Polycyclopentadiene compounds with saturated cyclopentane ring

POLYCYCLOPENTADIENE COMPOUNDS WITH SATURATED

CYCLOPENTANE RING

0003Technical Field

0004The present disclosure relates to polycyclopentadiene compounds and in particular to polycyclopentadiene compounds with a saturated cyclopentane ring.

0005Background

0006Various examples of polycyclopentadiene diphenols are seen in U.S. Patents Nos. 3,419,624 and 4,546,129. Polycyclopentadiene diphenols may be used to prepare epoxy, cyanate, and allyl thermosettable resins with some enhancement of specific physical and/or mechanical properties due to the presence of the

0007dicyclopentadienyl moiety. Polycyclopentadiene diphenols are typically prepared via reaction of a Lewis acid catalyst with polycyclopentadiene and an excess of phenol compound. The strong Lewis acid catalyst, notably boron trifluoride, required for efficient condensation reaction presents handling difficulties, especially due to moisture sensitivity and high reactivity. Also, such catalysts may tend to be nonselective, leading to extensive oligomerization and/or co-product formation.

0008Summary

0009For the various embodiments, the polycyclopentadiene compounds of the present disclosure are represented by compounds of the following Formula I:

0010(Formula I)

0011<img file="WO2011136846A1_D0001.tif" /> in which each X is either a hydrogen, a cyano group, a vinylbenzyl group, an allyl group, an acrylate group, or a structure of Formula II: Formula II <img file="WO2011136846A1_D0002.tif" />

0012; n has an average value from zero to 20; each m independently has a value of zero to 3; each R is mdependently a halogen, a nitriie group, a nitro group, an alkyl group, an alkoxy group, an alkenyl group, or an alkenyloxy group, where the alkyl group, the alkoxy group, the alkenyl group, and the alkenyloxy group each independently contain 1 to 6 carbon atoms; each R¹ is independently hydrogen or a methyl group, each Q is independently hydrogen or an alkyl group containing 1 to 6 carbon atoms, and T is either hydrogen or a structure of Formula III

0013(Formula III)

0014<img file="WO2011136846A1_D0003.tif" />

0015with the proviso that when X is a cyano group, then R is not an alkenyl group or an alkenyloxy group. Embodiments of the present disclosure also include a curable

0016composition that includes the polycyclopentadiene compound(s) of Formula I, which can optionally include a curing amount of a curing agent and/or a catalytic amount of a catalyst and/or a cure accelerating amount of a cure accelerating agent. For the various embodiments, the polycyclopentadiene compounds of Formula I can be used in forming a cured or partially cured composition. For the various

0017embodiments, the curable composition can include the polycyclopentadiene compounds of Formula I in the form of a thermosetable resin (e.g., when X is other than hydrogen in compound of Formula I). For the various embodiments, the curable composition can include the polycyclopentadiene compound of Formula I in the form of a curing agent (hardener).

0018For the various embodiments, the resin and/or the hardener of Formula I can be used either alone or in combination with other compounds as discussed herein. For example, when X of Formula I is hydrogen, the polycyclopentadiene compound can be used as a hardener. For the various embodiments, hardeners of the compound of Formula I can be used in combination with a number of different resins, including, but not limited to, resins derived from Formula I: polyurethane resins; polyester resins; thermosettable monomers like epoxy resins, di or polyisocyanates, and di or polymaleimides, among others; and combinations thereof.

0019The above summary of the present disclosure is not intended to describe each disclosed embodiment or every implementation of the present disclosure. The description that follows more particularly exemplifies illustrative embodiments. In several places throughout this disclosure, guidance is provided through lists of examples, which examples can be used in various combinations. In each instance, the recited list serves only as a representative group and should not be interpreted as an exclusive list.

0020Detailed Description

0021The present disclosure provides for polycyclopentadiene compounds that may be useful as curing agents for epoxy resins and/or as thermosettable monomers and/or thermosettable oligomers. Examples of the polycyclopentadiene compounds of the present disclosure include, but are not limited to, polycyclopentadiene diphenols with a saturated cyclopentane ring. For the various embodiments, the

0022polycyclopentadiene diphenols with the saturated cyclopentane ring of the present disclosure may be formed from polycyclopentadiene monoaldehydes and/or monoketones with a saturated cyclopentane ring. Condensation of

0023polycyclopentadiene monoaldehydes and/or monoketones with the saturated cyclopentane ring with a phenol or a substituted phenol compound can give the corresponding polycyclopentadiene diphenol with the saturated cyclopentane ring. For the various embodiments, polycyclopentadiene diphenol with the saturated cyclopentane ring can also be formed from polycyclopentadiene monoaldehydes and/or monoketones with an unsaturated cyclopentane ring that hydrogenates in situ during hydroformylation. The polycyclopentadiene diphenol with the saturated cyclopentane ring can then be used in preparing thermosettable monomers of the present disclosure, such as polycyclopentadiene diglycidyl ethers with the saturated cyclopentane ring, polycyclopentadiene dicyanates with the saturated cyclopentane ring, and/or polycyclopentadiene divinylbenzyl ether with the saturated cyclopentane ring, among others.

0024For the various embodiments, the use of polycyclopentadiene monoaldehydes and/or dialdehydes with a saturated cyclopentane ring allows for the

0025polycyclopentadiene compounds of the present disclosure to achieve a high level functionality with a relatively low molecular weight, which may allow for a relatively low melt viscosity of the curable composition. Curable compositions formed with the polycyclopentadiene compounds may also provide for cured compositions that have an enhanced glass transition temperature (Tg). Additionally, it is expected that the polycyclopentadiene compounds of the present disclosure will also provide improvements in both moisture resistance and corrosion resistance, as well as enhanced electrical properties of the cured composition, especially dissipation factor.

0026As used herein, "a," "an," "the," "at least one," and "one or more" are used interchangeably. The terms "includes" and "comprises" and variations thereof do not have a limiting meaning where these terms appear in the description and claims.

0027The term "and/or" means one, one or more, or all of the listed items.

0028The recitations of numerical ranges by endpoints include all numbers subsumed within that range (e.g., 1 to 5 includes 1 , 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.).

0029The term "thermoset" as used herein refers to a polymer that can solidify or "set" irreversibly when heated.

0030The terms "curable," "cured," "thermosettable" and "thermoset" are used synonymously throughout and mean that the composition is capable of being subjected to conditions which will render the composition to a cured or thermoset state or condition.

0031The term "B-stage" as used herein refers to a thermoset resin that has been thermally reacted beyond the A-stage so that the product has full to partial solubility in a solvent such as an alcohol or a ketone.

0032The term "alkyl group" means a saturated linear or branched monovalent hydrocarbon group including, for example, methyl, ethyl, n-propyl, isopropyl, t-butyl, pentyl, hexyl, and the like.

0033The term "alkoxy group" refers to groups where at least one hydrocarbon alkyl group is bonded to an oxygen. For example, a group represented by the formula -O-R or -O-R-O-R is an alkoxy group, where R is the hydrocarbon alkyl group.

0034The term "alkenyl group" means an unsaturated, linear or branched

0035monovalent hydrocarbon group with one or more olefmically unsaturated groups (i.e., carbon-carbon double bonds), such as a vinyl group.

0036The term "alkenyloxy group" refers to groups where at least one hydrocarbon alkenyl group is bonded to an oxygen.

0037As used herein, the prefix "poly" means that a compound has two or more of a particular moiety. For example, a cyclopentadiene compound having two

0038cyclopentadiene moieties (dicyclopentadiene) is a specific polycyclopentadiene.

0039As used herein, "compound" refers to a substance composed of atoms or ions of two or more elements in chemical combination.

0040For the various embodiments, the polycyclopentadiene compounds of the present disclosure are represented by a compound of the following Formula I:

0041(Formula I)

0042<img file="WO2011136846A1_D0004.tif" /><img file="WO2011136846A1_D0005.tif" /> where n has an average value from zero to 20; each m independently has a value of zero to 3; each R is independently a halogen, a nitrile group, a nitro group, an alkyl group, an alkoxy group, an alkenyl group, or an alkenyloxy group, where the alkyl group, the alkoxy group, the alkenyl group, and the alkenyloxy group each independently contain 1 to 6 carbon atoms; each R¹ is independently hydrogen or a methyl group, each Q is independently hydrogen or an alkyl group containing 1 to 6 carbon atoms, and T is either hydrogen or a compound of Formula III

0043(Formula III)

0044<img file="WO2011136846A1_D0006.tif" />

0045with the proviso that when X is a cyano group, then R is not an alkenyl group or an alkenyloxy group. For the various embodiments, the halogen of the polycyclopentadiene compounds is preferably selected from the group of fluorine, chlorine, bromine and combinations thereof. The various embodiments also provide that n can have an average value from zero to 20. Preferably, n has an average value from zero to 8. More preferably n has an average value from zero to 3, and most preferably n has an average value from zero to 2.

0046For the various embodiments,_, the alkyl group and the alkoxy group can preferably contain 1 to 2 carbon atoms. For the various embodiments, the alkenyl group and the alkenyloxy group can preferably contain 1 to 3 carbon atoms. For the various embodiments, when Q is an alkyl group it can preferably contain 1 to 2 carbon atoms. For the various embodiments, the R group may also be a fused ring group, producing a naphthalene structure with the ring group that contains the -OX group such as a naphthol (1-naphthol and/or 2-naphthol), tetrahydronaphthol, indanol, and combinations thereof.

0047For the various embodiments, m and n can preferably be zero and Q and T can preferably be hydrogen to provide a compound of Formula IV:

0048(Formula IV)

0049<img file="WO2011136846A1_D0007.tif" /> where X is as provided herein.

0050As appreciated, when n is zero, the polycyclopentadiene compounds of the present disclosure may also be referred to as a dicyclopentadiene compound. As used herein, however, the term polycyclopentadiene will be used, where it is understood that this term may be replaced with dicyclopentadiene when n is zero. Preparation of Polycyclopentadiene Diphenols with a Saturated Cyclopentane Ring

0051The polycyclopentadiene diphenols with the saturated cyclopentane ring (C ring) of the present disclosure can be produced from polycyclopentadiene

0052monoaldehydes and/or polycyclopentadiene monoketones having a saturated cyclopentane ring. For the various embodiments, polycyclopentadiene

0053monoaldehydes can be produced via hydroformylation of polycyclopentadiene, in particular, dicyclopentadiene, using syngas, a ligand, and a transition metal (from Groups 3 through 10) catalyst using a method such as described by G. Longoni, et al, J. of Molecular Catalysis 68, 7-21 (1991) or more generally in Kirk-Othmer, ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY, 2001, pp. 1-17. There are variations in this process, including a method (U.S. Patent No.

00546307108 B l ) that uses mixed polar/nonpolar solvents to ease the issue of catalyst recycle and product separation.

0055An example of such a polycyclopentadiene monoaldehyde with a saturated cyclopentane ring includes the compound of Formula V:

0056(Formula V)

0057<img file="WO2011136846A1_D0008.tif" />

0058For the various embodiments, the hydroformylation can occur at a pressure of 1 to 250 atmospheres (atm) and a temperature of 20 °C to 250 °C. For the various embodiments, the syngas can contain varying amounts of carbon monoxide (CO), hydrogen (¾) and, possibly, inert gases. Intermediate products formed during the hydroformylation can include compounds in which the cyclopentane ring has an olefin. Depending on process conditions,- olefinic, saturated, or mixtures of products can be obtained. As discussed herein, preferably the polycyclopentadiene diphenols have the saturated cyclopentane ring, but it is possible for unsaturated

0059cyclopentane rings to be formed. Preferably, less than 50 percent (%) of the polycyclopentadiene diphenols produced during the hydroformulation include an olefin (e.g., are unsaturated). The reaction also can be conducted using a rhodium catalyst without a ligand as disclosed in US 7,321 ,068, albeit at high syngas pressures of 200-350 atm. Examples of suitable ligands include carbon monoxide and

0060organophosphine ligands having the general formula PR²R³R⁴ where each R², R³, and R⁴ is a substituted or unsubstituted alkyl, an aryl, an aralkyl, an alkaryl, a halide, or a combination thereof. A specific example includes, but is not limited to, n- butyldiphenylphosphine. An example of a suitable catalyst includes, but is not limited to, Rh(CO)₂(acetylacetonate).

0061During the hydroformylation minor amounts, typically 5-25 weight percent (wt. %) or less of the total reaction products, of polycyclopentadiene

0062dialdehydes may also be produced along with the polycyclopentadiene monoaldehydes. The polycyclopentadiene monoaldehydes can be partially or totally separated from the polycyclopentadiene dialdehydes if desired. For example, a distillation process could be used to separate the

0063polycyclopentadiene monoaldehydes from the polycyclopentadiene dialdehydes.

0064In an additional embodiment, various weight percents of the

0065polycyclopentadiene monoaldehydes with the saturated cyclopentane ring could also be mixed with the polycyclopentadiene dialdehydes. Using combinations of the polycyclopentadiene monoaldehydes and the polycyclopentadiene dialdehydes may allow for control of a level of functionality in the resulting curable composition. Novolac chemistry can be used to form

0066polycyclopentadiene diphenols from the polycyclopentadiene monoaldehydes. Oligomers may also be present in the polycyclopentadiene diphenols. Thus, combinations of polycyclopentadiene diphenols and polyphenols with the saturated cyclopentane ring may be produced as an additional embodiment of the present disclosure. An example of such an oligomer of the

0067polycyclopentadiene diphenols can include, but is not limited to, the compound of Formula VI: Formula VI)

0068<img file="WO2011136846A1_D0009.tif" />

0069where n, m, R and Q are as herein defined.

0070For the various embodiments, polycyclopentadiene monoketones with the saturated cyclopentane ring useful in the present disclosure can be produced through a multistep synthesis, for example the chemistry given in Tetrahedron Letters, 28, 769 (1987); Tetrahedron Letters, 27, 3033 (1986); Tetrahedron Letters, 27, 933 (1986); Journal of the American Chemical Society, 107, 7179 (1985); and Journal of the Chemical Society: Chemical Communications, 1040 (1983). The polycyclopentadiene used in the present disclosure can be prepared by heating cyclopentadiene to temperatures above 100 °C as disclosed by Kirk-Othmer,

0071ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY, Third Edition, Vol. 7, pp. 417- 419 (1979). All of the references mentioned herein are incorporated herein in their entirety by reference.

0072As provided herein, using combinations of the polycyclopentadiene monoaldehydes, dialdehydes, and/or monoketones with the saturated cyclopentane . ring may allow control over the level of functionality in a given curable composition. So, for example, the crosslink density for a curable composition of the present disclosure can be adjusted (e.g., decreased or increased) based on the relative amounts of the polycyclopentadiene diphenols and the polycyclopentadiene polyphenols used in the composition. Adjusting the level of functionality in this way may allow for the properties such as glass transition temperature (Tg) of the cured composition to tailor to desired levels and/or balance with other properties (e.g., toughness) of the cured composition.

0073Moreover, it may be possible to control the amount of dicyclopentadiene and/or polycyclopentadiene moieties in the polycyclopentadiene monoaldehydes of the present disclosure. The dicyclopentadiene and/or polycyclopentadiene can be formed through Diels-Alder chemistry using cyclopentadiene where, as discussed herein, the average value for n of Formula I can be from zero to 20. So, for example, when the polycyclopentadiene moieties in the polycyclopentadiene monoaldehydes of the present disclosure are oligomers they can have a distribution of n values that is on average from 2 to 5. For other embodiments, n can have a value of zero or 1. The ability to control the dicyclopentadiene and/or polycyclopentadiene moieties in the polycyclopentadiene monoaldehydes may also allow for the ability to control and/or tailor a crosslink density of a curable composition while retaining or even increasing potential moisture resistance properties of the cured composition.

0074For the various embodiments, the resulting polycyclopentadiene

0075monoaldehydes with the saturated cyclopentane ring and/or polycyclopentadiene monoketones with the saturated cyclopentane ring can then be condensed with phenols to form the polycyclopentadiene diphenols with the saturated cyclopentane ring of the present disclosure. For the various embodiments the condensation reaction of the polycyclopentadiene monoaldehydes and/or the polycyclopentadiene monoketones to phenols can have a mole ratio of 1 :20 to 1 :6. preferably from 1 : 15 to 1 :8. For the various embodiments, the condensation reaction can take place in the presence of an acid catalyst which is preferably from 0.1 to 2 weight percent (wt.%), and more preferably from 0.1 to 1 wt.% based on the weight of phenol employed. For the various embodiments, phenols for the condensation reaction can include, but are not limited to, phenol, substituted phenol, o-cresol, w-cresol, p-cresol, 2,4- dimethylphenol, 2,6-dimethylphenol, 1-naphthol, 2-naphthol, and combinations thereof. Higher mole ratios than 1 :20 of the phenol or substituted phenol may also be employed, however doing so requires additional energy and thus expense to recover and recycle the excess phenol or substituted phenol. For the various embodiments, excess phenolic reactant can be removed by distillation.

0076Condensation reactions employing a large excess of the phenol and/or substituted phenol have been found to favor very low polydispersity products rich in

0077polycyclopentadiene diphenol with a saturated cyclopentane ring and low in oligomers. Likewise, as the. amount of the phenol and/or substituted phenol is reduced, there can be an increase in oligomers at the expense of

0078polycyclopentadiene diphenol with the saturated cyclopentane ring content.

0079Increased oligomer content favors higher hydroxyl functionality, which may be highly beneficial for certain end uses. Thus, while very large excesses of phenol and/or substituted phenol may be used, the present disclosure employs the molar ratio provided herein to produce products rich in polycyclopentadiene diphenol, and low in oligomers.

0080For the various embodiments, condensation reactions to form the

0081polycyclopentadiene diphenols of the present disclosure can also optionally include the use of a solvent. For these embodiments, the solvent can be inert to the reaction and reaction products may also be employed, such as, for example, toluene or xylene. The solvent may additionally serve as an agent for the azeotropic removal of water from the condensation reaction. With certain phenolic reactants with higher melt viscosities, use of one or more solvents may be beneficial for maintaining a suitable reaction medium.

0082Suitable acid catalysts include the protonic acids, such as hydrochloric acid, sulfuric acid, phosphoric acid; metal oxides, such as zinc oxide, aluminum oxide, magnesium oxide; organic acids, such as p-toluenesulfonic acid, oxalic acid, 3- mercapto-1 -propane sulfonic acid, and combinations thereof.

0083For the various embodiments, the 3-mercapto- l -propane sulfonic acid is a preferred acid catalyst or co-catalyst. Surprisingly, it has been found that 3- mercapto- 1 -propane sulfonic acid is so highly selective in forming the

0084polycyclopentadiene diphenols that there is no need for an azeotropic removal of water from the reaction. Rather, the water remains in the reactor, without quenching the reaction. Reaction temperatures and times vary, but can be from about 5 minutes to about 48 hours and reaction temperatures of from about 20 °C to about 175 °C may be employed. Preferably reaction temperatures and times can be from 15 minutes to 36 hours and reaction temperatures of from 30 °C to about 125 °C. Most preferably reaction temperatures and times can be from 30 minutes to 24 hours and reaction temperatures of from 35 °C to about 75 °C.

0085At the end of the reaction, the acidic catalyst can be removed by neutralization, for example by washing or extraction with water. Likewise, at the end of the reaction, excess phenol can be removed from the product, for example, by distillation or extraction.

0086Relative to the polycyclopentadiene diphenols of the prior art, in addition to the saturated cyclopentane ring, the compositions of the present disclosure structurally possess attachment of both phenolic rings substantially to the norbornyl ring, while those compositions of the prior art predominately have attachment of one phenolic ring to the norbornyl ring and the other phenolic ring to the cyclopentyl ring. Thus, in the oligomers or polymers prepared using the pair of phenolic hydroxyl groups of the present disclosure, the polycyclopentadiene moiety will be pendant with respect to the main chain of the oligomer or polymer. This structure of the saturated cyclopentane ring or the polycylopentane ring may allow for hydrophobic association between the chains in the developing thermoset. Packing variations are also possible, where the pendant structures found in the embodiments of the present disclosure could direct the packing of the chains or their molecular constraint in the matrix. Thus, the possibility for hydrophobic association of the pendant polycyclopentadiene moieties exists for the present disclosure and may enhance physical and mechanical properties of the resulting cured composition.

0087The polycyclopentadiene diphenols with the saturated cyclopentane ring have utility as an epoxy resin curing agent useful, for example, in high performance functional powder coatings. The polycyclopentadiene diphenol with the saturated cyclopentane ring may also be used as a "diluent" to decrease functionality when blended with polyfunctional curing agents, for example, a polycyclopentadiene tetraphenol. The polycyclopentadiene diphenol with the saturated cyclopentane ring of the present disclosure may used to linearly advance epoxy resins, such as, for example, the diglycidyl ether of bisphenol A, the diglycidyl ether of 10-(2',5'- dihydroxyphenyl)-9, 10-dihydro-9-oxa- 10-phosphaphenanthrene- 10-oxide (DOP-HQ), the diglycidyl ether of a dicyclopentadiene diphenol, among other epoxy resins, to produce thermosettable compositions of matter containing pendant saturated poly or dicyclopentadienyl moieties.

0088The resultant advanced epoxy resin may be cured using a curing agent or co- reacted with other thermosettable monomers, such as, for example, polycyanates. Improved moisture resistance and corrosion resistance are anticipated, as well as enchanced electrical properties, especially dissipation factor, for these advanced resins. For the various embodiments, it is additionally recognized that when "n" is greater than 1, additional hydrocarbon bulk is added to the pendant side chains and may beneficially impact physical and mechanical properties of the resultant thermosets. The packing of the pendant side chains may beneficially increase toughness of the thermoset matrix and may even induce hydrophobic association between the chains.

0089Aside from the aforementioned uses as curing agents for epoxy resins or for advancement reaction of epoxy resins, the polycyclopentadiene diphenols with the saturated cyclopentane ring of the present disclosure can also be used as precursors to additional thermoset resins. Such thermoset resins include cyanate, epoxy, allyl, allyloxy, acrylate, and vinylbenzyl ether (and other ethylenically unsaturated) resins which are useful in preparation of coatings, especially functional powder coatings and other protective coatings with high glass transition temperature, solvent resistance, moisture resistance, abrasion resistance, and toughness; electrical or structural laminates or composites; filament windings; moldings; castings;

0090encapsulation; multilayer electronic circuitry; integrated circuit packaging (such as "IC substrates"); composites for aerospace; adhesives; and formulation with other resins such as poly(maleimide)s, polycyanate)s. Thermosets with improved moisture resistance and corrosion resistance are anticipated, as well as enhanced electrical properties, especially dissipation factor, due to the presence of the polycyclopentadienyl moiety with the saturated cyclopentane ring. Diglycidyl Ethers of Polycyclopentadiene Diphenols with Saturated Cyclopentane Ring

0091Polycyclopentadiene diglycidyl ethers with the saturated cyclopentane ring and compositions thereof additionally containing oligomers of the present disclosure can be prepared as follows: The initial step in the preparation of the aforementioned compositions of the present disclosure generally consists of reacting the

0092polycyclopentadiene diphenol with the saturated cyclopentane ring with an

0093epihalohydrin in the presence of a basic acting substance, in the presence or absence of a catalyst and in the presence or absence of one or more solvents. For the various embodiments, the reaction can take place at a temperature from about 20 °C to about 120 °C, more preferably from about 30 °C to about 85 °C, most preferably from about 40 °C to about 75 °C. For the various embodiments, the reaction can take place at a pressures from about 4 KPa to about 500 KPa, more preferably from about 4 KPa to about 340 KPa, and most preferably from about 8 KPa to about 100 KPa (1 atmosphere). For the various embodiments, the reaction can take place a time sufficient to complete the reaction, usually from about 1 to about 120 hours, more usually from about 3 to about 72 hours, most usually from about 4 to about 48 hours.

0094For the various embodiments, the reaction also uses from about 1.1 : 1 to 25: 1, preferably from about 1.8: 1 to about 10: 1 , and most preferably from about 2: 1 to about 5:1 moles of epihalohydrin per phenolic hydroxy group. This initial reaction, unless the catalyst is an alkali metal or alkaline earth metal hydroxide employed in stoichiometric or greater quantities, produces a halohydrin intermediate which is then reacted with the basic acting substance to convert the vicinal halohydrin groups to epoxide groups. The resultant product is a glycidyl ether compound. Details concerning preparation of epoxy resins are given in U.S. Patent No. 5,736,620;

0095Handbook of Epoxy Resins by Lee and Neville, McGraw-Hill (1967); and Journal of Applied Polymer Science, volume 23, pages 1355-1372 (1972); and U.S. Patent No. 4,623,701 ; all of which are incorporated herein by reference in their entirety .

0096Suitable epihalohydrins which can be employed to prepare the compositions of the present disclosure include, for example, epichlorohydrin, epibromohydrin, epiiodohydrin, methylepichlorohydrin, methylepibromohydrin, methylepiiodohydrin, and combinations thereof. Most preferred as the epihalohydrin is epichlorohydrin. A suitable basic acting substance is employed to prepare the compositions of the present disclosure. Suitable basic acting substances include, for example, the alkali metal or alkaline earth metal hydroxides, carbonates and bicarbonates, and combinations thereof. Particularly suitable such compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, barium hydroxide, magnesium hydroxide, manganese hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, calcium carbonate, barium carbonate, magnesium carbonate, manganese carbonate, sodium bicarbonate, potassium bicarbonate, magnesium bicarbonate, lithium bicarbonate, calcium bicarbonate, barium bicarbonate, manganese bicarbonate, and combinations thereof. Most preferred is sodium hydroxide or potassium hydroxide.

0097For processes involving reaction of the polycyclopentadiene diphenol with the saturated cyclopentane ring with an alkali metal hydride followed by reaction with the epihalohydrin, suitable alkali metal hydrides include, for example, sodium hydride and potassium hydride, with sodium hydride being most preferred.

0098Suitable catalysts which can be employed to prepare the compositions of the present disclosure include, for example, the ammonium or phosphonium halides, such as, for example, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, tetrabutylammonium chloride, tetrabutyl ammonium bromide,

0099tetraoctylammonium chloride, tetrabutylammonium bromide, tetramethylammonium chloride, tetramethylammonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium iodide,

0100ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide, ethyltriphenylphosphonium iodide, and combinations thereof.

0101Suitable solvents which can be employed to prepare the compositions of the present disclosure include aliphatic and aromatic hydrocarbons, halogenated aliphatic hydrocarbons, aliphatic ethers, aliphatic nitriles, cyclic ethers, ketones, amides, sulfoxides, aliphatic and cycloaliphatic secondary and tertiary alcohols, and combinations thereof. Particularly suitable solvents include pentane, hexane, octane, toluene, xylene, methylethylketone, methylisobutylketone, Ν,Ν-dimethylformamide, dimethylsulfoxide, diethyl ether, tetrahydrofuran, 1,4-dioxane, dichloromethane, chloroform, ethylene dichloride, methyl chloroform, ethylene glycol dimethyl ether, Ν,Ν-dimethylacetarnide, acetonitrile, propylene glycol monomethyl ether,

0102isopropanol, and combinations thereof. The solvent may be removed at the completion of the reaction using conventional means, such as, for example, vacuum distillation. A further process of the present disclosure is conducted in the absence of a solvent, with epichlorohydrin being used in an amount to function as both solvent and reactant.

0103Analytical methods, such as high pressure liquid chromatography (HPLC), may be employed to monitor reaction of the polycyclopentadiene diphenol with the saturated cyclopentane ring concurrently with the formation of intermediate product, such as the halohydrin, and the final diglycidyl ether product.

0104Recovery and purification of the polycyclopentadiene diglycidyl ether with the saturated cyclopentane ring compositions of the present disclosure can be performed using a variety of methods. For example, gravity filtration, vacuum filtration, centrifugation, water washing or extraction, solvent extraction, decantation, column chromatography, vacuum distillation, falling film distillation, wiped film distillation, electrostatic coalescence, and other processing methods and the like may be used. Vacuum distillation is a most preferred method for removal and recovery of lighter boiling fractions, for example, unused epihalohydrin. This recovers epichlorohydrin, and solvent, if used, for recycle.

0105Oligomers may also be present in the polycyclopentadiene diglycidyl ethers with the saturated cyclopentane ring of the present disclosure. These typically arise from an epoxidation of oligomeric components present in the polycyclopentadiene diphenol with the saturated cyclopentane ring precursor or from the in situ advancement reaction of a portion of the glycidyl ether moieties. Advancement reaction is characterized by the formation of the 2- hydroxypropyl ether linkage (the structure of Formula VII) in the advanced epoxy resin product:

0106Formula VII

OH

I

0109— HR¹C— CR — CH₂— O—

0110where R¹ is as defined herein.

0111The polycyclopentadiene diglycidyl ethers with the saturated

0112cyclopentane ring of the present disclosure, as well as blends thereof with one or more conventional epoxy resins, may be used to prepare (1) advanced epoxy resins (thermosettable) (2) vinyl esters and vinyl ester resins (3) epoxy resin adducts useful as (a) epoxy resin curing agents, (b) reactants for thermoset polyurethanes, polyureaurethanes, and polyisocyanurates (c) initiators for polyols useful in preparation of polyurethanes, polyureaurethanes, polyisocyanurates, and (4) monomers in other thermoset resin systems, for example, in co-polymerization with di or polyisocyanates to give oxazolidinone-containing thermosets.

0113Dicyanates of Polycyclopentadiene Diphenols with Saturated Cyclopentane Ring

0114For the various embodiments, the dicyanates with the saturated cyclopentane ring of the present disclosure can be prepared by reacting one or more of the polycyclopentadiene diphenols with the saturated cyclopentane ring of the present disclosure with a stoichiometric quantity or a slight stoichiometric excess (up to about 20 percent excess) of a cyanogen halide per phenolic hydroxyl group. For the various embodiments, the reaction also takes place in the presence of a stoichiometric quantity or a slight stoichiometric excess (up to about 20 percent excess) of a base compound per phenolic hydroxyl group and in the presence of one or more suitable solvents.

0115Reaction temperatures of from about -40 °C to about 60 °C are preferred, with reaction temperatures of - 15 °C to 10 °C being more preferred, and with reaction temperatures of -10 °C to 0 °C being most preferred. Reaction times can vary substantially, for example, as a function of the reactants being employed, the reaction temperature, solvent(s) used, the scale of the reaction, and the like, but are generally between 15 minutes and 4 hours, with reaction times of 30 minutes to 90 minutes being preferred.

0116Suitable cyanogen halides include cyanogen chloride and cyanogen bromide. Alternately, the method of Martin and Bauer described in Organic Synthesis, volume 61, pages 35-68 (1983) published by John Wiley and Sons, incorporated herein by reference in its entirety, can be used to generate the required cyanogen halide in situ from sodium cyanide and a halogen such as chlorine or bromine.

0117Suitable base compounds include both inorganic bases and tertiary amines such as sodium hydroxide, potassium hydroxide, trimethylamine, triethylamine, and combinations thereof. Triethylamine is most preferred as the base.

0118Suitable solvents for the cyanation reaction include water, aliphatic ketones, chlorinated hydrocarbons, aliphatic and cycloaliphatic ethers and diethers, aromatic hydrocarbons, and combinations thereof. Acetone, methylethylketone, methylene chloride or chloroform are particularly suitable as the solvent.

0119The dicyanates with the saturated cyclopentane ring are cured (thermoset) by heating from about 50 °C to about 400 °C preferably by heating from 100 °C to 300 °C, optionally in the presence of a suitable catalyst. Suitable catalysts include, for example, acids, bases, salts, nitrogen and phosphorus compounds, such as for example, Lewis acids such as A1C1₃ BF₃, FeCl₃, TiCl₄, ZnCl₂, SnCl₄; protonic acids such as HC1; H₃P0₄; aromatic hydroxy compounds such as phenol, p-nitrophenol, pyrocatechol, dihydroxynaphthalene; sodium hydroxide, sodium methylate, sodium phenolate, trimethylamine, triethylamine, tributylamine, diazabicyclo[2.2.2]octane, quinoline, isoquinoline, tetrahydroisoquinoline, tetraethyl ammonium chloride, pyridine -N-oxide, tributylphosphine, zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, cobalt octoate, cobalt acetylacetonate and the like. Also suitable as catalysts are the metal chelates such as, for example, the chelates of transition metals and bidentate or tridentate ligands, particularly the chelates of iron, cobalt, zinc, copper, manganese, zirconium, titanium, vanadium, aluminum and magnesium. These and other operable catalysts are disclosed in U.S. Pat. -Nos. 3,694,410 and 4,094,852, which are incorporated herein by reference in their entirety. Cobalt naphthenate, cobalt octoate and cobalt acetylacetonate are most preferred as the catalysts. The quantity of catalyst used, if any, depends on the structure of the particular catalyst, the structure of the polycyanate being cured, the cure temperature, the cure time, and the like. Generally, catalyst concentrations of from about 0.001 to about 2 percent by weight are preferred.

0120For the various embodiments, B-staging or prepolymerization of the compositions of the dicyanates with the saturated cyclopentane ring of the present disclosure can be accomplished by using lower temperatures and/or shorter curing times. Curing of the thus formed B -staged (prepolymerized) resin can then be accomplished at a later time or immediately following B-staging (prepolymerization) by increasing the temperature and/or curing time. The cured (thermoset) products prepared from the dicyanates with the saturated cyclopentane ring possess the cyanate group homopolymerization structure, the polytriazine ring, unless other functionalities are present in the polycyanate that participate in the curing process.

0121In additional embodiments, the present disclosure can also provide for a blend, a partially polymerized (B-staged) product, or a cured (thermoset) product of (1) the polycyclopentadiene dicyanate with the saturated cyclopentane ring or a partially polymerized product from the dicyanate, with (2) one or more components selected from the group consisting of a bis or polymaleimide, a di or polycyanate other than that of the present disclosure, a di or polycyanamide, an epoxy resin, a polymerizable mono, di, or polyethylenically unsaturated monomer (including vinyl aromatic monomers, vinylbenzyl ethers, allyl, and allyloxy compounds).

0122Vinylbenzyl Ethers of Polycyclopentadiene Diphenols with Saturated Cyclopentane Ring

0123The vinylbenzyl ethers of the polycyclopentadiene diphenols with the saturated cyclopentane ring of the present disclosure can be prepared by reacting one or more of the polycyclopentadiene diphenols, with a stoichiometric excess of a vinylbenzyl halide per phenolic hydroxy! group in the presence of a stoichiometric excess of a base compound, such as lithium hydroxide, per phenolic hydroxyl group and in the presence of a suitable solvent, such as methanol. A free radical inhibitor, such as 2,6-di-tertiary-butyl-4-methylphenol or hydroquinone is typically employed as an in situ polymerization inhibitor.

0124Reaction temperatures of from about 10 °C to about 100 °C are operable, with reaction temperatures of 20 °C to 75 °C being preferred, and reaction temperatures of 25 °C to 60 °C being most preferred. Reaction times can vary substantially, for example, as a function of the reactants being employed, the reaction temperature, solvent(s) used, the scale of the reaction, and the like, but are generally between 4 hours to about 5 days.

0125Suitable vinylbenzyl halides include o-vinylbenzyl chloride, m-vinylbenzyl chloride, p-vinylbenzyl chloride, o-vinylbenzyl bromide, m-vinylbenzyl bromide, p- vinylbenzyl bromide, 3 -vinylbenzyl-5 -methyl chloride, and combinations thereof. Suitable base compounds include both inorganic bases and tertiary amines such as lithium hydroxide, sodium hydroxide, potassium hydroxide, trimethylarnine, triethylamine, and combinations thereof. Lithium hydroxide is most preferred as the base.

0126Suitable solvents for forming the vinylbenzyl ethers include water, aliphatic ketones, chlorinated hydrocarbons, aliphatic and cycloaliphatic ethers and diethers, aromatic hydrocarbons, and combinations thereof. Water, acetone, methanol and combinations thereof are particularly suitable as the solvent. The base and solvent may be combined before use in the reaction, with methanolic potassium hydroxide solution being one example.

0127The vinylbenzyl ethers of the polycyclopentadiene diphenols with the saturated cyclopentane ring can^' be cured (thermoset) by heating from about 30 °C to about 400 °C preferably by heating from 100 °C to 300 °C, optionally in the presence of one or more suitable catalysts. The quantity of catalyst used, if any, depends on the structure of the particular catalyst, the structure of the vinylbenzyl ether being cured, the cure temperature, the cure time, among other things. Generally, catalyst concentrations of from about 0.001 to about 2 percent by weight are preferred.

0128B-staging or prepolymerization of the compositions of the vinylbenzyl ethers of the present disclosure can be accomplished by using lower temperatures and/or shorter curing times. Curing of the thus formed B-staged (prepolymerized) resin can then be accomplished at a later time or immediately following B-staging

0129(prepolymerization) by increasing the temperature and/or curing time.

0130Allyl Ethers of Polycyclopentadiene Diphenols with Saturated Cyclopentane Ring

0131The allyl (or 1-propenyl) ethers of the polycyclopentadiene diphenols with the saturated cyclopentane ring of the present disclosure can be prepared by allylation of one or more of the polycyclopentadiene diphenols, where the aromatic hydroxyl group(s) (-OH) are converted to HR⁵C=CR⁵-CH₂-0- and/or H₂R⁵C-CR⁵=HC-0-, where each R⁵ is independently selected from the group consisting of hydrogen and alkyl groups having from 1 to 3 carbon atoms. For the various embodiments, the alkyl group can be unsubstituted or substituted. For one or more embodiments it is preferred that X is unsubstituted. For one or more embodiments it is preferred that each X is the same.

0132Formation of the allyl ether of polycyclopentadiene diphenols is discussed in

0133U.S. Utility Application serial number _/ , titled "POLY( ALLYL ETHER) S

0134OF POLYCYCLOPENTADIENE POLYPHENOL", The Dow Chemical Company docket number 68992, filed herewith, the disclosure which is incorporated herein by reference. Briefly, allylation of the polycyclopentadiene diphenol can be

0135accomplished via a transcarbonation reaction. The transcarbonation reaction can include allylmethyl carbonate that is reacted with the polycyclopentadiene diphenol in the presence of a catalytic amount of palladium on carbon and triphenylphosphine. Allylmethyl carbonate can be prepared from a reaction of allyl alcohol and dimethyl carbonate. This reaction can provide a mixture of allylmethyl carbonate and diallyl carbonate. This mixture and/or pure_^ allylmethyl carbonate can be employed in the transcarbonation reaction.

0136Allylation of the polycyclopentadiene diphenol can be accomplished by a direct allylation reaction that can include a halide, an alkaline agent, and optionally a catalyst, such as a phase transfer catalyst. Examples of the halide include, but are not limited to, allyl halides and methallyl halides. Examples of allyl halides include, but are not limited to, allyl chloride and allyl bromide.

0137Examples of methallyl halides include, but are not limited to, methallyl chloride and methallyl bromide. An example of the alkaline agent includes, but is not limited to, an aqueous solution of an alkali metal hydroxide. Examples of the alkali metal hydroxide include, but are not limited to, potassium hydroxide and sodium hydroxide. Examples of the catalyst include, but are not limited to, benzyltrialkylammonium halides and tetraalkylammonium halides. The allylation can include allylmethyl carbonate, diallyl carbonate, the halide, the alkaline agent, the catalyst, and combinations thereof along with the polycyclopentadiene polyphenol.

0138Direct allylation of the polycyclopentadiene diphenol can occur at a temperature of 25 °C to 150 °C. For some applications a temperature of 50 °C to 100 °C is preferred for the allylation. Allylation of the polycyclopentadiene diphenol can have a reaction time of 15 minutes to 8 hours. For some applications a reaction time of 2 hours to 6 hours is preferred. Allylation of the polycyclopentadiene diphenol can include a solvent. An example of the solvent includes, but is not limited to, 1,4- dioxane.

0139In a direct allylation reaction, the allyl halide may be stoichiometrically reacted with the hydroxy groups of the polycyclopentadiene diphenol. For various reaction conditions, variable amounts of a Claisen rearrangement product may be observed in this reaction, and can result in a mixture of O- and C-allylated products.

0140A reaction of a 1 to 1 mole ratio of the allyl halide with the hydroxy groups of the polycyclopentadiene diphenol can provide an allylated bisphenol, wherein a maj or amount (about 80 or more percent) of the hydroxy groups of the polycyclopentadiene diphenol have been converted to -0-CH₂-CH=CH₂ groups . Additionally, a minor amount (about 20 percent or less) of the allyl groups may have undergone thermally induced Claisen rearrangement and be present on the aromatic ring ortho and/or para to the hydroxy groups from which the rearrangement occurred. A reaction of less than a 1 to 1 mole ratio of allyl methyl carbonate in the transcarbonation reaction or of allyl halide in the direct allylation reaction with the hydroxy groups can provide partial allylation, with some free hydroxy groups remaining. Although the partially allylated compounds may be less preferred for some applications, they are within the scope of the present disclosure.

0141A preferred process uses a transcarbonation reaction wherein

0142allylmethyl carbonate is stoichiometrically reacted^' with the polycyclopentadiene diphenol to provide essentially total allylation of the hydroxy groups of the polycyclopentadiene diphenol and provide the corresponding allylether (allyloxy) groups.

0143Isomerization of the allyloxy and allyl groups, if present, to the more reactive 1-propenyl groups may be performed in the presence of a base using the methods reported by T. W. Green and P. G. M. Wuts in Protective Groups in Organic

0144Synthesis, Wiley-Interscience, New York, 67-74, 708-71 1 (1999) or in the presence of a catalytic amount of a ruthenium complex as described in Journal of Molecular Catalysis A: Chemical volume 219, issue 1 , pages 29-40 (September 1 , 2004). Both of the aforementioned references are incorporated herein in their entirety.

0145Acrylates and Metacrylates of Polycyclopentadiene Diphenols with Saturated

0146Cyclopentane Ring

0147Acrylates and methacrylates can be prepared via reaction of an acid chloride, such as, acryloyl chloride (2-propenoyl chloride) or methacryloyl chloride, respectively, using a Schotten-Baumann type .reaction as described in C. Schotten, Ber. 17, 2544 (1884) and E. Baumann, ibid. 19, 3218 (1886). For this acylation reaction, one or more basic acting substances, such as aqueous sodium hydroxide, triethylamine or pyridine, can be employed. Additionally, it may be beneficial to employ one of more polymerization inhibitors, such as, for example, hydroquinone. Transesterification reaction may also be employed to prepare acrylates and methacrylates. A method for synthesis of high purity acylates and methacrylates which are free of acrylic or methacrylic anhydride as a crosslinkable diene impurity was described by Stacy B. Evans, J. E. Mulvaney, H. K. Hall Jr. in Journal of Polymer Science Part A: Polymer Chemistry, volume 28, issue 5, pages 1073 - 1078, published online March 10, 2003. All of the aforementioned references are incorporated herein in their entirety.

0148The following examples are illustrative of the present invention, but are not to be construed as to limiting the scope thereof in any manner.

0149Examples

0150The following examples are given to illustrate, but not limit, the scope of this disclosure. Unless otherwise indicated, all parts and percentages are by .weight. Unless otherwise specified, all instruments and chemicals used are commercially available.

0151Materials

0152Rh(CO)₂(acetylacetonate) available from Strem Chemicals Inc.

0153n-butyldiphenylphosphine available from Organometallics, Inc (E. Hampstead, NH,

0154USA).

0155Dicyclopentadiene available from The Dow Chemical Company.

0156Syngas available from Airgas Great Lakes, Inc.

01573 -Mercaptopropane-1 -sulfonic acid, sodium salt, 90% purity, available from Sigma- Aldrich.

0158Hydrochloric acid, A.C.S. reagent grade, 37.5% by acid base titration, available from

0159Mallinckrodt Baker, Inc.

0160Phenol, >99%, available from The Dow Chemical Company.

0161Tetrahydrofuran, anhydrous, >99.9 %, inhibitor-free, available from Sigma- Aldrich.

0162Benzyltriethylammonium chloride, 99%, available from Sigma-Aldrich.

0163Isopropanol, A.C.S. reagent grade, >99.5%, available from Sigma-Aldrich.

0164Sodium hydroxide, reagent grade, >98%, pellets, anhydrous, available from Sigma- Aldrich.

0165Methylisobutylketone (4-methyl-2-pentanone), >99%, manufactured by Eastman Chemical Company, available from Sigma-Aldrich. Epichlorohydrin available from The Dow Chemical Company.

01664,4'-Diaminodiphenyl methane, >97% gas chromatographic purity, available from Sigma-Aldrich.

0167Dicyandiamide, pulverized, (unaccelerated), available as Amicure^® CG series from

0168Air Products.

0169KBr, FT-IR grade, > 99% trace metals basis, available from Sigma-Aldrich. Diatomaceous earth, available as Celite^® 545, from Celite Corporation

0170Example 1 - Preparation of Dicyclopentadiene Diphenol with Saturated Cyclopentane

0171Ring

0172A. Preparation of Dicyclopentadiene Monoaldehyde with Saturated

0173Cyclopentane Ring

0174A reaction mixture of Rh(CO)₂ acetylacetonate (70.2 milligrams (mg); 0.272 millimole (mmol)) and n-butyldiphenylphosphine (0.33 gram (g); 1.36 mmol) in slightly warm dicyclopentadiene (140 g; 1.06 moles) was prepared in a purge box under dry nitrogen, and then placed in a 250 milliliter (mL) Parr reactor and sparged three times with 1 : 1 syngas (1 : 1 molar ratio CO:H₂) at 20 °C. The reaction mixture was then heated to 100 °C under a pressure of 90 psi of syngas with stirring for 1 day and then at 130 °C and under a pressure of 90 psi of syngas for 6 days with stirring. The product formation from the reaction mixture was monitored by gas

0175chromatography (GC) using an Agilent 6890 Gas Chromatography system. The final GC analysis of the resulting mixture showed the dicyclopentadiene monoaldehyde with saturated cyclopentane ring accounting for 65.5 area%.

0176The reactor was cooled, the mixture was recovered, and the crude product (177.8 grams) was distilled under vacuum using a 10 cm Vigreux distillation column to give 78.2 grams of the dicyclopentadiene monoaldehyde with saturated cyclopentane ring with a boiling point of 65-68 °C at 0.17 mm Hg. Gas chromatographic/mass spectroscopic (GC/MS) analysis using an Agilent 6890 GC with Agilent 5973 Mass Selective Detector of the transparent, liquid, distilled product supported the formation of the desired dicyclopentadiene monoaldehyde with saturated cyclopentane ring: M⁺ = 164, 146, 136, 107, 95, 79, 67.

0177B. Preparation of 3 -Mercapto-1 -propane sulfonic Acid Catalyst 3-Mercaptopropane-l -sulfonic acid, sodium salt (10.75 grams) was added to concentrated hydrochloric acid (35.7 % aqueous, 200 mL) which was magnetically stirred in a glass beaker. After covering with a sheet of Parafilm "M" (American National Can, Greenwich, CT) to prevent uptake of atmospheric moisture, the resulting white crystalline slurry was stirred for 5 minutes then filtered over a medium fritted glass funnel. The filtrate was rotary evaporated to give 8.88 g of a pale yellow colored, tacky, solid product which was used as the catalyst without further processing.

0178C. Phenolation Reaction

0179Dicyclopentadiene monoaldehyde with saturated cyclopentane ring (43.31 grams, 0.2845 mole uncorrected) and molten phenol (850.2 grams, 9.0345 moles) were added to a 5 liter glass three neck round bottom reactor. The reactor was additionally outfitted with an ambient temperature (22 °C) condenser and a thermometer, both affixed to the reactor via a Claisen adaptor, plus an overhead nitrogen inlet, a glass stirring shaft with a Teflon (E.I. duPont de Nemours) stirrer blade which was coupled to a variable speed motor to provide mechanical stirring and a

0180thermostatically controlled heating mantle.

0181Overhead nitrogen flow (0.5 liter per minute) commenced, followed by heating, then stirring. When the temperature reached 64 °C a transparent solution was noted. At this time, addition of aliquots of the 3-mercaptopropane-l -sulfonic acid (total catalyst used was 2.22 grams, 0.05 mole % with respect to dicyclopentadiene monoaldehyde with saturated cyclopentane ring) commenced into the stirred solution. The initial aliquot of catalyst (0.42 gram) induced a maximum exotherm to 70 °C after 2 minutes, turning the solution a golden amber color. The heating mantle was removed from the reactor, and fan was engaged to cool the reactor exterior to 65 °C. A second aliquot of the catalyst was added (0.31 gram), with cessation of the cooling and replacement of the heating mantle back on the reactor. The second aliquot of catalyst did not induce an exotherm, with a temperature of 64 °C noted one minute after addition. At this time, additional aliquots of catalyst were added over the next 1 1 minutes while maintaining temperature of the amber colored solution at 63 - 65 °C. The reaction temperature was maintained at 65 °C for the next 72 hours during which time, the course of the reaction was followed via HPLC analysis. A Hewlett Packard 1090 Liquid Chromatograph was employed using a Zorbax Eclipse^® (Agilent) XDB-C8 analytical column (5 μ, 4.6 x 150 mm) with an Eclipse^® (Agilent) XDB-C8 analytical guard column (5 μ, 4.6 x 12.5 mm). The columns were maintained in the chromatograph oven at 40°C. Acetonitrile and water (treated with 0.05 % aqueous o-phosphoric acid) were used as the eluents and were initially delivered via the pump at a rate of 1.000 mL per min as a 50 / 50 % solution, respectively, changing after 5 min to a 90 / 10 % solution and held therein for the next 15 min. The acetonitrile used was HPLC grade, 100.0 % purity (by gas

0182chromatography), with a UV cutoff of 189 nm. The o-phosphoric acid used was nominally 85 % pure (actual assay 85.1 %). The water used was HPLC grade. A diode array detector employed for the sample analysis was set at 225 nm and the reference was set at 550 nm. After 2.4 hours of reaction, HPLC analysis revealed full conversion of the dicyclopentadiene monoaldehyde to a distribution of products, with little change in the product thereafter.

0183At the end of the reaction time, the reactor contents were diluted with deionized (DI) water to fill the 5 L reactor to 95 % of capacity. Stirring ceased after one hour and the contents of the reactor was allowed to settle overnight. The following day, the aqueous layer was siphoned from the reactor and disposed of as waste. The reactor was refilled with fresh DI water and stirring commenced for the next 65 minutes. Stirring ceased and the contents of the reactor were allowed to settle overnight. The following day, the aqueous layer was siphoned from the reactor and disposed of as waste. The washing sequence was repeated two additional times followed by collection of the solids from the reactor by decantation through filter paper. The solids thus recovered were added to a ceramic dish and dried in the vacuum oven at 100 °C for 24 hours, removed, ground to a fine powder and dried in the vacuum oven for an additional 48 hours to provide 84.32 grams of light purple colored powder.

0184FTIR analysis of a KBr pellet revealed complete disappearance of the aldehyde carbonyl stretch with appearance of strong aromatic ring absorbance at 1609.6 (shoulder at 1595.8) and 1509.8 cm^'1; broad, strong hydroxyl O-H stretching centered at 3379.7 cm^"1 ; and broad, strong C-0 stretching at 1230.4 (shoulder at 1 171.1) cm^"1. HPLC analysis revealed 39 components with 4 predominant components comprising 18.7, 7.9, 6.5 and 5.8 area %, along with 6.5 area % residual unreacted phenol that was not removed during work-up of the product.

0185Example 2 - Epoxidation of Dicyclopentadiene Diphenol with Saturated

0186Cyclopentane Ring

0187A one liter, three neck, glass, round bottom reactor was charged with

0188dicyclopentadiene diphenol with saturated cyclopentane ring from Example 1 (33.44 grams, 0.20 hydroxyl equivalent, based on a 167.22 nominal hydroxyl equivalent weight) and epichlorohydrin (138.86 grams, 1.50 moles). The reactor was

0189additionally equipped with a condenser (maintained at 0 °C), a thermometer, a Claisen adaptor, an overhead nitrogen inlet (1 liter per minute N₂ used), and a stirrer assembly

0190(Teflon paddle, glass shaft, variable speed motor). Sodium hydroxide (7.2 grams, 0.18 mole) dissolved in DI water (28.8 grams) to form an aqueous sodium hydroxide solution was added to a side arm vented addition funnel. Stirring of the slurry in the reactor commenced with heating using a thermostatically controlled heating mantle. Once a stirred solution formed when the temperature reached 30 °C, isopropanol (74.77 grams, 35 weight percent of the epichlorohydrin used) was added with continued stirring and heating. Once 40 °C was achieved, DI water (12.08 grams, 8 % weight of the epichlorohydrin used) was added by rapid dropwise addition to the solution. Once 50 °C was achieved, dropwise addition of the aqueous sodium hydroxide solution commenced causing the solution in the reactor to initially turn a dark amber color. Continued dropwise addition of the aqueous sodium hydroxide at 50 °C slightly clouded the dark amber colored solution. The addition of aqueous sodium hydroxide was completed over 30 minutes.

0191After 23 minutes of postreaction, stirring ceased and the reactor contents were added to a separatory funnel and allowed to settle. The progress of the epoxidation reaction was monitored by high pressure liquid chromatographic (HPLC) analysis as previously discussed. At the end of the 7 minute settling time, the aqueous layer was removed, discarded as waste and the organic layer recovered and added back into the reactor. Heating and stirring of the solution resumed to re-establish the 50 °C temperature within 5 minutes. Dropwise addition of a second portion of sodium hydroxide (3.2 grams, 0.08 mole) dissolved in DI water (12.8 grams) commenced and was completed over 20 minutes while maintaining the temperature at 50 °C. After 23 minutes of postreaction, stirring ceased, the reactor contents allowed to settle for 5 minutes in a separatory funnel, the aqueous layer removed from the product, and the slightly cloudy, light orange colored, organic layer added back into the reactor. A sample was removed for HPLC analysis. Heating and stirring then resumed re-establishing the 50 °C temperature 7 minutes later. A third portion of sodium hydroxide (1.0 gram, 0.025 mole) dissolved in DI water (4.0 grams) was added over 10 minutes and processed using the method employed for the second aqueous sodium hydroxide addition.

0192After 23 minutes of postreaction followed by removal of the aqueous layer from the final aqueous sodium hydroxide addition, the organic layer was washed with a portion (150 milliliters) of DI water. The recovered organic layer was diluted with methylisobutylketone (0.5 liter) and washed with a second portion (150 milliliters) of DI water. The aqueous layer along with about 20 grams of emulsion was removed after being resolved via centrifuging 30 minutes at 2300 RPM. Third and fourth washes with DI water (150 milliliters per wash) were completed using the method employed for the second wash (centrifuging was again necessary to resolve a minor amount of residual emulsion from each wash). The recovered organic solution was vacuum filtered over a bed of diatomaceous earth packed in a 600 milliliter medium fritted glass funnel with methylisobutylketone used as needed to wash product from the filter bed into the filtrate. Rotary evaporation of the organic layer using a maximum oil bath temperature of 75 °C to a vacuum of 9.3 mm of Hg removed the bulk of the volatiles. Further rotary evaporation at a maximum oil bath temperature of 175 °C to a final vacuum of 0.17 mm of Hg gave 36.1 1 grams of light yellow colored solid upon cooling to 23 °C.

0193Gas chromatographic (GC) analysis [Hewlett Packard 5890 Series II Gas Chromatograph using a 60m x 0.248mm x 0.25μηι J&amp;W GC column with DB-1 stationary phase, flame ionization detector operating at 300°C, a 300°C injector temperature, helium carrier gas flow through the column was maintained at 1.1 mL per min. and an initial 50°C oven temperature with heating at 12°C per minute to a final temperature of 300°C] revealed that essentially all light boiling components, including residual epichlorohydrin, had been removed. HPLC analysis revealed complete conversion of the dicyclopentadiene diphenol with saturated cyclopentane ring to product. Titration of a pair of aliquots of the product demonstrated an average of 17.57 % epoxide (244.9 epoxide equivalent weight). Titration of epoxy resins is described by Jay, R.R., "Direct Titration of Epoxy Compounds and Aziridines", Analytical Chemistry, 36, 3, 667-668 (March, 1964). Briefly, in our adaptation of this method, the weighed sample (sample weight ranges from 0.1 - 0.2 g using a scale with 3 decimal place accuracy) was dissolved in dichloromethane (15 mL) followed by the addition of tetraethylammonium bromide solution in acetic acid (15 mL). The resultant solution treated with 3 drops of crystal violet solution (0.1 % w/v in acetic acid) was titrated with 0.1N perchloric acid in acetic acid on a Metrohm 665 Dosimat titrator (Brinkmann). Titration of a blank consisting of dichloromethane (15 mL) and tetraethylammonium bromide solution in acetic acid (15 mL) provided correction for solvent background.

0194Example 3 - Thermally Induced Curing of Dicyclopentadiene Di lycidyl Ether with

0195Saturated Cyclopentane Ring using 4,4^,-Diaminodiphenyl methane

0196Dicyclopentadiene diglycidyl ether with saturated cyclopentane ring (0.1220 gram, 0.000498 epoxide equivalent) from Example 2 and 4,4'-diaminodiphenyl methane (0.0247 gram, 0.000498 -NH equivalent) were weighed into a glass vial and thoroughly ground together to a homogeneous fine powder. Differential scanning calorimetry (2910 Modulated DSC, TA Instruments) analysis of portions (8.50 and 9.20 milligrams) of the blend was completed using a rate of heating of 7 °C per minute from 25 °C to 400 °C under a stream of nitrogen flowing at 35 cubic , centimeters per minute. A second scan using the aforementioned conditions gave an average glass transition temperature of 220.6 °C. A third scan using the

0197aforementioned conditions gave an average glass transition temperature of 221.7 °C. The product from the DSC analyses was a transparent, amber colored, rigid solid.

0198Example 4 - Thermally Induced Curing of Dicyclopentadiene Diglycidyl Ether with

0199Saturated Cyclopentane Ring using Dicyanadiamide

0200Dicyclopentadiene diglycidyl ether with saturated cyclopentane ring (0.4010 gram, 0.00164 epoxide equivalent) from Example 2 and powdered (unaccelerated) dicyandiamide (0.0160 gram, 4 % weight of the dicyclopentadiene diglycidyl ether with saturated cyclopentane ring) were weighed into a glass vial and thoroughly ground together to a homogeneous fine powder. DSC analysis of portions (7.90 and 8.30 milligrams) of the blend was completed using a rate of heating of 7 °C per minute from 25 °C to 350 °C under a stream of nitrogen flowing at 35 cubic centimeters per minute. An endotherm was observed with an average 176.7 °C onset, a 209.3 °C minimum, a 264.2 °G endpoint and an enthalpy of 175.1 joules per gram. An exotherm was observed with an average 281.5 °C onset, a 313.8 °C maximum and a 348.3 °C endpoint accompanied by an enthalpy of 28.7 joules per gram. A third scan using the aforementioned conditions gave an average glass transition temperature of 208.1 °C. The product from the DSC analyses was a transparent, amber colored, rigid solid.

0201Example 5 - Thermally Induced Curing of Dicyclopentadiene Diglycidyl Ether with

0202Saturated Cyclopentane Ring using Dicyclopentadiene Diphenol with Saturated Cyclopentane Ring and Catalyst

0203Dicyclopentadiene diglycidyl ether with saturated cyclopentane ring (0.2077 gram, 0.00085 epoxide equivalent) from Example 2, dicyclopentadiene diphenol with saturated cyclopentane ring (0.1418 gram, 0.00085 hydroxyl equivalent weight) from Example 1 and benzyltriethylammonium chloride (0.0037 gram, 0.000016 mole) were weighed in a dry nitrogen glovebox into a glass vial followed by addition of uninhibited, anhydrous tetrahydrofuran (2 milliliters). The dicyclopentadiene diphenol with saturated cyclopentane ring from Example 1 was used after additional drying in the vacuum oven at 175 °C to remove residual phenol. The resultant solution was devolatilized at ambient temperature (24 °C) in the glovebox followed by drying in the vacuum oven at room temperature (22 °C) for 2 hours. DSC analysis (2910 Modulated DSC, TA Instruments) of portions (8.50 and 9.10 milligrams) of the blend was completed using a rate of heating of 7 °C per minute from 25 °C to 400 °C under a stream of nitrogen flowing at 35 cubic centimeters per minute. A second scan using the aforementioned conditions gave an average glass transition temperature of 231.2 °C. The product from the DSC analyses was a transparent, amber colored, rigid solid.

0204Example 6 - Replicate of Thermally Induced Curing of Dicyclopentadiene Diglycidyl

0205Ether with Saturated Cyclopentane Ring using Dicyclopentadiene

0206Diphenol

0207With Saturated Cyclopentane Ring and Catalyst Dicyclopentadiene diphenol with saturated cyclopentane ring (0.1418 gram, 0.00085 nominal hydroxyl equivalent) from Example 1 after additional drying in the vacuum oven at 175 °C was used as a curing agent for the corresponding epoxy resin of dicyclopentadiene diphenol with saturated cyclopentane ring (0.2077 gram, 0.00085 epoxide equivalent) from Example 2. Both components were weighed into a glass vial which was then transferred into the dry nitrogen glovebox.

0208Benzyltriethylammonium chloride (0.0037 gram, 0.000016 mole) was added to the ^' vial followed by anhydrous tetrahydrofuran (2 milliliters). Stirring provided a solution which was poured into an aluminum dish and tetrahydrofuran evaporated off in the glovebox. After removal from the glovebox and drying in the vacuum oven for 2 hours under ambient conditions, DSC analysis of a portion (8.50 milligrams) of the blend was completed using a rate of heating of 7 °C per minute from 25 °C to 400 °C under a stream of nitrogen flowing at 35 cubic centimeters per minute. A second scanning was completed using the aforementioned conditions, resulting in a glass transition temperature of 229.7 °C. The product from the DSC analysis was a transparent, amber colored, rigid solid.