EPOXIDATION PROCESS

FIELD

The present invention is related to a process for epoxidizing an aromatic compound containing a multiple number of olefin ("multi-olefin") functionalities to form an epoxy compound containing a multiple number of corresponding epoxide ("multi-epoxide") functionalities. More specifically, the present invention relates to a process for epoxidizing an aromatic compound having more than one olefin functionality, such as a di vinyl compound, in the presence of hydrogen peroxide as an oxidant and an iron-containing compound as a catalyst in the epoxidation process. BACKGROUND

The epoxidation of aromatic compounds containing one olefin functionality, such as styrene, a mono-olefin compound, is well known and there are numerous methods to carry out such epoxidation for example as described in U.S. Patent No. 5,041,569.

Processes for epoxidizing styrene can readily provide epoxy compounds in yields of greater than 80 percent (%). However, compounds containing more than one olefin functionality (i.e., two or more olefin groups); and particularly aromatic compounds containing two or more olefin functionalities, such as divinylarene dioxides, are very difficult to epoxidize; and yields for such compounds containing multiple olefin functionalities can be less than 80 %. For example, processes for epoxidizing divinylbenzene (DVB) to produce

divinylbenzene dioxide (DVBDO), a divinylarene dioxide, can provide only yields of DVBDO of at most 77 % such as described in WO2010077483A1. More typically, processes for the preparation of DVBDO from DVB such as described in Inoue et al (Bull. Chem. Soc. Jpn., 1991, 64, 3442); and JP 09286750 provide yields of 30 % or less of DVBDO product because of product instability and catalyst decomposition.

In addition, the epoxidation of aromatic compounds containing more than one olefin functionality such as DVB requires significantly different process conditions to oxidize the olefin functionalities of the divinylarene than the process conditions required for the epoxidation of an aromatic compound containing a single olefin functionality such as styrene. In general, for example, the know processes for epoxidizing DVB to DVBDO require a catalyst loading of at least 5 mol % to provide a DVBDO yield of 77 % or less. In addition, for example, known processes attempt to completely convert the multiple olefin functionalities of an aromatic compound to multiple epoxide functionalities by adding to the process reaction mixture at least two equivalents of oxidant, such as hydrogen peroxide, for every vinyl group; thus, doubling the theoretical amount of hydrogen peroxide required in the process, which is wasteful and costly. Furthermore, the hydrogen peroxide oxidant, when present in excess amount to the olefin in the reaction mixture, is problematic in an epoxidation process because the excess oxidant usually causes an epoxidation reaction to proceed slowly; and the excess oxidant promotes catalyst decomposition, and/or forms undesirable byproducts during the epoxidation reaction.

Another known process for epoxidizing aromatic di-olefins is disclosed in WO2013070392. WO2013070392 discloses a process for epoxidizing DVB using an iron- containing catalyst and hydrogen peroxide oxidant to epoxidize the DVB to form DVBDO. The reaction process disclosed in WO2013070392 requires the presence of an amine hydrohalide in excess to the iron-containing catalyst. The iron-containing catalyst disclosed in WO2013070392 includes for example Fe compounds containing Pydic (pyridine-2,6- dicarboxylate) ligands or mixtures made from FeCl ₃ ^' 6H ₂ 0, H ₂ Pydic (pyridine-2,6- dicarboxylic acid). While the iron-containing catalyst disclosed in WO2013070392 is suitable for use in an epoxidation process for producing divinylarene dioxides, the turnover number and the period to deactivation of the iron-containing catalyst can still be improved to make the iron-containing catalyst even more feasible and economical for an industrial scale manufacturing process.

SUMMARY

The present invention provides unique solutions to the problems of the known prior art processes for epoxidizing an aromatic compound containing multi-olefin functionalities (e.g. a compound containing two or more olefin functionalities). The present invention is directed to an epoxidation process for epoxidizing an aromatic compound containing multi-olefin functionalities (such as a divinyl compound which contains two olefin functionalities), in the presence of an oxidant such as hydrogen peroxide, and in the presence of a specific iron-containing catalyst such as an iron (Fe) -porphyrin catalyst (e.g., a fluorinated Fe-porphyrin catalyst) to form an aromatic epoxy compound containing multi- epoxide functionalities such as a divinylarene dioxide (which contains two e epoxide functionalities).

For example, in one embodiment, the divinyl compound can be a divinylarene compound and the aromatic epoxy compound formed by epoxidizing the divinylarene can be a divinylarene dioxide compound (such as for example DVBDO). The process of the present invention advantageously provides a divinylarene dioxide product (i.e., an aromatic diolefin) at a selectivity and at a yield sufficient to make the process economical and feasible when carried out on an industrial scale.

By using the Fe-porphyrin catalyst in the epoxidation process of the present invention, advantageously, the process does not require the use of other auxiliary additives, such as amine hydrohalides, for the epoxidation process to be carried out.

In accordance with the present invention, one embodiment is directed to a process for epoxidizing an aromatic compound containing multiple olefin functionalities to form an epoxy compound containing multiple epoxide functionalities including the step of reacting the following compounds: (a) at least one aromatic compound containing multiple olefin functionalities; (b) at least one oxidant, and (c) at least one iron-containing catalyst; wherein the catalyst is an iron-porphyrin catalyst.

In one preferred embodiment, the process of the present invention includes for example, a process for epoxidizing an aromatic divinyl compound such as a divinylarene to form an aromatic epoxy compound such as divinylarene dioxide; and in another preferred embodiment, the divinylarene dioxide can be for example divinylbenzene dioxide made by epoxidizing divinylbenzene.

The resulting epoxy resin compound produced by the above epoxidation process of the present invention, in turn, can be used to prepare a curable composition; and the curable composition can, in turn, be used to prepare a thermoset. The curable compositions and thermosets of the present invention can be useful in various applications such as composite applications.

DETAILED DESCRIPTION

In its broadest scope, the present invention includes a process for epoxidizing an aromatic compound containing multi-olefin functionalities to form an epoxy compound containing multi-epoxide functionalities including the step of reacting the following compounds: (a) at least one aromatic compound containing multi-olefin functionalities; (b) at least one oxidant, and (c) at least one catalyst; wherein the catalyst is an iron- porphyrin catalyst. One or more other optional components can be added to the above reaction mixture including for example an organic solvent.

The aromatic compound, component (a), used to prepare the epoxy compound product of the present invention includes any aromatic compound containing more than one olefin functionality (herein referred to as "an aromatic multi-olefin compound"). For example, the aromatic multi-olefin compound may contain two or more olefin groups.

In one preferred embodiment, the aromatic multi-olefin compound may include for example a divinyl compound such as a divinylarene. In the above preferred embodiment, the source of divinylarene useful in the present invention may come from any known sources and particular to known processes for preparing divinylarenes. For example, divinylarenes can be prepared with salt or metal wastes from arenes and ethylene.

The divinylarene reactant useful in the process of the present invention may be illustrated by general chemical Structure (I) as follows:

Structure (I)

In the above Structure (I) of the divinylarene reactant of the present invention, each R ₅ R ₂ , R ₃ and R4 individually may be hydrogen; an alkyl, cycloalkyl, an aryl or an aralkyl group, wherein the alkyl, cycloalkyl, aryl, and aralkyl groups may have from 1 to about 18 carbon atoms and preferably from 1 to 4 carbon atoms; or an oxidant- resistant group including for example a halogen, a nitro, an isocyanate, or an R'O group, wherein R' may be an alkyl, an aryl or an aralkyl group each individually having from 1 to about 18 carbon atoms and preferably from 1 to 4 carbon atoms; x may be an integer of 0 to 4; y may be an integer greater than or equal to 2; x+y may be an integer less than or equal to 6; z may be an integer of 0 to 6; z+y may be an integer less than or equal to 8; and Ar is an arene fragment including for example, 1,3-phenylene group.

In one embodiment of the present invention, the divinylarene useful in the present invention may comprise any substituted or unsubstituted arene nucleus bearing two vinyl (also referred to herein as "C=C bonds", "olefinic" or "ethylenic double bonds") groups in any ring position. The arene may include for example benzene, substituted benzenes, or (substituted) ring-annulated benzenes, and mixtures thereof. In one embodiment, divinylbenzene may be ortho, meta, or para isomers or any mixture thereof. Additional substituents may consist of oxidation-resistant groups including for example a saturated alkyl, or an aryl, wherein the saturated alkyl may have from 1 to about 18 carbon atoms and preferably from 1 to 4 carbon atoms, and wherein the aryl may have from 4 to about 18 carbon atoms and preferably from 6 to 10 carbon atoms; a halogen; a nitro, an isocyanate; or a R'O-wherein R' may be a saturated alkyl, an aryl, or an aralkyl each individually having from 1 to about 18 carbon atoms and preferably from 1 to 4 carbon atoms; or mixtures thereof. Ring-annulated benzenes may include for example

naphthlalene, tetrahydronaphthalene, and the like, and mixtures thereof.

In another embodiment, the divinylarene may contain quantities of substituted arenes. The amount and structure of the substituted arenes depend on the process used in the preparation of the divinylarene. For example, DVB prepared by the dehydrogenation of diethylbenzene (DEB) may optionally contain quantities of

ethylvinylbenzene (EVB), naphthalene, polyethylbenzenes (e.g. diethylbenzene, triethylbenzene, tetraethylbenzene, pentaethylbenzene, diphenylethane, other aklylated benzenes, and higher molecular weight oils), free radical inhibitors, or mixtures thereof.

In one embodiment of the present invention, DVB may be epoxidized wherein DVB may optionally contain EVB. The DVB used can be a high purity DVB to make DVBDO with a very low amount of ethylvinylbenzene oxide (EVBO). "High purity" with reference to DVB herein means, for example, a DVB which contains greater than about 80 % DVB in one embodiment, greater than about 90 % DVB in another

embodiment, and greater than about 95 % DVB in yet another embodiment with the remainder being impurities or other compounds such as EVB.

In another embodiment, the process may provide, as a co-product, one or more divinylarene monoxides, alkyl-vinyl-arene monoxides, or mixtures thereof. When a monoxide product is produced as a co-product, the monoxide may be purified such that the purified monoxide product may have a purity of greater than about 50 % in one

embodiment, greater than about 80 % in another embodiment, and greater than about 90 % in yet another embodiment.

The divinylarene used in the process of the present invention may include for example divinylbenzene, divinylnaphthalene, divinylbiphenyl, divinyldiphenylether; or mixtures thereof. In one preferred embodiment, the present invention uses divinylbenzene as the divinylarene reactant. In the above preferred embodiment using divinylbenzene as the divinylarene reactant, the divinylarene dioxide formed comprises divinylbenzene dioxide.

The concentration of the divinylarene used in the present invention may range generally from 0.01 mol/L (M) to about 10 M in one embodiment, from about 0.01 M to about 5 M in another embodiment, and from about 0.1 M to about 2 M in still another embodiment, based on the total mol and volume of the composition, In another preferred embodiment, the concentration of the divinylarene used in the present invention may range from about 0.2 M to about 1 M, from about 0.3 M to about 0.5 M in still another embodiment, and from about 0.3 M to about 0.4 M in yet another embodiment, based on the total weight of the composition.

The oxidizing agent or oxidant useful in the present invention may include any oxygen transfer type oxidant well-known in the art. For example, the oxidant useful for preparing the epoxy compound of the present invention may include one or more of the oxidant compounds under the general classification of: (i) peroxo compounds or organic peroxides and (ii) positive oxidation state halogen compounds; and mixtures thereof.

Generally, examples of the peroxo compounds used as the oxidants in the process of the present invention include compounds with 0-0 linkages that are capable of losing one oxygen and forming an epoxide with a double bond. For example, the peroxo compounds used as the oxidants in the process of the present invention may include peroxocarboxylic acids, peroxosulfates, organic hydroperoxides, and mixtures thereof. More specifically, examples of the peroxo compounds may include hydrogen peroxide, Oxone ®; potassium peroxomonsulfate or its ammonium or alkylammonium salts; meta- chloro-perbenzoic acid (mCPBA); peracetic acid; ieri-butylhydroperoxide; cumene hydroperoxide; and mixtures thereof.

Generally, examples of the positive oxidation state halogen compounds used as the oxidants in the process of the present invention include compounds that contain halogens with an oxidation number of, for example, +1, +3, +5 or +7; and mixtures thereof. For example, compounds belonging to the group of positive oxidation state halogen compounds include for example, hypochlorites and hypobromites (+1); chlorites and bromites (+3); chlorates and bromates (+5); perchlorates, perbromates and periodates (+7); and mixtures thereof. More specifically, examples of the positive oxidation state halogen compounds include sodium periodate (+7); sodium hypochlorite (+1); iodosyl benzene (+3); iodosylmesitylene (+3); and mixtures thereof.

In one preferred embodiment, the oxidant used in the process of the present invention may be for example hydrogen peroxide (H ₂ O ₂ ). H ₂ 0 ₂ may be

pre-manufactured or generated in-situ in the course of the reaction with the divinylarene, for example as disclosed in Edwards et al., J. Mater. Res., 22, (4) 831, 2007; or

Hayashi et al., J. Catal., 178, 566, 1998. H ₂ 0 ₂ may also be pre-manufactured using the anthraquinone/tetrahydroanthtraquinone process with an appropriate hydrogenation catalyst such as palladium on alumina or Raney nickel such as described in U.S. Patent No.

3,635,841.

One advantage of the present invention process is that a low amount of oxidant can be used in the process of the present invention compared to other known processes. For example, the amount of oxidant useful in the process of the present invention, measured in terms of moles of oxidant per double bond of the aromatic multi-olefin compound, generally can be less than about 4: 1 in one embodiment. In another embodiment, for example when the oxidant is hydrogen peroxide and the divinyl compound is divinylarene, the molar ratio of hydrogen peroxide: divinylarene useful in the present invention can be from about 1: 1 to about 4: 1 ; from about 1 : 1 to about 3: 1 in still another embodiment; and from about 1 : 1 to about 2: 1 in yet another embodiment. If less than the minimum ratio of H ₂ 0 ₂ per divinylarene (described above) is used, there may not be a sufficient amount of oxidant to epoxidize both of the double bonds in the divinylarene, i.e., a product that contains one epoxide group and one double bond on average. In addition, if less than the minimum ratio of H ₂ 0 ₂ per divinylarene is used, the resulting reaction product may be unstable, i.e., the reaction product may have an increase in viscosity, and ultimately may gel prior to further processing. If more than the maximum ratio of H ₂ 0 ₂ per divinylarene (described above) is used, the benefits of using the H ₂ 0 ₂ oxidant in the reaction may no longer be economical; and use of more H ₂ 0 ₂ oxidant may be wasteful.

The catalyst useful in the process of the present invention may include for example an iron-containing catalyst. The iron-containing catalysts may be a catalyst that is soluble in the reaction mixture (i.e., a homogeneous catalyst), a catalyst that is insoluble in the reaction mixture (i.e., a heterogeneous catalyst), or a homogeneous catalyst that is supported on a variety of carrier materials.

In one embodiment, the iron-containing catalyst can be for example an iron- porphyrin catalyst. More specifically, the iron-porphyrin catalyst used in the epoxidation process of the present invention can be for example one or more fluorinated Fe-porphyrins. For example, in one preferred embodiment, component (c) of the epoxidation reaction mixture can include [tetrakis (pentafluorophenyl)porphyrinato] iron (III) chloride - referred to herein as (TPFPP)FeCl - as the catalyst for the epoxidation process of the present invention.

The amount of the homogeneous iron-containing catalyst used in the reactive composition, measured in terms of moles of catalyst per double bond of the aromatic multi- olefin compound, generally can range from 0.05 mol % to 5 mol % and preferably from 0.5 mol % to 1.5 mol %.

In an alternative embodiment, the iron-containing catalyst material can be a heterogeneous catalyst. For example, a homogeneous catalyst can be bound or immobilized on a variety of carrier materials to form a heterogeneous catalyst. The carrier material may include, for example, chitosan membranes; carbon xerogels; silicas such as SBA-15 and MCM 41; aluminas; MgO; clays; activated carbon; polystyrene; and mixtures thereof.

One advantage of using the above iron-porphyrin catalyst in the process of the present invention is that the catalyst can used for several cycles, that is, the catalyst achieves a high "turnover number (TON)". For example, the TON of the catalyst can range up to about 700 and preferably from about 600 to about 700. The TON can be determined by moles of double bond converted relative to moles of catalyst used.

Another advantage of using the above iron-porphyrin catalyst in the reaction process of the present invention is that the catalyst deactivates (i.e., after a period of time the catalyst loses its reaction activity) at a slower rate than other conventional catalysts.

An optional organic solvent, component (d), can be used to prepare the epoxy compound of the present invention if desired and may include for example one or more of the following general class of compounds: hydrocarbons, halogenated

hydrocarbons, aromatic solvents, and mixtures thereof. The optional solvent, when used in the epoxidation reaction mixture of the process of the present invention, may include for example any inert organic solvent that is inert to the oxidant and other components in the composition and under the reaction conditions. For example, the solvent may include halogenated alkanes such as dichloromethane; aromatics such as toluene; polar organic solvents such as dimethylformamide, acetonitrile, or ethers such as tetrahydrofuran;

alcohols such as organic alcohols, fluorinated alcohols, chlorinated alcohols, and mixtures thereof; or ketones, such as acetone or methyl-ethyl ketone; or mixtures thereof.

Examples of suitable solvents useful in the process of the present invention, but not to be limited thereto may include methanol, ethanol, propanol,

tert-amy\ alcohol, ieri-butanol, trifluoroethanol, dichloromethane, chloroform,

dichlorobenzene, dichloroethane, toluene; acetone, MIBK, and mixtures thereof. Methanol and dichloromethane are examples of preferred embodiments of the solvent that can be used in the epoxidation reaction process of the present invention.

Generally, the concentration of the optional solvent, when used in the present invention, may range for example, from 0 wt % to about 99 wt % in one embodiment, from about 20 wt % to about 99 wt % in another embodiment, from about 40 wt % to about 99 wt % in still another embodiment, from about 60 wt % to about 90 wt % in yet another embodiment, and from about 80 wt % to about 90 wt % in even still another embodiment.

An assortment of other optional additives known in the art may be added to the reaction mixture composition to prepare the epoxy compound of the present invention such as compounds that are normally used in epoxidation reactions known to those skilled in the art. For example, the optional components may include compounds that can be added to enhance (1) the properties of the final epoxy product such as surface tension modifiers or flow aids; (2) the reaction rate; (3) the selectivity of the reaction; and/or (4) the catalyst lifetime. The optional additives may include, for example, other resins, stabilizers, fillers, plasticizers, catalyst de-activators, and the like; and mixtures thereof.

The amount of the one or more several optional components or additives that can be used to prepare the epoxy compound, when used, may range generally from 0 wt % to about 99.9 wt % in one embodiment, from about 0.1 wt % to about 99.9 wt % in another embodiment, from about 1 wt % to about 99 wt % in still another embodiment, and from about 2 wt % to about 98 wt %, in yet another embodiment, base on the weight of all the components in the composition.

The process of the present invention for epoxidizing an aromatic olefin compound containing multi-olefin functionalities, such as a divinyl compound, to prepare an epoxy compound includes the step of reacting the above components after admixing or during the admixing of the compounds described above and adding any of the optional compounds/additives described above. Optional components known to the skilled artisan commonly used in an epoxidation reaction and other additives can be used for various enduse applications.

For example, the reaction components of the present invention described above, and optionally any desirable additives, can be mixed or blended together, in known mixing equipment, in any order. The reactants and optional additives, for example, may be added to the reaction mixture during the mixing or prior to the mixing to form a reaction mixture. In one embodiment, for example, the reaction components may be added to a reaction vessel all at once, added intermittently in portions over time, or added continuously over time. In another embodiment, the reaction mixture may exist in multiple phases.

All the compounds of the reaction mixture are typically mixed and dispersed at a temperature enabling the formation of well mixed reaction mixture for use in the epoxidation reaction. For example, the mixing temperature of the components may be generally from about 0 °C to about 60 °C in one embodiment, and from about 0 °C to about 25 °C in another embodiment.

The mixing step of the present invention, and/or any of the steps thereof, may be a batch or a continuous process. The mixing equipment used in the process may be any vessel and ancillary equipment well known to those skilled in the art.

The process of the present invention includes the step of reacting the reaction mixture described above to form an epoxy compound. The reaction process may be a homogenous reaction or a heterogeneous reaction based on the use of a homogenous catalyst or a heterogeneous catalyst as described above. The reaction may be carried out at a predetermined temperature and for a predetermined period of time sufficient to epoxidize the aromatic multi-olefin compound and to form a resultant epoxy product having desirable properties for a particular application. One of the advantages of the present invention is that the process of reacting the reaction mixture composition can be carried out under mild reaction conditions. For example, in one embodiment, the reaction may be carried out at various temperatures such as for example, generally from about -20 °C to about 100 °C, from about 0 °C to about 80 °C in another embodiment, from about 0 °C to about 60 °C in still another embodiment, from about 20 °C to about 60 °C in yet another embodiment, and from about 20 °C to about 25 °C in even still another embodiment.

The pressure of the reaction may be generally from about 10.13 kPa to about 1013 kPa (0.1 atmosphere [atm] to about 10 atm). Generally, the reaction time for the reaction may be chosen between about 1 hour (hr) to about 24 hr in one embodiment, between about 3 hr to about 20 hr in another embodiment, and between about 6 hr to about 14 hr in still another embodiment. Below a period of time of about 1 hr, the time may be too short to ensure sufficient reaction under the processing conditions; and above about 24 hr, the time may be too long to be practical or economical.

In one embodiment, the reaction of the present invention may be carried out in a single stage. In another embodiment, the reaction of the present invention may be carried out in multiple stages with separation of components between the multiple stages. In addition, the reaction of the present invention, and/or any of the steps thereof, may be carried out batch- wise or continuously. The reaction equipment (reactor) used in the process may be any vessel and ancillary equipment well known to those skilled in the art.

For example, the present invention may include a process for epoxidizing an aromatic compound containing multi-olefin functionalities to form an epoxy compound including the steps of: (i) admixing the following compounds: (a) at least one aromatic olefin compound containing multi-olefin functionalities; (b) at least one oxidant, and (c) at least one catalyst; wherein the catalyst is an iron-porphyrin catalyst; and then (ii) heating the mixture of step (i) to a reaction temperature of from about 0 °C to about 100 °C.

In one preferred embodiment, the process of the present invention may include for example, a process for epoxidizing a divinyl compound such as a divinylarene to form an epoxy compound such as divinylarene dioxide. More preferably, the resulting epoxy compound produced by the above process can be for example divinylbenzene dioxide produced by epoxidizing divinylbenzene. In this preferred embodiment, the preparation of a divinylarene dioxide may be achieved for example by (i) adding to a reactor the following reactants: a divinylarene, an iron-containing catalyst, and optionally an inert organic solvent; (ii) contacting the reactants with an oxidant; and then (iii) allowing the components in the reaction mixture to react under reaction conditions to produce the corresponding divinylarene dioxide.

After the reaction of the present invention, undesirable by-products; and any remaining catalyst, and solvent, may be removed to recover the divinylarene dioxide product. The resulting divinylarene dioxide reaction product can be isolated by any known means. Optionally, the product may be purified by well-known means in the art such as by chromatography, distillation, crystallization, and the like. In one preferred embodiment, the isolated divinylarene dioxide reaction product is purified by a distillation process.

One advantage of the present invention process is that high yields of divinylarene dioxides may be produced by the process of the present invention. With high yields of divinylarene dioxides produced, the process of the present invention

advantageously requires less recycle and produces less waste. For example, "high yield" of product such as divinylarene dioxide produced by the process of the present invention herein means generally greater than about 50 % in one embodiment, from about 60 % to about 100 % in another embodiment; from about 70 % to about 100 % in still another embodiment, and from about 80 % to about 100 % in yet another embodiment, based on divinylarene starting material.

Another advantage of the present invention process is that high selectivities of divinylarene dioxides may be produced by the process of the present invention. For example, "high selectivity" of product such as divinylarene dioxide produced by the process of the present invention herein means generally greater than about 70 % in one

embodiment, from about 80 % to about 100 % in another embodiment; from about 85 % to about 100 % in still another embodiment, and from about 90 % to about 100 % in yet another embodiment if running the reaction at 0 °C, and based on the product formed.

Still another advantage of the present invention process is that the process of the present invention can provide a substantially complete conversion of olefin groups to epoxy groups, i.e., a higher percentage of the divinyl functionalities present in an aromatic olefin compound can be converted to epoxide groups than for an olefin compound processed by other conventional processes. Preferably, it is desired to obtain 100 % complete conversion of olefin groups to epoxy groups using the process of the present invention. However, for the purposes of the present invention, it is sufficient to achieve slightly less than 100 % conversion of olefin groups to epoxy groups in the present invention. Therefore, by "substantially complete conversion" of the olefin groups to epoxy groups of a divinylarene dioxide product produced by the process of the present invention, herein it is meant that generally at least greater than about 80 % of the olefin groups are converted to epoxy groups, preferably from about 90 % to about 100 %; more preferably from about 95 % to about 100 %, and most preferably from about 98 % to about 100 %, based on the number of olefin groups in the divinylarene starting material. The conversion percentage above can be measured by quantitative GC analysis, or NMR analysis, using an appropriate internal standard as is known by one skilled in the art.

Yet another advantage of the present invention process is that the process provides a faster epoxidation reaction. For example, the epoxidation reaction rate of the process of the present invention can be generally about 50 TON per hour.

In one embodiment, the process of the present invention may be particularly suited for the preparation of a divinylarene dioxide such as divinylbenzene dioxide

(DVBDO), a low viscosity liquid epoxy resin. The divinylarene dioxide prepared by the process of the present invention, particularly divinylbenzene dioxide derived from divinylbenzene, are class of diepoxides which have a relatively low liquid viscosity but a higher rigidity than conventional epoxy resins.

The divinylarene dioxide prepared by the process of the present invention may comprise, for example, any substituted or unsubstituted arene nucleus bearing two vinyl groups in any ring position. The arene portion of the divinylarene dioxide may consist of benzene, substituted benzenes, or (substituted) ring-annulated benzenes or homologously bonded (substituted) benzenes, or mixtures thereof. The divinylarene portion of the divinylarene dioxide may be ortho, meta, or para isomers or any mixture thereof.

Additional substituents may consist of oxidant-resistant groups including saturated alkyl, aryl, halogen, nitro, isocyanate, or R'O- wherein R' may be the same as defined above. Ring-annulated benzenes may consist of naphthalene, tetrahydronaphthalene, and the like. Homologously bonded (substituted) benzenes may consist of biphenyl, diphenylether, and the like.

The divinylarene dioxide product prepared by the process of the present invention may be illustrated generally by general chemical Structure (II) as follows:

In the above Structure (II) of the divinylarene dioxide product of the present invention, each R ₅ R ₂ , R ₃ and R ₄ individually may be hydrogen, an alkyl, cycloalkyl, an aryl or an aralkyl group, where the alkyl, cycloalkyl, aryl, and aralkyl groups may have from 1 to about 18 carbon atoms in one embodiment and from 1 to 4 carbon atoms in another embodiment; or an oxidant-resistant group including for example a halogen, a nitro, an isocyanate, or an R'O group, wherein R' may be an alkyl, aryl or aralkyl group having from 1 to about 18 carbon atoms in one embodiment and from 1 to 4 carbon atoms in another embodiment; x may be an integer of 0 to 4; y may be an integer greater than or equal to 2; x+y may be an integer less than or equal to 6; z may be an integer of 0 to 6; z+y may be an integer less than or equal to 8; and Ar is an arene fragment including for example, 1,3-phenylene group.

The divinylarene dioxide product produced by the process of the present invention may include for example alkyl-vinyl-arene monoxides depending on the presence of alkyl-vinyl-arene in the starting material. The structure of the divinylarene dioxide, and composition of structural isomers, is determined by the divinylarene feedstock used. The reaction to epoxidize the ethylenic bonds do not generally impact the isomer distribution of the reactants as they are converted.

In one embodiment of the present invention, the divinylarene dioxide produced by the process of the present invention may include for example divinylbenzene dioxide, divinylnaphthalene dioxide, divinylbiphenyl dioxide, divinyldiphenylether dioxide, and mixtures thereof.

In a preferred embodiment of the present invention, the divinylarene dioxide used in the epoxy resin formulation may be for example DVBDO. In another preferred embodiment, the divinylarene dioxide component that is useful in the present invention includes, for example, a DVBDO as illustrated by the following chemical formula of Structure (III):

Structure (III) The chemical formula of the above DVBDO compound may be as follows: C1 ₀ H1 ₀ O2; the molecular weight of the DVBDO is about 162.2; and the elemental analysis of the DVBDO is about: C, 74.06; H, 6.21; and O, 19.73 with an epoxide equivalent weight of about 81 g/mol.

Divinylarene dioxides, particularly those derived from divinylbenzene such as for example DVBDO, are class of diepoxides which have a relatively low liquid viscosity but a higher rigidity and crosslink density than conventional epoxy resins.

Structure (IV) below illustrates an embodiment of a preferred chemical structure of the DVBDO useful in the present invention:

Structure (IV)

Structure (V) below illustrates another embodiment of a preferred chemical structure of the DVBDO useful in the present invention:

Structure (V)

When DVBDO is prepared by the process of the present invention, it may be possible to obtain one of three possible isomers: ortho, meta, and para. Accordingly, the present invention includes a DVBDO illustrated by any one of the above structures individually or as a mixture thereof. Structures (IV) and (V) above show the meta

(1,3-DVBDO) isomer of DVBDO and the para (1,4-DVBDO) isomer of DVBDO, respectively. The ortho isomer is rare; and usually DVBDO is mostly produced generally in a range of from about 9: 1 to about 1 :9 ratio of meta isomer (Structure (IV)) to para isomer (Structure (V). The present invention preferably includes as one embodiment a range of from about 6: 1 to about 1 :6 ratio of Structure (IV) to Structure (V), and in other embodiments the ratio of Structure (IV) to Structure (V) may be from about 4: 1 to about 1:4 or from about 3: 1 to about 1 :3. The structure of the divinylarene dioxide, and composition of structural isomers, is determined by the divinylarene feedstock used. In one embodiment, divinylbenzene feedstock contains a meta:para ratio of generally in a range of from about 9:1 to about 1:9. In another embodiment, the divinylbenzene feedstock may be from about 6:1 to about 1:6; from about 5:1 to about 1:5 in yet another embodiment; from about 4:1 to about 1:4 in still another embodiment; or from about 3:1 to about 1:3 another embodiment. In a preferred embodiment, the meta:para ratio of the divinylbenzene and the

divinylbenzene dioxide both may range from about 3: 1 to about 1:1 ratio; and in another embodiment, the meta:para ratio of the divinylbenzene and the divinylbenzene dioxide both may range from about 2.5: 1 to abut 2: 1 ratio.

The feedstock may also contain impurities including, but not limited to, ethylvinylbenzene (EVB), naphthalene, polyethylbenzenes (e.g. diethylbenzene, triethylbenzene, tetraethylbenzene, pentaethylbenzene, diphenylethane, other aklylated benzenes, and higher molecular weight oils), free radical inhibitors, or mixtures thereof. The divinylbenzene content of the feed may be greater than or equal to (>) 55 % in one embodiment; > 63 % in another embodiment; > 80 % in still another embodiment;

> 90 % in still another embodiment; or > 95 % in yet another embodiment. In even yet other embodiments, the divinylbenzene content of the feed may be from about 70 % to about 95 % and from about 80 % to about 90 %. The amount of co-product EVBO that is produced and that must be separated to obtain higher purity DVBDO is determined by DVB feed stock composition. In one preferred embodiment, the divinylarene feed stock purity may be greater than about 80 %.

In one embodiment, the process of the present invention may be particularly suited for the preparation of divinylbenzene dioxide, a low viscosity liquid epoxy resin. The viscosity of the divinylarene dioxides produced by the process of the present invention ranges generally from about 10 mP-s to about 100 mP-s at 25 °C in one embodiment; from about 10 mP-s to about 50 mP-s at 25 °C in another embodiment; and from about 10 mP-s to about 25 mP-s at 25 °C in still another embodiment.

The utility of the divinylarene dioxides of the present invention requires thermal stability to allow formulating or processing the divinylarene dioxides at moderate temperatures (for example, at temperatures of from about 100 °C to about 200 °C) for up to several hours (for example, for at least 2 hr or more) without oligomerization or homopolymerization. Oligomerization or homopolymerization during formulation or processing is evident by a substantial increase (e.g., greater than 50 fold) in viscosity or gelling (cros slinking). The divinylarene dioxides of the present invention have sufficient thermal stability such that the divinylarene dioxides do not experience a substantial increase in viscosity or gelling during formulation or processing at the aforementioned moderate temperatures.

The epoxy product produced by the process of the present invention, such as a divinylarene dioxide product, can be used in any application that conventional epoxy resins are used. For example, the epoxy product produced by the process of the present invention may be used as a component in a curable formulation or composition, which in turn, can be used to manufacture a cured thermoset product for various enduses such as coatings, films, adhesives, laminates, electronics, composites, and the like.

EXAMPLES

The following examples and comparative examples further illustrate the present invention in detail but are not to be construed to limit the scope thereof.

Various terms and designations used in the following examples are explained herein below:

"TPFPP" stands for [tetrakis (pentafluorophenyl)porphyrinato].

"GC" stands for gas chromatography.

"NMR" stands for nuclear magnetic resonance.

"DVB" stands for divinylbenzene.

"DVBDO" stands for divinylbenzene dioxide.

"DVBMO" stands for divinylbenzene monoxide.

"EVBO" stands for ethylvinylbenzene oxide.

"EVB" stands for ethylvinylbenzene.

"TON" stands for turnover number.

Example 1

In this example, an epoxidation reaction of DVB was carried out at room temperature (about 25 °C) resulting in a TON of 176 as follows: Into a 1.5 dram glass vial equipped with a magnetic stir bar, (TPFPP)FeCl (3.0 mg, 0.0028 mmol), DVB (36.6 mg, 40 μΐ,, 0.28 mmol), methanol (0.54 mL), and dichloromethane (0.18 mL) were added. Then, an aliquot of H ₂ 0 ₂ solution (15

0.022 mmol, 0.078 equivalent [equiv]) was added into the reaction mixture by a micropipette every 20 minutes (min). Finally, a total of 3.4 equiv of H ₂ 0 ₂ was added. Using GC and NMR techniques, the DVB conversions and DVBDO selectivities were measured.

The calculated DVB conversion (100 % based on GC) was calculated using the following equation (based on NMR):

([DVB] _initial - [DVB] _final ) / [DVB] _initial

The calculated yields of the reaction product including DVBDO (based on DVB), DVBMO (based on DVB), and EVBO (based on EVB) were calculated to be 75 %, 5 %, and 52 %, respectively.

Example 2

In this example, an epoxidation reaction of DVB at room temperature was carried out resulting in a TON of 441 as follows:

The same procedure of Example 1 was followed except that (TPFPP)FeCl (1.0 mg, 0.00094 mmol), DVB (30.6 mg, 33.5 μΐ,, 0.235 mmol), methanol (0.50 mL), and dichloromethane (0.17 mL) were used. Then, an aliquot of H ₂ 0 ₂ solution (5 μ ,

0.0074 mmol, 0.032 equiv) was added into the reaction mixture by a micropipette every 10 min (slower and more distributed H ₂ 0 ₂ addition extends the catalyst lifetime). And then, a total of 2.7 equiv of H ₂ 0 ₂ was added. The calculated yields of the reaction product including DVBDO (based on DVB), DVBMO (based on DVB), and EVBO (based on EVB) are 70 %, 4 %, and 37 %, respectively.

Example 3

In this example, an epoxidation reaction of DVB at room temperature was carried out resulting in a TON of 529 as follows:

The same procedure of Example 1 was followed except that (TPFPP)FeCl (1.0 mg, 0.00094 mmol), DVB (36.7 mg, 40.1 μΐ,, 0.282 mmol), methanol (0.60 mL), and dichloromethane (0.20 mL) were used. Then, an aliquot of H ₂ 0 ₂ solution (5 μλ _^ ,

0.0074 mmol, 0.030 equiv) was added into the reaction mixture by a micropipette every 10 min. And then, a total of 2.5 equiv of Η ₂ 0 ₂ was added. The calculated yields of the reaction product including DVBDO (based on DVB), DVB MO (based on DVB), and EVBO (based on EVB) are 66 %, 6 %, and 42 %, respectively.

Example 4

In this example, an epoxidation reaction of DVB at room temperature was carried out resulting in a TON of 598 as follows:

The same procedure of Example 1 was followed except that (TPFPP)FeCl (1.0 mg, 0.00094 mmol), DVB (44.1 mg, 48 μΐ,, 0.339 mmol), methanol (0.72 mL), and dichloromethane (0.24 mL) were used. Then, an aliquot of H ₂ 0 ₂ solution (5 μλ _^ ,

0.0074 mmol, 0.021 equiv) was added into the reaction mixture by a micropipette every 10 min. And then, a total of 1.8 equiv of H ₂ 0 ₂ was added. The calculated yields of the reaction product including DVBDO (based on DVB), DVB MO (based on DVB), and EVBO (based on EVB) are 49 %, 17 %, and 42 %, respectively.

Example 5

In this example, an epoxidation reaction of DVB at a temperature of 0 °C was carried out resulting in a high TON of 630 as follows:

The same procedure of Example 1 was followed except that (TPFPP)FeCl (1.0 mg, 0.00094 mmol), DVB (44.1 mg, 48 μΐ,, 0.339 mmol), methanol (0.72 mL), and dichloromethane (0.24 mL) were used. Then, an aliquot of H ₂ 0 ₂ solution (5 μλ _^ ,

0.0074 mmol, 0.021 equiv) was added into the reaction mixture by a micropipette every 10 min. Finally, a total of 1.8 equiv of H2O2 was added. The calculated yields of the reaction product including DVBDO (based on DVB), DVB MO (based on DVB), and EVBO (based on EVB) are 80 %, trace by GC, and 65 %, respectively.

Example 6

In this example, an epoxidation reaction of DVB at room temperature, and using imidazole as an additive, was carried out as follows:

The same procedure of Example 1 was followed except that (TPFPP)FeCl (3.0 mg, 0.0028 mmol), DVB (36.6 mg, 40 μΐ,, 0.28 mmol), imidazole (3.8 mg, 0.0559 mmol), methanol (0.54 mL), and dichloromethane (0.18 mL) were used. Then, an aliquot of H ₂ 0 ₂ solution (15 μ , 0.022 mmol, 0.078 equiv) was added into the reaction mixture by a micropipette every 20 min. Finally, a total of 3.2 equiv of H2O2 was added. The calculated yields of the reaction product including DVBDO (based on DVB), DVBMO (based on DVB), and EVBO (based on EVB) are 53 %, 27 %, and 82 %, respectively.

Example 7

In this example, an epoxidation reaction of DVB at room temperature, using acetonitrile (MeCN) and dichloromethane as solvents, and without the use of methanol, was carried out as follows:

The same procedure of Example 1 was followed except that (TPFPP)FeCl (1.5 mg, 0.0014 mmol), DVB (18.3 mg, 20 μΐ,, 0.14 mmol), acetonitrile (0.27 mL), and dichloromethane (0.09 mL) were used. Then, an aliquot of H ₂ 0 ₂ solution (7.5

0.011 mmol, 0.078 equiv) was added into the reaction mixture by a micropipette every 10 min. The color of the solution turned from black green to dark red. The total epoxide yield (after 8 hr) was calculated as follows (based on NMR): 34.81 (the epoxide integration at 2.55 ppm)/130.71 (the alkene integration at 5.56 ppm) x 100 % = 27 % yield. (GC measurement is unnecessary due to the low epoxide yield; presumably most of the epoxide is partially oxidized DVBMO due to the low yield.)

Example 8

In this example, an epoxidation reaction of DVB at room temperature, using water to dilute 50 % aqueous H ₂ 0 ₂ to 5 % to prepare the oxidant, and without the use of MeCN, was carried out as follows:

The same procedure of Example 1 was followed except that (TPFPP)FeCl

(2.0 mg, 0.00188 mmol), DVB (24.4 mg, 26.5 μΐ,, 0.188 mmol), methanol (0.42 mL), and dichloromethane (0.14 mL) were used. Then, an aliquot of H ₂ 0 ₂ oxidant solution

(10 μλ _^ , 0.015 mmol, 0.078 equiv) was added into the reaction mixture by a micropipette every 20 min. The calculated yields (after 9 hr) of the reaction product including DVBDO (based on DVB), DVBMO (based on DVB), and EVBO (based on EVB) are 42 %, 2.5 %, and 33 %, respectively.

Example 9

In this example, an epoxidation reaction of DVB at room temperature, using methanol to dilute 50 % aqueous H ₂ 0 ₂ to 5 % to prepare the oxidant, and without the use of MeCN, was carried out as follows: The same procedure of Example 1 was followed except that (TPFPP)FeCl (2.0 mg, 0.00188 mmol), DVB (24.4 mg, 26.5 fiL, 0.188 mmol), methanol (0.42 mL), and dichloromethane (0.14 mL) were used. Then, an aliquot of H ₂ 0 ₂ oxidant solution

(10 μλ _^ , 0.015 mmol, 0.078 equiv) was added into the reaction mixture by a micropipette every 20 min. The calculated yields (after 10 hr) of DVBDO (based on DVB), DVBMO (based on DVB), and EVBO (based on EVB) are 61 %, 2.9 %, and 45 %, respectively.

Example 10

In this example, an epoxidation reaction of DVB was carried out at room temperature; and the methanol (MeOH) concentration was reduced and the dichloromethane was increased to keep the same volume of solvent. The epoxidation reaction was carried out as follows:

The same procedure of Example 1 was followed except that (TPFPP)FeCl (2.0 mg, 0.00188 mmol), DVB (24.4 mg, 26.5 μΐ,, 0.188 mmol), methanol (0.21 mL), and dichloromethane (0.35 mL) were used. Then, an aliquot of H ₂ 0 ₂ solution (10 μλ _^ ,

0.015 mmol, 0.078 equiv) was added into the reaction mixture by a micropipette every 20 min. The calculated yields (after 5 hr) of the reaction product including DVBDO (based on DVB), DVBMO (based on DVB), and EVBO (based on EVB) are 16 %, 50 %, and 90 %, respectively.

Example 11

In this example, an epoxidation reaction of DVB at room temperature, using isopropyl alcohol was carried out as follows:

The same procedure of Example 1 was followed except that (TPFPP)FeCl (2.0 mg, 0.00188 mmol), DVB (24.4 mg, 26.5 μΐ,, 0.188 mmol), isopropyl alcohol (0.42 mL), and dichloromethane (0.14 mL) were used. Then, an aliquot of H ₂ 0 ₂ solution (10 μλ _^ , 0.015 mmol, 0.078 equiv) was added into the reaction mixture by a micropipette every 20 min. The calculated yields (after 4 hr) of the reaction product including DVBDO (based on DVB), DVBMO (based on DVB), and EVBO (based on EVB) are 11 %, 45 %, and 71 %, respectively. Example 12

In this example, an epoxidation reaction of DVB at room temperature, including increasing the concentration of DVB by using less solvent, was carried out as follows:

The same procedure of Example 1 was followed except that (TPFPP)FeCl

(1.0 mg, 9.4 x 10 ^"4 mmol), DVB (24.4 mg, 26.5 fiL, 0.188 mmol), methanol (0.21 mL), and dichloromethane (0.07 mL) were used. Then, an aliquot of H ₂ 0 ₂ solution (10 μλ _^ , 0.015 mmol, 0.078 equiv) was added into the reaction mixture by a micropipette every 20 min. The calculated yields (after 5 hr) of the reaction product including DVBDO (based on DVB), DVBMO (based on DVB), and EVBO (based on EVB) are 24 %, 46 %, and 85 %, respectively.

Example 13

In this example, an epoxidation reaction of DVB at room temperature, and using only methanol as solvent, without the use of dichloromethane, was carried out as follows:

The same procedure of Example 1 was followed except that (TPFPP)FeCl (2.0 mg, 0.00188 mmol), DVB (24.4 mg, 26.5 μΐ,, 0.188 mmol), and methanol (0.56 mL) were used. Then, 1,3,5-tribromobenzene (10.0 mg, 0.0318 mmol) was added into the reaction mixture as a GC internal standard. A GC sample was measured by taking one drop of the reaction mixture then adding into a GC vial. And then, 1.5 mL of benzene was added into the GC vial. The GC sample was measured as the reaction at 0 hr. An aliquot of H ₂ 0 ₂ solution (10 μ , 0.015 mmol, 0.078 equiv) was added into the reaction mixture by a micropipette every 20 min. Progress of the reaction was monitored by GC using the above mentioned procedure for GC sample preparation until the ratio of the areas of the alkene peaks to those for the 1,3,5-tribromobenzene internal standard stops decreasing. The calculated yields (after 10 hr) of the reaction product including DVBDO (based on DVB), DVBMO (based on DVB), and EVBO (based on EVB) are 21 %, 2.4 %, and 4.8 %, respectively.

Example 14

In this example, an epoxidation reaction of DVB at a temperature of 0 °C and using only methanol as solvent, without the use of dichloromethane, was carried out as follows: The same procedure of Example 1 was followed except that (TPFPP)FeCl (2.0 mg, 0.00188 mmol), DVB (24.4 mg, 26.5 fiL, 0.188 mmol), and methanol (0.56 mL) were added. 1,3,5-tribromobenzene (10.0 mg, 0.0318 mmol) was used into the reaction mixture as a GC internal standard. A GC sample was measured by taking one drop of the reaction mixture then adding into a GC vial. Then, 1.5 mL of benzene was added into the GC vial. The GC sample was measured as the reaction at 0 nr. The reaction mixture was kept at 0 °C in an ice bath during the reaction. An aliquot of Η ₂ 0 ₂ solution (10 μλ _^ ,

0.015 mmol, 0.078 equiv) was added into the reaction mixture by a micropipette every 20 min. Progress of the reaction was monitored by GC using the above mentioned procedure for GC sample preparation until the ratio of the areas of the alkene peaks to those for the 1 ,3,5-tribromobenzene internal standard stops decreasing. The calculated yields (after 10 hr) of the reaction product including DVBDO (based on DVB), DVB MO (based on DVB), and EVBO (based on EVB) are 44 %, 3.3 %, and 38 %, respectively.

Example 15

In this example, an epoxidation reaction of DVB was carried out at room temperature using Fe-porphyrin 2. The chemical structure of Fe-porphyrin 2 is as shown in the following Structure (VI):

Structure (VI) The epoxidation reaction was carried out as follows:

The same procedure of Example 1 was followed except that Fe-porphyrin 2 (2.5 mg, 0.0015 mmol), DVB (19.5 mg, 21.5 μΐ,, 0.150 mmol), methanol (0.3 mL), and dichloromethane (0.1 mL) were used. Then, an aliquot of H ₂ 0 ₂ solution (8.0 μλ _^ ,

0.0117 mmol, 0.078 equiv) was added every 20 min. The calculated yield of total number epoxide based on total number of alkene is 46 % after 10 hr. The calculated yields of the reaction product including DVBDO (based on DVB), DVB MO (based on DVB), and EVBO (based on EVB) are 3 %, 28 %, and 26 %, respectively.

Example 16

In this example, an epoxidation reaction of DVB was carried out at room temperature using Fe-porphyrin 3. The chemical structure of Fe-porphyrin 3 is as shown the following Structure (VII):

Structure (VII)

The epoxidation reaction was carried out as follows:

The same procedure of Example 1 was followed except that Fe-porphyrin 3

(2.0 mg, 0.0015 mmol), DVB (20.0 mg, 22 μΐ,, 0.154 mmol), methanol (0.33 mL), and dichloromethane (0.11 mL) were used. Then, an aliquot of H ₂ O ₂ solution (8.5

0.08 equiv) was added every 20 min. The calculated yield of total number epoxide based on total number of alkene is 21 % after 4 hr. (GC measurement is unnecessary due to the low epoxide yield, presumable most of the epoxide are the partially oxidized DVBMO due to the low yield.)

Example 17

In this example, an epoxidation reaction of DVB was carried out at room temperature using Fe-porphyrin 4. The chemical structure of Fe-porphyrin 4 is as shown in the following Structure (VIII):

Structure (VIII)

The epoxidation reaction was carried out as follows:

The same procedure of Example 1 was followed except that Fe-porphyrin 4 (1.8 mg, 0.0015 mmol), DVB (20.0 mg, 22 fiL, 0.154 mmol), methanol (0.33 mL), and dichloromethane (0.11 mL) were used. Then, an aliquot of H ₂ O ₂ solution (8.5

0.08 equiv) was added every 20 min. The calculated yields of total number epoxide based on total number of alkene is 61 % after 10 nr. The calculated yield of DVBDO (based on DVB), DVBMO (based on DVB), and EVBO (based on EVB) are 38 %, 43 %, and 74 %, respectively.

Example 18

In this example, an epoxidation reaction of DVB was carried out at room temperature using Fe-porphyrin 5. The chemical structure of Fe-porphyrin 5 is as shown in the following Structure (ΓΧ):

Structure (IX) The epoxidation reaction was carried out as follows:

The same procedure of Example 1 was followed except that Fe-porphyrin 5 (1.7 mg, 0.0015 mmol), DVB (20.0 mg, 22 μΐ,, 0.154 mmol), methanol (0.33 mL), and dichloromethane (0.11 mL) were used. Then an aliquot of Η ₂ 0 ₂ solution (8.5 μλ _^ ,

0.08 equiv) was added every 20 min. The calculated yield of total number epoxide based on total number of alkene is 35 % after 12 nr. The calculated yields of DVBDO (based on DVB), DVBMO (based on DVB), and EVBO (based on EVB) are 35 %, 3 %, and 21 %, respectively.

Example 19

In this example, an epoxidation reaction of DVB was carried out at room temperature using Fe-porphyrin 6. The chemical structure of Fe-porphyrin 6 is as shown in the following Structure (X):

Structure (X) The epoxidation reaction was carried out as follows:

The same procedure of Example 1 was followed except that Fe-porphyrin 6 (3.0 mg, 0.0019 mmol), DVB (24.6 mg, 27 μΐ,, 0.189 mmol), methanol (0.40 mL), and dichloromethane (0.14 mL) were used. Then, an aliquot of H ₂ 0 ₂ solution (10 μλ _^ ,

0.078 equiv) was added every 20 min. The calculated yields of total number epoxide based on total number of alkene is 77 % after 12 nr. The calculated yield of DVBDO (based on DVB), DVBMO (based on DVB), and EVBO (Based on EVB) are 69 %, 0 %, and 62 %, respectively. Example 20

In this example, an epoxidation reaction of DVB at room temperature, using in situ formed [ieirafc 5-(pentafluorophenyl)porphyrinato]iron(III) nitrate was carried out as follows:

A catalyst stock solution was prepared by the following described procedure:

Into a 1.5 dram glass vial of which the top screw part was wrapped by Teflon tape to ensure a good seal, (TPFPP)FeCl (12.5 mg, 0.0118 mmol) and AgN0 ₃ (2.0 mg, 0.012 mmol), acetonitrile (0.9 mL) and dichloromethane (0.3 mL) were added. The catalyst stock solution was kept at room temperature for 10 hr before being used.

The same procedure of Example 1 was followed except that the catalyst stock solution prepared above (0.19 mL, 0.00188 mmol), DVB (24.3 mg, 27 μλ _^ ,

0.188 mmol), methanol (0.3 mL), and dichloromethane (0.1 mL) were used. Then, an aliquot of H ₂ O ₂ solution (9.5 μλ _^ , 0.075 equiv) was added every 20 min. And then, a total of 2.0 equiv of H ₂ O ₂ was added to the solution. The calculated yields of total number epoxide based on total number of alkene is 52 % after 6 hr. The calculated yield of DVBDO (based on DVB), DVB MO (based on DVB), and EVBO (based on EVB) are 29 %, 43 %, and 66 %, respectively.

Comparative Example A - Epoxidation Reaction of Styrene Using Fe-Porphyrin 2

Into a 1.5 dram glass vial equipped with a magnetic stir bar, Fe-porphyrin 2 (3.0 mg, 0.00179 mmol), styrene (18.6 mg, 20.5 μΐ,, 0.179 mmol), methanol (0.39 mL), and dichloromethane (0.13 mL) were added. Then, an aliquot of H ₂ O ₂ solution (6.0 0.0088 mmol, 0.05 equiv) was added into the reaction mixture by a micropipette every 20 min. And then, a total of 2.2 equiv of H ₂ O ₂ was added to the reaction mixture. The calculated yield of styrene oxide (based on styrene) is 81 %.

Example 21 - Epoxidation Reaction of Divinylbenzene (DVB) with Fe-Porphyrin 2

This Example was carried out following the procedure similar to the "Procedure for Epoxidation Reaction of Divinylbenzene (DVB) using (TPFPP)FeCl" as described above and . The structure of Fe-porphyrin 2 is shown in Structure (VI).

Fe-porphyrin 2 (2.5 mg, 0.0015 mmol), DVB (19.5 mg, 21.5 μΐ,, 0.150 mmol), methanol (0.3 mL), and dichloromethane (0.1 mL) were mixed together to form a reaction mixture. An aliquot of H ₂ O ₂ solution (8.0 μλ _^ , 0.0117 mmol, 0.078 equiv) was added every 20 min to the reaction mixture. Then, a total of 2.1 equiv of H ₂ C>2 was added to the reaction mixture. The calculated yield of total number epoxide based on total number of alkene is 46 % after 10 hr.