Improved polycycloolefin compositions having stable shelf life and capable of being polymerized in bulk

Abstract

Embodiments of the present invention relate to compositions comprising one or more polycycloolefinic monomers and at least one multifunctional olefinic monomer, which have a longer shelf life and undergo bulk polymerization at suitable temperatures to provide 3D insulating articles. Embodiments of the present invention possess properties not previously achievable, such as low dielectric constants, low loss characteristics, and very high thermal properties. The compositions of the present invention may further comprise one or more organic or inorganic filler materials, which provide very low dielectric properties and further improved thermomechanical properties. The compositions are stable at room temperature for up to several weeks and undergo bulk polymerization only when exposed to suitable elevated temperatures, typically above 100°C. The compositions of the present invention are useful in a variety of applications, particularly 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 / 107,522, filed October 30, 2020, which is incorporated herein by reference.

[0002] Embodiments of the present invention generally relate to compositions comprising one or more polycycloolefin monomers, an organopalladium catalyst, an activator, and a solvent. The compositions may optionally include one or more multifunctional olefin monomers. The compositions exhibit excellent stability under atmospheric conditions, resulting in long shelf-life stability. However, upon exposure to suitable elevated temperatures, they readily undergo bulk polymerization, providing 3D insulating articles exhibiting previously unattainable low dielectric constants, low loss, and ultra-high thermal properties. More specifically, the present invention relates to compositions comprising a series of substituted norbornene derivatives and a solvent, optionally further comprising one or more difunctional monomer compounds, that undergo bulk polymerization in the presence of specific organopalladium compounds to form 3D articles, such as films. These compositions exhibit very high glass transition temperatures of 300°C or greater, low dielectric constants (less than 2.4 at 10 GHz), and low loss properties. Thus, the compositions of the present invention are useful as insulating materials in a variety of applications, including electromechanical devices used in the manufacture of various automotive components. [Background technology]

[0003] It is well known that insulating materials with low dielectric constant (Dk) and low loss factor (Df) are important elements in printed circuit boards, which are widely used in electrical products, automotive components, and other applications. Generally, suitable insulating materials for many devices must have a dielectric constant of less than 3 and a loss factor of less than 0.002 (or even less than 0.001) at high frequencies, e.g., above 50 GHz. In addition, there has been growing interest in developing organic dielectrics due to their ease of fabrication.

[0004] However, many technical problems must be solved to develop an insulating material that meets all the requirements. One of these problems is that the insulating material must have a low coefficient of thermal expansion (CTE), which is preferably in the range of 50 to 100 ppm / K to prevent peeling of the copper layer. In addition, the insulating material must have a low glass transition temperature (T g ) must be very high, preferably exceeding 150°C or even 250°C, taking into account the process conditions used in the manufacture of printed circuit boards and the harsh conditions to which such devices may be exposed, such as millimeter wave radar antennas used in automobiles.

[0005] For example, films prepared by addition polymerization of norbornene derivatives containing long side chains, such as 5-hexylnorbornene (HexNB) and 5-decylnorbornene (DecNB), have low Dk and Df due to their hydrophobicity, but have high CTE (>200 ppm / K) and low T g is low. See, for example, Japanese Patent Application Laid-Open Nos. 2016-037577 and 2012-121956.

[0006] In addition, certain polymers such as fluorinated polyethylene, polyethylene, and polystyrene are characterized by low Dk / Df, but the glass transition temperature of these polymers is much lower than 150°C, and it has been reported in the literature that they are unsuitable as organic insulating materials. Furthermore, when they contain certain substituted norbornenes substituted with polar groups such as ester or alcohol groups, they generally have low CTE and T g It has also been reported in the literature that it is possible to produce polymers with low Dk and Df. However, the incorporation of such groups results in high 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 the insulating materials of the present invention.

[0007] Therefore, there remains a demand for the development of new insulating materials that exhibit not only low dielectric constant but also ultra-high thermal properties. Summary of the Invention [Problem to be solved by the invention]

[0008] It is an object of the present invention to provide a composition comprising one or more substituted norbornene monomers and a polyfunctional monomer, which undergoes bulk polymerization to provide an insulating material with previously unattainable properties.

[0009] Further objects and scope of application of the present invention will be set forth in the detailed description below. [Means for solving the problem]

[0010] It has been discovered that by using a composition comprising one or more monomers of formula (I) described herein, a solvent, an organopalladium compound, and an activator (i.e., cocatalyst), it is possible to form 3D articles that provide previously unobtainable dielectric and thermal properties. In one embodiment, the composition may further comprise at least one multifunctional compound of formula (A1), (A2), or (A3), as described herein. Thus, the compositions of the present invention are useful in the manufacture of various electronic, optical, and optoelectronic devices. More specifically, the compositions of the present invention can be used to form various 3D and other solid objects, such as coating materials, fillers, and films.

[0011] In yet another aspect of the invention, kits are provided that include the compositions of the invention.

[0012] Embodiments according to the present invention will now be described with reference to the accompanying drawings and / or images, which show various embodiments of the invention in simplified form and for illustrative purposes only. [Brief explanation of the drawings]

[0013] [Figure 1] FIG. 1 shows differential scanning calorimeter (DSC) thermograms obtained with various embodiments of the present invention using any type of catalyst activator, as described herein. [Figure 2] FIG. 2 shows differential scanning calorimeter (DSC) thermograms obtained with various embodiments of the present invention using other types of catalyst activators, as described herein. [Figure 3] FIG. 3 shows the correlation between the dielectric loss factor (Df) and the percentage of residual monomer present in films made with various composition embodiments of the present invention. [Figure 4] FIG. 4 shows a bar graph of the dielectric loss factor (Df) at cure temperature for films produced with various composition embodiments of the present invention compared to a catalyst (e.g., Pd785) delivered in methylcyclohexane (MCH) and an activator or co-catalyst (e.g., DANFABA) delivered in ethyl acetate (EA) when the catalyst and co-catalyst were all delivered in tetrahydrofuran (THF). [Figure 5] FIG. 5 shows the ultraviolet-visible (UV-VIS) spectrum of a freestanding film made with an embodiment of the composition of the present invention. [Figure 6] FIG. 6 shows differential scanning calorimetry (DSC) thermograms obtained for an embodiment of the invention in which the catalyst contains a small amount of moisture, as described herein, and another embodiment in which the catalyst does not contain moisture. DETAILED DESCRIPTION OF THE INVENTION

[0014] Terms used in this specification have the following meanings.

[0015] The use of the articles "a," "an," and "the" is deemed to include a plurality of objects unless expressly limited to one object.

[0016] All numbers, values ​​and / or formulas expressing quantities of ingredients, reaction conditions, and the like described in this specification and the claims appended hereto reflect uncertainties of the measurements performed to arrive at those numbers, values ​​and / or formulas and, therefore, are deemed to include the term "about" unless otherwise indicated.

[0017] When a range of numbers is disclosed herein, the range is considered continuous and includes the maximum and minimum values ​​of the range, as well as all values ​​between the maximum and minimum values. When a range relates to integer values, it includes all integers between the maximum and minimum values ​​of the range. Furthermore, when multiple ranges are presented for the purpose of describing a feature or characteristic, these ranges are combinable. In other words, unless otherwise indicated, all ranges disclosed herein encompass all subranges encompassed by that range. For example, when a range is presented as "1 to 10," that range should be considered to include all subranges between the minimum value of 1 and the maximum value of 10. Examples of subranges between 1 and 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8, and 5.5 to 10.

[0018] As used herein, "hydrocarbyl" refers to a group containing carbon and hydrogen atoms, including, but not limited to, alkyl, cycloalkyl, aryl, aralkyl, alkaryl, alkenyl, etc. "Halohydrocarbyl" refers to a hydrocarbyl group in which at least one hydrogen has been replaced with a halogen. "Perhalocarbyl" is a hydrocarbyl group in which all hydrogens have been replaced with halogens.

[0019] As used herein, "alkyl" refers to a saturated, straight-chain or branched hydrocarbon substituent having the specified number of carbon atoms. Particular alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and the like. Derived expressions such as "alkoxy," "thioalkyl," "alkoxyalkyl," "hydroxyalkyl," "alkylcarbonyl," "alkoxycarbonylalkyl," "alkoxycarbonyl," "diphenylalkyl," "phenylalkyl," "phenylcarboxyalkyl," and "phenoxyalkyl" are to be construed similarly.

[0020] As used herein, "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 in the same manner.

[0021] As used herein, "perhaloalkyl" refers to an alkyl as defined above, wherein all of the hydrogen atoms of the alkyl group are replaced with halogen atoms selected from fluorine, chlorine, bromine, or iodine. Representative examples include trifluoromethyl, trichloromethyl, tribromomethyl, triiodomethyl, pentafluoroethyl, pentachloroethyl, pentabromoethyl, pentaiodoethyl, linear or branched heptafluoropropyl, heptachloropropyl, heptabromopropyl, nonafluorobutyl, nonachlorobutyl, undecafluoropentyl, undecachloropentyl, tridecafluorohexyl, tridecachlorohexyl, and the like. The derived expression "perhaloalkoxy" should be interpreted in the same way. 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 the derived expression should be interpreted in the same way.

[0022] As used herein, "acyl" is synonymous with "alkanoyl" and can be represented by the structural formula "R-CO-," where R is "alkyl" as defined herein having the specified number of carbon atoms. Additionally, "alkylcarbonyl" is synonymous with "acyl" as defined herein. In particular, "(C1-C4)acyl" refers to formyl, acetyl, or ethanoyl, propanoyl, n-butanoyl, and the like. Derived expressions such as "acyloxy" and "acyloxyalkyl" are to be construed similarly.

[0023] As used herein, "aryl" refers to substituted or unsubstituted phenyl or naphthyl. Specific examples of substituted phenyl or substituted naphthyl include o-, p-, m-tolyl, 1,2-, 1,3-, 1,4-xylyl, 1-methylnaphthyl, 2-methylnaphthyl, etc. Furthermore, "substituted phenyl" or "substituted naphthyl" includes all possible substituents defined herein or known in the art.

[0024] As used herein, "arylalkyl" refers to an aryl, as defined herein, bonded to an alkyl, as defined herein. Representative examples include benzyl, phenylethyl, 2-phenylpropyl, 1-naphthylmethyl, 2-naphthylmethyl, and the like.

[0025] As used herein, "alkenyl" refers to an acyclic, straight or branched hydrocarbon chain having the specified number of carbon atoms and containing at least one carbon-carbon double bond, including ethenyl, straight or branched propenyl, butenyl, pentenyl, hexenyl, and the like. The derived expressions "arylalkenyl" and 5- or 6-membered "heteroarylalkenyl" are construed similarly. Representative examples of such derived expressions include furan-2-ethenyl, phenylethenyl, 4-methoxyphenylethenyl, and the like.

[0026] As used herein, "heteroaryl" refers to all known aromatic radicals containing heteroatoms. Representative five-membered heteroaryl radicals include furanyl, thienyl, thiophenyl, pyrrolyl, isopyrrolyl, pyrazolyl, imidazolyl, oxazolyl, thiazolyl, isothiazolyl, and the like. Representative six-membered heteroaryl radicals include pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, and the like. Representative examples of bicyclic heteroaryl radicals include benzofuranyl, benzothiophenyl, indolyl, quinolinyl, isoquinolinyl, cinnolyl, benzimidazolyl, indazolyl, pyridofuranyl, pyridothienyl, and the like.

[0027] As used herein, the term "heterocycle" includes all known reduced heteroatoms, including known cyclic radicals. Representative five-membered heterocyclic radicals include tetrahydrofuranyl, tetrahydrothiophenyl, pyrrolidinyl, 2-thiazolinyl, tetrahydrothiazolyl, tetrahydrooxazolyl, and the like. Representative six-membered heterocyclic radicals include piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, and the like. Heterocyclic radicals include, but are not limited to, aziridinyl, azepanyl, diazepanyl, diazabicyclo[2.2.1]hebut-2-yl, triazocanyl, and the like.

[0028] "Halogen" or "halo" means chloro, fluoro, bromo, and iodo.

[0029] In the broadest sense, "substituted" can be construed to include all permissible substituents of organic compounds. In certain embodiments disclosed herein, "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, other suitable substituents known to those of ordinary skill in the art may also be used in such embodiments.

[0030] In the text, illustrations, examples, and tables of this specification, when an atom cannot satisfy a valence, it is assumed to have the appropriate number of hydrogen atoms to satisfy the valence.

[0031] As used herein, the terms "dielectric" and "insulating" are used interchangeably. Thus, a reference to an insulating material or insulating layer includes a dielectric material or layer, and vice versa. Also, as used herein, the term "organic electronic device" should be understood to include "organic semiconductor devices," particular embodiments of such devices used, for example, in the automotive industry.

[0032] As used herein, the dielectric constant (Dk) of a material refers to the ratio of the charge stored in an insulating material placed between two metal plates to the charge that can be stored when the insulating material is replaced by a vacuum or air. It is also called the electrical permittivity or dielectric constant. It is also called the relative permittivity because it is measured relative to the permittivity of free space.

[0033] "Low loss" as used herein refers to the dissipation factor (Df), which is a measure of the rate at which a vibration mode (mechanical, electrical, or electromechanical) loses energy in a dissipative system. It is the inverse of the quality factor, which indicates the "quality" or durability of the vibration.

[0034] As used herein, "derived" means that the repeating units of the polymer are polymerized (formed) from polycyclic norbornene-type monomers, such as those according to formula (I), where the resulting polymer is formed from the 2,3 double bond of the norbornene-type monomer:

[0035] [ka]

[0036] The above polymerizations are known as vinyl addition polymerizations which generally occur in the presence of organometallic compounds such as organopalladium or organonickel compounds, as will be explained in more detail below.

[0037] Thus, according to the practice of the present invention, in a film-forming composition: a) one or more olefin monomers of formula (I): [ka] (where, m is 0, 1, or 2; [ka] is a single or double bond, R1, R2, R3, and R4 are the same or different and each independently represent hydrogen, halogen, methyl, ethyl, straight-chain or branched (C3-C 16 ) alkyl, perfluoro(C1-C 12 ) alkyl, (C3-C 12 ) cycloalkyl, (C6-C 12 )bicycloalkyl, (C7-C 14 )tricycloalkyl, (C6-C 10 ) aryl, (C6-C 10 )aryl(C1-C6)alkyl, perfluoro(C6-C 10 ) aryl, perfluoro(C6-C 10 )aryl(C1-C6)alkyl, methoxy, ethoxy, straight or branched (C3-C 16 ) alkoxy, epoxy (C1-C 10 ) alkyl, epoxy (C1-C 10 )Alkyloxy(C1-C 10 ) Alkyl, Epoxy (C3-C 10 ) cycloalkyl, perfluoro(C1-C 12 ) alkoxy, (C3-C 12 ) cycloalkoxy, (C6-C 12 ) bicycloalkoxy, (C7-C 14 )tricycloalkoxy, (C6-C 10 )aryloxy, (C6-C 10 )aryl(C1-C6)alkoxy, perfluoro(C6-C 10 ) aryloxy, and perfluoro(C6-C 10 )aryl(C1-C3)alkoxy; or One of R1 and R2, together with one of R3 and R4 and the carbon atom to which they are attached, may optionally be a substituted or unsubstituted (C5-C 14 )monocyclic ring, (C5-C 14 ) bicyclic ring, or (C5-C 14 ) forms a tricyclic ring. b) 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) (Pd893); Palladium(II) bis(tricyclohexylphosphine)bis(triflate) (Pd965); 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(benzonitrile)palladium(II); Platinum(II) chloride; Platinum(II) bromide; and Platinum bis(triphenylphosphine) dichloride; c) an active agent selected from the group consisting of: Lithium tetrafluoroborate; Lithium triflate; Lithium tetrakis(pentafluorophenyl)borate; Lithium tetrakis(pentafluorophenyl)borate etherate (LiFABA); sodium tetrakis(pentafluorophenyl)borate etherate (NaFABA); Trityl tetrakis(pentafluorophenyl)borate etherate (tritylFABA); Tropylium tetrakis(pentafluorophenyl)borate etherate (tropyliumFABA); 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); and d) a solvent selected from the group consisting of water, o-xylene, p-xylene, m-xylene, benzene, fluorobenzene, 1,2-difluorobenzene, 1,3-difluorobenzene, 1,4-difluorobenzene, 1,2,4-trifluorobenzene, 1,3,5-trifluorobenzene, 1,2,3,4-tetrafluorobenzene, 1,2,4,5-tetrafluorobenzene, pentafluorobenzene, hexafluorobenzene, toluene, ethylbenzene, trifluorotoluene, pentafluoroethylbenzene, chlorobenzene, nitro Benzene, 1,4-dioxane, dimethylacetamide, dimethylformamide, diethylformamide, furan, tetrahydrofuran, diethyl ether, dimethoxyethane, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, acetone, methyl ethyl ketone, cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, ethylcyclopentane, ethylcyclohexane, dibromomethane, dichloromethane, chloroform, tetrachloromethane, 1,2-dichloroethane, and mixtures thereof.

[0038] It has been discovered that the use of a suitable solvent in the compositions of the present invention not only facilitates the delivery of catalysts and activators, but also increases the shelf life of the compositions. In other words, compositions of the present invention prepared with a suitable solvent remain stable at ambient temperatures, but when the compositions are exposed to temperatures higher than ambient temperatures, e.g., temperatures above 100°C, instantaneous bulk polymerization of the monomers contained therein occurs. In fact, this has been one of the unresolved problems in the art of bulk-polymerizable compositions, particularly when bulk-polymerizable compositions contain high concentrations of monomers, making it difficult to control the polymerization rate under thermally and photocatalytic conditions, due to the inherently short shelf life of catalysts compared to similar solution polymerization conditions.

[0039] Furthermore, as polymerization proceeds, loss of monomer mobility leads to the entrapment of residual monomers and nonvolatile oligomeric components. Nonvolatile oligomeric monomers can include dimers, trimers, tetramers, etc. The oligomers can also contain some low-molecular-weight crosslinking components, which can impart undesirable properties to the resulting film and / or solid-state composition. Thus, the presence of low-molecular-weight residual materials can lead to unfavorable properties such as low thermal decomposition temperatures, low glass transition temperatures (possibly due to plasticization), poor transparency, and increased dielectric loss factors. Therefore, highly reactive compositions must be used, and quantitative conversion of the monomers must be achieved within minutes, rather than hours as in solution polymerization.

[0040] Another significant problem in the prior art is that most palladium compounds used as catalysts are polar and do not readily dissolve or disperse in most hydrophobic norbornene monomers, such as those exemplified by the various monomers of formula (I). This slows or inhibits the rate of bulk polymerization of the monomers of formula (I). Additionally, the activators or co-catalysts described herein (e.g., DANFABA and LiFABA, described below) are salts and do not readily dissolve or disperse in the hydrophobic norbornene monomers of formula (I). This slows or inhibits the rate of bulk polymerization, as demonstrated in the comparative examples below.

[0041] It has been found that using a small amount of a low-boiling solvent to deliver the catalyst and activator (cocatalyst) can address one or more of the aforementioned unmet needs of those skilled in the art. Generally, using a small amount of solvent can dissolve the catalyst components in the monomer, increasing the polymerization rate and conversion. It has also been demonstrated that systematically changing the catalyst delivery solvent can control the polymerization rate and extend the shelf life of more reactive monomers. The choice of solvent depends on the solvent's coordination ability with the transition metal, which can then be used to control reactivity. In other words, the solvent's coordination ability can increase or decrease the catalyst's reactivity. See Chem.Eur.J.2020,26,4350-4377. It has been found that solvents with a coordination ability index (α) less than 0 are more suitable for the compositions of the present invention containing hydrophobic monomers. The coordination ability index (α) is a measure of the solvent's coordination ability with the transition metal. A lower value of α indicates a lower coordination ability. That is, solvents with a value less than 0 are generally considered non-coordinating solvents. In one embodiment, the solvent used in the composition of the present invention has a coordinating ability index (α) of about 0.1 to about 2.5. In another embodiment, the solvent used in the composition of the present invention has a coordinating ability index (α) of about 0.2 to about 2.0. As mentioned above, the amount of solvent used is generally small. The amount used can be adjusted to obtain desirable results. Generally, the amount used may be less than 5 wt % based on the total weight of the composition. For example, 1 wt %, 2 wt %, 3 wt %, or 4 wt %. In one embodiment, the amount of solvent used is about 5 wt % to about 10 wt % based on the total weight of the composition, and in another embodiment, it is about 10 wt % to about 20 wt % based on the total weight of the composition.

[0042] It should also be noted that the compositions of the present invention can be used under both thermal and photopolymerization conditions. As mentioned above, under thermal bulk polymerization conditions, the compositions undergo bulk polymerization by exposure to an appropriate temperature, generally above about 100°C, as described below. However, as described below, the polymerization temperature can be significantly reduced if the solvent mixture contains a small amount of water.

[0043] The compositions of the present invention undergo bulk polymerization upon exposure to suitable actinic radiation, as is well known to those skilled in the art. To effect photopolymerization, the compositions typically comprise an organopalladium compound, as described herein, that can be activated with a photoactivator (typically a photoacid generator). In one embodiment, examples of suitable photoactive organopalladium compounds include, but are not limited to:

[0044] [ka]

[0045] Examples of suitable photoacid generators include, but are not limited to:

[0046] [ka] [ka] [ka]

[0047] Thus, the hydrophobic monomer of formula (I) m is 0 or 1, [ka] is a single or double bond, R1, R2, R3, and R4 are the same or different and each independently represent hydrogen, straight-chain or branched (C4-C 16 ) alkyl, (C3-C 10 ) cycloalkyl, (C3-C 10 ) cycloalkenyl, (C6-C 12 )bicycloalkyl, (C6-C 12 ) aryl, and (C6-C 12 )aryl(C1-C6)alkyl; or One of R1 and R2, together with one of R3 and R4 and the carbon atoms to which they are attached, may form a substituted or unsubstituted (C5-C8) monocyclic ring, optionally containing one or more double bonds; 10 ) forming a bicyclic ring.

[0048] In one embodiment, the hydrophobic monomer of formula (I) is m is 0, [ka] is a single bond, R1, R2, R3, and R4 are the same or different and are each independently selected from the group consisting of hydrogen, n-butyl, n-hexyl, cyclohexyl, cyclohexenyl, and norbornyl.

[0049] Aryl as defined in formula (I) may include various aromatic groups known to those skilled in the art, for example, Aryl is:

[0050] [ka]

[0051] The monomers of formula (I) described herein are either known in the literature or can be prepared by any method known to those skilled in the art for the preparation of monomers of the same or similar type.

[0052] As mentioned above, the composition of the present invention may further comprise at least one polyfunctional monomer compound. Such a compound can be added to the composition of the present invention as needed. Any polyfunctional monomer compound that can facilitate the formation of a three-dimensional crosslinked structure can be used in the present invention. In one embodiment, a bifunctional monomer compound can be used as the polyfunctional monomer compound. Examples of bifunctional monomer compounds include, but are not limited to, the following:

[0053] Compounds of formula (A1): [ka] (where, b is an integer from 2 to 6, Z is a bond or R9R 10 SiOSiR 11 R 12 where R9, R 10 , R 11 and R 12 are the same or different and each independently selected from the group consisting of methyl, ethyl, and straight-chain or branched (C-C) alkyl; R5, R6, R7 and R8 are the same or different and each independently represent hydrogen, methyl, ethyl, and straight-chain or branched (C3-C 16 ) alkyl. Compounds of formula (A2): [ka] (where, R 13 , R 14 , R 15 , and R 16 are the same or different and each independently represent hydrogen, methyl, ethyl, and straight-chain or branched (C3-C 16 ) alkyl; and Compounds of formula (A3): [ka] (where, L is a bond or a methylene, ethylene, straight or branched (C3-C 16 ) alkylene, (C3-C 16 ) cycloalkylene, (C5-C8) heterocycle, (C6-C 12 ) arylene, (C5-C 12 ) heteroarylene, and -(CH2) c O(CH2) c-, c is an integer from 1 to 6, and optionally each CH2 is methyl, ethyl, straight or branched (C3-C 16 ) alkyl, and (C6-C 12 )aryl, where methylene, ethylene or (C-C 16 The hydrogen moiety on the alkylene is fluorine, trifluoromethyl, pentafluoroethyl, and straight-chain or branched perfluoro(C3-C 16 ) alkyl, R 17 , and R 18 are the same or different and each independently represent methyl, ethyl, straight-chain or branched (C3-C 12 ) alkyl, (C6-C 12 ) aryl, and (C6-C 12 )Aryl(C1-C 12 ) alkyl, optionally selected from the group consisting of methyl, ethyl or (C-C 12 The hydrogen moiety on the alkyl is fluorine, trifluoromethyl, pentafluoroethyl, and straight or branched (C3-C 12 ) perfluoroalkyl; Ar1 and Ar2 are the same or different and each independently represent (C6-C 12 ) arylene group or (C6-C 12 ) heteroarylene groups, which are optionally selected from (C1-C4) alkyl, (C1-C4) alkoxy, (C6-C 10 ) aryl, (C6-C 12 )aryloxy, (C6-C 12 )aryl(C1-C4)alkyl, and (C6-C 12 ) aryl(C1-C4) alkyloxy.

[0054] The film formed from the composition has a dielectric constant (Dk) of less than 2.4 at 10 GHz, a glass transition temperature of greater than 150°C, and a coefficient of thermal expansion (CTE) of less than 150 ppm / K.

[0055] It should be noted that the compositions of the present invention are bulk polymerizable compositions when exposed to appropriate temperature conditions. That is, when a composition of the present invention, which generally includes one or more monomers of Formula (I), optionally at least one compound of Formula (A1), (A2), or (A3), a solvent as described herein, at least one organopalladium compound, and an activator as described herein, is heated to a specific temperature, the composition undergoes bulk polymerization to form a solid object. Temperature conditions that induce bulk polymerization are contemplated herein without limitation. In one embodiment, the composition of the present invention is heated to a temperature of about 60°C to about 150°C for a sufficient time, e.g., about 1 hour to 8 hours. In another embodiment, the composition of the present invention is heated to a temperature of about 90°C to about 130°C for a sufficient time, e.g., about 1 hour to 4 hours. As described above, the organopalladium compound and the activator used to affect bulk polymerization can be dissolved in the designated solvent or monomer to form a homogeneous solution. The solution thus formed may be mixed with one or more monomers of Formula (I) and, optionally, compounds of Formula (A1), (A2), or (A3) to form a homogeneous solution. The bulk polymerization process is well known in the art and procedures well known to those skilled in the art may be used to form the films of the present invention, see, for example, U.S. Patent No. 6,825,307, incorporated herein.

[0056] In one embodiment, the film-forming composition comprises m is 0, [ka] is a single bond, R1, R2, R3, and R4 are the same or different and each comprise a monomer of formula (I) independently selected from the group consisting of hydrogen, n-butyl, n-hexyl, cyclohexyl, cyclohexenyl, and norbornyl.

[0057] Any monomer of formula (I) can be used to form the film-forming composition of the present invention. The monomer of formula (I) can be selected from the group consisting of, but not limited to:

[0058] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0059] Additionally, specific compounds within the scope of formula (A1) can be used in the film-forming composition of the present invention to achieve the desired effect. The compound of formula (A1) can be selected from the group consisting of, but not limited to:

[0060] [ka]

[0061] Certain compounds within the scope of formula (A2) can be used in the film-forming compositions of the present invention to achieve the desired effect. The compound of formula (A2) can be selected from the group consisting of, but not limited to:

[0062] [ka]

[0063] Certain compounds within the scope of formula (A3) can be used in the film-forming compositions of the present invention to achieve the desired effect. The compound of formula (A3) can be selected from the group consisting of, but not limited to:

[0064] [ka]

[0065] As described above, the film-forming composition of the present invention comprises at least one monomer of Formula (I) and, optionally, a compound of Formula (A1), (A2), or (A3). The amounts of the monomer of Formula (I) and the compound of Formula (A1), (A2), or (A3) are not particularly limited, so long as they are sufficient to form the composition of the present invention and provide the intended benefits, such as the low dielectric constant and / or low thermal / mechanical properties described herein, or other desirable properties depending on the intended end use. Thus, the molar ratio of the monomer of Formula (I) to the compound of Formula (A1), (A2), or (A3) may be from 100:0 to 90:10. In one embodiment, the molar ratio of the monomer of Formula (I) to the compound of Formula (A1), (A2), or (A3) ranges from 99:1 to 95:5, and in other embodiments, may range from 98:2 to 91:9, 97:3 to 92:8, 96:4 to 93:7, etc.

[0066] Additionally, one or more monomers of Formula (I) and one or more compounds of Formula (A1), (A2), or (A3) can also be used in the compositions of the present invention. Thus, the molar ratio of the first monomer of Formula (I) to the second monomer of Formula (I) can be 1:99 to 99:1. In one embodiment, the molar ratio of the first monomer of Formula (V) to the second monomer of Formula (V) can be in the range of 5:95 to 95:5, and in other embodiments, can be in the range of 10:90 to 90:10, 15:85 to 85:15, 20:80 to 80:20, 30:70 to 70:30, 60:40 to 40:60, 50:50, etc. Similarly, when one or more compounds of Formula (A1), (A2), or (A3) are used in the compositions of the present invention, the one or more monomers of Formula (I) can be used in any suitable amount, such as the various ratios presented herein, when applied to the compositions of the present invention.

[0067] Generally, compositions according to the present invention comprise one or more monomers of formula (I) as described above, and as will be seen below, various composition embodiments can be tailored to suit a variety of specific applications, with the various composition embodiments being selected to suit the application and provide preferred properties. Thus, in one embodiment, a composition of the present invention may comprise two or more monomers of formula (I), for example, three different monomers of formula (I), or four different monomers of formula (I), and any desired number of compounds of formula (A1), (A2), or (A3).

[0068] For example, as already discussed above, by using appropriate combinations of various monomers represented by formula (I), it is possible to obtain compositions that exhibit, among other properties, desirable low dielectric constants and thermo-mechanical properties. It is also preferable to include other compatible polymeric or monomeric materials to provide desirable low loss and low dielectric constants depending on the end use, as described in more detail below.

[0069] It has been discovered that one or more compounds of formula (A1) or (A2) or (A3) can be used to form crosslinked structures within a polymer backbone. In other words, crosslinking can occur intramolecularly (i.e., between two crosslinkable sites on the same polymer chain). This can occur statistically, and all such combinations are part of the present invention. By forming intermolecular or intramolecular crosslinks, polymers formed from the compositions of the present invention can obtain properties not previously available. For example, these can include improved thermal properties, i.e., a glass transition temperature much higher than that observed in non-crosslinked polymers of similar composition. Such crosslinked polymers also remain stable at temperatures above 350°C. High temperature stability can also be measured by thermogravimetric analysis (TGA) methods well known to those skilled in the art. One such measurement is the temperature at which a polymer loses 5% of its weight (T d5 As can be seen from the specific examples below, the T of the polymers formed from the compositions of the present invention d5 Generally, the T of the polymer formed from the composition of the present invention can range from about 270°C to about 320°C. d5 The temperature is in the range of about 280°C to about 300°C.

[0070] It should also be noted that the use of one or more compounds of formula (A1), (A2), or (A3) is not required to achieve crosslinking of the polymer formed from the composition. That is, when the monomer of formula (I) includes one or more separate monomers containing unsaturated double bonds that can function as inter- or intramolecular crosslinkable monomers with other polymer chains, as described above. Thus, in one embodiment, a composition is provided that includes at least two monomers of formula (I), at least one of which contains a double bond. All such combinations are part of the present invention.

[0071] The crosslinked polymers formed from the compositions of the present invention can be thermoset, which can provide additional advantages in certain applications where thermoplastic polymers are undesirable, such as in applications involving high temperatures, where the polymeric material may flow and is not suitable for high temperature environments, including millimeter wave radar antennas, as specifically contemplated herein.

[0072] As described below, the compositions of the present invention can be formed into films. Films formed from the compositions of the present invention exhibit a previously unobtainable combination of low dielectric constant and high glass transition temperature. Thus, in one embodiment, a film formed from a composition of the present invention has a dielectric constant (Dk) of 2.0 to 2.38 at 10 GHz, a glass transition temperature of about 160°C to about 350°C, and a coefficient of thermal expansion (CTE) of about 100 ppm / K to about 140 ppm / K. In another embodiment, a film formed from a composition of the present invention has a dielectric constant (Dk) of 2.10 to 2.30 at 10 GHz, a glass transition temperature of about 190°C to about 350°C, and a coefficient of thermal expansion (CTE) of about 100 ppm / K to about 140 ppm / K. In another embodiment, a film formed from a composition of the present invention has a glass transition temperature of about 220°C to about 350°C.

[0073] It has been found that the low dielectric constant of films formed from the compositions of the present invention can be further improved by including one or more fillers. The fillers can be organic or inorganic. Any of the well-known fillers can be used in the present invention, provided that they provide the intended benefits.

[0074] Therefore, in one embodiment, the film-forming composition according to the present invention contains an inorganic filler. Suitable inorganic fillers have a coefficient of thermal expansion (CTE) lower than that of the film formed from the composition of the present invention. Examples of inorganic fillers include, but are not limited to, 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 (hard and heavy); carbonates such as magnesium carbonate, dolomite, and dolomite; sulfates such as calcium sulfate, barium sulfate, ammonium sulfate, and calcium sulfite; silicates such as talc, mica, clay, glass fiber, calcium silicate, montmorillonite, and bentonite; borates such as zinc borate, barium metaborate, aluminum borate, calcium borate, and sodium borate; carbon black; carbon such as carbon fiber; iron powder; copper powder; aluminum powder; zinc oxide; molybdenum sulfide; boron fiber; potassium titanate; and lead zirconate.

[0075] In another embodiment, the film-forming composition according to the present invention further comprises an organic filler. The organic filler may be a synthetic resin, typically in powder form, or in other suitable forms or polymers. Examples of polymer fillers include, but are not limited to, poly(α-methylstyrene), poly(vinyl-toluene), and copolymers of α-methylstyrene and vinyl-toluene. Further examples of synthetic resin powders include powders of various thermosetting or thermoplastic resins, such as alkyd resins, epoxy resins, silicone resins, phenolic resins, polyesters, acrylic and methacrylic resins, acetal resins, polyethylene, polyethers, polycarbonates, polyamides, polysulfones, polystyrenes, polyvinyl chlorides, fluororesins, polypropylenes, and ethylene-vinyl acetate copolymers, or powders of copolymers of these resins. Further examples of organic fillers include aromatic or aliphatic polyamide fibers, polypropylene fibers, polyester fibers, and aramid fibers.

[0076] In one embodiment, the filler is an inorganic filler, which can effectively reduce the coefficient of thermal expansion. Furthermore, heat resistance can be improved. In one embodiment, the inorganic filler is silica. This can reduce the coefficient of thermal expansion and improve dielectric properties. Various silica fillers known in the art can be used in the compositions of the present invention. Examples of silica fillers include, but are not limited to, fused silica, including fused spherical silica, fused ground silica, and crystalline silica. In one embodiment, fused silica is used. It has been found that the use of spherical silica allows for the formation of compositions containing the maximum silica loading, e.g., 80% by weight. The use of an appropriate silica filler can result in particularly excellent dielectric properties. Generally, the amount of filler can vary from about 5% by weight to 80% by weight or more. In one embodiment, the filler content in the composition is about 30-80% 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, the balance between dielectric properties and the coefficient of thermal expansion can be improved. In another embodiment, the amount of filler in the composition is about 40-70% by weight based on the total solids content of the composition.

[0077] 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 a single molecule. Examples of the silane compound include silanes having an alkyl group such as ethyltriethoxysilane, propyltriethoxysilane, and butyltriethoxysilane (alkylsilanes); silanes having a phenyl group such as phenyltriethoxysilane, benzyltriethoxysilane, and phenethyltriethoxysilane; silanes having a styryl group such as styryltrimethoxysilane, butenyltriethoxysilane, propenyltriethoxysilane, and vinyltrimethoxysilane (vinylsilane); silanes having an acrylic group or a methacrylic group such as γ-(methacryloxypropyl)trimethoxysilane; silanes having an amino group such as γ-aminopropyltriethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, and N-phenyl-γ-aminopropyltriethoxysilane; and silanes having an epoxy group such as γ-(3,4-epoxycyclohexyl)ureidotriethoxysilane. Silanes having a mercapto group, such as γ-mercaptopropyltrimethoxysilane, can also be used. One or more of the aforementioned silane compounds may be used in combination.

[0078] It should also be noted that when inorganic fillers are used as fillers, they 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. It has been found that treatment with a "non-polar silane compound" can eliminate or reduce the adverse effects on dielectric properties. As used herein, "non-polar silane compound" refers to a silane compound that does not contain a polar substituent. A polar substituent is a group that can hydrogen bond or ionically dissociate. Examples of polar substituents include -OH, -COOH, -COOM, NH3, and NR4. + A -, -CONH2, etc., where M is a cation such as an alkali metal, alkaline earth metal, or quaternary ammonium salt, R is H or an alkyl group of up to 8 carbon atoms, and A is an anion such as a halogen atom.

[0079] In one embodiment, the surface of the filler is modified with a vinyl group. The vinyl group is a non-polar substituent that provides the low dielectric constant required for the present invention, so it is preferable to use a vinyl group. For example, when modifying the surface of the filler with a vinyl group, a vinylsilane can be used. Specific examples of vinylsilane are as described above.

[0080] Generally, the average particle size of the filler ranges from about 0.1 to 10 μm. In one embodiment, it is about 0.3 to 5 μm, and in another embodiment, it is about 0.5 to 3 μm. The average particle size is defined as the average diameter of the particles measured by light scattering. When two or more fillers are used, the average particle size of at least one of the fillers falls within the aforementioned 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 adversely affect the dielectric properties is reduced, easily improving the dielectric properties. Furthermore, when the average particle size of the filler is suitably small, it becomes easy to polymerize and form a film from the composition of the present invention. The film / sheet thus formed has the uniform thickness and flatness required for various applications.

[0081] The composition of the present invention may contain components other than those described above. These components include coupling agents, flame retardants, mold release agents, antioxidants, etc. Examples of coupling agents include, but are not limited to, silane coupling agents such as vinyl silane, acrylic and methacrylic silane, styryl silane, and isocyanatosilane. The use of a silane coupling agent can improve the adhesion between the composition of the present invention and a substrate, etc.

[0082] Examples of flame retardants include, but are not limited to, phosphorus-based flame retardants such as trixylenyl phosphate, xylenyl phosphate, 10(2,5-dihydroxyphenyl)-10H-9-oxa-10phosphaphenanthrene-10-oxide, halogen-based flame retardants such as brominated epoxy resins, and inorganic flame retardants such as aluminum hydroxide and magnesium hydroxide.

[0083] The compositions of the present invention may further comprise one or more compounds or additives that have utility such as adhesion promoters, surface leveling agents, synergists, plasticizers, cure accelerators, free radical initiators, and the like. The use of one or more thermal free radical generators can accelerate the crosslinking of polymers formed from the compositions of the present invention to produce crosslinked polymers that exhibit further improved thermal properties. For example, the glass transition temperature (T g ) and the temperature at which a 5 wt% weight loss of the polymer occurs (T d5 ) will be higher. T g The increase in T may range from about 10°C to 50°C. In one embodiment, the T g The T of the polymer can be increased by 20 to 40°C using an appropriate amount of thermal free radical generator. d5 The temperature will also rise by about 3 to 10 degrees Celsius.

[0084] Any compound that forms radicals when exposed to heat can be used for this purpose, with general examples including peroxides, peracids, azo compounds, N-alkoxyamines, N-acyloxyamines, etc., and specific examples of thermal free radical generators including, but not limited to, benzoyl peroxide, dicumyl peroxide (DCP), m-chloroperbenzoic acid, methyl ethyl ketone peroxide, azobisisobutyronitrile (AIBN), 1-phenyl-3,3-dipropyltriazene, 1-(phenyldiazenyl)pyrrolidine, 1-(phenyldiazenyl)piperidine, 1-(phenyldiazenyl)azepane, etc.

[0085] The thermal free radical generator can be used in various amounts in the composition of the present invention as long as it produces the intended effect. Generally, the amount ranges from about 2 parts per hundred parts of resin (pphr) to 10 pphr or more. In one embodiment, the amount of photoradical generator used is about 3 pphr to 6 pphr.

[0086] Examples of the film-forming composition of the present invention can be selected from the group consisting of, but not limited to:

[0087] 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (HexTD), palladium(II) bis(tricyclohexylphosphine) diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); tetracyclododecene (TD), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), palladium(II) bis(tricyclohexylphosphine) diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); 2,2'-bi(bicyclo[2.2.1]heptan-5-ene) (NBANB), palladium(II) bis(tricyclohexylphosphine) diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); 5-cyclohexylbicyclo[2.2.1]hept-2-ene (CyHexNB), palladium(II) bis(tricyclohexylphosphine) diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), 2,2′-bi(bicyclo[2.2.1]heptan-5-ene) (NBANB), 1,3-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3-tetramethyldisiloxane (NBC2DMSC2NB), palladium(II) bis(tricyclohexylphosphine) diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); 3a,4,7,7a-tetrahydro-1H-4,7-methanoindene (DCPD), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), palladium(II) bis(tricyclohexylphosphine) diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); 3a,4,7,7a-tetrahydro-1H-4,7-methanoindene (DCPD), 5-phenethylbicyclo[2.2.1]hept-2-ene (PENB), palladium(II) bis(tricyclohexylphosphine) diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); 5-cyclohexylbicyclo[2.2.1]hept-2-ene (CyHexNB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), palladium(II) bis(tricyclohexylphosphine) diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); 5-cyclohexylbicyclo[2.2.1]hept-2-ene (CyHexNB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), bicyclo[2.2.1]hepta-2,5-diene (NBD), palladium(II) bis(tricyclohexylphosphine) diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); 1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (TD), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), palladium(II) bis(tricyclohexylphosphine) diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); 5-(cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyclohexeneNB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), palladium(II) bis(tricyclohexylphosphine) diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); 1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (TD), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), bicyclo[2.2.1]hepta-2,5-diene (NBD), palladium(II) bis(tricyclohexylphosphine) diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); and 5-Cyclohexylbicyclo[2.2.1]hept-2-ene (CyhexNB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), 3a,4,4a,5,8,8a,9,9a-octahydro-1H-4,9:5,8-dimethanocyclopenta[b]naphthalene (CPD3), palladium(II) bis(tricyclohexylphosphine) diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA).

[0088] It should be noted that the composition of the present invention can be formed into any shape or form and is not particularly limited to a film. Thus, in one embodiment, the composition of the present invention can be formed into a sheet. The thickness of the sheet is not particularly limited, but considering its use as a dielectric material, it is 0.01 to 0.5 mm. In another embodiment, the thickness is approximately 0.02 to 0.2 mm. Sheets formed in this manner generally do not have fluidity at room temperature (25°C). The sheet may be provided on an optional support layer or alone. Examples of support layers include polyimide films, and other well-known peelable films can also be used.

[0089] As described above, the film / sheet formed by the present invention has excellent dielectric properties. Quantitatively, the relative permittivity, i.e., the dielectric constant (Dk), of the film / sheet at a frequency of 10 GHz is approximately 2.0 to 2.38. The dielectric loss tangent at a frequency of 10 GHz is approximately 0.0003 to 0.005, and in another embodiment, approximately 0.0004 to 0.003. The composition of the present invention can be used in a variety of devices requiring such low dielectric constant materials, such as millimeter-wave radar and antennas. See, for example, Japanese Patent Application Publication Nos. 2018-109090 and 2003-216283. Antennas generally consist of an insulator and a conductor layer (e.g., copper foil). The composition or sheet of the present invention can be used as part or the entire insulator. Antennas using the composition or sheet of the present invention as part or the entire insulator have excellent high-frequency characteristics and reliability (durability).

[0090] The conductor layer of the antenna is formed, for example, from a metal having a desired conductivity. A circuit is formed on the conductor layer using a known circuit processing method. Examples of conductors that form the conductor layer include various conductive metals such as gold, silver, copper, iron, nickel, aluminum, and alloy metals thereof. The conductor layer can be formed by known methods, such as vapor deposition, electroless plating, or electrolytic plating. Alternatively, a metal foil (e.g., copper foil) may be pressure-bonded by thermal compression bonding. The metal foil that forms the conductor layer is a metal foil commonly used for electrical connections. In addition to copper foil, various metal foils such as gold, silver, nickel, and aluminum can be used. An alloy foil containing a significant portion (e.g., 98% by weight or more) of the metal may also be used. Among the metal foils, copper foil is commonly used. The copper foil may be rolled copper foil or electrolytic copper foil.

[0091] As mentioned above, the compositions of the present invention are generally used directly to form films or sheets. However, in one embodiment, the compositions may contain a small amount of solvent to dissolve the catalyst as described herein. The compositions of the present invention may also be used as low-molecular-weight varnish-type materials for specific applications. In such cases, an appropriate amount of a suitable solvent may be added to maintain the solids content of the composition at about 10 to 70% by weight during polymerization. Solvents suitable for forming the solution may be used as a single solvent or a mixture of solvents as required for the application.

[0092] In another aspect of the present invention, a film-forming kit is provided. The composition of the present invention is dispersed within the kit. Thus, in one embodiment, a kit is provided that includes dispersed therein one or more olefin monomers of formula (I) described herein, one or more compounds of formula (A1), (A2), or (A3) described herein, an organopalladium compound described herein, and an activator described herein. In one embodiment, the kit of the present invention includes one or more monomers of formula (I) and one or more compounds of formula (A1), (A2), or (A3) in combination to achieve a desired result or for an intended purpose.

[0093] In another aspect of one embodiment of the present invention, the kits of the present invention undergo bulk polymerization only when exposed to an appropriate temperature for a time sufficient to form a polymer film. In other words, the compositions of the present invention, as described herein, are poured onto a surface or substrate, encapsulated thereon, and upon exposure to an appropriate heat treatment, the monomers undergo polymerization to form a solid polymer in the form of a film or sheet.

[0094] Generally, as noted above, such polymerizations may be carried out at various temperatures, e.g., by heating to 90°C, followed by 110°C, and finally to 150°C, for a sufficient time, e.g., 5 minutes to 2 hours, at each temperature step, with further heating to above 150°C for various periods, e.g., 5 minutes to 15 minutes, if necessary. Polymerization may be carried out at a single temperature between about 100°C and 250°C for a sufficient time, e.g., 1 hour to 3 hours, or longer. By practicing the present invention, it is possible to obtain a polymerized film on a substrate that is a substantially uniform film. The thickness of the film can be adjusted as desired, as specifically noted above, and generally ranges from 50 to 500 microns or more.

[0095] Various well-known heating methods can be used to ensure the flatness of the sheet and suppress unintended shrinkage during sheet production. For example, the sheet is initially heated at a relatively low temperature and then gradually increased in temperature. To ensure the flatness, the sheet may be pressed with a flat plate (glass plate) before heating, or may be heated while being pressed with a flat plate. The pressure used for such pressing may be, for example, 0.1 to 8 MPa, and in another embodiment, may be in the range of about 0.3 to 5 MPa.

[0096] In one embodiment of the present invention, the kit described herein comprises a composition comprising two or more monomers of formula (I) and two or more compounds of formula (A1), (A2), or (A3). Any of the monomers of formula (I) or compounds of formula (A1), (A2), or (A3) described herein can be used in this embodiment in any preferred amount depending on the nature of the intended use.

[0097] In one embodiment, the kits described herein include various exemplary compositions as described above.

[0098] In yet another aspect of the present invention, there is further provided a method of forming a film for the manufacture of various optoelectronic and / or automotive devices, including: forming a homogeneous transparent composition comprising a combination of one or more monomers of Formula (I) with one or more compounds of Formula (A1) or (A2) or (A3); an organopalladium compound as described herein; an activator as described herein, and optionally a filler as described herein; coating or pouring the composition onto a suitable substrate to form a film; It consists of heating the film to an appropriate temperature to induce polymerization of the monomers.

[0099] In the step of coating the composition of the present invention onto a suitable substrate to form a film, the substrate may be coated using one of the coating methods described herein or known to those skilled in the art, such as spin coating. Other suitable coating methods include, but are not limited to, spray coating, doctor blading, meniscus coating, inkjet coating, and slot coating. The mixture may also be poured onto the substrate to form a film. The substrate is not particularly limited as long as it is suitable, and may be a substrate used in electrical, electronic, or optoelectronic devices, such as a semiconductor substrate, a ceramic substrate, or a glass substrate.

[0100] The coated substrate is then heated, i.e., baked, for example, at a temperature of about 50°C to about 150°C for about 1 minute to 180 minutes (temperature and time are adjustable) to promote bulk polymerization. In one embodiment, the substrate is baked at a temperature of about 100°C to about 120°C for 120 minutes to 180 minutes. In another embodiment, the substrate is baked at a temperature of about 110°C to about 150°C for 60 minutes to 120 minutes.

[0101] The electrical properties of the films thus formed were evaluated using any method known to those skilled in the art. For example, the dielectric constant (Dk) or dielectric constant and dielectric loss tangent were measured using a cavity resonator dielectric constant measurement device (manufactured by AET, JIS C 2565 standard) at a frequency of 10 GHz. The coefficient of thermal expansion (CTE) was measured using a thermodynamic analyzer (Seiko Instruments, SS 6000) under the following conditions: a measurement sample size of 4 mm (width) x 40 mm (length) x 0.1 mm (thickness), a measurement temperature range of 30 to 350°C, and a heating rate of 5°C / min. The linear expansion coefficient was measured between 50°C and 100°C. Generally, films formed according to the present invention exhibit excellent dielectric properties and can be tailored to desired dielectric properties as described herein.

[0102] In one embodiment of the present invention, there is provided a film or sheet obtained by bulk polymerization of the composition as described herein, and in another embodiment, there is provided an electronic device comprising the film / sheet of the present invention as described herein.

[0103] In another aspect of the present invention, it has been discovered that adding a small amount of water to a catalyst can form a more reactive system, further increasing the polymerization rate and providing a polymerization product with improved properties. Accordingly, in one embodiment of the present invention, the composition comprises a catalyst solution containing at least about 5% by weight of water. In yet another embodiment of the present invention, the composition comprises a catalyst solution containing about 5% to about 20% by weight of water. In another example of the present invention, the composition comprises a catalyst solution containing about 6% to about 10% by weight of water.

[0104] As can be seen from the following specific examples, by adding a certain amount of water to the catalyst system, it is possible to accelerate the polymerization of the composition of the present invention at a significantly lower temperature. That is, by adding about 8% by weight of water to the catalyst system, it is possible to lower the polymerization initiation temperature to 30°C. An example of a significant reduction in the polymerization initiation temperature is shown in Figure 6, which compares the polymerization initiation point of a composition containing about 7.6% by weight of water with a water-free composition. It can be seen that the addition of water lowers the polymerization initiation temperature to 30°C.

[0105] Furthermore, it has been found that aging the aqueous catalyst solution further improves the activity of the catalyst. Thus, in some embodiments of the present invention, the catalyst solution is aged for at least about 10 days. In other embodiments of the present invention, the catalyst solution is aged for about 10 to about 18 days. In some other embodiments of the present invention, the catalyst solution is aged for about 14 to 18 days. In one embodiment, the aqueous catalyst solution is aged for less than 10 days or for more than 20 days, depending on the type of catalyst used, all of which are within the scope of the present invention.

[0106] 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 methods fall within the scope of the general preparation methods described above and are further illustrative thereof. The examples are for illustrative purposes only and are not intended to limit the scope of the present invention. In the examples and herein, the ratio of monomer to catalyst is a molar ratio.

[0107] Example (general) The following abbreviations are used herein to describe some of the compounds, instruments and / or methods used to describe certain embodiments of the present invention.

[0108] HexTD-2: hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene; TD: tetracyclododecene; BuNB-5-butylbicyclo[2.2.1]hept-2-ene; PENB: 5-phenethylbicyclo[2.2.1]hept-2-ene; PhNB: 5-phenylbicyclo[2.2.1]hept-2-ene; DecNB: 5-decylbicyclo[2.2.1]hept-2-ene; HexNB: 5-hexylbicyclo[2.2.1]hept-2-ene; NBANB: 2,2'-bi(bicyclo[2.2.1]heptan-5-ene); CyHexNB: 5-cyclohexylbicyclo[2.2.1]hept-2-ene; DCPD: 3a,4,7,7a-tetrahydro-1H-4,7-methanoindene; NBD: bicyclo[2.2.1]hepta-2,5-diene; TDD: 1,4,4a,5,8,8a-hexahydro-1,4:5,8-dimethanonaphthalene; NBC2DMSC2NB: 1,3-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3-tetramethyldisiloxane; CPD3: 3a,4,4a,5,8,8a,9,9a-octahydro-1H-4,9:5,8-dimethanocyclopenta[b]naphthalene; Pd785: Palladium(II) bis(tricyclohexylphosphine) diacetate; DANFABA: dimethylanilinium tetrakis(pentafluorophenyl)borate; DCP: dicumyl peroxide; Rhodorsil-2074: Tolylcumyliodonium-tetrakispentafluorophenylborate; UV-CATA: Iodonium, diphenyl-, 4,4'-di-C 10-13 - alkyl derivatives, tetrakis(2,3,4,5,6-pentafluorophenyl)borate; EA: ethyl acetate; THF: tetrahydrofuran; CH: cyclohexane; MCH: methylcyclohexane; TFT: trifluorotoluene; GPC: gel permeation chromatography; M w :Weight average molecular weight; GC: gas chromatography; DSC: differential scanning calorimetry; TGA: thermogravimetric analysis; TMA: Thermodynamic analysis; UV-VIS spectra: Ultraviolet-visible light spectrometer.

[0109] The various monomers used herein are commercially available or can be readily prepared by the procedures described in US Pat. No. 9,944,818.

[0110] Examples 1 to 6 For each of Examples 1 to 6, catalyst stock solutions were prepared in sealed glass vials under a nitrogen atmosphere by dissolving Pd785 (0.031 g, 0.039 mmol) in the following catalyst transfer solvents (3.2 g): Example 1: THF, Example 2 and Example 5: toluene, Example 3: CH, Example 4: MCH, and Example 6: TFT. Cocatalyst stock solutions were prepared in sealed glass vials under a nitrogen atmosphere by dissolving DANFABA (0.176 g, 0.22 mmol) in the cocatalyst transfer solvent THF or EA (3.2 g). The desired amount of catalyst or cocatalyst solution was extracted with a syringe and added to the monomer. A sample of HexTD (2.44 g, 9.98 mmol) was mixed with a Pd785 solution dissolved in the desired solvent (0.07–0.08 g, 0.00098 mmol) and a DANFABA solution dissolved in the desired solvent (0.08 g, 0.0055 mmol). The molar ratio of monomer / Pd785 / DANFABA in the mixture was approximately 10,000 / 1 / 5.6 for all mixtures, regardless of the type of catalyst transfer solvent.

[0111] The compositions of Examples 1 to 6 prepared above were heated in sealed glass vials on a hot plate in an air atmosphere at 110°C for 3 hours. The formed polymer was extracted with 5 to 10 g of THF by ultrasonic treatment for 1 hour. The M of the extracted polymer was w To determine the degree of curing, the THF extract was analyzed by GPC using THF as the solvent. The extracted portion was also analyzed by GC to confirm the content of unreacted HexTD monomer. GC analysis of the unreacted monomer content measured the percentage of HexTD monomer converted to polymer during heating (conversion rate, %). After THF extraction, the insoluble material remaining in the glass vial was dried in a vacuum oven at 110°C for 20 hours to measure the percentage of THF-insoluble polymer (insoluble fraction, %), which indicates the degree of curing.

[0112] The catalyst and co-catalyst used, the solvent, and the M of the THF-soluble portion of the cured material wThe percentage of insoluble matter and polymer conversion of HexTD monomer catalyzed by Pd785 / DANFABA are summarized in Table 1. According to the data shown in Table 1, the use of a polar solvent such as THF to deliver the Pd785 catalyst or the DANFABA co-catalyst significantly increased the polymer conversion of the monomer and the M of the resulting polymer. w (Examples 1 and 2). When Pd785 was transferred in a nonpolar solvent such as toluene (Example 5), CH (Example 3), MCH (Example 4), or TFT (Example 6) in combination with EA as a cocatalyst transfer solvent, the conversion and molecular weight of HexTD increased.

[0113] [Table 1]

[0114] Examples 7 to 13 As summarized in Table 2, Pd785 and DANFABA solutions were prepared exactly as described in Examples 1-6, with minor modifications to the solvent, and then mixed with HexTD to form the compositions of Examples 7-13. These compositions were then individually heated in sealed glass vials on a hot plate under ambient conditions at 110 °C. The time it took for the liquid mixture to gel (gel time) was recorded. The results are summarized in Table 2. As can be seen from the results shown in Table 2, the data are consistent with those observed in Examples 1-6. That is, the polymer conversions shown in Table 1 correspond to the polymerization rates measured by gel time. The gel time of each of Examples 7-13 was affected by the catalyst or cocatalyst delivery solvent. Polar solvents such as THF used to deliver Pd785 or DANFABA decreased the polymerization rate, as observed by increased gel time (Examples 7-9). Nonpolar solvents increased the polymerization rate, as observed by decreased gel time (Examples 10-13).

[0115] [Table 2]

[0116] Examples 14 to 17 (DSC measurement) Catalyst and cocatalyst stock solutions were prepared in sealed glass vials under a nitrogen atmosphere using mixtures of Pd785 (0.015 g, 0.019 mmol) dissolved in 1.6 g of TD (Examples 15 and 16), Pd785 (0.03 g, 0.038 mmol) dissolved in 3.2 g of THF (Example 14), Pd785 (0.031 g, 0.039 mmol) dissolved in 3.2 g of MCH (Example 17), DANFABA (0.174 g, 0.22 mmol) dissolved in 3.2 g of THF (Examples 14 and 15), and DANFABA (0.174 g, 0.22 mmol) dissolved in 3.2 g of EA (Examples 16 and 17).

[0117] A mixture of TD (1.92 g, 12 mmol) and BuNB (1.2 g, 7.98 mmol) prepared in a glass vial was used in Examples 14-17, respectively. To this mixture was added a solution of Pd785 dissolved in the desired catalyst transfer solvent, as previously described, and DANFABA dissolved in the desired co-catalyst transfer solvent, as previously described. The molar ratio of monomer / Pd785 / DANFABA in the mixture was maintained at approximately 10500 / 1 / 5 for all compositions, regardless of the type of catalyst transfer solvent.

[0118] A small amount of the mixture was heated from 20°C to 150°C at a rate of 5°C / min and used for DSC measurements. The exotherm generated during polymerization was measured. Approximately 1 g of each of the mixtures was placed in an aluminum pan and heated on a hot plate at 110°C for 3 hours in an air atmosphere. The weight of the material was measured before and after heating to determine the weight loss rate. Similarly, approximately 2 g of each of the remaining mixtures was heated in a sealed glass vial at 110°C. The time required for the liquid composition to gel (gel time) was recorded. The results are summarized in Table 3.

[0119] The observed exotherm was lowest (82 J / g) and the gel time was even longer (60 seconds) when the catalyst and cocatalyst were all transferred in THF (Example 14). When Pd785 was transferred in MCH and DAFABAEA, a high exotherm (237 J / g), short gel time (45 seconds), and lowest weight loss (20%) were recorded, consistent with the results observed in Examples 1 to 13. Polar solvents such as THF were found to have low polymerization efficiency, while nonpolar solvents such as MCH were found to have high polymerization efficiency. Figure 1 shows a DSC thermograph, which shows that the use of THF as the catalyst and cocatalyst transfer solvent resulted in an increase in peak temperature, while the use of MCH to transfer Pd785 and EA to transfer DAFABA resulted in a decrease in peak temperature. The gel time was longest in Comparative Example 1, which did not use any catalyst or cocatalyst transfer solvent. The DSC thermograph in Figure 1 shows that in Comparative Example 1, polymerization began at a higher temperature of approximately 88°C, as evidenced by the later onset of the exotherm. The results of Examples 14-17 and Comparative Example 1 demonstrate that the use of a catalyst transfer solvent is advantageous not only for more efficiently dissolving or dispersing the catalyst and cocatalyst in the monomer, but also for obtaining polymers with higher molecular weights and superior properties. Furthermore, as can be seen from the data presented in Table 3, nonpolar solvents such as MCH are more advantageous than polar solvents such as THF in terms of polymerization efficiency.

[0120] [Table 3]

[0121] Examples 18 to 22 (DSC measurement) The Pd785 catalyst stock solutions prepared in Examples 14-17 were used in Examples 18-21. In Example 22, a Pd785 stock solution was prepared in TFT, and LiFABA was used as the cocatalyst. Pd785 (0.032 g, 0.041 mmol) was dissolved in 3.2 g of TFT, and LiFABA (0.174 g, 0.2 mmol) was dissolved in 3.2 g of THF.

[0122] A mixture of TD (1.92 g, 12 mmol) and BuNB (1.2 g, 7.98 mmol) was prepared in a glass vial and used in Examples 18-22, respectively. To each of these compositions, a Pd785 solution (0.16 g, 0.0019 mmol) dissolved in the desired catalyst transfer solvent was added, followed by a DANFABA solution (0.16 g, 0.01 mmol) dissolved in the desired cocatalyst transfer solvent, as described above. The monomer / Pd785 / DANFABA or LiFABA molar ratio of the compositions was maintained at approximately 10500 / 1 / 5.3 in all examples, regardless of the catalyst transfer solvent.

[0123] A portion of the composition was heated from 20°C to 250°C at a rate of 5°C / min and used for DSC measurements. The heat generated during polymerization was measured. Approximately 1 g of each of the compositions was placed in an aluminum pan and heated on a hot plate at 110°C for 3 hours in an air atmosphere. The weight of the material was measured before and after heating to determine the weight loss rate. Similarly, approximately 2 g of each of the remaining mixtures was heated in a sealed glass vial at 110°C. The time required for the liquid mixture to gel (gel time) was recorded. The results are summarized in Table 4.

[0124] [Table 4]

[0125] The polymerization efficiency, measured by the weight loss rate, gel time, and exotherm generated in the Pd785 / LiFABA system (Example 22), exhibits the same behavior as that observed with the Pd785 / DANFABA system in Examples 14-17, although the effect is less pronounced. However, the DSC thermograms shown in Figure 2 clearly demonstrate that the polymerization temperature is lower when Pd785 is delivered using nonpolar solvents such as MCH or TFT, while LiFABA is delivered with EA. Comparative Example 2 exhibited a 100% weight loss rate after 3 hours of heating at 100°C, indicating that no gel formed during the curing step and that polymerization of the monomer did not occur under these conditions. The absence of an exotherm during DSC measurement of the composition of Comparative Example 2 further confirmed the absence of polymerization. The results of Examples 18-22 and Comparative Example 2 demonstrate that the use of an appropriate catalyst delivery solvent is advantageous not only for more efficient dissolution or dispersion of the catalyst and cocatalyst in the monomer, but also for obtaining polymers with excellent film-forming properties, among other physical properties.

[0126] Examples 23 to 28 Stock solutions of Pd785 and DANFABA were prepared according to the procedures set forth in Examples 14-17. Subsequently, various compositions were prepared according to the procedures of Examples 14-17, using NBANB (Examples 23 and 24), CyHexNB (Examples 25 and 26), and TD (Examples 27 and 28) as the monomer and various solvents, as summarized in Table 5. The molar ratio of monomer / Pd785 / DANFABA was maintained at approximately 10,000 / 1 / 5 in each of Examples 23-28. To obtain weight loss data, the compositions were cured in open aluminum pans at 110°C for 3 hours. The mixtures were also cured in sealed glass vials at 110°C to observe gelation times. Table 5 summarizes the results obtained for Examples 23-28. The polymerizations using MCH for delivery of Pd785 and EA for delivery of DANFABA were again found to be advantageous compared to the polymerizations using THF for delivery of Pd785 and DANFABA, in terms of polymerization efficiency measured by the weight loss (monomer loss) during 3 hours of curing at 110 °C in open aluminum pans or the time taken for gelation (solid polymer formation) at 110 °C in sealed glass vials.

[0127] [Table 5]

[0128] Examples 29 to 37 (Shelf life studies) Various compositions were prepared according to the procedures set forth in Examples 14-22. In Examples 29-37, the monomers used were TD and BuNB in ​​a molar ratio of 60:40. Other solvents were used to deliver the catalyst and cocatalyst, as summarized in Tables 6 and 7. The compositions prepared in glass vials were stored at room temperature and the viscosity was visually observed. Viscosity increases were described as non-viscous, weakly viscous, viscous, gum, soft film, or film, and the degree of viscosity or thermal cure at room temperature was estimated. A good pot-life was considered if the mixture remained non-viscous, weakly viscous, or viscous enough to form a film when poured onto a curing substrate. The results are summarized in Table 6 (cocatalyst LiFABA) and Table 7 (cocatalyst DANFABA). The compositions containing LiFABA as a cocatalyst (Examples 29-33) generally exhibited superior pot-life compared to DANFABA (Examples 34-37). This observation is consistent with the DSC thermograms shown in Figure 2 (LiFABA) and Figure 1 (DANFABA), which show that the composition containing LiFABA as a cocatalyst begins to cure (exotherm) at approximately 70°C (Figure 2), whereas the composition containing DANFABA as a cocatalyst begins to cure (exotherm) at approximately 30°C (Figure 1). The choice of catalyst and cocatalyst delivery solvent also affected service life. Using THF to deliver the catalyst and cocatalyst extended service life, while using TFT or MCH shortened service life.

[0129] [Table 6]

[0130] [Table 7]

[0131] Example 38 A stock solution of Pd785 (1 wt%) and LiFABA (5 wt%) was prepared using THF as the solvent. PENB (5.95 g, 30 mmol) was then mixed with the Pd785 solution (0.24 g, 0.003 mmol) and LiFABA solution (0.15 g, 0.009 mmol). The molar ratio of monomer:Pd785:LiFABA was approximately 10,000:1:3. This composition was doctor-bladed onto glass substrates and cured in an oven at 80 °C, 110 °C, 120 °C, and 130 °C for 1 h to produce films approximately 100–300 μm thick. The temperature at which 5 wt% of the film was lost (T) was measured using TGA at a heating rate of 10 °C / min under a nitrogen atmosphere. d5 ) were measured. The results showed that the films still contained residual monomer due to insufficient curing or less than 100% conversion of the monomer to polymer. The dielectric constant (Dk) and dielectric loss factor (tan δ or Df) were measured for the various films at a frequency of 10 GHz. Additionally, approximately 0.1–0.2 g of films produced at various curing temperatures were extracted with THF (6–8 g) at 30°C for 60 minutes to remove any unreacted monomer present in the films. The THF extracts were analyzed by GC to determine the residual monomer content of the films, and the percentage of PENB monomer converted to polymer films was calculated. The data presented in Table 8 are the conversion (amount of residual monomer present in the film), TGA, and the residual monomer content. d5 The data presented in Table 8 show that there is a correlation between residual monomer and low dielectric loss factor (Df). Figure 3 shows the relationship between residual monomer and Df. The conversion (%) is calculated based on the amount of residual monomer remaining in the film. From the data presented in Table 8, it can be seen that the higher the residual monomer, the lower the T d5 It can be seen that Df decreases as the residual monomer content increases.

[0132] This Example 38 shows that it is important to use appropriate conditions for bulk polymerization to achieve maximum conversion of monomers and improve thermal and dielectric properties.

[0133] [Table 8]

[0134] Example 39 Pd785 (1 wt%) in THF or MCH and DANFABA (5 wt%) in THF or EA were prepared in sealed vials. Two compositions were prepared by adding Pd785 / THF and DANFABA / THF to HexNB (3.56 g, 21.2 mmol) or Pd785 / MCH and DANFABA / EA to HexNB (3.56 g, 21.2 mmol). The molar ratio of monomer:Pd785:DANFABA was maintained at approximately 10,000:1:5. The compositions were doctor-bladed onto glass substrates and cured at 80 °C, 100 °C, and 120 °C for 1 h, respectively. Low dielectric loss factors (Df) were measured at 10 GHz. Figure 4 shows that the Df values ​​were even lower when Pd785 was delivered in MCH and DANFABA in EA compared to when the catalyst and cocatalyst were delivered entirely in THF.

[0135] Examples 40 to 45 Pd785 and DANFABA stock solutions were prepared according to the procedures specified in Examples 14 to 17, using MCH as the Pd785 solvent and EA as the DANFABA solvent. Then, Example 40 (CyHexNB / BuNB, 60 / 40 molar ratio), Example 41 (TD / BuNB, 60 / 40 molar ratio), Example 42 (CyHexNB / BuNB / NBD, 50 / 40 / 10 molar ratio), Example 43 (TD / BuNB / NBD, 50 / 40 / 10 molar ratio), Example 44 (CyHexNB / BuNB / CPD3, 50 / 40 / 10 molar ratio), and Example 45 (CyHexNB / BuNB / CPD3, 50 / 40 / 10 molar ratio) were prepared using 4 pphr of DCP as a thermal radical initiator. The molar ratio of monomer / Pd785 / DANFABA in each composition was maintained at approximately 10,000 / 1 / 5. The compositions were poured onto glass substrates and doctor-bladed to form rectangles of approximately 10 cm x 6 cm, followed by curing at 110°C for 3 hours to form rectangular films of approximately 200-500 μm thickness. The films were further treated at approximately 120-150°C for 3-6 hours under vacuum to remove residual monomer. The rectangular films were cut into smaller rectangles to measure electrical properties such as dielectric constant (Dk) and dielectric loss factor (Df) at 10 GHz frequency, as well as TMA. The glass transition temperature (T) of the films prepared by the procedures specified herein was g ), the temperature at which 5% of the film weight is lost (T d5 The thermal decomposition temperature, coefficient of thermal expansion (CTE), Dk, and Df measured by the method described above are summarized in Table 9.

[0136] [Table 9]

[0137] The film has a high T g , high T d5In addition, when a second curing route was used to remove residual monomers by adding a thermal free radical generator such as DCP, as in Example 45, Df was further reduced to 0.001 at 10 GHz compared to Example 44, which did not use a second curing route to remove residual monomers.

[0138] Example 46 A series of compositions were prepared by mixing Pd785 (1 wt % in THF or MCH), Rhodorsil-2074 (approximately 5.5 wt % in THF, EA, or BuNB), and UV-CATA (approximately 7 wt %) with BuNB (3 g, 20 mmol). The molar ratio of BuNB to Pd785 was set to 10,000:1 (0.002 mmol of Pd785), and the molar ratio of BuNB to Rhodorsil-2074 or UV-CATA was set to 10,000:4 (0.008 mmol of Rhodorsil-2274 or UV-CATA). Each composition (1 g) was cured on a hot plate in an aluminum pan (under air) at 110 °C for 2 hours. The final weight of the formed film was measured to calculate the amount of monomer lost during curing. The weight loss rate or monomer loss rate is an indicator of the efficiency of the curing process when different solvents are used to deliver the catalyst and cocatalyst. The weight loss data are summarized in Table 10. The data show that the catalyst and cocatalyst are less reactive when delivered in a coordinating solvent such as THF, whereas delivering Pd785 in a non-coordinating solvent such as MCH increases the cure efficiency.

[0139] The shelf-life stability of the compositions was evaluated at room temperature. The compositions underwent slow polymerization, gradually converting to a viscous material and eventually forming a gum or film. The compositions were useful for film formation if they remained pourable despite the increased viscosity. However, once the compositions formed a gum or film, they were no longer useful. Viscous, weakly viscous, and highly viscous solutions were considered pourable. Table 11 summarizes the shelf-life of the compositions of Example 46, demonstrating that the catalyst or co-catalyst delivery solvent can affect shelf-life. UV-CAT as a co-catalyst exhibited superior shelf-life stability to ARhordorsil-2074. MCH for delivering Pd785 and EA for delivering UV-CATA exhibited the highest shelf-life stability (2 weeks) and the highest cure efficiency with the lowest weight loss during cure (69% monomer converted to film, 31% weight loss).

[0140] [Table 10]

[0141] [Table 11]

[0142] Example 47 A series of compositions were prepared by mixing Pd520 (0.9 wt % in THF, EA, or BuNB) and Rhordorsil-2074 (approximately 5.5 wt % in THF or EA) with BuNB (3 g, 20 mmol). The molar ratio of BuNB to Pd520 was maintained at 10,000:1 (0.001 mmol of Pd520), and the molar ratio of BuNB to Rhordorsil-2074 was maintained at 10,000:4 (0.016 mmol of Rhordorsil-2074). 1 g of each of these compositions was placed in an aluminum pan and subjected to 3 J / cm irradiation at 365 nm. 2 After irradiation, all compositions were converted to viscous films or gums, demonstrating photocurability.

[0143] The shelf-life stability of the photocurable compositions was evaluated at room temperature under yellow light to prevent photoreaction. Gradual thermal polymerization of the mixture resulted in the development of viscosity and eventual formation of a gum or film. The composition was useful for film formation if it remained pourable despite the increased viscosity. However, once the composition formed a gum or film, it was no longer useful. Viscous, weakly viscous, and highly viscous solutions were considered pourable. Table 12 summarizes the shelf-life of the composition of Example 47, demonstrating that the use of a coordinating solvent for the catalyst or cocatalyst in these photocurable compositions can affect their shelf-life stability. The use of a coordinating solvent, such as THF, to deliver Rhodosil-2074 can enhance the shelf-life stability of the photocurable compositions.

[0144] [Table 12]

[0145] Example 48 A mixture of Pd785 (0.039 g, 0.005 mmol) and LiFABA (0.13 g, 0.015 mmol) was mixed with THF (4.97 g), and 0.1 g of this mixture was added to HexNB (8.92 g, 53.1 mmol). The molar ratio of HexNB to Pd785 was set to 52100:1 (Pd785 0.001 mmol), and the molar ratio of HexNB to LiFABA was set to 52100:3 (LiFABA 0.003 mmol). The solution was sonicated at room temperature for 90 minutes and filtered through a 0.2 μm PTFE filter. The solution was doctor-bladed onto a glass substrate and cured at 110 °C for 3 hours under a nitrogen atmosphere to obtain a 140 μm thick film. The UV-VIS spectrum of this freestanding film is shown in Figure 5. A transparency (%T) of over 90% was obtained in the wavelength range of 400-800 nm, which is close to the expected maximum %T of about 92%. Therefore, the films produced by the method described in this invention are suitable for optical applications where highly transparent films are required.

[0146] Examples 49 to 52 A 1 wt% solution of Pd785 (0.03 g) was prepared by dissolving it in anhydrous THF (3.2 g). A portion of this solution (1.01 g) was mixed with distilled water (0.083 g) to prepare a Pd785 / water / THF mixture in a glass vial, with the water content of the mixture adjusted to approximately 7.6 wt%. The mixture was then sealed with a septum cap. LiFABA (0.174 g) was dissolved in anhydrous THF (3.2 g) or anhydrous EA (3.2 g) to prepare an approximately 5 wt% LiFABA solution in a glass vial, with the vial sealed with a septum cap. TD (1.92 g, 12 mmol) and BuNB (1.2 g, 8 mmol) were mixed in a glass vial (TD / BuNB, molar ratio 60 / 40). LiFABA (0.16 g) and the Pd785 (0.16 g) solution were added to the monomer mixture. Regardless of the type of catalyst transfer solvent, the monomer / Pd785 / LiFABA molar ratio of the compositions in all examples was maintained at approximately 10,000 / 1 / 5. The aqueous Pd785 solutions were used fresh (fresh) for less than one hour after preparation or aged for 16 days (aged) to allow for Pd785 transformation due to reaction with water present in the medium. Small mixture samples (approximately 0.8 g / 1 g) were heated to 110 °C in glass vials, and the time it took for the liquid mixture to become solid (gelation time) was recorded for each mixture. The compositions of Examples 49–52 are summarized in Table 13, including Examples 18 and 20, in which no water was added to the Pd785 / THF solution. The gelation times clearly demonstrate increased polymerization efficiency when water was present in the Pd785 / THF catalyst transfer medium. Polymerization efficiency further increased when the Pd785 / THF / water mixture was aged. As shown in Figure 6, which compares the DSC plots of Examples 18 and 49, the presence of water in the Pd785 / THF catalyst transfer medium accelerates the polymerization efficiency by initiating the exotherm at a lower temperature.

[0147] [Table 13]

[0148] Examples 53-57 (Shelf life studies) Pd785 was dissolved in various solvents (dichloromethane, toluene, xylene, or THF) to form 1 wt% solutions. A portion of the Pd785 / THF solution (3 g) was mixed with distilled water (0.3 g, 10 wt% water in the catalyst system) and aged at room temperature for 15 days. LiFABA was dissolved in anhydrous EA to form a 5 wt% solution. HexNB (3.56 g, 20 mmol) was mixed with the Pd785 solution (0.16 g) and LiFABA solution (0.1 g). The molar ratio of monomer / Pd785 / LiFABA in each composition was maintained at approximately 10,000 / 1 / 3. These mixtures were stored at ambient temperature of approximately 23°C, and the shelf life of these compositions was assessed by visually classifying the viscosity as viscous, slightly viscous, viscous, or gel. All compositions were viscous immediately after preparation and maintained this state for a minimum of 1 day (24 hours) before the viscosity began to increase. Tables 15 and 16 summarize these observations. A composition was considered to have a good shelf life if it could be poured onto a substrate such as glass and form a film (i.e., it was not gelled). The shelf life of a composition varied depending on the Pd785 catalyst transfer solvent and its coordinating ability, as described by the coordinating ability index (α), which is a measure of the solvent's ability to coordinate with transition metals (see Chem. Eur. J. 2020, 26, 4350-4377). Solvents with high coordinating ability for transition metals, such as THF (α = -0.3), had a long shelf life, while solvents with low coordinating ability for transition metals, such as toluene (α = -1.3), had a shorter shelf life. Dichloromethane is generally considered a polar, non-coordinating solvent with an α value of -1.8 (see J. Am. Chem. Soc. 1998, 110, 5293), but due to the presence of a lone pair of chlorine atoms, it can coordinate to transition metals (see J. Am. Chem. Soc. 1989, 111, 3762-3764). The shelf-life results listed in Table 14 suggest that dichloromethane acts as a non-coordinating solvent. Therefore, the shelf-life of the compositions of the present invention can be adjusted by selecting a suitable Pd785 catalyst transfer solvent. The Pd785 / THF / water composition is an exception, suggesting that such catalyst systems may be converted to more active species in the presence of water during aging, as previously described.

[0149] Approximately 1 g of each composition from Examples 53, 56, and 57 was heated to 120°C on a hot plate in a sealed glass vial, and the time it took for the mixture to gel was recorded. The composition of Example 53 gelled in 3 minutes and 30 seconds. The composition of Example 56 gelled in 5 minutes, and the composition of Example 57 gelled in 3 minutes and 15 seconds. As shown in Table 14, the presence of water in the catalyst transfer medium increases polymerization efficiency while decreasing shelf life. The reactivity of the composition of Example 57 was similar to that of Example 53 but not to that of Example 56, despite the use of more coordinating THF in the catalyst transfer medium in both Examples 56 and 57. The presence of water in the catalyst transfer medium in Example 57 did not result in a lower degree of coordination of the catalyst, because water has a higher degree of coordination for metal transition due to the presence of the lone electron pair of oxygen. The alpha value of water is set to 0 in the coordination order, indicating a higher degree of coordination for transition metals than THF. This difference in catalytic activity is likely due to the generation of more active catalytic species in situ by the reaction of water with Pd785. The catalytic activity of Pd785 / THF / water (gel time of 3 minutes 15 seconds at 120 °C for Example 57) is similar to that of Pd785 / CH2Cl2 (gel time of 3 minutes 30 seconds for Example 53), yet the shelf life of Example 57 is at least 2 times longer than that of Example 53 (see Table 15).

[0150] [Table 14]

[0151] [Table 15]

[0152] Example 58 The compositions of Examples 53, 55, 56, and 57 were spread onto glass substrates by doctor blade to produce rectangular films of approximately 100-160 μm and cured at 130°C for 2 hours under a nitrogen atmosphere. The film of Example 53 was 115 μm thick, the film of Example 55 was 110 μm thick, the film of Example 56 was 160 μm thick, and the film of Example 57 was 150 μm thick. The glass transition temperatures (T g ) and coefficient of thermal expansion (CTE) were measured by thermomechanical analysis (TMA), and the 5 wt% decomposition temperature (T d5 The dielectric constant (Dk) and dielectric loss factor (Df) were measured by thermogravimetric analysis (TGA), and the tensile strength, Young's modulus, and elongation at break (ETB) were measured by an Instron. The dielectric constant (Dk) and dielectric loss factor (Df) were also measured at 10 GHz. The results are summarized in Table 16. The results suggest that films produced using compositions that modulate polymerization efficiency and shelf life (i.e., by modifying the catalyst reactivity by changing the catalyst delivery solvent) can produce films with not only low dielectric constants and low dielectric loss factors, but also improved thermomechanical properties when sufficiently high polymerization temperatures and long reaction times are applied. The examples clearly demonstrate the benefits obtained by practicing the present invention. As described herein, modulating the catalyst reactivity and shelf life of the compositions of the present invention does not affect the thermal, mechanical, or electrical properties of the polymer films formed therefrom.

[0153] [Table 16]

[0154] Comparative Example 1 A mixture of TD (3.85 g, 24.0 mmol) and BuNB (2.4 g, 16 mmol) was prepared in a glass vial and used for polymerization. Pd785 (0.0031 g, 0.0039 mmol) and DANFABA (0.016 g, 0.02 mmol) were added to this mixture. The molar ratio of the monomer / Pd785 / DANFABA mixture was approximately 10250 / 1 / 5.1, similar to the catalyst used in Examples 14-17. Some of the powder settled to the bottom of the vial, indicating that the catalyst and cocatalyst were not completely dissolved without the catalyst carrier solvent. A sample of this composition was analyzed by DSC. Approximately 1 g of this mixture was placed in an aluminum pan and heated on a hot plate at 110 °C in air for 3 hours. The weight of the material before and after curing was measured to determine the weight loss rate. Similarly, approximately 2 g of the mixture was heated in a sealed glass vial at 110 °C. The time it took for the liquid mixture to become a gel (gel time) was recorded, and the results are shown in Table 3.

[0155] Comparative Example 2 A mixture of TD (3.85 g, 24 mmol) and BuNB (2.4 g, 16 mmol) was prepared in a glass vial and used for polymerization. Pd785 (0.0031 g, 0.0039 mmol) and LiFABA (0.017 g, 0.02 mmol) were added to this mixture. The molar ratio of the monomer / Pd785 / LiFABA mixture was approximately 10250 / 1 / 5.1, similar to the catalyst used in Examples 18-22. Some of the powder settled to the bottom of the vial, indicating that the catalyst and cocatalyst were not completely dissolved without the catalyst carrier solvent. A sample of this composition was analyzed by DSC. Approximately 1 g of this mixture was placed in an aluminum pan and heated on a hot plate at 110 °C in air for 3 hours. The weight of the material before and after curing was measured to determine the weight loss rate. Similarly, approximately 2 g of the mixture was heated in a sealed glass vial at 110 °C. The time it took for the liquid mixture to become a gel (gel time) was recorded and the results are shown in Table 4.

[0156] Comparative Example 3 Pd785 (0.031 g, 0.039 mmol) was dissolved in approximately 3.2 g of TESNB, which corresponds to the catalytic transfer medium. DANFABA (0.174 g, 0.22 mmol) was dissolved in 3.2 g of TESNB, which corresponds to the cocatalytic transfer medium. TD (1.6 g, 9.98 mmol), BuNB (1.2 g, 7.98 mmol), and TESNB (0.24 g, 1.11 mmol) were mixed in a glass vial, and Pd785 (0.16 g) in TESNB and DANFABA (0.14 g) in TESNB were added. The total amount of TESNB in ​​the mixture was 0.54 g (1.99 mmol). The molar ratio of the TD / BuNB / TESNB mixture was 50 / 40 / 10. Approximately 1 g of this mixture was placed in an aluminum pan and heated on a hot plate at 110 °C in air for 3 hours. The material was weighed before and after curing, revealing a weight loss of 18%. Similarly, approximately 2 g of the mixture was heated in a sealed glass vial at 110 °C. The time it took for the liquid mixture to gel (gel time) was 150 seconds. This Comparative Example 3 demonstrates that polar monomers, such as TESNB, can be used as catalyst transfer media instead of catalyst transfer solvents. The measured properties of a TD / BUNB / TESNB (50 / 40 / 10) film fabricated using MCH to transfer Pd785 and EA to transfer DANFABA are shown in Table 9. While the glass transition temperature and CTE were not negatively affected by the introduction of polar monomers (e.g., TESNB) instead of MCH and EA, the dielectric loss factor (Df) of this composition increased significantly (0.0082). This indicates that polar monomers capable of dissolving catalyst or cocatalyst components are not necessarily beneficial for properties such as dielectric loss factor.

[0157] Although the present invention has been described by the above examples, the present invention is not limited to the examples and encompasses the general scope disclosed in this specification. Various modifications and embodiments can be made without departing from the spirit of the present invention.

Claims

1. A film-forming composition comprising: a) one or more olefin monomers selected from the group consisting of: 【Chemistry 21】 b) an organopalladium compound selected from the group consisting of: Palladium(II) bis(tricyclohexylphosphine) dichloride; Palladium(II) bis(tricyclohexylphosphine) dibromide; Palladium(II) bis(tricyclohexylphosphine)diacetate (Pd785); and Palladium(II) bis(tricyclohexylphosphine)bis(trifluoroacetate); c) an active agent selected from the group consisting of: Tolylcumyliodonium-tetrakispentafluorophenylborate; 4,4'-di(C 10 -C 13 )alkyldiphenyliodonium tetrakis(2,3,4,5,6-pentafluorophenyl)borate; Lithium tetrakis(pentafluorophenyl)borate etherate (LiFABA); and Dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); and d) a solvent selected from the group consisting of: water, toluene, trifluorotoluene, tetrahydrofuran, ethyl acetate, cyclohexane, methylcyclohexane, and mixtures thereof; And, A film-forming composition that exhibits shelf-life stability at 25°C for at least 1 hour and that undergoes bulk polymerization upon exposure to a suitable temperature above 100°C.

2. A compound of formula (A1): 【Chemistry 4】 (where, b is an integer from 2 to 6, Z is a bond or R 9 R 10 SiOSiR 11 R 12 where R 9 , R 10 , R 11 and R 12 are the same or different and each independently represent methyl, ethyl, and straight-chain or branched (C 3 -C 6 ) alkyl; R 5 , R 6 , R 7 and R 8 are the same or different and each independently represent hydrogen, methyl, ethyl, and straight-chain or branched (C 3 -C 16 ) alkyl; and Compound of formula (A2): 【Transformation 5】 (where, R 13 , R 14 , R 15 , and R 16 are the same or different and each independently represent hydrogen, methyl, ethyl, and straight-chain or branched (C 3 -C 16 ) alkyl; 2. The film-forming composition of claim 1, further comprising a compound selected from the group consisting of:

3. The film-forming composition of claim 1, wherein the monomer is selected from the group consisting of: 【Chemistry 22】

4. 3. The film-forming composition of claim 2, wherein the compound of formula (A1) is selected from the group consisting of: 【Transformation 8】

5. The compound of formula (A2) is 【Chemistry 9】 The film-forming composition according to claim 2, wherein

6. The film-forming composition according to claim 1 , further comprising an inorganic filler.

7. 10. The film-forming composition of claim 1 selected from the group consisting of: 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (HexTD), palladium(II) bis(tricyclohexylphosphine)diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); 1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (TD), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), palladium(II) bis(tricyclohexylphosphine) diacetate (Pd785), and lithium tetrakis(pentafluorophenyl)borate etherate (LiFABA); 2,2′-bi(bicyclo[2.2.1]heptan-5-ene) (NBANB), palladium(II) bis(tricyclohexylphosphine)diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); 5-cyclohexylbicyclo[2.2.1]hept-2-ene (CyHexNB), palladium(II) bis(tricyclohexylphosphine)diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); 1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (TD), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), palladium(II) bis(tricyclohexylphosphine)diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); 5-phenethylbicyclo[2.2.1]hept-2-ene (PENB), palladium(II) bis(tricyclohexylphosphine)diacetate (Pd785), and lithium tetrakis(pentafluorophenyl)borate etherate (LiFABA); 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), palladium(II) bis(tricyclohexylphosphine)diacetate (Pd785), and tolylcumyliodonium-tetrakispentafluorophenylborate; 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), palladium(II) bis(tricyclohexylphosphine)diacetate (Pd785), and 4,4'-di(C10-C13)alkyldiphenyliodonium tetrakis(2,3,4,5,6-pentafluorophenyl)borate; 5-cyclohexylbicyclo[2.2.1]hept-2-ene (CyHexNB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), palladium(II) bis(tricyclohexylphosphine)diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); 5-cyclohexylbicyclo[2.2.1]hept-2-ene (CyHexNB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), bicyclo[2.2.1]hepta-2,5-diene (NBD), palladium(II) bis(tricyclohexylphosphine)diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); 1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (TD), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), palladium(II) bis(tricyclohexylphosphine)diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); 1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (TD), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), bicyclo[2.2.1]hepta-2,5-diene (NBD), palladium(II) bis(tricyclohexylphosphine)diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); and 5-Cyclohexylbicyclo[2.2.1]hept-2-ene (CyhexNB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), 3a,4,4a,5,8,8a,9,9a-octahydro-1H-4,9:5,8-dimethanocyclopenta[b]naphthalene (CPD3), palladium(II) bis(tricyclohexylphosphine)diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA).

8. A film-forming kit comprising a composition comprising: a) one or more olefin monomers selected from the group consisting of: 【Chemistry 23】 b) an organopalladium compound selected from the group consisting of: Palladium(II) bis(tricyclohexylphosphine) dichloride; Palladium(II) bis(tricyclohexylphosphine) dibromide; Palladium(II) bis(tricyclohexylphosphine)diacetate (Pd785); Palladium(II) bis(tricyclohexylphosphine)bis(trifluoroacetate); and c) an active agent selected from the group consisting of: Tolylcumyliodonium-tetrakispentafluorophenylborate; 4,4'-di(C 10 -C 13 )alkyldiphenyliodonium tetrakis(2,3,4,5,6-pentafluorophenyl)borate; Lithium tetrakis(pentafluorophenyl)borate etherate (LiFABA); and Dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); and d) a solvent selected from the group consisting of: water, toluene, trifluorotoluene, tetrahydrofuran, ethyl acetate, cyclohexane, methylcyclohexane, and mixtures thereof; And, A film-forming kit, wherein the composition exhibits shelf-life stability at 25°C for at least 1 hour and undergoes bulk polymerization upon exposure to a suitable temperature above 100°C.

9. 9. The kit of claim 8, wherein the monomer of formula (I) is selected from the group consisting of: 【Chemistry 24】

10. A compound of formula (A1): 【Chemistry 14】 (where, b is an integer from 2 to 6, Z is a bond or R 9 R 10 SiOSiR 11 R 12 where R 9 , R 10 , R 11 and R 12 are the same or different and each independently represent methyl, ethyl, and straight-chain or branched (C 3 -C 6 ) alkyl; R 5 , R 6 , R 7 and R 8 are the same or different and each independently represent hydrogen, methyl, ethyl, and straight-chain or branched (C 3 -C 16 ) alkyl; and Compound of formula (A2): 【Chemistry 15】 (where, R 13 , R 14 , R 15 , and R 16 are the same or different and each independently represent hydrogen, methyl, ethyl, and straight-chain or branched (C 3 -C 16 ) alkyl; 9. The kit of claim 8, further comprising a compound selected from the group consisting of:

11. The kit of claim 10, wherein the compound of formula (A1) is selected from the group consisting of: 【Chemistry 17】

12. The compound of formula (A2) is [Chemistry 18] The kit of claim 10, wherein

13. The kit of claim 8 , wherein the filler is an inorganic filler.

14. The kit of claim 8, wherein the kit is selected from the group consisting of: 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (HexTD), palladium(II) bis(tricyclohexylphosphine)diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); 1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (TD), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), palladium(II) bis(tricyclohexylphosphine) diacetate (Pd785), and lithium tetrakis(pentafluorophenyl)borate etherate (LiFABA); 2,2′-bi(bicyclo[2.2.1]heptan-5-ene) (NBANB), palladium(II) bis(tricyclohexylphosphine)diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); 5-cyclohexylbicyclo[2.2.1]hept-2-ene (CyHexNB), palladium(II) bis(tricyclohexylphosphine)diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); 1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (TD), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), palladium(II) bis(tricyclohexylphosphine)diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); 5-phenethylbicyclo[2.2.1]hept-2-ene (PENB), palladium(II) bis(tricyclohexylphosphine)diacetate (Pd785), and lithium tetrakis(pentafluorophenyl)borate etherate (LiFABA); 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), palladium(II) bis(tricyclohexylphosphine)diacetate (Pd785), and tolylcumyliodonium-tetrakispentafluorophenylborate; 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), palladium(II) bis(tricyclohexylphosphine)diacetate (Pd785), and 4,4'-di(C10-C13)alkyldiphenyliodonium tetrakis(2,3,4,5,6-pentafluorophenyl)borate; 5-cyclohexylbicyclo[2.2.1]hept-2-ene (CyHexNB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), palladium(II) bis(tricyclohexylphosphine)diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); 5-cyclohexylbicyclo[2.2.1]hept-2-ene (CyHexNB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), bicyclo[2.2.1]hepta-2,5-diene (NBD), palladium(II) bis(tricyclohexylphosphine)diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); 1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (TD), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), palladium(II) bis(tricyclohexylphosphine)diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); 1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (TD), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), bicyclo[2.2.1]hepta-2,5-diene (NBD), palladium(II) bis(tricyclohexylphosphine)diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); and 5-Cyclohexylbicyclo[2.2.1]hept-2-ene (CyhexNB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), 3a,4,4a,5,8,8a,9,9a-octahydro-1H-4,9:5,8-dimethanocyclopenta[b]naphthalene (CPD3), palladium(II) bis(tricyclohexylphosphine)diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA).

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