.

[0025] 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.

[0026] 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.

[0027] 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.

[0028] 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.

[0029] "Halogen" or "halo" means chlorine, fluorine, bromine, or iodine.

[0030] 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.

[0031] 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.

[0032] It is understood that the terms "dielectric" and "insulating" are used interchangeably herein. Thus, a reference to an insulating material or layer includes a dielectric material or layer, and vice versa. Also, as used herein, the term "organic electronic device" is understood to include "organic semiconductor device" and various specific implementations of such devices used, for example, in the automotive industry.

[0033] 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.

[0034] 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.

[0035] 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.

[0036] 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.

[0037] 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]

[0038] 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 described in more detail below.

[0039] Thus, in accordance with the practice of the present invention, the polymer is: a) 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, (C6-C 12 ) aryl (C1-C6) alkyl, methylidene, ethylidene, vinyl, linear or branched (C3-C 16 ) alkenyl, (C3-C 10 ) cycloalkenyl, (C6-C 12 ) bicycloalkenyl, (C6-C 12 )Aryl(C2-C 16 )alkenyl, epoxy(C1-C6)alkyl, and epoxy(C3-C8)cycloalkyl; 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 b) 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 selected from the group consisting of acrylate, methacrylate, (C1-C6) alkyl acrylate, and (C1-C6) alkyl methacrylate, and the remaining R5, R6, R7, and R8 may be the same or different and each may be 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 R5 and R6, together with one of R7 and R8 and the carbon atom to which they are attached, is a substituted or unsubstituted (C5-C 14 )monocyclic ring, (C5-C 14 ) bicyclic ring, or (C5-C 14 ) forming a tricyclic ring; and The second repeat unit is present in an amount of 4 mole % or greater, based on the total number of moles of the first and second repeat units.

[0040] The polymers 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 acrylate functional groups present on the monomers of formula (II) do not react during the vinyl addition polymerization, and such functional groups may be used in other applications of the polymer. Thus, for example, the polymers of the present invention can be used in a variety of applications where they can be further crosslinked with other materials. Such methods include forming prepregs suitable for the manufacture of printed circuit boards, such as copper-clad laminates. Even small amounts of the monomers 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.

[0041] Advantageously, it has been found that the additional acrylate 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 polymer of the present invention. That is, one of the acrylate groups present at R5, R6, R7, and R8 of the monomer of formula (II) remains available in the polymer formed by the present invention. Thus, the polymer of the present invention is useful in a variety of applications where additional reactions involving olefin functional groups, such as crosslinking with other materials, are required. Furthermore, it has been further observed that to observe the crosslinking ability of the polymer of the present invention, the amount of monomer of formula (II) used can be as little as 4 mol % of the total amount of combined monomers of formulas (I) and (II).

[0042] Thus, in one embodiment, the amount of repeat units of the monomer of formula (IIA) present in the polymer is at least 4 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 5 mol % to about 40 mol %, from about 10 mol % to about 30 mol %, from about 15 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 is from about 6 mol % to 30 mol %, based on the total number of moles of the first and second repeat units of formulae (IA) and (IIA).

[0043] As described above, one or more monomers of Formula (I), including 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) in combination with at least 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. In one embodiment, three or more separate monomers of Formula (I) can be used in combination with at least one monomer of Formula (II). Furthermore, as described herein, preferred amounts of three 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) may be 10:10:80, 10:20:70, 20:30:50, 10:40:50, 40:40:20, and the like.

[0044] In one embodiment, the polymers of the present invention have repeating units of formula (IA) where m is 0 or 1. In another embodiment, the polymers of the present invention have repeating units of formula (IA) where m is 0. That is, the repeating units of formula (IA) are 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 polymers 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 combinations of monomers of formula (I) having m=0 and m=1 can also be used to form the polymers 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 polymers of the present invention. In other words, suitable amounts of these separate monomers of formula (I) that can provide the intended benefits can be used to form the polymers 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).

[0045] Similarly, in some other embodiments, polymers according to the present invention have repeating units of formula (IIA) where n is 0 or 1. In another embodiment, polymers according to the present invention have repeating units of formula (IIA) where n is 0. That is, the repeating units of formula (IIA) are 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 polymers of the present invention. In another embodiment, the monomer of formula (II) used has n=1. That is, the monomer used in this embodiment comprises 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 polymers 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 polymers of the present invention. In other words, suitable amounts of these separate monomers that provide the intended benefits can be used to form the polymers of the present invention. Thus, in one embodiment, two separate monomers of formula (II) are used to form the polymers of the present invention.

[0046] 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, norbornyl, ethylidene, vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, cyclopentenyl, cyclohexenyl, and epoxycyclohexyl.

[0047] 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.

[0048] In yet another embodiment, at least one of R5, R6, R7, and R8 is selected from the group consisting of acryloyl, methylacryloyl, ethylacryloyl, methacryloyl, methylmethacryloyl, and ethylmethacryloyl, and the remaining R5, R6, R7, and R8 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.

[0049] 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.

[0050] 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:

[0051] [ka] [ka]

[0052] 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:

[0053] [ka]

[0054] Illustrative, non-limiting examples of polymers according to the present invention include: A quaternary copolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), 5-cyclohexylbicyclo[2.2.1]hept-2-ene (CyHexaneNB), and bicyclo[2.2.1]hept-5-en-2-yl methacrylate (NB-methacrylate); and A quaternary copolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), 5-(cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyHexeneNB), and bicyclo[2.2.1]hept-5-en-2-yl methacrylate (NB-methacrylate).

[0055] Surprisingly, it has been observed that polymers according to the present invention can be formed by uniformly applying as little as about 4 mole % of the monomer of formula (II), based on the total moles of the monomers of formula (I) and (II). The polymers exhibit effective crosslinking capabilities with other materials when forming composite materials useful in a variety of applications, as described below. In one embodiment, polymers according to the present invention include a second repeat unit of formula (II), which is present in an amount ranging from about 5 mole % to about 30 mole %, based on the total moles of the first repeat unit of formula (I) and the second repeat unit of formula (II). In another embodiment, polymers according to the present invention include a second repeat unit of formula (II), which is present in an amount ranging from about 10 mole % to about 25 mole %, based on the total moles of the first repeat unit of formula (I) and the second repeat unit of formula (II). In yet another embodiment, the polymer according to the present invention includes a second repeat unit of formula (II) present in an amount ranging from about 15 mol % to about 20 mol %, based on the total number of moles of the first repeat unit of formula (I) and the second repeat unit of formula (II). However, it should be noted that in one embodiment, the amount of repeat unit of formula (II) may be less than 4 mol % or may be 30 mol % or more, depending on the intended application. Thus, all combinations of usable amounts are within the scope of the present invention.

[0056] 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:

[0057] 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); and (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.

[0058] 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:

[0059] 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).

[0060] 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.

[0061] 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.

[0062] Advantageously, vinyl addition polymers are formed from palladium compounds and monomers of formulas (I) and (II) at very high conversions at low catalyst loadings (e.g., 8,000-15,000:1), where the molecular weight of the polymer is controlled using a chain transfer agent, e.g., 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, e.g., U.S. Pat. No. 9,771,443 B2 and related portions incorporated herein by reference.

[0063] 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.

[0064] 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.

[0065] Thus, in yet another aspect of the present invention, there is also provided a composition comprising: a) a polymer produced according to the present invention; b) a cross-linking agent selected from the group consisting of: [ka] Compounds of formula (III): X-(A) p (III) In the above formula: p is an integer from 2 to 6; A is an acrylate or methacrylate; X is a substituted or unsubstituted (C1-C 16 ) alkyl, (C3-C 16 ) cycloalkyl, (C3-C 16 )cycloalkyl(C1-C6)alkyl, (C6-C 16 )bicycloalkyl, (C6-C 16 )bicycloalkyl(C1-C6)alkyl, (C8-C 16 ) tricycloalkyl, and (C8-C 16 )tricycloalkyl(C1-C6)alkyl; Compounds of formula (IV): Y-(B) q (IV) In the above formula: q is an integer from 2 to 6; B is a radical of formula (V); [ka] In the above formula, R9 and R 10 are the same or different and each is independently selected from the group consisting of hydrogen, methyl, ethyl, and straight-chain or branched (C3-C6) alkyl; Y is a substituted or unsubstituted (C3-C 16 ) cycloalkyl, (C3-C 16 )cycloalkyl(C1-C6)alkyl, (C6-C 16 )bicycloalkyl, (C6-C 16 )bicycloalkyl(C1-C6)alkyl, (C8-C 16 ) tricycloalkyl, and (C8-C 16)tricycloalkyl(C1-C6)alkyl; selected from mixtures of any combination thereof, and c) one or more additives selected from the group consisting of tackifiers and free radical initiators.

[0066] As discussed above, specific polymers within the general scope described herein include one or more monomers of formula (I) and at least one monomer of formula (II), any of which can be used in the compositions of the present invention. It should also be noted that the polymer contains at least 4 mol % of repeating units of formula (IIA) derived from the corresponding monomer of formula (II), based on the total moles of repeating units of formulas (IA) and (IIA). In one embodiment, the compositions of the present invention contain repeating units derived from the corresponding monomer of formula (IIA) in an amount ranging from about 5 mol % to about 40 mol %, from about 10 mol % to about 30 mol %, from about 15 mol % to about 25 mol %, etc., based on the total mole % of repeating units of formulas (IA) and (IIA) present in the polymer. However, it should be noted that the polymer can contain less than 4 mol % or more than 40 mol % of repeating units of formula (IIA), depending on the intended application of the formed composition. Thus, all such possible combinations of mole percentages of repeat units of formula (IIA) are within the scope of the present invention.

[0067] Any compound of formula (III) can be used in the compositions of the present invention. Non-limiting examples of specific compounds within the scope of formula (III) include: [ka] [ka]

[0068] Similarly, any compound of formula (IV) can be used in the compositions of the present invention. Compounds of formula (IV) are known in the art or can be prepared by any method known in the art. One such method involves, for example, condensing an amine with maleic anhydride to form the preferred maleimide of formula (IV). Non-limiting examples of specific compounds within the scope of formula (IV) include: [ka]

[0069] Any amount of crosslinker can be used in the compositions of the present invention to provide the intended benefits. Thus, in one embodiment, the composition contains only TAIC as the crosslinker. In another embodiment, the composition contains only TAC as the crosslinker. In another embodiment, the composition contains a mixture of one of TAIC or TAC with one or more acrylate crosslinkers. In another embodiment, the composition contains a mixture of one of TAIC or TAC with one or more maleimide 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.

[0070] 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.

[0071] Non-limiting examples of tackifiers suitable for these compositions include: [ka]

[0072] 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.

[0073] Non-limiting examples of free radical generators that can be used in the compositions of the present invention are: [ka]

[0074] 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.

[0075] Non-limiting examples of compositions according to the present invention are selected from the group consisting of: A solution containing a mixture of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), 5-(cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyHexeneNB), and bicyclo[2.2.1]hept-5-en-2-yl methacrylate (NB-methacrylate); and dicumyl peroxide (DCP); a quaternary copolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), 5-cyclohexylbicyclo[2.2.1]hept-2-ene (CyHexaneNB), and bicyclo[2.2.1]hept-5-en-2-yl methacrylate (NB-methacrylate); a solution containing a mixture of 1,2-butadiene rubber (B1000), ethylene-propylene-ethylidene norbornene terpolymer (T67), 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), and dicumyl peroxide (DCP); a quaternary copolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), 5-(cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyHexeneNB), and bicyclo[2.2.1]hept-5-en-2-yl methacrylate (NB-methacrylate); a solution containing a mixture of 1,2-butadiene rubber (B1000), ethylene-propylene-ethylidene norbornene terpolymer (T67), 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), and dicumyl peroxide (DCP); a quaternary copolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), 5-(cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyHexeneNB), and bicyclo[2.2.1]hept-5-en-2-yl methacrylate (NB-methacrylate); a solution containing a mixture of cyclohexane-1,4-diylbis(2-methylacrylate) (1,4-CyHex-dimethacrylate), 1,2-butadiene rubber (B1000), ethylene-propylene-ethylidene norbornene terpolymer (T67), 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), and dicumyl peroxide (DCP); a quaternary copolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), 5-(cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyHexeneNB), and bicyclo[2.2.1]hept-5-en-2-yl methacrylate (NB-methacrylate); a solution containing a mixture of 1,3,5-CyHex(trimethacrylate), 1,2-butadiene rubber (B1000), ethylene-propylene-ethylidene norbornene terpolymer (T67), 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), and dicumyl peroxide (DCP); a quaternary copolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), 5-(cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyHexeneNB), and bicyclo[2.2.1]hept-5-en-2-yl methacrylate (NB-methacrylate); a solution containing a mixture of 1,1'-(bicyclo[2.2.1]heptane-2,5-diylbis(methylene)bis(3,4-dimethyl-1H-pyrrole-2,5-dione) (2,5-NB(CH2-DMMI)2), and dicumyl peroxide (DCP); a quaternary copolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), 5-(cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyHexeneNB), and bicyclo[2.2.1]hept-5-en-2-yl methacrylate (NB-methacrylate); a solution containing a mixture of 1,1'-(bicyclo[2.2.1]heptane-2,5-diylbis(methylene))bis(3,4-dimethyl-1H-pyrrole-2,5-dione) (2,5-NB(CH2-DMMI)2), ethylene-propylene-ethylidene norbornene terpolymer (T67), and dicumyl peroxide (DCP); a 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 (CyHexeneNB); a solution containing a mixture of cyclohexane-1,4-diylbis(2-methylacrylate) (1,4-CyHex-dimethacrylate) and dicumyl peroxide (DCP); 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 (CyHexeneNB); a solution containing a mixture of cyclohexane-1,4-diylbis(2-methylacrylate) (1,4-CyHex-dimethacrylate), 1,2-butadiene rubber (B1000), and dicumyl peroxide (DCP); a 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); a solution containing a mixture of cyclohexane-1,4-diylbis(2-methylacrylate) (1,4-CyHex-dimethacrylate), 1,2-butadiene rubber (B1000), and dicumyl peroxide (DCP); a 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 (CyHexeneNB); a solution containing a mixture of cyclohexane-1,4-diylbis(2-methylacrylate) (1,4-CyHex-dimethacrylate), 1,2-butadiene rubber (B1000), ethylene-propylene-ethylidene norbornene terpolymer (T67), (NB-dimethacrylate), and dicumyl peroxide (DCP); 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 (CyHexeneNB); a solution containing a mixture of cyclohexane-1,4-diylbis(2-methylacrylate) (1,4-CyHex-dimethacrylate), 1,2-butadiene rubber (B1000), ethylene-propylene-ethylidene norbornene terpolymer (T67), (di-CyHex-dimethacrylate), and dicumyl peroxide (DCP); A 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 (CyHexeneNB); a solution containing a mixture of 1,4-CyHex(MI)2 and dicumyl peroxide (DCP); a 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 (CyHexeneNB); a solution containing a mixture of 1,1'-(bicyclo[2.2.1]heptane-2,5-diylbis(methylene))bis(3,4-dimethyl-1H-pyrrole-2,5-dione) (2,5-NB(CH2-DMMI)2), and dicumyl peroxide (DCP); and a 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 (CyHexeneNB); a solution containing a mixture of 1,1'-(bicyclo[2.2.1]heptane-2,5-diylbis(methylene))bis(3,4-dimethyl-1H-pyrrole-2,5-dione) (2,5-NB((CH2-DMMI)2), ethylene-propylene-ethylidene norbornene terpolymer (T67), and dicumyl peroxide (DCP).

[0076] 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).

[0077] 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.

[0078] 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 380°C or more, as will be seen from the specific examples below. d5 The temperature is in the range of about 350°C to about 375°C.

[0079] 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 TM 1076), 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]

[0080] It has also been discovered that, under certain conditions, in the presence of a palladium catalyst and an activator compound, monomers of formula (I) or (II) undergo bulk polymerization to form three-dimensional objects, such as films, as described herein. Therefore, it may be advantageous in certain circumstances to use monomers of formula (I) or (II) directly, without first converting them to polymers, to form compositions suitable for the various applications contemplated herein.

[0081] Accordingly, there is further provided a film-forming composition comprising: one or more olefin monomers of formula (I) as described herein; optionally a monomer of formula (II) as described herein; an organopalladium compound as described herein; an active agent as described herein; a cross-linking agent as described herein; and one or more additives selected from the group consisting of tackifiers and free radical initiators as described herein; provided that in the absence of a monomer of formula (II), the composition comprises at least one compound of formula (III) or one compound of formula (IV); and Films formed from the composition have a dielectric constant (Dk) of less than 2.4 at a frequency of 10 GHz, a glass transition temperature of greater than 200° C., and a coefficient of thermal expansion (CTE) of less than 180 ppm / K.

[0082] Any one or more monomers of formula (I) as described herein can be used in the composition in an appropriate amount as needed for the intended application. Similarly, any one of the monomers of formula (II) as described herein can be used in the composition of the present invention, if desired. Similarly, any of the crosslinking agents described herein, including TAIC, TAC, and compounds of formula (III) or (IV), can be used in the composition. However, as noted above, if a monomer of formula (II) is not used in the composition of the present invention, at least one compound of formula (III) or one compound of formula (IV) must be used to achieve the intended benefits. It should also be noted that any combination of mixtures of crosslinking agents can be used in the composition. Finally, any of the tackifiers and free radical generators described herein can be used in this embodiment of the composition of the present invention.

[0083] Advantageously, compositions such as those described herein undergo bulk polymerization upon exposure to suitable temperature conditions to form a solid object, such as a film. Any temperature conditions that result in such polymerization can be used herein. In one embodiment, the compositions of the present invention are heated at a temperature of about 60°C to about 150°C for a sufficient time, e.g., about 1 hour to about 8 hours, to form a B-staged film. In another embodiment, the compositions of the present invention are heated at a temperature of about 90°C to about 130°C for a sufficient time, e.g., about 1 hour to about 4 hours, to form a B-staged film. The B-staged film is then further heated at an elevated temperature, e.g., about 150°C to about 200°C, to form a fully cured film.

[0084] In most cases, the organopalladium compound and the activator, crosslinker, and tackifier used in the bulk polymerization can be dissolved in the monomers used to form a homogeneous solution. If not, the organopalladium compound and activator can be dissolved in a suitable solvent, such as tetrahydrofuran (THF), and then mixed with one or more monomers of Formula (I), or, if a monomer of Formula (II) is used, the crosslinker, tackifier, and free radical generator to form a homogeneous solution. Other solvents that can be used to dissolve the organopalladium compound and / or activator described herein include ethyl acetate (EA), toluene, trifluorotoluene (TFT), cyclohexane (CH), methylcyclohexane (MCH), and the like. While bulk polymerization of compositions in the presence of a combination of components as described herein is not known in the art, bulk polymerization methods are known in the art, and modified procedures suitable for forming the films of the present invention can be used herein. See, for example, U.S. Patent No. 6,825,307 and the relevant portions incorporated herein by reference.

[0085] Non-limiting examples of bulk polymerizable film-forming compositions according to the present invention are selected from the group consisting of: Mixture of 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), bicyclo[2.2.1]hept-5-en-2-yl methacrylate (NB-methacrylate), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl ester benzenepropanoic acid (Irganox-1076), tris(2,4-ditert-butylphenyl)phosphite (Irgafos-168), palladium(II) bis(tricyclohexylphosphine) diacetate (Pd785), dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); A mixture of 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), bicyclo[2.2.1]hept-5-en-2-yl methacrylate (NB-methacrylate), palladium(II) bis(tricyclohexylphosphine)diacetate (Pd785), dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA), and dicumyl peroxide (DCP); A mixture of 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), bicyclo[2.2.1]hept-5-en-2-yl methacrylate (NB-methacrylate), 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB), palladium(II) bis(tricyclohexylphosphine)diacetate (Pd785), dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA), and dicumyl peroxide (DCP); A mixture of 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), bicyclo[2.2.1]hept-5-en-2-yl methacrylate (NB-methacrylate), 5-(cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyHexeneNB), palladium(II) bis(tricyclohexylphosphine)diacetate (Pd785), dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA), and dicumyl peroxide (DCP); A mixture of 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), bicyclo[2.2.1]hept-5-en-2-yl methacrylate (NB-methacrylate), 5-cyclohexylbicyclo[2.2.1]hept-2-ene (CyHexaneNB), palladium(II) bis(tricyclohexylphosphine)diacetate (Pd785), dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA), and dicumyl peroxide (DCP); 5-Hexylbicyclo[2.2.1]hept-2-ene (HexNB), 5-(cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyHexeneNB), (octahydro-1H-4,7-methanoindene-1,5-diyl)bis(methylene)bis(2-methylacrylate) (NB-CP(CH 2- a mixture of methylmethacrylate (2), palladium(II) bis(tricyclohexylphosphine) diacetate (Pd785), dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA), and dicumyl peroxide (DCP); and A mixture of 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), 5-(cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyHexeneNB), palladium(II) bis(tricyclohexylphosphine)diacetate (Pd785), dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA), cyclohexane-1,4-diylbis(2-methylacrylate) (1,4-CyHex-dimethacrylate), di-tert-butyl peroxide (DTBP), or di-cumyl peroxide (DCP).

[0086] Thus, the compositions of the present invention as described herein can be readily formed into films by conventional film casting techniques, including, for example, doctor blading, drum rolling, extrusion, and / or spin coating. Films formed from the compositions of the present invention are also provided. For example, the compositions of the present invention can be doctor bladed onto a suitable substrate, such as a glass plate. The coated plate is then heated to a suitable temperature in an inert atmosphere to remove residual solvent. Such 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 minutes to about 75 minutes is required. This initial film formation stage is generally referred to as a B-staged film. Under these conditions, the film is still dissolved in a suitable solvent, such as THF, and is not fully crosslinked. 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 180 minutes to ensure complete crosslinking of the composition, as evidenced by the insolubility of the polymer film.

[0087] Thus, 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, 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.

[0088] 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 polymers of the present invention are also provided.

[0089] In yet another embodiment, the films according to the present invention have a dielectric constant (Dk) of less than 3 at a frequency of 10 GHz, a glass transition temperature greater than 150° C., and a coefficient of thermal expansion (CTE) of less than 50 ppm / K.

[0090] 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.

[0091] 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 one or more filler materials. The filler materials may be organic or inorganic. Any known filler material that provides the intended benefits may be used herein.

[0092] Therefore, in one embodiment, the film-forming composition according to the present invention contains 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 oxides such as silica, alumina, diatomaceous earth, titanium oxide, iron oxide, zinc oxide, magnesium oxide, and metal ferrites; hydroxides such as aluminum hydroxide and magnesium hydroxide; calcium carbonate (light and heavy); magnesium carbonate, dolomite; carbonates; sulfates such as calcium sulfate, barium sulfate, ammonium sulfate, and calcium sulfite; talc, mica; clay; glass fiber; calcium silicate; silicates such as montmorillonite; bentonite; boric acid 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; zinc oxide; molybdenum sulfide; boron fiber; potassium titanate; and lead zirconate. A variety of inorganic filler materials are commercially available, for example, silica nanoparticles available as SC2300-SVJ from Adamatech Co. Ltd., ceramic filler Lithafrax-2121 available from St. Gobain, and many other filler materials that may be suitable for use with the compositions of the present invention.

[0093] 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, polyester, acrylic and methacrylic resins, acetal resins, polyethylene, polyether, polycarbonate, polyamide, polysulfone, polystyrene, polyvinyl chloride, fluororesins, polypropylene, ethylene-vinyl acetate copolymers, melamine, 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.

[0094] In one embodiment, the filler is an inorganic filler, which can effectively reduce the coefficient of thermal expansion. Furthermore, heat resistance can also be improved. Therefore, in one embodiment, the inorganic filler is silica, which can improve the dielectric properties and reduce the coefficient of thermal expansion. Various forms of silica fillers are known in the art, and any suitable silica filler can be used in the compositions of the present invention. Examples of such silica fillers include, but are not limited to, fused silica, i.e., fused spherical silica and fused ground silica, crystalline silica, silica nanoparticles, and the like. In one embodiment, the filler used is silica nanoparticles. Surprisingly, it has been observed that by using a suitable amount of silica nanoparticles, it is possible to form a composition exhibiting very low dielectric constants and very low loss characteristics. In one embodiment, the use of suitable silica nanoparticles in an amount of about 60 pphr to 80 pphr can reduce the dielectric constant (Dk) to 2.25 and the loss (Df) to about 0.0009. In another embodiment, Dk is 2.3 and Df is about 0.001. Generally, the amount of filler material varies from about 5% by weight to 80% by weight or more. In one embodiment, the filler content in the composition is about 30% to 80% by weight, based on the total solids content of the composition when polymerized to form a film / sheet as described herein. By appropriately adjusting the filler content, an improved balance between dielectric properties and coefficient of thermal expansion (CTE) can be achieved. In some other embodiments, the filler content in the composition is about 40% to 70% by weight, based on the total solids content of the composition.

[0095] Furthermore, the composition of the present invention may also contain a filler such as hexagonal boron nitride (h-BN). It is generally known that the incorporation of h-BN with a suitable particle size not only improves the high thermal properties required for various applications, but also improves the peel strength when applied to metal substrates such as copper, providing additional benefits in various applications where copper-clad laminates are used (e.g., printed circuit boards, mm-wave radar antennas, etc.).

[0096] It should also be noted 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 exhibit even lower dielectric constants (Dk) and dissipation factors (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 plate-like. The exact shape of the plate is not critical. In this regard, h-BN platelets can have irregular shapes. In this application, the term "plate-like" is generally used to describe thin, flat particles, including flakes. However, other forms of h-BN, including fibers, rods, whiskers, sheets, nanosheets, aggregates, or boron nitride nanotubes, may also be used, which may vary by crystal type, shape, or size, and may include distributions of the foregoing. The h-BN particles may have an average aspect ratio (ratio of particle width or diameter to length) of 1:2 to 1:100,000, or 1:5 to 1:1,000, or 1:10 to 1:300. Representative particle shapes with particularly high aspect ratios include plate-like and rod-like particles, fibers, whiskers, etc. 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.

[0097] It should be noted that 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. 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.

[0098] Generally, the particle size distribution of h-BN is quite variable, and further reduction in particle size is preferred to form the uniform compositions of the present invention. Thus, in one embodiment, if used, the average particle size of h-BN is less than 0.05 μm (i.e., less than 50 nm). In another embodiment, if used, the average particle size of h-BN is in the range of about 0.05 μm to about 70 μm. In still other embodiments, if h-BN is used, its average particle size 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 20 μm, etc.

[0099] 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 by methods known in the art, such as the procedure set forth in ASTM D5470-17 using a TIM Tester 1300.

[0100] 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.

[0101] Generally, the filler is treated with a silane compound having an alkoxysilyl group and an organic functional group such as an alkyl group, an epoxy group, a vinyl group, a phenyl group, or a styryl group in one molecule. Examples of such silane compounds include silanes having an alkyl group such as ethyltriethoxysilane, propyltriethoxysilane, or butyltriethoxysilane (alkylsilanes); silanes having a phenyl group such as phenyltriethoxysilane, benzyltriethoxysilane, or phenethyltriethoxysilane; silanes having a styryl group such as styryltrimethoxysilane, butenyltriethoxysilane, propenyltriethoxysilane, or vinyltrimethoxysilane (vinylsilane); silanes having an acrylic or methacrylic group such as γ-(methacryloxypropyl)trimethoxysilane; silanes having an amino group such as γ-aminopropyltriethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, or N-phenyl-γ-aminopropyltrimethoxysilane; or silanes having an epoxy group such as γ-(3,4-epoxycyclohexyl)ureidotriethoxysilane. Silanes containing mercapto groups can also be used, such as γ-mercaptopropyltrimethoxysilane, etc. It should also be noted that any combination of one or more of the above-mentioned silane compounds can be used.

[0102] It should be noted that when inorganic fillers are used as fillers, the fillers are generally treated with a "non-polar silane compound." This can improve the adhesion between the cyclic olefin polymer formed from the composition of the present invention and the filler. 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 dielectric properties. In this application, "non-polar silane compound" refers to a silane compound that does not have a polar substituent. A polar substituent is a group that can hydrogen bond or ionically dissociate. Such polar substituents include -OH, -COOH, -COOM, NH3, NR4, and the like. + A -, -CONH2, etc., where M is a cation such as an alkali metal, alkaline earth metal, or quaternary ammonium salt, R is H or an alkyl group of up to 8 carbon atoms, and A is an anion such as a halogen atom.

[0103] In one embodiment, the surface of the filler is modified with a vinyl group. The use of a vinyl group is advantageous because it is a non-polar substituent, thereby providing the much-needed low dielectric properties. For example, vinyl silane can be used to modify the filler surface with a vinyl group. Specific examples of vinyl silane are described above.

[0104] Typically, the average particle size of the filler used is about 0.1 to 10 μm thick. In one embodiment, the average particle size is about 0.3 to 5 μm, and in another embodiment, about 0.5 to 3 μm. The average particle size is defined as the average diameter of the particles measured by light scattering. When one or more fillers are used, the average particle size of one or more of such fillers remains within the above-mentioned numerical range. A suitably small average particle size of the filler reduces the specific surface area of ​​the filler. As a result, the number of polar functional groups that can negatively affect the dielectric properties is reduced, facilitating improved dielectric properties. Furthermore, a suitably small average particle size of the filler facilitates polymerization and film formation from the composition of the present invention. More importantly, the film / sheet thus formed exhibits the uniform thickness and flatness required for many intended applications.

[0105] 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.

[0106] Non-limiting examples of flame retardants include phosphorus-based flame retardants such as trisilylenyl phosphate, disilenyl phosphate, and 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10phosphaphenanthrene-10-oxide; halogen-based flame retardants such as brominated epoxy resins and melamine formaldehyde resins; and inorganic flame retardants such as aluminum hydroxide and magnesium hydroxide.

[0107] The compositions of the present invention may further comprise one or more compounds or additives having uses such as adhesion promoters, surface levelers, synergists, plasticizers, cure accelerators, and the like.

[0108] 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.

[0109] 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.

[0110] 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 film / sheet at a frequency of 10 GHz is about 2.2 to 2.4. The dielectric loss tangent (Df) at a frequency of 10 GHz is about 0.0004 to 0.002, and in some other embodiments, about 0.0009 to 0.0015. As a result, the compositions of the present invention are applicable to various devices requiring such low dielectric materials, such as millimeter-wave radar antennas used in automotive applications and dielectric polymer layers used in various other terminal devices used in 5G devices. See, for example, Japanese Patent Application Laid-Open Nos. 2018-109090 and 2003-216823. Antennas generally consist of an insulator and a conductor layer (e.g., copper foil). The compositions or sheets of the present invention can be used as part or all of the insulator. Antennas using the compositions or sheets of the present invention as part or all of the insulator have good high-frequency characteristics and reliability (durability). The use of such materials in printed circuit boards, such as copper-clad laminates, requires high-performance thermosetting resins with high glass transition temperatures, low coefficients of thermal expansion (CTE), low Dk / Df, high peel strength to copper, and excellent reliability during high-temperature storage. The ability to form prepregs (composites with glass cloth), B-stage (producing uncrosslinked or partially crosslinked material layers), and film fusion to create multilayer structures are also important. Most commercially available materials available in this field have not achieved all of these properties, particularly low Dk / Df and high glass transition temperatures.

[0111] The conductor layer of the antenna is formed, for example, from a metal having a suitable electrical conductivity. Circuits are formed on the conductor layer using known circuit processing methods. Conductors forming the conductor layer include various conductive metals such as gold, silver, copper, iron, nickel, aluminum, or alloy metals thereof. Known methods can be used to form the conductor layer. Examples include vapor deposition, electroless plating, and electrolytic plating. Alternatively, a metal foil (e.g., copper foil) can be pressure-bonded by thermocompression bonding. The metal foil constituting the conductor layer is a metal foil generally used for electrical connections. In addition to copper foil, various metal foils such as gold, silver, nickel, and aluminum can be used. Furthermore, alloy foils substantially composed of these metals (e.g., 98% by weight or more) can also be included. Among such metal foils, copper foil is commonly used. The copper foil may be rolled copper foil or electrolytic copper foil.

[0112] Advantageously, the compositions of the present invention fill a gap not previously available with prior art materials: as noted above, the compositions of the present invention not only exhibit the much-needed low Dk / Df properties, but also, as noted above, exhibit very high T g and very high T d5 As evidenced by the properties, it provides a very high thermal stability material.

[0113] 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.

[0114] 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.

[0115] As described above, the compositions of the present invention are generally 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. In such applications, a suitable amount of a suitable solvent can be added to maintain the solids content of the composition at about 10 to 70% by weight during polymerization. Furthermore, any solvent suitable for forming such a solution can be used as a single solvent or as a solvent mixture, as needed.

[0116] 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 (or a preferred yield of monomers of formulas (I) and (II)), one or more crosslinking agents as described herein, a tackifier and a free radical generator as described herein, and one or more optional additives as described herein. In one embodiment, the kit of the present invention includes a polymer having two separate monomers of formula (I) and a monomer of formula (II) in combination with at least one of a crosslinking agent, a tackifier, a free radical generator, and an optional additive, respectively, to achieve a preferred result and / or intended purpose. In another embodiment, the kit of the present invention includes one or more monomers of formula (I) and, optionally, a monomer of formula (II) in combination with at least one of a crosslinking agent, a tackifier, a free radical generator, and an optional additive, respectively, to achieve a preferred result and / or intended purpose.

[0117] In yet another aspect of this embodiment of the invention, the kits of the invention form B-stageable films when exposed to a suitable temperature for a sufficient period of time, i.e., by encapsulating the compositions of the invention and pouring them onto a surface or substrate where, upon suitable heat treatment, the monomers polymerize to form a solid polymer that can be in the form of a film or sheet.

[0118] Generally, as discussed above, such polymerization can occur at a variety of temperature conditions. For example, heating can be performed in stages, e.g., heating to 90°C, then to 110°C, and finally to 150°C for a sufficient time at each temperature step, e.g., 5 minutes to 2 hours. The B-staged film can be further heated at temperatures above 150°C for various periods, e.g., 90 minutes to 180 minutes, to cure the film and form a 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 discussed above, typically ranging from 50 to 500 microns or more.

[0119] 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.

[0120] In one embodiment, the kits described herein include various exemplary compositions described above.

[0121] 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 (or one or more monomers of formula (I) and any monomer of formula (II)); 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.

[0122] 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.

[0123] 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.

[0124] The electrical properties of the films thus formed were evaluated using methods known in the art. For example, the dielectric constant (Dk) or permittivity and dielectric loss tangent at a frequency of 10 GHz were measured using a device for measuring permittivity by the cavity resonator method (manufactured by AET, in accordance with JIS C 2565). The coefficient of thermal expansion (CTE) was measured using a 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.

[0125] 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.

[0126] 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.

[0127] 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.

[0128] Thus, in one embodiment, there is provided a glass cloth composite film / cloth (i.e., prepreg) formed from the polymer of the present invention, which exhibits a dielectric constant (Dk) of less than 2.8 at a frequency of 10 GHz, a peel strength of greater than 6 N / cm, and a coefficient of thermal expansion (CTE) of less than 40 ppm / K.

[0129] 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.

[0130] 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 200°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.

[0131] 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.

[0132] Example (general) The following abbreviations have been used previously and hereinafter in some of the compounds, devices and / or methods used to describe certain embodiments of the present invention. NB···bicyclo[2.2.1]hept-2-ene; HexNB···5-hexylbicyclo[2.2.1]hept-2-ene; ButenylNB···5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene; CyHexeneNB···5-(cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene; CyHexaneNB···5-cyclohexylbicyclo[2.2.1]hept-2-ene; Pd785···Palladium(II) bis(tricyclohexylphosphine) diacetate; Pd1206···(acetonitrile)bis(triisopropylphosphine)-palladium(acetate)tetrakis(pentafluorophenyl)borate; Pd1602···bis(n-butyl-di-1-adamantylphosphine)palladium acetate(acetonitrile)tetrakis(pentafluorophenyl)borate; LiFABA···lithium tetrakis(pentafluorophenyl)borate diethyl etherate; DANFABA···dimethylanilinium tetrakis(pentafluorophenyl)borate; 1,4-CyHex-dimethacrylate···cyclohexane-1,4-diylbis(2-methylacrylate); 1,4-CyHex(CH2 methacrylate)2···cyclohexane-1,4-diylbis(methylene)bis(2-methylacrylate); 1,3,5-CyHex-trimethacrylate···cyclohexane-1,3,5-triyltris(2-methylacrylate); di-CyHex-dimethacrylate···[1,1′-bi(cyclohexane)]-4,4′-diylbis(2-methylacrylate); NB-dimethacrylate···bicyclo[2.2.1]heptane-2,5-diylbis(2-methylacrylate); NB-CP(CH2-acrylate)2···(octahydro-1H-4,7-methanoindene-1,5-diyl)bis(methylene)diacrylate; 1,4-CyHex(MI)2···1,1′-(cyclohexane-1,4-diyl)bis(1H-pyrrole-2,5-dione); 1,4-CyHexCH2-MI2···1,1′-(cyclohexane-1,4-diylbis(methylene))bis(1H-pyrrole-2,5-dione); 2,5-NB(CH2-DMMI)2···1,1'-(bicyclo[2.2.1]heptane-2,5-diylbis(methylene))bis(3,4-dimethyl-1H-pyrrole-2,5-dione); TAIC···1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione; DCP···dicumyl peroxide; B1000···1,2-butadiene rubber; T67···Ethylene-propylene-ethylidenenorbornene terpolymer; Irganox-1076···3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl ester benzenepropanoic acid; Irgafos-168···Tris(2,4-ditert-butylphenyl)phosphite; BCO···bicyclo[4.2.0]oct-7-ene; TES···triethylsilane; TEA···triethylamine; MCH···methylcyclohexane; EA···ethyl acetate; THF···tetrahydrofuran; DMF···dimethylformamide; DMAC···dimethylacetamide; 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 100 parts resin, i.e., parts per 100 parts of total monomers of formulae (I) and (II) as specified below for a polymer according to the invention or as specified below.

[0133] 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.

[0134] [Example 1] NB / HexNB / CyHexeneNB terpolymer (50 / 25 / 25) A solution containing a mixture of NB (6.6 g, 70 mmol), HexNB (6.2 g, 35 mmol), CyHexeneNB (6.1 g, 35 mmol), BCO (0.122 g, 1.13 mmol), and LiFABA (5 wt % solution in anhydrous EA, 0.018 g, 0.021 mmol) was dissolved in anhydrous toluene (43 g) and then sealed in a crimp-cap vial and flushed with nitrogen. The solution was heated to 90 °C. Pd1602 solution (1 wt % solution in EA, 0.011 g, 0.007 mmol) was added to the solution via syringe. The mixture was stirred and heated at 90 °C for 6 h. The polymerized mixture was cooled to room temperature and poured into excess methanol (400 g) with rapid stirring to precipitate the polymer. The liquid was decanted, and the solid was dissolved in a solvent mixture of toluene (40 g) and THF (25 g). The solution was poured into methanol (400 ml) and stirred to precipitate the polymer. The liquid was decanted, the solid was washed with methanol (400 g), and then dried in a vacuum oven at 80 °C for 24 hours to obtain the purified polymer (14.7 g, 78% isolated yield, GPC (THF): M w =73,950, M n = 16,550 and PDI = 4.5. The molar composition of the title terpolymer (NB / HexNB / CyHexeneNB) was obtained with CDCl3. 13 The ratio was calculated to be 52 / 26 / 22 from the C-NMR spectrum.

[0135] [Example 2] NB / HexNB / ButenylNB terpolymer (35 / 40 / 25) A solution containing a mixture of NB (4.3 g, 45.5 mmol), HexNB (9.3 g, 52 mmol), ButenylNB (4.8 g, 32.5 mmol), BCO (0.06 g, 0.56 mmol), and LiFABA (5 wt % solution in anhydrous EA, 0.017 g, 0.02 mmol) was dissolved in anhydrous toluene (42 g) and then sealed in a crimp-cap vial and flushed with nitrogen. The solution was heated to 90 °C. Pd1602 solution (1 wt % solution in EA, 0.010 g, 0.007 mmol) was added to the solution via syringe. The mixture was stirred and heated at 90 °C for 6 h. The polymerized mixture was cooled to room temperature and poured into excess methanol (400 g) with rapid stirring to precipitate the polymer. The liquid was decanted, and the solid was dissolved in a solvent mixture of toluene (40 g) and THF (25 g). The solution was poured into methanol (400 ml) and stirred to precipitate the polymer. The liquid was decanted, the solid was washed with methanol (400 g), and then dried in a vacuum oven at 80 °C for 24 hours to obtain the purified polymer (16 g, 87% isolated yield, GPC (THF): M w =25,900, M n = 6,725 and PDI = 3.9. The molar composition of the title terpolymer (NB / HexNB / CyHexeneNB) was obtained with CDCl3. 13 The ratio was calculated to be 40 / 40 / 20 from the C-NMR spectrum.

[0136] [Example 3] NB / HexNB / CyHexeneNB terpolymer (60 / 20 / 20) A solution containing a mixture of NB (112.9 g, 1,200 mmol, as a 75 wt% solution in toluene), HexNB (71.3 g, 400 mmol), CyHexeneNB (69.7 g, 400 mmol), BCO (1.08 g, 10 mmol), and LiFABA (0.26 g, 0.3 mmol) was dissolved in anhydrous toluene (972 g) and placed in a glass reactor that was flushed with nitrogen. The solution was heated to 80 °C under a nitrogen atmosphere. Pd1602 solution (1.3 wt% solution in anhydrous EA, 0.16 g, 0.1 mmol) was added to the solution. The mixture was stirred and heated at 80 °C for 6 h. Anhydrous THF (850 g) was added to the reaction mixture. The diluted polymerization mixture was cooled to room temperature and poured into three portions of approximately 525 g each into excess isopropanol (approximately 2,800 g each) with rapid stirring to precipitate the polymer. The liquid was filtered, and the solid was dried in a vacuum oven at 80-90 °C for 20-30 hours to yield the purified polymer (164 g, 65% isolated yield). GPC (THF):M w =140,600,M n = 44,850, PDI = 3.1. The molar composition of the title terpolymer (NB / HexNB / CyHexeneNB) was obtained with CDCl3. 13 The ratio was calculated to be 62 / 20 / 17 from the C-NMR spectrum.

[0137] Example 3A Terpolymer of NB / HexNB / CyHexeneNB (molar ratio 60 / 20 / 20) A mixture of NB (113 g, 1,200 mmol, as a 75 wt% solution in toluene), HexNB (71.3 g, 400 mmol), CyHexeneNB (69.7 g, 400 mmol), BCO (1.08 g, 10 mmol), and LiFABA (0.26 g, 0.3 mmol) was dissolved in anhydrous toluene (545 g) in a glass reactor and flushed with nitrogen. The solution was heated to 80 °C under a nitrogen atmosphere. Pd1602 (0.16 g, 0.1 mmol, a 1.3 wt% solution in anhydrous EA) was added to the reaction mixture. The mixture was heated at 80 °C with stirring for 6 h. THF (850 g) was then added to the reaction mixture. The diluted polymerization mixture was cooled to room temperature and poured in three portions, approximately 560 g each, into excess methanol (approximately 2700 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 give the purified polymer (231 g, 91% isolated yield). GPC (THF): M w =166,600, M n =34,000, PDI=4.9. The monomer composition of the terpolymer (NB / HexNB / CyHexeneNB) is: 13 The carbon monoxide content was calculated as 64 / 19 / 17 through C-NMR spectrum (CDCl3) analysis.

[0138] [Example 4] NB / HexNB / CyHexeneNB / NB-Methacrylate Tetrapolymer (60 / 20 / 10 / 10) A solution containing a mixture of NB (8.5 g, 90 mmol), HexNB (5.3 g, 30 mmol), CyHexeneNB (6.1 g, 15 mmol), NB-methacrylate (2.7 g, 15 mmol), BCO (0.09 g, 0.8 mmol), and LiFABA (5 wt % solution in anhydrous EA, 0.02 g, 0.023 mmol) was dissolved in anhydrous toluene (44 g), sealed in a crimp-cap vial, and flushed with nitrogen. The solution was heated to 90 °C. Pd1602 solution (1 wt % solution in EA, 0.012 g, 0.008 mmol) was added to the solution via syringe. The mixture was stirred and heated at 90 °C for 6 h. The polymerized mixture was cooled to room temperature and poured into excess methanol (400 g) with rapid stirring to precipitate the polymer. The liquid was decanted and the solid was washed with excess methanol (400 ml) while stirring. The solid polymer was dried in a vacuum oven at 80 °C for 24 hours to give the purified polymer (10 g, 52% isolated yield, GPC (THF): M w =104,500, M n = 37,900, PDI = 2.8) was obtained. 1 H-NMR and 13 The C-NMR spectra all showed peaks representing cyclohexene and methacrylate groups.

[0139] [Example 5] NB / HexNB / CyHexaneNB / NB-Methacrylate Terpolymer (60 / 20 / 10 / 10) A solution containing a mixture of NB (2.3 g, 24 mmol), HexNB (1.4 g, 8 mmol), CyHexaneNB (0.7 g, 4 mmol), NB-methacrylate (0.7 g, 4 mmol), BCO (0.035 g, 0.32 mmol), and DANFABA (5 wt % solution in anhydrous EA, 0.005 g, 0.006 mmol) was dissolved in anhydrous toluene (12 g), sealed in a crimp-cap vial, and flushed with nitrogen. The solution was heated to 90 °C. A solution of Pd12O6 (1 wt % solution in EA, 0.002 g, 0.002 mmol) was added to the solution via syringe. The mixture was heated at 90 °C with stirring for 6 h. The polymerized mixture was cooled to room temperature and poured into excess methanol (200 g) with rapid stirring to precipitate the polymer. The solid polymer was dried in a vacuum oven at 80°C for 24 hours to give the purified polymer (4.6g, 90% isolated yield). GPC (THF):M w =102,000, M n = 18,800, PDI = 5.4. Obtained in CDCl3 1 The 1 H-NMR spectrum showed peaks representative of methacrylate groups.

[0140] [Example 6] 1,4-CyHex-dimethacrylate A three-neck round-bottom flask equipped with a thermometer, dropping funnel, and nitrogen inlet / outlet was charged with a solution of cyclohexane-1,4-diol (10 g, 85 mmol) and TEA (20.8 g, 205 mmol) dissolved in anhydrous THF (150 g). The solution was cooled to 0 °C with stirring. Methacryloyl chloride (21.4 g, 205 mmol) was dissolved in anhydrous THF (50 g) and transferred to the dropping funnel. This solution was slowly added dropwise to the cyclohexane-1,4-diol / TEA / THF solution at 0 °C (addition time: approximately 1 h). The reaction mixture was allowed to warm to ambient temperature and stirred for 24 h. Toluene (100 g) and hexane (100 g) were added, and the precipitated triethylamine hydrochloride was removed by filtration. The liquid portion was washed three times with 20 wt% sulfuric acid solution (150 g) and then four times with water (150 g). The product was dried over anhydrous magnesium sulfate, filtered, and then rotary evaporated at 40-60°C to remove the solvent, yielding a semi-solid crude product (13 g, isolated yield 50%). Gas chromatography revealed two peaks of approximately equal intensity. 1 H-NMR was consistent with the 1,4-CyHex-dimethacrylate structure.

[0141] [Example 7] 1,4-CyHex(CH2 methacrylate)2 A three-necked round-bottom flask equipped with a thermometer, dropping funnel, and nitrogen inlet / outlet was charged with a solution of cyclohexane-1,4-dimethanol (20 g, 140 mmol) and TEA (34.4 g, 340 mmol) dissolved in anhydrous THF (150 g). The solution was cooled to 0 °C with stirring. Methacryloyl chloride (35.1 g, 340 mmol) was dissolved in anhydrous THF (50 g) and transferred to the dropping funnel. This solution was slowly added dropwise to the cyclohexane-1,4-dimethanol / TEA / THF solution at 0 °C (addition time: approximately 1 h). The reaction mixture was allowed to warm to ambient temperature and stirred for 24 h. Hexane (100 g) was added, and the precipitated triethylamine hydrochloride was removed by filtration. The liquid portion was washed three times with 20 wt% sulfuric acid solution (100 g) and then six times with water (150 g). The product was dried over anhydrous magnesium sulfate, filtered, and then rotary evaporated at 50-60 °C to remove the solvent, yielding a solid product (21 g, 49% isolated yield). GC-MS detected a potential molecular ion (m / z = 281). The product was obtained in deuterated chloroform. 1 H-NMR was consistent with the CyHex(CH2 methacrylate)2 structure.

[0142] [Example 8] 1,3,5-CyHex-trimethacrylate A solution of cyclohexane-1,3,5-triol (7 g, 53 mmol) and TEA (19.2 g, 190 mmol) was dissolved in methylene chloride (100 mL) in a three-neck round-bottom flask equipped with a thermometer, dropping funnel, and nitrogen inlet / outlet. The solution was cooled to 0 °C with stirring. Methacryloyl chloride (19.9 g, 190 mmol) was dissolved in methylene chloride (50 g) and transferred to the dropping funnel. This solution was slowly added dropwise to the cyclohexane-1,3,5-triol / TEA / methylene chloride solution at 0 °C. The reaction mixture was allowed to warm to ambient temperature and then stirred for 20 h. The reaction mixture was filtered to remove precipitated triethylamine hydrochloride. The liquid portion was washed with 20 wt% sulfuric acid solution (200 g) followed by four washes with water (200 mL). Approximately 25 g of THF was added during each water wash to facilitate phase separation. The product was dried over anhydrous magnesium sulfate, filtered, and then rotary evaporated at 40-60°C to remove the solvent, yielding a crude product (9.2 g, 52% isolated yield). The crude product was dissolved in THF (50 g), filtered through a silica gel pad, and then rotary evaporated to remove the THF, yielding a liquid product (6.1 g, 34% isolated yield). The product was obtained with deuterated chloroform. 1 H-NMR was consistent with the presence of approximately 71% 1,3,5-CyHex-trimethacrylate structures and approximately 29% CyHex(OH) dimethacrylate structures.

[0143] [Example 9] Di-CyHex-dimethacrylate A three-neck round-bottom flask equipped with a thermometer, dropping funnel, and nitrogen inlet / outlet was charged with a solution of [1,1'-bi(cyclohexane)]-4,4'-diol (20 g, 100 mmol) and TEA (24.3 g, 240 mmol) dissolved in methylene chloride (200 g). The solution was cooled to 0 °C with stirring. Methacryloyl chloride (25 g, 240 mmol) was dissolved in methylene chloride (100 g) and transferred to the dropping funnel. This solution was slowly added dropwise to the above solution at 0 °C. The reaction mixture was allowed to warm to ambient temperature and then stirred for 24 h. A mixture of THF (100 g) and hexane (100 g) was added, and the reaction mixture was filtered to remove precipitated triethylamine hydrochloride. The liquid portion was washed twice with 20 wt% sulfuric acid solution (100 g) and then five times with water (150 mL). THF (approximately 25 g) was added during each water wash to facilitate phase separation. The product was dried over anhydrous magnesium sulfate, filtered, and then rotary evaporated at 40-60 °C to remove the solvent, yielding a semi-solid crude product (23 g, isolated yield 68%). 1 H-NMR was consistent with the di-CyHex-dimethacrylate structure.

[0144] [Example 10] NB-Dimethacrylate A three-neck flask equipped with a nitrogen outlet, mechanical stirrer, and dropping funnel was charged with a solution of 2,5-norbornene diol (2 g, 15.4 mmol) and TEA (8 mL) dissolved in THF (50 mL). The solution was then cooled to 0 °C. Methacryloyl chloride (4 mL, 41 mmol, dissolved in 8 mL of DCM) was added dropwise to the 2,5-norbornene diol solution over 1 h. During the addition, a white precipitate began to form. After stirring the reaction mixture overnight, the white precipitate was filtered and washed with DCM (2 × 20 mL), and the filtrate was concentrated in vacuo. The residue was dissolved in 50 mL of toluene. The toluene solution was washed with 2 M HCl (3 × 25 mL), water (3 × 25 mL), 2 M NaOH (3 × 25 mL), water (3 × 25 mL), and brine (25 mL) and then dried over MgSO4. The solvent was removed in vacuo to give 1.5 g (36% yield) of a clear oil, the potential molecular ion (m / z=264) was detected by GC-MS. 1 The 1 H NMR spectrum was consistent with the expected product.

[0145] [Example 11] 1,4-CyHex(MI)2 A round-bottom flask was charged with a solution of 1,4-diaminocyclohexane dissolved in a 1:1 solvent mixture of toluene (25 mL) and DMF (25 mL). This solution was heated to 60 °C, and maleic anhydride (5.2 g, 53.2 mmol) was added. Polyphosphoric acid (79 g) was added to the reaction mixture, and heating continued at 60 °C for 2 hours. The reaction temperature was increased to 90 °C, and the mixture was heated for an additional 12 hours. At this time, the reaction mixture was cooled to room temperature and poured into water. The resulting precipitate was collected. The precipitate was purified using column chromatography using a gradient of 50% ethyl acetate in heptane to 100% EA to afford the title compound (0.5 g, 7% yield) as a white substance. GC-MS detected a potential molecular ion (m / z = 274). 1 H and 13 The C NMR spectrum was consistent with the expected product.

[0146] [Example 12] 1,4-Bis(maleimidomethyl)cyclohexane (1,4-CyHexCH2-MI2) A round-bottom flask was charged with a solution of 1,4-diaminomethylcyclohexane (5.08 g, 35.8 mmol) and maleic anhydride (6.93 g, 70.7 mmol) in DMAC (30 mL). The solution was heated to 50 °C for 1 h and then concentrated. To the concentrate was added acetic anhydride (30 mL) and sodium acetate (5.83 g, 71.7 mmol). The mixture was heated to reflux for 3 h. The reaction mixture was cooled to room temperature and poured into 200 mL of water. The aqueous mixture was extracted with EA (3 × 60 mL). The combined organic layers were washed with water (2 × 60 mL) and brine (60 mL), dried over MgSO4, and concentrated in vacuo. The material was purified by column chromatography using EA as the eluent to give the title compound as a white material (0.7 g, 6% yield). A potential molecular ion (m / z = 302) was detected by GC-MS. 1 H and 13 The C NMR spectrum was consistent with the expected product.

[0147] Example 12A 1,1'-(bicyclo[2.2.1]heptane-2,5-diylbis(methylene))bis(3,4-dimethyl-1H-pyrrole-2,5-dione) (2,5-NB(CH2-DMMI)2) Dimethylmaleic anhydride (DMMA) (8.18 g, 64.8 mmol) was suspended in toluene in a 250 mL reactor equipped with a thermowell, addition funnel, and Dean-Stark trap. The mixture was heated to reflux. All of the DMMA dissolved during heating. A solution of bis(2,5-aminomethyl)norbornane (5 g, 32.4 mmol) in 10 mL of toluene was added dropwise over 1.5 hours. Visible bubbling occurred during the first half of the addition, and a solid formed. The bubbling subsided during the second half of the addition, and a clear solution formed. The reaction solution was refluxed for an additional 4 hours. Water (0.75 mL) was collected in the Dean-Stark trap. The mixture was allowed to cool overnight, and GC analysis indicated the reaction was complete. The mixture was concentrated and dried under high vacuum overnight to provide the title compound.

[0148] [Example 13] Reliability study under storage conditions at 125°C This Example 13 illustrates the superiority of polymers formed from acrylate pendant norbornene monomers of formula (II) in accordance with the practice of the present invention, as compared to various other olefins and / or other reactive monomers known in the art when used under similar conditions.

[0149] A monomer mixture of HexNB (1.6 g, 9 mmol) and NB-methacrylate (0.18 g, 1 mmol) was added with Irganox-1076 (0.5 pphr of monomer), Irgafos-168 (0.125 pphr of monomer), Pd-785 / MCH (0.08 g), and DANFABA / EA (0.08 g). The molar ratio of monomer:Pd-785:DANFABA was approximately 10,000:1:5. The monomer, catalyst, and antioxidant mixture was applied to a glass substrate with a doctor blade and cured at 120 °C for 3 hours under nitrogen atmosphere, followed by 1 hour at 160 °C under vacuum in an oven. Under these conditions, the monomer mixture polymerized in bulk to form a film approximately 100 μm thick. The dielectric constant (Dk) and dielectric dissipation factor (Df) were measured at 10 GHz, and the films were stored in an oven in air at 125°C. The Dk and Df of the films were measured periodically for 1,056 hours to evaluate their reliability under high-temperature storage, which is essential for devices such as automotive mm-wave antennas. The dielectric constant (Dk) of the composition of Example 13 changed only slightly (a 2.3% decrease) from 2.17 to 2.12 over 1,056 hours, demonstrating the excellent reliability of the Dk of this film containing reactive methacrylate groups. Furthermore, Df remained stable, as shown in Figure 1, unlike in the presence of reactive groups such as olefin or epoxy groups. All films formed from the compositions of Comparative Examples 1A to 1C were observed to have poor Df reliability during high-temperature storage. Comparative Example 1A contained CyHexeneNB as the reactive olefin monomer, Comparative Example 1B contained ButenylNB as the reactive olefin monomer, and Comparative Example 1C contained CHEpNB as the reactive monomer. As can be seen from the data shown in Figure 1, excellent reliability of Df was observed for the composition of Example 13, while all of the compositions of Comparative Examples 1A to 1C exhibited poor reliability performance under the same conditions. This therefore demonstrates the superiority of compositions formed according to embodiments of the present invention.

[0150] [Examples 14A to 14D] Mass polymerization of NB-methacrylate-containing compositions Separately, a 1 wt% Pd785 solution in MCH and a 5 wt% DANFABA solution in EA were prepared in crimp-cap vials and sealed. These stock solutions were used in Examples 14A-14D. Four separate compositions were prepared as follows: a mixture of HexNB (1.42 g, 8 mmol) and NB-methacrylate (0.36 g, 2 mmol) was used in Example 14A (HexNB / NB-methacrylate, molar ratio 80 / 20); a mixture of HexNB (1.42 g, 8 mmol), ButenylNB (0.15 g, 1 mmol), and NB-methacrylate (0.18 g, 1 mmol) was used in Example 14B (HexNB / ButenylNB / NB-methacrylate, molar ratio 80 / 10 / 10); and a mixture of HexNB (1.42 g, 8 mmol) and ButenylNB (0.15 g, 1 mmol) was used in Example 14C (HexNB / ButenylNB / NB-methacrylate, molar ratio 80 / 10 / 10). A mixture of HexNB (0.07 g, 6 mmol), CyHexeneNB (0.52 g, 3 mmol), and NB-methacrylate (0.18 g, 1 mmol) was used in Example 14C (HexNB / CyHexeneNB / NB-methacrylate, 60 / 30 / 10), and a mixture of HexNB (1.07 g, 6 mmol), CyHexaneNB (0.53 g, 3 mmol), and NB-methacrylate (0.18 g, 1 mmol) was used in Example 14D (HexNB / CyHexaneNB / NB-methacrylate, 60 / 30 / 10). To each of these compositions was added Pd785 / MCH (0.08 g), DANFABA / EA (0.08 g), and di-tert-butyl peroxide (approximately 4 pphr of monomer as a thermal free radical initiator). The molar ratio of monomer:Pd785:DANFABA in each composition was approximately 10,000:1:5. Each composition was then applied to a glass substrate with a doctor blade and cured at 120°C for 3 hours under a nitrogen atmosphere, followed by 3 hours at 160°C in an oven under nitrogen. Under these conditions, each composition was polymerized in bulk to form a film approximately 100-150 μm thick. The dielectric constant (Dk) at 10 GHz, the dielectric dissipation factor (Df) at 10 GHz, and the glass transition temperature (T g ), coefficient of thermal expansion (CTE), and the temperature at which the film loses 5% of its weight (T d5) were measured. The results are summarized in Table 1. As can be seen from the data presented in Table 1, low Dk and Df were observed for all films, indicating their suitability for various low-loss applications as described herein. It is also noteworthy that the CTE was low and that the CTE can be further reduced by incorporating inorganic fillers suitable for low-loss applications. Additionally, the compositions of Examples 14A-14D exhibited high glass transition temperatures (T g ) and high decomposition temperature (T d5 ) was further demonstrated.

[0151] [Table 1]

[0152] [Example 15] Bulk polymerization of HexNB / CyclohexeneNB using acrylate crosslinkers To a monomer mixture of HexNB / CyHexeneNB (1.8 g, 70 / 30 molar ratio) was added a 1 wt% solution of Pd785 in MCH (0.08 g), a 5% solution of DANFABA in EA (0.08 g), and di-tert-butyl peroxide (approximately 4 pphr of monomer as a thermal free radical initiator). The molar ratio of monomer:Pd785:DANFABA was approximately 10,000:1:5. NB-CP(CH2-acrylate)2 was also added (10 pphr of polymer). The composition was applied to a glass substrate with a doctor blade and cured at 120 °C under nitrogen for 3 hours, followed by 3 hours at 160 °C in an oven under nitrogen. The composition was bulk polymerized to form a film approximately 100 μm thick. The film exhibited a low dielectric constant (Dk) of 2.15 at 10 GHz and a low dielectric dissipation factor (Df) of 0.00197 at 10 GHz.

[0153] [Examples 16A to 16C] Bulk polymerization of HexNB / CyclohexeneNB using various acrylate crosslinkers To a monomer mixture of HexNB / CyHexeneNB (1.8 g, 70 / 30 molar ratio), a 1 wt % solution of Pd785 in MCH (0.08 g) and a 5% solution of DANFABA in EA (0.08 g) were added. This solution was divided into three separate portions, and a methacrylate crosslinker (1,4-CyHex-dimethacrylate), di-tert-butyl peroxide (DTBP), or di-cumyl peroxide (DCP) was added in different amounts to each portion, as listed in Table 2, to form three separate compositions, Example 16A, Example 16B, and Example 16C. The molar ratio of monomer:Pd785:DANFABA in each of these compositions was approximately 10,000:1:5. Each composition was applied to a glass substrate with a doctor blade and cured at 120°C under nitrogen for 3 hours, followed by 2 hours at 160°C under vacuum in an oven. Under these conditions, the monomer mixture completely polymerized to form films approximately 100 μm thick. The dielectric constant (Dk) and dielectric dissipation factor (Df) at 10 GHz for each of these films were measured and are listed in Table 2. As can be seen from the data presented in Table 2, all of the compositions of Examples 16A-16C exhibit very low Dk and Df values. It was also observed that increasing the amount of crosslinker, as seen in Example 16C, further reduced the Dk while maintaining similar low-loss properties.

[0154] [Table 2]

[0155] [Examples 17A to 17B] NB / HexNB / CyHexeneNB / NB-Methacrylate Polymer Composition The polymer formed in Example 4 (NB / HexNB / CyHexeneNB / NB-methacrylate, molar ratio 60 / 20 / 10 / 10) was dissolved in mesitylene to prepare a 20 wt. % solution (Example 17A). Dicumyl peroxide (DCP, 2 pphr, Example 17B) was added to this solution. These compositions were doctor-bladed onto glass substrates and heated at 130°C for 1 hour to remove the solvent (B-staging). The solubility of small pieces of the B-staged film was measured in THF. These B-staged films were further cured at 180°C for 1 hour under nitrogen and then cured in a vacuum oven at 180°C for 1 hour to form films approximately 100 μm thick. The solubility of small pieces of the fully cured film was measured in THF. The dielectric constant (Dk) and dielectric dissipation factor (Df) were measured at 10 GHz. The results are summarized in Table 3. The B-staged films of both examples maintained at least partial solubility in THF. The fully cured film of Example 17A, without the thermal free radical initiator, still maintained solubility in THF, indicating no crosslinking. The fully cured film of Example 17B lost solubility in THF, indicating crosslinking to form a thermoset in the presence of a thermal free radical initiator. The films also had low Dk and Df. Therefore, the polymer composition of Example 17B was considered suitable for use in copper-clad laminates, which require low-loss, high-performance thermosets.

[0156] [Table 3]

[0157] [Example 18] NB / HexNB / CyHexaneNB / NB-Methacrylate Polymer Composition The polymer formed in Example 5 (NB / HexNB / CyHexaneNB / NB-methacrylate, molar ratio 60 / 20 / 10 / 10) was dissolved in mesitylene to prepare a 20 wt% solution. To this solution, B1000 (20 pphr), T67 (15 pphr), TAIC (10 pphr), and DCP (1 pphr) were added. The composition was doctor-bladed onto a glass substrate and heated at 130°C for 1 hour under a nitrogen atmosphere to remove the solvent (B-staged). The B-staged film was further cured under two conditions: at 180°C for 1.5 hours under vacuum (Cure-1) or at 200°C for 1.5 hours under vacuum (Cure-2). The THF solubility, dielectric constant (Dk) at 10 GHz, and dielectric dissipation factor (Df) were measured and summarized in Table 4. Research results indicated that this composition is suitable for use in copper-clad laminates requiring low-loss, high-performance thermosets.

[0158] [Table 4]

[0159] [Examples 19A to 19B] NB / HexNB / CyHexeneNB polymer composition The polymer formed in Example 1 (NB / HexNB / CyHexeneNB, 50 / 25 / 25 molar ratio) was dissolved in mesitylene to prepare a 25 wt. % solution. 1,4-CyHex-dimethacrylate (15 pphr) and DCP (2 pphr) were added to this solution. Additionally, B1000 (15 pphr) was added to Example 19B. These compositions were doctor-bladed onto glass substrates and heated to 130°C under a nitrogen atmosphere for 1 hour to remove the solvent (B-staged). These B-staged films were fully cured at 170°C under a nitrogen atmosphere for 1 hour, followed by 2 hours at 170°C in a vacuum oven to produce films approximately 100 μm thick. THF solubility, CTE, and T gThe dielectric constant (Dk) and dielectric dissipation factor (Df) at 10 GHz were measured and are summarized in Table 5. Research results show that these compositions are suitable for use in copper-clad laminates requiring low loss and high performance thermosets.

[0160] [Example 20] NB / HexNB / ButenylNB polymer composition The polymer formed in Example 2 (NB / HexNB / ButenylNB, molar ratio 35 / 40 / 25) was dissolved in mesitylene to prepare a 35 wt. % solution. To this solution was added 1,4-CyHex-dimethacrylate (15 pphr), B1000 (15 pphr), and DCP (2 pphr). The composition was doctor-bladed onto a glass substrate and heated at 130°C for 1 hour under a nitrogen atmosphere to remove the solvent (B-staged). The B-staged film was fully cured at 170°C for 1 hour under a nitrogen atmosphere, followed by 2 hours at 170°C in a vacuum oven to produce a film approximately 100 μm thick. THF solubility, CTE, and T g The dielectric constant (Dk) and dielectric dissipation factor (Df) at 10 GHz were measured and are summarized in Table 5. Research results show that these compositions are suitable for use in copper-clad laminates requiring low loss and high performance thermosets.

[0161] [Table 5]

[0162] [Example 21] NB / HexNB / CyHexeneNB polymer composition The polymer formed in Example 1 (NB / HexNB / CyHexeneNB, 50 / 25 / 25 molar ratio) was dissolved in mesitylene to prepare a 25 wt. % solution. To this solution was added 1,4-CyHex-dimethacrylate (20 pphr), B1000 (10 pphr), and DCP (2 pphr). The composition was doctor-bladed onto a glass substrate and heated at 120°C for 30 minutes under a nitrogen atmosphere to remove the solvent (B-staged). The B-staged film was fully cured at 180°C for 1 hour under a nitrogen atmosphere and then in a vacuum oven at 180°C for 1 hour, producing a film approximately 100 μm thick. Film properties were measured as follows: CTE (89 ppm / K), T g (264°C), a dielectric constant (Dk) at 10 GHz of 2.29, and a dielectric dissipation factor (Df) at 10 GHz of 0.0014. Research has shown that this composition is suitable for use in copper-clad laminates requiring low-loss, high-performance thermosets.

[0163] [Examples 22A to 22E] NB / HexNB / CyHexeneNB / NB-Methacrylate Polymer Composition The polymer formed in Example 4 (NB / HexNB / CyHexeneNB / NB-methacrylate, molar ratio 60 / 20 / 10 / 10) was dissolved in mesitylene to prepare a 20 wt. % solution. To this solution, B1000, T67, TAIC, 1,4-CyHex-dimethacrylate or 1,3,5-CyHex-trimethacrylate, and DCP (2 pphr for all examples) were added, as shown in Table 6. These compositions were doctor-bladed onto glass substrates and heated to 130°C for 1 hour under a nitrogen atmosphere to remove the solvent (B-staged). These B-staged films were fully cured at 180°C for 1 hour under a nitrogen atmosphere, followed by 2 hours at 180°C in a vacuum oven, yielding films approximately 100-200 μm thick. The fully cured films were analyzed for THF solubility, CTE, and T gThe dielectric constant (Dk) and dielectric dissipation factor (Df) at 10 GHz were measured and the results are summarized in Table 7. Research results show that these compositions are suitable for use in copper clad laminates requiring low loss, high performance thermosets.

[0164] [Table 6]

[0165] [Table 7]

[0166] [Examples 23A to 23B] NB / HexNB / CyHexeneNB(60 / 20 / 20) polymer composition The polymer formed in Example 3 (NB / HexNB / CyHexeneNB, 60 / 20 / 20 molar ratio) was dissolved in mesitylene to prepare a 20 wt. % solution. To this solution, 20 pphr of B1000, 15 pphr of T67, and 10 pphr of NB-dimethacrylate were added for Example 23A, and 10 pphr of di-CyHex-dimethacrylate for Example 23B, both with 2 pphr of DCP. These compositions were doctor-bladed onto glass substrates and heated at 110°C for 30 minutes and then at 130°C for 1 hour under a nitrogen atmosphere to remove the solvent (B-staged). These B-staged films were fully cured at 180°C for 1 hour under a nitrogen atmosphere and then at 200°C for 2 hours in a vacuum oven to produce films approximately 100 μm thick. The fully cured films were analyzed for CTE, T g , T d5 The dielectric constant (Dk) and dielectric dissipation factor (Df) at 10 GHz were measured and the results are summarized in Table 8. The results of the study indicate that these compositions are suitable for use in copper clad laminates requiring low loss and high performance thermosets.

[0167] [Table 8]

[0168] [Examples 24A to 24B] Maleimides as crosslinkers The polymer formed in Example 3A (NB / HexNB / CyHexeneNB, 60 / 20 / 20 molar ratio) was dissolved in decalin to prepare a 15 wt. % solution. To this solution, 1,4-CyHex(MI)2 (10 pphr) and DCP (1 pphr) were added for Example 24A, and 2,5-NB(CH2-DMMI)2 (10 pphr) and DCP (0.5 pphr) were added for Example 24B. These compositions were doctor-bladed onto glass substrates and heated to 130°C for 1 hour under a nitrogen atmosphere to remove the solvent (B-staged). These B-staged films were fully cured in a vacuum oven at 190°C for 2 hours to produce films with thicknesses of approximately 75 μm (Example 24A) and 85 μm (Example 24B). The fully cured films were characterized by their CTE, T g , T d5 The dielectric constant (Dk) and dielectric dissipation factor (Df) at 10 GHz were measured and the results are summarized in Table 9. Research results show that these compositions are suitable for use in copper clad laminates requiring low loss, high performance thermosets.

[0169] [Table 9]

[0170] [Example 25] Maleimides as crosslinkers The polymer formed in Example 3A (NB / HexNB / CyHexeneNB, 60 / 20 / 20 molar ratio) was dissolved in decalin to prepare a 15 wt. % solution. To this solution was added 2,5-NB(CH2-DMMI)2 (10 pphr), T67 (15 pphr), and DCP (1 pphr). The composition was doctor-bladed onto a glass substrate and heated at 130°C for 1 hour under a nitrogen atmosphere to remove the solvent (B-staged). The B-staged film was fully cured in a vacuum oven at 190°C for 1.5 hours to produce a film approximately 100 μm thick. The film exhibited the following properties: CTE = 110 ppm / K, T g = 268°C, T d5 = 357°C and 10 GHz. Dielectric constant (Dk = 2.13) and dielectric dissipation factor (Df = 0.0005). Research has shown that this composition is suitable for use in copper-clad laminates requiring low loss, high performance thermosets.

[0171] [Examples 26A to 26B] Maleimides as crosslinkers The polymer formed in Example 4 (NB / HexNB / CyHexeneNB / NB-methacrylate, molar ratio 60 / 20 / 10 / 10) was dissolved in mesitylene to prepare a 20 wt. % solution. To this solution, 10 pphr of 2,5-NB(CH2-DMMI)2 and 1 pphr of DCP were added for Example 26A, and 10 pphr of 2,5-NB(CH2-DMMI)2, 15 pphr of T67, and 1 phr of DCP were added for Example 26B. These compositions were doctor-bladed onto glass substrates and heated to 130°C under a nitrogen atmosphere for 1 hour to remove the solvent (B-staged). These B-staged films were fully cured in a vacuum oven at 190°C for 1.5 hours to produce films with thicknesses of approximately 100-150 μm. The fully cured films were analyzed for CTE, T gThe dielectric constant (Dk) and dielectric dissipation factor (Df) at 10 GHz were measured and the results are summarized in Table 10. Research results show that these compositions are suitable for use in copper clad laminates requiring low loss and high performance thermosets.

[0172] [Table 10]

[0173] [Example 27] Film Fusion Research The B-staged films of Examples 22B, 22D, and 22E were fused by pressing two films together at 160°C for 1.5 hours under 10 MPa pressure. These films demonstrate the suitability of these compositions for copper-clad laminates that must be fused together to produce complex layer structures. Table 11 summarizes the results of the film fusion examples. The film thickness of the fused films was approximately twice the size of the individual films or slightly less, indicating that some films were able to flow during pressing at 10 MPa and 160°C.

[0174] [Table 11]

[0175] [Comparative Examples 1A to 1C] Reliability study when stored at 125℃ A mixture of HexNB (1.34 g, 7.53 mmol) and CyHexeneNB (0.44 g, 2.53 mmol) was used in Comparative Example 1A, a mixture of HexNB (1.34 g, 7.98 mmol) and ButenylNB (0.37 g, 2.50 mmol) was used in Comparative Example 1B, and a mixture of HexNB (1.42 g, 7.98 mmol) and CHEpNB (0.38 g, 2.00 mmol) was used in Comparative Example 1C. To each of these mixtures was added Irganox-1076 (0.5 pphr of monomer), Irgafos-168 (0.125 pphr of monomer), Pd785 / MCH (0.08 g), and DANFABA / EA (0.08 g), as prepared in Example 13. The molar ratio of monomer:Pd785:DANFABA in each mixture was approximately 10,000:1:5. These compositions were applied to glass substrates using a doctor blade and cured in a nitrogen-atmosphere oven at 120°C for 3 hours, followed by a vacuum oven at 160°C for 1 hour. The monomer mixtures were bulk polymerized to form films approximately 100–150 μm thick. The dielectric constant (Dk) and dielectric dissipation factor (Df) of each film were measured, and the films were stored in an oven at 125°C in air. The Dk and Df of the films were measured periodically for 500–700 hours to evaluate their reliability under high-temperature storage, which is essential for devices such as automotive mm-wave antennas. Figure 1 shows the reliability of Df during high-temperature storage for these compositions containing reactive groups such as olefins and epoxies. Reliability was poor; the dielectric dissipation factor increased significantly during storage compared to the reliability shown in Example 13.

[0176] Although the present invention has been described through the above 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) 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, (C ６ -C １２ ) aryl (C １ -C ６ ) alkyl, methylidene, ethylidene, vinyl, linear or branched (C ３ -C １６ ) alkenyl, (C ３ -C １０ ) cycloalkenyl, (C ６ -C １２ ) bicycloalkenyl, (C ６ -C １２ ) aryl (C ２ -C １６ ) alkenyl, epoxy (C １ -C ６ ) alkyl, and epoxy (C ３ -C ８ ) cycloalkyl; 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 b) 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 the above is an acrylate, a methacrylate, (C １ -C ６ ) alkyl acrylate, and (C １ -C ６ ) alkyl methacrylates, 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 4 mole percent or greater, based on the total moles of the first and second repeat units.

2. The polymer of claim 1, wherein the monomer of formula (I) is selected from the group consisting of: 【Chemistry 5-1】 【Chemistry 5-2】

3. 2. The polymer of claim 1, wherein the monomer of formula (II) is selected from the group consisting of: 【Chemistry 6】

4. The polymer of claim 1 selected from the group consisting of: a quaternary copolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), 5-cyclohexylbicyclo[2.2.1]hept-2-ene (CyHexaneNB), and bicyclo[2.2.1]hept-5-en-2-yl methacrylate (NB-methacrylate); and A quaternary copolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), 5-(cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyHexeneNB), and bicyclo[2.2.1]hept-5-en-2-yl methacrylate (NB-methacrylate).

5. a) a polymer of: i) at least one first repeat unit derived from a monomer of formula (I) and represented by formula (IA): 【Chemistry 7】 In the above formula: 【Chemistry 8】 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, (C ６ -C １２ ) aryl (C １ -C ６ ) alkyl, methylidene, ethylidene, vinyl, linear or branched (C ３ -C １６ ) alkenyl, (C ３ -C １０ ) cycloalkenyl, (C ６ -C １２ ) bicycloalkenyl, (C ６ -C １２ ) aryl (C ２ -C １６ ) alkenyl, epoxy (C １ -C ６ ) alkyl, and epoxy (C ３ -C ８ ) cycloalkyl; 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) a second repeat unit derived from the monomer of formula (II) and represented by formula (IIA): 【Chemistry 9】 In the above formula: 【Chemistry 10】 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 the above is an acrylate, a methacrylate, (C １ -C ６ ) alkyl acrylate, and (C １ -C ６ ) alkyl methacrylates, 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 about 0 mole % to about 20 mole % based on the total number of moles of the first and second repeat units; b) a cross-linking agent selected from the group consisting of: 【Chemistry 11】 Compounds of formula (III): ︃() ｐ (_=) (In the above formula: p is an integer from 2 to 6; A is an acrylate or methacrylate; X is a substituted or unsubstituted (C １ -C １６ ) alkyl, (C ３ -C １６ ) cycloalkyl, (C ３ -C １６ ) cycloalkyl (C １ -C ６ ) alkyl, (C ６ -C １６ ) bicycloalkyl, (C ６ -C １６ ) bicycloalkyl (C １ -C ６ ) alkyl, (C ８ -C １６ ) tricycloalkyl, and (C ８ -C １６ ) tricycloalkyl (C １ -C ６ ) alkyl); Compound of formula (IV): Y-(B) ｑ (IV) (In the above formula: q is an integer from 2 to 6; B is a radical of formula (V); 【Chemistry 12】 In the above formula, R ９ and R １０ are the same or different, and each represents hydrogen, methyl, ethyl, and straight-chain or branched (C ３ -C ６ ) alkyl; Y is a substituted or unsubstituted (C ３ -C １６ ) cycloalkyl, (C ３ -C １６ ) cycloalkyl (C １ -C ６ ) alkyl, (C ６ -C １６ ) bicycloalkyl, (C ６ -C １６ ) bicycloalkyl (C １ -C ６ ) alkyl, (C ８ -C １６ ) tricycloalkyl, and (C ８ -C １６ ) tricycloalkyl (C １ -C ６ ) alkyl); and Mixtures of any combination thereof; and c) one or more additives selected from the group consisting of tackifiers and free radical initiators; A composition comprising:

6. 6. The composition of claim 5, wherein the first repeat unit of the polymer is derived from a monomer of formula (I) selected from the group consisting of: 【Chemistry 13-1】 【Chemistry 13-2】

7. 6. The composition of claim 5, wherein the first repeat unit of the polymer is derived from a monomer of formula (I) selected from the group consisting of: 【Chemistry 14】

8. The composition of claim 5, wherein the compound of formula (III) is selected from the group consisting of: 【Chemistry 15-1】 【Chemistry 15-2】

9. The composition of claim 5, wherein the compound of formula (IV) is selected from the group consisting of: 【Chemistry 16】

10. 6. The composition of claim 5, wherein the tackifier is selected from the group consisting of: 【Chemistry 17】

11. 6. The composition of claim 5, wherein the free radical generator is selected from the group consisting of: 【Chemistry 18】

12. 6. The composition of claim 5, selected from the group consisting of: a solution comprising a mixture of a quaternary copolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), 5-(cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyHexeneNB), and bicyclo[2.2.1]hept-5-en-2-yl methacrylate (NB-methacrylate); and dicumyl peroxide (DCP); a quaternary copolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), 5-cyclohexylbicyclo[2.2.1]hept-2-ene (CyHexaneNB), and bicyclo[2.2.1]hept-5-en-2-yl methacrylate (NB-methacrylate); a solution containing a mixture of 1,2-butadiene rubber, ethylene-propylene-ethylidene norbornene terpolymer, 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), and dicumyl peroxide (DCP); a quaternary copolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), 5-(cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyHexeneNB), and bicyclo[2.2.1]hept-5-en-2-yl methacrylate (NB-methacrylate); a solution containing a mixture of 1,2-butadiene rubber, ethylene-propylene-ethylidene norbornene terpolymer, 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), and dicumyl peroxide (DCP); a quaternary copolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), 5-(cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyHexeneNB), and bicyclo[2.2.1]hept-5-en-2-yl methacrylate (NB-methacrylate); a solution containing a mixture of cyclohexane-1,4-diylbis(2-methylacrylate) (1,4-CyHex-dimethacrylate), 1,2-butadiene rubber, ethylene-propylene-ethylidene norbornene terpolymer, 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), and dicumyl peroxide (DCP); a quaternary copolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), 5-(cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyHexeneNB), and bicyclo[2.2.1]hept-5-en-2-yl methacrylate (NB-methacrylate); a solution containing a mixture of 1,3,5-CyHex(trimethacrylate), 1,2-butadiene rubber, ethylene-propylene-ethylidene norbornene terpolymer, 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), and dicumyl peroxide (DCP); quaternary copolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), 5-(cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyHexeneNB), and bicyclo[2.2.1]hept-5-en-2-yl methacrylate (NB-methacrylate); 1,1′-(bicyclo[2.2.1]heptane-2,5-diylbis(methylene)bis(3,4-dimethyl-1H-pyrrole-2,5-dione) (2,5-NB(CH ２ -DMMI) ２ a solution containing a mixture of methyl methyl acrylate (MMBA) and dicumyl peroxide (DCP); Quaternary copolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), 5-(cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyHexeneNB), and bicyclo[2.2.1]hept-5-en-2-yl methacrylate (NB-methacrylate); 1,1′-(bicyclo[2.2.1]heptane-2,5-diylbis(methylene))bis(3,4-dimethyl-1H-pyrrole-2,5-dione) (2,5-NB(CH ２ -DMMI) ２ a solution containing a mixture of ethylene-propylene-ethylidene norbornene terpolymer and dicumyl peroxide (DCP); A 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 (CyHexeneNB); a solution containing a mixture of cyclohexane-1,4-diylbis(2-methylacrylate) (1,4-CyHex-dimethacrylate) and dicumyl peroxide (DCP); a 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 (CyHexeneNB); a solution containing a mixture of cyclohexane-1,4-diylbis(2-methylacrylate) (1,4-CyHex-dimethacrylate), 1,2-butadiene rubber, and dicumyl peroxide (DCP); a 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); a solution containing a mixture of cyclohexane-1,4-diylbis(2-methylacrylate) (1,4-CyHex-dimethacrylate), 1,2-butadiene rubber, and dicumyl peroxide (DCP); a 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 (CyHexeneNB); a solution containing a mixture of cyclohexane-1,4-diylbis(2-methylacrylate) (1,4-CyHex-dimethacrylate), 1,2-butadiene rubber, ethylene-propylene-ethylidene norbornene terpolymer (NB-dimethacrylate), and dicumyl peroxide (DCP); a 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 (CyHexeneNB); a solution containing a mixture of cyclohexane-1,4-diylbis(2-methylacrylate) (1,4-CyHex-dimethacrylate), 1,2-butadiene rubber, ethylene-propylene-ethylidene norbornene terpolymer (di-CyHex-dimethacrylate), and dicumyl peroxide (DCP); 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 (CyHexeneNB); 1,4-CyHex (MI) ２ a solution containing a mixture of methyl methyl acrylate and dicumyl peroxide (DCP); 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 (CyHexeneNB); 1,1′-(bicyclo[2.2.1]heptane-2,5-diylbis(methylene))bis(3,4-dimethyl-1H-pyrrole-2,5-dione) (2,5-NB(CH ２ -DMMI) ２ a solution containing a mixture of methyl methyl acrylate (MMBA) and dicumyl peroxide (DCP); 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 (CyHexeneNB); 1,1′-(bicyclo[2.2.1]heptane-2,5-diylbis(methylene))bis(3,4-dimethyl-1H-pyrrole-2,5-dione) (2,5-NB(CH ２ -DMMI) ２ ), a solution containing a mixture of ethylene-propylene-ethylidene norbornene terpolymer, and dicumyl peroxide (DCP).

13. A film formed from the composition of claim 5.

14. A film-forming composition comprising: a) one or more olefin monomers of formula (I); 【Chemistry 19】 In the above formula: 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, (C ６ -C １２ ) aryl (C １ -C ６ ) alkyl, methylidene, ethylidene, vinyl, linear or branched (C ３ -C １６ ) alkenyl, (C ３ -C １０ ) cycloalkenyl, (C ６ -C １２ ) bicycloalkenyl, (C ６ -C １２ ) aryl (C ２ -C １６ ) alkenyl, epoxy (C １ -C ６ ) alkyl, and epoxy (C ３ -C ８ ) cycloalkyl; 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 b) optionally a monomer of formula (II); 【Chemistry 20】 In the above formula: n is an integer of 0, 1, or 2; R ５ , R ６ , R ７ , and R ８ At least one of the above is an acrylate, a methacrylate, (C １ -C ６ ) alkyl acrylate, and (C １ -C ６ ) alkyl methacrylates, 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; c) an organopalladium compound selected from the group consisting of: 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; Dichlorobis(acetonato)palladium(II); Dichlorobis(benzonitrile)palladium(II); Platinum(II) chloride; Platinum(II) bromide; and Platinum bis(triphenylphosphine) dichloride; and d) an active agent selected from the group consisting of: Lithium tetrafluoroborate; Lithium triflate; Lithium tetrakis(pentafluorophenyl)borate; Lithium tetrakis(pentafluorophenyl)borate etherate (LiFABA); 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; Dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); e) a cross-linking agent selected from the group consisting of: 【Chemical 21】 Compounds of formula (III): ︃() ｐ (_=) (In the above formula: p is an integer from 2 to 6; A is an acrylate or methacrylate; X is a substituted or unsubstituted (C １ -C １６ ) alkyl, (C ３ -C １６ ) cycloalkyl, (C ３ -C １６ ) cycloalkyl (C １ -C ６ ) alkyl, (C ６ -C １６ ) bicycloalkyl, (C ６ -C １６ ) bicycloalkyl (C １ -C ６ ) alkyl, (C ８ -C １６ ) tricycloalkyl, (C ８ -C １６ ) tricycloalkyl (C １ -C ６ ) alkyl, (C ８ -C １６ ) tricycloalkyl, and (C ８ -C １６ ) tricycloalkyl (C １ -C ６ ) alkyl); and Compound of formula (IV): Y-(B) ｑ (IV) (In the above formula: q is an integer from 2 to 6; B is a radical of formula (V); 【Chemical 22】 In the above formula, R ９ and R １０ are the same or different, and each represents hydrogen, methyl, ethyl, and straight-chain or branched (C ３ -C ６ ) alkyl; Y is a substituted or unsubstituted (C ３ -C １６ ) cycloalkyl, (C ３ -C １６ ) cycloalkyl (C １ -C ６ ) alkyl, (C ６ -C １６ ) bicycloalkyl, (C ６ -C １６ ) bicycloalkyl (C １ -C ６ ) alkyl, (C ８ -C １６ ) tricycloalkyl, and (C ８ -C １６ ) tricycloalkyl (C １ -C ６ ) alkyl); and Mixtures of any combination thereof; and f) one or more additives selected from the group consisting of tackifiers and free radical initiators; provided that in the absence of a monomer of formula (II), the composition comprises at least one compound of formula (III) or one compound of formula (IV); and Films formed from the composition have a dielectric constant (Dk) of less than 2.4 at a frequency of 10 GHz, a glass transition temperature of greater than 200° C., and a coefficient of thermal expansion (CTE) of less than 180 ppm / K.

15. 15. The composition of claim 14, wherein the monomer of formula (I) is selected from the group consisting of: 【Chemistry 23-1】 【Chemistry 23-2】

16. 15. The composition of claim 14, wherein the monomer of formula (II) is selected from the group consisting of: 【Chemistry 24】

17. 15. The composition of claim 14, wherein the compound of formula (III) is selected from the group consisting of: 【Chemistry 25-1】 【Chemistry 25-2】

18. The composition of claim 14, wherein the compound of formula (IV) is selected from the group consisting of: 【Chemistry 26-1】 【Chemistry 26-2】

19. Tackifiers are: 【Chemical 27】 is selected from the group consisting of Free radical generators include: 【Chemical formula 28】 15. The composition of claim 14, selected from the group consisting of:

20. 6. The composition of claim 5, selected from the group consisting of: 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), bicyclo[2.2.1]hept-5-en-2-yl methacrylate (NB-methacrylate), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl ester benzenepropanoic acid, tris(2,4-ditert-butylphenyl)phosphite, palladium(II) bis(tricyclohexylphosphine)diacetate (Pd785), dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA) mixture; a mixture of 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), bicyclo[2.2.1]hept-5-en-2-yl methacrylate (NB-methacrylate), palladium(II) bis(tricyclohexylphosphine)diacetate (Pd785), dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA), and dicumyl peroxide (DCP); a mixture of 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), bicyclo[2.2.1]hept-5-en-2-yl methacrylate (NB-methacrylate), 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB), palladium(II) bis(tricyclohexylphosphine)diacetate (Pd785), dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA), and dicumyl peroxide (DCP); a mixture of 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), bicyclo[2.2.1]hept-5-en-2-yl methacrylate (NB-methacrylate), 5-(cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyHexeneNB), palladium(II) bis(tricyclohexylphosphine)diacetate (Pd785), dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA), and dicumyl peroxide (DCP); a mixture of 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), bicyclo[2.2.1]hept-5-en-2-yl methacrylate (NB-methacrylate), 5-cyclohexylbicyclo[2.2.1]hept-2-ene (CyHexaneNB), palladium(II) bis(tricyclohexylphosphine)diacetate (Pd785), dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA), and dicumyl peroxide (DCP); 5-Hexylbicyclo[2.2.1]hept-2-ene (HexNB), 5-(cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyHexeneNB), (octahydro-1H-4,7-methanoindene-1,5-diyl)bis(methylene)bis(2-methylacrylate) (NB-CP(CH ２－ methacrylate) ２ ), a mixture of palladium(II) bis(tricyclohexylphosphine)diacetate (Pd785), dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA), and dicumyl peroxide (DCP); and 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), 5-(cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyHexeneNB), palladium(II) bis(tricyclohexylphosphine)diacetate (Pd785), dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA), cyclohexane-1,4-diylbis(2-methylacrylate) (1,4-CyHex-dimethacrylate), di-tert-butyl peroxide (DTBP), or a mixture of di-cumyl peroxide (DCP).

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