TWI859391B - Oligomer resin compositions - Google Patents

Abstract

A resin has a structure defined by Formula (I) wherein: (a) each R₅ is independently a methylene group (CH₂ ), or a methylene group substituted with one or more -H, -CH₃ , or halogen functionalities; (b) each R₆ is independently a bond or a straight-chain or branched, linear or cyclic, saturated or unsaturated, substituted or unsubstituted, aliphatic or aromatic group having between 1 and 2 carbon atoms; (c) each X is independently a functionality possessing at least one non-aromatic alkene or alkyne moiety; (d) each Z is independently either H or X; (e) each Z is independently either H or X, and each p is independently an integer from 1-4; (f) each w is independently 0, or an integer greater than or equal to 1, and (i) when w is 0, the bracket region represents a bond and n is 0, or an integer greater than or equal to 1; and (ii) when n is 0, the bracket region represents a bond. The resin is especially well suited for use in a base station, circuit board, server, router, radome or satellite structure, as well as such processes as digital light printing (DLP), continuous liquid interface printing (CLIP), and Stereolithography (SL).

Description

Oligomeric resin composition

The present invention relates to resins and composite materials; and more particularly to oligomer resin compositions exhibiting high glass transition temperatures and having low dielectric properties, which are suitable for use in high-frequency printed circuit boards, antennas, antenna housings, and other electronic devices.

Bis(cyclopentadienyl) terminated organics and their Diels-Alder oligomers have been described in patent numbers: US 3,210,331; US 5,262,501, and CN 103232589A. US 2,726,232 discloses dimers and oligomers of bis(cyclopentadiene) from reaction with aromatic bis(chloromethyl), but these compounds have low storage stability, thereby limiting their use as laminating resins. US 5,262,501 describes the synthesis of dimers of bis(cyclopentadiene) by reaction with 1,4-dichloro-2-butene and their use as laminating resins. Although this resin is known to be more stable than aromatically linked bis(cyclopentadiene), it has been shown to have a low glass transition temperature and therefore limited use as a high temperature resin. In addition, US 5,262,501 describes the modification of dimers and oligomers of bis(cyclopentadiene) by reaction with aromatic bis(chloromethyl) compounds to form spiroheptadiene and is shown to be more stable than pure bis(cyclopentadiene) oligomers and these aromatic linked species can produce high glass transition temperatures. However, these prior art workers do not teach the effect of multiple reactive species on dicyclopentadiene formed during dimerization and oligomerization of bis(cyclopentadienyl) compounds.

It has now been discovered that bis(substituted (aryl/alkyl)-cyclopentadiene) compounds and dimers/oligomers thereof have increased stability compared to their previously described pure alkyl or aryl counterparts. Advantageously, these bis(substituted (aryl/alkyl)-cyclopentadiene) compounds can achieve high glass transition temperatures and have low dielectric properties suitable for use in high frequency printed circuit boards, antennas, antenna housings, and other electronic devices.

In one aspect, the present invention provides a compound having a structure defined by formula (I):

wherein: (a) each R ₅ is independently a methylene (CH ₂ ) group or a methylene group substituted with one or more -H, -CH ₃ or halogen functional groups; (b) each R ₆ is independently a bond or a straight-chain or branched, linear or cyclic, saturated or unsaturated, substituted or unsubstituted aliphatic or aromatic group having 1 to 20 carbon atoms; (c) each X is independently a group having at least one non-aromatic alkene, alkynyl, CH ₃ -(CH ₂ ) _n - (wherein n = 0 to 12) or a functional group of an aromatic moiety; (d) each Z is independently H or X and each p is independently an integer from 1 to 4; (e) each w is independently 0, or an integer greater than or equal to 1; and (i) when w is 0, the bracketed region represents a bond and n is 0, or an integer greater than or equal to 1; and (ii) when n is 0, the bracketed region represents a bond.

In some embodiments of formula (I), the value of w is equal to zero, indicating a bond between the R ₅ group and the cyclopentadiene or dicyclopentadiene. Such compounds of formula (I) can be defined by formula (II):

Polymers, copolymers and oligomers derived from resins having structures defined by formula (I) can be thermosetting polymers having high glass transition temperatures and other properties suitable for use in advanced materials applications. The properties of these polymers can be adjusted by using resins and resin blends containing more than one X moiety and/or more than one _R6 moiety.

Without being limited by example, a resin of formula (I) wherein R ₆ is an alkyl group may produce a polymer having a desired polymerization rate but a low glass transition temperature, while a resin of formula (I) wherein R ₆ is an aryl group may produce a polymer having a high glass transition temperature but an undesirable polymerization rate. Combining a resin having an alkyl R ₆ group and a resin having an aryl R ₆ group may produce a polymer having improved overall properties compared to a polymer derived from any single resin of formula (I).

The present invention provides thermosetting resins with high glass transition temperatures, excellent dielectric properties and low moisture absorption. Embodiments of the present invention include thermosetting resins suitable for applications requiring ultra-low loss dielectric properties and ultra-low moisture absorption properties. Polymers, copolymers, or oligomers derived from such thermosetting resins have dissipation (Df) values in the range of about 0.0001 to about 0.004; dielectric (Dk) values in the range of about 1.5 to about 3 at 1 to 50 GHz; Tg greater than 150°C; and molecular weights in the range of about 200 to about 1,000,000 Da.

It should also be understood that, unless otherwise indicated to the contrary, in any method claimed herein that includes more than one step or action, the order of the steps or actions of the method is not necessarily limited to the order in which the steps or actions of the method are described. It should also be understood that where a variable (e.g., "w") is used more than once in any chemical formula or chemical structure, each use of the variable in the chemical formula or chemical structure is independent of any other use unless otherwise expressly noted. For example, if the variable "w" is used twice in the same chemical formula, each "w" may be the same or different, that is, if "w" is defined as 0 or an integer in the range of 1 to 150, each "w" may be independently selected from 0 or an integer in the range of 1 to 150. Likewise, and again by way of example, if the moiety "R ₅ " is defined as -CH- or -CR ₁₂ , then each time R ₅ is used in a chemical formula or chemical structure, each R ₅ may be independently selected from -CH- or -CR ₁₂ .

As used herein, the singular terms "a", "an", and "the" include plural referents unless the context clearly indicates otherwise. Similarly, the word "or" is intended to include "and" unless the context clearly indicates otherwise. The term "include" is defined inclusively, so "includes A or B" means includes A, B, or A and B.

Ranges may be expressed herein as from "about" one particular value, and/or to "about" another particular value. When such a range is expressed, an alternative aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations by using the antecedent "about," it should be understood that the particular value forms an alternative aspect. It will be further understood that each of the endpoints of such ranges is significant both relative to the other endpoint and independently of the other endpoint.

As used herein in this specification and the scope of the patent application, the phrase "at least one" in relation to a list of one or more elements should be understood to mean at least one element selected from any one or more elements in the list of elements, but does not necessarily include at least one of each element explicitly listed in the list of elements and does not exclude any combination of elements in the list of elements. This definition also allows for the presence of elements other than the elements explicitly identified in the list of elements referred to by the phrase "at least one", whether related or unrelated to the specifically identified elements, as necessary. Thus, as a non-limiting example, "at least one of A and B" (or equivalently, "at least one of A or B", or equivalently, "at least one of A and/or B") may refer to at least one, optionally including more than one A, and no B (and optionally including elements other than B) in one embodiment; at least one, optionally including more than one B, and no A (and optionally including elements other than A) in another embodiment; at least one, optionally including more than one A, and at least one, optionally including more than one B (and optionally including other elements) in yet another embodiment; and so on.

As used herein in this specification and the claims, the terms "comprising," "including," "having," and the like are used interchangeably and have the same meaning. Similarly, "comprises," "includes," "has," and the like are used interchangeably and have the same meaning. Specifically, each of these terms is defined consistent with the common United States patent law definition of "comprising" and is thus interpreted as an open term meaning "at least the following," and should also be interpreted as not excluding additional features, limitations, aspects, etc. Thus, for example, "a device having components a, b, and c" means that the device includes at least components a, b, and c. Similarly, the phrase: "a method involving steps a, b, and c" means that the method includes at least steps a, b, and c. Furthermore, although the steps and processes may be outlined herein in a particular order, skilled artisans will recognize that the sequenced steps and processes may vary.

As used herein in the specification and claims, "or" shall be understood to have the same meaning as "and/or" as defined above. For example, when separating items in a list, "or" or "and/or" shall be interpreted as inclusive, that is, including at least one of a number of elements or a list of elements, but also including more than one, and additional unlisted items as necessary. The terms only (such as "only one" or "exactly one") or "consisting of" when used in the claims shall mean including a number of elements or exactly one element of a list of elements. In general, when preceding exclusive terminology (such as "either," "one of," "only one of," or "exactly one of"), the term "or," as used herein, should be construed to mean only exclusive alternatives (i.e., "one or the other but not both").

As used herein, the term "alkyl" refers to a straight or branched hydrocarbon chain containing a fully saturated (no double or triple bonds) hydrocarbon group. By way of example only, an alkyl group may have 1 to 20 carbon atoms (whenever it appears herein, a numerical range such as "1 to 20" refers to each integer within the given range; for example, "1 to 20 carbon atoms" means that the alkyl group may consist of 1 carbon atom, 2 carbon atoms, 3 carbon atoms, etc., up to and including 20 carbon atoms, although this definition also encompasses the occurrence of the term "alkyl" in which no numerical range is specified). As further noted herein, an alkyl group of a compound may be designated as "C ₁ -C ₄ alkyl" or similar designations. By way of example only, "C ₁ -C ₄ alkyl" indicates that there are one to four carbon atoms in the alkyl chain, i.e., the alkyl chain is selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl and t-butyl. Typical alkyl groups include, but are by no means limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl and hexyl. Alkyl groups may be substituted or unsubstituted.

As used herein, the term "alkenyl" refers to an alkyl group containing one or more double bonds in a straight or branched hydrocarbon chain. Alkenyl groups may be unsubstituted or substituted.

As used herein, the term "alkynyl" refers to an alkyl group containing one or more triple bonds in a straight or branched hydrocarbon chain. Alkynyl groups may be unsubstituted or substituted.

As used herein, the term "aryl" means an aromatic carbocyclic group or a substituted carbocyclic group preferably containing 6 to 15 carbon atoms, such as phenyl, naphthyl or anthracenyl, or phenyl or naphthyl or anthracenyl which is optionally substituted with at least one substituent selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, aralkyl, hydroxy, alkoxy, aryloxy, aralkyloxy, carboxyl, arylyl, halogen, nitro, trihalomethyl, cyano, alkoxycarbonyl, aryloxycarbonyl, aralkyloxycarbonyl, acylamino, arylamino, aminoformyl, alkylaminoformyl, dialkylaminoformyl, alkylthio, arylthio, alkylene or -NYY ' (wherein Y and Y ' are independently hydrogen, alkyl, aryl or aralkyl).

As used herein, the term "resin" refers to a compound or mixture of compounds that is capable of being converted into a polymeric material.

As used herein, the term "blend" refers in some embodiments to a mixture of two or more different types of resins or a resin and another polymer or copolymer.

As used herein, the term "cure" or "curing" refers to the process of hardening a resin material.

As used herein, the term "cycloalkyl" and similar terms (e.g., cyclic alkyl groups) refer to fully saturated (no double or triple bonds) monocyclic or polycyclic hydrocarbon ring systems. When composed of two or more rings, the rings may be joined together in a fused manner. Cycloalkyl groups may contain 3 to 10 atoms in the ring or 3 to 8 atoms in the ring. Cycloalkyl groups may be unsubstituted or substituted. Typical cycloalkyl groups include, but are by no means limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl.

As used herein, " _Ca to _Cb " (wherein "a" and "b" are integers) refers to the number of carbon atoms in an alkyl, alkenyl or alkynyl group, or the number of carbon atoms in the ring of a cycloalkyl, cycloalkenyl, cycloalkynyl or aryl group, or the total number of carbon atoms and heteroatoms in a heteroalkyl, heterocyclo, heteroaryl or heteroalicyclic group. That is, the ring of an alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heteroaryl or heteroalicyclic group may contain "a" to "b" (inclusive) carbon atoms. Thus, for example, a " _C1 to _C4 alkyl" group refers to all alkyl groups having 1 to 4 carbons, i.e., _CH3- , _CH3CH2- , _{CH3CH2CH2- ,} ( _CH3 ) _2CH- , _{CH3CH2CH2CH2- , CH3CH2CH} ( _{CH3 )} -, and ( _CH3 ) _3C- . If "a" and "b" are not specified for an alkyl, alkenyl, alkynyl, _{cycloalkyl , cycloalkenyl} , _cycloalkynyl , aryl, heteroaryl, or heteroalicyclic group, the broadest scope described by these definitions should be assumed.

As used herein, the term "halogen atom" or "halogen" means any of the radio-stable atoms in column 7 of the Periodic Table of the Elements, such as fluorine, chlorine, bromine, and iodine.

As used herein, the term "interpenetrating network" refers to a polymer system comprising two or more networks that are at least partially intertwined on a molecular scale to form both chemical and physical bonds between the networks, according to the definition adopted by IUPAC. The network of an IPN will not separate unless the chemical bonds are broken. In other words, the IPN structure represents two or more polymer networks that are partially chemically cross-linked and/or partially physically entangled.

As used herein, the term "polymer" is defined to include homopolymers, copolymers, interpenetrating networks, and oligomers. Thus, the term polymer may be used interchangeably herein with the terms homopolymer, copolymer, interpenetrating polymer network, etc. The term "homopolymer" is defined as a polymer derived from a single type of monomer. The term "copolymer" is defined as a polymer derived from more than one type of monomer, including copolymers obtained by copolymerizing two monomer types, those obtained from three monomer types ("terpolymers"), those obtained from four monomer types ("quaternary polymers"), etc. The term "oligomer" is defined as a low molecular weight polymer in which the number of repeating units does not exceed twenty. The term "copolymer" is further defined to include random copolymers, alternating copolymers, graft copolymers, and block copolymers. Copolymers, as the term is generally used, include interpenetrating polymer networks. The term "random copolymer" is defined as a copolymer comprising macromolecules in which the probability of finding a given monomer unit at any given point in the chain is independent of the properties of the neighboring units. In a random copolymer, the order of the monomer units follows Bernoullian statistics. The term "alternating copolymer" is defined as a copolymer comprising macromolecules that include two types of monomer units in an alternating order.

Whenever a group or moiety is described as "substituted" or "optionally substituted" (or "optionally having" or "optionally containing"), the group may be unsubstituted or substituted with one or more of the indicated substituents. Similarly, when a group is described as "substituted or unsubstituted," if substituted, the substituent may be selected from one or more of the indicated substituents. If no substituents are indicated, it means that the indicated "optionally substituted" or "substituted" group may be substituted with one or more groups individually and independently selected from the following groups: alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heteroaryl, heteroalicyclic, aralkyl, heteroaralkyl, (heteroalicyclic)alkyl, hydroxy, protected hydroxy, alkoxy, aryloxy, acyl, hydroxyl, alkylthio, arylthio, cyano, cyanate, halogen, thiocarbonyl, O-carbamyl, N- Carbamoyl, O-thiocarbamoyl, N-thiocarbamoyl, C-amido, N-amido, S-sulfonamido, N-sulfonamido, C-carboxyl, protected C-carboxyl, O-carboxyl, isocyanato, thiocyanato, isothiocyanato, nitro, silyl, sulfenyl, sulfinyl, sulfonyl, halogen, halogenoxy, trihalomethanesulfonyl, trihalomethanesulfonamido, amino, ether, amino (e.g., monosubstituted amino or disubstituted amino), and protected derivatives thereof. Any of the above groups may include one or more heteroatoms, including O, N or S. For example, in the case where a portion is substituted with an alkyl group, the alkyl group may contain a heteroatom selected from O, N or S (eg, -(CH ₂ -CH ₂ -O-CH ₂ -CH ₂ )-).

The term "prepreg" as used herein refers to a reinforced fabric that has been pre-impregnated with a resin system.

In one aspect, the present invention provides a compound having a structure defined by formula (I):

wherein: (a) each R ₅ is independently a methylene (CH ₂ ) group or a methylene group substituted with one or more -H, -CH ₃ or halogen functional groups; (b) each R ₆ is independently a bond or a linear or branched, linear or cyclic, saturated or unsaturated, substituted or unsubstituted aliphatic or aromatic group having 1 to 20 carbon atoms; (c) each X is independently a group having at least one non-aromatic alkene, alkynyl, CH ₃ -(CH ₂ ) _n - (wherein n = 0 to 12) or a functional group of an aromatic moiety; (d) each Z is independently H or X, and each p is independently an integer from 1 to 4; (e) each w is independently 0, or an integer greater than or equal to 1; and i. when w is 0, the bracketed region represents a bond and n is 0, or an integer greater than or equal to 1; and ii. when n is 0, the bracketed region represents a bond.

In some embodiments of formula (I), the value of w is equal to zero, indicating a bond between the R ₅ group and the cyclopentadiene or dicyclopentadiene. Such compounds of formula (I) can be defined by formula (II):

In some embodiments, each R ₅ group in the compound of formula (I) is the same.

In some embodiments, each R ₆ group in the compound of formula (I) is the same.

In some embodiments, each X group in the compound of formula (I) is the same.

In some embodiments, compounds of Formula (I) may contain more than one independently defined R ₅ group.

In some embodiments, compounds of Formula (I) may contain more than one independently defined R ₆ group.

In some embodiments, compounds of formula (I) may contain more than one independently defined X group.

In some embodiments, R ₅ is a methylene (—CH ₂ —) group.

In some embodiments, X is selected from the group consisting of vinylbenzyl, propenylbenzene, vinylbenzene, (methyl)vinylbenzene, styryl, allyl, propargyl or butenyl groups.

In some embodiments, X is a vinylbenzyl, acrylbenzene, vinylbenzene, (methyl)vinylbenzene or styryl group.

In some embodiments, X is an allyl, propargyl, or butenyl group. In other embodiments, X is an allyl group.

In some embodiments, X is an alkenyl or alkynyl group of 1 to 20 carbons in length having at least one unsaturated unit, including an α-olefin group.

及其異構體。 In some embodiments, X has a structure selected from the group consisting of:

and its isomers.

In some embodiments, X is an aliphatic group including but not limited to a CH ₃ (CH ₂ ) _n group (where n=0 to 12), a benzyl group, or a naphthyl group.

In some embodiments, _R6 is an aryl group, including but not limited to phenyl, naphthyl, anthracenyl and biphenyl. In other embodiments, _R6 is an aryl group, including but not limited to phenyl or biphenyl.

Each R ₆ is independently a bond or a straight or branched chain, straight or cyclic, saturated or unsaturated, substituted or unsubstituted aliphatic group having 1 to 20 carbon atoms. In some embodiments, R ₆ is a straight aliphatic chain substituted with one or more aliphatic groups. In some embodiments, R ₆ contains a saturated or unsaturated cycloaliphatic group. In some embodiments, R ₆ is a cyclohexyl or cyclohexenyl group.

In some embodiments, _R6 is an alkyl group, including but not limited to -( _CH2 ) _y- , wherein y=1 to 20. In other embodiments, _R6 is an alkyl group, including but not limited to -( _CH2 ) _y- , wherein y=1 to 12. In other embodiments, _R6 is an alkyl group, including but not limited to -( _CH2 ) _y- , wherein y=1 to 4.

。 In some embodiments, R ₆ is an alkenyl group with a carbon length of 2 to 20 having at least one carbon-carbon double bond. In some embodiments, R ₆ is an alkenyl group with a carbon length of 2 to 10 having at least one carbon-carbon double bond. In some embodiments, R ₆ is an alkenyl group with a carbon length of 2 to 5 having one carbon-carbon double bond. In some embodiments, R ₆ is

.

。 In some embodiments, R ₆ is an alkynyl group with a carbon length of 2 to 20 having at least one carbon-carbon triple bond. In some embodiments, R ₆ is an alkynyl group with a carbon length of 2 to 10 having at least one carbon-carbon triple bond. In some embodiments, R ₆ is an alkynyl group with a carbon length of 2 to 5 having one triple bond. In some embodiments, R ₆ is

.

In some embodiments, R ₆ is a bond.

In some embodiments, R ₅ is a methylene group and R ₆ is a bond, such that the -R ₅ -R ₆ -R ₅ - unit is equivalent to ethylidene (or -(CH ₂ ) ₂ -). In some embodiments, R ₅ is a methylene group and R ₆ is -(CH ₂ ) _y -, where y=1, such that the -R ₅ -R ₆ -R ₅ - unit is equivalent to propylidene (or -(CH ₂ ) ₃ -). In some embodiments, R ₅ is a methylene group and R ₆ is -(CH ₂ ) _y -, where y=2, such that the -R ₅ -R ₆ -R ₅ - unit is equivalent to butylidene (or -(CH ₂ ) ₄ -). In some embodiments, R ₅ is a methylene group, and R ₆ is -(CH ₂ ) _y -, wherein y=4, such that the -R ₅ -R ₆ -R ₅ - unit is equivalent to hexylene (or -(CH ₂ ) ₆ -).

)及其異構體。 In some embodiments, R ₅ is a methylene group and R ₆ is a phenyl group, such that the -R ₅ -R ₆ -R ₅ - unit is equivalent to a xylyl group (or

) and its isomers.

)及其異構體。 In some embodiments, R ₅ is a methylene group and R ₆ is a naphthyl group, such that the -R ₅ -R ₆ -R ₅ - unit is equivalent to dimethylnaphthalene (or

) and its isomers.

)及其異構體。 In some embodiments, R ₅ is methylene and R ₆ is anthracene, such that the -R ₅ -R ₆ -R ₅ - unit is equivalent to dimethylanthracene (or

) and its isomers.

)及其異構體。 In some embodiments, R ₅ is a methylene group and R ₆ is a biphenyl group, such that the -R ₅ -R ₆ -R ₅ - unit is equivalent to dimethylbiphenyl (or

) and its isomers.

In some embodiments, the resin of formula (I) or formula (II) can be further oligomerized by a thermal process with or without an added catalyst. Alternatively, in some embodiments, the resin of formula (I) or formula (II) can be further oligomerized by a UV process with or without an added catalyst.

In one aspect of the invention, a resin is included, including a resin defined by formula (I). In another aspect of the invention, a composition comprising a mixture of resins defined by formula (I). For example, the composition may comprise a first resin of formula (I) and a second resin of formula (I), wherein the first and second resins differ in at least one substituent or moiety or in the number of any repeating groups. Of course, a skilled artisan will appreciate that any composition may comprise any number of resins of formula (I), and any different resins may be present in the composition in the same or different amounts. As another example, the composition may include a first resin of formula (I), a second resin of formula (I), and a third resin of formula (I), wherein each of the first, second, and third resins differ in at least one substituent or moiety or in the number of any repeating groups, and wherein the first resin is present in an amount ranging from about 1% to about 99% by weight of the composition, the second resin is present in an amount ranging from 1% to about 99% by weight of the composition, and the third resin constitutes the remainder of the composition by weight of the composition.

When it is stated that any of the resins of formula (I) may differ from one another, it is meant that the resins may differ in (i) any portion of the resin; (ii) the number of any of the repeating groups of the portion present; (iii) the positioning of any portion along any ring or aromatic group; and/or (iv) isomerism or stereochemical differences between different portions and/or groups.

In some embodiments, the resin of formula (I) may contain more than one independently defined R ₆ group. In some embodiments, the resin of formula (I) may contain more than one independently defined X group.

As used herein, the term "cyclopentadiene-based ring" or "cyclopentadiene" (used interchangeably herein) is not limited to cyclopentadiene, but includes derivatives of cyclopentadiene, i.e., those containing substituents other than hydrogen or those capable of being substituted with X and/or _R5 groups as defined in formula (I). For example, "cyclopentadiene ring" can encompass cyclopentadiene and cyclopentadiene substituted with one or more _C1 to _C4 straight or branched chain alkyl groups.

A skilled artisan will appreciate that the functional groups on the cyclopentadiene rings, i.e., the X and _R groups in formula (I), can be located at any position along each cyclopentadiene ring. A skilled artisan will also appreciate that any functional group can be located at the same or different positions in each cyclopentadiene ring. For example, one cyclopentadiene ring of the resin of formula (I) can include the X group at the first ring position (e.g., one carbon away from the carbon bearing the _R group) and another cyclopentadiene ring of the resin of formula (I) can include the X group at the second or third ring position (e.g., two or three carbons away from the carbon bearing the _R group). Likewise, and again by way of example, one cyclopentadiene ring of the resin of formula (I) may comprise an X group at the first ring position (e.g., one carbon away from the carbon bearing the _-CH2- group) and another cyclopentadiene ring of the resin of formula (I) may comprise an X group at the second or third ring position (e.g., two or three carbons away from the carbon bearing the _-CH2- group).

而內部環戊二烯環具有結構：

In embodiments of formula (I) where w>0, there will be a terminal cyclopentadiene ring (having at least one X group and at least one _R5 group) and there will be an internal cyclopentadiene ring (having at least two _R5 groups). For example, the terminal cyclopentadiene ring has the structure:

The internal cyclopentadiene ring has the structure:

By definition, the terminal cyclopentadiene ring has at least two functional groups: at least one X group and one R ₅ group. By definition, the internal cyclopentadiene ring has at least two functional groups: at least two independent R ₅ groups, and in embodiments where Z is equal to X, may also have an X group.

For example, the substitution pattern of the functional groups on each difunctional cyclopentadiene ring of the compound of formula (I) may be represented by any or all of the following structures:

Likewise, for example, the substitution pattern of the functional groups on each trifunctional cyclopentadiene ring of the compound of formula (I) may be represented by any or all of the following structures:

The skilled artisan will appreciate that the substitution pattern of each cyclopentadiene ring within the resin of formula (I) may have a different configuration of substituents independent of the substitution pattern of any other cyclopentadiene ring within the same or different compound of formula (I).

It will be appreciated by those skilled in the art that while the present invention is defined by compounds characterized by terminal cyclopentadiene rings having one R ₅ group and at least one X group, the nature of the synthesis can produce complex mixtures characterized by a certain percentage of cyclopentadiene rings having 1) multiple R ₅ groups and no X groups, 2) multiple X groups and no R ₅ groups, and/or 3) three or more R ₅ groups or X groups.

As used herein, the term "dicyclopentadiene" is not limited to dicyclopentadiene but includes derivatives of dicyclopentadiene, i.e., those containing substituents other than hydrogen or those capable of being substituted with X and/or _R5 groups as defined in formula (I). For example, "dicyclopentadiene group" may encompass dicyclopentadiene and dicyclopentadiene substituted with one or more _C1 to _C4 straight or branched chain alkyl groups.

The skilled artisan will appreciate that the substitution pattern of the functional groups on the dicyclopentadienyl group can be likewise variable. Since the dicyclopentadienyl group is formed by the reaction of two disubstituted cyclopentadienyl rings of variable substitution patterns, a large number of substitution patterns are possible. For example, the substitution pattern of the functional groups on each dicyclopentadienyl unit of the compound of formula (I) can be represented by any or all of the following structures:

The substitution patterns presented in these figures are non-limiting and do not represent the full range of possible substitution patterns possible in compounds of formula (I).

In some embodiments, a polymer is provided, the polymer being derived from one or more resins of formula (I) (or any similar resin disclosed herein). In some embodiments, the polymer further comprises an additive selected from the group consisting of an adhesive, a peroxide/crosslinking agent, an antioxidant, a flame retardant, a diluent, and a filler.

In some embodiments, a copolymer is provided, the copolymer is derived from a first resin of formula (I) and a second resin of formula (I), wherein the first and second resins are different. In some embodiments, an interpenetrating polymer network is provided, the interpenetrating polymer network is derived from a first resin of formula (I) and a second resin of formula (I), wherein the first and second resins are different.

In some embodiments, a copolymer or an interpenetrating polymer network is provided, the copolymer or the interpenetrating polymer network being derived from a resin of formula (I) and a second component different from the resin of formula (I). In some embodiments, the second component is selected from the group consisting of polyethylene, polypropylene, polybutylene, low-carbon vinyl polybutadiene, high-carbon vinyl polybutadiene, polystyrene, butadiene-styrene copolymer, styrene-maleic anhydride (SMA) polymer, acrylonitrile-butadiene-styrene (ABS) polymer, polydicyclopentadiene, epoxy resin, polyurethane, cyanate ester, polyphenylene oxide, ethylene-propylene-diene monomer (EPDM) polymer, cyclic olefin copolymer (COC), polyimide, dimaleimide, phosphazene, olefin-modified phosphazene, acrylate, vinyl ester, polylactone, polycarbonate, polysulfide, polyetheretherketone (PEEK), polydimethylsiloxane (PDMS), polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) and other commercially available polymers. In some other embodiments, the second component is selected from the group consisting of styrene, divinylbenzene, 1,2-bis(vinylphenyl)ethane, vinylbenzyl ether compounds, vinyl ether compounds, allyl ether compounds, vinylphenyl monomers, vinyl monomers, allyl monomers, or derivatives of such components. Suitable components include, but are not limited to, vinyl functionalized cyanate HTL-300 (available from Lonza Chemicals), low carbon number and high carbon number vinyl Ricon polybutadiene (Total/Cray Valley), butadiene-styrene Ricon copolymer (Total/Cray Valley), Sartomer acrylate monomer (Arkema), olefin-containing phosphazene SPV-100 (Otsuka Chemicals), bismaleimide BMPI-300 (Lonza Chemicals), bismaleimide Cycom 5250 (Cytec Solvay), bismaleimide BMI-1700 (Designer Molecules Inc.), bismaleimide BMI-3000 (Designer Molecules, Inc.), bismaleimide BMI-689 (Designer Molecules, Inc.), bismaleimide Homide 250 (HOS-Technik GmbH), bismaleimide BMI- 2300 (Daiwakaskei Industry Co., LTD), bismaleimide BMI-TMH (Daiwakaskei Industry Co., LTD), bismaleimide Compimide 353A (Evonik), bismaleimide Compimide C796 (Evonik), methacrylate functionalized polyphenylene ether SA9000 (Sabic, Saudi Basic Industries Corporation), functionalized polyphenylene ether oligomers OPE-2EA and OPE-2St (MGC, Mitsubishi Gas Company), polyimide PETI 330 (UBE Industries, Ltd), vinyl ester resin Advalite 35070-00 (Reichhold), epoxy resin Celloxide 8000 and Celloxide 2021P (Daicel) or Araldite MY 721 and GY 281 and GY 240 (Huntsman).

The resin composition of the present invention can be used separately or as a blend with other copolymers, adhesives, peroxides/crosslinking agents, antioxidants, flame retardants, diluents and other additives or fillers known in the art.

As will be appreciated by those skilled in the art, the resins disclosed herein may be blended with other polymers. Such other polymers may be reactive so that they copolymerize with the resin composition of the present invention to form random or block copolymers. Alternatively, such other polymers may be formed by alternative means so that an interpenetrating polymer network or polymer phase dispersion is formed. Such other polymers include, but are not limited to, polyethylene, polypropylene, polybutylene, low carbon number vinyl polybutadiene (predominantly 1,3 addition), high carbon number vinyl polybutadiene (apparent 1,2 addition), polystyrene, butadiene-styrene copolymers, SMA polymers (styrene maleic anhydride polymers), ABS polymers (acrylonitrile butadiene styrene polymers), polydicyclopentadiene, epoxies, polyurethanes, cyanates, polyphenylene ethers, EPDM polymers (polymers derived from ethylene propylene diene monomers), cyclic olefin copolymers (COC), polyimides, dimaleimides, phosphazenes, olefin-modified phosphazenes, acrylates, vinyl esters, polylactones, polycarbonates, polysulfides, polyetheretherketones (PEEK), polydimethylsiloxane (PDMS), polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and other commercially available polymers. These polymers can be modified or functionalized as needed.

Other comonomers include, but are not limited to, styrene, divinylbenzene, vinyltoluene, methylstyrene, tert-butylstyrene, α-methylstyrene, α-methylstyrene dimer, vinylcyclohexene, ethylidene norbornene, vinyl norbornene, α-pinene, β-pinene, limonene, other terpenes, polybutadiene, modified polybutadiene, polystyrene (homopolymer and block copolymer), modified polystyrene, polyterpene, other vinyl reactive monomers and reactive dimers/oligomers/polymers/copolymers thereof.

In some embodiments, the resin disclosed herein may be blended with an electrical property modifier. Examples of electrical property modifiers may include cyanate-derived compounds and bismaleimide triazine copolymers. Cyanate-derived compounds broadly refer to chemical substances generally based on bisphenol or novolac phenolic resin derivatives, wherein the hydrogen atom of at least one hydroxyl group of the bisphenol or novolac phenolic resin derivative is replaced by a cyanide group. Therefore, cyanate-derived compounds generally have an OCN group. In some embodiments, cyanate-derived compounds may refer to, but are not limited to, 4,4' -ethylenebis(phenylene)cyanate ... -Dicyanobiphenyl, 2,2-bis(4-cyanophenyl)propane, bis(4-cyano-3,5-dimethylphenyl)methane, bis(4-cyanophenyl)sulfide, bis(4-cyanophenyl)ether, prepolymer of bisphenol A dicyanate in methyl ethyl ketone, 1,1-bis(4-cyanophenyl)ethane, 1,1-bis(4-cyanophenyl)methane, 1,3-bis(4-cyanophenyl-1-(methylethylidene))benzene, bis(4-cyanophenyl)ether, bis(4-cyanophenyl)-2,2-butane, 1,3-bis[2-(4-cyanophenyl)propyl]benzene, tris(4-cyanophenyl)ethane, cyanide varnish type phenolic resin and cyanide phenol dicyclopentadiene adduct.

The resins of the present invention may be blended with various additives and adhesives to improve resin adhesion and compatibility with reinforcing substrates such as glass, carbon or aramid fibers. Suitable additives for promoting adhesion include, but are not limited to, maleic anhydride, styrene maleic anhydride, functionalized trialkoxysilanes, maleic anhydride grafted polyolefins, and other polymers previously described in detail in the present invention that are capable of improving substrate adhesion.

The resin composition of the present invention can be cured into a solid material by self-polymerization reaction at high temperature or by adding a catalyst. Suitable catalysts include free radical initiators and Lewis acid catalysts. Suitable Lewis acid catalysts include, but are not limited to, cationic thermal acid generators, cationic photoacid generators or other Lewis acid catalysts, including but not limited to transition metal complexes, boron compounds, aluminum compounds, titanium compounds or tin compounds.

Suitable free radical initiators include, but are not limited to, dialkyl peroxides, diacyl peroxides and azo compounds. Particularly suitable free radical initiators include dicumyl peroxide and 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexyne-3 (Trigonox 145-E85). The free radical initiator may be added at any concentration suitable to achieve sufficient polymerization (ranging from ppm concentration to 5% by weight, depending on the initiator used). The free radical initiator may be combined with other free radical initiators or other types of suitable catalysts as needed to affect polymerization.

Thermal acid generators and photoacid generators generate strong acids after activation at high temperatures or after absorbing specific energy wavelengths. Suitable thermal acid generators and photoacid generators include onium salts, such as iodine salts and coronium salts. Suitable catalysts include, but are not limited to, diaryl iodine compounds or triaryl _{coronium compounds paired with anions (such as BF4-, B(C6F5)4-, PF6-, AsF6-, SbF6-} ^and _their ^variants _{) . Other} ^suitable _Lewis ^acid _catalysts ^include boron compounds, aluminum compounds, titanium compounds, tin compounds and transition metal compounds known in the art. Particularly suitable Lewis acid initiators include bis(4-dodecylphenyl)iodinium hexafluoroantimonate (available as SpeedCure 937 from Arkema), bis-(4-tert-butylphenyl)-iodinium hexafluorophosphate (available as SpeedCure 938 from Arkema), 4-isopropyl-4'-methyldiphenyliodinium tetrakis(pentafluorophenyl)borate (available as SpeedCure 939 from Arkema), and (sulfanediyldiphenyl-4,1-diyl)bis(diphenylarsium)bis(hexafluoroantimonate) (available as SpeedCure 976s from Arkema) and stannous octoate (available as Reaxis C129 from Reaxis). The Lewis acid initiator can be added at any concentration suitable for achieving sufficient polymerization (ranging from ppm concentration to 5 wt %, depending on the initiator used). The Lewis acid initiator can be combined with other Lewis acid initiators or other types of suitable catalysts as needed to affect polymerization.

The resin composition of the present invention can be cured to a solid material at a temperature in the range of about 120°C to about 250°C for about 30 minutes to about 240 minutes. In some embodiments, the resin composition can be cured to a solid material at a temperature in the range of about 150°C to about 220°C for about 60 minutes to about 180 minutes. The present invention can then be heated to a higher temperature as needed to perform additional polymer curing as needed. In some embodiments, the resin of the present invention produces a solid thermosetting material having a glass transition temperature (Tg) greater than 100°C when fully cured. In some embodiments, the resin of the present invention produces a solid thermosetting material having a glass transition temperature (Tg) greater than 150°C when fully cured. In some embodiments, the resin of the present invention produces a solid thermoset material having a glass transition temperature (Tg) greater than 200°C when fully cured. In some embodiments, the resin of the present invention produces a solid thermoset material having a glass transition temperature (Tg) in the range of about 100°C to about 400°C when fully cured. In still other embodiments, the resin of the present invention produces a solid thermoset material having a glass transition temperature (Tg) in the range of about 125°C to about 400°C when fully cured. In still other embodiments, the resin of the present invention produces a solid thermoset material having a glass transition temperature (Tg) in the range of about 175°C to about 400°C when fully cured.

The mechanical properties of the polymerized resin composition of the present invention can be modified by incorporating a crosslinking agent. Such crosslinking agents include, but are not limited to, triallyl cyanurate, triallyl isocyanurate, polybutadiene dimethacrylate, polybutadiene diacrylate, divinylbenzene, 1,2-bis(vinylphenyl)ethane, vinyl benzyl ether compounds, vinyl ether compounds, allyl ether compounds, vinyl phenyl monomers, vinyl monomers, allyl monomers, and similar compounds containing two or more carbon-carbon bond forming moieties per molecule.

As desired, the resin composition of the present invention may be blended with a solvent prior to polymerization for use in certain applications. Any solvent known to those skilled in the art for use in conjunction with the resin composition may be used. Particularly useful solvents include methyl ethyl ketone (MEK), xylene, toluene, DMF, and mixtures thereof. In some embodiments, the solvent is selected from MEK or toluene. When used, the solvent is present in the resin composition in an amount ranging from about 1% to about 99% by weight of the composition. In other embodiments, the solvent is present in the resin composition in an amount ranging from about 10% to about 60% by weight of the composition. In other embodiments, the solvent is present in the resin composition in an amount ranging from about 15% to about 30% by weight of the composition. In yet other embodiments, the solvent is present in the resin composition in an amount ranging from about 20% to about 25% by weight of the composition. Such solvent-doped resin compositions of the present invention are most useful for producing prepreg-type reinforcement layers.

The thermosetting resin composition of the present invention may be formulated with other standard antioxidants, flame retardants, fillers, diluents, stabilizers, processing aids and other additives commonly used in such applications. Such additives include, but are not limited to, phenolic antioxidants, dielectric fillers and commercially available flame retardants. Most commercial flame retardants are suitable for use with the resin of the present invention. Suitable flame retardants also include phosphazenes and olefin-modified phosphazenes. In addition, resin laminates made from the resin composition can be made into halogenated flame retardant-free V0 using reactive phosphorus flame retardants such as (vinyl or other free radical reactive FR), and non-reactive phosphorus flame retardants.

Applications

The thermosetting resin compositions of the present invention can also be used to provide prepregs with and without tack. The compositions are particularly useful for preparing high Tg laminates with ultra-low dielectric constants and ultra-low dielectric loss. These electrical properties help solve signal speed and signal integrity issues encountered with high-speed analog and digital circuit applications. The thermosetting resin compositions of the present invention can be used to prepare prepregs in a continuous process with and without solvents. The viscosity of the compositions of the present invention can be adjusted for use in hot/melt prepregs and saves a lot of cost in the production of prepregs. Prepregs are generally made using reinforcing materials, including but not limited to woven glass, carbon, Kevlar, spectra, aromatic polyamide or quartz fiber. The thermosetting resin composition of the present invention can also be directly coated on any polymer film of a build-up PCB. The thermosetting resin composition of the present invention can also be directly coated on copper using a slot-die or other related coating techniques for resin coated copper (RCC). Prepreg materials made from the thermosetting resin of the present invention can also be converted into laminates. The lamination process is usually followed by the stacking of one or more prepreg layers between one or more conductive foils (such as copper foil). This process is usually described as copper clad laminate (CCL) and is generally well known to those familiar with this technology. Pressure and temperature applied to the prepreg stack result in the formation of a laminate. Laminates produced by the present invention exhibit high Tg. Compositions of the present invention can also be produced that produce laminates of intermediate Tg (>150°C) with considerable flexibility. Flexible laminates are extremely useful for a variety of bendable electronic devices. The thermosetting resins of the present invention having a sufficiently low viscosity can also be used in vacuum infusion applications, where a reinforcing material as previously defined is impregnated with the resin formulation of the present invention by the action of vacuum pressure. The resins of the present invention having a sufficiently low viscosity can be used in solvent-free or environmentally friendly manufacturing techniques for a variety of applications. The resin of the present invention can also be used in 3D printing applications, including continuous liquid interface printing (CLIP) and stereolithography (SLA) applications.

This combination allows for improved surface adhesion properties in coatings, adhesives, composites and laminates.

The resin of formula (I) can be used as an additive, reactive diluent, or copolymer for commercial polymers used in electronic applications to improve resin viscosity and dielectric properties. In some embodiments, the resin of formula (I) can be combined with a cyanate-, epoxy-, dimaleimide-, or polyolefin-based resin to produce a blend with improved manufacturing properties, mechanical properties, or electrical properties.

In another aspect of the invention are kits comprising any resin, polymer, blend, etc. disclosed herein. In some embodiments, the resin, polymer, blend, etc. is mixed with a suitable solvent. In some embodiments, the kits comprise a plurality of resins, polymers, blends, etc., wherein each of the resins, polymers, blends, etc. is provided in a separate container. In some embodiments, the kits comprise a resin and other reactants, reagents, or solvents. In some embodiments, the kits further comprise instructions for use.

For example, the kit may include any resin of formula (I) and may also include a bismaleimide, such that the resin and the bismaleimide may react to form a product. Any bismaleimide may be included in the kit, including any of those listed herein. In some embodiments, the kit includes a bismaleimide selected from 1,6 ' -bismaleimide-(2,2,4-trimethyl)hexane, 4,4 ' -diphenylmethane bismaleimide, polyphenylmethane bismaleimide, N,N ' -(4-methyl-m-phenylene)-bismaleimide, N,N ' -m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3 ' -dimethyl-5,5 ' -diethyl-4,4 ' -diphenylmethane bismaleimide, N,N ' -[methylenebis(2,6-diethyl-4,1-phenylene)]bis(maleimide, N,N ' -Bismaleimides of the group consisting of [methylenebis(2-isopropyl-6-methyl-4,1-phenylene)]bis(maleimide), 1,2-bis(maleimido)ethane, 1,4-bis(maleimido)butane and 1,6-bis(maleimido)hexane.

In some embodiments, the kit may include any resin of formula (I) and may also include a crosslinking agent, such as a crosslinking agent selected from the group consisting of triallyl cyanurate, triallyl isocyanurate, polybutadiene dimethacrylate, polybutadiene diacrylate, divinylbenzene, 1,2-bis(vinylphenyl)ethane, vinyl benzyl ether compounds, vinyl ether compounds, allyl ether compounds, vinyl phenyl monomers, vinyl monomers and allyl monomers.

The resins, reaction products, blends, polymers, compositions, etc. described herein can be used in any suitable application. For example, the resins, reaction products, blends, polymers, compositions, etc. can be used as a substrate on which other materials can be applied. In some embodiments, the resins, reaction products, blends, polymers, compositions, etc. can be applied in the form of a film on the surface of another substrate, or a laminate can be prepared from the resins, reaction products, blends, polymers, compositions, etc. disclosed herein.

In some embodiments, the resins, reaction products, blends, polymers, compositions, etc. disclosed herein can be used to manufacture printed circuit boards or for general use in any electronic device. In other embodiments, the resins, reaction products, blends, polymers, compositions, etc. disclosed herein can be used in copper clad laminates (CCLs), high-density interconnect substrates, or integrated circuits. In other embodiments, the resins, reaction products, blends, polymers, compositions, etc. disclosed herein can be used in antenna covers, antennas (e.g., mobile phone antennas, satellite phone antennas, antennas for 5G communication devices, etc.) or in radar structures. In yet other embodiments, the resins, reaction products, blends, polymers, composites, etc. disclosed herein can be used as part of an underfill adhesive composition. In other embodiments, the resins, reaction products, blends, polymers, compositions, etc. disclosed herein can be used in mobile base stations, wireless base stations, modems and routers. In other embodiments, the resins, reaction products, blends, polymers, compositions, etc. disclosed herein can be used in radio frequency identification tags and other sensors. In other embodiments, the resins, reaction products, blends, polymers, compositions, etc. disclosed herein can be used in microwave communication systems. In other embodiments, the resins, reaction products, blends, polymers, compositions, etc. disclosed herein can be used in communication and network servers. In other embodiments, The resins, reaction products, blends, polymers, compositions, etc. disclosed herein can be used in backplanes.

The following examples are provided to more fully describe the invention described herein. The specific techniques, conditions, materials, proportions, and reported data set forth to illustrate the principles and practice of the invention are exemplary only and should not be construed as limiting the scope of the invention.

Examples

Material:

Cyclopentadiene was separated by thermal cracking of dicyclopentadiene (Ultrene 97 from Cymetech Corporation) at 150-200°C according to the literature method. Allyl chloride, 1,4-dichlorobutane, α, α' -dichloroxylene, and diisophenylpropyl peroxide were obtained from Sigma Aldrich and used as received. 1,6-Dichlorohexane was obtained from Evonik and used as received. 1,2-Dichloroethane was obtained from Occidental Chemical Company and used as received. Methyltributylammonium chloride aqueous solution (75 wt%) was obtained from Sachem, Inc. Potassium hydroxide flakes were obtained from Chengdu Huarong Chemical and used as received. K-Pure catalyst was obtained from King Industries Specialty Chemicals. SpeedCure catalyst was obtained from Lambson Limited/Arkema. Reaxis catalyst was obtained from Reaxis Inc. and Deuteron catalyst was obtained from Deuteron GmbH. Manganese octanoate was obtained from Pfaltz & Bauer. Benzyl chloride was obtained from Valtris and used as received.

Example 1: Bis(allylcyclopentadienyl)butane

79.27 g of freshly distilled cyclopentadiene was added to 514.86 g of 50 wt% aqueous KOH along with 11.66 g of aqueous methyltributylammonium chloride (75 wt%). This mixture was stirred at 400 RPM for 30 minutes to build up the cyclopentadiene concentration. This solution was cooled to 4°C and 76.56 g of 1,4-dichlorobutane was added and the reaction temperature was raised to 92°C over 10 minutes. The reaction was cooled to 44°C in an ice bath over 5 minutes and the solution was removed from the ice bath and allowed to stir for 1 hour and the stirring was increased to 600 RPM.

After 1 hour, the reaction was cooled to 8°C and 91.88g of allyl chloride was added over 10 minutes and the reaction temperature was raised to 26°C. An additional 423.64g of 50 wt% KOH solution was then added and the reaction was heated to 40°C and stirred for 3 hours.

1L of water was added to the reaction and the aqueous layer was removed. The organics were washed 3 times with water and 300mL of xylene was added. This mixture was washed once with dilute HCl followed by another water wash and then dried over sodium sulfate, filtered and the solvent removed using a rotary evaporator at 15 torr and 80°C to give a non-viscous orange liquid resin.

Example 2: Bis(allylcyclopentadienyl)butane-dicyclopentadiene-oligomer:

The recovered orange non-viscous resin of Example 1 was heated at 160°C for 2 hours and at 180°C for 5 hours to obtain an orange viscous liquid.

Example 3: Bis(allylcyclopentadienyl)hexane

760 g of 50 wt% KOH was flushed with _N2 in a 2L glass reactor for 15 minutes. 150 g of freshly distilled cyclopentadiene and 21.2 g of aqueous methyltributylammonium chloride (75 wt%) were added and the mixture was stirred at 400 RPM for 30 minutes at room temperature to form cyclopentadiene. After 30 minutes, an ice water bath was added and 211 g of 1,6-dichlorohexane was added portionwise over 60 minutes, maintaining the reaction temperature below 25°C. After the last addition, the reaction was stirred at 7°C for another 60 minutes. The reaction was then heated to 55°C with hot water and stirred for another 60 minutes. The reaction was then cooled to 31°C and 173g of allyl chloride was added, which caused the reaction temperature to rise to 43°C, at which point a water bath was added to maintain the temperature below 43°C. The reaction was stirred for an additional 60 minutes, after which 500mL of distilled water was added and the aqueous layer was removed by siphoning. 600g of fresh 50 wt% KOH was then added and the reaction temperature was raised to 48°C. The reaction was then stirred at 460 RPM for 2 days. The reaction was then heated to 70°C for 1 hour, and 500g of _H2O was then added, and the aqueous layer was removed by siphoning. The organics were transferred to a separatory funnel and washed 3 times with water. The organic layer was diluted with hexanes, dried _over 50 g _Na2SO4 , filtered over basic alumina, and 0.334 g freshly ground tert-butylcatechol was added. The solvent was removed by rotary evaporation at 60°C at 11 torr for 1.5 hours to give an orange non-viscous liquid.

Example 4: Bis(allylcyclopentadienyl)hexane-dicyclopentadiene-oligomer:

The recovered orange non-viscous resin of Example 3 was then heated at 160°C for 2 hours and at 180°C for 5 hours to obtain an orange viscous liquid.

Example 5: Bis(allylcyclopentadienyl)ethane

96.36 g of freshly distilled cyclopentadiene was added to 491 g of 50 wt % aqueous KOH solution along with 10.3 g of methyltributylammonium chloride (75 wt %). This mixture was stirred at 400 RPM for 30 minutes to build up the cyclopentadiene concentration. This solution was cooled to 4°C and 72.24 g of 1,2-dichloroethane was added and the reaction temperature was raised to 92°C over 10 minutes. The reaction was cooled to 44°C in an ice bath over 5 minutes and then stirred at 600 RPM at room temperature for 1 hour. After 1 hour, the reaction was cooled to 8°C and 111.69 g of allyl chloride was added over 10 minutes and the reaction temperature was raised to 26°C. Then add another 423.64g of 50 wt% KOH solution and heat the reaction to 40°C and stir for 3 hours. Add 1L of water to the reaction and remove the aqueous layer. Wash the organics 3 times with water and add 300mL of xylene. Wash this mixture once with dilute HCl followed by an additional water wash and then dry over sodium sulfate, filter, and remove the solvent using a rotary evaporator at 15 torr and 80°C to give a non-viscous orange liquid.

Example 6: Bis(allylcyclopentadienyl)ethane-dicyclopentadiene-oligomer:

The recovered orange non-viscous resin of Example 5 was heated at 160°C for 2 hours and then at 180°C for 5 hours to obtain an orange viscous liquid.

Example 7: Bis(allylcyclopentadienyl)xylene

96.36 g of freshly distilled cyclopentadiene was added to 491 g of 50 wt % aqueous KOH solution along with 10.3 g of methyltributylammonium chloride (75 wt %). This mixture was stirred at 400 RPM for 30 minutes to build up the cyclopentadiene concentration. This solution was cooled to 4°C and 127.79 g of α, α' -dichloroxylene as a 50 wt % solution in xylene was added and the reaction temperature was raised to 92°C over 10 minutes. The reaction was cooled to 44°C in an ice bath over 5 minutes and the reactor was removed from the ice bath and allowed to stir for 1 hour and the stirring was increased to 600 RPM.

After 1 hour, the reaction was cooled to 8°C and 111.69 g of allyl chloride was added over 10 minutes and the reaction temperature was raised to 26°C. An additional 423.64 g of 50 wt% KOH solution was then added and the reaction was heated to 40°C and stirred for 3 hours. 1 L of water was added to the reaction and the aqueous layer was removed. The organics were washed 3 times with water and 300 mL of xylene was added. This mixture was washed once with dilute HCl followed by an additional water wash and then dried over sodium sulfate, filtered and the solvent removed using a rotary evaporator at 15 torr and 80°C to give a non-viscous orange liquid.

Example 8: Bis(allylcyclopentadienyl)xylene-dicyclopentadiene-oligomer:

The recovered orange non-viscous resin of Example 7 was heated at 160°C for 2 hours and then at 180°C for 5 hours to obtain an orange viscous liquid.

Example 9: Mixed bis(allylcyclopentadienyl)xylene and bis(allylcyclopentadienyl)ethane

145.0 g of freshly distilled cyclopentadiene was combined with 87.3 g of α, α' -dichloroxylene, 49.3 g of 1,2-dichloroethane, 152.6 g of allyl chloride, and 18.8 g of aqueous methyltributylammonium chloride (75 wt%). This mixture was stirred at 400 to 600 RPM and cooled in an ice bath under a nitrogen atmosphere. 1,342.5 g of aqueous KOH (50 wt%) was added dropwise to the stirred solution at a moderate exothermic rate. After all the KOH solution was added, the reaction was heated to 40°C and stirred for 1 hour. 400 mL of water was added to the reaction, and the aqueous layer was removed. The organics were diluted with 200 mL of xylene and washed twice with 250 mL portions of aqueous NaHCO ₃ (10 wt %) and the aqueous phase removed. The organics were washed three times with 200 mL portions of water and the aqueous phase removed. The organics were dried over sodium sulfate, filtered, and the solvent removed using a rotary evaporator at 15 Torr and 60° C. to give a non-viscous orange liquid.

Example 10: Mixed bis(allylcyclopentadienyl)xylene-dicyclopentadiene- and bis(allylcyclopentadienyl)ethane-dicyclopentadiene-oligomers:

The recovered orange non-viscous resin of Example 9 was then heated at 150°C for 3 hours to obtain an orange viscous liquid.

Example 11: Mixed bis((allyl/benzyl)cyclopentadienyl)ethane

Combine 61.0 g of freshly distilled cyclopentadiene with 45.0 g of 1,2-dichloroethane, 57.5 g of benzyl chloride, 34.9 g of allyl chloride, and 9.0 g of aqueous methyltributylammonium chloride (75 wt %). Stir this mixture at 200 RPM and cool in an ice bath under a nitrogen atmosphere. Add 600 g of aqueous KOH (50 wt %) to the stirred solution at a moderately exothermic rate. After all the KOH solution is added, remove the ice bath, increase the stirring rate to 450 RPM, and heat the reaction to 57° C. for one hour. Add 700 mL of water to the reaction, and remove the aqueous layer. Wash the organics with 500 g of aqueous NaHCO ₃ (10 wt %), and remove the aqueous phase. The organics were washed three times with 500 mL portions of water and the aqueous phase was removed. The organics were dried over sodium sulfate, filtered, and diluted with 25 g of hexanes. The solvent was removed using a rotary evaporator at 11 Torr and 40° C. to give a non-viscous orange liquid.

Example 12: Mixed bis((allyl/benzyl)cyclopentadienyl)ethane-dicyclopentadiene-oligomer:

The recovered orange non-viscous resin of Example 10 was then heated at 150°C for 3 hours and at 180°C for 2 hours to obtain an orange viscous liquid.

Example 13: Mixed bis(allylcyclopentadienyl)xylene and bis(allylcyclopentadienyl) pentadienyl)butane

76.0 g of freshly distilled cyclopentadiene was combined with 36.3 g of α, α' -dichloroxylene, 26.3 g of 1,4-dichlorobutane, 63.4 g of allyl chloride, and 7.9 g of aqueous methyltributylammonium chloride (75 wt%). This mixture was stirred at 250 RPM and cooled in an ice bath under a nitrogen atmosphere. 558 g of aqueous KOH (50 wt%) was added dropwise to the stirred solution at a moderate exothermic rate, and the stirring rate was increased to 520 RPM. After all the KOH solution was added, the reaction was heated to 40°C and stirred for 1 hour. 500 mL of water was added to the reaction, and the aqueous layer was removed. The organics were diluted with 200 g xylene and washed twice with a total of 400 g NaHCO ₃ aqueous solution (10 wt %), then the aqueous phase was removed. The organics were washed three times with a total of 900 mL water, and the aqueous phase was removed. The organics were dried over sodium sulfate, filtered, and the solvent was removed by distillation at 150° C. under nitrogen to give a non-viscous orange liquid.

Example 14: Mixed bis(allylcyclopentadienyl)xylene-dicyclopentadiene- and bis(allylcyclopentadienyl)butane-dicyclopentadiene-oligomers:

The orange non-viscous resin of Example 12 was heated at 150°C for a total of 2 hours to obtain an orange viscous liquid.

Example 15: Mixed Bis((allyl/benzyl)cyclopentadienyl)xylene and Bis((allyl/benzyl)cyclopentadienyl)ethane

145.0 g of freshly distilled cyclopentadiene was combined with 87.3 g of α,α' - dichloroxylene, 49.3 g of 1,2-dichloroethane, 63.1 g of benzyl chloride, 114.4 g of allyl chloride, and 18.8 g of aqueous methyltributylammonium chloride (75 wt%). This mixture was stirred at 400 RPM and cooled in an ice bath under a nitrogen atmosphere. 1200 g of aqueous KOH (50 wt%) was added dropwise to the stirred solution at a moderate exothermic rate, and the stirring rate was increased to 400 RPM. After all the KOH solution was added, the reaction was heated to 35-40°C and stirred for 1 hour. 400 mL of water was added to the reaction, and the aqueous layer was removed. The organics were diluted with 200 mL of xylene and washed twice with a total of 500 mL of aqueous NaHCO ₃ (10 wt %), then the aqueous phase was removed. The organics were washed three times with 200 mL portions of water and the aqueous phase was removed. The organics were dried over sodium sulfate, filtered, and the solvent removed by vacuum distillation at 55° C. to give a non-viscous orange liquid.

Example 16: Mixed bis((allyl/benzyl)cyclopentadienyl)xylene-dicyclopentadiene- and bis((allyl/benzyl)cyclopentadienyl)ethane-dicyclopentadiene-oligomers:

The orange non-sticky resin of Example 15 was heated at 150°C for a total of 3 hours to obtain an orange semi-solid.

Aggregation Example 1

The oligomer of Example 16 was mixed with the thermal acid generators 0.2% K-pure CXC-1612 and 2.2% diisophenylpropyl peroxide and sandwiched between glass plates using Teflon spacers. The panels were cured at 120°C for 2 hours and at 220°C for 2 hours. The cured solid material exhibited an E' of 173°C and Df<0.003 at 5 GHz.

Aggregation Example 2

The oligomer of Example 16 was mixed with 1.0% thermal acid generator K-pure CXC-1614 and sandwiched between glass plates using Teflon spacers. The panels were cured at 120°C for 2 hours and at 220°C for 2 hours. The cured solid material exhibited an E' of 173°C and Df<0.003 at 5 GHz.

Aggregation Example 3

The oligomer of Example 16 was mixed with 0.54% of the transition metal complex Reaxis C129 and 2.0% of bis(isophenylpropyl)peroxide and sandwiched between glass plates using Teflon spacers. The panels were cured at 120°C for 2 hours and at 220°C for 2 hours. The cured solid material exhibited a Tg(TMA) of 223°C and Df<0.0025 at 5 GHz.

Aggregation Example 4

The oligomer of Example 16 was mixed with 1.0% of the transition metal complex manganese octoate and sandwiched between glass plates using Teflon spacers. The panels were cured at 120°C for 2 hours and at 220°C for 2 hours. The cured solid material exhibited Df<0.003 at 5 GHz.

Aggregation Example 5

The oligomer of Example 16 was mixed with 0.2% acid catalyst SpeedCure 939 and sandwiched between glass plates using Teflon spacers. The panels were cured at 150°C for 2 hours and at 220°C for 2 hours. The cured solid material exhibited E'=261°C at 5 GHz; Df<0.0025.

Aggregation Example 6

The oligomer of Example 16 was mixed with 1.0% acid catalyst SpeedCure 938 and sandwiched between glass plates using Teflon spacers. The panels were cured at 150°C for 2 hours and at 220°C for 2 hours. The cured solid material exhibited E'=268°C at 5 GHz; Df<0.003.

Aggregation Example 7

The oligomer of Example 16 was mixed with 3% Trigonox E145-85 and sandwiched between glass plates using Teflon spacers. The panels were cured at 150°C for 2 hours and at 220°C for 2 hours. The cured solid material exhibited Tg(TMA)=190°C and Df<0.003 at 5 GHz.

Aggregation Example 8

The oligomer of Example 2 was mixed with 1% diisopropyl peroxide and the resin was sandwiched between glass plates using Teflon spacers. The panels were cured at 250°C for 2 hours. The cured solid material exhibited E’ and Df<0.002 at 200°C at 5 GHz.

Aggregation Example 9

The oligomer of Example 2 was mixed with 1% photoacid catalyst Deuteron 1242 and the resin was sandwiched between glass plates using Teflon spacers. The panels were cured at 250°C for 2 hours. The cured solid material exhibited an E' of 180°C and Df<0.002 at 5 GHz.

Aggregation Example 10

The oligomer of Example 16 was mixed with 1% photoacid catalyst Deuteron 1242 and the resin was sandwiched between glass plates using Teflon spacers. The panels were cured at 120°C for 2 hours and at 220°C for 2 hours. The cured solid material exhibited an E' of 260°C and Df<0.003 at 5 GHz.

Aggregation Example 11

The oligomer of Example 14 was mixed with 1% diisophenylpropyl peroxide and the resin was sandwiched between glass plates using Teflon spacers. The panels were cured at 250°C for 2 hours. The cured solid material exhibited Df<0.003 at 5 GHz.

Having thus described the present invention in considerable detail, it will be appreciated that it is not necessary to strictly adhere to such details, but rather that persons skilled in the art may themselves suggest additional changes and modifications which fall within the scope of the present invention as defined by the appended claims.

Claims (24)

A polymer derived from a resin having a structure defined by formula (I)

wherein: (a) each R ₅ is independently a methylene group (CH ₂ ) or a methylene group substituted by one or more -H, -CH ₃ or halogen functional groups; (b) each R ₆ is independently a bond or a straight-chain or branched, linear or cyclic, saturated or unsaturated, substituted or unsubstituted aliphatic or aromatic group having 1 to 20 carbon atoms; (c) each X is independently a substituted or unsubstituted aliphatic or aromatic group having at least one non-aromatic alkene, alkynyl, CH ₃ -(CH ₂ ) _n - (wherein n = 0 to 12) or a functional group of an aromatic moiety; (d) each Z is independently H or X, and each p is independently an integer from 1 to 4; (e) each w is independently 0, or an integer greater than or equal to 1, and when w is 0, the bracketed region represents a bond and n is an integer greater than or equal to 1; and wherein the polymer comprises a dissipation (Df) value in the range of about 0.0001 to about 0.004. The polymer of claim 1, wherein w=0, the resin is defined by formula (II)

The polymer of claim 1, wherein R ₅ is a methylene group (—CH ₂ —) and R ₆ is a bond or an aliphatic carbon chain of the form —(CH ₂ ) _y —, wherein y=1 to 12. The polymer of claim 1, wherein R ₅ is methylene (-CH ₂ -), and R ₆ is a member selected from the group consisting of phenyl, naphthyl, anthracenyl and biphenyl. The polymer of claim 1, wherein R ₅ is methylene (-CH ₂ -), and each R ₆ is selected from at least two groups as defined in claim 1. A polymer as claimed in claim 1, wherein X is a member selected from the group consisting of propenylbenzene, vinylbenzene, (methyl)vinylbenzene, styryl, allyl, propargyl, butenyl and benzyl groups. The polymer of claim 1, wherein X is a member selected from the group consisting of

and its isomers. A polymer derived from one or more resins having a structure defined by formula (II)

wherein: (a) each R ₅ is a methylene group (CH ₂ ); (b) each R ₆ is independently a bond, a phenyl group or an aliphatic carbon chain of the form -(CH ₂ ) _y -, wherein y=1 to 12; (c) each X is independently an allyl, propargyl, butenyl, benzyl or styryl group; (d) each Z is independently H or X, and each p is independently an integer from 1 to 4; (e) n is an integer greater than or equal to 1. A polymer as claimed in claim 8, wherein the polymer is soluble in an organic solvent selected from the group consisting of methyl ethyl ketone (MEK), xylene, N-methylpyrrolidone (NMP), dimethylformamide (DMF), dichloromethane (DCM), acetonitrile, acetone, dimethyl sulfoxide (DMSO) and tetrahydrofuran (THF). A polymer as claimed in claim 8, wherein the polymer comprises a molecular weight in the range of about 200 to about 1,000,000 Da. The polymer of claim 8 further comprises an additive selected from the group consisting of adhesives, peroxides, crosslinking agents, antioxidants, flame retardants, diluents and fillers. A polymer as claimed in claim 8, wherein the polymer comprises a dielectric (Dk) value in the range of about 1.5 to about 3 at 1 to 50 GHz. A polymer as claimed in claim 8, wherein the polymer comprises a dissipation (Df) value in the range of about 0.0001 to about 0.004 at 1 to 50 GHz. A composition comprising (i) a polymer as claimed in claim 8; and (ii) a polymer selected from polyethylene, polypropylene, polybutylene, low carbon number vinyl polybutadiene, high carbon number vinyl polybutadiene, polystyrene, butadiene-styrene copolymer, styrene-maleic anhydride (SMA) polymer, acrylonitrile-butadiene-styrene (ABS) polymer, polydicyclopentadiene, epoxy resin, polyurethane, cyanate ester, polyphenylene ether, ethylene-propylene-diene monomer (EPDM) polymer, cyclic olefin copolymer (COC), polyimide, The second component of the group consisting of bismaleimide, phosphazene, olefin-modified phosphazene, acrylate, vinyl ester, polylactone, polycarbonate, polysulfide, polyetheretherketone (PEEK), polydimethylsiloxane (PDMS), polyethylene terephthalate (PET), and polybutylene terephthalate (PBT), styrene, divinylbenzene, 1,2-bis(vinylphenyl)ethane, vinylbenzyl ether compound, vinyl ether compound, allyl ether compound, vinylphenyl monomer, vinyl monomer and allyl monomer. A copolymer derived from the polymerization of a polymer as claimed in claim 8 and a comonomer, wherein the comonomer is selected from the group consisting of styrene, divinylbenzene, vinyltoluene, methylstyrene, tert-butylstyrene, α-methylstyrene, α-methylstyrene dimer, vinylcyclohexene, ethylidene norbornene, vinyl norbornene, α-pinene, β-pinene, limonene, other terpenes, polybutadiene, modified polybutadiene, polystyrene (homopolymer and block copolymer), modified polystyrene, polyterpenes, other vinyl reactive monomers and reactive dimers/oligomers/polymers/copolymers thereof. A polymer as claimed in claim 8, wherein the polymer is a solid material with a Tg greater than 150°C, and the polymer is thermally cured without a catalyst or cured using a peroxide or other free radical catalyst with or without another co-catalyst. The polymer of claim 8, wherein the polymer is a solid material with a Tg greater than 150°C, and the polymer is cured using a cationic catalyst, a thermal acid generator (TAGS) and/or a photoacid generator (PAG) with or without an additional co-catalyst. An article for electronic devices, comprising a printed circuit board, prepreg or laminate containing a polymer material as claimed in claim 8. An electronic device comprising an antenna housing or satellite structure containing a material such as the polymer of claim 8. An electronic device comprising a base station, a circuit board, a server or a router containing a material such as the polymer of claim 8. A material comprising a polymer as claimed in claim 8, which is used as a substrate, film or laminate in any of the following: (i) copper clad laminate (CCL), (ii) high density interconnect (HDI) substrate, (iii) integrated circuit (IC) substrate in printed circuit boards under high temperature and low Df applications; (iv) molding compound in power device applications; and (v) radio frequency (RF) heating in oil and gas applications. A 3D printing resin composition comprising a polymer as claimed in claim 8, which is suitable for digital light printing (DLP), continuous liquid interface printing (CLIP), and stereolithography (SL). A polymer derived from at least two resins, wherein (a) the first resin comprises the structure:

and isomers thereof, and; (b) the second resin comprises the structure:

and isomers thereof; wherein (i) each X is independently an allyl, vinylbenzyl, benzyl or styryl group, and; (ii) each Z is independently H or X, and each p is independently an integer from 1 to 4; (iii) n is 0 and the bracketed region represents a bond, or n is an integer greater than or equal to 1, and; (iv) y=1 to 12, and the polymer comprises a dissipation (Df) value in the range of about 0.0001 to about 0.004. A polymer as claimed in claim 23, comprising a solid material having a Tg greater than 150°C, wherein: (a) the polymer is thermally cured in the absence of a catalyst, (b) the polymer is thermally catalyzed using a thermal acid generator (TAGS) and/or a peroxide, or (c) the polymer is catalyzed using a photoacid generator (PAG) via UV light.