Flame retardant compositions comprising polycyclic olefin polymers containing olefin functional groups for forming low loss films with improved dielectric and thermal properties

Abstract

Embodiments according to the present invention include a composition comprising a polymer formed from polycyclic olefin monomers wherein at least one monomer comprises, as desired, other unpolymerized ethylene bonds, an organophosphorus compound, as desired, hexagonal boron nitride, a crosslinking agent, a free radical initiator, a tackifier, and one or more suitable additives. 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 composition of the present invention exhibit low dielectric constant, low loss characteristics, flame retardancy, and extremely high thermal characteristics that have not been achieved up to now. The composition of the present invention may further contain one or more organic or inorganic filler materials that provide improved thermomechanical properties in addition to excellent thermal and 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. The film formed from the composition of the present invention has a UL-94V-0 rating, a dielectric constant (Dk) of less than 2.7, and a dielectric loss factor (Df) of less than 0.0009.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of U.S. Provisional Application No. 63 / 404,374, 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 is generally related to a composition, which comprises a polymer containing an olefin functional group, and a flame retardant organophosphorus compound, hexagonal boron nitride, a tackifier, a crosslinking agent, a free radical initiator and one or more additives. More specifically, the polymer used in this specification is formed by two or more polycyclic olefin monomers such as norbornene-type monomers, wherein at least one monomer contains a free olefin functional group. The composition of the present invention can be easily formed into a film, which can be used as a low-loss thermoset and prepreg of a copper-clad laminate that not only exhibits low dielectric constant and low loss characteristics but also exhibits extremely high thermal characteristics and excellent flame retardant properties. For example, the film formed by the composition of the present invention generally exhibits a high glass transition temperature (ranging from about 250°C to 280°C), and also exhibits a low dielectric constant (about 2.4 to 2.8 at a frequency of 10 GHz) and a low dielectric loss factor (about 0.0008 to 0.002 at a frequency of 10 GHz). Therefore, the polymer and composition of the present invention can be used as an insulating material in various 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 250°C.

[0006] In addition, there are huge technical challenges in developing insulating materials that meet all the requirements. One challenge is that such materials need to exhibit a very high glass transition temperature (T g ), preferably above 150°C or even above 250°C, this is because of the processing conditions used in the manufacture of printed circuit boards and the harsh conditions that the equipment may encounter, such as millimeter wave radar antennas used in automobiles and other terminal equipment used in 5G devices.

[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. In addition, it is necessary to further ensure that the materials used in such applications are flame retardant because high heat is generated in many applications.

[0009] U.S. Patent No. 10,104,769 B2 discloses a circuit subassembly embodiment comprising a thermosetting composition comprising a low polarity resin, an aromatic compound containing oxaphosphorinoxide, and at least UL-94 V-1 rating. However, the embodiment described therein exhibits a high Dk of about 3.8 and a high Df of about 0.006.

[0010] Therefore, there is still a need to develop a new insulating material that not only exhibits low dielectric properties and high thermal properties, but also exhibits excellent flame retardant 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 flame retardant composition exhibiting UL-94 V-0 rating and excellent dielectric and thermal properties, the flame retardant composition comprising a polymer of one or more monomers containing substituted norbornene (one of which monomers may contain at least one free olefin functional group), an organic phosphorus compound, and, if necessary, hexagonal boron nitride, the flame retardant composition being capable of forming an insulating material having properties that have not been achieved to date.

[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 composition comprising a combination of one or more polycyclic olefin monomers having the general formula (I) described in the present specification and, as required, a polymer of a monomer having the general formula (II), one or more organic phosphorus compounds having the general formula (III) or (IV) described in the present specification and, as required, hexagonal boron nitride, and specific other components described in the present specification, it is possible to form various three-dimensional objects including films that provide dielectric properties and thermal properties that have not been achieved to date.

[0016] In another embodiment, a film-forming composition is also provided, which comprises a polymer of two or more polycyclic olefin monomers having the general formula (I) and (II) described in the present specification, one or more organic phosphorus compounds having the general formula (III) or (IV) and hexagonal boron nitride as required, as well as some other components described in the present specification, and the film-forming composition can form a film suitable as an insulating material and exhibiting excellent flame retardant properties.

[0017] In another aspect of the present invention, a film, a composite material, or a prepreg comprising the composition of the present invention is also provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] 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.

[0019] Figure 1 is a graph showing a dielectric reliability study of an exemplary film formed from a composition of the present invention over a storage temperature of 125° C. over a period of more than 1000 hours, compared to a comparative composition.

[0020] Figure 2is a graph showing a dielectric reliability study of an exemplary film formed from a composition of the present invention at a storage temperature of 125°C over a period of more than 1000 hours, compared to storage of another film formed from the same composition at 85°C / 85% relative humidity.

[0021] Figure 3 is a graph showing a dielectric reliability study of various exemplary films formed from various compositions according to embodiments of the present invention at 85° C. storage temperature / 85% relative humidity over a period of more than 1000 hours. 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, a composition is provided, which comprises:

[0048] a) a polymer comprising:

[0049] 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):

[0050]

[0051] in,

[0052] indicates the position of bonding to another repeating unit;

[0053] m is an integer of 0, 1 or 2;

[0054] 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

[0055] 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

[0056] 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):

[0057]

[0058] in,

[0059] indicates the position of bonding to another repeating unit;

[0060] n is an integer of 0, 1 or 2;

[0061] 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

[0062] 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

[0063] 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 in the range of about 0 mol % to about 40 mol %;

[0064] b) a cross-linking agent selected from the group consisting of:

[0065]

[0066] 1,3,5-Triallyl-1,3,5-triazinane-2,4,6-trione, also known as triallyl isocyanurate (TAIC); and

[0067]

[0068] 2,4,6-tri(allyloxy)-1,3,5-triazine, also known as triallyl cyanurate (TAC);

[0069] c) an organic phosphorus compound selected from the group consisting of:

[0070] Compounds of general formula (III):

[0071]

[0072] in,

[0073] a and b are each independently an integer from 0 to 5;

[0074] c is an integer from 2 to 4;

[0075] Q is selected from a divalent or trivalent (C2-C 24 )alkyl, divalent NH(C2-C6)alkylNH and divalent O(C2-C6)alkylNH, wherein the alkyl group may be selected from methyl, ethyl, straight or branched (C3-C6)alkyl, (C6-C 12 )aryl and (C5-C 12 ) is substituted by one or more groups selected from the group consisting of heteroaryl;

[0076] R9 and R 10 Each is independently selected from the group consisting of hydrogen, methyl, ethyl and linear or branched (C3-C6) alkyl;

[0077] Compounds of general formula (IV):

[0078]

[0079] in,

[0080] R 11 and R 12 Each is independently selected from the group consisting of methyl, ethyl, linear or branched (C3-C6) alkyl, phenyl, methoxy, ethoxy, linear or branched (C3-C6) alkoxy, phenoxy and 6H-phosphathridine 5-oxide-(C1-C3) alkyl;

[0081] d) tackifiers; and

[0082] e) one or more additives selected from the group consisting of free radical initiators, antioxidants, synergists and any combination thereof.

[0083] It should be noted that the content of one or more organic phosphorus compounds of general formula (III) or (IV) is higher than 70% by weight relative to the amount of the polymer, and the composition, when formed into a film, has at least UL-94V-1 grade, a dielectric loss factor (Df) of less than 0.001 at 10 GHz, and a dielectric constant (Dk) of less than 2.5 at 10 GHz.

[0084] 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.

[0085] 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 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 when used in the compositions of the present invention, the amount of the monomers of formula (II) can be as little as 10 mol% of the total amount of the monomers of formula (I) and (II).

[0086] 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 10 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 10 mol% to about 40 mol%, about 15 mol% to about 30 mol%, about 18 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 relative to the total moles of the first repeating unit and the second repeating unit of the general formula (IA) and (IIA) may be less than 10 mol% depending on the desired crosslinking density, and may be greater than 40 mol% when a high crosslinking density is required.

[0087] 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.

[0088] In some embodiments, the polymer used in the composition 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 used in the composition 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).

[0089] Likewise, in other embodiments, the polymer used in the composition 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. Likewise, 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) described 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. Likewise, any appropriate amount of these different monomers can be used to form the polymer of the present invention, thereby achieving the desired effect.

[0090] 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.

[0091] 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.

[0092] 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.

[0093] 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.

[0094] 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:

[0095]

[0096] Bicyclo[2.2.1]hept-2-ene (norbornene or NB);

[0097]

[0098] 5-Butylbicyclo[2.2.1]hept-2-ene (BuNB);

[0099]

[0100] 5-Hexylbicyclo[2.2.1]hept-2-ene (HexNB);

[0101]

[0102] 5-Decylbicyclo-[2.2.1]hept-2-ene (DecNB);

[0103]

[0104] 5-Cyclohexylbicyclo[2.2.1]hept-2-ene (CyHexNB);

[0105]

[0106] 5-phenylbicyclo[2.2.1]hept-2-ene (PhNB);

[0107]

[0108] 5-Phenethylbicyclo[2.2.1]hept-2-ene (PENB);

[0109]

[0110] 2,2'-Bis(bicyclo[2.2.1]heptane-5-ene) (NBANB);

[0111]

[0112] 1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylnaphthalene (TD); and

[0113]

[0114] 2-Hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylnaphthalene (HexTD).

[0115] 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:

[0116]

[0117] 5-vinylbicyclo[2.2.1]hept-2-ene (VNB);

[0118]

[0119] 5-Ethylidenebicyclo[2.2.1]hept-2-ene (ENB);

[0120]

[0121] 5-(But-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB);

[0122]

[0123] 5-(Hex-5-en-1-yl)bicyclo[2.2.1]hept-2-ene (HexenylNB);

[0124]

[0125] 5-(Cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (Cyclohexene NB);

[0126]

[0127] 1,4,4a,5,8,8a-Hexahydro-1,4:5,8-dimethylnaphthalene (TDD);

[0128]

[0129] 3a,4,7,7a-Tetrahydro-1H-4,7-methanoindene (DCPD); and

[0130]

[0131] 3a,4,4a,5,8,8a,9,9a-Octahydro-1H-4,9:5,8-dimethylcyclopenta[b]naphthalene (CPD3).

[0132] Illustrative, non-limiting examples of polymers according to the present invention can be cited as follows:

[0133] Copolymers of norbornene (NB) and 5-vinylbicyclo[2.2.1]hept-2-ene (VNB);

[0134] Copolymers of norbornene (NB) and 5-ethylidenebicyclo[2.2.1]hept-2-ene (ENB);

[0135] Copolymers of norbornene (NB) and 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB);

[0136] Copolymers of norbornene (NB) and 5-(hex-5-en-1-yl)bicyclo[2.2.1]hept-2-ene (HexenylNB); and

[0137] Copolymers of norbornene (NB) and 5-(cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyclohexeneNB);

[0138] 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);

[0139] 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);

[0140] 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);

[0141] 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

[0142] 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).

[0143] In another aspect of the invention, the polymer used in the composition of the invention comprises only repeating units of the general formula (IA) derived from monomers of the general formula (I). That is, in this embodiment of the invention, the polymer used does not contain any repeating units of the general formula (IIA) containing free olefin functional groups. Therefore, such polymers cannot be crosslinked in order to form a thermosetting composition. Therefore, when such a composition is needed, a thermoplastic composition containing only repeating units of the general formula (IA) is also provided. Any monomer of one or more of the general formula (I) that can form a homopolymer, a copolymer, or a terpolymer can be used in this aspect of the composition of the invention.

[0144] Illustrative, non-limiting examples of polymers according to this aspect of the invention can be listed below:

[0145] Homopolymer of norbornene (NB);

[0146] Homopolymers of 5-(butyl)bicyclo[2.2.1]hept-2-ene (BuNB);

[0147] Homopolymers of 5-(hexyl)bicyclo[2.2.1]hept-2-ene (HexNB);

[0148] Homopolymers of 5-(decyl)bicyclo[2.2.1]hept-2-ene (DecNB);

[0149] Copolymers of norbornene (NB) and 5-(butyl)bicyclo[2.2.1]hept-2-ene (BuNB);

[0150] Copolymers of norbornene (NB) and 5-(hexyl)bicyclo[2.2.1]hept-2-ene (HexNB); and

[0151] Copolymers of norbornene (NB) and 5-(cyclohexyl)bicyclo[2.2.1]hept-2-ene (CyclohexaneNB);

[0152] A terpolymer of norbornene (NB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB) and 5-(hexyl)bicyclo[2.2.1]hept-2-ene (HexNB);

[0153] A terpolymer of norbornene (NB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB) and 5-(cyclohexyl)bicyclo[2.2.1]hept-2-ene (CyclohexaneNB); and

[0154] A terpolymer of norbornene (NB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB) and 5-(decyl)bicyclo[2.2.1]hept-2-ene (DecylNB).

[0155] 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:

[0156] Bis(triphenylphosphine)palladium(II) dichloride;

[0157] Bis(triphenylphosphine)palladium(II) dibromide;

[0158] Bis(triphenylphosphine)palladium(II)diacetate;

[0159] Bis(triphenylphosphine)bis(trifluoroacetate)palladium(II);

[0160] Bis(tricyclohexylphosphine)palladium(II) dichloride;

[0161] Bis(tricyclohexylphosphine)palladium(II) dibromide;

[0162] Bis(tricyclohexylphosphine)palladium(II)diacetate (Pd785);

[0163] Bis(tricyclohexylphosphine)bis(trifluoroacetate)palladium(II);

[0164] Bis(tri-p-tolylphosphine)palladium(II) dichloride;

[0165] Bis(tri-p-tolylphosphine)palladium(II) dibromide;

[0166] Bis(tri-p-tolylphosphine)palladium(II) diacetate;

[0167] Bis(tri-p-tolylphosphine)bis(trifluoroacetate)palladium(II);

[0168] Palladium(II) ethylhexanoate;

[0169] Bis(acetone)palladium(II);

[0170] Dichlorobis(benzonitrile)palladium(II);

[0171] n-Butyldi-1-adamantylphosphine palladium diacetate (H2O) (Pd601);

[0172] n-Butyldi-tert-butylphosphinediacetatepalladium(H2O) (Pd445);

[0173] Bis(n-butyldi-1-adamantylphosphine)acetatepalladium(acetonitrile)tetrakis(pentafluorophenyl)borate (Pd1602);

[0174] (Acetonitrile)bis(triisopropylphosphine)(acetic acid)palladiumtetrakis(pentafluorophenyl)borate (Pd1206);

[0175] [(Allyl)(trinaphthylphosphine)(trifluoroacetic acid)palladium];

[0176] [(Allyl)(trinaphthylphosphine)(trifluoromethanesulfonate)palladium];

[0177] Platinum(II) chloride;

[0178] Platinum(II) bromide; and

[0179] Bis(triphenylphosphine)platinum dichloride.

[0180] As is well known in the art, such palladium compounds are further activated when various activator compounds are used. Non-limiting examples of such activators may be selected from the group consisting of:

[0181] Lithium tetrafluoroborate;

[0182] Lithium trifluoromethanesulfonate;

[0183] Lithium tetrakis(pentafluorophenyl)borate;

[0184] Lithium tetrakis(pentafluorophenyl)borate ethyl ether complex (LiFABA);

[0185] Sodium tetrakis(pentafluorophenyl)borate ethyl ether complex (NaFABA);

[0186] Tetrakis(pentafluorophenyl)borate trityl ethyl ether complex (tritylFABA);

[0187] Tropylium tetrakis(pentafluorophenyl)borate ethyl ether complex (tropyliumFABA);

[0188] Lithium tetrakis(pentafluorophenyl)borate isopropanol complex;

[0189] Lithium tetraphenylborate;

[0190] Lithium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate;

[0191] Lithium tetrakis(2-fluorophenyl)borate;

[0192] Lithium tetrakis(3-fluorophenyl)borate;

[0193] Lithium tetrakis(4-fluorophenyl)borate;

[0194] Lithium tetrakis(3,5-difluorophenyl)borate;

[0195] Lithium hexafluorophosphate;

[0196] Lithium hexaphenylphosphate;

[0197] Lithium hexa(pentafluorophenyl)phosphate;

[0198] Lithium hexafluoroarsenate;

[0199] Lithium hexaphenylarsenate;

[0200] Lithium hexa(pentafluorophenyl)arsenate;

[0201] Lithium hexa(3,5-bis(trifluoromethyl)phenyl)arsenate;

[0202] Lithium hexafluoroantimonate;

[0203] Lithium hexaphenylantimonate;

[0204] Lithium hexa(pentafluorophenyl)antimonate;

[0205] Lithium hexa(3,5-bis(trifluoromethyl)phenyl)antimonate;

[0206] Lithium tetrakis(pentafluorophenyl)aluminate;

[0207] Lithium tris(nonafluorobiphenyl)fluoroaluminate;

[0208] Lithium (octyloxy)tris(pentafluorophenyl)aluminate;

[0209] Lithium tetrakis(3,5-bis(trifluoromethyl)phenyl)aluminate;

[0210] Lithium methyl tris(pentafluorophenyl)aluminate; and

[0211] Dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA).

[0212] 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.

[0213] 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.

[0214] 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), with chain transfer agents such as triethylsilane (TES) being 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 comprising any combination thereof. 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. Pat. No. 9,771,443 B2, the relevant portions of which are incorporated herein by reference.

[0215] 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.

[0216] 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 2 to 8 N / cm, and can therefore be used in many applications such as copper clad laminates.

[0217] Any amount of the polymers described in this specification that provide the desired benefit can be used in the compositions of the present invention. Typically, such amounts can be in the range of about 20% to about 80% by weight relative to the total weight of the composition. However, it should be noted that in some embodiments, the amount of the polymer used can be less than 20% by weight or greater than 80% by weight, and all permissible combinations are fully within the scope of the present invention.

[0218] As mentioned above, the composition according to the present invention comprises at least one cross-linking agent, which may be TAIC or TAC. In some embodiments, the composition according to the present invention may comprise a mixture of both TAIC and TAC.

[0219] 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.

[0220] Advantageously, it has been found that various other crosslinking agents that can provide similar effects as TAIC or TAC can also be used in the compositions of the present invention. Some such crosslinking agents include, without limitation, 1,2,4-trivinylcyclohexane, trimethylolpropane triacrylate, trimethylolpropane trimethyl triacrylate, and the like.

[0221] As mentioned above, the composition according to the invention further comprises at least one organophosphorus compound of the general formula (III) or one organophosphorus compound of the general formula (IV) or a phosphazene.

[0222] In some embodiments, the composition of the present invention comprises at least one compound of the general formula (III), wherein each a and b are independently 0, 1, 2, 3, 4 or 5. Typically, c is 2, but may also be 3 or 4. Q is typically a divalent linking group selected from the group consisting of vinyl, propenyl, butenyl, pentalene, hexalene, 1,2-diaminovinyl, 1,3-diamino-propenyl, -OCH2NH- and -OCH2CH2NH-. Any of these methylene groups may be substituted with methyl, ethyl, n-propyl, isopropyl, n-butyl, isopropyl, tert-butyl, n-pentyl, n-hexyl, phenyl, biphenyl, naphthyl, furanyl, pyrrolyl, imidazolyl and pyridyl. Furthermore, R9 and R 10 It can be selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isopropyl, tert-butyl, n-pentyl and n-hexyl.

[0223] Non-limiting examples of monomers of formula (III) may be selected from the group consisting of:

[0224]

[0225] 6,6'-(Ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphaphenanthrene 6-oxide), also known as DiDOPO;

[0226]

[0227] 6,6'-(1-phenylethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphaphenanthrene 6-oxide), also known as DiDOPO2;

[0228]

[0229] 6,6'-(1-(naphthalene-2-yl)ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphaphenanthrene 6-oxide), also known as DiDOPO3;

[0230]

[0231] 6,6'-(1-(Naphthalen-1-yl)ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphaphenanthrene 6-oxide);

[0232]

[0233] 6,6'-(1,2-diphenylethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphaphenanthrene 6-oxide);

[0234]

[0235] 6,6'-(1-phenylpropane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphaphenanthrene 6-oxide);

[0236]

[0237] 6,6'-(1-(Furan-2-yl)ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphaphenanthrene 6-oxide);

[0238]

[0239] 6-((6-oxydibenzo[c,e][1,2]oxophosphaphenanthrene-6-yl)methoxy)dibenzo[c,e][1,2]oxy-phosphaphenanthrene 6-oxide, also known as DiDOPOMeO;

[0240]

[0241] 6,6'-(Ethane-1,2-diylbis(azanediyl))bis(dibenzo[c,e][1,2]oxaphosphaphenanthrene 6-oxide), also known as EDAB-DOPO;

[0242]

[0243] 6-(2-((6-oxydibenzo[c,e][1,2]oxaphosphaphenanthrene-6-yl)amino)methoxy)dibenzo[c,e][1,2]oxaphosphaphenanthrene 6-oxide, also known as EAB-DOPO.

[0244] In some embodiments, the composition of the present invention comprises at least one compound of formula (IV), wherein R 11 and R 12 The group may be selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isopropyl, tert-butyl, n-pentyl, n-hexyl, phenyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentyloxy, n-hexyl, phenoxy, 6H-phosphanthridine 5-oxide-methyl, 6H-phosphanthridine 5-oxide-ethyl and 6H-phosphanthridine 5-oxide-propyl.

[0245] Non-limiting examples of monomers of formula (IV) may be selected from the group consisting of:

[0246]

[0247] 3,9-Dimethyl-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide (ThorFlame Retardants PCO-900 is commercially available);

[0248]

[0249] 3,9-Diphenoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide (ThorFlame Retardants PCO 910 is commercially available); and

[0250]

[0251] 3,9-Bis((6-oxydibenzo[c,e][1,2]oxaphosphaphenanthren-6-yl)methoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide.

[0252] In still other embodiments, the composition of the present invention comprises a phosphazene as the organophosphorus compound.

[0253] Any amount of the organophosphorus compound that brings the desired benefits can be used, depending on the final application of the composition. For example, by adding an appropriate amount of the organophosphorus compound to the composition of the present invention, not only can excellent flame retardant properties such as UL-94 V-0 rating be obtained, but also excellent dielectric properties and storage stability at a temperature in the range of about 80° C. to 150° C., and a relative humidity of 85% can be exhibited.

[0254] Therefore, in some embodiments, the amount of the organophosphorus compound used in the composition of the present invention is at least 60% by weight for the amount of the polymer used in the composition. That is, in the composition of the present invention, 60 parts of the organophosphorus compound are used for every 100 parts of the polymer, which is also expressed as 60 parts per 100 parts of the resin in this specification. In other embodiments, the content of the organophosphorus compound in the composition of the present invention is an amount in the range of about 60pphr to about 120pphr. In some other embodiments, such an amount can be about 65pphr to about 110pphr, about 70pphr to about 100pphr, about 80pphr to about 90pphr, etc. However, it should be noted that organophosphorus compounds less than 60pphr or greater than 120pphr can also be used in the composition of the present invention required for the manufacture of suitable devices. The amount of the organophosphorus compound used also depends on the various other ingredients present in the composition that will bring expected benefits, especially flame retardant properties.

[0255] Surprisingly, it has been found that the use of hexagonal boron nitride (h-BN) in the composition according to the present invention provides a multiplier benefit. That is, it has been found that by using h-BN with an appropriate particle size, not only the high thermal properties required for various applications are improved, but also the highly desirable flame retardant properties are improved, among other things, for example, the peel strength when coated on a metal substrate such as copper is improved, thereby providing additional advantages in various applications using copper clad laminates such as printed circuit boards, millimeter wave radar antennas, etc.

[0256] Advantageously, it is further found that the low dielectric properties of the film formed by the composition of the present invention can be improved by adding h-BN. That is, when an appropriate amount of h-BN is used in the composition of the present invention, the composition of the present invention generally exhibits a lower dielectric constant (Dk) and a lower dielectric loss factor (Df). Generally, the form of the boron nitride used in the composition of the present invention is a hexagonal crystal structure. It is well known in the art that h-BN can be powdered, including flakes, platelets, and other shapes. In some embodiments, the h-BN used in the composition of the present invention is platelet-shaped. The precise shape of the platelet is not important. In this regard, the h-BN platelet can have an irregular shape. As recorded in this specification, the term "platelet" generally refers to any thin and flat particles, including flakes. However, other forms of h-BN may also be used, including fibers, rods, whiskers, sheets, nanosheets, agglomerates, or boron nitride nanotubes, and may be different in crystal type, shape, or size, and include the following distribution. The h-BN may have an average aspect ratio (ratio of the width or diameter of the particle to the length) of 1:2 to 1:100,000, 1:5 to 1:1,000, or 1:10 to 1:300. Exemplary shapes of particles having relatively high aspect ratios include platelets, rod-like particles, fibers, whiskers, etc. The platelets may have an average aspect ratio (ratio of the width or diameter of the particle to the length) of 4:5 to 1:300, 1:2 to 1:300, 1:2 to 1:200, 3:5 to 1:100, or 1:25 to 1:100.

[0257] The composition of the present invention contains hexagonal boron nitride. Other forms of boron nitride can also be used in the composition of the present invention, including cubic, wurtzite, rhombohedral or other synthetic structures. h-BN has a layered structure similar to graphite, in which the layers are aligned and stacked so that the hexagonal rings within the layer overlap. The positions of the N and B atoms alternate layer by layer. h-BN particles can be obtained from a variety of commercial sources. Crystalline or partially crystalline boron nitride particles can be prepared by processes known in the art. These include, for example, boron nitride powders prepared by the pressing process disclosed in U.S. Patents Nos. 5,898,009 and 6,048,511, and boron nitride agglomerate powders disclosed in U.S. Patent No. 2005 / 0041373. Various boron nitride powders are available for purchase on the market, such as those sold by St. Gobain.

[0258] In general, the particle size distribution of h-BN can vary greatly, and the smaller the particle size, the easier it is to form a homogeneous composition of the present invention. Therefore, in some embodiments, the average particle size of the h-BN used can be less than 0.05 μm (e.g., less than 50 nm). In other embodiments, the average particle size of the h-BN used is in the range of about 0.05 μm to about 70 μm. In still other embodiments, the average particle size of the h-BN used is in the range of about 0.1 μm to about 30 μm; 0.1 μm to about 20 μm; 0.1 μm to about 10 μm, etc.

[0259] Any amount of h-BN that brings the expected benefits can be used, depending on the final application of the composition. For example, by adding an appropriate amount of h-BN to the composition of the present invention, not only excellent dielectric properties and low loss characteristics can be obtained, but also extremely high thermal properties, including excellent flame retardant properties, can be obtained. In addition, it should be noted that h-BN is not only used as an insulating material in various electronic applications, but also provides excellent thermal conductivity and heat dissipation is faster than traditional insulating materials. Therefore, the composition of the present invention is particularly suitable for manufacturing microelectronic devices that generate heat and need to dissipate heat, such as millimeter wave radar antennas, etc. It is well known in the art that boron nitride is one of the materials with the highest thermal conductivity in semiconductors and electrical insulators (751W / mK at room temperature), and due to less intralayer coupling, its thermal conductivity increases with the reduction of thickness. In contrast, the thermal conductivity of silica particles is about 1.3W / mK at room temperature. Therefore, according to the type of h-BN used in the composition of the present invention and the amount of h-BN, a composition with extremely high thermal conductivity can be prepared. Thermal conductivity can be measured by any method known in the art, for example, using a TIM Tester 1300 according to the procedure described in ASTM D5470-17.

[0260] In some embodiments, the amount of h-BN used in the composition of the present invention can be at least 10% by weight relative to the amount of polymer used in the composition. In other embodiments, the content of h-BN in the composition of the present invention is in the range of about 15% by weight to about 120% by weight relative to the amount of polymer. In still other embodiments, such amount can be in the range of about 20% by weight to about 100% by weight, about 30% by weight to about 80% by weight, about 40% by weight to about 70% by weight relative to the amount of polymer used in the composition, etc. However, it should be noted that h-BN less than 10% by weight or greater than 120% by weight relative to the polymer used can also be used in the composition of the present invention required for the manufacture of suitable devices.

[0261] It has been further found that when using an organophosphorus compound of formula (IV), it may be advantageous to use a specific piperidine compound as a synergist to enhance the flame retardant properties. Therefore, in some embodiments, a compound selected from the group consisting of:

[0262] Compounds of general formula (V):

[0263]

[0264] Wherein d is an integer from 6 to 16;

[0265] R 13 , R 14 , R 16 and R 17 The same or different and each independently selected from hydrogen, methyl, ethyl and straight or branched (C3-C 20 ) a group consisting of an alkyl group;

[0266] R 15 Selected from hydrogen, hydroxy, methyl, ethyl, straight chain or branched (C3-C 20 ) alkyl, methoxy, ethoxy, straight chain or branched (C3-C 20 ) alkoxy and (C3-C 10 ) the group consisting of cycloalkyl; and

[0267] Compounds of general formula (VI):

[0268]

[0269] R 18 , R 19 , R 20 and R 21 The same or different and each independently selected from hydrogen, methyl, ethyl and straight or branched (C3-C 20 ) a group consisting of an alkyl group;

[0270] R 23 Selected from methyl, ethyl, straight chain or branched (C3-C 20 ) alkyl, methoxy, ethoxy, straight chain or branched (C3-C 20 ) alkoxy, (C3-C 10 )cycloalkyl, substituted or unsubstituted (C3-C 10 ) a group consisting of a heterocycle and a substituted urea;

[0271] R 22 Selected from methyl, ethyl, straight chain or branched (C3-C 20 ) alkyl, methoxy, ethoxy, straight chain or branched (C3-C 20 ) alkoxy and (C3-C 10) a group consisting of cycloalkyl.

[0272] Exemplary compounds of general formula (V) can be listed below without any limitation:

[0273]

[0274] Bis(1,2,2,6,6-pentamethylpiperidin-4-yl) suberate;

[0275]

[0276] Bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate (HALS-1);

[0277]

[0278] Bis(2,2,6,6-tetramethyl-1-(octyloxy)piperidin-4-yl)sebacate (HALS-2);

[0279]

[0280] Bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate (HALS-3);

[0281]

[0282] 1-(1,2,2,6,6-pentamethylpiperidin-4-yl)10-(1,2,2-triethyl-6,6-dimethylpiperidin-4-yl)sebacate;

[0283]

[0284] Bis(1-(cyclopentyloxy)-2,2,6,6-tetramethylpiperidin-4-yl)sebacate;

[0285]

[0286] Bis(1-(cyclohexyloxy)-2,2,6,6-tetramethylpiperidin-4-yl)sebacate;

[0287]

[0288] Bis(1-(cycloheptyloxy)-2,2,6,6-tetramethylpiperidin-4-yl)sebacate; and

[0289]

[0290] Bis(1-(cyclooctyloxy)-2,2,6,6-tetramethylpiperidin-4-yl)sebacate.

[0291] Exemplary compounds of the general formula (VI) can be listed below without any limitation:

[0292]

[0293] 1-(Cyclohexyloxy)-4-(2,5-dimethylpyrrolidin-1-yl)-2,2,6,6-tetramethylpiperidine; and

[0294] 1-(1-(cyclohexyloxy)-2,2,6,6-tetramethylpiperidin-4-yl)-3-(3-((3-(1-(cyclohexyloxy)-2,2,6,6-tetramethylpiperidin-4-yl)ureido)methyl)-3,5,5-trimethylcyclohexyl)urea.

[0295] It should be noted that other inorganic fillers or organic fillers can be used in combination with h-BN. Therefore, in some embodiments, the film-forming composition according to the present invention contains an inorganic filler. Suitable inorganic fillers are fillers with a lower coefficient of thermal expansion (CTE) than the film formed by the composition of the present invention. Non-limiting examples of inorganic fillers include inorganic oxides such as silica, alumina, diatomaceous earth, titanium oxide, iron oxide, zinc oxide, magnesium oxide, metal ferrites, germanium oxide, molybdenum oxide, tungsten oxide, zirconium dioxide, yttrium oxide; inorganic carbides such as silicon carbide, boron carbide, aluminum carbide, titanium carbide; inorganic nitrides such as aluminum nitride, silicon nitride, titanium nitride, gallium nitride, boron carbonitride; inorganic borides such as silicon boride, titanium boride, yttrium boride, iron boride; inorganic sulfides such as gallium sulfide, molybdenum disulfide, tungsten disulfide; inorganic hydroxides such as aluminum hydroxide, zinc hydroxide, silicon hydroxide, magnesium hydroxide; inorganic carbonates such as calcium carbonate (light and heavy), magnesium carbonate, dolomite; inorganic phosphides such as aluminum phosphide, calcium phosphide, iron phosphide, nickel phosphide, nickel iron phosphide; inorganic silicates such as aluminum silicate (SiO2 / Al2O 10 )(It can be montmorillonite (SiO2 / Al2O 10) or kaolinite (Al2Si2O5(OH)4)), lithium aluminum silicate (which may be Lithafrax manufactured by St. Gobain); inorganic molybdates such as zinc molybdate, which may be Kemguard; inorganic stannates such as zinc stannate, which may be Flamtard; inorganic sulfates such as calcium sulfate, barium sulfate, ammonium sulfate; and calcium sulfite; talc, mica; clay; glass fiber; montmorillonite; silicates such as calcium silicate and bentonite; borates such as zinc borate, barium metaborate, aluminum borate, calcium borate and sodium borate; carbon black; carbon such as carbon fiber; iron powder; copper powder; aluminum powder; boron fiber; potassium titanate; and lead zirconate. Various inorganic filler materials are commercially available, for example, the silica nanoparticles are SC2300-SVJ commercially available from Adamatech Co. Ltd., the ceramic filler is Lithafrax-2121 commercially available from St. Gobain, and many other filler materials suitable for use in combination with the composition of the present invention.

[0296] 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.

[0297] In some embodiments, h-BN is treated with a coupling agent such as silane, zirconate, titanate, etc. Exemplary silanes include silane compounds having organic functional groups such as alkoxysilyl, alkyl, epoxy, vinyl, phenyl, and styryl groups in one molecule. Such silane compounds include, for example, silanes having an alkyl group such as ethyltriethoxysilane, propyltriethoxysilane or butyltriethoxysilane (alkylsilane); silanes having a phenyl group such as phenyltriethoxysilane, benzyltriethoxysilane or phenethyltriethoxysilane; silanes having a styryl group such as styryltrimethoxysilane, butenyltriethoxysilane, propenyltriethoxysilane or vinyltrimethoxysilane (vinylsilane); silanes having 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 silanes having an epoxy group 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 silane compounds can be used in any combination. Other coupling agents include, without limitation, vinyl trichlorosilane, trivinyl methoxysilane, vinyl triethoxysilane, vinyl tri(b-methoxymethoxy)silane, b-(3,4-epoxycyclohexyl)ethyl tri-methoxysilane, γ-glycidyloxypropyl trimethoxysilane, γ-glycidyloxypropyl methyl dimethoxysilane, γ-glycidyloxypropyl triethoxysilane, γ-methacryloyl propyl methyl dimethoxysilane, γ-methacryloyl-oxypropyl trimethoxysilane, γ-methacryloyl-propyl methyl dimethoxysilane, γ-methacryloyl- ... Triethoxysilane, Nb(aminoethyl)g-aminopropylmethyldimethoxysilane, Nb(amino-ethyl)g-aminopropyltrimethoxysilane, bis(trimethoxysilylethyl)benzene, bis(triethoxysilyl)-vinyl, triethoxysilyl-modified butadiene, styrylethyltrimethoxysilane, Nb(aminoethyl)g-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-g-aminopropyltrimethoxysilane, trimethoxyphenylsilane, perfluorooctyltriethoxysilane and g-mercaptopropyltrimethoxysilane.

[0298] It should also be noted that h-BN is usually treated with a "non-polar silane compound". Therefore, the adhesion between the cycloolefin polymer used in the composition of the present invention and the h-BN 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. A polar substituent refers to a group that is capable of hydrogen bonding or ion dissociation. 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.

[0299] In some embodiments, the surface of h-BN is modified with a vinyl group. The use of a vinyl group is advantageous because the vinyl group is a non-polar substituent that provides highly desirable low dielectric properties. To modify the surface of h-BN with a vinyl group, for example, any of the specific silanes described above can be used.

[0300] It has been found that by adding h-BN and various other inorganic fillers described in this specification, the low thermal expansion coefficient (CTE) of the composition of the present invention can be reduced. In addition, heat resistance can also be improved. Therefore, the thermal expansion coefficient can be reduced while improving dielectric properties. In some embodiments, by using an appropriate amount of h-BN of about 20pphr to 80pphr, the dielectric constant (Dk) of the composition can be as low as less than 2.4 or the low loss (Df) is less than about 0.002. In other embodiments, Dk is in the range of about 2.4 to about 2.7 and the dielectric loss factor (Df) is in the range of about 0.0005 to 0.002 at a frequency of 10GHz.

[0301] 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.

[0302] Non-limiting examples of such tackifiers suitable for the composition can be listed below:

[0303]

[0304] Ethylene-propylene-ethylidene norbornene terpolymer, wherein e is at least 100 (Lion Elastomers, LLC T67 is commercially available);

[0305]

[0306] Ethylene-propylene-dicyclopentadiene terpolymer, wherein e is at least 100 (Lion Elastomers, LLC T65 is commercially available);

[0307]

[0308] 1,2-butadiene rubber, wherein e is at least 100 (commercially available as B1000 from Nisso America Inc.);

[0309]

[0310] Partially hydrogenated styrene / butadiene rubber 1 (commercially available as Tuftec P1083 from Asahi Kasei Corp.);

[0311]

[0312] Partially hydrogenated styrene / butadiene rubber 2 (commercially available as Tuftec 1500 from Asahi Kasei Corp.);

[0313]

[0314] Hydrogenated styrene / butadiene rubber 1 (commercially available as Tuftec H 1052 from Asahi Kasei Corp.); and

[0315]

[0316] Hydrogenated styrene / butadiene rubber2.

[0317] 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.

[0318] Non-limiting examples of free radical initiators that can be used in the compositions of the present invention include the following:

[0319]

[0320] 1,1'-(diazene-1,2-diyl)bis(cyclohexane-1-carbonitrile) (V-40 commercially available from Sigma Aldrich);

[0321]

[0322] Di-tert-butyl peroxide;

[0323]

[0324] 2,5-Bis(tert-butylperoxy)-2,5-dimethylhexane (Luperox-101);

[0325]

[0326] 1,1-Bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane (Luperox-231);

[0327]

[0328] Dicumyl peroxide (DCP commercially available from Sigma Aldrich);

[0329]

[0330] Benzoyl peroxide;

[0331]

[0332] Lauroyl peroxide (Luperox-LP);

[0333]

[0334] Tert-butyl peroxybenzoate (Luperox-P); and

[0335]

[0336] (2-Ethylhexyl) tert-butyl peroxide (Luperox-TBEC).

[0337] 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.

[0338] Non-limiting examples of compositions according to the present invention are selected from the group consisting of:

[0339] A dispersion 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), dicumyl peroxide (DCP) and 6,6'-(ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphaphenanthrene 6-oxide) (DiDOPO);

[0340] A dispersion 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), dicumyl peroxide (DCP) and 6,6'-(ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphaphenanthrene 6-oxide) (DiDOPO);

[0341] A terpolymer comprising norbornene (NB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB) and 5-(hex-5-en-1-yl)bicyclo[2.2.1]hept-2-ene (HexenylNB); and 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), 1,2-butadiene rubber (B1000), ethylene-propylene-ethylidene norbornene terpolymer (T67), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecylphenylpropanoate (Irganox 1076), tris(2,4-di-tert-butylphenyl)phosphite (Irgafos 168), a dispersion of a mixture of dicumyl peroxide (DCP) and 6,6'-(ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphaphenanthrene 6-oxide) (DiDOPO); and

[0342] A terpolymer comprising 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 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), 1,2-butadiene rubber (B1000), ethylene-propylene-ethylidene norbornene terpolymer (T67), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl ester phenylpropionic acid (Irganox 1076), a dispersion of a mixture of tris(2,4-di-tert-butylphenyl)phosphite (Irgafos 168), dicumyl peroxide (DCP) and 6,6'-(ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphaphenanthrene 6-oxide) (DiDOPO).

[0343] In other embodiments, as described in this specification, the composition of the present invention comprises h-BN and an organic phosphorus compound. Non-limiting examples of compositions comprising h-BN according to the present invention are selected from the group consisting of:

[0344] A dispersion 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), dicumyl peroxide (DCP), 6,6'-(ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphaphenanthrene 6-oxide) (DiDOPO) and hexagonal boron nitride (h-BN);

[0345] A dispersion 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), dicumyl peroxide (DCP), 6,6'-(ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphaphenanthrene 6-oxide) (DiDOPO) and hexagonal boron nitride (h-BN);

[0346] A terpolymer comprising norbornene (NB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB) and 5-(hex-5-en-1-yl)bicyclo[2.2.1]hept-2-ene (HexenylNB); and 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), 1,2-butadiene rubber (B1000), ethylene-propylene-ethylidene norbornene terpolymer (T67), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecylphenylpropanoate (Irganox 1076), tris(2,4-di-tert-butylphenyl)phosphite (Irgafos 168), a dispersion of a mixture of dicumyl peroxide (DCP), 6,6'-(ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphaphenanthrene 6-oxide) (DiDOPO) and hexagonal boron nitride (h-BN); and

[0347] A terpolymer comprising 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 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), 1,2-butadiene rubber (B1000), ethylene-propylene-ethylidene norbornene terpolymer (T67), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl ester phenylpropionic acid (Irganox 1076), tris(2,4-di-tert-butylphenyl)phosphite (Irgafos 168), diisopropylbenzene peroxide (DCP), 6,6'-(ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxyphosphaphenanthrene 6-oxide) (DiDOPO) and a dispersion of a mixture of hexagonal boron nitride (h-BN).

[0348] Generally, the composition according to the present invention includes a polymer recorded in this specification, and the polymer includes one or more different monomers of general formula (I) and at least one monomer of general formula (II) in a small amount as required, as described below, the composition of various embodiments can be selected to give the desired properties for the intended use to the embodiment, thereby being able to adjust the embodiment according to various specific uses. Therefore, in some embodiments, the composition of the present invention includes a polymer, and the polymer contains two or more different monomers of general formula (I) (such as three different monomers of general formula (I) or four different monomers of general formula (I)) and any desired amount of monomers of general formula (II), as described above, which can be as low as 4 mol%. In addition, as shown in some embodiments, only one or more monomers of general formula (I) are used.

[0349] 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.

[0350] 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 420°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.

[0351] 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:

[0352]

[0353] Dioctadecyl thiodipropionate (TDPDLE)

[0354] 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.

[0355] 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, and more importantly, flame retardant properties. 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 280°C or more. g ). In other embodiments, T g The temperature of the film according to the present invention may be higher than 150°C, 200°C and 250°C. In some other embodiments, the film according to the present invention exhibits a coefficient of thermal expansion (CTE) in the range of about 80ppm / K to 120ppm / K and a CTE of less than 50ppm / K when compounded with glass cloth. The composition of the present invention also exhibits excellent flame retardant properties. For example, in some embodiments, the film formed by the composition of the present invention exhibits at least a UL-94V-1 rating.

[0356] In some embodiments, the film formed from the composition of the present invention comprises 6,6'-(ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphaphenanthrene 6-oxide) (DiDOPO) at a weight percentage of greater than 80%, 90%, or greater than 100% relative to the polymer, and the film has a dielectric constant (Dk) of less than 2.5 at a frequency of 10 GHz, a dielectric loss factor (Df) of less than 0.001, and a UL-94 V-1 rating of at least 10 GHz. In other embodiments, the film formed according to the present invention exhibits a dielectric constant (Dk) in the range of about 2.4 to about 2.5, a dielectric loss factor (Df) of about 0.0004 to 0.002, and a UL-94 V-0 rating of at least 10 GHz. In yet other embodiments, a film formed from the composition of the present invention comprises greater than 100 wt % of 6,6'-(ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphaphenanthrene 6-oxide) (DiDOPO) relative to the polymer, an amount of hexagonal boron nitride in the range of about 10 wt % to about 75 wt % relative to the polymer, and the film has a dielectric constant (Dk) less than 2.7 at a frequency of 10 GHz, a dielectric loss factor (Df) less than 0.0009, and at least a UL-94 V-0 rating.

[0357] 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, a film formed from the composition of the present invention is also provided.

[0358] 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.

[0359] 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.

[0360] As described in this specification, various other flame retardant materials can also be used in combination with the organophosphorus compound. Non-limiting examples of such flame retardants include various other phosphorus flame retardants, such as trixylyl phosphate, ditolyl phosphate, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphophanthenanthrene-10-oxide; halogen flame retardants, such as brominated epoxy resins; and inorganic flame retardants, such as aluminum hydroxide and magnesium hydroxide.

[0361] 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.

[0362] 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℃.

[0363] 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.

[0364] 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 2.4 to 2.7 at a frequency of about 10 GHz to 80 GHz. The dielectric loss tangent (Df) is about 0.0004 to 0.0008 at a frequency of 10 GHz to 80 GHz. It is clear from these characteristics that the composition exhibits excellent dielectric properties with marginal variations of Dk / Df at extremely high frequencies, and therefore, the composition of the present invention can be applied to equipment requiring such low dielectric materials, such as dielectric polymer layers used in millimeter wave radar antennas used in automotive applications and other terminal devices for 5G equipment. For example, refer 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 part or as a 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.

[0365] 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.

[0366] 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 Tg And very high T d5 Characteristics confirmed.

[0367] 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.

[0368] 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.

[0369] 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.

[0370] 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 a polymer recorded in this specification, one or more cross-linking agents recorded in this specification, an appropriate amount of h-BN, a tackifier, a free radical initiator 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 two different monomers with general formula (I) and a monomer of general formula (II), and a cross-linking agent, a flame retardant compound of general formula (III) or (IV) (combined with one or more compounds of general formula (V) or (VI) as needed), at least one of h-BN, a tackifier recorded in this specification, a free radical initiator and a selective additive as needed to obtain the desired result and / or intended purpose.

[0371] 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 in this specification, the composition of the invention is cast on a surface or substrate to be encapsulated and subjected to a suitable heat treatment to form the composition into a solid cross-linked material, which can be in the form of a film or sheet.

[0372] Typically, as described above, such crosslinking is performed in stages, first heated to a temperature below 150°C for a sufficient period of time, such as 5 minutes to 2 hours at each temperature stage to form a partially crosslinked solvent-free B-stage film / sheet. The B-stage film can then be further heated to above 150°C (e.g., temperatures up to above 190°C) for various lengths of time (e.g., 90 minutes to 150 minutes) to cure the film to form a fully crosslinked polymer network. By practicing the present invention, a polymer film that is a substantially uniform film can be obtained on such a substrate. The thickness of the film can be specified or defined as above, and can typically be above 50 to 500 μm.

[0373] 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.

[0374] In some embodiments, the kits described herein include the various exemplary compositions described above.

[0375] 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:

[0376] A uniform and transparent composition is formed, which comprises: a polymer described in the present specification; an appropriate amount of one or more flame retardant materials of the general formula (III) or (IV); one or more compounds of the general formula (V) or (VI) added as required, and an appropriate amount of h-BN; one or more crosslinking agents described in the present specification; a tackifier described in the present specification; a free radical initiator described in the present specification; and one or more additives added as required, including a filler described in the present specification;

[0377] coating a suitable substrate with the composition or injecting the composition into a suitable substrate to form a film; and

[0378] The film is cured after heating the film in stages to a suitable temperature to form a B-stageable film.

[0379] 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 step 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. Other coating methods also include chemical vapor deposition, depending on the type of material to be coated. 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.

[0380] 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 140°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.

[0381] 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) measures 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 (e.g., Seiko Instruments Inc., SS 6000 or Mettler Toledo, TMA / STDA 2+STAR system) 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.

[0382] 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.

[0383] The composition of the present invention can also form various composite structures used as prepreg materials when manufacturing metal-clad laminates. Various types of metals can be used for this purpose, for example, including 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. Afterwards, 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. It should be noted that various other materials that can replace glass fabrics well known to those skilled in the art can also be used in the present invention. Other commonly used materials that are usually in the form of fabrics include polyimide cloth / fabric, polybenzimidazole (PBI) cloth / fabric, etc. without any restriction.

[0384] 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.

[0385] Thus, in some embodiments, a glass fabric (fiber cloth) composite film / cloth formed from the composition of the present invention comprising one or more organic phosphorus compounds of formula (III) or (IV) is provided, exhibiting a dielectric constant (Dk) of less than 2.8, typically in the range of about 2.4 to about 2.5 at a frequency of 10 GHz, a dielectric loss factor (Df) of less than 0.002, typically in the range of about 0.001 to 0.0009 at a frequency of 10 GHz, at least UL-94 V-0 rating, a glass transition temperature of greater than 250° C. (the temperature at which 5% weight loss occurs is greater than 380° C.), a coefficient of thermal expansion (CTE) of less than 40 ppm / K, and excellent peel strength. In other embodiments, the glass fabric composite material of the present invention exhibits a dielectric constant (Dk) of about 2.4 to about 2.45 and a dielectric loss factor (Df) of about 0.0009 at a frequency of 10 GHz.

[0386] In other embodiments, a glass fabric (fiber cloth) composite film / cloth (i.e., prepreg) formed from a composition of the present invention comprising one or more organic phosphorus compounds of general formula (III) or (IV) and h-BN is provided, which exhibits a dielectric constant (Dk) in the range of about 2.5 to about 2.7 and a dielectric loss factor (Df) of about 0.001 to 0.0008 at a frequency of 10 GHz, and is at least UL-94 V-0 grade.

[0387] 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.

[0388] 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.

[0389] 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.

[0390] Embodiment (general)

[0391] 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:

[0392] NB: bicyclo[2.2.1]hept-2-ene; HexNB: 5-hexylbicyclo[2.2.1]hept-2-ene; CyHexeneNB: 5-(cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene; Pd601: diadamantyl-(n-butyl)phosphine palladium diacetate (H2O); Pd1602: [Pd(OAc)(MeCN)(PAd2-n-Bu)2]B(C6F5)4; LiFABA: lithium tetrakis(pentafluorophenyl)borate diethyl ether; Red P: red phosphorus; DiDOPO: 6,6'-(ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphaphenanthrene 6-oxide); PCO-900: 3,9-dimethyl-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide; FCP-796: a mixture of 3,9-dimethyl-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide and substituted 2,2,6,6-tetramethylpiperidine derivatives; SPB-100-phosphazene; h-BN: hexagonal boron nitride; TAIC: 1,3,5-Triallyl-1,3,5-triazinane-2,4,6-trione; DCP: dicumyl peroxide; B1000: 1,2-butadiene rubber; T67: ethylene-propylene-ethylidene norbornene terpolymer; Irganox-1076: 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecylphenylpropanoate; Irgafos-168: tris(2,4-di-tert-butylphenyl)phosphite; BCO: bicyclo[4.2.0]oct-7-ene; TES: triethylsilane; EA: ethyl acetate; THF: tetrahydrofuran; GPC: gel permeation chromatography; M w : weight average molecular weight; M n : number average molecular weight; PDI: polydispersity index; NMR: nuclear magnetic resonance spectroscopy; DSC: differential scanning calorimetry; TGA: thermogravimetric analysis; TMA: thermomechanical analysis; pphr: parts per hundred parts of resin (i.e., the polymer according to the present invention specifically described below).

[0393] 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.

[0394] Example 1

[0395] NB / HexNB / CyHexeneNB (60 / 20 / 20 molar ratio) terpolymer

[0396] A mixture of NB (113 g, 1200 mmol), HexNB (71.3 g, 400 mmol), CyHexeneNB (69.7 g, 400 mmol), BCO (1.62 g, 15 mmol) and LiFABA (0.26 g, 0.3 mmol) dissolved in anhydrous toluene (972 g) was placed in a suitable reactor flushed with nitrogen. The solution was heated to 80°C under a nitrogen atmosphere. Pd601 (0.06 g, 0.1 mmol, 1.3 wt.% in THF) was added to the solution. The mixture was heated at 80°C for 6 hours while stirring. Toluene (1280 g) was 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 560 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 (238 g, 94% yield). GPC (THF): M w =153,470,M n =31,590, PDI = 4.9. 13 C-NMR (CDCl3) analysis calculated that the monomer composition of the terpolymer (NB / HexNB / CyHexeneNB) was 60 / 20 / 20.

[0397] Example 2

[0398] NB / HexNB / CyHexeneNB (60 / 20 / 20 molar ratio) terpolymer

[0399] A mixture of NB (113 g, 1200 mmol), HexNB (71.3 g, 400 mmol), CyHexeneNB (69.7 g, 400 mmol), TES (1.63 g, 14 mmol), anhydrous ethanol (0.21 g, 200 mmol) and LiFABA (0.26 g, 0.3 mmol) dissolved in anhydrous toluene (969 g) was placed in a suitable reactor flushed with nitrogen. The solution was heated to 80°C under a nitrogen atmosphere. Pd601 (0.06 g, 0.1 mmol, 1.3 wt.% in anhydrous THF) was added to the solution. The mixture was heated at 80°C for 6 hours while stirring. Toluene was added to the reaction mixture as in Example 1. The diluted polymerization mixture was cooled to room temperature and poured into an excess of isopropanol in 3 portions of about 560 g each time with rapid 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): Mw =174,230,M n =57,360, PDI = 3. 13 C-NMR (CDCl3) analysis calculated that the monomer composition of the terpolymer (NB / HexNB / CyHexeneNB) was 62 / 20 / 18.

[0400] Example 3

[0401] NB / HexNB / CyHexeneNB (60 / 20 / 20 molar ratio) terpolymer

[0402] A mixture of NB (113 g, 1200 mmol), HexNB (71.3 g, 400 mmol), CyHexeneNB (69.7 g, 400 mmol), BCO (1.08 g, 10 mmol) and LiFABA (0.26 g, 0.3 mmol) dissolved in anhydrous toluene (545 g) was placed in a suitable reactor flushed with nitrogen. The solution was heated to 80°C under a nitrogen atmosphere. Pd1602 (0.16 g, 0.1 mmol, 1.3 wt.% in anhydrous EA) was added to the solution. The mixture was heated at 90°C for 6 hours while stirring. THF (850 g) was added to the reaction mixture. The diluted polymerization mixture was cooled to room temperature and poured into an excess of isopropanol (about 2800 g each) in 3 portions of about 550 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 (164 g, 65% yield). GPC (THF): M w =140,600,M n =44,840, PDI = 3.01. 13 C-NMR (CDCl3) analysis calculated that the monomer composition of the terpolymer (NB / HexNB / CyHexeneNB) was 62 / 21 / 17.

[0403] Example 4

[0404] Preparation of NB / HexNB / HexenylNB (60 / 20 / 20 molar ratio) terpolymer precomposition

[0405] The terpolymer of Example 1 (NB / HexNB / CyHexeneNB, 60 / 20 / 20 molar ratio) was dissolved in mesitylene to prepare a 15 wt.% solution. B1000 (20 pphr), T67 (15 pphr), TAIC (10 pphr), DCP (0.75 pphr), Irganox-1076 (1.75 pphr) and Irgafos-168 (0.6 pphr) were added to a portion of the solution.

[0406] Example 5

[0407] Preparation of pre-composition

[0408] The terpolymer of Example 2 (NB / HexNB / CyHexeneNB, 60 / 20 / 20 molar ratio) was dissolved in mesitylene to prepare a 15 wt.% solution. B1000 (20 pphr), T67 (15 pphr), TAIC (10 pphr), DCP (0.5 pphr), Irganox-1076 (1.75 pphr) and Irgafos-168 (0.6 pphr) were added to a portion of the solution. Additional mesitylene (25 pphr) was also added to facilitate dissolution of all components.

[0409] Example 6

[0410] Preparation of pre-composition

[0411] The terpolymer of Example 2 (NB / HexNB / CyHexeneNB, 60 / 20 / 20 molar ratio) was dissolved in decalin 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 decalin (50 pphr) was also added to promote the solubility of all ingredients.

[0412] Example 7

[0413] Preparation of pre-composition

[0414] The terpolymer of Example 3 (NB / HexNB / CyHexeneNB, 60 / 20 / 20 molar ratio) was dissolved in decalin 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 the solution. An additional amount of decalin (50 pphr) was also added to promote the solubility of all ingredients.

[0415] Examples 8A-8B

[0416] Flame retardant composition

[0417] The pre-composition of Example 5 was mixed with DiDOPO (181 pphr) (Example 8A) and PCO-900 (181 pphr) (Example 8B) to form two compositions of the present invention, namely, Example 8A and Example 8B. The two compositions were rotated overnight to fully disperse the organophosphorus compound. Glass cloth composites of the two compositions were prepared as follows. At least about 7 layers of rectangular glass cloth were wetted with the compositions of Examples 8A and 8B and heated on a hot plate at 120°C for 1 hour to remove the solvent, thereby preparing a glass cloth (NE glass cloth, model #1280, 50 μm thickness) composite material. The B-staged glass cloth composite stack was cured in an oven at 190°C under a nitrogen atmosphere for 1 hour to produce a composite material with a thickness of about 700 to 800 μm. According to the procedure similar to ASTM D3801 (UL-94 flammability test), a test of a flammable rectangular sample (about 13mm width and 125mm length) was carried out using a propane Bunsen burner with a blue flame of about 2cm, placing a cotton pad under the flame in an aluminum pan. The aluminum pan is used to catch any drips from the burning sample. Keep the sample vertical and use a metal clip to keep one end of the sample in contact with the flame for 10 seconds. Remove the sample from the flame and record the afterflame time (the time required for the burning sample to extinguish itself). The sample was contacted with the flame again (the same end as the first contact) for 10 seconds and the second afterflame time was recorded. After the sample extinguished itself, the ember signs were also checked according to the requirements of the UL-94 flammability test, but no such embers were observed for the test composition. Any dripping that caused the cotton pad to catch fire and any violent burning of the sample that caused the flame to spread to the metal clip were also recorded. The results of the flame test are shown in Table 1. Adding DiDOPO or PCO-900 to the pre-composition enables the cured samples to achieve UL-94 V-0 rating under flame test conditions. However, as shown in Table 1, PCO-900 does not exhibit excellent reliability characteristics. As shown in Examples 12 and 14, the films containing PCO-900 have poor reliability under storage conditions of 125°C or 85°C / 85% relative humidity.

[0418] Table 1

[0419] Example No. <![CDATA[Afterglow (t1)]]> <![CDATA[Afterglow (t2)]]> Flame dripping UL-94 Rating Reliability Example 8A 4 seconds 1 second no V-0 good Example 8B 1 second 3 seconds no V-0 Difference

[0420] Examples 9A to 9C

[0421] A portion of the pre-composition of Example 4 was mixed with hexagonal boron nitride (h-BN manufactured by Showa Denko KK, average particle size of 0.7 μm) and DiDOPO and swirled overnight to completely disperse the insoluble particles. The sample preparation and flame test shown in Example 8 were essentially repeated to prepare a glass cloth composite stack. The results are shown in Table 2. As is apparent from the data shown in Table 2, as a result of adding 85 pphr of DiDOPO, the cured sample achieved a UL-94 V-0 rating under the conditions where the h-BN provided a synergistic effect while the flame test was being conducted.

[0422] Table 2

[0423] Example No. h-BN DiDOPO <![CDATA[Residual flame t1]]> <![CDATA[Afterglow t2]]> UL-94 Rating Example 9A 85pphr 85pphr <2 seconds <1 second V-0 Example 9B 15pphr 85pphr 7 seconds 3 seconds V-0 Example 9C 100pphr 50pphr >40 seconds -- NR (Complete Combustion)

[0424] Embodiments 10A-10B

[0425] A portion of the pre-composition of Example 6 was mixed with DiDOPO (80 pphr for Example 10A and 100 pphr for Example 10B) and h-BN (35 pphr, average particle size 30 μm, manufactured by St. Gobain), and the composition was further mixed using a Thinky mixer to fully disperse all the ingredients in the composition. A glass cloth (NE glass cloth, model #1280, 50 μm thickness) composite material was prepared by wetting at least about 7 layers of rectangular glass cloth with the composition and heating in an oven at 130°C under a nitrogen atmosphere for 1 hour to remove the solvent. These B-staged glass cloth composite stacks were cured in a vacuum oven at 190°C for 1.5 hours to produce a composite material with a thickness of about 700 to 800 μm. The flammable rectangular samples (about 13 mm width and 125 mm length) were tested using the steps described in Example 8. The results of these flame tests are shown in Table 3. The addition of DiDOPO and h-BN to the composition can enable the cured samples to achieve UL-94V-0 rating under the conditions of the flame test. In Comparative Examples 1A and 1B, melamine, a common flame retardant, was used instead of DiDOPO, and the glass cloth composite material did not reach the UL-94 V-0 rating.

[0426] Table 3

[0427] Example No. Flame retardants <![CDATA[Afterflame t1]]> <![CDATA[Afterflame t2]]> UL-94 Rating Example 10A DiDOPO, 80 pphr 7 seconds 0 seconds V-0 Example 10B DiDOPO, 100 pphr 7 seconds 0 seconds V-0 Comparative Example 1A Melamine, 80pphr 25 seconds -- NR (Complete Combustion) Comparative Example 1B Melamine, 100pphr 25 seconds -- NR (Complete Combustion)

[0428] Examples 11A to 11D

[0429] A portion of the pre-composition of Example 6 was mixed with various amounts of h-BN (h-BN manufactured by Showa Denko KK, average particle size of 0.7 μm) and various amounts of DiDOPO and swirled overnight to disperse the insoluble particles. Samples of these compositions were knife coated on glass substrates and heated to 90°C on a hot plate for 1 hour to remove the solvent. One of these B-staged films was cut into approximately 2 cm x 10 cm rectangles. These film pieces were alternately sandwiched with 7 layers of glass cloth (NE glass cloth, model #1280, 50 μm thickness), pressed together at 4-6 MPa and heated to 200°C for 1 hour. The cured composite stack was dried at 190°C under vacuum for 1.5 hours. Combustible rectangular samples (approximately 13 mm width and 125 mm length) were tested using the procedures described in Example 8. The results of these flame tests are shown in Table 4A. The addition of DiDOPO and h-BN to the composition allowed the cured samples to achieve UL-94 V-0 rating under the conditions of the flame test. It is important to note that the addition of h-BN alone, as shown in Example 11D, resulted in a fully burned cured sample as shown in Table 4A. Similarly, the B-staged film (without glass cloth) was heated to 190°C in a vacuum oven for 1.5 hours to crosslink the composition to produce a thermoset. The Dk and Df of these resin films at 10 GHz, their coefficient of thermal expansion (CTE) and glass transition temperature (T g ) and the results are shown in Table 4B.

[0430] Table 4A

[0431] Example No. h-BN DiDOPO <![CDATA[Afterflame t1]]> <![CDATA[Afterflame t2]]> UL-94 Rating Example 11A 0pphr 95pphr 6 seconds 2 seconds V-0 Example 11B 12pphr 106pphr 13 seconds 5 seconds V-0 Example 11C 73pphr 106pphr 8 seconds 6 seconds V-0 Example 11D 95pphr 0pphr Complete combustion -- NR

[0432] Table 4B

[0433]

[0434] Embodiment 12A~12B

[0435] Reliability study of films after storage at 125°C

[0436] A portion of the pre-composition of Example 7 was mixed with h-BN (manufactured by Showa Denko KK, 0.7 μm average particle size, 25 pphr), DiDOPO (25 pphr) (Example 12A), and PCO-900 (25 pphr) (Example 12B). The two compositions were rotated overnight to disperse the insoluble particles. These compositions were then dispersed on a glass plate and wetted a rectangular glass cloth (NE glass cloth, model #1280, 50 μm thickness) sample. The solvent was removed by heating to 130°C in an oven with a nitrogen inlet and outlet for 1 hour. These B-staged samples were cured in a vacuum oven at 190°C for 1.5 hours. The dielectric constant (Dk) and dielectric loss factor (Df) of the glass cloth composite material were measured at 10 GHz. The samples were placed in an 85°C / 85% relative humidity (RH) oven and their Dk and Df were measured periodically at 10 GHz to determine the reliability of these low-loss compositions containing DiDOPO or PCO-900 flame retardants under humid, high temperature storage conditions. Figure 1 It is shown that the Df of the composite material of Example 12A remains unchanged, which confirms excellent reliability, and the Df of Example 12B (as shown in Example 8B, it is confirmed that it can achieve UL-94V-0 level) rises rapidly due to poor reliability under storage conditions. In addition, the Dk of Example 12A at 10GHz changes from 2.7 (initial) to 2.68 (1130 hours), which is a decrease of less than 1%. The Dk of Example 12B at 10GHz changes from 2.77 (initial) to 3.2 (125 hours), which is an increase of about 16%. Comparison of the reliability of the glass cloth composite materials of Example 12A and Example 12B shows that although DiDOPO and PCO-900 can both impart flame retardancy to low-loss films while maintaining low Dk (at 10GHz), the reliability of the glass cloth composite materials of Example 12A and Example 12B is relatively stable. ＜ 3) and Df (at 10GHz ＜ 0.0015), but the reliability of the composition containing DiDOPO was superior under the storage conditions utilized. Figure 1 A graph showing the excellent reliability of the dielectric loss factor (Df) of the composition of Example 12A over a period of more than 1130 hours. Therefore, the composition of the present invention can be used in various applications described in this specification such as millimeter wave radar antenna layers operating under severe conditions.

[0437] Examples 13A to 13D

[0438] A portion of the pre-composition of Example 6 was mixed with DiDOPO (85 pphr) and h-BN (35 pphr, average particle size 30 μm, particle size less than 200 nm manufactured by St. Gobain or SS-nano), and the DiDOPO and h-BN were dispersed by mixing using a Thinky mixer to form a homogeneous composition. A glass cloth (NE glass cloth, model #1280, 50 μm thickness) composite material was prepared by wetting a rectangular glass cloth with the composition and heating it in an oven at 130°C under a nitrogen atmosphere for 1 hour to remove the solvent. These B-staged glass cloth composites were cured in a vacuum oven at 190°C for 1.5 hours to produce a composite material with a thickness of about 100 to 200 μm. The Dk and Df of these glass cloth composites were measured at 10 GHz. The results are shown in Table 5A. The composite materials containing DiDOPO maintained low Dk and low Df values ​​or even slightly decreased them. The sample of Example 13B was stored in an oven at 85°C / 85% relative humidity (RH) in air and stored for a long time at 125°C in air, and Dk and Df were measured at 10 GHz at predetermined intervals. The results are shown in Figure 2 . Excellent reliability was obtained under high temperature and storage conditions of about 900 hours. Similarly, the B-stage films (without glass cloth) of Examples 13B and 13D were heated to 190°C in a vacuum oven for 1.5 hours to crosslink the composition to produce a thermoset. The coefficient of thermal expansion (CTE) and glass transition temperature (T g ) and the results are shown in Table 5B.

[0439] Table 5A

[0440] Example No. h-BN DiDOPO Dk at 10GHz Df at 10GHz Example 13A 30μm no 2.61 0.0011 Example 13B 30μm yes 2.59 0.0009 Example 13C <200nm no 2.66 0.0012 Example 13D <200nm yes 2.69 0.0011

[0441] Table 5B

[0442]

[0443] Embodiment 14

[0444] The copolymer NB / HexNB (80 / 20, molar ratio; M w =197,000, PDI = 1.8), (100.3 g) was dissolved in mesitylene (400 g) to prepare a 20 wt.% solution. To several portions (13 g each) of this solution placed in vials, various flame retardant materials (DiDOPO (3 mm), DiDOPO (30 mm), Red P, PCO-900, FCP-796 and SPB-100) were added at two different concentrations (25 pphr and 100 pphr) as shown in Table 6. The sample was swirled to mix the ingredients.

[0445] The solution was coated on a glass substrate, dried overnight at room temperature, heated on a hot plate at 90°C for 2 hours, and then further dried overnight in a vacuum oven at 100°C. Each film thickness of these samples was about 100 mm. The film was then lifted with a blade or water droplets and then cut into appropriate sample sizes: one 3x5 cm for determination of Dk / Df and three 2x4 cm films for ion chromatography (IC) determination. At time 0, Dk / Df determination was performed and a set of 2x4 cm samples were used for ion chromatography.

[0446] Table 6

[0447] Example No. Flame retardants Amount (pphr) Example 14A Control (polymer only) - Example 14B DiDOPO(3μm) 25 Example 14C DiDOPO(30μm) 25 Example 14D Red P 25 Example 14E PCO-900 25 Example 14F FCP-796 25 Example 14G SPB-100 25 Example 14H DiDOPO(3μm) 100 Example 14I DiDOPO(30μm) 100 Example 14J Red P 100 Example 14K PCO-900 100 Example 14L FCP-796 100 Example 14M SPB-100 100

[0448] The Dk / Df films and the remaining IC samples were placed in a temperature and humidity chamber at 85°C / 85% relative humidity (RH) for 1000 hours. Dk / Df was measured at different times. A set of 2x4 cm samples were removed at 500 hours for IC measurement. The remaining 2x4 cm samples were removed at the end of the test (1000 hours) for IC measurement. Figure 3 In the figure, the ratio of the Df value to the initial value is shown in a curve graph. Figure 3 It is clear from the data shown that the membrane samples of Examples 14A (control), 14B (DiDOPO, 3 mm, 25 pphr), 14C (DiDOPO, 30 mm, 25 pphr), 14G (SPB-100, 25 pphr), 14H (DiDOPO, 3 mm, 100 pphr), 14M (SPB-100, 100 pphr) and 14I (DiDOPO, 30 mm, 100 pphr) exhibit extremely stable Df values ​​with time-dependent increases of less than 150%. More specifically, the membranes of Examples 14A and 14C begin to rise in their initial values ​​within the first 48 hours, while Examples 14B, 14G, 14H, 14M and 14I remain substantially the same as their initial t=0 values. The Df values ​​of Examples 14K (PCO-900, 100 pphr), 14E (PCO-900, 25 pphr), 14F (FCP-796, 25 pphr), 14L (FCP-796, 100 pphr) and 14D (Red P, 25 pphr) all increased significantly by more than 1000%. In the case of Example 14D (Red P, 25 pphr), it is known that red phosphorus decomposes in the presence of air and moisture and produces phosphate ions, which also increase the Df value. According to the phosphate (PO4 -3 ) concentration (ppb) further confirmed that it was >700ppm. In the case of FCP-796 and PCO-900 samples, Figure 3The Df is shown to increase significantly, but no significant concentration is detected. The increase can be attributed to two different explanations. The first is that the flame retardant is soluble in water. The increase in Df may be caused by a sharp increase in water absorption. Another explanation is that high concentrations of nitrite ions of >1000ppm were detected by IC. The formation of ions will also increase Df. In the case of Example 14J (Red P, 100pphr), the film curled and the Dk / Df determination could not be performed. The DiDOPO sample did not increase the phosphate concentration or nitrite concentration, further indicating that it is stable under these conditions. The Dk values ​​of stable samples are in the range of 2.2 to 2.5. The Dk values ​​of samples that failed the reliability study (i.e., Df increased by >150%) and whose Df increased sharply, such as PCO-900 and Red P, increased to 3 or 4.

[0449] Embodiment 15

[0450] The compositions of Examples 14A (control), 14H (DiDOPO, 3 mm, 100 pphr) and 14J (Red P, 100 pphr) were coated on copper foil (texture side up), dried overnight at room temperature, heated on a hot plate at 90°C for 2 hours, and then further dried in an oven at 100°C overnight. The sample was cut into 3 pieces. One sample was retained for observation at time 0 (t=0). The other two samples were placed in an 85°C / 85% relative humidity (RH) box. The samples were taken out at 500 hours (t=500) and 1000 hours (t=1000). Visual observations were recorded as shown in Table 7. There were no visual factors indicating aging and corrosion on the DiDOPO and control films. At the same time, the Red P sample showed a catastrophic failure. At the bottom of the film, corrosion was observed only on the copper on the opposite side of the film.

[0451] Table 7

[0452]

[0453] Comparative Examples 1A to 1B

[0454] A portion of the pre-composition of Example 6 was mixed with melamine (80 pphr for Comparative Example 1A and 100 pphr for Comparative Example 1B) and h-BN (35 pphr, average particle size 30 μm, purchased from St. Gobain), and the melamine and h-BN were dispersed using a Thinky mixer. A glass cloth (NE glass cloth, model #1280, 50 μm) composite material was prepared by wetting at least about 7 layers of rectangular glass cloth with the formulation dispersed with melamine and h-BN and heating in an oven at 130°C under a nitrogen atmosphere for 1 hour to remove the solvent. The B-staged glass cloth composite stack was cured in a vacuum oven at 190°C for 1.5 hours to produce a composite material with a thickness of about 700 to 800 μm. The combustible rectangular samples (about 13 mm wide and 125 mm long) were tested using the steps described in Example 8. The results of these flame tests are shown in Table 3. The addition of melamine and h-BN to the formulation did not result in the cured samples achieving a UL-94 V-0 rating under the conditions subjected to the flame test.

[0455] Although the present invention has been described by way of some embodiments, it should not be construed as being limited thereto, 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 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 in the range of about 0 mol % to about 40 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); c) an organic phosphorus compound selected from the group consisting of: Compounds of general formula (III): in, a and b are each independently an integer from 0 to 5; c is an integer from 2 to 4; Q is selected from a divalent or trivalent (C2-C 24 )alkyl, divalent NH(C2-C6)alkylNH and divalent O(C2-C6)alkylNH, wherein the alkyl group may be selected from methyl, ethyl, straight or branched (C3-C6)alkyl, (C6-C 12 )aryl and (C5-C 12 ) is substituted by one or more groups selected from the group consisting of heteroaryl; R9 and R 10 Each is independently selected from the group consisting of hydrogen, methyl, ethyl and linear or branched (C3-C6) alkyl; Compounds of general formula (IV): in, R 11 and R 12 Each is independently selected from the group consisting of methyl, ethyl, linear or branched (C3-C6) alkyl, phenyl, methoxy, ethoxy, linear or branched (C3-C6) alkoxy, phenoxy and 6H-phosphathridine 5-oxide-(C1-C3) alkyl; d) tackifiers; and e) one or more additives selected from the group consisting of free radical initiators, antioxidants, amino compounds, synergists and mixtures of any combination thereof; The content of the organic phosphorus compound relative to the amount of the polymer is higher than 70% by weight, and the composition has at least UL-94V-1 grade when formed into a film, a dielectric loss factor (Df) of less than 0.001 at 10 GHz, and a dielectric constant (Dk) of less than 2.5 at 10 GHz.

2. The composition according to claim 1, 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).

3. The composition according to claim 1, 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-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).

4. The composition according to claim 1, wherein The compound of formula (III) is selected from the group consisting of: 6,6'-(Ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphaphenanthrene 6-oxide), also known as DiDOPO; 6,6'-(1-phenylethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphaphenanthrene 6-oxide), also known as DiDOPO2; 6,6'-(1-(naphthalene-2-yl)ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphaphenanthrene 6-oxide), also known as DiDOPO3; 6,6'-(1-(Naphthalen-1-yl)ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphaphenanthrene 6-oxide); 6,6'-(1,2-diphenylethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphaphenanthrene 6-oxide); 6,6'-(1-phenylpropane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphaphenanthrene 6-oxide); 6,6'-(1-(Furan-2-yl)ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphaphenanthrene 6-oxide); 6-((6-oxydibenzo[c,e][1,2]oxophosphaphenanthrene-6-yl)methoxy)dibenzo[c,e][1,2]oxy-phosphaphenanthrene 6-oxide, also known as DiDOPOMeO; 6,6'-(Ethane-1,2-diylbis(azanediyl))bis(dibenzo[c,e][1,2]oxaphosphaphenanthrene 6-oxide), also known as EDAB-DOPO; 6-(2-((6-oxydibenzo[c,e][1,2]oxaphosphaphenanthrene-6-yl)amino)methoxy)dibenzo[c,e][1,2]oxaphosphaphenanthrene 6-oxide, also known as EAB-DOPO.

5. The composition according to claim 1, wherein The compound of formula (IV) is selected from the group consisting of: 3,9-Dimethyl-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide (Thor FlameRetardants PCO-900 is commercially available); 3,9-Diphenoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide (ThorFlame Retardants PCO 910 is commercially available); and 3,9-Bis((6-oxydibenzo[c,e][1,2]oxaphosphaphenanthren-6-yl)methoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide.

6. The composition according to claim 1, further comprising hexagonal boron nitride having a particle size ranging from about 0.05 μm to about 50 μm, and the hexagonal boron nitride is in the form of small plates.

7. The composition according to claim 1, wherein The content of hexagonal boron nitride is in the range of about 10 wt % to about 120 wt % relative to the amount of the polymer.

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

9. The composition of claim 1 further comprises a material selected from silicon carbide, boron carbide, silicon dioxide, aluminum oxide, aluminum silicate (SiO2 / Al2O 10 ), lithium aluminum silicate, zirconium dioxide, silicon nitride, aluminum nitride, aluminum hydroxide, titanium nitride, gallium nitride, boron carbonitride, titanium boride, tungsten disulfide, zinc borate, zinc molybdate, zinc stannate and a mixture of any combination thereof.

10. The composition according to claim 1, wherein The tackifier is selected from the group consisting of: Ethylene-propylene-ethylidene norbornene terpolymer, wherein e is at least 100 (T67); Ethylene-propylene-dicyclopentadiene terpolymers, wherein e is at least 100 (T65); 1,2-Butadiene rubber, wherein e is at least 100 (B1000); Styrene / butadiene rubber 1; Styrene / butadiene rubber 2; Hydrogenated styrene / butadiene rubber1; and Hydrogenated styrene / butadiene rubber2.

11. The composition according to claim 1, wherein The free radical initiator is selected from the group consisting of: 1,1'-(diazene-1,2-diyl)bis(cyclohexane-1-carbonitrile) (V-40); Di-tert-butyl peroxide; 2,5-Bis(tert-butylperoxy)-2,5-dimethylhexane (Luperox-101); 1,1-Bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane (Luperox-231); Dicumyl peroxide (DCP); Benzoyl peroxide; Luperox-LP Tert-butyl peroxybenzoate (Luperox-P); and (2-Ethylhexyl) tert-butyl peroxide (Luperox-TBEC).

12. The composition according to claim 1, selected from the group consisting of: A dispersion 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), dicumyl peroxide (DCP) and 6,6'-(ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphaphenanthrene 6-oxide) (DiDOPO); A dispersion 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), dicumyl peroxide (DCP) and 6,6'-(ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphaphenanthrene 6-oxide) (DiDOPO); A terpolymer comprising norbornene (NB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB) and 5-(hex-5-en-1-yl)bicyclo[2.2.1]hept-2-ene (HexenylNB); and 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), 1,2-butadiene rubber (B1000), ethylene-propylene-ethylidene norbornene terpolymer (T67), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecylphenylpropanoate (Irganox 1076), tris(2,4-di-tert-butylphenyl)phosphite (Irgafos 168), a dispersion of a mixture of dicumyl peroxide (DCP) and 6,6'-(ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphaphenanthrene 6-oxide) (DiDOPO); and A terpolymer comprising 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 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), 1,2-butadiene rubber (B1000), ethylene-propylene-ethylidene norbornene terpolymer (T67), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl ester phenylpropionic acid (Irganox 1076), a dispersion of a mixture of tris(2,4-di-tert-butylphenyl)phosphite (Irgafos 168), dicumyl peroxide (DCP) and 6,6'-(ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphaphenanthrene 6-oxide) (DiDOPO).

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

14. The film of claim 13 comprising more than 90 wt% of 6,6'-(ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphaphenanthrene 6-oxide) (DiDOPO) relative to the polymer and having a dielectric constant (Dk) of less than 2.5 at a frequency of 10 GHz, a dielectric loss factor (Df) of less than 0.001 and at least a UL-94 V-0 rating.

15. The composition according to claim 6, selected from the group consisting of: A dispersion 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), dicumyl peroxide (DCP), 6,6'-(ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphaphenanthrene 6-oxide) (DiDOPO) and hexagonal boron nitride (h-BN); A dispersion 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), dicumyl peroxide (DCP), 6,6'-(ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphaphenanthrene 6-oxide) (DiDOPO) and hexagonal boron nitride (h-BN); A terpolymer comprising norbornene (NB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB) and 5-(hex-5-en-1-yl)bicyclo[2.2.1]hept-2-ene (HexenylNB); and 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), 1,2-butadiene rubber (B1000), ethylene-propylene-ethylidene norbornene terpolymer (T67), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecylphenylpropanoate (Irganox 1076), tris(2,4-di-tert-butylphenyl)phosphite (Irgafos 168), a dispersion of a mixture of dicumyl peroxide (DCP), 6,6'-(ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphaphenanthrene 6-oxide) (DiDOPO) and hexagonal boron nitride (h-BN); and A terpolymer comprising 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 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione (TAIC), 1,2-butadiene rubber (B1000), ethylene-propylene-ethylidene norbornene terpolymer (T67), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl ester phenylpropionic acid (Irganox 1076), tris(2,4-di-tert-butylphenyl)phosphite (Irgafos 168), diisopropylbenzene peroxide (DCP), 6,6'-(ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxyphosphaphenanthrene 6-oxide) (DiDOPO) and a dispersion of a mixture of hexagonal boron nitride (h-BN).

16. The film of claim 15, comprising greater than 100 wt% of 6,6'-(ethane-1,2-diyl)bis(dibenzo[c,e][1,2]oxaphosphaphenanthrene 6-oxide) (DiDOPO) relative to the polymer, an amount of hexagonal boron nitride in the range of about 10 wt% to about 75 wt% relative to the polymer, and the film having a dielectric constant (Dk) of less than 2.7 at a frequency of 10 GHz, a dielectric loss factor (Df) of less than 0.0009 and at least UL-94 V-0 rating.

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

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

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

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

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