TW201202284A - Polycyclopentadiene compounds with saturated cyclopentane ring - Google Patents

Abstract

Polycyclopentadiene compounds represented by compounds of the following Formula I: (Formula I) 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); 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 structure of Formula III (Formula III) with the proviso that when X is a cyano group, then R is not an alkenyl group or an alkenyloxy group.

Description

201202284 VI. Description of the Invention: [Technical Field 3 of the Invention] The present disclosure relates to a polycyclopentadiene compound, and particularly to a polycyclopentadiene compound having a saturated cyclopentane ring. L. Prior Art 3 Backgrounds Various examples of polycyclopentadiene diphenols are found in U.S. Patent Nos. 3,419,624 and 4,546,129. Polycyclopentadiene diphenols can be used to prepare certain promoted epoxy, cyanate, and propylene thermosettable resins which have particular physical and/or mechanical properties due to the presence of the dicyclopentadienyl moiety. Polycyclopentadiene diphenol is typically prepared by reacting a Lewis acid with polycyclopentadiene and an excess of a compound. The strong Lewis acid catalysts required for efficient condensation reactions, especially boron trifluoride, have handling difficulties, particularly due to moisture sensitivity and high reactivity. Moreover, such catalysts may be susceptible to non-selectivity, resulting in large scale oligopolymerization and/or co-product formation. SUMMARY OF THE INVENTION For various embodiments, the polycyclopentadiene compound of the present disclosure is represented by a compound of the following formula I: 201202284 (chemical formula i) (R)m

Wherein each X is a hydrogen, a cyano group, a monovinylbenzyl group, an allyl group, an acrylate group, or one of the formula II: (Formula II)

η has an average value from 〇 to 20; each m independently has a value from 0 to 3; each R is independently a halogen, a nitrile group, a stone Schottky group, an alkyl group a monoalkoxy group, a monoalkenyl group, or an alkenyloxy group, wherein the alkyl group, the alkoxy group, the alkenyl group, and the alkenyloxy group are each independently The ground contains 1 to 6 carbon atoms; each R1 is independently hydrogen or a methyl group, and each Q is independently hydrogen or an alkyl group having 1 to 6 carbon atoms, and the T is hydrogen or One of Chemical Formula III 201202284 (Chemical Formula III) (R)m

The proviso is that when the 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 composition comprising a polycyclopentadiene compound of formula j, which optionally comprises a curing agent and/or a catalytic amount of one of the catalysts and/or one One of the curing acceleration accelerators. For various embodiments, the polycyclopentadiene compound of the formula 可 can be used to form a cured or partially cured composition. For various embodiments, the curable composition may comprise a polycyclopentadiene compound of formula I in the form of a heat curable resin (e.g., when X is not hydrogen in the compound of the formula). For various embodiments, the curable composition may comprise a polycyclopentadiene compound of the formula of a curing agent (hardener) type. For various embodiments, the resin and/or hardener of Formula I may be used alone or in combination with other compounds discussed herein. For example, when the chemical formula is hydrogen, the polycyclopentadiene compound acts as a hardener. For various embodiments, the hardener of the compound of Chemical Formula 1 can be used in combination with a plurality of different resins, including, without limitation, a resin derived from Chemical Formula I; a polyurethane resin, a polyester resin; a thermosetting monomer, For example, an epoxy resin, a di- or polyisocyanate, and a di- or polymaleimide; and the like. The above summary of the disclosure is not intended to describe each disclosure of the present invention 201202284 (four) or parent. The lower ship Ming system is more specifically illustrated. The disclosure of the present disclosure is provided by way of example, and the examples can be used in various combinations. In each of the examples, the list is for a specific representative group and should not be construed as an exclusive list. DETAILED DESCRIPTION OF THE INVENTION The present disclosure provides a polycyclopentene which can be used as a curing agent for an epoxy resin and a thermosetting monomer and/or a thermosetting oligomer. An example of a polycyclopentadiene compound of the present disclosure is not limited to a polycyclopentadiene dimer having a saturated cyclopentane ring. For the present disclosure, the polycyclopentadiene having a saturated cyclopentane ring is applied to a polycyclopentanyl group having a -saturated cyclopentane ring and/or a single =. Condensation of a polycyclopentadiene having a saturated ring ring and/or a mono- and _ or a substituted phenolic compound produces a corresponding polycyclopentadiene having a saturated 2 pentane. For various enthalpy, polycyclopentane H with saturation pentane can also be hydrogenated in situ from a pentadiene monoaldehyde and/or a monoketone having a saturated cyclopentane ring during hydrohalogenation. And formed. Then, a polycyclopentadiene diphenol having a saturated cyclopentane ring can be used to prepare the heat-curable monomer of the present disclosure, such as a polycyclopentadiene diglycidyl ether having a saturated cyclopentane ring, a polycyclodecadiene dicyanate of a saturated cyclopentane ring, and/or a polycyclopentadienyl divinyl benzoate ether having a saturated cyclopentane ring or the like. For various embodiments, the polycyclopentadiene compound of the present disclosure is used to achieve a high degree of functionality with a relatively low molecular weight of 201202284, using a polycyclopentanyl monoaldehyde having a saturated cyclopentane ring and/or a dialdehyde. This allows for a relatively low melt viscosity curable composition. The curable composition formed by such a polycyclopentadiene compound can also provide a cured composition having a promoted glass transition temperature (Tg). In addition, it is contemplated that the polycyclopentadiene compounds of the present disclosure will also provide improved properties in terms of wetness and corrosion, as well as enhanced electrical properties of the cured composition, particularly dissipative factors. As used herein, "a,""""""""""""""""Conclusions of ''and πinclude' and its variants are used in the context of the description and patent application, and such terms are not intended to be limiting. The term "and/or" is used to mean one, one or more, or all of the items listed. The range of values by endpoints is inclusive of all values included in the range (eg, 1 to 5 inclusive) 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.) "thermoset" as used herein refers to a polymer that irreversibly cures or "solidifies" when heated. "Curable π "cured π, "heat-curable" and "heat-cured" are used synonymously everywhere, and means that the composition is capable of accepting the composition in a cured or heat-cured state or Conditions of the situation. The term "Β-stage" as used herein means that a thermosetting resin has been thermally reacted beyond the Α-stage to render the product completely soluble in a solvent such as an alcohol or ketone. "Alkyl group" By language is meant a saturated linear or branched monovalent hydrocarbon group including, for example, methyl, ethyl, n-propyl, isopropyl, 8201202284 tributyl, pentyl, hexyl, etc. ''Alkane The term "oxy group" refers to a group in which at least one alkoxy group is bonded to an oxygen. For example, a group represented by the formula -0-R or -OR-0-R a monoalkoxy group, wherein R is via an alkyl group. The term "alkenyl group" means one of having one or more hydrocarbon ethylenically unsaturated groups (eg, a carbon-carbon double bond). Unsaturated linear or branched monovalent hydrocarbon group, such as a vinyl group. The term 'enoxy group' refers to a group in which at least one hydroalkenyl group is bonded to an oxygen bond. As used herein, the word "poly" means a compound having one or two of a particular part. For example, having two cyclopentanes One of the (dicyclopentadiene) cyclopentadiene compounds is a special polycyclopentadiene. As used herein, "compound" means a chemical combination of atoms or ions of two or more elements. One of the characteristics of the composition. For various embodiments, the polycyclopentadiene compound of the present disclosure is represented by one of the following chemical formula I: (Chemical Formula I) (R)m

9 201202284 wherein each X is a hydrogen, a cyano group (N tri C —-), a monovinyl benzoyl group, an allyl group, an acrylate group, or a formula II A structure: (Chemical Formula II)

Wherein η has an average value from 〇 to 20; each m independently has a value from 0 to 3; each R is independently a halogen, a nitrile group, a stone Schottky group, an alkyl group a group, a monoalkoxy group, a monoalkenyl group, or an alkenyloxy group, wherein each of an alkyl group, an alkoxy group, an alkenyl group, and an alkenyloxy group Independently containing from 1 to 6 carbon atoms; each R1 is independently hydrogen or a methyl group, each Q is independently hydrogen or an alkyl group containing from 1 to 6 carbon atoms; and T-hydrogen Or a compound of formula III (chemical formula III)

The proviso is that when the 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 compound is preferably selected from the group consisting of fluorine, gas, bromine, and the like. Various embodiments also provide that η 10 201202284 may have an average value from 0 to 20. Preferably, n has an average value from 〇 to 8. More preferably, η has an average value from 〇 to 3, and optimally, η has an average value from 0 to 2. For various embodiments, the alkyl group and the alkoxy group may preferably contain from 1 to 2 carbon atoms. For various embodiments, the fluorenyl group and the alkenyloxy group may preferably contain from 1 to 3 carbon atoms. For various embodiments, when q is an alkyl group, it may preferably contain from 丨 to 2 carbon atoms. For various embodiments, the R group can also be a fused ring group that produces a naphthalene structure having a ring group containing a 〇χ group, such as a naphthoquinone (1-naphthol and/or 2-Qin), tetrahydronaphthalene, sterol, and the like. For various embodiments, m&n may preferably be deuterium, and Q and deuterium may preferably be hydrogen to provide a compound of formula IV: (Formula III)

Where 'X is as provided herein. As understood, the polycyclodecadiene compound of the present disclosure may also be referred to as a dicyclopentadiene compound when η is oxime. However, when used here, polycyclopentadiene is used, and it is necessary to understand that when η is 〇, this term can be replaced by 201202284 bicyclononadiene. Preparation of Polycyclopentadiene Diphenol with a Saturated Cyclopentane Ring The polycyclopentadiene diol having a saturated cyclopentane ring (c 5 ring) may have a self-saturated cyclopentane ring. Polycyclopentadiene monoaldehyde and / or polycyclopentadiene monoketone production. For various embodiments, polycyclopentadiene monoaldehyde can be used using syngas, a ligand, and a transition metal (from Group 3 to 1 lanthanum) catalysts such as 'G, Longoni et al.' J. 〇 f Molecular

Catalysis 68, 7-21 (1991) or more generally by Kirk-Othmer, ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY, 2001, pages 1-17 via polycyclopentadiene, especially dicyclopentadiene, Produced by hydroformylation. Variations of this method include a method of using a mixed polar/non-polar solvent to mitigate catalyst cycling and product separation problems (U.S. Patent No. 6,307,108 B1). An example of such a polycyclopentadiene monoaldehyde having a saturated cyclopentane ring comprises a compound of formula V: (Formula V)

For various embodiments, the hydroformylation can be at a pressure of from 1 to 250 atmospheres (atm) and from 20 °C to 25 Torr. (: One of the temperatures occurs. For various embodiments, the syngas may contain varying amounts of one of carbon monoxide (CO), hydrogen (h2), and possibly an inert gas. Intermediates formed during hydroformylation may include cyclopentyl The alkane ring has a compound of an olefin. Depending on the processing conditions, 12 201202284 an olefin, a saturated, or a mixture of products can be obtained. As discussed herein, preferably, the polycyclopentadiene diphenol has a saturated cyclopentane ring, However, an unsaturated saturated cyclopentane ring may be obtained. Preferably, less than 50% (%) of the polycyclopentadiene diphenol produced during hydroformylation includes an olefin (eg, unsaturated) The reaction can also be carried out using a rhodium-free catalyst disclosed in US 7,321,068, etc. at a high synthesis pressure of 200-350 atm. Examples of suitable ligands include carbon monoxide and an organophosphine ligand having the general formula PR2R3R4. Wherein each of R2, R3, and R4 is a substituted or unsubstituted alkyl group, an aryl group, an arylalkyl group, a aryl group, a halide, or a combination thereof. Restricted Butyl diphenyl phosphine. One example of a suitable catalyst includes, without limitation, Rh(CO) 2 (ethyl phthalate). During hydrogenation, a trace amount, typically the total reaction product. 5-25% by weight (wt.%) or less, the polycyclopentadiene can also be produced together with polycyclopentadiene monoaldehyde. If desired, polycyclopentadiene monoaldehyde can be combined with polycyclopentene The pentadiene dialdehyde is partially or completely separated. For example, a distillation process can be used to separate the polycyclopentadiene monoaldehyde from the polycyclopentadiene dialdehyde. In an additional embodiment, various weight percentages have saturated cyclopentane. The polycyclopentadiene monoaldehyde of the alkane ring may also be mixed with the polycyclopentadiene dialdehyde. The composition of the polycyclopentadiene monoaldehyde and the polycyclopentadiene dialdehyde can be used to control the formed curable composition. The amount of functionality. Novolac chemistry can be used to form polycyclopentadiene diphenol from polycyclopentadiene monoaldehyde. Oligomers can also be present in polycyclopentadiene diphenol. Therefore, polycyclopentadiene A composition of a diphenol and a polyphenol having a 13 201202284 saturated cyclopentane ring can be produced in another embodiment of the present disclosure. This pentadiene oligomer An example of diphenols include without restriction of a compound having the formula vi: (Formula VI)

Wherein η, m, R and Q are as defined herein. For various embodiments, the polycyclopentazenone having a saturated cyclopentane ring for use in the present disclosure can be produced via a multi-step synthesis, for example, 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 heated to above 1 揭示 as disclosed in Kirk-Othmer, ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY, Third Edition, Volume 7, pages 417-419 (1979). Prepared at a temperature of 〇 °c. All references cited herein are hereby incorporated by reference in their entireties. The composition of a polycyclopentadiene mono-, di-acid and/or monoketone having a saturated cyclopentane ring as described herein controls the amount of functionality in a particular curable composition 14 201202284. Thus, for example, the parent-density density of the curable composition of the present disclosure can be adjusted based on the relative amount of polycyclic red bismuth and polycyclopentadiene (tetra) used in the towel (eg, reduced or ~ In this way, the light functional amount is lacking, and the balance such as the breaking temperature (Tg) of the glass is adjusted to the amount and/or the other properties (for example, toughness) of the silk is controlled. The disclosure of the content of the dicyclopentadiene and cyclopentane 4 in the polycyclopentadienic acid of the disclosure. The bicyclic red and/or poly-alkene can be formed by using cyclopentadiene by Diels-Alder chemistry. Wherein, as discussed herein, the average value of the chemical core can be edited (4)/thus, for example, when the polycyclopentadiene moiety of the polycyclopentadiene monomer is oligomeric, which may have an average system η value distribution from 2 to 5. For the pot, the example '11 may have a value of G or 1. The ability to control the dicyclopentadiene and/or polycyclopentadiene portion of the polycyclopentadiene It is also permissible to simultaneously control and/or trim while maintaining or possibly increasing the possible moisture resistance of the cured composition. The ability to combine densities. For various embodiments, the formation of a polycyclopentadiene with a saturated cyclopentane ring and/or the money and ring society "red ketone then °" tangled t cost disclosure content has The polycyclopentane ring of the saturated cyclopentane ring is a dilute. For the various embodiments, the condensation reaction of the polycyclic ring 4 and/or the polycyclopentadiene phase may have a ratio of 1:20 to 1:6. From 1:15 to 1:8, the molar ratio. For various embodiments, the condensation reaction can occur in the presence of -@catalyzed, based on the weight of the use, the acid catalyst is preferably from (UW) % by weight (wt%), and more preferably from 〇(1) by weight 15 201202284%. For various examples, the phenols used in the condensation reaction may include, without limitation, phenol, substituted phenol 'o-cresol, m- A combination of indophenol, p-nonanol, 2,4-dinonylphenol, 2,6-dimethylphenol, 1-naphthol, 2-naphthol, and the like, higher than 1:2〇 A molar ratio of phenol or substituted phenol can also be used, but this requires additional energy's. Therefore, it is necessary to recover and recycle excess phenol or substituted phenol. For example, an excess of the phenol reactant can be removed by distillation. A condensation reaction using a large excess of the discretion and/or substituted S is found to be advantageous for polycyclopentadiene diphenol having a saturated cyclopentane ring. a product which is abundant and has a very low polydispersity in the oligomer system. Similarly, when the amount of phenol and/or substituted phenol is reduced, a polycyclopentadiene diphenol having a saturated cyclopentane ring is used. At the expense of the content, the polymer will increase. The increased oligomer content favors higher hydroxyl functionality, which is highly advantageous for certain end uses. Therefore, 'although extremely large amounts of phenol and/or substituted Thereafter, the present disclosure can be used to produce a product rich in polycyclopentadiene diphenol and low in oligomers using the molar ratios provided herein. The s-reaction of the polycyclopentadiene which forms the present disclosure for various embodiments may also optionally include the use of a solvent. For these examples/reads, the reaction may be inert and the reaction product may also be used. The granules may additionally be used as a supplement for the self-condensation of water. The reactants or solvents are advantageous for maintaining a suitable reaction medium. Suitable for the catalyzed acidity of the catalyst; metal hydride, ^ instrument, 5! For example, silk acid, sulfuric acid, rolling, alumina, magnesium oxide; there are 16 201202284 organic acid, such as p-toluene acid, oxalic acid , 3-巯-1-propanthic acid, and combinations thereof. For various embodiments, 3-indol-1-propanesulfonic acid is a preferred acidic catalyst or cocatalyst. Surprisingly, it has been found that 3-indol-1-propane sulfonic acid is also highly selective in forming polycyclopentadiene diphenol without the need to azeotropically remove water from the reaction. Conversely, the water system remains in the reactor without quenching the reaction. The reaction temperature and time are in a variety 'but can be from about 5 minutes to about 48 hours, and a reaction temperature of from about 20 ° C to about 175 ° C can be used. Preferably, the reaction temperature and time can range from 15 minutes to 36 hours and from 30 minutes. (: to a reaction temperature of about 125 ° C. Preferably, the reaction temperature and time may be from 30 minutes to 24 hours and from 35 ° C to about 75 ° C. At the end of the reaction, the acidic catalyst can be used Neutralization is removed, for example, by washing or extraction with water. Similarly, at the end of the reaction, excess phenol can be removed from the product, for example, by distillation or extraction. Polycyclopentane relative to conventional techniques Dienediol, in addition to the saturated cyclopentane ring, the composition of the present disclosure has a structure in which the two rings are substantially attached to the phlegm-based ring, and such compositions of the prior art have a major The halo ring attachment and the attachment of another phenol ring to the cyclopentyl ring. Thus, the oligomer or polymer prepared using the phenolic hydroxyl group of the present disclosure, relative to the oligomer or polymer The main chain, the polycyclopentadiene moiety is pendant. The structure of the saturated cyclopentane ring or the polycyclopentane ring allows the intermetallic chain hydrophobic association of the developing thermoset. It is also possible to accumulate variants. Wherein, the side suspension structure that can be found in the embodiment of the disclosure can guide the pile of chains Or its molecular confinement within the matrix 17 201202284. Thus, the possibility of hydrophobic association of the pendant polycyclopentadiene moiety is present in the present disclosure and can promote the physical and mechanical properties of the formed cured composition. Polycyclopentadiene diphenol having a saturated cyclopentane ring has, for example, an epoxy resin curing agent for a high performance functional powder coating. When combined with a polyfunctional curing agent, for example, The cyclopentadiene is dilute. When blended, the polycyclopentadiene diphenol having a saturated cyclopentane ring can also serve as a "diluent" to reduce the functionality. The present invention has a saturated cyclopentane ring. Cyclopentadiene diphenol can be used to make an epoxy resin such as bis-A diglycidyl, 10-(2',5'-dihydroxyphenyl)-9,10-dihydro-9-oxa -10-phosphaphenanthrene-10-oxide (DOP-HQ) diglycidyl ether, dicyclopentadiene diphenol diglycidyl ether, and other epoxy resins, linearly promoted to produce side suspensions A thermosettable composition of a saturated poly or dicyclopentadienyl moiety. Formed Advanced Epoxy It can be cured with a curing agent or with other thermosetting monomers such as polycyanates. Improved moisture and corrosion resistance and promoted electrical properties, especially dissipation factors, for these advanced steps Resin is contemplated. For various embodiments, it is additionally recognized that when "n" is greater than 1, additional hydrocarbon bodies are added to the side suspension side chains and may advantageously impact the physical and mechanical properties of the thermoset. Side suspension side bonds The stacking can advantageously increase the toughness of the thermosetting matrix and induce hydrophobic bonding between the chains. In addition to the foregoing as a curing agent for epoxy resins or for the purpose of promoting the reaction of epoxy resins, the present disclosure has The saturated cyclopentane ring of polycyclopentadiene diphenol can also be used as a precursor to another thermosetting resin. These heats 18 201202284 solid resins include cyanate esters, epoxy, allyl 'allyloxy, internal return Mannyl ester, and vinyl stearic methyl ether (and other ethylenically unsaturated) resins, which are used to prepare coatings, especially functional powder coatings, and have high discontinuity, solvent resistance, moisture resistance Wear resistance, Protective coatings or structural laminates or composites of toughness; filament windings; mold potentials, cuts; scales; encapsulants; multilayer electronic circuits; integrated circuit packages (such as substrates) "); aerospace composites; and formulations with other resins such as poly(maleimide), polyester. Due to the presence of a polyfluorene ring having a saturated cyclopentane ring = a dilute moiety, a thermoset having improved wettability and resistance to decay and promoting electrical properties, particularly dissipation factors, is expected. A diglycidyl ether having a saturated cyclopentane ring and a polycyclopentadienyl glyceryl ether having a saturated cyclopentane ring and a composition thereof additionally containing an oligomer It can be prepared as above. The initial step in the preparation of the aforementioned composition of the present disclosure is generally due to the presence of an inhibitory substance, in the presence or absence of a catalyst, and in the presence or absence of a plurality of solvents, A polypentadiene diphenol having a saturated cyclopentane ring is reacted with an epimerol. For various embodiments, the reaction can range from about 20 ° C to about 120 ° C, more preferably from about 30 ° C to about 85%, and most preferably from about 4 Torr. (: occurs to a temperature of about 75 ° C. For various embodiments, the reaction may range from about 4 KPa to about 500 KPa, more preferably from about 4 KPa to about 340 KPa ' and preferably from about 8 KPa to A pressure of about 100 KPa (1 atm) occurs. For various embodiments, the reaction can occur at a time sufficient to complete the reaction, typically from about 1 to about 120 hours, more usually from about 3 to about 72 hours. Typically from about 4 to about 48 hours. 19 201202284 For various embodiments, this reaction also uses from about 1丄1 to 25:1' each preferred base map from about 18:1 to about 1 〇1, and the best system is from about!! to about 5:1 mole table _ 1 non-catalyst is based on the amount of chemical or a large amount of alkali metal or alkaline earth metal hydroxide used, this initial reaction produces a A halo alcohol intermediate product, which reacts with a test substance to convert an adjacent hydroxyl group into an epoxide group. The resulting product is a glycidyl ether compound. Details regarding the preparation of the epoxy resin are US Patent No. 5,736,620; Lee and Neville Handbook of Epoxy Resins, McGraw-Hill (1967); and J0urnal Applied Polymer Science, Vol. 23, pp. 1355-1372 (1972); and U.S. Patent No. 4,623, 701, the entire disclosure of each of which is incorporated herein by reference in its entirety in Suitable for the table!|Alcohol includes, for example, epichlorohydrin, epibromohydrin, epieol, sulfhydryl alcohol, sulfhydryl bromohydrin, decyl iodinol, and the like. The best alcohol is a gas alcohol. A suitable test substance is used to prepare the composition of the present disclosure. Suitable alkaline acting substances include, for example, alkali metal or alkaline earth metal hydroxides, carbonates And bicarbonate, and combinations thereof, etc. Particularly suitable for such compounds include sodium oxynitride, potassium hydroxide, lithium hydroxide, methane hydroxide, barium hydroxide, nitrous oxide money, hydrazine hydroxide, sodium carbonate, Carbonate oblique, carbonic acid clock, carbonic acid, acid breaker, carbonic acid town, manganese carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, magnesium hydrogencarbonate, lithium hydrogencarbonate, calcium hydrogencarbonate, barium hydrogencarbonate, magnesium hydrogencarbonate, etc. Combination of the best Or oxyhydrogen 20 201202284 potassium. Suitable methods for reacting a polycyclopentadiene diphenol having a saturated cyclopentane ring with an alkali metal hydroxide and then reacting with an alcohol of Table ii include For example, sodium hydride and hydrogenation clocks, and sodium hydride is preferred. Suitable catalysts for use in preparing the compositions of the present disclosure include, for example, sulphur compounds such as benzyltrimethyl gasification 4 amps. , benzyltrimethylammonium bromide, tetrabutylammonium hydride, tetrabutylammonium bromide, tetraoctyl ammonium hydride, tetrabutylammonium bromide, tetradecyl ammonium hydride, tetramethyl bromide Ammonium, tetrabutyl chlorinated scale, tetrabutyl bromide, tetrabutyl iodide scale, ethyl tributyl gasification scale, ethyl triphenyl bromide, ethyl triphenyl iodide scale , and combinations of them. Suitable solvents which can be used to prepare the compositions of the present disclosure include aliphatic and aromatic hydrocarbons, halogenated aliphatic hydrocarbons, aliphatic ethers, aliphatic nitriles, cyclic ethers, ketones, decylamines, sulfoxides, aliphatics and rings. Aliphatic secondary and tertiary alcohols, and combinations thereof. Particularly suitable solvents include pentane, hexane, octyl, terpene, xylene, methyl ethyl ketone, decyl isobutyl ketone, N,N-didecyl decylamine, dimercapto sulfoxide, Diethyl ether, tetrahydrofuran, 1,4-dioxane, di-methane, chloroform, dichloroethane, sulfhydryl gas, ethylene glycol didecyl ether, N,N-dimercaptoacetamide, A combination of acetonitrile, propylene glycol monomethyl ether, isopropanol, and the like. The solvent can be removed by conventional means when the reaction is completed, such as vacuum distillation. Another method of the present disclosure is carried out in the absence of a solvent, and epichlorohydrin is used in an amount as a solvent and a reactant. Analytical methods such as high pressure liquid chromatography (HPLC) can be used to simultaneously monitor the reaction of a polycyclopentadiene diphenol having a saturated cyclopentane ring, and an intermediate such as a halogen 21 201202284 alcohol and a final diglycidyl group. Formation of the ether product. The recovery and purification of the composition of the polycyclopentadiene diglycidyl ether having a saturated cyclopentane ring of the present disclosure can be carried out by various methods. For example, gravity filtration, vacuum filtration, centrifugation, water washing or extraction, solvent extraction, decantation, column chromatography, vacuum distillation, falling film evaporation, wipe film distillation, electrostatic condensation, and other treatment methods Etc. can be used. Vacuum distillation is the best method for removing and recovering higher boiling fractions, for example, the unused alcohol. This recycles the surface alcohol and solvent (if used) for recycling. Oligomers may also be present in the polycyclopentadiene diglycidyl ether of the present disclosure having a saturated cyclopentane ring. These are typically epoxidized from an oligomer component present in the precursor of a polycyclopentadiene diphenol having a saturated cyclopentane ring or from a portion of the glycidyl ether moiety. The position is generated by an advanced reaction. The advanced reaction is characterized by the formation of a 2-hydroxypropyl ether linkage (structure of Chemical Formula VII) in the advanced epoxy resin product:

Chemical formula VII

Wherein R1 is as defined herein. A polycyclopentadiene diglycidyl ether having a saturated cyclopentane ring and a blend thereof with one or more conventional epoxy resins can be used to prepare (1) advanced epoxy resin (heat curable) (2) Vinyl ester and ethylene ester resin (3) Epoxy resin adduct, which can be used as (a) epoxy resin curing 22 201202284 agent, (8) for thermosetting polyurethane urethane, polyurea formate Resin, and the reaction of polyisocyanuric acid vinegar (c) is used to prepare polyurethane vinegar, polyurea carboxylic acid vinegar, and polyisocyanate _13 polyol starter, and (4) for other The monomer of the thermosetting resin system, for example, is copolymerized with di- or polyisocyanuric acid to produce a thermosetting substance containing the same. Polycyclopentadiene di-cyanate bis- cyanate having a saturated cyclopentane ring. For various embodiments, the present disclosure has saturated cyclopentane bis- cyanate § by means of - or a plurality of A poly( pentadiene diphenol) having a saturated cyclopentane ring is reacted with one of the stoichiometric amount or some micro-stoichiometric excess (up to about 2% by weight excess) of one of the phenolic hydroxyl groups. preparation. For various embodiments, the reaction is also in the presence of one stoichiometric amount or some microstoichiometric excess (up to about 2% by weight) of one of the base compounds per phenolic hydroxyl group and in one or more suitable Occurs in the presence of a solvent. From about -40 ° C to about 60. (: The reaction temperature is preferably, and _15. (3 to 1 〇 ° (: the reaction temperature is better 'and _i 〇〇 c to 〇. (: the reaction temperature is the best. The reaction time can be large The change 'for example, is a function of the reactants, reaction temperature, solvent used, reaction size, etc., but usually between 15 minutes and 4 hours, and a reaction time of 30 minutes to 90 minutes is preferred. Suitable cyanogen halides include Gasification cyanide and cyanogen bromide. In addition, by j〇hn

The method of Martin and Bauer described in Wiley and Sons, Organic Chemistry, Vol. 61, pp. 35-68 (1983), which is hereby incorporated by reference in its entirety herein in The sodium hydride such as gas or bromine produces the desired functional cyanide. 23 201202284 Appropriate. The test compound includes an inorganic test and a tertiary amine such as sodium oxyhydroxide, dimethylamine, triethylamine, and the like. Triethylamine is the best test. Suitable solvents for the cyanation reaction include water, aliphatic ketones, gasified fumes, aliphatic and cycloaliphatic _ and bisaki, aromatic nucleus, and combinations thereof. Propionyl mercapto ethyl ketone, dioxane, or gas imitation is particularly suitable as a solvent. The dicyano(4) with a saturated ring of money is selective in the presence of a suitable catalyst by heating from (10). . To about. c, preferably cured (heat-cured) by heating from 100 〇C to 300 〇C '. Suitable catalysts include, for example, &amp;L class salts, nitrogen and scaly compounds such as Lewis acid, such as A1C13 BF3, FeCl3, Ticu, ZnCl2, SnCU; protonic acids such as HC1 'H3P〇4, aromatic a compound of a sulfhydryl group, such as an age-dependent succinyl group, a diazepam, a dipyridyl naphthalene; sodium hydroxide, sodium methoxide, phenol sodium, dimethylamine, triethylamine, tributylamine, diterpenoid Cyclo [2 2 2]octane, quinoline, isoquinoline, tetrahydroisoquinolinone, tetraethylammonium hydride, pyridine_N oxide, dibutylphosphine, zinc octoate, tin octoate, benzoic acid Zinc, cobalt sulphonate, cobalt octoate, cobalt acetylacetonate, and the like. Also suitable as a catalyst metal complex, such as a transition metal and a chelate compound of a bi- or tri-coordinated ligand, especially 疋铁, 姑, 辞, 铜, 猛, 错, 钦, 饥, 绍And magnesium ligands. </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; The ring-burning acid, the octanoic acid, and the ethoxylated propionate are the best catalysts. The amount of catalyst used, if any, depends on the structure of the particular catalyst, the structure of the polycyanate to be cured, the cure temperature, the cure time 201202284, and the like. Generally, a catalyst concentration of from about 0.001 to about 2% by weight is preferred. For various embodiments, the Β-stage or prepolymerization of the composition of the cyanuric acid having a saturated cyclopentane ring of the present disclosure can be accomplished by using a lower temperature and/or a shorter curing time. The curing of the thus formed Β stage (prepolymerized) resin can then be accomplished at a later time or immediately after the Β stage (prepolymerization) by increasing the temperature and/or curing time. Unless the other functionality is present in the polycyanate participating in the curing process, the cured (thermoset) product prepared from the dicyanate having a saturated cyclopentane ring possesses a homopolymerized structure of cyanate groups, Gathering three farming rings. In a further embodiment, the present disclosure also provides (1) a polycyclopentaise diacrylate having a saturated cyclopentane ring, or a partially polymerized product of the dicyanate 'and (2) - or a plurality of selected from the group consisting of a double or polymaleimide, a non-discloser or a polycyanate, a di- or melamine, an epoxy resin - a polymerizable single, two, or polyethylene a blend of one of the components of the group consisting of unsaturated monomers (including vinyl aromatic monomers, vinylbenzyl ethers, allyl groups, and allyloxy compounds). Partially polymerized (Β The product of the stage _ or the product of curing (heat curing). Vinylbenzyl ether of polycyclopentadiene diphenol having a saturated cyclopentane ring. The present invention discloses a polycyclopentadiene having a saturated cyclopentane ring. a phenolic hydroxyl group is in the presence of a stoichiometric amount of an alkali compound such as lithium hydroxide, and in the presence of a suitable granule such as methanol, one or more polycyclopentadienes are aged and each The phenolic hydroxyl group is prepared in a stoichiometric excess of one of the vinyl benzoyl-based compounds 25 201202284. A free radical initiator such as 2,6-di-t-butyl-4-nonylphenol or hydroquinone is typically used as an inhibitor of in-situ polymerization. The reaction temperature is from about 10 ° C to about 10 ° C, and the reaction temperature is preferably from 20 ° C to 75 ° C, and the reaction temperature of 25 0 (: to 6 ° C is optimal. The reaction time can be large. The change, for example, is a function of the reactant to be used, the reaction temperature, the solvent used, the reaction specification, etc., but is generally between 4 hours and about 5 days. Suitable vinyl stray methyl halide including adjacent -vinylbenzyl vapor, m-benzyl benzyl vapor, p-ethylene benzyl vapor, o-vinylbenzyl evolution, meta-vinyl benzoyl desert, a combination of p-vinyl benzoic acid, 3 - ethyl phenyl fluorenyl _ 5-methyl chloride, and the like. Suitable compounds include inorganic and tertiary amines such as hydrogen peroxide and hydrogen. Sodium oxide, hydrogen hydroxide, trimethylamine, triethylamine, and combinations thereof. Lithium hydroxide is the best base. Suitable solvents for the formation of vinyl stupid methyl ether include water, aliphatic鲷, gasification hydrocarbons, aliphatic and cycloaliphatic _ and diethers, aromatic fumes, and their σ &amp; methanol, and combinations thereof, etc. It is suitable as a cold test and can be combined before use in the reaction, and the methanol hydroxide unloading solution is an example. The 转 转 转 转 转 转 二 二 二 二 Γ Γ Γ Γ Γ Γ Γ Γ Suitable for the presence of a catalyst by heating from about 30 C to about 2,000 C, preferably by heating from _ 〇c to 300 〇c to cure (heat) the right amount of the catalyst used, depending on the particular catalyst The structural slave is cured by a vinyl benzyl structure, a curing temperature, a curing time of 201202284, etc. Generally, a catalyst concentration of from about 0.001 to about 2% by weight is preferred. The B-stage or prepolymerization of the composition of the mercapto ether can be accomplished by using a lower temperature and/or a shorter curing time. Then, the thus formed bismuth-stage (prepolymerized) resin can be cured. Completed at a later time or immediately after the stage (prepolymerization) by increasing the temperature and/or curing time. Allyl oxime of a polycyclopentadiene diphenol having a saturated cyclopentane ring is disclosed. Content of polycyclopentadiene with a saturated cyclopentane ring Allyl (or 1-propenyl) ether can be prepared by allylation of one or more polycyclopentadiene diphenols, wherein the aromatic hydroxyl group (_〇Η) is converted to HR5C=CR5 -CH2-〇- and/or H2R5C-CR5=HC-0-, wherein each R5 is independently selected from the group consisting of hydrogen and an alkyl group having from 1 to 3 carbon atoms. For example, the alkyl group can be unsubstituted or substituted. For one or more embodiments, preferably x is unsubstituted. For one or more embodiments, preferably each X is the same. The formation of the allyl ether of polycyclopentadiene diphenol is the same as the US new application serial number given in this case, and the name is "poly(alkyl ether) of polycyclodecadiene polyphenol", Tao The company's Archives No. 68992, the disclosure of which is incorporated herein by reference. Briefly, allylation of polycyclopentadiene can be accomplished via a one-pass carbonation reaction. This transcarbonation reaction can include the reaction of allyl methyl carbonate with polycyclopentadiene diphenol in the presence of a catalytic amount of carbon and triphenylphosphine. Allyl methyl carbonate can be prepared from allylic alcohol and dimethyl carbonate. 27 201202284 should be prepared. This reaction provides a mixture of allyl methyl carbonate g and diallyl carbonate. This mixture and/or pure allyl methyl carbonate can be used in the transcarbonation reaction. The dipropylation of polycyclopentadiene can be accomplished by a direct allylation reaction which may include a catalyst, a reagent, and a selective catalyst such as a catalyst for the __ phase inversion catalyst. Examples of the halide include, without limitation, allyl halides and methallyl halides. Examples of allyl complexes* are limited to include a base gas and a propylene (tetra) compound. Examples of the methyl propyl carboxylate include, without limitation, methyl-based vapors and methallyl bromides. An example of an alkali reagent includes, without limitation, an aqueous solution of one of alkali metal hydroxides. Examples of the alkali metal hydroxide include, without limitation, potassium hydroxide and sodium hydroxide. Examples of the catalyst include, without limitation, benzoyltrialkylammonium and tetraalkylammonium. The allylation may include a combination of allyl methyl carbonate, diallyl carbonate, a dentate, an alkali reagent, a catalyst, and the like, and a polycyclopentadiene polyphenol. Direct propylation of poly% pentane can occur at temperatures between 25 ° C and 150 ° C. For some applications, 50. (The temperature to 100 〇C is preferred for allylation. The allylation of polycyclopentadiene diol can have a reaction time of 15 minutes to 8 hours. For some applications, 2 hours to 6 hours The reaction time is preferably preferred. The allylation of polycyclopentadiene diphenol may include a solvent. One example of such a solvent includes, without limitation, 1,4-dioxane. The allylic complex can be stoichiometrically reacted with a polycyclopentadienyl group. For one of the various reaction conditions, a Claisen rearrangement product can be observed for this reaction, and can be caused by 28 201202284 a mixture of 〇- and c-allylized products. The ratio of ~1 to 1 molar ratio of the propyl group and the polycyclopentadiene, the reaction of the group can provide - allylation A major amount (about 80 or more percentages) of a hydroxyl group converted to a -q-CH2-CH=CH2 group (8), a small amount (about 2% or The allyl group of more V) may be thermally induced (5) (iv) rearranged and may be present in the ortho and/or para position to the radical group where the rearrangement occurs. % of fragrance: less than 1 ratio! molar ratio of the propyl fluorenyl carbonate in the transcarbonation reaction or the reaction of the allylic group and the thiol group in the direct allylation reaction Partial allylation with some of the remaining radical groups may be provided. While partially allylated compounds are preferred for certain applications, they are still within the scope of the disclosure. A preferred method uses a stoichiometric reaction of allyl decyl carbonate with polycyclopentadiene diphenol to provide substantially complete allylation of the hydroxyl group of the polycyclopentadiene diphenol and provide corresponding One of the allyl ether (allyl emulsion) groups is converted to a carbonation reaction. If the presence of the 'allyloxy group and the allyl group isomerized to a more reactive 1-propenyl group, In the presence of a base, the method reported in TW Green and PGM Wuts in Protective Groups in Organic Synthesis 'Wiley-Interscience, New York, 67-74, 708-711 (1999) or in Journal of Molecular Catalysis A: Chemical volume 219, Issue 1, 29-40 (September 1, 2004) One of the catalytic amounts is practiced in the presence of a complex. The foregoing reference is hereby incorporated by reference in its entirety in its entirety in its entirety in the the the the the the the the the the the the the the the the Ester acrylates and methacrylates can be used in a Schotten-Baumann type reaction via an acid vapor hydride as described in C. Schotten, Ber. 17, 2544 (1884) and Ε Baumann, ibid 19, 3218 (1886). It is prepared, for example, by reacting acrylonitrile (2-acrylonitrile) or methyl propylene. For this thiolation reaction, one or more test substances such as aqueous sodium hydroxide, triethylamine or hydrazine can be used. Further, it is advantageous to use one of a plurality of polymerization inhibitors such as hydroquinone. The transesterification reaction can also be used to prepare acrylates and methacrylates. A method for synthesizing high purity acrylates and mercapto acrylates having no acrylic acid or mercaptoacrylic anhydride as crosslinkable diene impurities is by Stacy B. Evans, J. Mulvaney, H. K_ Hall Jr • Opened online on March 10, 2003

Journal of Polymer Science Part A: Polymer Chemistry, Vol. 28, No. 5, pp. 1073 - 1078. All of the aforementioned references are incorporated herein by reference in its entirety. The following examples are illustrative of the invention, but are not to be construed as limiting the scope thereof in any way. EXAMPLES The following examples are intended to illustrate, but not to limit, the scope of the disclosure. All parts and percentages are by weight unless otherwise indicated. All instruments and chemicals used are commercially available unless otherwise specified. material

Rh(CO)2 (ethyl phthalate) available from Strem Chemicals 30 201202284

Inc. n-butyldiphenylphosphine, available from Organometallics, Inc (E. Hampstead, NH, USA). Dicyclopentadiene, available from The Dow Chemical Company. Syngas is available from Airgas Great Lakes, Inc. 3-anthracene-1-acid, sodium salt, 90% purity, available from Sigma-A丨drich. Hydrogen acid, A.C.S. reagent grade, 37.5%, available from Mallinckrodt Baker, Inc by acid-base titration. Phenol, &gt; 99%, is available from The Dow Chemical Company. Tetrahydrofuran, anhydrous, 29.9%, without inhibitor, available from Sigma-Aldrich. The present methyl diethyl ammonium chloride '99%' is available from Sigma-Aldrich. Isopropanol' ACS reagent grade, 39.5%, available from Sigma-Aldrich cesium hydroxide, reagent grade '298%, pellets, anhydrous, available from sigma-Aldrich decyl isobutyl hydrazine (4-曱) Base-2-Bingo),299% by Eastman

Made by Chemical Company' available from Sigma_Aldrich. Epigas alcohol is available from The Dow Chemical Company. 4,4'-Diaminodiphenylnonane' is 97% gas chromatographic purity and is available from Sigma-Aldrich. Diacyanamide, powdered (unaccelerated) is available from Air Products' Amicure® CG range. KBr, FT-IR grade, 2 99% trace metal benchmark, available from 31 201202284

Sigma-Aldrich 0 Shixiazao, available from Celite® 545 from Celite Corporation. Example 1 - Preparation of dicyclopentadiene diphenol having a saturated cyclopentane ring A. Preparation of dicyclopentadiene monoaldehyde having a saturated cyclopentane ring. Preparation of slightly warm dicyclopentadiene (14 〇) Rh(CO)2 Acetylpyruvate vinegar (70. 2 mg (mg); 0.272 mmol (mmol)) and n-butyldiphenylphosphine (0.33 g (g)) The 1.36 millimolar reaction mixture was prepared in a rinse tank under dry nitrogen and then placed in a 250 mL (mL) Parr reactor at 1:1 syngas at 20 °C (1: 1 molar ratio of CO: H2) is sprayed three times. The reaction mixture was then heated to 10 ° C under a syngas pressure of 90 psi and stirred for 1 day, then at 130 ° C under a pressure of 90 psi for 6 days and stirred. Product formation from the reaction mixture was monitored by gas chromatography (GC) using an Agilent 6890 Gas Chromatography System. The final GC analysis of the resulting mixture showed a dicyclopentadiene monoaldehyde with a saturated cyclopentane ring. 65.5 area% » The reactor was cooled, the mixture was recovered, and the crude product (177.8 g) was used under vacuum to purify 78.2 g of dicyclopentadiene with a saturated cyclopentane ring using a 10 cm Vigreux distillation tower. An aldehyde having a boiling point of 65-68 ° C at 0.17 mm Hg. Gas chromatography/mass spectrometry (GC/MS) analysis of transparent liquid distillation products using an Agilent 6890 GC with one of the Agilent 5973 mass selective detectors supports the desired dicyclopentadiene monoaldehyde with a saturated cyclopentane ring. Form: M+ = 164, 146, 136, 107, 95, 79, 67. B. Preparation of 3_巯-1-propanesulfonic acid catalyst 3-Silphafur-1-ry acid, sodium salt (10.75 g) was added to concentrated hydrogen acid (35.7 % water, 32 201202284 200 ml), which was Magnetic stirring in the glass bottle. After covering with a parafllm "M" (American National Can, Greenwich, CT) sheet to avoid ingesting the moisture in the atmosphere, the white crystal slurry formed was stirred for 5 minutes, and then filtered through a medium-sintered glass funnel. Rotary evaporation gave 8.88 g of a pale yellow viscous solid product which was used as a catalyst without further work. C. Phenolization reaction Dicyclopentadiene monoaldehyde (43.31 g, 0.2845 mol, uncorrected) with saturated cyclopentane ring and molten phenol (850.2 g, 9.0345 mol) added to _5 liter glass three neck Round bottom reactor. The reactor is additionally provided with an ambient temperature (22. 〇 condenser and a thermometer, both of which are fixed to the reactor via a claisen adapter, plus a top nitrogen inlet, a glass stirring shaft, which has A Teflon (EIduPont de Nemours) mixing blade that is coupled to a variable speed motor to provide mechanical agitation and a thermostatically controlled heating pack. Start the top nitrogen flow (〇·5 liters/min), then heat and then stir At a temperature of 64 ° C, a clear solution was detected. At this point, a portion of the 3-indol propane-1 sulfonic acid was added (the total catalyst used was 22 g, which is equivalent to having a saturated cyclopentane). The dicyclopentadiene monoaldehyde of the alkane ring was 0.05 mol. / 〇) to the stirred solution. The starting portion of the catalyst (0.42 g) induced a maximum exotherm of 70 ° C in 2 minutes, and the solution became golden amber. The heating pack was removed from the reactor and joined to the air leak to cool the reaction section to 65. 0. Add the second part of the catalyst (〇_31 g) and stop cooling and reposition the heating pack back to the reactor. The first part of the catalyst did not induce an exotherm and was added after the addition. The clock was found to be 64 °C; © electricity, + &lt; _ degrees. At this time, 'the other part of the catalyst was added during the next η minutes' while maintaining the temperature of the amber (five) solution at 63 65 °C. Reverse 33 201202284 The temperature should be maintained at 65 °C for the next 72 hours, during which the 'reaction process was visualized by HPLC analysis. A Hewlett Packard 1090 liquid chromatograph was equipped with an Eclipse® (Agilent) XDB-C8 analytical protective tube ( 5 μ, 4.6 X 12.5 mm) One of the Zorbax Eclipse® (Agilent) XDB-C8 analytical tubes (5 μ, 4.6 x 150 mm). These columns are maintained in a 40 ° C chromatography furnace. And water (0.05% aqueous o-phosphoric acid) as an eluent, and individually delivered by a pump at a rate of 1.000 ml/min with a 50/50% solution, and changed to one after 5 minutes. 90/10% solution, and maintained for 15 minutes thereafter. The acetonitrile-based HPLC grade, 100.0% purity (by gas chromatography) has a UV cutoff of 189 NM. Upper system 85 ° / purity (actual analysis 85.1 water system HPLC grade used. Used for sample analysis The diode array detector was set to 225 nm and the reference frame was set to 550 nm. After 2.4 hours of reaction, HPLC analysis showed complete conversion of dicyclopentadiene monoacid to a product distribution, and thereafter little change in the product system. At the end of the time, the reactor contents were diluted with deionized (DI) water to fill a 5 liter reactor to 95% of capacity. The mixing was stopped after 1 hour and the contents of the reactor settled overnight. The next day, the aqueous layer was aspirated from the reactor and disposed of as waste. The reactor was refilled with new deionized water and the search was started for 65 minutes. Stirring was stopped and the contents of the reactor settled overnight. After a while, the aqueous layer is aspirated from the reactor and disposed of as waste. The cleaning procedure was repeated twice more, after which the solid was collected from the reactor by decantation through a filter paper. The recovered solid was thus added to a ceramic dish and dried in a vacuum oven 34 201202284 for 1 hour, removed, ground to a fine powder, and additionally dried in a vacuum oven for 48 hours to provide 84.32 grams of lavender. powder. The FTIR analysis of KBr pellets showed that the extension of the radicals disappeared completely, and strong aromatic ring absorption occurred at 1609.6 (shoulders at 1595.8) and 1509.8 cm-1; the broad strong OH stretching center was at 3379.7 cm-1; The broad strong CO stretch is at 1230.4 (shoulders are ΙΠΙ.ΐχπΓ1. HPLC analysis shows 39 components, and 4 major components contain 18.7, 7.9, 6.5, and 5.8 area%, and 6.5 area% of residual unreacted phenol , which was not removed during processing of the product. Example 2 - Epoxidation of a 1 liter three-neck glass round bottom reactor with dicyclopentadiene diphenol having a saturated cyclopentane ring is an example Dicyclopentadiene diphenol (33-44 g, 0.20 hydroxyl equivalent, based on a 167.22 nominal hydroxyl equivalent) and surface gas alcohol (138 86 g, 丨5 〇 Mo) with a saturated cyclopentane ring. Install a condenser (maintained in 〇.匸), a thermometer, a Claisen adapter, a nitrogen inlet at the top of the tower (using n2 liters per minute), and a stirrer assembly (TeflonTM paddle, glass shaft) , variable speed motor). Dissolved in deionized water (28.8 grams) to form a hydrogen Sodium hydroxide in aqueous sodium solution (7.2 g '0·18 mol) was added to the - side arm vented addition funnel. The slurry in the reactor was started to be stirred and heated using a thermostatically controlled heating pack. Once the solution was stirred, The temperature is up to 30. (: When forming, isopropanol (74 77 g, using 35 wt% of surface gas alcohol) is added, and stirring and heating are continued. Once it reaches 4 〇〇 (:, deionized water (12_08 g, Adding 8% by weight of epigas alcohol) to the solution by rapid drop addition. Once it reaches 50%, it starts to add liquid sodium hydroxide to the solution, which causes the solution in the reactor to start darkening. Add % sodium hydroxide solution in a continuous drip-type solution to make the dark amber solution slightly mixed 35 201202284 turbid. Add the sodium hydroxide aqueous solution to 30 minutes after the reaction in 23 minutes, stop (4), the contents of the domain Add to the separatory funnel and settling. The development of the epoxidation reaction was monitored by high pressure liquid chromatography (HPLC) analysis of the previous capture. At the end of the 7 minute settling time, the water (4) was removed to waste. Dispose of, and the organic layer is recycled and added Reaction (4). Reheat the solution and re-establish 50 in 5 minutes. 〇: Temperature. Start with the addition of the second part of sodium hydroxide dissolved in deionized water (12 8 grams) (3.2克, 〇·〇8mol), and finished at the rider' while maintaining the temperature at 5〇〇c. After 23 minutes, the reaction was stopped and the reactor contents were allowed to settle in a separatory funnel for 5 minutes. The layers were removed from the product and some slightly turbid light-colored organic layer was added back to the reactor. A sample was removed for analysis. Then, reheating and batching were repeated 5 minutes after 7 minutes. The temperature of 匸. A third portion of sodium hydroxide (1 g, 0.025 mol) dissolved in deionized water (4.0 g) was added over a period of 10 minutes and treated using a solution for the second aqueous sodium hydroxide solution. After the reaction after 23 minutes, the aqueous layer was removed from the final aqueous sodium hydroxide solution, and the organic layer was washed with a portion (15 mL) of deionized water. The recovered organic layer was diluted with decyl isobutyl ketone (0.5 liter) and washed with a second wound (150 ml) of deionized water. The aqueous layer was removed by dissolution with about 2 gram of emulsion after centrifugation at 2300 RPM for 30 minutes. The third and fourth washes with deionized water (150 ml per wash line) were completed using the second wash method (centrifugation was again required to dissolve the small residual emulsion from each wash). The recovered organic solution was filtered through a bed of diatomaceous earth in a sintered glass funnel filled in a 600 ml 36 201202284, and the product was washed from the filter bed into the filtrate using methyl isobutyl ketone if necessary. The organic layer was rotary evaporated to a Hg vacuum of 93 mm using a 75 〇Ci maximum oil bath temperature to remove a large amount of volatiles. At 175. (: The maximum oil bath temperature was further rotary evaporated to a Hg vacuum of 0.17 mm, yielding 36.11 g of a pale yellow solid upon cooling to 23 ° C. Gas chromatography (GC) analysis [Hewlett Packard 5890 series η gas phase layer The analyzer uses a 60m X 0.248mm X 0.25μιη J&amp;W GC column.

With a DB-1 stationary phase, the flame ionization detector is at 3 〇〇 (&gt;c operation, 3 〇〇〇c syringe temperature, and the enthalpy flow through the column is maintained at 丨丨 cc / min, starting 50. (: Furnace temperature' and heating to 3 〇〇ΰ at 12 〇C/min (: final temperature) shows that substantially all of the light boiling components containing residual galactitol have been removed. HPLC analysis shows The dicyclopentadiene diphenol of the saturated cyclopentane ring was completely converted into the product. Titration of a pair of product aliquots confirmed an average of 17 57 % of the epoxide (244_9 epoxide equivalent). The titration of the epoxy resin was determined by Jay, RR in "Direct Titration of Epoxy Compounds and Aziridines,,,

Described in Analytical Chemistry, 36, 3, 667-668 (March, 1964). Briefly, in this method, the weighed sample (sample weight range 0.1 - 0.2 g 'using a scale with 3 decimal digits accuracy) is dissolved in dichloromethane (15 ml), which is then added to A solution of tetraethylammonium bromide in acetic acid (manual milliliters). The solution formed by treatment of 3 drops of crystal violet solution ((U %w/v in acetic acid) was titrated with 0.1 N perchloric acid in acetic acid in a Metrohm 665 Dosimat titrator (Brinkmann). The titration of a blank group consisting of 5 mL) and tetraethylammonium bromide solution (15 ml) in acetic acid provides correction for the dissolution of the solution of 201202284. Example 3 - Thermal Induction of Dicyclopentadiene Diglycidyl Ether with Saturated Cyclopentane Ring Using 4,4,-Diaminodiphenylnonane The cured cyclopentane ring of Example 2 was cured. Dicyclopentadiene diglycidyl ether (0.1220 g, 0.000498 epoxide equivalent) and 4,4,-diaminodiphenyl decane (0.0247 g, 0.000498-NH equivalent) weighed in a glass jar 'And fully grind together into a homogeneous fine powder. Partial (8.50 and 9.20 mg) blends of differential scanning calorimetry (2910 Modulated DSC, TA Instruments) were analyzed at a flow rate of 35 cubic centimeters per minute of II flow using 7 °C/min. The heating rate is completed from 25 °C to 400 °C. A second scan using the foregoing conditions produces an average glass transition temperature of 220.6 °C. A third scan using the foregoing conditions yielded an average glass transition temperature of 221.7 °C. The product of the DSC analysis was a clear amber rigid solid. Example 4 - Thermal induction of dicyclopentadiene diglycidyl ether having a saturated cyclopentane ring using dicyandiamide to cure dicyclopentadiene diglycidyl group having a saturated cyclopentane ring of Example 2. Ether (0.4010 g, 0.00164 epoxide equivalent) and powdered (unaccelerated) dicyandiamide (0.0160 g, 4% by weight of a pentadiene diglycidyl ether with a saturated cyclopentane ring) It is heavier than a glass bottle' and is thoroughly ground together into a homogeneous fine powder. The DSC analysis of the blend of the fractions (7.90 and 8.30 mg) was carried out under a stream of nitrogen flowing at 35 cubic centimeters per minute using a heating rate of 70 °C/min from 25 °C to 350 °C. (: Completed. Observed an average of 176 7 〇c starting, 209.3. (: minimum, 264.2. (: endpoint ' and 175.1 joules / gram of sputum endotherm. Observed an average of 281·5 °C, 313·8 °C max, 38 201202284 and 348.3. (: endpoint with an exotherm of 28.7 joules per gram of entropy. The third scan using the above conditions yields 208.1. (: average glass transition temperature. The product of DSC analysis is transparent Solid amber solid. Example 5 - Curing of a dicyclopentadiene diglycidyl ether with a saturated cyclopentane ring using a second ring of pentylene pentoxide with a saturated cyclopentane ring and a catalyst Example 2 is a dicyclopentadiene diglycidyl ether having a saturated cyclopentane ring (0.2077 g, 0.00085 epoxide equivalent), and the second embodiment of a cyclopentadiene having a saturated cyclopentane ring (实施) 1418 g, 0.00085 via base )) and a clumpy hydrazine diethylated gas (0.0037 g, 0.000016 mol) were weighed into a glass vial in a dry nitrogen box and then added unrepressed Anhydrous tetrahydrofuran (2 ml). Example with saturated cyclopentane The dicyclopentadiene diphenol is used in a vacuum furnace at 175. After drying to remove residual phenol, the formed solution is used to remove volatile components in the box at ambient temperature, and then at room temperature (22 ° C). Drying in a vacuum oven for 2 hours. DSC analysis (2910 Modulated DSC, TA Instruments) of a blend of some (85 〇 and 9.1 mg) was carried out under a nitrogen flow of 35 cubic centimeters per minute. The heating rate of 7 ° C / min was completed from 25 to 4 (10) c. A second scan using the foregoing conditions yielded an average glass transition temperature of 23 丨 2 %. The product of the DSC analysis was a clear solid of amber color. Example 6 - Reproduction using a dicyclopentadiene diphenol having a saturated cyclopentane ring and a catalyst to thermally induce the curing of a dicyclopentadiene diglycidyl group having a saturated cyclopentane ring in a vacuum oven at 175 C for additional drying The dicyclopentadiene diphenol having a saturated 39 201202284 cyclopentane ring (0.1418 g, 0.00085 nominal hydroxyl equivalent) was used as the dicyclopentadiene having a saturated cyclopentane ring of Example 2. Phenol (0.2077 g, 0.00085 epoxide equivalent) Corresponding to the epoxy resin curing agent. The two components are weighed in a glass bottle, and then transferred to a dry nitrogen box. Phenylmercaptotriethylammonium hydride (0.0037 g, 0.000016 mol) is added. To the glass bottle, followed by anhydrous tetrahydrofuran (PmL). Stirring provides a solution which is poured into a dish and the tetrahydro-sulphur is evaporated in the box. It is removed from the box and placed in a vacuum oven. After drying for 2 hours under ambient conditions, a portion of the (8.50 mg) blend was subjected to DSC analysis under a stream of nitrogen flowing at 35 cm3/min using a heating rate of 7 °C/min from 25 °C. Finished at 400 °C. The second scan was done using the conditions described above, resulting in a glass transition temperature of 229.7 °C. The product of the DSC analysis was a clear amber rigid solid. [Circular Simple Description] (None) [Explanation of Main Component Symbols] (None) 40

Claims (1)

201202284 VII. Patent application scope: 1. A polycyclopentadiene compound of formula I, (Formula I) (R)m Wherein each X is a hydrogen, a cyano group, a monovinylphenylenyl group, an allyl group, an acrylate group, or a structure of the formula II: (Chemical Formula II) /0 \ R1HC-CR1-CH2- η has an average value from 0 to 20; each m independently has a value from 0 to 3; each R is independently a il, a nitrile group, a nitro group a group, an alkyl group, a monoalkoxy group, a monoalkenyl group, or an alkenyloxy group, wherein the alkyl group, the alkoxy group, the alkenyl group, And the alkenyloxy group each independently contains from 1 to 6 carbon atoms; each R1 is independently hydrogen or a mercapto group, and each Q is independently 41 201202284 hydrogen or contains 1 to 6 carbons One of the atoms of an alkyl group, and the T-hydrogen or one of the chemical formula III (chemical formula III) The proviso is that when the X is a cyano group, then R is not an alkenyl group or a diloxy group. 2. The polycyclopentadiene compound of claim 1, wherein η has an average value from 0 to 8. 3. The polycyclopentadiene compound according to claim 1, wherein the alkyl group and the alkoxy group have 1 to 2 carbon atoms. 4. The polycyclopentadiene compound according to claim 1, wherein Q is a monoalkyl group which has 1 to 2 carbon atoms. 5. The polycyclopentadiene compound according to claim 1, wherein the alkenyl group and the alkenyloxy group have 1 to 3 carbon atoms. 6. The polycyclopentadiene compound according to claim 1, wherein m is 0, η is 0, and Q and T are hydrogen. 7. The polycyclopentadiene compound according to claim 1, wherein m is 0, η is 0, Q and T are each hydrogen, and X is a compound of formula II, wherein R1 is Η . 8. A curable composition comprising the polycyclopentadiene compound of formula I as defined in claim 1 of the scope of the patent. The method of claim 8, wherein the polycyclopentadiene compound of the formula I is a hardener. 10. The curable composition of claim 8, wherein the polycyclopentadiene compound of the formula I is a resin. 43 201202284 IV. Designated representative map: (1) The representative representative map of this case is: ( ). (None) (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: (R)m