Polycyclic olefin polymers containing olefin functional groups for forming low-loss films with improved thermal properties

Abstract

In accordance with embodiments of the present invention, copolymers and terpolymers of various polycyclic olefin monomers are included, where at least one monomer contains other unpolymerized ethylene bonds. In another aspect of the invention, embodiments of a composition containing the polymers of the invention, a cross-linking agent, a free radical initiator, a tackifier, and more than one suitable additive are provided. The compositions of the present invention are capable of forming various three-dimensional insulators, such as films, when exposed to suitable high temperatures. Objects formed from the compositions of the present invention exhibit low dielectric constant, low loss characteristics, and very high thermal characteristics, which have not been achieved so far. The compositions of the present invention may also contain one or more organic or inorganic filler materials that provide improved thermomechanical properties in addition to very low dielectric properties. The composition of the present invention can be used in various applications, including as an insulating material for millimeter wave radar antennas, and the like.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of U.S. Provisional Application No. 63 / 404,335, filed on September 7, 2022, the entire contents of which are incorporated by reference into this specification. Technical Field

[0003] According to an embodiment of the present invention, it generally relates to a polymer formed by two or more polycyclic olefin monomers, wherein at least one monomer contains a free olefin functional group. More specifically, the present invention relates to a polymer comprising two or more substituted norbornene derivatives, wherein at least one monomer comprises at least one free olefin functional group. An embodiment of the present invention also relates to a composition, which comprises such a polymer, as well as a tackifier, a crosslinking agent, a free radical initiator and one or more additives. The composition of the present invention can be easily formed into a film, which can be used as a prepreg for a low-loss thermosetting material and a copper-clad laminate, not only exhibiting low dielectric constant and low loss characteristics, but also exhibiting extremely high thermal properties. For example, a film formed by the composition of the present invention generally exhibits a high glass transition temperature (about 150°C to 280°C), and also exhibits a low dielectric constant (about 2.2 to 3.0 at a frequency of 10 GHz), a low dielectric loss factor (about 0.001 to 0.002 at a frequency of 10 GHz) and a thermal expansion coefficient (CTE) as low as 50 ppm / K. Thus, the polymers and compositions of the present invention can be used as insulating materials in a variety of applications, including electromechanical devices used in the manufacture of various automotive parts. Background Art

[0004] The importance of insulating materials with low dielectric constant (Dk) and low loss (also known as dielectric loss factor (Df)) for printed circuit boards used in electrical appliances, automotive parts and other applications is well known in the art. Generally, in most such devices, suitable insulating materials must have a dielectric constant of less than 3 and a low loss of less than 0.002 at high frequencies (e.g., above 10 GHz). In addition, organic dielectric materials have attracted much attention due to their advantages such as ease of manufacture.

[0005] However, when such materials are used as copper-clad laminates in printed circuit boards, they need to have a high glass transition temperature (T g), low CTE, low Dk / Df, high peel strength to copper and good reliability during high temperature storage. When making layered structures, the ability to form prepregs (compounded with glass cloth), B-stage ability (generating uncrosslinked or partially crosslinked material layers) and film fusing ability are also important. Most commercially available materials in this field do not achieve all of these properties, especially low Dk / Df and high glass transition temperatures above 150°C.

[0006] There are also huge technical challenges in developing insulating materials that meet all the requirements. One challenge is that such materials need to exhibit a low coefficient of thermal expansion (CTE), preferably less than 50ppm / K, due to concerns about copper peeling. Another challenge is that such materials need to exhibit a very high glass transition temperature (Tg), given the processing conditions used when manufacturing printed circuit boards and the harsh conditions that equipment may encounter, such as millimeter wave radar antennas used in automobiles and other terminal equipment used in 5G devices. g ), preferably above 150°C or even above 250°C.

[0007] Although films formed 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, these films exhibit high CTE (>200 ppm / K) and low T g For example, refer to JP2016037577A and JP2012121956A.

[0008] It is also reported in the literature that some polymers (e.g., fluorinated polyethylene, polyethylene, and polystyrene) have low Dk / Df, but all of these polymers exhibit extremely low glass transition temperatures (possibly well below 150°C), and are therefore not suitable as organic insulating materials. In addition, it is also reported in the literature that when certain substituted norbornenes substituted with polar groups such as ester or alcohol groups are added, they can generally generate materials with low CTE and high T g However, due to the polarizability of such groups in electromagnetic fields (especially at high frequencies), the addition of such groups will increase Dk and Df. Therefore, such norbornene substituted with polar groups is not suitable for forming the insulating material described in this specification.

[0009] U.S. Patent No. 10,897,818B2 discloses a composition comprising a modified polyphenyl containing a vinyl benzyl terminal group, a crosslinking agent such as 1,3,5-triallyl-1,3,5-triazine-2,4,6-trione (also known as triallyl isocyanurate (TAIC)), and an epoxy compound. However, although the composition described therein has a relatively high T of about 200-230°C, g , but still exhibited a high Dk of about 3.7 and a Df of about 0.005.

[0010] Therefore, there is still a need to develop new insulating materials that not only have low dielectric properties but also have very high thermal properties.

[0011] There is also a need to develop materials that can form thermoset films rather than thermoplastic films. That is, thermosets are generally cross-linked structures that are more stable at high temperatures and do not have the heat fluidity of thermoplastics. Summary of the invention

[0012] Therefore, an object of the present invention is to provide a polymer and a composition derived therefrom, the polymer comprising two or more monomers substituted with norbornene, one of which monomers comprises at least one olefin functional group, the composition being capable of forming an insulating material having hitherto unattainable properties.

[0013] Hereinafter, other objects and further applicable scope of the present invention will be described in detail.

[0014] Effects of the Invention

[0015] Surprisingly, it has been found that by using a polymer comprising two or more polycyclic olefin monomers of the general formula (I) and (II) described in the present specification (wherein the monomer of the general formula (II) is contained in an amount of at least 4 mol %), a polymer can be formed which can be used in the composition described in the present specification to form various three-dimensional objects including films, thereby providing dielectric and thermal properties that have not been achieved to date.

[0016] In another aspect, the present invention also provides a film, a composite material, or a prepreg comprising the composition of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Hereinafter, embodiments according to the present invention will be described with reference to the following drawings and / or images. When drawings are provided, they are simplified portions of various embodiments of the present invention and are for illustration purposes only.

[0018] Figure 1is a graph showing dielectric reliability studies of some exemplary films formed from the compositions of the present invention at a storage temperature of 125° C. over a period of 1000 hours and compared with comparative compositions available in the art as described in this specification.

[0019] Figure 2 is a graph showing a dielectric reliability study of some exemplary films formed from other compositions according to embodiments of the present invention at a storage temperature of 125° C. over a period of 1000 hours.

[0020] Figure 3 is a graph showing the dielectric stability of some exemplary films formed from compositions according to embodiments of the present invention over a period of 1400 hours at 85°C / 85% relative humidity (RH).

[0021] Figure 4 Graphs illustrating the effect of resin fluidity when a copper clad laminate is formed using a composition according to an embodiment of the present invention, the composition comprising a combination of a high molecular weight polymer and a low molecular weight polymer in different amounts. DETAILED DESCRIPTION

[0022] The terms used in this manual have the following meanings:

[0023] Unless otherwise specified, the articles "a / an" and "the" used in this specification include plural referents.

[0024] Since all numbers, values ​​and / or expressions relating to amounts of ingredients, reaction conditions, etc. used in this specification and the claims appended hereto are subject to various measurement uncertainties encountered in obtaining these values, they should be understood as being modified by the term "about" in all cases unless otherwise specified.

[0025] The numerical ranges disclosed in this specification are continuous, including the minimum and maximum values ​​of the range, and each value between the minimum and maximum values. In addition, when a range refers to an integer, each integer between the minimum and maximum values ​​of the range is included. Moreover, when multiple ranges are provided to describe characteristics or features, these ranges can be combined. In other words, unless otherwise specified, all ranges disclosed in this specification should be understood to cover all any sub-ranges therein. For example, the specified range of "1 to 10" should be deemed to include all any sub-ranges between the minimum value 1 and the maximum value 10. Exemplary sub-ranges of the range 1 to 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8, 5.5 to 10, etc.

[0026] As used herein, "hydrocarbyl" refers to a group containing carbon atoms and hydrogen atoms, non-limiting examples of which are alkyl, cycloalkyl, aryl, aralkyl, alkaryl, and alkenyl. The term "halohydrocarbyl" refers to a hydrocarbyl in which at least one hydrogen is replaced by a halogen. The term perhalohydrocarbyl refers to a hydrocarbyl in which all hydrogens are replaced by halogens.

[0027] The expression "alkyl" as used in this specification refers to a saturated, straight or branched hydrocarbon substituent having a specified number of carbon atoms. Specific alkyl groups include methyl, ethyl, n-propyl, isopropyl, tert-butyl, etc. Derivative expressions such as "alkoxy", "thioalkyl", "alkoxyalkyl", "hydroxyalkyl", "alkylcarbonyl", "alkoxycarbonylalkyl", "alkoxycarbonyl", "diphenylalkyl", "phenylalkyl", "phenylcarboxyalkyl" and "phenoxyalkyl" should be interpreted accordingly.

[0028] The expression "cycloalkyl" as used in this specification includes all known cyclic groups. Representative examples of "cycloalkyl" include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc. Derivative expressions such as "cycloalkoxy", "cycloalkylalkyl", "cycloalkylaryl" and "cycloalkylcarbonyl" should be interpreted accordingly.

[0029] The expression "perhaloalkyl" as used in this specification refers to the above-mentioned alkyl group, wherein all hydrogen atoms in the alkyl group are replaced by halogen atoms selected from fluorine, chlorine, bromine or iodine. Illustrative examples include trifluoromethyl, trichloromethyl, tribromomethyl, triiodomethyl, pentafluoroethyl, pentachloroethyl, pentabromoethyl, pentaiodoethyl and straight-chain or branched heptafluoropropyl, heptachloropropyl, heptabromopropyl, nonafluorobutyl, nonachlorobutyl, undecafluoropentyl, undecachloropentyl, tridecafluorohexyl, tridecachlorohexyl and the like. The derived expression "perhaloalkoxy" should be interpreted accordingly. It should also be noted that some of the alkyl groups described in this specification may be partially fluorinated, i.e., only some of the hydrogen atoms in the alkyl group are replaced by fluorine atoms, and should be interpreted accordingly.

[0030] The expression "acyl" used in this specification shall have the same meaning as "alkanoyl", which can also be represented by "R-CO-" in structure, wherein R is an "alkyl" having a specified number of carbon atoms as described in this specification. In addition, the meaning of "alkylcarbonyl" shall be the same as that of "acyl" as described in this specification. Specifically, "(C1-C4) acyl" shall refer to formyl, acetyl (acetyl / ethanoyl), propionyl, n-butyryl, etc. For example, the derived expressions "acyloxy" and "acyloxyalkyl" shall also be interpreted accordingly.

[0031] The expression "aryl" used in this specification refers to substituted or unsubstituted phenyl or naphthyl. Specific examples of substituted phenyl or naphthyl include o-tolyl, p-tolyl, m-tolyl, 1,2-xylyl, 1,3-xylyl, 1,4-xylyl, 1-methylnaphthyl, 2-methylnaphthyl, etc. "Substituted phenyl" or "substituted naphthyl" also includes any possible substituents further described in this specification or known in the art.

[0032] The expression "arylalkyl" used in the present specification means that the above aryl group is further connected to the above alkyl group. Representative examples include benzyl, phenylethyl, 2-phenylpropyl, 1-naphthylmethyl, 2-naphthylmethyl and the like.

[0033] The expression "alkenyl" as used in this specification refers to a non-cyclic, straight or branched hydrocarbon chain having the specified number of carbon atoms and at least one carbon-carbon double bond, including vinyl and straight or branched propenyl, butenyl, pentenyl and hexenyl, etc. The derived expressions "arylalkenyl" and 5-membered or 6-membered "heteroarylalkenyl" should be interpreted accordingly. Illustrative examples of such derived expressions include furan-2-vinyl, phenylvinyl, 4-methoxyphenylvinyl, etc.

[0034] The expression "heteroaryl" used in this specification includes all known aromatic groups containing heteroatoms. Representative 5-membered heteroaryls include furanyl, thienyl or thiophenyl, pyrrolyl, isopyrrolyl, pyrazolyl, imidazolyl, oxazolyl, thiazolyl, isothiazolyl, etc. Representative 6-membered heteroaryls include groups such as pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl. Representative examples of bicyclic heteroaryls include groups such as benzofuranyl, benzothienyl, indolyl, quinolyl, isoquinolyl, cinnolinyl, benzimidazolyl, indazolyl, pyridinylfuranyl, pyridinylthienyl.

[0035] The expression "heterocycle" used in this specification includes all known cyclic groups containing reduced heteroatoms. Representative 5-membered heterocyclic groups include tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl, 2-thiazolinyl, tetrahydrothiazolyl, tetrahydrooxazolyl, etc. Representative 6-membered heterocyclic groups include piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, etc. Other various heterocyclic groups include but are not limited to aziridinyl, azepanyl, diazepanyl, diazabicyclo [2.2.1] hept-2-yl, triazocanyl, etc.

[0036] "Halogen" or "halo" refers to chlorine, fluorine, bromine and iodine.

[0037] In a broad sense, the term "substituted" includes all permissible substituents of an organic compound. In some embodiments disclosed in this specification, the term "substituted" refers to substitution with one or more substituents independently selected from the group consisting of (C1-C6) alkyl, (C2-C6) alkenyl, (C1-C6) perfluoroalkyl, phenyl, hydroxyl, -CO2H, ester, amide, (C1-C6) alkoxy, (C1-C6) alkylthio and (C1-C6) perfluoroalkoxy. However, any other suitable substituent known to those skilled in the art can also be applied to these embodiments.

[0038] It should be noted that any atom with unsatisfied valences in the text, schemes, examples and tables of this specification is assumed to have the appropriate number of hydrogen atoms to satisfy those valences.

[0039] In this specification, the terms "dielectric" and "insulating" are understood to be used interchangeably. Thus, reference to an insulating material or insulating layer includes a dielectric material or dielectric layer, and vice versa. Furthermore, the term "organic electronic device" as used in this specification is understood to include the term "organic semiconductor device" and various examples of such devices used, for example, in the automotive industry.

[0040] The dielectric constant (Dk) of a material as used in this specification is the ratio of the charge stored in an insulating material 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 electric permittivity or permittivity for short. It is sometimes called the relative permittivity because it is measured relative to the permittivity of free space.

[0041] As used in this specification, "low loss" refers to the loss factor (Df) which measures the rate of energy loss in an oscillating mode (mechanical, electrical or electromechanical) in a dissipative system. It is the inverse of the quality factor and represents "quality" or oscillation durability.

[0042] As used herein, "B-stage" refers to a material in which the reaction between the base polymer and the curing agent (curing agent / hardener) has not yet been completed. That is, such "B-staged" materials are in a partially cured stage and do not contain any solvent used to prepare the composition comprising the base polymer and the curing agent. Typically, when such "B-staged" materials are reheated at an elevated temperature, crosslinking is completed and the material is fully cured.

[0043] The term "prepreg" as used herein refers to a material pre-impregnated with a polymer material, which may be a thermoplastic material or a thermosetting material. Typically, a fibrous material such as glass cloth is pre-impregnated with a polymer material to form a prepreg, which is then cured by reheating at a high temperature after being formed through a "B-stage" process.

[0044] The term "derived" means that the polymerizable repeating unit is obtained by, for example, polymerizing (forming) a polycyclic norbornene-type monomer based on general formula (I) or (II), wherein the obtained polymer is formed by 2,3-matching linkage of the norbornene-type monomer as shown below.

[0045]

[0046] As described in further detail below, the above polymerization is also well-known vinyl addition polymerization, which is usually carried out in the presence of an organometallic compound such as an organopalladium compound or an organonickel compound.

[0047] Therefore, according to the implementation of the present invention, there is provided a polymer comprising:

[0048] a) at least one first repeating unit represented by the general formula (IA), wherein the first repeating unit is derived from a monomer of the general formula (I):

[0049]

[0050] in,

[0051] indicates the position of bonding to another repeating unit;

[0052] m is an integer of 0, 1 or 2;

[0053] R1, R2, R3 and R4 are the same or different and are independently selected from hydrogen, methyl, ethyl, straight or branched (C3-C 16 )alkyl, (C3-C 10 )cycloalkyl, (C6-C 12 ) bicycloalkyl, (C6-C 12 )aryl and (C6-C 12 ) the group consisting of aryl(C1-C6)alkyl; or

[0054] One of R1 and R2 together with one of R3 and R4 and the carbon atom to which they are attached form a substituted or unsubstituted (C5-C 14 ) ring, (C5-C 14 )bicyclic, (C5-C 14 ) tricyclic; and

[0055] b) at least one second repeating unit represented by the general formula (IIA), wherein the second repeating unit is derived from a monomer of the general formula (II):

[0056]

[0057] in,

[0058] indicates the position of bonding to another repeating unit;

[0059] n is an integer of 0, 1 or 2;

[0060] At least one of R5, R6, R7 and R8 is selected from methylene, ethylene, vinyl, straight chain or branched (C3-C 16 )alkenyl, (C3-C 10 )cycloalkenyl, (C6-C 12 )bicycloalkenyl and (C6-C 12 )Aryl(C2-C 16 ) alkenyl, the remaining R5, R6, R7 and R8 are the same or different and are independently selected from hydrogen, methyl, ethyl, straight or branched (C3-C 16 )alkyl, (C3-C 10 )cycloalkyl, (C6-C 12 ) bicycloalkyl, (C6-C 12 )aryl and (C6-C 12 ) the group consisting of aryl(C1-C6)alkyl; or

[0061] One of R5 and R6 together with one of R7 and R8 and the carbon atom to which they are attached form a substituted or unsubstituted (C5-C 14 ) ring, (C5-C 14 ) bicyclic or (C5-C 14 ) tricyclic; and

[0062] Wherein, relative to the total molar number of the first repeating unit and the second repeating unit, the content of the second repeating unit is not less than 4 mol %.

[0063] The polymer of recording in this specification can be prepared by any vinyl addition polymerization known in the art. It has been found that the copolymerization of more than one monomer of general formula (I) and more than one monomer of general formula (II) can form a polymer according to the present invention, wherein the additional olefin functional group present in the monomer of general formula (II) keeps unreactive during vinyl addition polymerization and this olefin functional group can still be used for other purposes in the polymer. Therefore, the polymer of the present invention can be used in various applications that are further crosslinked with other materials. Such method includes forming a prepreg suitable for manufacturing printed circuit boards, such as copper foil laminate. It has been found that even if a small amount of monomer of general formula (II) is still combined to form a polymer according to the present invention, as described in detail below, the polymer is quite effective when forming a crosslinkable composition of the present invention.

[0064] Advantageously, it has been found that the additional olefin functional groups present in the monomers of formula (II) are unreactive with vinyl addition polymerization catalysts and therefore remain present after forming the polymer according to the present invention. That is, one of the olefin groups present in R5, R6, R7 and R8 of the monomers of formula (II) can still be used in the polymer formed according to the present invention. Therefore, the polymers of the present invention can be used in various applications requiring further reactions involving olefin functional groups, such as crosslinking with other materials. It has further been found that in order to observe the crosslinking ability of the polymers of the present invention, the amount of the monomers of formula (II) used can be as little as 4 mol% of the total amount of the monomers of formulas (I) and (II).

[0065] Therefore, in some embodiments, the amount of the repeating unit of the monomer of the general formula (IIA) present in the polymer is at least 4 mol% relative to the total moles of the first repeating unit and the second repeating unit of the general formula (IA) and (IIA). In other embodiments, the amount of the repeating unit of the monomer of the general formula (IIA) present in the polymer is about 5 mol% to about 40 mol%, about 10 mol% to about 30 mol%, about 15 mol% to about 25 mol%, etc. relative to the total moles of the first repeating unit and the second repeating unit of the general formula (IA) and (IIA). In still other embodiments, the amount of the repeating unit of the monomer of the general formula (IIA) present in the polymer is about 6 mol% to 30 mol% relative to the total moles of the first repeating unit and the second repeating unit of the general formula (IA) and (IIA).

[0066] As described above, more than one monomer of general formula (I) and at least one monomer of general formula (II) can be used to form the polymer of the present invention. Advantageously, it has been found that at least two different monomers of general formula (I) are used together with a monomer of general formula (II). Similarly, as described in this specification, any appropriate amount of different monomers of general formula (I) can be used in combination with monomers of general formula (II). In some embodiments, the molar ratio of different monomers of general formula (I) can be 10:90, 20:80, 30:70, 40:60, 50:50, etc.

[0067] In some embodiments, the polymer according to the present invention has a repeating unit of the general formula (IA), wherein m is 0 or 1. In other embodiments, the polymer according to the present invention has a repeating unit of the general formula (IA), wherein m is 0. That is, the repeating unit of the general formula (IA) is derived from a monomer of the general formula (I), which is a derivative of norbornene. Similarly, more than one different monomer of the general formula (I) can be used to form the polymer of the present invention. In other embodiments, m is equal to 1 in the monomer of the general formula (I) used. That is, the monomer used in this embodiment comprises a dimeric norbornene monomer unit, which is also known as tetracyclodecene (TD). However, it should be noted that a combination of monomers of the general formula (I) with m=0 and m=1 can also be used to form the polymer of the present invention. That is, a mixture of norbornene derivatives of the general formula (I) recorded in this specification can be used together with a suitable tetracyclodecene derivative of the general formula (I) recorded in this specification to form the polymer of the present invention. Similarly, any appropriate amount of these different monomers of the general formula (I) can be used to form the polymer of the present invention, so as to achieve the desired effect. Thus, in some embodiments, the polymer according to the present invention comprises first repeating units derived from two different monomers of formula (I).

[0068] Similarly, in other embodiments, the polymer according to the present invention has a repeating unit of the general formula (IIA), wherein n is 0 or 1. In other embodiments, the polymer according to the present invention has a repeating unit of the general formula (IIA), wherein n is 0. That is, the repeating unit of the general formula (IIA) is derived from a monomer of the general formula (II), which is a derivative of norbornene. Similarly, more than one different monomer of the general formula (II) can be used to form the polymer of the present invention. In other embodiments, n is equal to 1 in the monomer of the general formula (II) used. That is, the monomer used in this embodiment comprises a dimeric norbornene monomer unit, which is also referred to as tetracyclodecene (TD). However, it should be noted that a combination of monomers of the general formula (II) with n=0 and n=1 can also be used to form the polymer of the present invention. That is, a mixture of norbornene derivatives of the general formula (II) recorded in this specification can be used together with a suitable tetracyclodecene derivative of the general formula (II) to form the polymer of the present invention. Similarly, any appropriate amount of these different monomers can be used to form the polymer of the present invention, thereby achieving the desired effect.

[0069] In some embodiments, R1, R2, R3 and R4 are the same or different and are each independently selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, n-butyl, n-hexyl, cyclopentyl, cyclohexyl and norbornyl.

[0070] In other embodiments, one of R1 and R2 together with one of R3 and R4 and the carbon atoms to which they are attached form a cyclopentyl, cyclohexyl, cycloheptyl, bicycloheptyl, bicyclooctyl or adamantane ring.

[0071] In some other embodiments, at least one of R5, R6, R7 and R8 is selected from the group consisting of ethylene, vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, cyclopentenyl and cyclohexenyl, and the remaining R5, R6, R7 and R8 are the same or different and are each independently selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, n-butyl, n-hexyl, cyclopentyl, cyclohexyl and norbornyl.

[0072] In some embodiments, one of R5 and R6 together with one of R7 and R8 and the carbon atoms to which they are attached form a cyclopentenyl, cyclohexenyl, cycloheptenyl, bicycloheptenyl or bicyclooctenyl ring.

[0073] Likewise, any monomer of formula (I) within the scope of the present invention can be used to form the polymer of the present invention. Non-limiting examples of monomers of formula (I) can be selected from the group consisting of:

[0074]

[0075] Bicyclo[2.2.1]hept-2-ene (norbornene or NB);

[0076]

[0077] 5-Butylbicyclo[2.2.1]hept-2-ene (BuNB);

[0078]

[0079] 5-Hexylbicyclo[2.2.1]hept-2-ene (HexNB);

[0080]

[0081] 5-Decylbicyclo-[2.2.1]hept-2-ene (DecNB);

[0082]

[0083] 5-Cyclohexylbicyclo[2.2.1]hept-2-ene (CyHexNB);

[0084]

[0085] 5-phenylbicyclo[2.2.1]hept-2-ene (PhNB);

[0086]

[0087] 5-Phenethylbicyclo[2.2.1]hept-2-ene (PENB);

[0088]

[0089] 2,2'-Bis(bicyclo[2.2.1]heptane-5-ene) (NBANB);

[0090]

[0091] 1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylnaphthalene (TD); and

[0092]

[0093] 2-Hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylnaphthalene (HexTD).

[0094] Likewise, any monomer of formula (II) within the scope of the present invention can be used to form the polymer of the present invention. Non-limiting examples of monomers of formula (II) can be selected from the group consisting of:

[0095]

[0096] 5-Methylenebicyclo[2.2.1]hept-2-ene (MNB);

[0097]

[0098] 5-vinylbicyclo[2.2.1]hept-2-ene (VNB);

[0099]

[0100] 5-Ethylidenebicyclo[2.2.1]hept-2-ene (ENB);

[0101]

[0102] 5-(But-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB);

[0103]

[0104] 5-(Hex-5-en-1-yl)bicyclo[2.2.1]hept-2-ene (HexenylNB);

[0105]

[0106] 5-(Cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (Cyclohexene NB);

[0107]

[0108] 1,4,4a,5,8,8a-Hexahydro-1,4:5,8-dimethylnaphthalene (TDD);

[0109]

[0110] 3a,4,7,7a-Tetrahydro-1H-4,7-methanoindene (DCPD); and

[0111]

[0112] 3a,4,4a,5,8,8a,9,9a-Octahydro-1H-4,9:5,8-dimethylcyclopenta[b]naphthalene (CPD3).

[0113] Illustrative, non-limiting examples of polymers according to the present invention can be cited as follows:

[0114] Copolymers of norbornene (NB) and 5-vinylbicyclo[2.2.1]hept-2-ene (VNB);

[0115] Copolymers of norbornene (NB) and 5-ethylidenebicyclo[2.2.1]hept-2-ene (ENB);

[0116] Copolymers of norbornene (NB) and 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB);

[0117] Copolymers of norbornene (NB) and 5-(hex-5-en-1-yl)bicyclo[2.2.1]hept-2-ene (HexenylNB); and

[0118] Copolymers of norbornene (NB) and 5-(cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyclohexeneNB);

[0119] A terpolymer of norbornene (NB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB) and 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB);

[0120] A terpolymer of norbornene (NB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB) and 5-(cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyclohexeneNB);

[0121] A terpolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB) and 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB);

[0122] A terpolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB) and 5-(hex-5-en-1-yl)bicyclo[2.2.1]hept-2-ene (HexenylNB); and

[0123] A terpolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB) and 5-cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyclohexeneNB).

[0124] Surprisingly, it has been found that even with about 4 mol% of monomers of formula (II) relative to the total molar number of monomers of formula (I) and (II), it is still possible to form a polymer according to the present invention, which, as described below, brings effective crosslinking capabilities with other materials in the formation of composite materials that can be used in various applications. In some embodiments, the polymer according to the present invention comprises a second repeating unit of formula (II) in an amount ranging from about 5 mol% to about 30 mol% relative to the total molar number of the first repeating unit of formula (I) and the second repeating unit of formula (II). In other embodiments, the polymer according to the present invention comprises a second repeating unit of formula (II) in an amount ranging from about 10 mol% to about 25 mol% relative to the total molar number of the first repeating unit of formula (I) and the second repeating unit of formula (II). In yet other embodiments, the polymer according to the present invention comprises a second repeating unit of formula (II) in an amount ranging from about 15 mol% to about 20 mol% relative to the total molar number of the first repeating unit of formula (I) and the second repeating unit of formula (II). However, it should be noted that in some embodiments, the amount of the repeating unit of formula (II) can be lower than 4 mol% or higher than 30 mol% depending on the intended application. Therefore, all possible combinations of amounts that can be used are within the scope of the present invention.

[0125] As described above, the monomers of formula (I) and (II) are subjected to vinyl addition polymerization using any suitable catalyst known in the art. For example, various palladium compounds, platinum compounds, and various nickel compounds have been used to form polymers of the type described in this specification. In some embodiments of the present invention, the polymers of the present invention are formed by using palladium compounds. Various palladium compounds known in the art can be used. Non-limiting examples of such palladium compounds, including some platinum compounds, can be listed as follows:

[0126] Bis(triphenylphosphine)palladium(II) dichloride;

[0127] Bis(triphenylphosphine)palladium(II) dibromide;

[0128] Bis(triphenylphosphine)palladium(II)diacetate;

[0129] Bis(triphenylphosphine)bis(trifluoroacetate)palladium(II);

[0130] Bis(tricyclohexylphosphine)palladium(II) dichloride;

[0131] Bis(tricyclohexylphosphine)palladium(II) dibromide;

[0132] Bis(tricyclohexylphosphine)palladium(II)diacetate (Pd785);

[0133] Bis(tricyclohexylphosphine)bis(trifluoroacetate)palladium(II);

[0134] Bis(tri-p-tolylphosphine)palladium(II) dichloride;

[0135] Bis(tri-p-tolylphosphine)palladium(II) dibromide;

[0136] Bis(tri-p-tolylphosphine)palladium(II) diacetate;

[0137] Bis(tri-p-tolylphosphine)bis(trifluoroacetate)palladium(II);

[0138] Palladium(II) ethylhexanoate;

[0139] Bis(acetone)palladium(II);

[0140] Dichlorobis(benzonitrile)palladium(II);

[0141] n-Butyldi-1-adamantylphosphine palladium diacetate (H2O) (Pd601);

[0142] n-Butyldi-tert-butylphosphinediacetatepalladium(H2O) (Pd445);

[0143] Bis(n-butyldi-1-adamantylphosphine)acetatepalladium(acetonitrile)tetrakis(pentafluorophenyl)borate (Pd1602); and

[0144] (Acetonitrile)bis(triisopropylphosphine)(acetic acid)palladiumtetrakis(pentafluorophenyl)borate (Pd1206);

[0145] [(Allyl)(trinaphthylphosphine)(trifluoroacetic acid)palladium];

[0146] [(Allyl)(trinaphthylphosphine)(trifluoromethanesulfonate)palladium];

[0147] Platinum(II) chloride;

[0148] Platinum(II) bromide; and

[0149] Bis(triphenylphosphine)platinum dichloride.

[0150] As is well known in the art, such palladium compounds are further activated when using various activator compounds. Non-limiting examples of such activators can be selected from the group consisting of:

[0151] Lithium tetrafluoroborate;

[0152] Lithium trifluoromethanesulfonate;

[0153] Lithium tetrakis(pentafluorophenyl)borate;

[0154] Lithium tetrakis(pentafluorophenyl)borate ethyl ether complex (LiFABA);

[0155] Sodium tetrakis(pentafluorophenyl)borate ethyl ether complex (NaFABA);

[0156] Tetrakis(pentafluorophenyl)borate trityl ethyl ether complex (tritylFABA);

[0157] Tropylium tetrakis(pentafluorophenyl)borate ethyl ether complex (tropyliumFABA);

[0158] Lithium tetrakis(pentafluorophenyl)borate isopropanol complex;

[0159] Lithium tetraphenylborate;

[0160] Lithium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate;

[0161] Lithium tetrakis(2-fluorophenyl)borate;

[0162] Lithium tetrakis(3-fluorophenyl)borate;

[0163] Lithium tetrakis(4-fluorophenyl)borate;

[0164] Lithium tetrakis(3,5-difluorophenyl)borate;

[0165] Lithium hexafluorophosphate;

[0166] Lithium hexaphenylphosphate;

[0167] Lithium hexa(pentafluorophenyl)phosphate;

[0168] Lithium hexafluoroarsenate;

[0169] Lithium hexaphenylarsenate;

[0170] Lithium hexa(pentafluorophenyl)arsenate;

[0171] Lithium hexa(3,5-bis(trifluoromethyl)phenyl)arsenate;

[0172] Lithium hexafluoroantimonate;

[0173] Lithium hexaphenylantimonate;

[0174] Lithium hexa(pentafluorophenyl)antimonate;

[0175] Lithium hexa(3,5-bis(trifluoromethyl)phenyl)antimonate;

[0176] Lithium tetrakis(pentafluorophenyl)aluminate;

[0177] Lithium tris(nonafluorobiphenyl)fluoroaluminate;

[0178] Lithium (octyloxy)tris(pentafluorophenyl)aluminate;

[0179] Lithium tetrakis(3,5-bis(trifluoromethyl)phenyl)aluminate;

[0180] Lithium methyl tris(pentafluorophenyl)aluminate; and

[0181] Dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA).

[0182] Typically, the polymerization is carried out in a suitable solvent at a suitable temperature. Any solvent that can dissolve the palladium compound and the monomers used or is miscible with the liquid can be used for this purpose. Suitable polymerization solvents include without any limitation alkane and cycloalkane solvents such as pentane, hexane, heptane, decahydronaphthalene, cyclohexane and methylcyclohexane; halogenated alkane solvents such as dichloromethane, chloroform, carbon tetrachloride, ethyl chloride, 1,1-dichloroethane, 1,2-dichloroethane, 1-chloropropane, 2-chloropropane, 1-chlorobutane, 2-chlorobutane, 1-chloro-2-methylpropane and 1-chloropentane; ethers such as THF and diethyl ether; aromatic solvents such as benzene, xylene, toluene, mesitylene, chlorobenzene and o-dichlorobenzene; halocarbon solvents such as 112; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, amyl acetate; and mixtures of any combination thereof.

[0183] Any temperature conditions capable of carrying out such polymerization can be used in the present specification. In some embodiments, the polymer of the present invention is formed by heating a mixture containing an appropriate amount of monomers of general formula (I) and (II) for a sufficiently long time (e.g., about 1 hour to 8 hours) in the presence of a palladium compound and an activator described in the present specification in a temperature range of about 60°C to about 150°C. In other embodiments, the monomer mixture and the catalyst are heated to a temperature of about 90°C to about 130°C for a sufficiently long time (e.g., about 1 hour to 4 hours) to form the polymer of the present invention. Furthermore, solution polymerization is carried out using an anhydrous solvent under an inert atmosphere such as a nitrogen, helium or argon atmosphere.

[0184] Advantageously, the vinyl addition polymers formed from the palladium compounds and the monomers of formula (I) and (II) have extremely high conversions at low catalyst loadings (e.g., 20,000-25,000:1), wherein a chain transfer agent such as triethylsilane (TES) is used to control the molecular weight of the polymer. Various other chain transfer agents can also be used to control the molecular weight of the polymers obtained as described in this specification, including, for example, bicyclo[4.2.0]oct-7-ene (BCO), formic acid, various other silanes, and mixtures thereof in any combination. The use of various CTAs in vinyl addition polymerizations to control the properties of the polymers obtained is well known in the art. For example, reference is made to U.S. Patent No. 7,910,674 B2, the relevant portions of which are incorporated herein by reference.

[0185] The polymers formed according to the present invention generally exhibit a weight average molecular weight (M) of at least about 1,000. w In another embodiment, the polymer of the present invention has M w is at least about 3,000, 5,000, 10,000, or 20,000. In another embodiment, the polymer of the present invention has an M of at least about 3,000, 5,000, 10,000, or 20,000. w is at least about 50,000. In another embodiment, the polymer of the present invention has an M w is at least about 60,000. In another embodiment, the polymer of the present invention has an M w is at least about 70,000. In another embodiment, the polymer of the present invention has an M w is at least about 80,000. In other embodiments, the polymers of the present invention have an M w is at least about 100,000. In another embodiment, the polymer of the present invention has an M w The weight average molecular weight (M) of the polymer is greater than 150,000 or greater than 200,000, and in other embodiments may be greater than 500,000. w ) can be defined, for example, by any known technique such as gel permeation chromatography (GPC) with a suitable detector and calibration standards, such as a differential refractive index detector calibrated with narrow distribution polystyrene standards or polybutadiene (PBD) standards. The polymers of the present invention generally exhibit a polydispersity index (PDI) greater than 3, which is a function of the weight average molecular weight (M). w ) and number average molecular weight (M n ). Typically, the PDI of the polymers of the present invention ranges from 3 to 5. In some embodiments, the PDI is higher than 3.5, 4, 4.5, or may be higher than 5. However, it should be noted that in some embodiments, the PDI may be lower than 3, such as 2.5.

[0186] As described in this specification, the polymers thus formed are then used to prepare compositions that are used to make composite materials with properties that have not been achieved to date, such as extremely low coefficients of thermal expansion (CTE) as low as 100 ppm / °K, less than 90 ppm / °K, 80 ppm / °K, 50 ppm / °K, or 40 ppm / °K. The polymers of the present invention also exhibit extremely low dielectric constants and low loss characteristics. For example, the dielectric constant (Dk) of the polymers of the present invention can be as low as less than 2.8 at a frequency of 10 GHz, and can be in the range of about 2.2 to about 3.2. The low loss (Df) of the polymer can be less than 0.0015, and can be in the range of about 0.001 to 0.002. In addition, the polymers of the present invention exhibit extremely high glass transition temperatures (T g), which may be above 250°C, and is typically in the range of about 250°C to 350°C. More importantly, as further described below, the polymers of the present invention are easily combined with other cross-linkable materials in various compositions prepared according to the present invention. The compositions so formed exhibit excellent peel strength, typically in the range of 6 to 8 N / cm, and therefore find use in many applications such as copper clad laminates.

[0187] Therefore, in another aspect of the present invention, there is also provided a composition comprising:

[0188] a) polymers prepared according to the invention;

[0189] b) a cross-linking agent selected from the group consisting of:

[0190]

[0191] 1,3,5-Triallyl-1,3,5-triazinane-2,4,6-trione (TAIC); and

[0192]

[0193] 2,4,6-tri(allyloxy)-1,3,5-triazine (TAC); and

[0194] c) one or more additives selected from the group consisting of adhesion promoters and free radical initiators.

[0195] As described above, any specific polymer within the general range described in this specification that includes more than one monomer of general formula (I) and at least one monomer of general formula (II) can be used in the composition of the present invention. It should also be noted that the polymer includes at least 4 mol% of the total moles of the repeating units of general formula (IIA) derived from the corresponding monomer of general formula (II) relative to the total moles of the repeating units of general formula (IA) and (IIA). In some embodiments, the composition of the present invention includes the repeating units of general formula (IIA) derived from the corresponding monomer of general formula (II), and the amount thereof is about 5 mol% to about 40 mol%, about 10 mol% to about 30 mol%, about 15 mol% to about 25 mol%, etc. relative to the total mole % of the repeating units of general formula (IA) and (IIA) present in the polymer. However, it should be noted that the polymer may include less than 4 mol% or more than 40 mol% of the repeating units of general formula (IIA) according to the intended application of the composition thus formed. Therefore, all possible combinations of the mol % of the repeating units of general formula (IIA) are within the scope of the present invention.

[0196] In the composition of the present invention, any amount of crosslinking agent, TAIC or TAC can be used alone or in combination to bring the expected benefits. Therefore, in some embodiments, the composition contains only TAIC as a crosslinking agent. In other embodiments, the composition contains only TAC as a crosslinking agent. In yet other embodiments, the composition contains a mixture of both TAIC and TAC as a crosslinking agent. Generally, the amount of TAIC or TAC when used alone in the composition of the present invention can be in the range of about 5 to 20 pphr, 8 to 18 pphr, 10 to 16 pphr, etc. per 100 parts of polymer. When a combination of TAIC and TAC is used in the composition, the respective amounts can be the same or different. The total amount of TAIC and TAC can be about 10 to 30 pphr, 15 to 25 pphr, etc. It should also be noted that these amounts can be high or low depending on the intended use of the composition.

[0197] As described above, the composition according to the present invention comprises a tackifier. Generally, the purpose of the tackifier is not only to improve the adhesion of the composition, but also to improve the softness of the composition, especially when manufactured at a temperature higher than 130°C, the composition can have some fluidity to penetrate the glass cloth or fuse with other layers of the device. The composition of the present invention is generally cross-linkable at a temperature higher than 130°C, and is conducive to keeping the composition soft at this temperature. Therefore, any tackifier that brings this advantage can be used in the composition of the present invention. In addition, the amount of tackifier used can vary according to the intended use. Generally, these amounts can be about 5 to 30 pphr, 8 to 25 pphr, 10 to 20 pphr, etc. per 100 parts of polymer. It should be noted that a combination of two or more tackifiers can also be used in the composition of the present invention. At this time, the combined amount can be adjusted to provide the expected benefit.

[0198] Non-limiting examples of such tackifiers suitable for the composition can be listed below:

[0199]

[0200] Ethylene-propylene-ethylidene norbornene terpolymers, wherein a is at least 100 (Lion Elastomers, LLC T67 is commercially available);

[0201]

[0202] Ethylene-propylene-dicyclopentadiene terpolymer, wherein a is at least 100 (Lion Elastomers, LLC T65 is commercially available);

[0203]

[0204] 1,2-butadiene rubber, wherein a is at least 100 (commercially available as B1000 from Nisso America Inc.);

[0205]

[0206] Partially hydrogenated styrene / butadiene rubber 1 (commercially available as Tuftec P1083 from Asahi Kasei Corp.);

[0207]

[0208] Partially hydrogenated styrene / butadiene rubber 2 (commercially available as Tuftec 1500 from Asahi Kasei Corp.);

[0209]

[0210] Hydrogenated styrene / butadiene rubber 1 (commercially available as Tuftec H 1052 from Asahi Kasei Corp.); and

[0211]

[0212] Hydrogenated styrene / butadiene rubber2.

[0213] As mentioned above, the composition of the present invention further comprises a free radical initiator. Any free radical initiator that can cause a crosslinking reaction with other components in the polymer and the composition and promote adhesion to other suitable substrates (e.g., copper and / or glass cloth) can be used in the composition of the present invention. Similarly, any amount of free radical initiator that brings the expected benefit can be used. These amounts are variable, for example, the free radical initiator can be in the range of about 1 pphr to 6 pphr.

[0214] Non-limiting examples of free radical initiators that can be used in the compositions of the present invention include the following:

[0215]

[0216] 1,1'-(diazene-1,2-diyl)bis(cyclohexane-1-carbonitrile) (V-40 commercially available from Sigma Aldrich);

[0217]

[0218] Di-tert-butyl peroxide;

[0219]

[0220] 2,5-Bis(tert-butylperoxy)-2,5-dimethylhexane (Luperox-101);

[0221]

[0222] 1,1-Bis(tert-butylperoxide)-3,3,5-trimethylcyclohexane (Luperox-231);

[0223]

[0224] Dicumyl peroxide (DCP commercially available from Sigma Aldrich);

[0225]

[0226] Benzoyl peroxide;

[0227]

[0228] Lauroyl peroxide (Luperox-LP);

[0229]

[0230] Tert-butyl peroxybenzoate (Luperox-P); and

[0231]

[0232] (2-Ethylhexyl) tert-butyl peroxide (Luperox-TBEC).

[0233] As described above, any polymer described in this specification can be used in the composition of the present invention. Generally, the composition of the present invention is dissolved in a suitable solvent to form a homogeneous solution. Such suitable solvents may be the same as the solvents listed above for forming the polymer of the present invention. Generally, such solvents for forming the composition of the present invention include, for example, aromatic solvents such as toluene, mesitylene, and xylene; hydrocarbon solvents such as decalin, cyclohexane, and methylcyclohexane; ether solvents such as tetrahydrofuran (THF); ester solvents such as ethyl acetate; and mixtures of any combination thereof.

[0234] Non-limiting examples of compositions according to the present invention are selected from the group consisting of:

[0235] A solution comprising a terpolymer of norbornene (NB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB) and 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB); and a mixture of 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC) and dicumyl peroxide (DCP);

[0236] A solution comprising a terpolymer of norbornene (NB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB) and 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB); and a mixture of 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), 1,2-butadiene rubber (B1000) and dicumyl peroxide (DCP);

[0237] A solution comprising a terpolymer of norbornene (NB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB) and 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB); and a mixture of 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), 1,2-butadiene rubber (B1000), a polyarylether crosslinker terminated with methacrylate groups (SA9000) and dicumyl peroxide (DCP);

[0238] A solution comprising a terpolymer of norbornene (NB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB) and 5-(cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyclohexeneNB); and a mixture of 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), 1,2-butadiene rubber (B1000) and dicumyl peroxide (DCP);

[0239] A solution comprising a copolymer of norbornene (NB) and 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB); and a mixture of 1,2-butadiene rubber (B1000) and dicumyl peroxide (DCP);

[0240] A solution comprising a copolymer of norbornene (NB) and 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB); and a mixture of an ethylene-propylene-dicyclopentadiene terpolymer (T65) and dicumyl peroxide (DCP);

[0241] A solution comprising a copolymer of norbornene (NB) and 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB); and a mixture of an ethylene-propylene-ethylidene norbornene terpolymer (T67) and dicumyl peroxide (DCP);

[0242] A solution comprising a terpolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB) and 5-cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyclohexeneNB); and a mixture of 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), 1,2-butadiene rubber (B1000) and dicumyl peroxide (DCP);

[0243] A solution comprising a terpolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB) and 5-cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyclohexeneNB); and a mixture of 1,2-butadiene rubber (B1000) and dicumyl peroxide (DCP);

[0244] A solution comprising a terpolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB) and 5-cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyclohexeneNB); and a mixture of 1,2-butadiene rubber (B1000), ethylene-propylene-ethylidene norbornene terpolymer (T67) and dicumyl peroxide (DCP);

[0245] A solution comprising a terpolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB) and 5-cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyclohexeneNB); and a mixture of 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), 1,2-butadiene rubber (B1000), ethylene-propylene-ethylidene norbornene terpolymer (T67) and dicumyl peroxide (DCP); and

[0246] A solution comprising a terpolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB) and 5-cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyclohexeneNB); and a mixture of 2,4,6-tri(allyloxy)-1,3,5-triazine (TAC), 1,2-butadiene rubber (B1000) and dicumyl peroxide (DCP).

[0247] Typically, the composition according to the present invention comprises a polymer described in this specification, the polymer comprising one or more different monomers of formula (I) and a small amount of at least one monomer of formula (II), as described below, the composition of various embodiments can be selected to impart the desired properties to the embodiment for the intended use, thereby enabling the embodiment to be adjusted according to various specific uses. Therefore, in some embodiments, the composition of the present invention comprises a polymer, the polymer containing two or more different monomers of formula (I) (e.g., three different monomers of formula (I) or four different monomers of formula (I)) and any desired amount of monomers of formula (II), as described above, which can be as low as 4 mol%.

[0248] For example, as described above, by using appropriate combinations of different monomers of formula (I), compositions having desired low dielectric properties, thermomechanical properties and other properties can be prepared. In addition, as discussed in further detail below for the end use, it may also be necessary to include other compatible polymers or monomer materials to provide the desired low loss and low dielectric properties.

[0249] Even more advantageously, surprisingly, it has been found that even with small amounts of at least one monomer of the general formula (II), it is still possible to form a crosslinked structure within the polymer backbone in combination with the crosslinking agents described in this specification. That is, the crosslinking can occur both intermolecularly (i.e. between two crosslinkable sites in different polymer chains) and intramolecularly (i.e. between two crosslinkable sites in the same polymer chain). This is statistically possible, and all these combinations are part of the present invention. By forming such intermolecular or intramolecular crosslinks, the polymer formed by the composition of the present invention provides a property that has not been obtained so far. These may include, for example, improved thermal properties. That is, the glass transition temperature is much higher than that observed for non-crosslinked polymers of similar composition. In addition, such crosslinked polymers are more stable at high temperatures, which can be above 350°C. High temperature stability can also be determined by thermogravimetric analysis (TGA) methods known in the art. One of the measurements includes the temperature at which the polymer loses 5% of its weight (T d5 As shown in the following specific examples, the following polymers formed from the composition of the present invention have a T d5 Typically, it is in the range of about 330°C to about 380°C or more. In some embodiments, the T of the polymer formed from the composition of the present invention is d5 In the range of about 360°C to about 400°C.

[0250] The composition according to the present invention may further contain any additives for improving the properties of the composition and the objects made therefrom. Examples of such any additives may include antioxidants and synergists. Any antioxidant that provides the desired benefit can be used in the composition of the present invention. Non-limiting examples of such antioxidants include pentaerythritol tetrakis (3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate) (IRGANOX from BASF Corporation) TM 1010), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecylphenylpropionic acid (IRGANOX TM 1076) and diethylene thiobis[3-(3,5-di-tert-butyl-4-hydroxy-phenyl) propionate] (IRGANOX TM 1035). Non-limiting examples of such synergists include some secondary antioxidants that provide additional advantages, such as preventing degradation of the composition of the present invention by preventing self-oxidation and prolonging the effectiveness of the primary antioxidant. Examples of such synergists include tris (2,4-di-tert-butylphenyl) phosphite (IRGAFOS168 commercially available from BASF), various diamine synergists such as N, N'-di-2-naphthyl-1,4-phenylenediamine, etc. Other synergists suitable for use as additives in the composition include specific diesters such as di(octadecyl) thiodipropionate, the structure of which is shown below:

[0251]

[0252] Therefore, the composition of the present invention can be simply formed into a film according to any known film casting technique, such as doctor blade coating, drum rotation, extrusion and / or spin coating and other known methods. Therefore, a film formed by the composition of the present invention is further provided. For example, any composition of the present invention can be doctor blade coated on a suitable substrate such as a glass plate. Thereafter, the coated plate is heated to a suitable temperature under an inert atmosphere to remove any residual solvent. Such a temperature can be in the range of about 80°C to 150°C or 120°C to 140°C. A suitable inert atmosphere can be nitrogen or argon. Heating at these temperatures for a sufficient time will remove all residual solvents, for example, at a time interval of about 45 minutes to about 75 minutes. The initial stage of film formation is generally referred to as a B-staged film. Under these conditions, the film is still soluble in a suitable solvent such as THF and is not completely cross-linked. Thereafter, the B-staged film is further heated to a higher temperature in the range of about 150°C to 220°C or 160°C to 190°C under an inert atmosphere for a sufficient time to affect the cross-linking of the film. Typically, such heating is performed for about 90 minutes to about 150 minutes to ensure complete crosslinking of the composition, as confirmed by insolubility of the polymer film.

[0253] The films formed according to the present invention exhibit unusually low dielectric constants, low losses, low coefficients of thermal expansion (CTE), and high glass transition temperatures. In some embodiments, the films formed according to the present invention exhibit dielectric constants (Dk) below 3, 2.8, 2.6, 2.5, 2.4, 2.3, and 2.2 at a frequency of 10 GHz and glass transition temperatures (Tk) in the range of about 150°C to above 280°C. g ). In other embodiments, T g It may be higher than 150° C., 200° C. and 250° C. In yet other embodiments, the film according to the present invention exhibits a coefficient of thermal expansion (CTE) in the range of about 80 ppm / K to 120 ppm / K and a CTE lower than 50 ppm / K when compounded with glass cloth.

[0254] As described above, the film according to the present invention can be formed from the composition of any specific embodiment. In another aspect of the present invention, there is also provided a film formed from the polymer of the present invention.

[0255] In another embodiment, the film according to the present invention exhibits a dielectric constant (Dk) lower than 3 at a frequency of 10 GHz, a glass transition temperature higher than 150° C., a coefficient of thermal expansion (CTE) lower than 50 ppm / K.

[0256] It should also be noted that the crosslinked polymers formed from the compositions of the present invention can form thermosets, thus providing additional advantages, particularly in certain applications where thermoplasticity is not desired. For example, in any application involving high temperatures, thermoplastic polymers become less desirable because such polymer materials may flow and be unsuitable for such high temperature applications. Such applications include millimeter wave radar antennas and other applications contemplated in this specification.

[0257] Advantageously, it has been further found that the low dielectric properties of the film formed by the composition of the present invention can be improved by adding more than one filler material. The filler material can be an organic material or an inorganic material. Any known filler material that brings the desired effect can be used in this specification.

[0258] Therefore, in some embodiments, the film-forming composition according to the present invention contains an inorganic filler. Suitable inorganic fillers are fillers having a coefficient of thermal expansion (CTE) lower than that of the film formed by the composition of the present invention. Non-limiting examples of such inorganic fillers include: oxides, such as silicon dioxide, aluminum oxide, diatomaceous earth, titanium oxide, iron oxide, zinc oxide, magnesium oxide, metal ferrites; hydroxides, such as aluminum hydroxide, magnesium hydroxide; calcium carbonate (light and heavy); magnesium carbonate, dolomite (anhydrous calcium magnesium carbonate mineral); carbonates; sulfates, such as calcium sulfate, barium sulfate, ammonium sulfate and calcium sulfite; talc, mica; clay; glass fiber; calcium silicate; montmorillonite; silicates, such as 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 disulfide; boron fiber; potassium titanate; and lead zirconate. Various inorganic filler materials are commercially available, for example, silica nanoparticles are SC2300-SVJ commercially available from Adamatech Co. Ltd., ceramic fillers are Lithafrax-2121 commercially available from St. Gobain, and many other filler materials suitable for use in combination with the composition of the present invention.

[0259] In other embodiments, the film-forming composition according to the present invention further comprises an organic filler, which is generally a synthetic resin in powder or other suitable form or polymer form. Examples of such polymer fillers include, but are not limited to, poly(α-methylstyrene), poly(vinyl-toluene), copolymers of α-methylstyrene and vinyl-toluene, etc. Further examples of such synthetic resin powders include powders of various thermosetting resins 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, polystyrene, polyvinyl chloride, fluororesins, polypropylene, ethylene-vinyl acetate copolymers, and powders of copolymers of these resins. Other examples of organic fillers include aromatic or aliphatic polyamide fibers, polypropylene fibers, polyester fibers, aramid fibers, etc.

[0260] In some embodiments, the filler is an inorganic filler. Therefore, the thermal expansion coefficient can be effectively reduced. In addition, heat resistance can also be improved. Therefore, in some embodiments, the inorganic filler is silica. Therefore, the thermal expansion coefficient can be reduced while improving dielectric properties. Various forms of silica fillers are known in the art, and all such suitable silica fillers can be used in the composition of the present invention. Examples of such silica fillers include fused silica without any limitation, including fused spherical silica and fused crushed silica, crystalline silica, silica nanoparticles, etc. In some embodiments, the filler used is silica nanoparticles. Surprisingly, it has been found that by using an appropriate amount of silica nanoparticles, a composition showing extremely low low dielectric constant and extremely low loss characteristics can be formed. In some embodiments, by using suitable silica nanoparticles in an amount of about 60pphr to 80pphr, the dielectric constant (Dk) can be reduced to less than 2.25, and the low loss (Df) is about 0.0009. In other embodiments, Dk is 2.3 and Df is about 0.001. Typically, the amount of filler material can be in the range of about 5% to 80% by weight or more. In some embodiments, as described in this specification, when polymerizing to form a film / sheet, the content of filler in the composition is about 30 to 80% by weight relative to the total solid content of the composition. By appropriately adjusting the content of the filler, the balance between dielectric properties and the coefficient of thermal expansion (CTE) can be improved. In other embodiments, the content of the filler in the composition is about 40 to 70% by weight relative to the total solid content of the composition.

[0261] 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, and a styryl group in one molecule. For example, such silane compounds include silanes having an alkyl group such as ethyltriethoxysilane, propyltriethoxysilane or butyltriethoxysilane (alkylsilane); silanes having a phenyl group such as phenyltriethoxysilane, benzyltriethoxysilane or phenylethyltriethoxysilane; silanes having a styryl group such as styryltrimethoxysilane, butenyltriethoxysilane, propenyltriethoxysilane or vinyltrimethoxysilane (vinylsilane); silanes having a propenyl group or a methacryl group such as γ-(methacryloxypropyl)trimethoxysilane; silanes having an amino group such as γ-aminopropyltriethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane; or epoxy groups such as γ-(3,4-epoxycyclohexyl)ureidotriethoxysilane, etc. Silanes having a mercapto group such as γ-mercaptopropyltrimethoxysilane can also be used. It should also be noted that more than one of the above-mentioned silane compounds can be used in any combination.

[0262] It should also be noted that when an inorganic filler is used as a filler, the filler is usually treated with a "non-polar silane compound". Therefore, the adhesion between the cycloolefin polymer formed by the composition of the present invention and the filler can be improved. As a result, the mechanical properties of the molded body can be improved. Advantageously, it has been observed that by treating with a "non-polar silane compound", the adverse effects on dielectric properties can be eliminated or reduced. The "non-polar silane compound" used in this specification refers to a silane compound that does not have a polar substituent. The polar substituent refers to a group that can hydrogen bond or ion dissociate. Such polar substituents include, but are not limited to -OH, -COOH, -COOM, NH3, NR4 + A - , -CONH2, etc. Wherein, M is a cation, such as an alkali metal, an alkaline earth metal or a quaternary ammonium salt; R is H or an alkyl group having 8 or less carbon atoms; A is an anion, such as a halogen atom.

[0263] In some embodiments, the surface of the filler is modified with a vinyl group. Since the vinyl group is a non-polar substituent and provides a very desirable low dielectric property, it is advantageous to use a vinyl group. For example, vinyl silane can be used to modify the surface of the filler with a vinyl group. Specific examples of vinyl silane are as described above.

[0264] Typically, the average particle size of the filler used is in the range of about 0.1 to 10 μm. In some embodiments, the average particle size is about 0.3 to 5 μm, and in other embodiments, the average particle size 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 more than one type of filler is used, the average particle size of more than one such filler is still within the above numerical range. Since the average particle size of the filler is appropriately small, the specific surface area of ​​the filler is reduced. As a result, the number of polar functional groups that may have an adverse effect on the dielectric properties is reduced, and the dielectric properties are easily improved. In addition, since the average particle size of the filler is appropriately small, it is easy to polymerize and form a film from the composition of the present invention. More importantly, the film / sheet formed in this way exhibits uniform thickness and flatness that are very desirable in the intended application.

[0265] The composition of the present invention may contain ingredients other than the above ingredients. Ingredients other than the above ingredients include coupling agents, flame retardants, release agents, antioxidants, etc. Non-limiting examples of coupling agents include silane coupling agents such as vinyl silane, acrylic acid and methacrylic acid silane, styryl silane, isocyanato silane, etc. By using a silane coupling agent, the adhesion between the composition of the present invention and the matrix material, etc. can be improved.

[0266] Non-limiting examples of flame retardants include phosphorus-based flame retardants such as trixylene phosphate, dixylene phosphate, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide; halogen-based flame retardants such as brominated epoxy resins; and inorganic flame retardants such as aluminum hydroxide and magnesium hydroxide.

[0267] The composition of the present invention may further contain one or more compounds or additives having the functions of, in particular, an adhesion promoter, a surface leveling agent, a synergist, a plasticizer, a curing accelerator, and the like.

[0268] Surprisingly, it has been found that by using one or more thermal free radical initiators described in this specification, crosslinking of polymers formed from the composition of the present invention can be promoted, resulting in the crosslinked polymers exhibiting significantly improved thermal properties. For example, the glass transition temperature (T g ) and the temperature at which 5% weight loss occurs (T d5 ) can be improved. g The increase in T of the polymer may be large, possibly in the range of about 10°C to 50°C. In some embodiments, by using an appropriate amount of a thermal free radical initiator, the T of the polymer may be increased by about 10°C to 50°C. g will increase by 20℃~40℃. Similarly, the T d5 It may also increase by about 3℃ to 10℃.

[0269] 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. Therefore, in some embodiments, the composition of the present invention can be formed into a sheet. The thickness of the sheet is not particularly limited, but when considering use as a dielectric material, the thickness is, for example, 0.01 to 0.5 mm. In other embodiments, the thickness is about 0.02 to 0.2 mm. Typically, the sheet so formed will not flow substantially at room temperature (25° C.). The sheet can be disposed on any carrier layer or separately. Examples of carrier layers include polyimide films or or glass sheets. Any other known strippable film substrates can also be used as carrier layers.

[0270] As described above, the film / sheet formed according to the present invention has excellent dielectric properties, and can be adjusted according to the type of components used in the composition of the present invention as described in this specification. In terms of quantity, the relative permittivity of the film / sheet, i.e., the dielectric constant (Dk), is about 2.2 to 2.8 at a frequency of 10 GHz. The dielectric loss tangent (Df) is about 0.0004 to 0.002 at a frequency of 10 GHz, and in other embodiments, the dielectric loss tangent is about 0.0009 to 0.0015. As a result, the composition of the present invention can be applied to devices requiring such low dielectric materials, such as dielectric polymer layers used in millimeter wave radar antennas for automotive applications, and other terminal devices used in 5G devices. For example, with reference to JP2018-109090 and JP2003-216823. The antenna is generally composed of an insulator and a conductor layer (e.g., copper foil). The composition or sheet of the present invention can be used as a part or the whole of an insulator. Antennas using the composition or sheet of the present invention as part or all of an insulator have high frequency characteristics and reliability (durability). When such materials are used as copper-clad laminates in printed circuit boards, they need to have high glass transition temperature, low thermal expansion coefficient CTE, low Dk / Df, high peel strength to copper, and high reliability under high temperature storage conditions. When manufacturing layered structures, the ability to form prepregs (compounded with glass cloth), the ability to B-stage (generate uncrosslinked or partially crosslinked material layers) and the ability to film fusing are also important. Most commercially available materials in this field do not achieve all of these characteristics, especially low Dk / Df and high glass transition temperature.

[0271] The conductor layer in the antenna is formed, for example, of a metal having the desired conductivity. A circuit is formed on the conductor layer using a known circuit manufacturing method. The conductor layer forming the conductor includes various metals having conductivity, such as gold, silver, copper, iron, nickel, aluminum or their alloy metals. As a method for forming the conductor layer, a known method can be used. For example, it includes vapor deposition, electroless plating and electrolytic plating. Alternatively, a metal foil (for example, a copper foil) can be crimped by hot pressing bonding. The metal foil constituting the conductor layer is generally a metal foil for electrical connection. In addition to copper foil, various metal foils such as gold, silver, nickel and aluminum can be used. It may also include an alloy foil substantially (for example, more than 98wt%) composed of these metals. Among these metal foils, copper foil is generally used. The copper foil may be a rolled copper foil or an electrolytic copper foil.

[0272] Advantageously, the compositions of the present invention fill a gap that cannot be achieved by prior art materials. That is, as described above, the compositions of the present invention not only exhibit the much-needed low Dk / Df characteristics, but also provide a material with extremely high thermal stability, as shown above by the extremely high T g And very high T d5Characteristics confirmed.

[0273] Even more importantly, the composition of the present invention can be formed into a film / sheet of desired thickness to form various prepregs using glass cloth for making copper-clad laminates. In some embodiments, the film thickness of the film formed by the composition of the present invention can be in the range of about 75 to 150 μm, and 90 to 120 μm is suitable for forming metal-clad laminates. In some embodiments, the thickness can be less than 75 μm or greater than 150 μm.

[0274] It should also be noted that the various dielectric materials used in the applications mentioned in this specification must also withstand very severe temperature conditions and must maintain their dielectric properties for a long time. Surprisingly, when the film formed according to the present invention is subjected to high temperatures above about 125°C, it can also maintain low dielectric properties for a long time (up to 1000 hours or more), thus providing additional advantages. The change in Dk or Df is extremely low, which can be as low as 3% or 1%. Therefore, in some embodiments of the present invention, the film formed according to the present invention maintains its Dk / Df characteristics for more than 1000 hours in a temperature range of about 120°C to 150°C or more.

[0275] As mentioned above, the composition of the present invention is used in this way to form a film or sheet. In addition, in specific applications, the composition of the present invention can also be used as a low molecular weight varnish type material. The weight average molecular weight of the polymer used in such applications can be as low as 1,000, 2,000 or 3,000, or less than 10,000. In such applications, an appropriate amount of the required solvent can be added to maintain the solid content of the composition at about 10 to 70% by weight during polymerization. Similarly, any solvent suitable for forming such a solution can be used as a single solvent or solvent mixture required for such applications.

[0276] Advantageously, it has been found that the use of a mixture of a low molecular weight polymer and a high molecular weight polymer described in this specification provides the best performance in terms of resin fluidity control during the manufacture of a copper clad laminate. That is, the best process for improving the process can be achieved, which can not only provide a uniform copper clad laminate layer, but also maintain a copper clad laminate with excellent properties after curing. Therefore, in some embodiments, a low molecular weight polymer having a weight average molecular weight of less than 5,000, 4,000, 3,000, 2,000 or less than 1,000 is combined with a high molecular weight polymer having a weight average molecular weight of more than 80,000, 90,000, 100,000 or more than 150,000 to form a composition according to the present invention. Any amount of low molecular weight polymers described in this specification that can bring expected benefits can be used for this purpose. In some embodiments, the amount of low molecular weight polymer used in the composition of the present invention can be in the range of about 10% by weight to about 40% by weight or 20% by weight to about 30% by weight relative to the total amount of low molecular weight polymer and high molecular weight polymer. It is easy to understand by those skilled in the art that using too little amount of low molecular weight polymer may not completely wet the glass cloth or copper surface. At the same time, using too much low molecular weight polymer will plasticize the surface and make the polymer (i.e., resin) flow a lot, which is not desirable. Therefore, using the optimal amount of low molecular weight polymer and high molecular weight polymer mixture in the composition can provide the expected benefits shown in the following specific examples.

[0277] In another aspect of the present invention, a set for forming a film is provided. The composition of the present invention is distributed in the set. Therefore, in some embodiments, a set is provided, wherein the polymer recorded in this specification, one or more cross-linking agents recorded in this specification, tackifiers, free radical initiators recorded in this specification, and one or more selective additives recorded in this specification are distributed. In some embodiments, the set combination of the present invention comprises a polymer of two different monomers with general formula (I) and a monomer of general formula (II), and at least one of the cross-linking agent, tackifier, free radical initiator and selective additive to obtain the desired result and / or intended purpose.

[0278] In another aspect of this embodiment of the invention, the kit of the invention forms a B-stageable film when exposed to a suitable temperature for a sufficient period of time. That is, as described herein, the composition of the invention is cast on a surface or substrate to be encapsulated and subjected to a suitable heat treatment to polymerize the monomers to form a solid polymer, which can be in the form of a film or sheet.

[0279] Typically, as described above, such polymerization can be carried out under various temperature conditions, for example, heating can also be carried out in stages, such as heating to 90°C followed by heating at 110°C and finally heating at 150°C for a sufficiently long time, such as heating for 5 minutes to 2 hours in each temperature stage. The B-stage film can be further heated to above 150°C for various lengths of time (e.g., 90 minutes to 150 minutes) to cure the film to form a cross-linked polymer network. By practicing the present invention, a polymer film that is substantially a uniform film can be obtained on such a substrate. The thickness of the film can be specified or defined as above, and can generally be above 50 to 500 μm.

[0280] When manufacturing the sheet, in order to ensure the flatness of the sheet and suppress unexpected shrinkage, various known heating methods for manufacturing sheet materials can be used. For example, it can be heated at a relatively low temperature first, and then the temperature can be gradually increased. In order to ensure flatness, etc., the heating can be performed by pressurizing by a flat plate (metal plate) or the like before heating and / or by pressurizing by a flat plate. The pressure used in such pressurization is, for example, 0.1 to 8 MPa. In other embodiments, the pressure is in the range of about 0.3 to 5 MPa.

[0281] In some embodiments, the kits described herein include the various exemplary compositions described above.

[0282] In another aspect of the present invention, a method for forming a film for manufacturing various optoelectronic and / or automotive equipment is further provided, the method comprising the following steps:

[0283] A uniform and transparent composition is formed, which comprises: a polymer described in this specification; one or more cross-linking agents described in this specification; a tackifier described in this specification; a free radical initiator described in this specification; and one or more additives added as needed, including a filler described in this specification;

[0284] coating a suitable substrate with the composition or injecting the composition into a suitable substrate to form a film; and

[0285] The film is heated in stages to appropriate temperatures to form a B-stageable film and to cure the film.

[0286] The step of coating the desired substrate with the composition of the present invention to form a film can be implemented by any coating step known to those skilled in the art such as the steps recorded in this specification and / or spin coating. Other suitable coating methods include but are not limited to spraying, blade coating, meniscus coating, inkjet coating and slit coating. The mixture can also be injected into the substrate to form a film. Suitable substrates include any suitable substrates that can be used for electrical, electronic or optoelectronic devices, such as semiconductor substrates, ceramic substrates, glass substrates.

[0287] Next, the coated substrate is baked, i.e., heated, to promote solvent removal and crosslinking, for example, heated to a temperature of 50°C to 150°C for about 1 to 180 minutes, but other suitable temperatures and times can also be used. That is, first, a film is formed by a B-stage process, partially cured after removing all solvents present, and fully cured at a higher temperature in the next step. In some embodiments, the substrate is baked at a temperature of about 100°C to about 120°C for 120 minutes to 180 minutes. In other embodiments, the substrate is baked at a temperature of about 110°C to about 1400°C for 60 minutes to 120 minutes. That is, these are B-staged films. Finally, the B-staged film thus formed is further heated to a temperature above about 150°C to fully cure the film.

[0288] Then, the electrical properties of the film thus formed are evaluated using any method known in the art. For example, a device for measuring the permittivity using the resonant cavity method (manufactured by AET, in accordance with JIS C 2565 standard) is used to measure the dielectric constant (Dk) or the permittivity and the dielectric loss tangent at a frequency of 10 GHz. The coefficient of thermal expansion (CTE) is measured using a thermomechanical analysis device (Seiko Instruments Inc., SS 6000) according to a measurement sample having a size of about 4 mm (width) × 40 mm (length) × 0.1 mm (thickness), and the measurement temperature is within the range of 30 to 350 ° C, and the heating rate is 5 ° C / minute. The linear expansion coefficient at 50 ° C to 100 ° C is used as the linear expansion coefficient. Generally, as described in this specification, the film formed according to the present invention exhibits excellent dielectric properties and thermal properties and can be adjusted to the desired dielectric properties and thermal properties.

[0289] Therefore, in some embodiments of the present invention, a film or sheet obtained by the composition described in this specification is also provided. In another embodiment, as described in this specification, an electronic device comprising the film / sheet of the present invention is also provided.

[0290] The composition of the present invention can also be formed into various composite structures used as prepreg materials when making metal-clad laminates. Various types of metals can be used for this purpose, including, for example, copper, aluminum, stainless steel, etc. Metal-clad laminates are well known in the art, wherein the metal layer is coated with an insulating material such as the composition of the present invention. For example, as described in this specification, the composition of the present invention can be impregnated into a glass fabric, and then a prepreg is formed by heating to a suitable temperature in a B-stage process. Thereafter, the prepreg so formed is sandwiched between copper layers or other metal foils and cured at a temperature above 150° C. to form a copper-clad laminate.

[0291] It has been found that the laminate formed according to the present invention exhibits excellent peel strength. That is, the cured film of the present invention is firmly bonded to the glass surface or the metal surface, so it is not easy to peel the film from such substrates. Even more advantageously, surprisingly, it has been found that the peel strength can be improved by using an optimal level of free radical initiator. For example, the use of an extremely low content, i.e., a free radical initiator less than 0.5pphr, can cause the composition to exhibit unacceptable peel strength. However, using a free radical initiator in the range of about 2 to 3pphr, extremely excellent peel strength can be provided. Therefore, in some embodiments, the peel strength of the composite material formed according to the present invention can be in the range of about 5N / cm to about 8N / cm or 9N / cm or 11N / cm or 13N / cm or more, depending on the optimal amount of the free radical initiator used and the type of composite material prepared.

[0292] Thus, in some embodiments, a glass cloth composite film / cloth (e.g., prepreg) formed from the polymer of the present invention is provided that exhibits a dielectric constant (Dk) of less than 2.8 at a frequency of 10 GHz, a peel strength of greater than 6 N / cm, and a coefficient of thermal expansion (CTE) of less than 40 ppm / K.

[0293] Advantageously, it has been further found that the composition of the present invention can be uniformly coated on various glass or metal surfaces before curing, thereby covering any gaps on the surface of such materials. Thereafter, the coated surface is cured at a higher temperature to form a fully cured insulating layer that is firmly bonded to the glass or metal surface. That is, for example, it is now possible to provide a metal foil coated with the composition for the manufacture of printed wiring boards or metal-clad laminates, wherein the bonding performance between the insulating layer (i.e., the film formed by the composition of the present invention) and the metal layer is excellent, and the loss during signal transmission is further reduced.

[0294] Even more advantageously, it has been found that when the composition of the present invention is applied to a suitable surface, it is still able to flow and fill gaps before the two layers are well bonded. This is particularly advantageous when manufacturing metal-clad laminates such as copper-clad laminates, because all gaps must be insulated to further minimize losses during signal transmission. Therefore, in one aspect of the present invention, a method for manufacturing a prepreg or metal-clad laminate is provided, wherein the composition of the present invention is applied to a suitable glass fabric or metal foil and heated to a suitable temperature in the range of about 80°C to 120°C to form an uncured film of the composition of the present invention on the glass fabric and / or metal foil. Thereafter, the composite material so formed is cured at a higher temperature in the range of about 160°C to 180°C to form a fully cured laminate. It should be particularly noted that the molecular weight of the polymer used in this aspect of the present invention can be extremely low. That is, the weight average molecular weight (M) of the polymer used in this aspect of the present invention is about 100%.w ) can be as low as 1,000 or in the range of about 1,000 to 5,000. The composition of the present invention exhibits excellent flow characteristics before it is fully cured and is uniformly filled onto the surface of such glass fabric or metal foil, thereby providing an excellent insulating layer exhibiting extremely low dielectric constant and low loss characteristics as described in the present specification.

[0295] In the following examples, the preparation methods and uses of some compounds / monomers, polymers and compositions of the present invention are described in detail. These detailed preparation methods fall within the scope of the preparation methods generally described above and are used for illustration. The examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The ratio of monomer to catalyst used in the examples and throughout the specification is a molar ratio.

[0296] Embodiment (general)

[0297] The following abbreviations used in this specification are used to describe some compounds, instruments and / or methods used in specific embodiments of the present invention:

[0298] NB: bicyclo[2.2.1]hept-2-ene; HexNB: 5-hexylbicyclo[2.2.1]hept-2-ene; BuNB: 5-butylbicyclo[2.2.1]hept-2-ene; ButenylNB: 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene; CyHexeneNB: 5-(cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene; HexenylNB: 5-(hex-5-en-1-yl)bicyclo[2.2.1]hept-2-ene; VNB: 5-ethyl ENB: 5-ethylidenebicyclo[2.2.1]hept-2-ene; Pd785: bis(tricyclohexylphosphine)palladium(II)diacetate; Pd1206-(acetonitrile)bis(triisopropylphosphine)(acetic acid)palladiumtetrakis(pentafluorophenyl)borate; Pd601: diadamantyl-(n-butyl)phosphinepalladiumdiacetate(H2O); Pd1602: [Pd(OAc)(MeCN)(PAd2-n-Bu)2]B(C6F5)4; DANFABA: dimethylaniliniumtetrakis(pentafluorophenyl)boronic acid salt; LiFABA: lithium tetrakis(pentafluorophenyl)borate diethyl ether; TAIC: 1,3,5-triallyl-1,3,5-triazine-2,4,6-trione; TAC: 2,4,6-tri(allyloxy)-1,3,5-triazine; V-40: 1,1'-(diazene-1,2-diyl)bis(cyclohexane-1-carbonitrile); DCP: diisopropylbenzene peroxide; B1000: 1,2-butadiene rubber; T65: ethylene-propylene-dicyclopentadiene terpolymer; T67: ethylene-propylene-ethylidene norbornene terpolymer ; SA9000: polyarylether crosslinker terminated with methacrylate groups; SC2300-SVJ: silica nanoparticles; Irganox-1076: 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecylphenylpropanoic acid; Irgafos-168: tris(2,4-di-tert-butylphenyl)phosphite; BCO: bicyclo[4.2.0]oct-7-ene; TES: triethylsilane; MCH: methylcyclohexane; EA: ethyl acetate; THF: tetrahydrofuran; GPC: gel permeation chromatography; M w : weight average molecular weight; M n : number average molecular weight; PDI: polydispersity index; NMR: nuclear magnetic resonance spectroscopy; DSC: differential scanning calorimetry; TGA: thermogravimetric analysis; TMA: thermomechanical analysis; pphr: parts per hundred parts of resin (e.g., a polymer according to the present invention as specifically described hereinafter).

[0299] Various monomers used in this specification may be commercially available or can be easily prepared according to the steps described in US Patent Application No. 9,944,818.

[0300] Example A

[0301] NB / HexNB / CyHexeneNB (60 / 20 / 20 molar ratio) terpolymer

[0302] A mixture of NB (10.2 g, 109 mmol, 75 wt.% in toluene), HexNB (6.46 g, 36 mmol), CyHexeneNB (6.32 g, 36 mmol), TES (8.43 g, 72 mmol), ethanol (0.84 g, 18 mmol) and DANFABA (0.09 g, 0.11 mmol) was dissolved in anhydrous toluene (222 g) in a glass reactor and flushed with nitrogen. The solution was heated to 80°C under nitrogen atmosphere. Pd1206 (0.04 g, 0.04 mmol, 0.9 wt.% in anhydrous ethyl acetate) was added to the solution. The mixture was heated at 80°C for 4 hours while being stirred. Toluene was then added to the reaction mixture. The diluted polymerization mixture was cooled to room temperature and poured into excess isopropanol while rapidly stirring to precipitate the polymer. The liquid was filtered off and the solid was dried in a vacuum oven at 50°C to obtain a purified polymer. GPC(THF):M w =102,000, M n =18,800, PDI=5.4.

[0303] Example B

[0304] NB / CyHexeneNB (85 / 15 molar ratio) copolymer

[0305] A mixture of NB (14.5 g, 154 mmol, 75 wt.% in toluene), CyHexeneNB (4.74 g, 27 mmol), TES (8.43 g, 72 mmol), ethanol (0.83 g, 18 mmol) and DANFABA (0.09 g, 0.11 mmol) was dissolved in anhydrous toluene (192 g) in a glass reactor and flushed with nitrogen. The solution was heated to 80°C under a nitrogen atmosphere. Pd1206 (0.04 g, 0.04 mmol, 1.0 wt.% in anhydrous ethyl acetate) was added to the solution. The mixture was heated at 80°C for 4 hours while being stirred. Toluene was then added to the reaction mixture. The diluted polymerization mixture was cooled to room temperature and poured into an excess of isopropanol while rapidly stirring to precipitate the polymer. The liquid was filtered off and the solid was dried in a vacuum oven at 50°C to obtain a purified polymer. GPC (THF): M w =102,000, M n =18,800, PDI=5.4.

[0306] Example C

[0307] NB / VNB (85 / 15 molar ratio) copolymer

[0308] A mixture of NB (14.5 g, 154 mmol, 75 wt.% in toluene), VNB (3.27 g, 27 mmol), TES (8.43 g, 72 mmol), ethanol (0.84 g, 18 mmol) and DANFABA (0.09 g, 0.11 mmol) was dissolved in anhydrous toluene (182 g) in a glass reactor and flushed with nitrogen. The solution was heated to 80°C under a nitrogen atmosphere. Pd1206 (0.04 g, 0.04 mmol, 1.0 wt.% in anhydrous ethyl acetate) was added to the solution. The mixture was heated at 80°C for 4 hours while being stirred. Toluene was then added to the reaction mixture. The diluted polymerization mixture was cooled to room temperature and poured into an excess of isopropanol while rapidly stirring to precipitate the polymer. The liquid was filtered off and the solid was dried in a vacuum oven at 50°C to obtain a purified polymer. GPC (THF): M w =102,000, M n =18,800, PDI=5.4.

[0309] Example D

[0310] NB / HexNB / HexenylNB (60 / 20 / 20 molar ratio) terpolymer

[0311] A mixture of NB (11.3 g, 120 mmol, 75 wt.% toluene solution), HexNB (7.13 g, 40 mmol), HexenylNB (7.05 g, 40 mmol), BCO (8.65 g, 80 mmol) and LiFABA (0.025 g, 0.03 mmol) was dissolved in anhydrous toluene (112 g) in a glass reactor and flushed with nitrogen. The solution was heated to 80°C under a nitrogen atmosphere. Pd601 (0.06 g, 0.01 mmol, 0.7 wt.% anhydrous THF solution) was added to the solution. The mixture was heated at 80°C for 4 hours while being stirred. Toluene was then added to the reaction mixture. The diluted polymerization mixture was cooled to room temperature and poured into an excess of isopropanol while stirring rapidly to precipitate the polymer. The liquid was filtered off and the solid was dried in a vacuum oven at 50°C to obtain a purified polymer. GPC (THF): M w =102,000, M n =18,800, PDI=5.4.

[0312] Example 1

[0313] Terpolymer of NB / HexNB / CyHexeneNB (50 / 25 / 25 molar ratio)

[0314] A mixture of NB (5.64 g, 60 mmol), HexNB (5.34 g, 30 mmol), CyHexeneNB (5.22 g, 30 mmol), BCO (0.104 g, 0.96 mmol) and LiFABA (0.008 g, 0.01 mmol, 5 wt.% in anhydrous ethyl acetate) dissolved in anhydrous toluene (48 g) was placed in a flip-top vial, sealed and flushed with nitrogen. The solution was heated to 90°C. Pd1602 (0.008 g, 0.005 mmol in 1 wt.% ethyl acetate solution) was added to the solution by pipetting via a syringe. The solution was heated at 90°C for 6 hours while stirring. The polymerization mixture was cooled to room temperature and poured into an excess of methanol (300 g) while stirring rapidly to precipitate the polymer. The liquid portion was decanted, and the solid was washed with methanol (300 g) and dried in a vacuum oven at 80° C. for 24 h to obtain a purified polymer (12.1 g, 79% isolated yield, GPC (THF): M w =40,150,M n =9,775, PDI=4.1).

[0315] Example 2

[0316] NB / HexNB / ButenylNB (50 / 25 / 25 molar ratio) terpolymer

[0317] A mixture of NB (5.64 g, 60 mmol), HexNB (5.34 g, 30 mmol), ButenylNB (4.44 g, 30 mmol), BCO (0.104 g, 0.96 mmol) and LiFABA (0.008 g, 0.01 mmol, 5 wt.% in anhydrous ethyl acetate) dissolved in anhydrous toluene (45 g) was placed in a flip-top vial, sealed and flushed with nitrogen. The solution was heated to 90°C. Pd1602 (0.008 g, 0.005 mmol, 1 wt.% in ethyl acetate) was added to the solution by pipetting via a syringe. The solution was heated at 90°C for 6 hours while stirring. The polymerization mixture was cooled to room temperature and poured into an excess of methanol (300 g) while stirring rapidly to precipitate the polymer. The liquid portion was decanted, and the solid was washed with methanol (300 g) and dried in a vacuum oven at 80° C. for 24 h to obtain a purified polymer (13.2 g, 81% isolated yield, GPC (THF): M w=95,550,M n =25,130, PDI=4.1).

[0318] Example 3

[0319] Terpolymer of NB / BuNB / CyHexeneNB (40 / 35 / 25 molar ratio)

[0320] A mixture of NB (4.52 g, 48 mmol), BuNB (6.3 g, 42 mmol), CyHexeneNB (5.22 g, 30 mmol), BCO (0.104 g, 0.96 mmol) and LiFABA (0.008 g, 0.01 mmol, 5 wt.% in anhydrous ethyl acetate) dissolved in anhydrous toluene (62 g) was placed in a flip-top vial, sealed and flushed with nitrogen. The solution was heated to 90°C. Pd1602 (0.008 g, 0.005 mmol, 1 wt.% in ethyl acetate) was added to the solution by pipetting with a syringe. The mixture was heated at 90°C for 6 hours while stirring (GPC (THF): M w =126,063,M n =35,337, PDI=3.6). The polymerization mixture was cooled to room temperature and poured into an excess of methanol (400 mL) while rapidly stirring to precipitate the polymer. The liquid portion was decanted, and the solid was washed with methanol (400 mL) and dried in a vacuum oven at 80° C. for 24 hours to obtain a purified polymer (9.4 g, 57% isolated yield).

[0321] Example 4

[0322] Terpolymer of NB / BuNB / ButenylNB (40 / 35 / 25 molar ratio)

[0323] A mixture of NB (4.52 g, 48 mmol), BuNB (6.3 g, 42 mmol), ButenylNB (4.44 g, 30 mmol), BCO (0.104 g, 0.96 mmol) and LiFABA (0.008 g, 0.01 mmol, 5 wt.% in anhydrous ethyl acetate) dissolved in anhydrous toluene (59 g) was placed in a flip-top vial, sealed and flushed with nitrogen. The solution was heated to 90°C. Pd1602 (0.008 g, 0.005 mmol, 1 wt.% in ethyl acetate) was added to the solution by pipetting with a syringe. The solution was heated at 90°C for 6 hours while stirring (GPC (THF): M w =33,775,M n=8,400, PDI=4). The polymerization mixture was cooled to room temperature and poured into an excess of methanol (400 mL) while rapidly stirring to precipitate the polymer. The liquid portion was decanted, and the solid was washed with methanol (400 mL) and dried in a vacuum oven at 80°C for 24 hours to obtain a purified polymer (9 g, 59% isolated yield).

[0324] Example 5

[0325] Terpolymer of NB / HexNB / CyHexeneNB (50 / 25 / 25 molar ratio)

[0326] A mixture of NB (6.59 g, 70 mmol), HexNB (6.23 g, 35 mmol), CyHexeneNB (6.09 g, 35 mmol), BCO (0.122 g, 1.13 mmol) and LiFABA (0.018 g, 0.021 mmol, 5 wt.% in anhydrous ethyl acetate) dissolved in anhydrous toluene (43 g) was placed in a flip-top vial, sealed and flushed with nitrogen. The solution was heated to 90°C. Pd1602 (0.011 g, 0.007 mmol, 1 wt.% in ethyl acetate) was added to the solution by pipetting via a syringe. The mixture was heated at 90°C for 6 hours while stirring. The polymerization mixture was cooled to room temperature and poured into an excess of methanol (400 g) while stirring rapidly to precipitate the polymer. The liquid was decanted and the solid was dissolved in a solvent of a mixture of toluene (40 g) and THF (25 g). The solution was then poured into methanol (400 mL) while stirring to precipitate the polymer. The liquid was decanted, and the solid was washed with methanol (400 g) and dried in a vacuum oven at 80° C. for 24 hours to obtain a purified polymer (14.7 g, 78% isolation yield, GPC (THF): M w =73,950, M n =16,550, PDI =4.5). 13 C-NMR (CDCl3) analysis calculated that the monomer composition of the terpolymer (NB / HexNB / CyHexeneNB) was 52 / 26 / 22.

[0327] Example 6

[0328] NB / HexNB / CyHexeneNB (35 / 40 / 25 molar ratio) terpolymer

[0329] A mixture of NB (4.28 g, 45.5 mmol), HexNB (9.26 g, 52 mmol), CyHexeneNB (5.66 g, 32.5 mmol), BCO (0.123 g, 1.05 mmol) and LiFABA (0.017 g, 0.02 mmol, 5 wt.% in anhydrous ethyl acetate) dissolved in anhydrous toluene (44 g) was placed in a flip-top vial, sealed and flushed with nitrogen. The solution was heated to 90°C. Pd1602 (0.01 g, 0.007 mmol, 1 wt.% in ethyl acetate) was then pipetted via a syringe. The solution was heated at 90°C for 6 hours while stirring. The polymerization mixture was cooled to room temperature and poured into an excess of methanol (400 g) while stirring rapidly to precipitate the polymer. The liquid was decanted and the solid was dissolved in a solvent mixture of toluene (40 g) and THF (25 g). The solution was poured into methanol (400 mL) while stirring to precipitate the polymer. The liquid was decanted, and the solid was washed with methanol (400 g) and dried in a vacuum oven at 80° C. for 24 hours to obtain a purified polymer (15 g, 78% isolation yield, GPC (THF): M w =85,250,M n =18,450, PDI =4.6). 13 C-NMR (CDCl3) analysis calculated that the monomer composition of the terpolymer (NB / HexNB / CyHexeneNB) was 39 / 40 / 21.

[0330] Example 7

[0331] NB / HexNB / ButenylNB (35 / 40 / 25 molar ratio) terpolymer

[0332] A mixture of NB (4.28 g, 45.5 mmol), HexNB (9.26 g, 52 mmol), ButenylNB (4.81 g, 32.5 mmol), BCO (0.06 g, 0.56 mmol) and LiFABA (0.017 g, 0.02 mmol, 5 wt.% in anhydrous ethyl acetate) dissolved in anhydrous toluene (42 g) was placed in a flip-top vial, sealed and flushed with nitrogen. The solution was heated to 90°C. Pd1602 (0.010 g, 0.007 mmol, 1 wt.% in ethyl acetate) was added to the solution by pipetting via a syringe. The solution was heated at 90°C for 6 hours while stirring. The polymerization mixture was cooled to room temperature and poured into an excess of methanol (400 g) while stirring rapidly to precipitate the polymer. The liquid was decanted and the solid was dissolved in a solvent mixture of toluene (40 g) and THF (25 g). The solution was poured into methanol (400 mL) while stirring to precipitate the polymer. The liquid was decanted, and the solid was washed with methanol (400 g) and dried in a vacuum oven at 80° C. for 24 hours to obtain a purified polymer (16 g, 87% isolation yield, GPC (THF): M w =25,900, M n =6,725, PDI =3.9). 13 C-NMR (CDCl3) analysis calculated that the monomer composition of the terpolymer (NB / HexNB / CyHexeneNB) was 40 / 40 / 20.

[0333] Example 8

[0334] NB / HexNB / CyHexeneNB (60 / 20 / 20 molar ratio) terpolymer

[0335] A mixture of NB (8.47 g, 90 mmol), HexNB (5.34 g, 30 mmol), CyHexeneNB (5.22 g, 30 mmol), BCO (0.087 g, 0.81 mmol) and LiFABA (0.020 g, 0.023 mmol, 5 wt.% in anhydrous ethyl acetate) dissolved in anhydrous toluene (44 g) was placed in a flip-top vial, sealed and flushed with nitrogen. The solution was heated to 90°C. Pd1602 (0.012 g, 0.008 mmol, 1 wt.% in ethyl acetate) was added to the solution by pipetting via a syringe. The mixture was heated at 90°C for 6 hours while being stirred. The polymerization mixture was cooled to room temperature and poured into an excess of methanol (400 g) while rapidly stirring to precipitate the polymer. The liquid was decanted, and the solid was washed with methanol (300 g) and dried in a vacuum oven at 80° C. for 24 h to obtain a purified polymer (15 g, 78% isolated yield, GPC (THF): M w =149,300,M n =43,875, PDI =3.4). 13 C-NMR (CDCl3) analysis calculated that the monomer composition of the terpolymer (NB / HexNB / CyHexeneNB) was 60 / 20 / 20.

[0336] Example 9

[0337] NB / HexNB / ButenylNB (60 / 20 / 20 molar ratio) terpolymer

[0338] A mixture of NB (8.47 g, 90 mmol), HexNB (5.34 g, 30 mmol), ButenylNB (4.44 g, 30 mmol), BCO (0.052 g, 0.48 mmol) and DANFABA (0.018 g, 0.023 mmol, 5 wt.% in anhydrous ethyl acetate) dissolved in anhydrous toluene (42 g) was placed in a flip-top vial, sealed and flushed with nitrogen. The solution was heated to 90°C. Pd1206 (0.009 g, 0.008 mmol, 1 wt.% in ethyl acetate) was added to the solution by pipetting via a syringe. The mixture was heated at 90°C for 6 hours while being stirred. The polymerization mixture was cooled to room temperature and poured into an excess of methanol (300 g) while rapidly stirring to precipitate the polymer. The liquid was decanted, and the solid was washed with methanol (300 g) and dried in a vacuum oven at 80° C. for 24 hours to obtain a purified polymer (17 g, 93% isolated yield. GPC (THF): M w =23,075,M n=6,250, PDI = 3.7. 13 C-NMR (CDCl3) analysis calculated that the monomer composition of the terpolymer (NB / HexNB / CyHexeneNB) was 64 / 21 / 15.

[0339] Example 10

[0340] NB / HexNB / CyHexeneNB (60 / 20 / 20 molar ratio) terpolymer

[0341] A mixture of NB (112.9 g, 1200 mmol, 75 wt.% toluene solution), HexNB (71.3 g, 400 mmol), CyHexeneNB (69.7 g, 400 mmol), TES (2.05 g, 17.6 mmol), ethanol (9.2 g, 200 mmol) and LiFABA (0.26 g, 0.3 mmol) was dissolved in anhydrous toluene (972 g) in a glass reactor and flushed with nitrogen. The solution was heated to 80°C under a nitrogen atmosphere. Pd601 (0.06 g, 0.1 mmol, 1.3 wt.% anhydrous THF solution) was added to the solution. The mixture was heated at 80°C for 6 hours while being stirred. Toluene (1280 g) was then added to the reaction mixture. The diluted polymerization mixture was cooled to room temperature and poured into excess isopropanol (about 1400 g each) in 3 portions of about 570 g each while rapidly stirring to precipitate the polymer. The liquid was filtered off and the solid was dried in a vacuum oven at 80-90°C for 20-30 hours to obtain a purified polymer. GPC (THF): M w =146,150,M n =58,749, PDI = 2.5. 13 C-NMR (CDCl3) analysis calculated that the monomer composition of the terpolymer (NB / HexNB / CyHexeneNB) was 63 / 19 / 18.

[0342] Example 10A

[0343] Terpolymer of NB / HexNB / CyHexeneNB (60 / 20 / 20 molar ratio) The terpolymer of Example 10A was prepared in substantially the same manner as described in Example 10. GPC (THF): M w =140,600,M n =44,777, PDI = 3.1. 13 C-NMR (CDCl3) analysis calculated that the monomer composition of the terpolymer (NB / HexNB / CyHexeneNB) was 62 / 21 / 17.

[0344] Example 10B

[0345] Terpolymer of NB / HexNB / CyHexeneNB (60 / 20 / 20 molar ratio) The terpolymer of Example 10B was prepared in substantially the same manner as described in Example 10. GPC (THF): M w =174,000, M n =57,237, PDI = 3. 13 C-NMR (CDCl3) analysis calculated that the monomer composition of the terpolymer (NB / HexNB / CyHexeneNB) was 62 / 20 / 18.

[0346] Embodiment 11

[0347] NB / HexNB / CyHexeneNB (60 / 20 / 20 molar ratio) terpolymer

[0348] A mixture of NB (113 g, 1200 mmol, 75 wt.% in toluene), HexNB (71.3 g, 400 mmol), CyHexeneNB (69.7 g, 400 mmol), BCO (1.08 g, 10.0 mmol) and LiFABA (0.26 g, 0.3 mmol) was dissolved in anhydrous toluene (545 g) in a glass reactor and flushed with nitrogen. The solution was heated to 80°C under a nitrogen atmosphere. Pd1602 (0.16 g, 0.1 mmol, 1.3 wt.% in anhydrous ethyl acetate) was added to the reaction mixture. The mixture was heated at 80°C for 6 hours while being stirred. THF (850 g) was then added to the reaction mixture. The diluted polymerization mixture was cooled to room temperature and poured into an excess of methanol (about 2700 g each) in 3 portions of about 560 g each while rapidly stirring to precipitate the polymer. The liquid was filtered off and the solid was dried in a vacuum oven at 80-90°C for 20-30 hours to obtain a purified polymer (231 g, 91% isolated yield). GPC (THF): M w =166,600,M n =34,000, PDI = 4.9. 13 C-NMR (CDCl3) analysis calculated that the monomer composition of the terpolymer (NB / HexNB / CyHexeneNB) was 64 / 19 / 17.

[0349] Example 12

[0350] NB / HexNB / CyHexeneNB (70 / 10 / 20 molar ratio) terpolymer

[0351] A mixture of NB (131.8 g, 1400 mmol, 75 wt.% in toluene), HexNB (35.7 g, 200 mmol), CyHexeneNB (69.7 g, 400 mmol), BCO (1.62 g, 15 mmol) and LiFABA (0.26 g, 0.3 mmol) was dissolved in anhydrous toluene (899 g) in a glass reactor and flushed with nitrogen. The solution was heated to 80°C under a nitrogen atmosphere. Pd1602 (0.16 g, 0.1 mmol, 1.3 wt.% in anhydrous ethyl acetate) was added to the solution. The mixture was heated at 80°C for 6 hours while being stirred. Toluene (1750 g) was then added to the reaction mixture. The diluted polymerization reaction mixture was cooled to room temperature and poured into an excess of isopropanol (about 2700 g each) in 3 portions of about 570 g each while rapidly stirring to precipitate the polymer. The liquid was filtered off and the solid was dried in a vacuum oven at 80-90°C for 20-30 hours to obtain a purified polymer (227 g, 96% isolated yield). GPC (THF): M w =117,325,M n =26,950, PDI = 4.4. 13 C-NMR (CDCl3) analysis calculated that the monomer composition of the terpolymer (NB / HexNB / CyHexeneNB) was 70 / 10 / 20.

[0352] Embodiment 13

[0353] NB / HexNB / HexenylNB (60 / 20 / 20 molar ratio) terpolymer

[0354] A mixture of NB (113 g, 1200 mmol, 75 wt.% in toluene), HexNB (71.3 g, 400 mmol), HexenylNB (70.5 g, 400 mmol), BCO (1.62 g, 15.0 mmol) and LiFABA (0.26 g, 0.30 mmol) dissolved in anhydrous toluene (976 g) was placed in a glass reactor and flushed with nitrogen. The solution was heated to 80°C under a nitrogen atmosphere. Pd601 (0.06 g, 0.1 mmol, 1.3 wt.% in anhydrous THF) was added to the solution. The mixture was heated at 80°C for 6 hours while being stirred. Toluene (1280 g) was then added to the reaction mixture. The diluted polymerization mixture was cooled to room temperature and poured into an excess of isopropanol (about 2500 g each) in 3 portions of about 570 g each while rapidly stirring to precipitate the polymer. The liquid was filtered off and the solid was dried in a vacuum oven at 80-90°C for 20-30 hours to obtain a purified polymer. GPC (THF): M w =169,775,M n =39,625, PDI = 4.3. 13 C-NMR (CDCl3) analysis calculated that the monomer composition of the terpolymer (NB / HexNB / HexenylNB) was 60 / 20 / 20.

[0355] Example 13A

[0356] NB / HexNB / CyHexeneNB (40 / 40 / 20 molar ratio) terpolymer

[0357] A mixture of NB (33.9 g, 360 mmol, 75 wt.% in toluene), HexNB (64.2 g, 360 mmol), CyHexeneNB (31.4 g, 180 mmol), BCO (1.27 g, 11.7 mmol) and LiFABA (0.12 g, 0.14 mmol) was dissolved in anhydrous toluene (579 g) in a glass reactor and flushed with nitrogen. The solution was heated to 80°C under a nitrogen atmosphere. Pd601 (0.027 g, 0.05 mmol, 0.6 wt.% in anhydrous THF) was added to the solution. The mixture was heated at 80°C for 4 hours while being stirred. Toluene (717 g) was then added to the reaction mixture. The diluted polymerization mixture was cooled to room temperature and added to an excess of isopropanol (about 4800 g each) while rapidly stirring to precipitate the polymer. The liquid was filtered off and the solid was dried in a vacuum oven at 50-55°C for about 12 hours, and then dried in a vacuum oven at 100°C for about 4 hours to obtain a purified polymer (118.8 g, 92% isolated yield). GPC (THF): M w =106,600,M n =23,400, PDI = 4.5. 13 C-NMR (CDCl3) analysis calculated that the monomer composition of the terpolymer (NB / HexNB / CyHexeneNB) was 44 / 41 / 15.

[0358] Embodiment 14

[0359] NB / HexenylNB (75 / 25 molar ratio) copolymer

[0360] A mixture of NB (150.7 g, 1500 mmol, 75 wt.% in toluene), HexenylNB (88.2 g, 500 mmol), BCO (1.62 g, 15.0 mmol) and LiFABA (0.26 g, 0.30 mmol) dissolved in anhydrous toluene (825 g) was placed in a glass reactor and flushed with nitrogen. The solution was heated to 80°C under a nitrogen atmosphere. Pd1602 (0.16 g, 0.1 mmol, 1.3 wt.% in anhydrous ethyl acetate) was added to the solution. The mixture was heated at 80°C for 6 hours while being stirred. Toluene (1156 g) was then added to the reaction mixture. The diluted polymerization mixture was cooled to room temperature and poured into an excess of isopropanol (about 3850 g each) in 3 portions of about 550 g each while rapidly stirring to precipitate the polymer. The liquid was filtered off and the solid was dried in a vacuum oven at 80-90°C for 20-30 hours to obtain a purified polymer (217 g, 91% yield). GPC (THF): M w =162,318,M n =32,780, PDI=5.

[0361] Embodiment 15

[0362] NB / CyHexeneNB (80 / 20 molar ratio) copolymer

[0363] A mixture of NB (150.7 g, 160 mmol, 75 wt.% in toluene), CyHexeneNB (69.7 g, 400 mmol), BCO (1.62 g, 15 mmol) and LiFABA (0.26 g, 0.3 mmol) was dissolved in anhydrous toluene (825 g) in a glass reactor and flushed with nitrogen. The solution was heated to 80°C under a nitrogen atmosphere. Pd1602 (0.16 g, 0.1 mmol, 1.3 wt.% in anhydrous ethyl acetate) was added to the solution. The mixture was heated at 80°C for 6 hours while stirring. Toluene (1152 g) was then added to the reaction mixture. The diluted polymerization mixture was cooled to room temperature and poured into an excess of isopropanol (about 3840 g each) in 3 portions of about 570 g each while stirring rapidly to precipitate the polymer. The liquid was filtered off and the solid was dried in a vacuum oven at 80-90°C for 20-30 hours to obtain a purified polymer (212 g, 96% yield). GPC (THF): M w =28,275,M n =8,950, PDI = 3.2. 1H-NMR (CDCl3) analysis calculated that the monomer composition of the copolymer (NB / CyHexeneNB) was 80 / 20.

[0364] Example 15A

[0365] HexNB / CyHexeneNB (80 / 20 molar ratio) copolymer

[0366] A mixture of HexNB (128.42 g, 720 mmol), CyHexeneNB (31.4 g, 180 mmol), BCO (1.27 g, 11.7 mmol) and LiFABA (0.12 mmol, 0.14 mmol) was dissolved in anhydrous toluene (728 g) in a glass reactor and flushed with nitrogen. The solution was heated to 80°C under a nitrogen atmosphere. Pd601 (0.027 g, 0.05 mmol, 0.6 wt.% in anhydrous THF) was added to the solution. The mixture was heated at 80°C for 4 hours while stirring. Toluene (717 g) was then added to the reaction mixture. The diluted polymerization mixture was cooled to room temperature and added to an excess of isopropanol (about 4700 g each) while stirring rapidly to precipitate the polymer. The liquid was filtered off and the solid was dried in a vacuum oven at 50-55°C for about 9 hours, followed by drying in a vacuum oven at 100°C for about 4 hours. GPC(THF):M w =92,600, M n =25,000, PDI = 3.7. 13 C-NMR (CDCl3) analysis calculated that the monomer composition of the copolymer (HexNB / CyHexeneNB) was 86 / 14.

[0367] Example 16

[0368] NB / VNB (80 / 20 molar ratio) copolymer

[0369] A mixture of NB (150.7 g, 160 mmol, 75 wt.% in toluene), VNB (48.1 g, 400 mmol), BCO (1.62 g, 15 mmol) and LiFABA (0.14 g, 0.16 mmol) was dissolved in anhydrous toluene (853 g) in a glass reactor and flushed with nitrogen. The solution was heated to 80°C under a nitrogen atmosphere. Pd1602 (0.13 g, 0.08 mmol, 1.3 wt.% in anhydrous ethyl acetate) was added to the solution. The mixture was heated at 80°C for 6 hours while being stirred. Toluene (480 g) was then added to the reaction mixture. The diluted polymerization mixture was cooled to room temperature and poured into an excess of isopropanol (about 1350 g each) in 4 portions of about 270 g each while rapidly stirring to precipitate the polymer. The liquid was filtered off and the solid was dried in a vacuum oven at 80-90°C for more than 12 hours to obtain a purified polymer (98 g, 49% yield). GPC (THF): M w =28,275,M n =8,950, PDI = 3.2. 1 H-NMR (CDCl3) analysis calculated that the monomer composition of the copolymer (NB / VNB) was 80 / 20.

[0370] Embodiment 17

[0371] NB / ENB (80 / 20 molar ratio) copolymer

[0372] A mixture of NB (150.7 g, 160 mmol, 75 wt.% in toluene), ENB (48.1 g, 400 mmol), BCO (1.62 g, 15 mmol) and LiFABA (0.14 g, 0.16 mmol) was dissolved in anhydrous toluene (853 g) in a glass reactor and flushed with nitrogen. The solution was heated to 80°C under a nitrogen atmosphere. Pd1602 (0.13 g, 0.08 mmol, 1.3 wt.% in anhydrous ethyl acetate) was added to the solution. The mixture was heated at 80°C for 6 hours while stirring. Toluene (480 g) was then added to the reaction mixture. The diluted polymerization mixture was cooled to room temperature and poured into an excess of isopropanol (about 1350 g each) in 4 portions of about 270 g each while stirring rapidly to precipitate the polymer. The liquid was decanted and the solid was washed with isopropanol (270 g) each time it precipitated. The liquid was filtered off and the solid was dried in a vacuum oven at 80-90°C for more than 12 hours to obtain a purified polymer (103 g, 52% yield). GPC (THF): M w =73,300, M n=17,550, PDI = 4.2. 1 H-NMR (CDCl3) analysis calculated that the monomer composition of the copolymer (NB / ENB) was 80 / 20.

[0373] Embodiment 18

[0374] NB / ButenylNB (75 / 25 molar ratio) copolymer

[0375] In a flip-top vial, a mixture of NB (8.47 g, 90 mmol, 75 wt% in toluene), ButenylNB (4.44 g, 30 mmol), BCO (0.14 g, 1.29 mmol) and LiFABA (0.008 g, 0.01 mmol, 5 wt.% in ethyl acetate) was dissolved in anhydrous toluene (53 g), sealed and flushed with nitrogen. The solution was heated to 90°C under a nitrogen atmosphere. Pd1602 (0.008 g, 0.005 mmol, 1 wt.% in anhydrous ethyl acetate) was added to the solution by syringe pipetting. The mixture was heated at 90°C for 6 hours while stirring. The polymerization mixture was cooled to room temperature and poured into methanol (300 g) while stirring rapidly to precipitate the polymer. The liquid was filtered off and the solid was dried in a vacuum oven at 80°C for 24 hours to obtain a purified polymer (12.5 g, 91% yield). GPC(THF):M w =61,150,M n =5,500, PDI=11.

[0376] Examples 19A to 19C

[0377] Evaluation of low-loss film characteristics

[0378] The terpolymer of Example 3 (terpolymer of NB / BuNB / CyHexeneNB, 40 / 35 / 25 molar ratio) was dissolved in mesitylene to prepare a 16.6wt.% solution. 15pphr of TAIC (Example 19A), B1000 (Example 19B) and 15pphr of SA9000, TAIC and B1000 (Example 19C) were added to 3 separate portions of the solution. A comparative composition was also prepared, which contained only a portion of the polymer solution of Example 3 and 15pphr of SA9000 (Comparative Example 1). 4.5pphr of DCP was added to each of the four compositions as a free radical initiator. These compositions were respectively knife-coated on a glass substrate and heated in an oven at 130°C under a nitrogen atmosphere for 1 hour to remove all residual solvents from the film. The solubility of these B-staged films was tested by ultrasonicating a small piece of the film in THF for 1 hour. The B-staged films were further cured in an oven at 170°C under a nitrogen atmosphere for 2 hours to produce cured films with a thickness ranging from about 75 to 150 μm. The solubility of these B-staged films was also tested by subjecting small pieces of the films to ultrasonic treatment in THF for 1 hour to ensure that the films lost solubility due to crosslinking to produce thermosetting properties. The dielectric constant (Dk) and dielectric loss factor (Df) of each cured film at 10 GHz were measured. The results are shown in Table 1. All films remained soluble (e.g., not crosslinked) in THF after B-staging at 130°C for 1 hour, indicating that these compositions are suitable for use in the copper clad laminate manufacturing process. As can be seen from the reduced solubility in THF after the curing step, SA9000, TAIC and B1000 are able to crosslink the films, indicating that these compositions are suitable for producing thermosets for copper clad laminates. The crosslinking agent (TAIC) and the tackifier (B1000) used in the present invention can form a cured film with low loss characteristics (e.g., low Dk and low Df), but the commonly used polyarylether crosslinking agent SA9000 terminated with methacrylate groups cannot form a film with low loss characteristics because its Df at 10 GHz is 0.0055 (Comparative Example 1). However, the combination of SA9000, TAIC and B1000 formed a film with low loss characteristics.

[0379] Table 1

[0380]

[0381] Examples 20A to 20C

[0382] Evaluation of low-loss film characteristics

[0383] The copolymer of Example 18 (NB / ButenylNB, 75 / 25 molar ratio) was dissolved in mesitylene to prepare a 20 wt.% solution. 15 pphr of B1000 (Example 20A), 15 pphr of T65 (Example 20B) and 15 pphr of T67 (Example 20C) were added to three separate portions of the solution. 4 pphr of DCP was added to each of the three compositions as a free radical initiator. The compositions were knife coated on a glass substrate and heated in an oven at 130°C under a nitrogen atmosphere for 1 hour to remove all residual solvent from the film. The solubility of these B-staged films was tested by subjecting a small piece of the film to ultrasonic treatment in THF for 1 hour. The B-staged film was further cured at 170-180°C for 1 hour, followed by further curing at 170-180°C under vacuum conditions for 1 hour to produce a cured film having a thickness of about 75-150 μm. The solubility of these B-staged films was also tested by ultrasonicating small pieces of the films in THF for 1 hour to ensure that the films lost solubility due to crosslinking to produce thermosetting properties. The dielectric constant (Dk) and dielectric loss factor (Df) of the cured films at 10 GHz were measured. The results are shown in Table 2. All films remained soluble in THF (e.g., not crosslinked) after 1 hour of B-stage at 130°C, indicating that these compositions are suitable for use in the copper clad laminate manufacturing process. As can be seen from the reduced solubility in THF after the curing step, all compositions are able to crosslink, indicating that these compositions are suitable for generating thermosets for copper clad laminates. This result further confirms that the crosslinking agents and tackifiers (e.g., B1000, T65 and T67) used in the compositions of the present invention can generate cured films that exhibit desired low loss properties (e.g., low Dk and low Df).

[0384] Table 2

[0385]

[0386] Examples 21A-21B

[0387] Evaluation of low loss and thermal properties of films

[0388] The terpolymer of Example 3 (NB / BuNB / CyHexeneNB, 40 / 35 / 25 molar ratio) (Example 21A) and the terpolymer of Example 4 (NB / BuNB / ButenylNB, 40 / 35 / 25 molar ratio) (Example 21B) were dissolved in mesitylene to prepare a 20 wt.% solution. 15 pphr of B1000, 15 pphr of TAIC and 5 pphr of DCP were added to the two solutions, respectively. These compositions were then knife-coated on glass substrates. The solvent was removed by heating to 130°C in an oven in a nitrogen atmosphere for 1 hour, and then cured at 180°C under vacuum conditions for 2 hours to produce a film with a thickness of about 75 to 150 μm. The glass transition temperatures (T g ) and thermal expansion coefficient (CTE). The film loss was determined by TGA to be 5 wt.% (T d5 ) decomposition temperature. Dk and Df were also measured at 10 GHz. The results are shown in Table 3. Excellent properties suitable for copper-clad laminates for printed circuit boards suitable for equipment such as millimeter-wave radar antennas were obtained. Millimeter-wave radar antennas require low loss properties such as low Dk and low Df, low CTE that can be further reduced by adding suitable fillers, and high T that can be used in high-temperature processes. g and the high decomposition temperature (T d5 ).

[0389] Table 3

[0390]

[0391] Examples 22A to 22D

[0392] Evaluation of low loss and thermal properties of films

[0393] The terpolymer of Example 1 (NB / HexNB / CyHexeneNB, 50 / 25 / 25 molar ratio) was dissolved in mesitylene to prepare a 22 wt.% solution. 15 pphr of B1000 (Example 22A), 15 pphr of B1000 and 15 pphr of TAIC (Example 22B), 15 pphr of B1000, 10 pphr of T67 (Example 22C), 20 pphr of B1000, 5 pphr of T67 and 10 pphr of TAIC (Example 22D) were added to 4 separate portions of the solution. DCP (4 pphr) was added to each of the 4 compositions. Each of these compositions was knife coated on a glass substrate. The solvent was removed in an oven at 130°C for 1 hour under a nitrogen atmosphere (B-stage). The B-staged film was cured at 170-180°C in a nitrogen atmosphere for 1 hour, and then cured at 170-180°C in a vacuum condition for 1 hour to produce a film with a thickness of about 75-150 μm. The glass transition temperature (T g ) and thermal expansion coefficient (CTE). The film loss was determined by TGA to be 5 wt.% (T d5 ) decomposition temperature. Dk and Df were also measured at 10 GHz. The results are shown in Table 4. Excellent properties suitable for copper-clad laminates for printed circuit boards suitable for equipment such as millimeter-wave radar antennas were obtained. Millimeter-wave radar antennas require low loss properties such as low Dk and low Df, low CTE that can be further reduced by adding suitable fillers (Examples 22A, 22B and 22D), and high T that can be used for high-temperature processes. g and the high decomposition temperature (T d5 ). As shown in Example 22D, the combination of additives such as B1000, TAIC and T67 has excellent performance in terms of low loss characteristics.

[0394] Table 4

[0395]

[0396] Examples 23A to 23D

[0397] Evaluation of low-loss film properties at different tackifier levels

[0398] The terpolymer of Example 6 (NB / HexNB / CyHexeneNB, 35 / 40 / 25 molar ratio) and the terpolymer of Example 8 (NB / HexNB / CyHexeneNB, 60 / 20 / 20 molar ratio) were dissolved in mesitylene to prepare a 25wt.% solution (derived from the terpolymer of Example 6) and a 20wt.% solution (derived from the terpolymer of Example 8). 20pphr of B1000, 10pphr of TAIC and 5pphr of T67 (designated as composition A), 20pphr of B1000, 10pphr of TAIC and 15pphr of T67 (designated as composition B) were added to these two solutions, respectively. As shown in Table 5, different amounts of DCP were added to these two compositions, forming a total of four different compositions. These four compositions were respectively coated on a glass substrate with a knife and heated to 130°C in an oven in a nitrogen atmosphere for 1 hour to remove the solvent (B-stage). The film was cured under vacuum at 175-180°C for 1.5 hours. The Dk and Df of the cured film at 10 GHz were measured. The results are shown in Table 5. The results shown in Table 5 show that the use of 15 pphr of T67 is beneficial for obtaining low Df, which is extremely desirable for low loss applications.

[0399] Table 5

[0400]

[0401] Examples 24A-24B

[0402] Evaluation of glass cloth composite materials

[0403] The terpolymer of Example 13A (NB / HexNB / CyHexeneNB, 40 / 40 / 20 molar ratio) (used in Example 24A) and the copolymer of Example 15A (HexNB / CyHexeneNB, 80 / 20 molar ratio) were dissolved in decalin to prepare 20 wt.% solutions respectively. B1000 (20 pphr), T67 (15 pphr), TAIC (10 pphr) and DCP (2 pphr) were added to these solutions respectively. These compositions were knife coated on glass substrates respectively and heated to 130°C in an oven under nitrogen for 1 hour to remove the solvent. These B-staged films were cured at 190°C under vacuum conditions for 1.5 hours to obtain films with a thickness of about 75 to 100 μm. Low Df glass fiber fabric (NE glass cloth, model #1280, 50 μm) was thoroughly wetted with these compositions to allow the low-loss composition to penetrate the glass cloth. The glass fabric composite material was heated to 130°C in an oven under nitrogen for 1 hour to remove the solvent and produce a prepreg. The prepreg was cured at 190°C under vacuum for 90 minutes. The Dk and Df measured at 10 GHz for the cured film sample and the prepreg are shown in Table 6.

[0404] Table 6

[0405] Example No. Glass cloth composite material Dk at 10GHz Df at 10GHz Example 24A no 2.29 0.0002 Example 24A yes 2.60 0.0018 Example 24B no 2.29 0.0004 Example 24B yes 2.64 0.0017

[0406] Examples 25A to 25D

[0407] Evaluation of low loss and thermal properties of films

[0408] The terpolymer of Example 10B (NB / HexNB / CyHexeneNB, 60 / 20 / 20 molar ratio) (used in Example 25A), the terpolymer of Example 13 (NB / HexNB / HexenylNB, 60 / 20 / 20 molar ratio) (used in Example 25B), the copolymer of Example 14 (NB / HexenylNB, 75 / 25 molar ratio) (used in Example 25C) and the copolymer of Example 15 (NB / CyHexeneNB, 80 / 20 molar ratio) (used in Example 25D) were dissolved in decahydronaphthalene to prepare 20 wt.% solutions respectively. B1000 (20 pphr), T67 (15 pphr), TAIC (10 pphr), DCP (0.75 pphr in Examples 25A, 25C and 25D and 1.0 pphr in Example 25B), Irganox-1076 (1.75 pphr) and Irgafos-168 (0.6 pphr) were added to the four solutions to form four different compositions. The compositions were respectively coated on a glass substrate with a knife and heated to 130°C in an oven under nitrogen for 1 hour to remove the solvent. The B-staged films were cured at 190°C under vacuum conditions for 1.5 hours to obtain films with a thickness of 90 μm (Example 25A), 110 μm (Example 25B), 85 μm (Example 25C) and 125 μm (Example 25D). The glass transition temperature (T g ) and thermal expansion coefficient (CTE). The film loss was determined by TGA to be 5 wt.% (T d5 ) decomposition temperature. Dk and Df were measured at 10 GHz. The results are shown in Table 7. Excellent properties suitable for copper-clad laminates for printed circuit boards suitable for equipment such as millimeter-wave radar antennas were obtained. Millimeter-wave radar antennas require low loss properties such as low Dk and low Df, low CTE that can be further reduced by adding suitable fillers, and high T that can be used in high-temperature processes. g and the high decomposition temperature (T d5 ).

[0409] Table 7

[0410]

[0411] Examples 26A to 26C

[0412] Comparison of low loss and thermal properties of films containing different cross-linkers

[0413] The terpolymer of Example 10 (NB / HexNB / CyHexeneNB, 60 / 20 / 20 molar ratio) was dissolved in decalin to prepare a 20 wt.% solution. B1000 (20 pphr), T67 (15 pphr), TAIC (10 pphr in Example 26A), TAC (10 pphr in Example 26B), DCP (2 pphr), Irganox-1076 (1.75 pphr) and Irgafos-168 (0.6 pphr) were added to a portion of the solution. Additional amounts of decalin (50-100 pphr) were also added to facilitate dissolution of all ingredients. The two compositions were separately knife coated on a glass substrate and heated to 130° C. in an oven under nitrogen for 1 hour to remove the solvent. A low Df glass fabric (NE glass cloth, model #1280, 50 μm) was thoroughly wetted with the composition of Example 26A (Example 26C) to saturate the glass fabric. The treated glass fabric was then heated to 130°C in an oven under nitrogen for 1 hour to remove the solvent. The B-staged films were cured at 190°C under vacuum for 1.5 hours to obtain a film with a thickness of about 105 μm (Example 26A), a film with a thickness of about 70 μm (Example 26B), and a film with a thickness of about 90 μm. The glass transition temperature (T) was determined by TMA. g ) and thermal expansion coefficient (CTE). Since the glass cloth composite material has a lower thermal expansion coefficient in a large temperature range, the CTE of the films of Examples 26A and 26B was measured in the temperature range of 50-100°C, and the CTE of Example 26C was measured in the temperature range of 50-100°C along the xy direction. The film loss was 5 wt.% (TGA) d5 The results are shown in Table 8. It is clear from the results shown in Table 8 that both TAIC and TAC are effective crosslinking agents in the composition of the present invention in forming a film having low loss characteristics and excellent thermal characteristics.

[0414] Table 8

[0415]

[0416] Examples 27A-27B

[0417] Evaluation of Silica Nanofiller Membranes

[0418] The terpolymer of Example 10A (NB / HexNB / CyHexeneNB, 60 / 20 / 20 molar ratio) was dissolved in decahydronaphthalene to prepare a 20 wt.% solution. B1000 (20 pphr), T67 (15 pphr), TAIC (15 pphr), Irganox-1076 (1.5 pphr), Irgafos-168 (0.38 pphr) and silica nanoparticles (71 pphr of SC2300-SVJ) were added to a portion of the solution. The composition thus formed was divided into two parts. DCP (0.7 pphr) was added to one of the compositions and designated as Example 27A. V-40 (1.25 pphr) was added to another portion of the composition and designated as Example 27B. An additional amount of decahydronaphthalene (100 pphr) was also added to promote the dissolution of all ingredients in the two compositions. The two compositions were then knife coated on glass substrates and heated to 130°C in an oven under nitrogen for 1 hour to remove the solvent. The B-staged films were cured at 190-195°C under vacuum for 1.5 hours to obtain films with a thickness of 105 μm. The film formed from the composition of Example 27A had a Dk of 2.24 and a Df of 0.0009 measured at 10 GHz. The film formed from the composition of Example 27B had a Dk of 2.34 and a Df of 0.0010 measured at 10 GHz.

[0419] Examples 28A-28B

[0420] Evaluation of Ceramic Filler Membranes

[0421] The terpolymer of Example 11 (NB / HexNB / CyHexeneNB, 60 / 20 / 20 molar ratio) was dissolved in decahydronaphthalene to prepare a 20 wt.% solution. B1000 (20 pphr), T67 (15 pphr), TAIC (10 pphr), DCP (0.6 pphr), Irganox-1076 (1.75 pphr) and Irgafos-168 (0.6 pphr) were added to a portion of the solution. An additional amount of decahydronaphthalene (50 pphr) was also added to promote the dissolution of the formulation ingredients. In a portion of the composition, different degrees of ceramic filler Lithafrax-2121 were dispersed. These compositions were respectively knife-coated on glass substrates and heated to 130°C in an oven under nitrogen for 1 hour to remove the solvent. These B-staged films were cured at 190°C under vacuum conditions for 1.5 hours to obtain films with a thickness of about 90 to 120 μm. The glass transition temperature (T) was determined by TMA. g ) and thermal expansion coefficient (CTE). The film loss was determined by TGA to be 5 wt.% (T d5The results are shown in Table 9. The addition of Lithafrax-2121 reduces the CTE compared to the film without filler (Example 28A), and from the observations of the compositions of Examples 28B and 28C, low CTE is desirable for copper clad laminates made from these materials.

[0422] Table 9

[0423]

[0424] Embodiment 29

[0425] Study on the reliability of membranes stored at 125℃

[0426] The terpolymer of Example 10A (NB / HexNB / CyHexeneNB, 60 / 20 / 20 molar ratio) was dissolved in decalin to prepare a 20 wt.% solution. B1000 (20 pphr), TAIC (10 pphr), DCP (0.5 pphr), Irganox-1076 (1.5 pphr) and Irgafos-168 (0.38 pphr) were added to a portion of the solution. In addition, T67 (15 pphr) was added only in Example 29A. The two compositions were separately knife-coated on a glass substrate and heated to 130°C in an oven under nitrogen for 1 hour to remove the solvent. The B-staged films were cured at 190°C under vacuum conditions for 1.5 hours to obtain a film with a thickness of about 100 μm (Example 29A) and a film with a thickness of about 95 μm (Example 29B). The dielectric constant (Dk) and dielectric loss factor Df were measured and the films were placed in an oven at 125° C. in air. Dk and Df were measured periodically at various time intervals during storage conditions at 125° C. in air for up to 1000 hours. Figure 1 In the graphs of Df versus storage time for the films of Examples 29A, 29B, Comparative Examples 2A, and Comparative Examples 2B, are compared. Figure 1 As can be seen, the films of Examples 29A and 29B exhibited excellent reliability under these storage conditions, which is required for devices containing low-loss components such as millimeter-wave radar antennas used in the automotive industry, as these devices must withstand harsh conditions during use. The early failure of the reliability test of Comparative Examples 2A and 2B, which removed the B1000 and TAIC additives, confirmed that TAIC is an essential component of the present invention and that B1000 is conducive to the production of films with reliability under high temperature storage conditions. In addition, Figure 1It is also shown that the film of Example 29B, although not containing T67, still exhibits the same degree of low-loss storage stability as Example 29A. However, Example 29A, which contains T67, exhibits lower low-loss characteristics under these storage conditions, thus confirming that the presence of T67 is beneficial in reducing Df. As shown by the initial Dk, average Dk during the test, and % reduction in Dk after the total test time listed in Table 10, the dielectric constants (Dk) of Examples 29A and 29B and Comparative Examples 2A and 2B remain stable throughout the test period of up to 1000 hours.

[0427] Table 10

[0428]

[0429] Examples 30A to 30C

[0430] Reliability study of films formed on glass cloth under 125℃ storage condition

[0431] A low Df glass fiber fabric (NE glass cloth, model #1280, 50 μm) was thoroughly wetted with the composition of Example 25A (Example 30A) to allow the low-loss composition of the present invention to penetrate the glass fiber fabric. The treated glass fabric was heated to 130°C in an oven under nitrogen for 1 hour to remove the solvent. The B-staged prepreg was cured at 190°C under vacuum conditions for 1.5 hours to obtain a film with a thickness of 210 μm. The CTE of the glass cloth composite material was measured along the xy direction in the temperature range of 150 to 250°C by TMA. The Dk and Df of the composite material were measured at 10 GHz. Similarly, a cured composite film was formed from the composition of Example 27A (Example 30B) and the composition of Example 27B (Example 30C). All three films were placed in an oven at 125°C in air. Dk and Df were measured at various time intervals for up to 1100 hours under storage conditions at 125°C in air. As Figure 2 As shown in Table 11, the films composed of silica fillers (Examples 30B and 30C) or glass fiber fabrics (Example 30A) are suitable for preparing prepregs in copper-clad laminates for printed circuit boards having excellent reliability under storage conditions of 125° C. As shown in Table 11, the dielectric constants (Dk) of Examples 30A to 30C remain stable over the entire test period of up to 1100 hours. Figure 2 A graph showing dielectric measurements over a period of more than 1000 hours is shown. This again demonstrates that all three films exhibit excellent dielectric property stability with marginal variations attributed to changes in dielectric constant measurements. Thus, the compositions of the present invention can be used in a variety of applications described in this specification.

[0432] Table 11

[0433]

[0434] Examples 31A-31B

[0435] Reliability Study at 85℃ / 85% RH

[0436] The terpolymer of Example 11 (NB / HexNB / CyHexeneNB, 60 / 20 / 20 molar ratio) was dissolved in mesitylene to prepare a 20 wt.% solution. B1000 (20 pphr), T67 (15 pphr), TAC (10 pphr), DCP (0.5 pphr), Irganox-1076 (1.75 pphr) and Irgafos-168 (0.5 pphr) were added to a portion of the solution. An additional amount of mesitylene (50 pphr) was also added to promote the dissolution of all components to form a transparent solution (Example 31A). The low Df glass fiber fabric (NE glass cloth, model #1280, 50 μm) was thoroughly wetted (impregnated) with the composition to allow the low-loss composition to penetrate the glass cloth. The glass fabric composite was heated to 130°C in an oven under nitrogen for 1 hour to remove the solvent and form a prepreg.

[0437] The terpolymer of Example 10A (NB / HexNB / CyHexeneNB, 60 / 20 / 20 molar ratio) was dissolved in decahydronaphthalene to prepare a 20 wt.% solution. B1000 (20 pphr), T67 (15 pphr), TAIC (10 pphr), DCP (0.5 pphr), Irganox-1076 (1.75 pphr) and Irgafos-168 (0.5 pphr) were added to a portion of the solution. An additional amount of decahydronaphthalene (50 pphr) was also added to promote the dissolution of all ingredients to form a clear solution (Example 31B). The composition was knife coated on a glass substrate and heated to 130° C. in an oven under nitrogen for 1 hour to remove the solvent.

[0438] The two B-staged films were cured at 190°C for 1.5 hours under vacuum to obtain a film having a thickness of about 95 μm (Example 31A) and a film having a thickness of about 105 μm (Example 31B). The dielectric constant (Dk) and dielectric loss factor Df were measured. The films were stored in an oven at 85°C / 85% RH (relative humidity) for 1400 hours while periodically measuring Dk and Df. Figure 3 The reliability of the cured films under these conditions is shown. The two films, which contain glass cloth (Example 31A) or consist of glass cloth itself (Example 31B), are suitable materials for copper-clad laminates for printed circuit boards, such as Figure 3This shows that the material exhibits excellent reliability under 85°C / 85%RH storage conditions. As shown in Table 12, the dielectric constant (Dk) of Examples 31A and 31B remained stable throughout the test period of up to 1317 hours.

[0439] Table 12

[0440]

[0441] Embodiment 32

[0442] Peel strength determination

[0443] The terpolymer of Example 10A (NB / HexNB / CyHexeneNB, 60 / 20 / 20 molar ratio) was dissolved in decahydronaphthalene to prepare a 20 wt.% solution. B1000 (20 pphr), T67 (15 pphr), TAIC (10 pphr), Irganox-1076 (1.75 pphr) and Irgafos-168 (0.75 pphr) were added to a portion of the solution. Various amounts of DCP were added as shown in Table 13. Additional amounts of decahydronaphthalene (100 pphr) were also added to promote the dissolution of all ingredients to form a clear solution. A thin layer of the composition was applied to a copper foil (Mitsui, CF-14X-SV-18) strip (approximately 2 cm x 7 cm), and a low Df glass cloth (NE glass cloth, model #1280, 50 μm) was placed in the liquid to thoroughly wet with the composition. The glass cloth composite on copper foil was heated to 130°C in an oven under nitrogen for 1 hour to remove the solvent, followed by a curing step at 190°C under vacuum for 1.5 hours. The peel strength of the sample formed on the copper foil was measured using Instron under 90 degree tilt conditions. The peel strength was calculated based on the average load of the highest 5 peaks and is shown in Table 13. Compared with Comparative Example 3 using a lower addition of DCP (0.5 pphr), Examples 32A, 32B and 32C achieved high peel strength suitable for copper clad laminates.

[0444] Table 13

[0445] Example No. DCP addition amount Peel strength Comparative Example 3 0.5pphr 2.7N / cm Example 32A 1.0pphr 5.5N / cm Example 32B 2.0pphr 7.6N / cm Example 32C 4.0pphr 6.4N / cm

[0446] Embodiment 33

[0447] Peel strength determination

[0448] The terpolymer of Example 10A (NB / HexNB / CyHexeneNB, 60 / 20 / 20 molar ratio) was dissolved in decalin to prepare a 20 wt.% solution. B1000 (20 pphr), T67 (15 pphr), TAIC (10 pphr), DCP (0.5 pphr), Irganox-1076 (1.75 pphr) and Irgafos-168 (0.75 pphr) were added to a portion of the solution. The thin layer formulation was coated on a copper foil (Mitsui, CF-14X-SV-18) strip (about 2 cm x 7 cm) and heated to 130°C in an oven under nitrogen for 1 hour to remove the solvent, followed by a curing step at 190°C under vacuum for 1.5 hours. The peel strength of the sample formed on the copper foil was measured using an Instron at a 90 degree tilt. The peel strength calculated based on the average load of the highest 5 peaks was 6.5 N / cm. This confirms again that high peel strength suitable for copper-clad laminates can be obtained by using the composition of the present invention.

[0449] Embodiment 34A~34B

[0450] Determination of peel strength of glass cloth composite materials

[0451] The thin layer composition of Example 24A (Example 34A) and composition 24B (Example 34B) were coated on a copper foil (Mitsui, CF-14X-SV-18) strip (about 1 cmx6 cm), and a low Df glass cloth (NE glass cloth, model #1280, 50 μm) was placed in a liquid to wet with each composition. The glass cloth composite material on the copper foil was then heated to 130°C in an oven under nitrogen for 1 hour to remove the solvent, followed by a curing step of 1.5 hours at 190°C under vacuum conditions. The peel strength of the sample formed on the copper foil was measured using an Instron under a 90-degree tilt condition. The peel strength was calculated based on the average load of the top 5 peaks. Example 34A (12.6 N / cm) Example 34B (11.2 N / cm) obtained high peel strength suitable for copper-clad laminates.

[0452] Embodiment 35

[0453] Determination of peel strength of glass cloth composite materials

[0454] The terpolymer of Example 10B (NB / HexNB / CyHexeneNB, 60 / 20 / 20 molar ratio) was dissolved in decahydronaphthalene to prepare a 15 wt.% solution. B1000 (20 pphr), T67 (15 pphr), TAIC (10 pphr) DCP (2.0 pphr), Irganox-1076 (1.75 pphr) and Irgafos-168 (0.60 pphr) were added to a portion of the solution. Additional amounts of decahydronaphthalene (50 pphr) were also added to promote the solubility of all ingredients. The composition was mixed by rotating overnight. A thin layer of the composition was coated on a copper foil (Mitsui, CF-14X-SV-18) strip (about 2 cmx7 cm) and heated to 130°C in an oven under nitrogen for 1 hour to remove the solvent, followed by a curing step at 190°C under vacuum conditions for 1.5 hours. The peel strength of the sample formed on the copper foil was measured by Instron under 90 degree tilting condition. The peel strength calculated based on the average load of the highest 5 peaks was 8.2N / cm. This once again confirms that the high peel strength suitable for copper clad laminates can be obtained by the composition prepared according to the present invention.

[0455] Embodiment 36

[0456] Determination of peel strength of glass cloth composite materials

[0457] The copolymer of Example 14 (NB / HexenylNB, 75 / 25 molar ratio) was dissolved in decahydronaphthalene to prepare a 15 wt.% solution. B1000 (20 pphr), T67 (15 pphr), TAIC (10 pphr), DCP (2 pphr), Irganox-1076 (1.75 pphr) and Irgafos-168 (0.6 pphr) were added to a portion of the solution. An additional amount of decahydronaphthalene (50 pphr) was also added to promote the dissolution of all ingredients. The thin layer composition was coated on a copper foil (Mitsui, CF-14X-SV-18) strip (about 2 cmx7 cm) and heated to 130°C in an oven under nitrogen for 1 hour to remove the solvent, followed by a curing step at 190°C under vacuum conditions for 1.5 hours. The peel strength of the sample formed on the copper foil was measured using an Instron under 90 degree tilt conditions. The peel strength calculated from the average load of the highest 5 peaks was 6.1 N / cm. This once again confirmed that a high peel strength suitable for a copper-clad laminate can be obtained by the composition prepared according to the present invention.

[0458] Embodiment 37

[0459] Film melting research

[0460] The composition prepared according to Example 25A was knife coated on a glass substrate and B-staged on a hot plate at 90°C for 1 hour to remove the solvent. Two rectangular samples of these B-staged films were stacked on top of each other in a crosshatch orientation. These samples were pressed using a mechanical press at a pressure of about 5 to 15 MPa while heating from 30°C to 120°C over 30 minutes and maintaining the temperature at 120°C for 35 minutes, and from 120°C to 200°C over 30 minutes and maintaining the temperature at 200°C for 90 minutes. The press was cooled to ambient temperature and the films were removed and inspected. The two films were completely fused and could not be separated.

[0461] Embodiments 38A to 38E

[0462] Cross-linking studies of polymer compositions containing different amounts of CyHexeneNB

[0463] A set of NB / HexNB / CyHexeneNB polymers were prepared according to the procedure described in Example 13. The polymer of Comparative Example 4 was prepared using a composition of NB / HexNB / CyHexaneNB of 60 / 20 / 20, wherein no reactive olefin groups were present in the composition (0% CyHexeneNB in ​​the polymer). The polymer used in Comparative Example 6 was a NB / vinyl copolymer, commercially available (GPC(THF):M w =84,650,M n =50,150,PDI=1.7). The feed ratios of NB / HexNB / CyHexeneNB are different, 60 / 37 / 3 for Comparative Example 5; 60 / 34 / 6 for Example 38A; 60 / 28 / 12 for Example 38B; 60 / 25 / 15 for Example 38C; and 70 / 10 / 20 for Example 38D. In addition to dissolving the polymers used in Comparative Example 6 and Example 38D in xylene, these polymers were dissolved in decahydronaphthalene to prepare 20 wt.% solutions, all of which contained 4 pphr of diisopropylbenzene peroxide (DCP) and also contained 4 pphr of DCP.

[0464] In addition, T-67 (15 pphr), TAIC (10 pphr), DCP (3 pphr), Irganox-1078 (1.75 pphr) and Irgafos-168 (0.75 pphr) were added to the composition of Comparative Example 6 (forming the composition of Comparative Example 7) and Example 38D (forming the composition of Example 38E).

[0465] These compositions were coated on a glass substrate and treated in an oven with nitrogen inlet and outlet for 1 hour at 130°C to remove the solvent. The obtained film was further cured in a vacuum oven at 190°C for 2 hours. About 0.14g to 0.35g of the cured film was mixed with THF (4g to 8g) and ultrasonically treated at about 30°C for 90 minutes. The insoluble portion of the film was separated from the solution and dried in an oven at 120°C under a nitrogen atmosphere for 1 hour. The dry weight obtained was used to calculate the solubility % of the cured film in THF. Table 14 lists the solubility of the cured film in THF by 13 The amount of CyHexene NB in ​​the polymer composition (mol %) and the solubility of the cured film in THF determined by C-NMR. The results show that a CyHexene NB composition of more than 4 mol % is sufficient to produce a fully crosslinked film. Although the polymer of Comparative Example 6, such as the NB / vinyl copolymer, exhibits low loss characteristics, it cannot produce a composition for forming a thermoset by free radical-initiated crosslinking, as envisioned by the present invention and confirmed by the results of Table 14. It should also be noted that the crosslink density of the composition of the present invention can be further increased by adding the reactive crosslinking agent and tackifier exemplified in the present invention.

[0466] Table 14 also shows the glass transition temperatures of some compositions measured by TMA in the pressurized mode. As shown by the reduced solubility of the cured film of Comparative Example 7, the crosslinking density of the composition containing TOPAS can be increased by adding a reactive tackifier such as T-67 and a crosslinking agent such as TAIC. However, the glass transition temperatures of the films of Comparative Examples 6 and 7 containing TOPAS as the base resin are significantly lower than those of the films of Examples 38D and 38E containing the compositions described in the present invention, thus confirming that excellent properties are obtained by the composition of the present invention.

[0467] Table 14

[0468] Example No. CyHexeneNB mol% THF soluble <![CDATA[T g (℃)]]> Comparative Example 4 0％ 100％ Comparative Example 5 3％ 90％ Comparative Example 6 0％ 54～79％ 119 Comparative Example 7 0％ 12％ 110 Example 38A 6％ 53％ Example 38B 12％ 36％ Example 38C 15％ 30％ Example 38D 20％ 6％ 190 Example 38E 20％ 9％ 261

[0469] Examples 39A to 39D

[0470] Evaluation of Resin Flowability in Glass Cloth Composites

[0471] The polymers of Examples A, B, C and D were dissolved in solvent / solvent mixtures to prepare the following polymer solutions: 50 wt.% solution in cyclohexane / xylene (3:1 weight ratio) of the polymers of Examples A and B from Examples 39A and 39B; 40 wt.% solution in toluene of the polymer of Example C from Example 39C; 40 wt.% solution in cyclohexane of the polymer of Example D from Example 39D. B1000 (20 pphr), T67 (15 pphr), TAIC (10 pphr) and Luperox TBEC (3 pphr) were added to these solutions respectively. A rectangular piece of low Df glass fiber fabric (NE glass cloth, model #1280, 50 μm) of about 4 cm x 8 cm was partially wetted with these compositions to cover about half of the rectangular glass cloth so that the low loss composition penetrated the glass cloth. The glass fabric composites were heated to 80°C in an oven under nitrogen for 30 minutes and then to 110°C for 30 minutes to remove the solvent and produce prepregs. Each prepreg was pressurized between 2 Teflon sheets and 2 rubber pads at 4-6 MPa, heated to 175°C for about 10-15 minutes and cured at 175°C for 90 minutes to form a glass fabric composite of about 50-60 μm. Visual inspection of the glass fabric showed that the resin in the prepreg flowed significantly into the untreated areas, indicating that these compositions are suitable for copper clad laminates, which require a certain fluidity of the B-staged resin to penetrate the glass fabric and possibly fuse with other layers of the device stack during the curing step. The Dk and Df of the cured composites were measured at 10 GHz and are shown in Table 15.

[0472] Table 15

[0473] Example No. polymer Resin flow Dk at 10GHz Df at 10GHz Example 39A Example A yes 2.80 0.0017 Example 39B Example B yes 2.85 0.0016 Example 39C Example C yes 2.68 0.0021 Example 39D Example D yes 2.82 0.0014

[0474] Examples 40A and 40B

[0475] Resin fluidity (melt flow) of B-stage film

[0476] In Examples 40A and 40B, the compositions from Examples 40A and 40B, respectively (1 mL each) were placed on 140 mm x 140 mm squares of polyester (PET) film and heated to 110°C in an oven under nitrogen for 1 hour to remove the solvent and produce B-staged test coins. A second square of PET film was placed on top of the test coin. On the upper PET film, the perimeter of the test coin was traced with a marker of one color. The test assembly was pressurized between two silicone sheets at 3 MPa and heated at 120°C for about 3 minutes. The test assembly was removed from the press and a new perimeter of the test coin was traced with a marker of a contrasting color. An image of the test assembly was taken and loaded into image processing software. Using the freehand selection tool of the software, the initial test coin perimeter was traced and the area was measured. This step was repeated for the post-pressurization test coin perimeter. Resin fluidity (melt flow) is characterized by the percentage change between the initial and post-pressurization test coin areas.

[0477] Example 40A

[0478] The high molecular weight NB / HexylNB / CyHexeny lNB terpolymer (M w =98,000; molar composition = 61 / 21 / 18) and low molecular weight NB / VNB (M w =1,700; molar composition = 87 / 13) in wt. / wt. ratios of 0 / 100, 20 / 80 and 60 / 40. The polymer mixture was dissolved in xylene to prepare 50 wt.% solutions. B1000 (10 pphr), T-67 (7.5 pphr), TAIC (10 pphr) and DCP (3 pphr) were added to these solutions. These solutions were then treated using the above test procedures. Figure 4 It is shown that in the B-staged sample, as the high M w The change in resin fluidity occurs with an increase in the weight percent of the polymer. As disclosed in the present invention, high M w and low M w When the polymer composition is variable, a composition having a certain range of resin flowability during processing of the copper clad laminate material can be developed from the composition.

[0479] Example 40B

[0480] Regarding the polymer used in this Example 40B, a low M w Polymers with high M w Polymer. Low molecular weight NB / CyhexeneNB (Mw <3K, 80 / 20 feed ratio) was dissolved in xylene to prepare a 60 wt.% solution. B-1000 (5 pphr), T-67 (15 pphr), TAIC (10 pphr), SA9000 (5 pphr), DCP (3 pphr), Irgnox-1076 (1.75 pphr) and Irgafos-168 (0.75 pphr) were added to the mixture. w >100K) polymers such as NB / CyhexeneNB (80 / 20 feed ratio), NB / HexylNB / CyHexeneNB (70 / 10 / 20 feed ratio), NB / PENB / CyHexeneNB (70 / 10 / 20 feed ratio), NB / VNB (80 / 20 feed ratio), NB / HexylNB / VNB (70 / 10 / 20 feed ratio) and NB / PENB / VNB (70 / 10 / 20 feed ratio) were dissolved in xylene to prepare a 20 wt.% solution. w T-67 (15 pphr), TAIC (10 pphr), DCP (3 pphr), Irgnox-1076 (1.75 pphr) and Irgafos-168 (0.75 pphr) were added to the polymer solution. w Polymer: Low M w Various high molecular weight compositions and low molecular weight compositions were mixed in such a way that the polymer ratio was 60:40. These solutions were then treated using the above test procedure. Table 16 lists various high molecular weight compositions. w Polymers and Low M w (M w <3K)NB / CyclohexeneNB (80 / 20) resin flow rate obtained when mixed. As disclosed in the present invention, high M w When the polymer composition is variable, a composition having a certain range of resin flowability during processing of the copper clad laminate material can be developed from the composition.

[0481] Table 16

[0482] <![CDATA[High M w Mixed auxiliaries]]> Resin flow rate (%) none >1280 NB / CyhexeneNB 1170 NB / HexNB / CyHexeneNB 364 NB / PENB / CyHexeneNB 518 NB / VNB 495 NB / HexNB / VNB 260 NB / PENB / VNB 317

[0483] Comparative Example 1

[0484] The terpolymer of Example 3 (NB / BuNB / CyHexeneNB, 40 / 35 / 25 molar ratio) was dissolved in mesitylene to prepare a 16.6wt.% solution. 15pphr of SA9000 and 4.5pphr of DCP were added to a portion of the solution as free radical initiators. The composition was knife-coated on a glass substrate and heated in an oven at 130°C under a nitrogen atmosphere for 1 hour to remove the solvent from the film. The solubility of the B-staged film was tested by ultrasonically treating a small piece of film in THF for 1 hour. The B-staged film was further cured in an oven at 170°C under a nitrogen atmosphere for 2 hours to generate a cured film with a thickness of 100μm. The solubility of the B-staged film was also tested by ultrasonically treating a small piece of film in THF for 1 hour to ensure that the film lost its solubility due to cross-linking to produce thermosetting properties. The dielectric constant (Dk) and dielectric loss factor (Df) of the cured film at 10GHz were measured. Table 1 shows the results compared with the results obtained for the composition of Example 19.

[0485] Comparative Examples 2A-2B

[0486] Reliability at 125°C storage condition

[0487] The terpolymer of Example 10A (NB / HexNB / CyHexeneNB, 60 / 20 / 20 molar ratio) was dissolved in decahydronaphthalene to prepare a 20 wt.% solution. T67 (15 pphr), DCP (0.5 pphr), Irganox-1076 (1.50 pphr) and Irgafos-168 (0.38 pphr) were added to a portion of the solution. In addition, TAIC (10 pphr) was added to the composition of Comparative Example 2A, but TAIC was not added to the composition of Comparative Example 2B. These compositions were respectively applied by a knife on a glass substrate and heated to 130°C in an oven under nitrogen for 1 hour to remove the solvent. These B-staged films were cured at 190°C under vacuum conditions for 1.5 hours to obtain a film with a thickness of about 90 μm (Comparative Example 2A) and a film with a thickness of about 100 μm (Comparative Example 2B). The dielectric constant (Dk) and dielectric loss factor Df of Comparative Examples 2A and 2B were measured, and the films were placed in an oven at 125°C in air. Dk and Df were measured at various time intervals for up to 1000 hours under storage conditions at 125°C in air. The results of this reliability measurement are shown in Figure 1 .

[0488] Comparative Example 3

[0489] The terpolymer of Example 10A (NB / HexNB / CyHexeneNB, 60 / 20 / 20 molar ratio) was dissolved in decalin to prepare a 20 wt.% solution. B1000 (20 pphr), T67 (15 pphr), TAIC (10 pphr), DCP (0.5 pphr), Irganox-1076 (1.75 pphr) and Irgafos-168 (0.75 pphr) were added to a portion of the solution. An additional amount of decalin (100 pphr) was also added to facilitate the dissolution of all ingredients. A thin layer of the composition was applied to a copper foil (Mitsui, CF-14X-SV-18) strip (approximately 2 cm x 7 cm), and a low Df glass cloth (NE glass cloth, model #1280, 50 μm) was placed in the liquid to thoroughly wet with the formulation. The glass cloth composite on copper foil was heated to 130°C in an oven under nitrogen for 1 hour to remove the solvent, followed by a curing step at 190°C under vacuum for 1.5 hours. The peel strength of the sample formed on copper foil was measured using an Instron at a 90 degree tilt. The peel strength was calculated based on the average load of the highest 5 peaks and is shown in Table 13.

[0490] Although the present invention has been described by way of some embodiments, it should not be construed as being limited thereby, but rather as encompassing the general scope set forth above. Various modifications may be made without departing from the spirit and scope of the present invention.

Claims

1. A polymer comprising: a) at least one first repeating unit represented by the general formula (IA), wherein the first repeating unit is derived from a monomer of the general formula (I): in, indicates the position of bonding to another repeating unit; m is an integer of 0, 1 or 2; R1, R2, R3 and R4 are the same or different and are independently selected from hydrogen, methyl, ethyl, straight or branched (C3-C 16 )alkyl, (C3-C 10 )cycloalkyl, (C6-C 12 ) bicycloalkyl, (C6-C 12 )aryl and (C6-C 12 ) the group consisting of aryl(C1-C6)alkyl; or One of R1 and R2 together with one of R3 and R4 and the carbon atom to which they are attached form a substituted or unsubstituted (C5-C 14 ) ring, (C5-C 14 )bicyclic, (C5-C 14 ) tricyclic; and b) at least one second repeating unit represented by the general formula (IIA), wherein the second repeating unit is derived from a monomer of the general formula (II): in, indicates the position of bonding to another repeating unit; n is an integer of 0, 1 or 2; At least one of R5, R6, R7 and R8 is selected from methylene, ethylene, vinyl, straight chain or branched (C3-C 16 )alkenyl, (C3-C 10 )cycloalkenyl, (C6-C 12 )bicycloalkenyl and (C6-C 12 )Aryl(C2-C 16 ) alkenyl, the remaining R5, R6, R7 and R8 are the same or different and are independently selected from hydrogen, methyl, ethyl, straight or branched (C3-C 16 )alkyl, (C3-C 10 )cycloalkyl, (C6-C 12 ) bicycloalkyl, (C6-C 12 )aryl and (C6-C 12 ) the group consisting of aryl(C1-C6)alkyl; or One of R5 and R6 together with one of R7 and R8 and the carbon atom to which they are attached form a substituted or unsubstituted (C5-C 14 ) ring, (C5-C 14 ) bicyclic or (C5-C 14 ) tricyclic; and Wherein, relative to the total molar number of the first repeating unit and the second repeating unit, the content of the second repeating unit is not less than 4 mol %.

2. The polymer according to claim 1, wherein m is 0 or 1; n is 0 or 1; R1, R2, R3 and R4 are the same or different and are each independently selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, n-butyl, n-hexyl, cyclopentyl, cyclohexyl and norbornyl; or One of R1 and R2 together with one of R3 and R4 and the carbon atoms to which they are attached form a cyclopentyl, cyclohexyl, cycloheptyl, bicycloheptyl, bicyclooctyl or adamantane ring; and At least one of R5, R6, R7 and R8 is selected from the group consisting of ethylene, vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, cyclopentenyl and cyclohexenyl, and the remaining R5, R6, R7 and R8 are the same or different and are each independently selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, n-butyl, n-hexyl, cyclopentyl, cyclohexyl and norbornyl; or One of R5 and R6 together with one of R7 and R8 and the carbon atom to which they are attached form a cyclopentenyl, cyclohexenyl, cycloheptenyl, bicycloheptenyl or bicyclooctenyl ring.

3. The polymer according to claim 1, wherein The monomer of general formula (I) is selected from the group consisting of: Bicyclo[2.2.1]hept-2-ene (norbornene or NB); 5-Butylbicyclo[2.2.1]hept-2-ene (BuNB); 5-Hexylbicyclo[2.2.1]hept-2-ene (HexNB); 5-Decylbicyclo-[2.2.1]hept-2-ene (DecNB); 5-Cyclohexylbicyclo[2.2.1]hept-2-ene (CyHexNB); 5-phenylbicyclo[2.2.1]hept-2-ene (PhNB); 5-Phenethylbicyclo[2.2.1]hept-2-ene (PENB); 2,2'-Bis(bicyclo[2.2.1]heptane-5-ene) (NBANB); 1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylnaphthalene (TD); and 2-Hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylnaphthalene (HexTD).

4. The polymer according to claim 1, wherein The monomer of general formula (II) is selected from the group consisting of: 5-Methylenebicyclo[2.2.1]hept-2-ene (MNB); 5-vinylbicyclo[2.2.1]hept-2-ene (VNB); 5-Ethylidenebicyclo[2.2.1]hept-2-ene (ENB); 5-(But-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB); 5-(Hex-5-en-1-yl)bicyclo[2.2.1]hept-2-ene (HexenylNB); 5-(Cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (Cyclohexene NB); 1,4,4a,5,8,8a-Hexahydro-1,4:5,8-dimethylnaphthalene (TDD); 3a,4,7,7a-Tetrahydro-1H-4,7-methanoindene (DCPD); and 3a,4,4a,5,8,8a,9,9a-Octahydro-1H-4,9:5,8-dimethylcyclopenta[b]naphthalene (CPD3).

5. The polymer according to claim 1, selected from the group consisting of: Copolymers of norbornene (NB) and 5-vinylbicyclo[2.2.1]hept-2-ene (VNB); Copolymers of norbornene (NB) and 5-ethylidenebicyclo[2.2.1]hept-2-ene (ENB); Copolymers of norbornene (NB) and 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB); Copolymers of norbornene (NB) and 5-(hex-5-en-1-yl)bicyclo[2.2.1]hept-2-ene (HexenylNB); and Copolymers of norbornene (NB) and 5-(cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyclohexeneNB); A terpolymer of norbornene (NB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB) and 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB); A terpolymer of norbornene (NB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB) and 5-(cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyclohexeneNB); A terpolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB) and 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB); A terpolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB) and 5-(hex-5-en-1-yl)bicyclo[2.2.1]hept-2-ene (HexenylNB); and A terpolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB) and 5-cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyclohexeneNB).

6. The polymer according to claim 1, wherein The content of the second repeating unit is in the range of about 5 mol % to about 30 mol % relative to the total molar number of the first repeating unit and the second repeating unit.

7. The polymer according to claim 1, wherein The first repeating unit is derived from two different monomers of general formula (I).

8. A composition comprising: a) a polymer comprising: i) at least one first repeating unit represented by the general formula (IA), wherein the first repeating unit is derived from a monomer of the general formula (I): in, indicates the position of bonding to another repeating unit; m is an integer of 0, 1 or 2; R1, R2, R3 and R4 are the same or different and are independently selected from hydrogen, methyl, ethyl, straight or branched (C3-C 16 )alkyl, (C3-C 10 )cycloalkyl, (C6-C 12 ) bicycloalkyl, (C6-C 12 )aryl and (C6-C 12 ) the group consisting of aryl(C1-C6)alkyl; or One of R1 and R2 together with one of R3 and R4 and the carbon atom to which they are attached form a substituted or unsubstituted (C5-C 14 ) ring, (C5-C 14 ) bicyclic, (C5-C 14 ) tricyclic; and ii) at least one second repeating unit represented by the general formula (IIA), wherein the second repeating unit is derived from a monomer of the general formula (II): in, indicates the position of bonding to another repeating unit; n is an integer of 0, 1 or 2; At least one of R5, R6, R7 and R8 is selected from methylene, ethylene, vinyl, straight chain or branched (C3-C 16 )alkenyl, (C3-C 10 )cycloalkenyl, (C6-C 12 )bicycloalkenyl and (C6-C 12 )Aryl(C2-C 16 ) alkenyl, the remaining R5, R6, R7 and R8 are the same or different and are independently selected from hydrogen, methyl, ethyl, straight or branched (C3-C 16 )alkyl, (C3-C 10 )cycloalkyl, (C6-C 12 ) bicycloalkyl, (C6-C 12 )aryl and (C6-C 12 ) the group consisting of aryl(C1-C6)alkyl; or One of R5 and R6 together with one of R7 and R8 and the carbon atom to which they are attached form a substituted or unsubstituted (C5-C 14 ) ring, (C5-C 14 ) bicyclic or (C5-C 14 ) tricyclic; and Wherein, relative to the total molar number of the first repeating unit and the second repeating unit, the content of the second repeating unit is not less than 4 mol%; b) a cross-linking agent selected from the group consisting of: 1,3,5-Triallyl-1,3,5-triazinane-2,4,6-trione (TAIC); and 2,4,6-tri(allyloxy)-1,3,5-triazine (TAC); and c) one or more additives selected from the group consisting of adhesion promoters and free radical initiators.

9. The composition according to claim 8, wherein The first repeating unit of the polymer is derived from a monomer of the general formula (I) selected from the group consisting of: Bicyclo[2.2.1]hept-2-ene (norbornene or NB); 5-Butylbicyclo[2.2.1]hept-2-ene (BuNB); 5-Hexylbicyclo[2.2.1]hept-2-ene (HexNB); 5-Decylbicyclo-[2.2.1]hept-2-ene (DecNB); 5-Cyclohexylbicyclo[2.2.1]hept-2-ene (CyHexNB); 5-phenylbicyclo[2.2.1]hept-2-ene (PhNB); 5-Phenethylbicyclo[2.2.1]hept-2-ene (PENB); 2,2'-Bis(bicyclo[2.2.1]heptane-5-ene) (NBANB); 1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylnaphthalene (TD); and 2-Hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylnaphthalene (HexTD).

10. The composition according to claim 8, wherein The second repeating unit of the polymer is derived from a monomer of the general formula (II) selected from the group consisting of: 5-Methylenebicyclo[2.2.1]hept-2-ene (MNB); 5-vinylbicyclo[2.2.1]hept-2-ene (VNB); 5-Ethylidenebicyclo[2.2.1]hept-2-ene (ENB); 5-(But-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB); 5-(Hex-5-en-1-yl)bicyclo[2.2.1]hept-2-ene (HexenylNB); 5-(Cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyHexeneNB); 1,4,4a,5,8,8a-Hexahydro-1,4:5,8-dimethylnaphthalene (TDD); 3a,4,7,7a-Tetrahydro-1H-4,7-methanoindene (DCPD); and 3a,4,4a,5,8,8a,9,9a-Octahydro-1H-4,9:5,8-dimethylcyclopenta[b]naphthalene (CPD3).

11. The composition according to claim 8, wherein The content of the second repeating unit in the polymer is in a range of about 5 mol % to about 30 mol % relative to the total molar number of the first repeating unit and the second repeating unit.

12. The composition according to claim 8, wherein The polymer is selected from the group consisting of: Copolymers of norbornene (NB) and 5-vinylbicyclo[2.2.1]hept-2-ene (VNB); Copolymers of norbornene (NB) and 5-ethylidenebicyclo[2.2.1]hept-2-ene (ENB); Copolymers of norbornene (NB) and 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB); Copolymers of norbornene (NB) and 5-(hex-5-en-1-yl)bicyclo[2.2.1]hept-2-ene (HexenylNB); and Copolymers of norbornene (NB) and 5-cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyclohexeneNB); A terpolymer of norbornene (NB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB) and 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB); A terpolymer of norbornene (NB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB) and 5-(cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyclohexeneNB); A terpolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB) and 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB); A terpolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB) and 5-(hex-5-en-1-yl)bicyclo[2.2.1]hept-2-ene (HexenylNB); and A terpolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB) and 5-cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyclohexeneNB).

13. The composition according to claim 8, wherein The tackifier is selected from the group consisting of: Ethylene-propylene-ethylidene norbornene terpolymer, wherein a is at least 100; Ethylene-propylene-dicyclopentadiene terpolymer, wherein a is at least 100; 1,2-Butadiene rubber, wherein a is at least 100; Styrene / butadiene rubber 1; Styrene / butadiene rubber 2; Hydrogenated styrene / butadiene rubber1; and Hydrogenated styrene / butadiene rubber2.

14. The composition according to claim 8, wherein The free radical initiator is selected from the group consisting of: 1,1'-(diazene-1,2-diyl)bis(cyclohexane-1-carbonitrile); Di-tert-butyl peroxide; 2,5-Bis(tert-butylperoxy)-2,5-dimethylhexane; 1,1-Bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane; Dicumyl peroxide; Benzoyl peroxide; Dodecyl peroxide; tert-Butyl peroxybenzoate; and Tert-butyl peroxy(2-ethylhexyl)carbonate.

15. The composition according to claim 8, selected from the group consisting of: A solution comprising a terpolymer of norbornene (NB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB) and 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB); and a mixture of 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC) and dicumyl peroxide (DCP); A solution comprising a terpolymer of norbornene (NB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB) and 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB); and a mixture of 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), 1,2-butadiene rubber and dicumyl peroxide (DCP); A solution comprising a terpolymer of norbornene (NB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB) and 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB); and a mixture of 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), 1,2-butadiene rubber, a polyarylether crosslinker terminated with methacrylate groups, and dicumyl peroxide (DCP); A solution comprising a terpolymer of norbornene (NB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB) and 5-(cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyclohexeneNB); and a mixture of 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), 1,2-butadiene rubber and dicumyl peroxide (DCP); A solution comprising a copolymer of norbornene (NB) and 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB); and a mixture of 1,2-butadiene rubber and dicumyl peroxide (DCP); A solution comprising a copolymer of norbornene (NB) and 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB); and a mixture of an ethylene-propylene-dicyclopentadiene terpolymer and dicumyl peroxide (DCP); A solution comprising a copolymer of norbornene (NB) and 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB); and a mixture of an ethylene-propylene-ethylidene norbornene terpolymer and dicumyl peroxide (DCP); A solution comprising a terpolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB) and 5-cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyclohexeneNB); and a mixture of 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), 1,2-butadiene rubber and dicumyl peroxide (DCP); A solution comprising a terpolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB) and 5-cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyclohexeneNB); and a mixture of 1,2-butadiene rubber and dicumyl peroxide (DCP); A solution comprising a terpolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB) and 5-cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyclohexeneNB); and a mixture of 1,2-butadiene rubber, ethylene-propylene-ethylidene norbornene terpolymer and dicumyl peroxide (DCP); A solution comprising a terpolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB) and 5-cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyclohexeneNB); and a mixture of 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), 1,2-butadiene rubber, ethylene-propylene-ethylidene norbornene terpolymer and dicumyl peroxide (DCP); and A solution comprising a terpolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB) and 5-cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyclohexeneNB); and a mixture of 2,4,6-tri(allyloxy)-1,3,5-triazine (TAC), 1,2-butadiene rubber and dicumyl peroxide (DCP).

16. A film formed from the composition of claim 8.

17. The film of claim 16 having a dielectric constant (Dk) lower than 3 at a frequency of 10 GHz, a glass transition temperature higher than 150°C, and a coefficient of thermal expansion (CTE) lower than 130 ppm / K.

18. The film of claim 16, formed from a composition selected from the group consisting of: A solution comprising a terpolymer of norbornene (NB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB) and 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB); and a mixture of 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC) and dicumyl peroxide (DCP); A solution comprising a terpolymer of norbornene (NB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB) and 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB); and a mixture of 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), 1,2-butadiene rubber and dicumyl peroxide (DCP); A solution comprising a terpolymer of norbornene (NB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB) and 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB); and a mixture of 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), 1,2-butadiene rubber, a polyarylether crosslinker terminated with methacrylate groups, and dicumyl peroxide (DCP); A solution comprising a terpolymer of norbornene (NB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB) and 5-(cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyclohexeneNB); and a mixture of 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), 1,2-butadiene rubber and dicumyl peroxide (DCP); A solution comprising a copolymer of norbornene (NB) and 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB); and a mixture of 1,2-butadiene rubber and dicumyl peroxide (DCP); A solution comprising a copolymer of norbornene (NB) and 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB); and a mixture of an ethylene-propylene-dicyclopentadiene terpolymer and dicumyl peroxide (DCP); A solution comprising a copolymer of norbornene (NB) and 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB); and a mixture of an ethylene-propylene-ethylidene norbornene terpolymer and dicumyl peroxide (DCP); A solution comprising a terpolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB) and 5-cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyclohexeneNB); and a mixture of 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), 1,2-butadiene rubber and dicumyl peroxide (DCP); A solution comprising a terpolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB) and 5-cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyclohexeneNB); and a mixture of 1,2-butadiene rubber and dicumyl peroxide (DCP); A solution comprising a terpolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB) and 5-cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyclohexeneNB); and a mixture of 1,2-butadiene rubber, ethylene-propylene-ethylidene norbornene terpolymer and dicumyl peroxide (DCP); A solution comprising a terpolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB) and 5-cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyclohexeneNB); and a mixture of 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), 1,2-butadiene rubber, ethylene-propylene-ethylidene norbornene terpolymer and dicumyl peroxide (DCP); and A solution comprising a terpolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB) and 5-cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyclohexeneNB); and a mixture of 2,4,6-tri(allyloxy)-1,3,5-triazine (TAC), 1,2-butadiene rubber and dicumyl peroxide (DCP).

19. A glass composite film formed from the polymer according to claim 1.

20. The film of claim 19 having a dielectric constant (Dk) lower than 2.6 at a frequency of 10 GHz, a peel strength higher than 5.5 N / cm and a coefficient of thermal expansion (CTE) lower than 40 ppm / K.

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