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WO2011136846A1 - Composés polycyclopentadiènes présentant un noyau cyclopentane saturé - Google Patents

Composés polycyclopentadiènes présentant un noyau cyclopentane saturé Download PDF

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WO2011136846A1
WO2011136846A1 PCT/US2011/000710 US2011000710W WO2011136846A1 WO 2011136846 A1 WO2011136846 A1 WO 2011136846A1 US 2011000710 W US2011000710 W US 2011000710W WO 2011136846 A1 WO2011136846 A1 WO 2011136846A1
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polycyclopentadiene
formula
cyclopentane ring
reaction
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Robert E. Hefner Jr.
Michael J. Mullins
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Dow Global Technologies LLC
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
    • C07D303/28—Ethers with hydroxy compounds containing oxirane rings
    • C07D303/30—Ethers of oxirane-containing polyhydroxy compounds in which all hydroxyl radicals are etherified with oxirane-containing hydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C08G59/08—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols from phenol-aldehyde condensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C08G59/245—Di-epoxy compounds carbocyclic aromatic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/56—Ring systems containing bridged rings
    • C07C2603/58—Ring systems containing bridged rings containing three rings
    • C07C2603/60—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members
    • C07C2603/66—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members containing five-membered rings
    • C07C2603/68—Dicyclopentadienes; Hydrogenated dicyclopentadienes

Definitions

  • the present disclosure relates to polycyclopentadiene compounds and in particular to polycyclopentadiene compounds with a saturated cyclopentane ring.
  • 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
  • Polycyclopentadiene diphenols are typically prepared via reaction of a Lewis acid catalyst with polycyclopentadiene and an excess of phenol compound.
  • a Lewis acid catalyst notably boron trifluoride
  • 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.
  • polycyclopentadiene compounds of the present disclosure are represented by compounds of the following Formula I:
  • each X is either a hydrogen, a cyano group, a vinylbenzyl group, an allyl group, an acrylate group, or a structure of Formula II:
  • 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 R 1 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
  • Embodiments of the present disclosure also include a curable
  • composition 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.
  • the polycyclopentadiene compounds of Formula I can be used in forming a cured or partially cured composition.
  • 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).
  • the curable composition can include the polycyclopentadiene compound of Formula I in the form of a curing agent (hardener).
  • the resin and/or the hardener of Formula I can be used either alone or in combination with other compounds as discussed herein.
  • X of Formula I is hydrogen
  • the polycyclopentadiene compound can be used as a hardener.
  • 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.
  • the 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.
  • the various embodiments the
  • polycyclopentadiene 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
  • polycyclopentadiene 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.
  • 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.
  • polycyclopentadiene monoaldehydes and/or dialdehydes with a saturated cyclopentane ring allows for the
  • polycyclopentadiene 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.
  • thermoset refers to a polymer that can solidify or “set” irreversibly when heated.
  • curable means that the composition is capable of being subjected to conditions which will render the composition to a cured or thermoset state or condition.
  • B-stage 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.
  • 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.
  • alkoxy group refers to groups where at least one hydrocarbon alkyl group is bonded to an oxygen.
  • a group represented by the formula -O-R or -O-R-O-R is an alkoxy group, where R is the hydrocarbon alkyl group.
  • alkenyl group means an unsaturated, linear or branched
  • monovalent hydrocarbon group with one or more olefmically unsaturated groups i.e., carbon-carbon double bonds
  • olefmically unsaturated groups i.e., carbon-carbon double bonds
  • alkenyloxy group refers to groups where at least one hydrocarbon alkenyl group is bonded to an oxygen.
  • poly means that a compound has two or more of a particular moiety.
  • cyclopentadiene moieties is a specific polycyclopentadiene.
  • compound refers to a substance composed of atoms or ions of two or more elements in chemical combination.
  • polycyclopentadiene compounds of the present disclosure are represented by a compound of the following Formula I:
  • 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 R 1 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
  • n can have an average value from zero to 20.
  • 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.
  • the alkyl group and the alkoxy group can preferably contain 1 to 2 carbon atoms.
  • the alkenyl group and the alkenyloxy group can preferably contain 1 to 3 carbon atoms.
  • Q when Q is an alkyl group it can preferably contain 1 to 2 carbon atoms.
  • 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.
  • n and n can preferably be zero and Q and T can preferably be hydrogen to provide a compound of Formula IV:
  • polycyclopentadiene compounds of the present disclosure may also be referred to as a dicyclopentadiene compound.
  • polycyclopentadiene will be used, where it is understood that this term may be replaced with dicyclopentadiene when n is zero.
  • polycyclopentadiene diphenols with the saturated cyclopentane ring (C ring) of the present disclosure can be produced from polycyclopentadiene
  • polycyclopentadiene monoaldehydes and/or polycyclopentadiene monoketones having a saturated cyclopentane ring.
  • polycyclopentadiene monoaldehydes and/or polycyclopentadiene monoketones having a saturated cyclopentane ring.
  • monoaldehydes 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.
  • polycyclopentadiene monoaldehyde with a saturated cyclopentane ring includes the compound of Formula V:
  • the hydroformylation can occur at a pressure of 1 to 250 atmospheres (atm) and a temperature of 20 °C to 250 °C.
  • the syngas can contain varying amounts of carbon monoxide (CO), hydrogen (3 ⁇ 4) 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.
  • the polycyclopentadiene diphenols have the saturated cyclopentane ring, but it is possible for unsaturated
  • cyclopentane rings to be formed.
  • 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.
  • suitable ligands include carbon monoxide and
  • organophosphine ligands having the general formula PR 2 R 3 R 4 where each R 2 , R 3 , and R 4 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).
  • hydroformylation minor amounts, typically 5-25 weight percent (wt. %) or less of the total reaction products, of polycyclopentadiene
  • dialdehydes 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
  • polycyclopentadiene monoaldehydes from the polycyclopentadiene dialdehydes.
  • polycyclopentadiene 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
  • polycyclopentadiene 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.
  • polycyclopentadiene diphenols can include, but is not limited to, the compound of Formula VI: Formula VI)
  • n, m, R and Q are as herein defined.
  • 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,
  • 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.
  • Tg glass transition temperature
  • 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.
  • 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.
  • 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.
  • 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.
  • excess phenolic reactant can be removed by distillation.
  • Increased oligomer content favors higher hydroxyl functionality, which may be highly beneficial for certain end uses.
  • the present disclosure employs the molar ratio provided herein to produce products rich in polycyclopentadiene diphenol, and low in oligomers.
  • polycyclopentadiene diphenols of the present disclosure can also optionally include the use of a solvent.
  • 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.
  • Suitable 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.
  • 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
  • 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.
  • the acidic catalyst can be removed by neutralization, for example by washing or extraction with water.
  • excess phenol can be removed from the product, for example, by distillation or extraction.
  • 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.
  • 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.
  • the 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.
  • 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 dicycl
  • the 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.
  • 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.
  • 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.
  • 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;
  • Polycyclopentadiene 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
  • 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.
  • 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).
  • 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.
  • 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;
  • Suitable 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.
  • alkali metal hydrides include, for example, sodium hydride and potassium hydride, with sodium hydride being most preferred.
  • Suitable 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,
  • tetraoctylammonium chloride tetrabutylammonium bromide, tetramethylammonium chloride, tetramethylammonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium iodide,
  • ethyltriphenylphosphonium chloride ethyltriphenylphosphonium bromide, ethyltriphenylphosphonium iodide, and combinations thereof.
  • Suitable 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, ⁇ , ⁇ -dimethylformamide, dimethylsulfoxide, diethyl ether, tetrahydrofuran, 1,4-dioxane, dichloromethane, chloroform, ethylene dichloride, methyl chloroform, ethylene glycol dimethyl ether, ⁇ , ⁇ -dimethylacetarnide, acetonitrile, propylene glycol monomethyl ether,
  • isopropanol 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.
  • HPLC high pressure liquid chromatography
  • Recovery 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.
  • Oligomers 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:
  • R 1 is as defined herein.
  • cyclopentane ring of the present disclosure 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.
  • advanced epoxy resins thermosettable
  • 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,
  • 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.
  • 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.
  • Reaction 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.
  • Suitable 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.
  • Suitable 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.
  • Suitable 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.
  • the 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 A1C1 3 BF 3 , FeCl 3 , TiCl 4 , ZnCl 2 , SnCl 4 ; protonic acids such as HC1; H 3 P0 4 ; 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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 ally
  • the 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.
  • Reaction 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.
  • Suitable 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.
  • Suitable 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.
  • the 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.
  • B-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
  • the alkyl group can be unsubstituted or substituted.
  • X is unsubstituted.
  • each X is the same.
  • 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.
  • Allylation 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.
  • a direct allylation reaction can include a halide, an alkaline agent, and optionally a catalyst, such as a phase transfer catalyst.
  • the halide include, but are not limited to, allyl halides and methallyl halides.
  • allyl halides include, but are not limited to, allyl chloride and allyl bromide.
  • 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.
  • Direct 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.
  • the allyl halide may be stoichiometrically reacted with the hydroxy groups of the polycyclopentadiene diphenol.
  • 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.
  • 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.
  • the partially allylated compounds may be less preferred for some applications, they are within the scope of the present disclosure.
  • a preferred process uses a transcarbonation reaction wherein
  • allylmethyl 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.
  • Isomerization 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
  • Acrylates 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).
  • an acid chloride such as, acryloyl chloride (2-propenoyl chloride) or methacryloyl chloride
  • a Schotten-Baumann type .reaction as described in C. Schotten, Ber. 17, 2544 (1884) and E. Baumann, ibid. 19, 3218 (1886).
  • one or more basic acting substances such as aqueous sodium hydroxide, triethylamine or pyridine, can be employed.
  • polymerization inhibitors such as, for example, hydroquinone.
  • Transesterification reaction may also be employed to prepare acrylates and meth
  • Rh(CO) 2 acetylacetonate
  • n-butyldiphenylphosphine available from Organometallics, Inc (E. Hampstead, NH,
  • Methylisobutylketone (4-methyl-2-pentanone), >99%, manufactured by Eastman Chemical Company, available from Sigma-Aldrich. Epichlorohydrin available from The Dow Chemical Company.
  • a 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:H 2 ) at 20 °C.
  • 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
  • Dicyclopentadiene monoaldehyde with saturated cyclopentane ring 43.31 grams, 0.2845 mole uncorrected
  • molten phenol 850.2 grams, 9.0345 moles
  • 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
  • thermostatically controlled heating mantle
  • 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.
  • 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 ⁇ , 4.6 x 150 mm) with an Eclipse ® (Agilent) XDB-C8 analytical guard column (5 ⁇ , 4.6 x 12.5 mm). The columns were maintained in the chromatograph oven at 40°C.
  • Acetonitrile and water 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
  • 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.
  • DI deionized
  • FTIR 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.
  • 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.
  • GC analysis Gas chromatographic (GC) analysis [Hewlett Packard 5890 Series II Gas Chromatograph using a 60m x 0.248mm x 0.25 ⁇ J&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.
  • GC Gas chromatographic
  • Dicyclopentadiene 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.
  • Dicyclopentadiene 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.
  • Dicyclopentadiene 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
  • 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
  • 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.
  • Benzyltriethylammonium 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.

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Abstract

L'invention concerne des composés polycyclopentadiènes représentés par des composés de la Formule suivante I : dans laquelle les X représentent chacun un hydrogène, un groupe cyano, un groupe vinylbenzyle, un groupe allyle, un groupe acrylate ou une structure de Formule II :; n a une valeur moyenne de zéro à 20 ; les m ont chacun indépendamment une valeur de zéro à 3 ; les R représentent chacun indépendamment un halogène, un groupe nitrile, un groupe nitro, un groupe alkyle, un groupe alcoxy, un groupe alcényle ou un groupe alcényloxy, où le groupe alkyle, le groupe alcoxy, le groupe alcényle et le groupe alcényloxy contiennent chacun indépendamment 1 à 6 atomes de carbone ; les R1 représentent chacun indépendamment hydrogène ou un groupe méthyle, les Q représentent chacun indépendamment hydrogène ou un groupe alkyle contenant 1 à 6 atomes de carbone, et T représente soit hydrogène soit une structure de Formule III.
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