Product containing monomer and polymers of titanyls and methods for making same

ES 2 345 705 T3

DESCRIPTION

Product containing titanyl monomer and polymers and methods of preparing them

Reference to related requests

This application claims priority over US Provisional Applications Nos.^you 60 / 924,214, filed May 3, 2007; 60 / 917,171, filed May 10, 2007; and 61 / 039,619 filed on March 26, 2008.

Countryside

The present invention relates generally to compounds of formula I. More specifically, the present invention relates to metal oxyalkoxide materials that can be precursors for nanoparticulate materials.

Background

Titanium dioxide (TiO2) is a ubiquitous white pigment used in the paint and coatings industry, and is also prevalent in the semiconductor industry. TiO2 exists both naturally and synthetically in three forms: rutile, anatase, and brookite. Synthetic methods for preparing TiO2 typically involve hydrolysis variants of titanium tetrachloride (TiCl4) or titanium oxychloride (titanyl chloride). For example, it has been known for over 100 years that reacting TiCl4 with water results in TiO2 by the following reaction (see BJ Harrington, Trans. Royal Soc. (Canada), [2], 1, 3 (1895)) :

TiCl4 + 2H2O TiO2 + 4HCl

As is quickly seen, HCl is a by-product of such hydrolysis. Such an acidic environment can also be problematic in many applications. For example, such an acidic environment can break down binders and other additives in materials that have incorporated TiO2, or it can react with coated substrates or TiO2-containing material. It should also be noted that TiCU is a hazardous material, mainly due to the acidic by-products produced by rapid hydrolysis, and requires special handling precautions.

As noted in the Encyclopedia of Chemical Reactions, vol. 7, page 404 "rutile crystals are obtained by the action of water vapor on volatile titanium chloride." The above reaction has been used by TiO2 producing industries to produce bulk TiO2 powders in large quantities. As used herein, "bulk powder" means a powder having an average particle size of greater than 100 nm, such as 1 micron or greater.

In Chemical Abstract 59: 33671 (Ukrainskii Khimicheskii Zhurnal (1963), 29, 440-9 (Russian edition)) complexes of titanium and glycerol have been disclosed. Patent document US 2005/0109677 discloses a process for purifying fuel streams containing organosulfur impurities; Silicon oxide catalysts containing titanium are used in this process.

For a wide variety of commercial applications, materials with one or more of the following properties are desirable: (a) the ability to form nanoparticles that can be dispersed in both water and organic solvents, (b) high optical transparency in the visible spectrum (400-700 nm) and high UV absorption (wavelength below 400 nm ), (c) maintaining the optical properties described in (b) above, while increasing the particle charge density in other materials beyond just a few percent by weight, such as beyond 5-10 percent in weigh, and (d) absence of a different material shell on the nanoparticles to allow the nanoparticles to bond or chemically bond with solid matrix materials, such as polymers. Sol-gels based on early transition metals (ie sols), such as those of Ti, Zr or Hf, can exhibit such desirable properties.

Therefore, the preparation of zirconium and titanium sols is desired in which residual acid and metal oxide formation due to hydrolysis is minimized, and electrical and optical properties of the materials are preserved.

Summary

In one aspect, a composition of a compound of formula I is provided: M_mOR_m(OR²)_n (I), or a mixture of any two or more thereof. M is Ti, Zr, or Hf; R² at each occurrence is individually a substituted alkyl group containing at least one OH group, a substituted cycloalkyl group containing at least one OH group, a substituted cycloalkylalkyl group containing at least one OH group, a substituted heterocyclyl group which

ES 2 345 705 T3 contains at least one OH group, or a heterocyclylalkyl containing at least one OH group; ymyn are independently an integer from one to eight. In some embodiments, the compound of formula I is a compound of formula II or III:

<img file="ES2345705T3_D0001.tif" />

an isomer of the compound of formula II or III, or a mixture of any two or more compounds and / or isomers. In such embodiments, M is Ti or Zr; R³ at each occurrence it is independently H, F, Cl, Br, I, CN, OR⁴, NR⁵R⁶, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted cycloalkylalkyl, unsubstituted heterocyclyl, or substituted or unsubstituted heterocyclylakyl; R⁴ is H, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted cycloalkylalkyl, unsubstituted heterocyclyl, or substituted or unsubstituted heterocyclylalkyl; R⁵ and R⁶ are independently H, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclylakyl, or R⁵ and R⁶ they can join to form a heterocyclic ring containing the N to which they are attached; and n 'is 0, 1, 2, 3, or 4.

In some embodiments of the compound, M is Ti. In some other embodiments of the compound, R³ at each occurrence is independently H, OR⁴, or a substituted or unsubstituted alkyl group. In other embodiments, the compound is bis (ethylene glycol) oxotitanium (IV), bis (glycerol) oxotitanium (IV), bis (erythritol) oxotitanium (IV), or bis (sorbitol) oxotitanium (IV). Such compounds described above may have a transmittance in the visible wavelength range of at least 90% and / or an ultraviolet light transmittance of less than about 20% in a wavelength range below about 400 nm. .

A method is disclosed that includes reacting a compound of formula MOX2 with a reagent comprising at least one hydroxyl group to form a first reaction mixture that includes the compound described above, HX, water, and the reagent; where the reagent is selected from alcohols, polyols, sugars, or starches; and X is a halide selected from the group consisting of F, Cl, Br, and I. Such procedures may also include removing the HX by at least one evaporation or neutralization to form a second reaction mixture. Reagents can include, but are not limited to, polyols such as ethylene glycol, glycerol, erythritol, and sorbitol. In some embodiments, the HX is removed by reacting a base with the first reaction mixture. Exemplary bases may include alkali metal alkoxides, alkaline earth metal alkoxides, primary amines, secondary amines, and tertiary amines, such as but not limited to triethylamine, diisopropylamine, trimethylamine, tripropylamine, tributylamine, or tert-butyl-methylamine.

In other aspects, compositions are also provided that include one or more of the above compounds and a solvent, or one or more of the above compounds in a polymeric resin. Such solvents can include polar organic solvents and water. Such polymeric resins can include polyurethanes; polyethylene glycol; epoxy resins; polyacrylates; polyamides; polyesters; polyacrylonitriles; cellulosic materials including, but not limited to acetates, nitrates, and the like; phenolic resins; pentaerythritol resins; polyvinylpyrrolidone; polysaccharides; polyglucuronates; copolymers of such materials, or combinations of any two or more. In some embodiments of the compound in a polymeric resin, the compound of formula II, III, or the mixture of any two or more causes a change in the refractive index of the resin compared to a pure resin. In such embodiments, the pure resin is the resin without any of the identified compounds added. In other embodiments, the compound of formula I, II, or III, or the mixture of any two or more hydrolyzes and causes a change in the refractive index of the resin compared to a pure resin.

In another aspect, devices are provided incorporating such compositions. In other aspects, a device is provided having a thin film of the compound of formula M_mOR_m(OR²) n on a substrate.

In another aspect, the method of adjusting the refractive index of a polymer is provided, which includes doping the polymer with one or more of the above compounds of formula M_mOR_m(OR²) n. The polymer can be doped at a level of from about 1% to about 90%.

The compound of formula M_mOR_m(OR²) n can be used as an esterification catalyst,

ES 2 345 705 T3 transesterification or crosslinking agent.

Multi-component UV stabilizer systems for coatings are disclosed. Such systems include a compound composition of formula MmO_m(OR²) not a hydrosylate of the compound; a substituted hydroxyphenyl-benzotriazole and a light stabilizer of hindered amines.

In another aspect, the compound of formula I can be used in a fuel decontamination method. In some embodiments, the method includes providing a fuel comprising a fuel source, preparing a mixture of the fuel, a compound of formula I, an organic acid; and an oxidant; and recovering a decontaminated fuel. In some embodiments, the compound of formula I is selected from the group consisting of bis (ethylene glycol) oxotitanium (IV), bis (glycerol) oxotitanium (IV), bis (erythritol) oxotitanium (IV), or bis (sorbitol) oxotitanium (IV ). In other embodiments, the organic acid is selected from the group consisting of HCO2H, CH3-xClxCO2H, CF3CO2H, and mixtures of any two or more thereof, where x is an integer from 0-3. In still other embodiments, the oxidant is selected from the group consisting of nitrogen oxides, nitric acid, hydrogen peroxide, ozone, organic peroxides, oxygen, air, peracids, and mixtures of any two or more thereof.

A sulfoxidation method is disclosed, comprising: providing a hydrocarbon solution, said solution comprising a sulfur compound; providing a catalytic solution, said catalytic solution comprising a metal alkoxide represented by the formula MmOm (OR) n; and contacting said hydrocarbon solution with said catalytic solution in the presence of an oxidant, resulting in said oxidant oxidizing said sulfur compound.

A catalytic sulfoxidation reagent is disclosed, comprising: an acidic solvent; a metal alkoxide represented by the formula MmOm (OR²) n dissolved in said solvent; and an oxidant dissolved in said solvent.

Another embodiment relates to a sulfoxidation method, comprising; introducing a hydrocarbon solution into a reaction vessel, said hydrocarbon solution comprising a sulfur compound; and introducing a catalyst solution into said container, resulting in said catalyst solution being contacted with said hydrocarbon solution, said catalyst solution comprising a metal alkoxide catalyst represented by the formula MmOm (OR) n, giving as a result the formation of a mixture, resulting in said catalyst catalyzing an oxidation reaction between said oxidant and said sulfur compound and oxidizing said sulfur compound. Resulting in said oxidized sulfur compound having higher solubility in said catalyst solution than in said hydrocarbon solution.

Brief description of the drawings

Figure 1 is a scheme (Scheme I) showing the compounds of the invention and methods of preparation. Titanyl compounds are given by way of example in the scheme.

Figure 2 is a flow chart of the preparation of neutralized titanyl compounds as a pure chemical species, in powder, according to one or more embodiments of the invention.

Figure 3 is a pseudo-first order diagram for the oxidation of benzothiophenes (ratio of oxidant: S 26: 1, ratio of S: Ti 9700, ratio of acetic acid: mass of petroleum 2).

Figure 4 is a Pareto analysis chart of samples 1-18 (AA = Acetic Acid, Temp = Temperature, Cat = Catalyst Loading, Perox = Peroxide Concentration).

Figure 5 is a schematic of potential oxidation reactions and relevant mass transfers and Figure 6 is a process flow diagram of one embodiment of a sulfoxidation process.

Detailed description

Compositions of matter and methods of preparing compounds of formula MmOm (OR²) n, where M is Ti or Zr, OR² is derived from a reagent containing at least two OH groups and myn are 1-

8. For example, the reagent can be a polyol or an alcohol such as, but not limited to, ethylene glycol, glycerol, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, erythritol, or sorbitol, and the like; a sugar; or a starch. In some embodiments, when m equals n, R² forms a ring structure with the titanium atom forming a ring that contains at least five members. As part of the synthesis procedure, residual acid is removed and / or neutralized from the reaction solution. The resulting compositions of matter are useful as precursors for TiO2 in that they do not produce HCl as a by-product of hydrolysis, but rather simple alcohols. This makes them much more suitable as additives for plastics, solvents, coatings, and the like where titanium oxychloride would be unsuitable. The reaction products are distinguished

ES 2 345 705 T3 of typical alkoxytitanates in which those incorporated herein appear to maintain the Ti = O bond. This bond appears to be important in maintaining strong UVC-UVB absorption compared to tetraalkoxytitanates. Furthermore, the compounds incorporated herein allow the formulation of visibly transparent, UV absorbing titanium materials without the milky white color provided by traditional titania and zirconia nanoparticles.

Definitions

For the purposes of this disclosure and unless otherwise specified, "a" or "an" means "one or more."

As used herein, "approximately" will be understood by those of ordinary skill in the art and will vary to some extent depending on the context in which it is used. If there are uses of the term that are not clear to those of ordinary skill in the art, given the context in which they are used, "about" will mean up to plus or minus 10% of the particular term.

In general, "substituted" refers to an alkyl, cycloalkyl, cycloalkylalkyl, heterocyclyl, or heterocyclylalkyl group, as defined below (eg, an alkyl group) in which one or more bonds with a hydrogen atom contained therein they are replaced by a bond with non-carbon or non-hydrogen atoms. Substituted groups also include groups in which one or more bonds with a carbon or hydrogen atom are replaced by one or more bonds, including double or triple bonds, with a heteroatom. Thus, a substituted group will be substituted with one or more substituents, unless otherwise specified. In some embodiments, a substituted group is substituted with 1, 2, 3, 4, 5, or 6 substituents. Examples of substituent groups include: halogens (ie, F, Cl, Br, and I); hydroxyls; alkoxy, alkenoxy, heterocyclyloxy, and heterocyclylalkoxy groups; carbonyls (oxo); carboxyls; esters; ethers; urethanes; alkoxyamines; thiols; sulfides; sulfoxides; sulfones; sulfonyls; sulfonamides; amines; N-oxides; isocyanates; cyanates; thiocyanates; nitro groups; nitriles (ie CN); and the like.

Substituted ring groups such as substituted cycloalkyl, aryl, heterocyclyl, and heteroaryl groups also include fused rings and ring systems in which a bond to a hydrogen atom is replaced by a bond to a carbon atom. Thus, substituted cycloalkyl, aryl, heterocyclyl, and heteroaryl groups can also be substituted with substituted or unsubstituted alkyl or alkenyl groups as defined below.

Alkyl groups include straight chain or branched alkyl groups having 1 to 12 carbon atoms or, in some embodiments, 1 to 8, 1 to 6, or 1 to 4 carbon atoms. Alkyl groups further include cycloalkyl groups as defined below. Examples of straight chain alkyl groups include those with from 1 to 8 carbon atoms such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl groups. Examples of branched alkyl groups include, but are not limited to, isopropyl, iso-butyl, sec-butyl, tert-butyl, neopentyl, isopentyl, and 2,2-dimethylpropyl groups. Representative substituted alkyl groups may be substituted one or more times with substituents such as those listed above.

Alkenyl groups include straight and branched chain and cycloalkyl groups as defined above, except that there is at least one double bond between two carbon atoms. Thus, alkenyl groups have from 2 to about 12 carbon atoms in some embodiments, from 2 to 10 carbon atoms in other embodiments, and from 2 to 8 carbon atoms in other embodiments. Examples include, but are not limited to, vinyl, allyl, -CH = CH (CHa), -CH = C (CH3) 2, -C (CHa) = CH2, -C (CHa) = CH (CHa), - C (CH2CHa) = CH2, cyclohexenyl, cyclopentenyl, cyclohexadienyl, butadienyl, pentadienyl and hexadienyl, among others. Representative substituted alkenyl groups may be monosubstituted or substituted more than once, such as, but not limited to, mono, di, or trisubstituted with substituents such as those listed above.

Cycloalkyl groups are cyclic alkyl groups such as, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. In some embodiments, the cycloalkyl group has 3 to 8 ring members, while in other embodiments the number of carbon atoms in the ring ranges from 3 to 5, 3 and 6, or 3 and 7. Cycloalkyl groups also include systems mono, bicyclic and polycyclic ring. Substituted cycloalkyl groups may be substituted one or more times with non-hydrogen and non-carbon groups as defined above. However, substituted cycloalkyl groups also include rings that are substituted with straight or branched chain alkyl groups as defined above. Representative substituted cycloalkyl groups may be monosubstituted or substituted more than once, such as, but not limited to, 2,2-, 2,3-, 2,4-, 2,5-, or 2,6-disubstituted cyclohexyl groups. , which may be substituted with substituents such as those listed above.

Cycloalkylalkyl groups are alkyl groups as defined above in which a carbon or hydrogen bond of an alkyl group is replaced with a bond with a cycloalkyl group as defined

ES 2 345 705 T3 above. In some embodiments, cycloalkylalkyl groups have from 4 to 20 carbon atoms, from 4 to 16 carbon atoms, and usually from 4 to 10 carbon atoms. Substituted cycloalkylalkyl groups can be substituted on the alkyl, cycloalkyl, or both alkyl and cycloalkyl portions of the group. Representative substituted cycloalkylalkyl groups may be monosubstituted or substituted more than once, such as, but not limited to, mono, di, or trisubstituted with substituents such as those listed above.

Aryl groups are cyclic aromatic hydrocarbons that do not contain heteroatoms. Aryl groups include monocyclic, bicyclic, and polycyclic ring systems. Thus, aryl groups include, but are not limited to, phenyl, azulenyl, heptalenyl, biphenylenyl, indacenyl, fluorenyl, phenanthrenyl, triphenylenyl, pyrenyl, naphthacenyl, chrysenyl, biphenyl, anthracenyl, indenyl, indanyl, pentalenyl, and naphthalenyl groups. In some embodiments, the aryl groups contain 6-14 carbons, and in others from 6 to 12 or even 6-10 carbon atoms in the ring portions of the groups. Although the term "aryl groups" includes groups that contain fused rings, such as fused aromatic-aliphatic ring systems (eg, indanyl, tetrahydronaphthyl, and the like), it does not include aryl groups that have other groups, such as alkyl or halo groups. , attached to one of the members of the ring. Rather, groups such as tolyl are called substituted aryl groups. Representative substituted aryl groups may be monosubstituted or substituted more than once. For example, monosubstituted aryl groups include, but are not limited to, 2-, 3-, 4-, 5- or 6-substituted naphthyl or phenyl groups, which may be substituted with substituents such as those listed above.

Aralkyl groups are alkyl groups as defined above in which a carbon or hydrogen bond of an alkyl group is replaced with a bond with an aryl group as defined above. In some embodiments, the aralkyl groups contain 7 to 20 carbon atoms, 7 to 14 carbon atoms, or 7 to 10 carbon atoms. Substituted aralkyl groups can be substituted on the alkyl, aryl, or both alkyl and aryl portions of the group. Representative aralkyl groups include but are not limited to benzyl and phenethyl groups and fused (cycloalkylaryl) alkyl groups such as 4-ethyl-indanyl. Representative substituted aralkyl groups may be substituted one or more times with substituents such as those listed above.

Heterocyclyl groups include aromatic (also referred to as heteroaryl) and non-aromatic ring compounds containing 3 or more ring members, one or more of which is a heteroatom such as, but not limited to, N, O, and S. In some In embodiments, heterocyclyl groups include 3 to 20 ring members, while other such groups have 3 to 6, 3 to 10, 3 to 12, or 3 to 15 ring members. Heterocyclyl groups encompass saturated, partially saturated, and unsaturated ring systems, such as, for example, imidazolyl, imidazolinyl, and imidazolidinyl groups. However, the term "heterocyclyl group" does not include heterocyclyl groups that have other groups, such as alkyl, oxo, or halo groups, attached to one of the ring members. Rather, these are called "substituted heterocyclyl groups." Heterocyclyl groups include, but are not limited to, aziridinyl, azetidinyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, thiazolidinyl, tetrahydrothiophenyl, tetrahydrofuranyl, dioxolyl, furanyl, thiophenyl, pyrrolyl, pyrrolinyl, imidazolidinyl, pyrazolinyl, imidazolidinyl, pyrazolinyl, imidazolyl, pyrazolinyl, pyrazolinyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, thiazolinyl, isothiazolyl, thiadiazolyl, oxadiazolyl, piperidyl, piperazinyl, morpholinyl, thiomorpholinyl, tetrahydropyranyl, tetrahydrothiopyranyl, oxathiano, dioxyl, dithianyl, pyranyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, dihydropyridyl, dihydrodithiinyl, dihydroditionyl, homopiperazinyl, quinuclidyl, indolyl, indolinyl, azaindolidazinyl, benzoindolinyl, indolinyl, azaindolidazinyl, benzoindolimidazinyl, indolinyl, azaindolidazinyl, , benzothiophenyl, benzothiazolyl, benzoxadiazolyl, benzoxazinyl, benzodithiinyl, benzoxatiinyl, benzothiazinyl, benzoxazolyl, benzothiazolyl, benzothiadiazolyl, benzo [1,3] dioxolyl, pyrazolopyridyl, imidazopyridyl (azabenzimidazolyl), triazolopyridyl, isoxazolopyridyl, purinyl, xanthinyl, adeninyl, guaninyl, quinolinyl, isoquinolinyl, quinolizinyl, quinoyloxalinyl, dyninyloxalinyl, cynininyloxalinyl, cynininyloxalinyl, cyninylophthylatedropyridyl, quinoidyloxalinyl, cynininyloxalinyl , dihydrobenzofuranyl, dihydroindolyl, dihydrobenzodioxinyl, tetrahydroindolyl, tetrahydroindazolyl, tetrahydrobenzimidazolyl, tetrahydrobenzotriazolyl, tetrahydropyrrolopyridyl, tetrahydropyrazolopyridyl, tetrahydroimidazopyridyl, tetrahydrotriazolopyridyl, and tetrahydroquinolinyl. Representative substituted heterocyclyl groups may be monosubstituted or substituted more than once, such as, but not limited to, pyridyl or morpholinyl groups, which are 2-, 3-, 4-, 5- or 6-substituted, or disubstituted with various substituents such as those listed above.

Heterocyclylalkyl groups are alkyl groups as defined above in which a carbon or hydrogen bond of an alkyl group is replaced with a bond with a heterocyclyl group as defined above. Substituted heterocyclylalkyl groups can be substituted on the alkyl, heterocyclyl, or both alkyl and heterocyclyl portions of the group. Representative heterocyclylalkyl groups include, but are not limited to, 4-ethyl-morpholinyl, 4-propylmorpholinyl, furan-2-yl-methyl, furan-3-yl-methyl, pyridin-3-yl-methyl, tetrahydrofuran-2- yl-ethyl and indol-2-yl-propyl. Representative substituted heterocyclylalkyl groups may be substituted one or more times with substituents such as those listed above.

Alkoxy groups are hydroxyl groups (-OH) in which the bond to the hydrogen atom is replaced by a bond to a carbon atom of a substituted or unsubstituted alkyl group as defined above. Examples of linear alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, and the like. Examples of branched alkoxy groups include but are not limited to

ES 2 345 705 T3 isopropoxy, sec-butoxy, tert-butoxy, isopentoxy, isohexoxy, and the like. Examples of cycloalkoxy groups include but are not limited to cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, and the like. Representative substituted alkoxy groups may be substituted one or more times with substituents such as those listed above. As used herein, the term "high boiling point" includes materials that have a boiling point greater than 50 ° C, 60 ° C, 70 ° C, 80 ° C, 90 ° C, 100 ° C, 120 ° C, 140 ° C, 160 ° C, 180 ° C or 200 ° C at atmospheric pressure. In some embodiments, a high boiling material has a boiling point of from about 200 ° C to about 600 ° C at atmospheric pressure.

The term "amine" (or "amino") as used herein refers to -NR groups⁵R⁶, in which R⁵ and R⁶are independently H, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclylakyl, or R⁵ and R⁶ they can join to form a heterocyclic ring and / or group containing the N to which they are attached. In some embodiments, the amine is NH₂, methylamino, dimethylamino, ethylamino, diethylamino, propylamino, dipropylamino, isopropylamino, diisopropylamino, phenylamino or benzylamino.

The term "nanoparticles" includes particles that have an average size of between about 2 and about 100 nm, in some embodiments, or an average size of between about 2 and about 50 nm, in other embodiments. Nanoparticles can also have an average size of between about 2 and about 10 nm. The first standard deviation of the size distribution can be 60% or less, 40% or less, or 10 to 25% of the average particle size, each in various embodiments. The nanoparticles can also include oxide nanoparticles, such as metal or semiconductor oxide nanoparticles, such as zirconium oxide or titanium oxide. Specifically, the nanoparticles can comprise nanoparticles of titania, zirconia or hafnium oxide, which in their pure stoichiometric state can be expressed by the following respective chemical formulas: TiO₂, ZrO₂ and HfO₂.

As used herein, the term "reactive distillation" is a process where the chemical reactor is also the still. Separating a material from the reaction mixture does not need a separate distillation step, which saves energy (for heating) and materials.

As used herein, the term "reactive extrusion" is a process where the chemical reactor is the extruder. The separation of a material from the reaction mixture occurs during the extrusion process, whereby the final product exits the extruder.

Compounds

In one aspect, a compound of formula M is provided._mOR_m(OR²) n, or a mixture of any two or more, where M is Ti, Zr or Hf; R² at each occurrence is a substituted alkyl group containing at least one OH group, a substituted cycloalkyl group containing at least one OH group, a substituted cycloalkylalkyl group containing at least one OH group, a substituted heterocyclyl group containing at least one group OH or a heterocyclylalkyl containing at least one OH group; ymyn are independently 1-8. For example, R² it can be derived from a polyol, a sugar or a starch. Suitable polyols include, but are not limited to, ethylene glycol, propylene glycol, glycerol, erythritol, ethylene glycol butyl ether, and sorbitol. In some embodiments, m is one and n is two. In some cases, the compositions may have two or more different compounds of formula M_mOR_m(OR²) n. In some embodiments, the compound has the formula (I):

<img file="ES2345705T3_D0002.tif" />

r²or or² .

In some embodiments, the compound of formula M_mOR_m(OR²) n, has the formula M_mOR_m(OCHR³CH (OH) R³) n (II), or a mixture of any two or more. In such compounds, M is selected from Ti, Zr, or Hf. In each occurrence, R³can be selected independently of, but not limited to, H, F, Cl, Br, I, CN, OR⁴, NR⁵R⁶, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted cycloalkylalkyl, unsubstituted or substituted heterocyclyl, or substituted or unsubstituted heterocyclylakyl; R⁴ is selected from, but not limited to, H, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted cycloalkylalkyl, unsubstituted or substituted heterocyclyl or heterocyclylalkyl; R⁵ and R⁶ are independently H, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclylakyl, or R⁵ and R⁶ they can join to form a heterocyclic ring containing the N to which they are attached; m is usually an integer from 1 to 8; and n is normally an integer from 1 to 8. The compound of formula II thus described can be represented by the following formula, where m is one and n is two:

ES 2 345 705 T3

<img file="ES2345705T3_D0003.tif" />

In other embodiments, the compound of formula M is provided_mOR_m(OR²) n where n is equal to m, and the oxygen O of the at least one OH group in R² it is deprotonated and attached to M, thus forming a ring structure that has five or more ring members. Such ring structures can be represented by the formula (III):

(III)

<img file="ES2345705T3_D0004.tif" />

where n 'is 0, 1,2, 3 or 4.

<img file="ES2345705T3_D0005.tif" />

In some embodiments, the compound of formula I is a titanyl compound. Examples of such titanyl compounds include bis (ethylene glycol) oxotitanium (IV), bis (glycerol) oxotitanium (IV), bis (erythritol) oxotitanium (IV) and bis (sorbitol) oxotitanium (IV), but are not limited to this. by way of the scope of the titanyl compounds incorporated herein.

When polyols or other reagents having multiple -OH groups are used to prepare the compounds incorporated herein, multiple -OH groups are available in the reagent to bind to the metal atom. This can result in several possible regioisomers of the prepared compounds. As a non-limiting example, when the compound is bis (glycerol) oxotitanium (IV), the compound can be represented by the following formulas:

<img file="ES2345705T3_D0006.tif" />

ES 2 345 705 T3

There are at least two other regioisomers. Such isomers are known to those of skill in the art and can include any of the -OH groups in the glycerol moiety attached to the metal. Such a regioisomer is:

<img file="ES2345705T3_D0007.tif" />

<img file="ES2345705T3_D0008.tif" />

and another such regioisomer is:

<img file="ES2345705T3_D0009.tif" />

<img file="ES2345705T3_D0010.tif" />

Since the glycerol residue contains a chiral center in cases where the compound has a TiOCH2C * H (OH) CH2 (OH) fragment, indicating * the chiral center, at least six stereoisomers of the above regioisomers are also known and will be recognized easily by those skilled in the art.

As a non-limiting example, when the compound is bis (ethylene glycol) oxotitanium, the compound can be represented by the following formula:

<img file="ES2345705T3_D0011.tif" />

In one embodiment, the compound has the following properties: a visible light transmittance of 90%, an ultraviolet light transmittance of less than about 20% below 400 nm, optical transparency, and / or colorless optically and spectroscopically. Transmission and absorbance are based on a 10% w / w solution as measured in a one cm quartz cell.

In some embodiments, the compounds are prone to hydrolysis to form organometallic polymers, such as polyoxometalates or other materials that arise as a result of incomplete hydrolysis of the compounds such that some polyol functionality remains at the periphery of the hydrolyzed product. Polyoxometalates can include materials such as, but not limited to, polyoxotitanates or polyoxozirconates having alcohol or polyol functionality.

In some other embodiments, the hydrolysis products can be calcined to form nanoparticles of the corresponding metal dioxide, such as titanium dioxide (ie, titania), zirconium dioxide (ie, zirconia), or hafnium dioxide. For example, the compound of formula II, where M is Ti, can be hydrolyzed in the presence of heat to form nanoparticles of TIO2.

ES 2 345 705 T3

A process for preparing compounds of formulas I, II and III is disclosed. As shown in Figure 1, in some embodiments, the first step in the process involves reacting a compound of formula MOX2 with a reagent having at least one hydroxyl group to form a first reaction mixture that includes the compound of formula I, II and / or III and HX. The first reaction mixture can also contain water and polyol. Optionally, a viscosity modifier, such as methoxypropanol, can be added to the first reaction mixture. Furthermore, as depicted in Figure 1, the HX can then be removed by evaporation, such as through simple evaporation, reactive distillation, or reactive extrusion; and / or through neutralization to form a second reaction mixture, containing the compound of formula I, II and / or III, water, and polyol. As mentioned above, M is a metal selected from Ti, Zr, and Hf; and X is a halogen atom such as F, Cl, Br, or I. Reagents that are suitable for use in the process include, but are not limited to, polyols, alcohols, sugars, and starches that have a high boiling point. . The first reaction mixture can be a UV absorbing, optically clear acidic material, which can then be neutralized by reaction with a base to form the second reaction mixture. The resulting solution can then be further modified by various procedures.

As noted above, HX can be removed via reactive distillation or reactive extrusion in some cases. In such procedures, hydrolysis is carried out either in the reactor or in the extruder, and the HX is removed from the reaction mixture. In the case of reactive distillation, the HX can be removed as gas from the reactor. In the case of reactive extrusion, the HX can be withdrawn from the extruder through vents located in the extruder. Without wishing to be bound by theory, it is believed that the removal of HX from the reaction mixture drives the hydrolysis reaction to completion.

The compound of formula MOX2 can be present at a concentration of from about 20% to about 50%, from about 25% to about 45%, from about 30% to about 40%, or from about 35%. % to about 36% before reaction with the organic reagent. In other embodiments, reagent is added in an amount of two equivalents for each equivalent of the compound of formula MOX2.

The polyol can be a substituted alkyl group, a substituted cycloalkyl group, a substituted cycloalkylalkyl group, a substituted heterocyclyl group, or a substituted heterocyclylalkyl group, having two or more OH groups that can react with the MOX2 compound. Suitable polyols include, but are not limited to, ethylene glycol, glycerol, propylene glycol, butanediols, butanetriols, erythritol, and sorbitol.

The step of removing the HX by neutralization involves reacting the compound with a base to remove the HX. Suitable bases include OH-free bases such as, but not limited to, alkali metal alkoxides, alkaline earth metal alkoxides, and amines, including, but not limited to, primary amines, secondary amines, tertiary amines, and heterocyclylalkylamines. Suitable amines can be selected from, but not limited to, triethylamine, diisopropylamine, trimethylamine, tripropylamine, tributylamine, and tert-butyl-methylamine. The HX that is generated by the compounding reaction reacts with the base to form a salt that can be removed from the reaction mixture in some embodiments. In the case where the base is selected from alkali metal alkoxides and alkaline earth metal alkoxides, the result is the formation of a salt of X and the alkali or alkaline earth metal. In the case where the base is selected from an amine, the result is an ammonium salt of X. In either case, the salt of X is then removed from the reaction mixture by decantation, centrifugation followed by decantation, cannulation, filtration. or sublimation.

As a non-limiting example, titanium compounds can be formed, as shown in Figure 1. For example, TiOCl2 can be reacted with glycerol, a high-boiling polyol, and after the first stage of the process, that is, On formation of the first reaction mixture, an acidic, optically clear, UV absorbing material is formed containing TiO (OCH2CH (OH) CH2OH) 2, or an isomer, HCl, glycerol, and optionally water. In some embodiments, the pH of the solution is less than one.

As discussed above, the second reaction mixture, ie, the base neutralization product, can be used in a number of other procedures. In some embodiments, the method includes precipitating a compound of formula I, II, or III from the filtrate. In some embodiments, this precipitation is accomplished by the addition of an antisolvent, as shown in Figure 1. Such anti-solvents can be any one of several non-polar solvents, or a mixture of any two or more solvents. For example, antisolvents may include, but are not limited to, acetone, alkanes such as pentane, hexane, or octane, benzene, toluene, tetrahydrofuran, diethyl ether, methyl-2-pentanyl, methyl tert-butyl ether, methyl ethyl ketone, and / or mixtures of any two or more anti-solvents.

Compositions / devices

Also provided are compositions containing the compounds of formula I, II, III, or mixtures of any two or more of these compounds in a solvent. The solvent can be a viscosity modifier. Suitable solvents and viscosity modifiers for such compositions include, but are not limited to,

ES 2 345 705 T3 polar organic solvents and water. For example, suitable polar organic solvents can include methanol, ethanol, propanol, butanol, tert-butanol, methoxypropanol, trimethoxypropanol, propylene glycol, ethylene glycol, glycerol, DMSO, DMF, pyridine, and / or a mixture of any two or more of such solvents. .

Other compositions can include the compounds of formulas I, II, III or a mixture of any two or more, and a polymeric resin. Suitable polymeric resins for such compositions include, but are not limited to, polyurethanes, polyethylene glycol, epoxy resins, polyacrylates, polyamides, polyesters, polyacrylonitriles, cellulosic materials such as acetates, nitrates, and the like, phenolic resins, pentaerythritol resins, polyvinyl pyrrolls, polyvinyne, polysaccharides, polyglucuronates or copolymers or mixtures of any two or more. Polymeric resins can be cured, or at least partially cured. As used herein, cured means that the resin can undergo a process that results in one or more hardening, polymerization, or thickening to provide a cured polymeric resin.

As with other materials containing the compounds of the specified formulas, the inclusion of the compounds of formula I, II, III, or a mixture of any two or more in the polymeric resin compositions produces a change in the refractive index, Δη , of the resin compared to the resin without the compound (s). For example, η can range from about 1 to about 2, from about 1.2 to about 1.95, from about 1.3 to about 1.9, or from about 1.33 to about 1.9, such as 1.52. In some embodiments, the addition of the compounds to a polymeric resin is called doping of the polymer with the compound (s). Such a doping includes when the compound (s) is (are) present at a level greater than about 1 ppm, in the polymer. The compound (s) may be present at a level of up to and including 90%, when doped into a polymer. Thus, doping, in some embodiments, includes when the compounds are present at a level of from about 1% to about 90%, in the polymer.

Compositions of the compound (s) in a polymeric resin can be formed, molded or machined into various devices. Such devices can include a thin film of the compound of formula I, II, III, or a mixture of any two or more on a substrate. Suitable substrates can include metal, glass, ceramic, and / or plastics. Transmittance of at least 90% and / or ultraviolet transmittance of less than about 20% in a wavelength range below about 400 nm. Figure 3 is a flow chart describing the process of formation of the neutralized titanyl compound as a pure, powdered chemical species. In some embodiments, the particles are a plurality of particles.

Devices can also be prepared from a substrate as described above. The substrate includes, but is not limited to, glass, metal, polymer, wood, ceramic, paper, fabric, or a combination of any two or more thereof. In some specific embodiments, the substrate is a spectacle lens, a camera lens, a binocular lens, a telescope lens, a mirror, a Fresnel lens, a compact disc, a DVD disc, a hologram, a window, a mobile phone, personal data assistant, calculator, television, electronic paper, computer privacy filter, or computer touch screen.

In other aspects, the compounds described herein are useful as esterification catalysts, transesterification catalysts, and / or crosslinking agents.

Due to a wide variety of applicability for such materials, the above compositions and compounds can be used in UV stabilizer systems for coatings. Such stabilizer systems can include a compound of formula I, II or III, a hydrosylate of a compound of formula I, II or III, or a particle of titania or zirconia obtained from any of the above methods, a substituted hydroxyphenyl-benzotriazole , and a hindered amine light stabilizer. The UV light protective efficacy of the multi-component system typically exceeds that of a system having the substituted hydroxyphenyl-benzotriazole and a hindered amine light stabilizer at the same levels, but without the added compounds or particles. Without wishing to be bound by theory, the combination of the above materials in the UV stabilizer system appears to have a synergistic effect on the additive properties of the components, individually or in binary combinations. In other such embodiments, suitable hydroxyphenyl benzotriazoles are known to those skilled in the art and include, but are not limited to, various of the hydroxyphenyl benzotriazoles in the Tinuvin® class of compounds, and the like. Exemplary Tinuvin® hydroxyphenyl-benzotriazole compounds are those such as Tinuvin® P, TP, 99-2, 171, 384, 400, R-796, 900, 928 and 1130. In still other such embodiments, the Hindered amine light stabilizers (HAL) are known to those skilled in the art, and include, but are not limited to, several of the HALs in the Tinuvin® class of compounds, and the like. Exemplary Tinuvin® HAL compounds are those such as Tinuvin® 111, 123, 144, 152, 292, 292-HP, 622 and 5100. CHIMASORB 119 is another suitable HAL compound. In some embodiments, the hydrosylate or composition is present from less than 1% by weight to about 5% by weight or from about 0.5% by weight to about 4% by weight, or from about 1% by weight. up to about 3% by weight. In additional embodiments, the hydroxyphenyl-benzotriazole is present from about 0.1% by weight to about 5% by weight, or from about 1% by weight to about 3% by weight; and the hindered amine light stabilizer is present from

ES 2 345 705 T3 about 0.5% by weight to about 4% by weight, or from about 0.5% by weight to about 2% by weight. Such UV stabilizers can be used in a variety of paints and coatings known to those of skill in the art.

Desulfurization

The compounds can be used in processes to reduce the sugar content of fuels. Reducing the sugar content in petroleum-derived fuels has long been considered a means of reducing air pollution from transport exhaust gas. The refining industry typically employs hydrodesulfurization processes to remove thiols, sulfides, and disulfides from crude oil. However, resistant compounds such as dibenzothiophene and its derivatives require much more extreme conditions, such as high hydrogen pressures at elevated temperatures, to achieve ultra-low sulfur levels.

An alternative to hydrodesulfurization is oxidative desulfurization (ODS) combined with extraction. The ODS of resistant compounds is based on the propensity of such resistant compounds to oxidize to sulfoxides or sulfones under mild conditions, which can be removed by polar extraction agents. Oxidizers such as nitrogen oxides, nitric acid, hydrogen peroxide, ozone, organic peroxides, oxygen, air, and peracids have been used. The oxidation of thiophene derivatives with hydrogen peroxide is known to take place in the presence of organic acid solvents such as HCO2H, CH3-xClxCO2H, CF3CO2H, and the like, where x is 0, 1, 2, or 3. Various catalysts and promoters studied include sulfuric acid, tungstphoric acid (TPA), methyltrioxorrenium (VII), vanadium acetylacetonate, titanium molecular sieves, vanadium silicates, and many others. Unfortunately, many such solid-supported catalysts suffer from deactivation that arises from metal leaching, sulfone adsorption, or combinations thereof. In addition, various extraction agents studied include: polar volatile organic compounds (VOCs), expensive ionic liquids, and corrosive acids; some of which pose additional environmental and safety concerns.

The compounds of formula I, described above, can be used as catalysts for the reduction of sulfur or nitrogen levels in fuels. Without wishing to be bound by theory, it is believed that the compounds of formula I act to catalyze peracid formation in the reaction mixture. The peracid then oxidizes the sulfur or nitrogen species to give sulfone or N-oxide species, respectively. The sulfones or the N-oxide are then removed from the fuel by extraction with the bulk acid that is part of the reaction mixture.

Methods of using the compounds as sulfoxidation catalysts are disclosed. In such embodiments, a fuel source containing a sulfur-containing refractive compound, or a sulfur contaminant, is mixed with an appropriate solvent and an aliquot of a solution of a compound of formula I is added. In other embodiments, an aliquot of a solution of a compound of formula I is added. provide methods of using the compounds as nitrogen oxidation catalysts. In such embodiments, a fuel source containing a nitrogen-containing contaminant is mixed with an appropriate solvent and an aliquot of a solution of a compound of formula I is added. Both sulfur and nitrogen contaminants may be present in the same fuel and can be treated with the same catalyst compositions.

Suitable fuel sources are any sulfur or nitrogen contaminated fuel source including, but not limited to, crude oil, diesel fuels, and thermally cracked gasoline such as gasoline, visbreaking gasoline, coker gasoline, and catalytically cracked gasoline. As used herein, the term "cracked gasoline" refers to any of a number of fuels formed by thermally degrading higher molecular weight hydrocarbons on catalysts. Such processes and cracking catalysts are well known in the art and are used routinely in the production of fuel sources.

As used herein, the term "contaminant" refers to any amount of a desired compound or compounds in a fuel, such as sulfur- or nitrogen-containing compounds. Furthermore, as used herein, decontaminated refers to a reduction in the level of contaminant in a product compared to the level of contaminant prior to treatment. Therefore, decontaminated does not necessarily mean that all contaminants are removed, although it may include complete decontamination, but rather decontaminated means that the amount of contaminant is reduced, compared to fuel prior to a decontamination treatment. In some embodiments, the decontaminated fuels have at least a 10% reduction in contamination compared to the contaminated fuel that is provided. In other embodiments, the reduction can be variously at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or even up to 100%.

Sulfur-containing refractive compounds include, but are not limited to, mercaptans, sulfides, disulfides, thiophene, benzothiophene (BT), alkylbenzothiophenes, dibenzothiophene (DBT), 4-methyldibenzothiophene (4-MDBT),

ES 2 345 705 T3 alkyldibenzothiophenes such as 4,6-dimethyldibenzothiophene (DMDBT), organic sulfur compounds of alkylnaphthalenes, and derivatives of such compounds.

Nitrogen-containing contaminants include, but are not limited to, nitrogen heterocycles. For example, such nitrogen heterocycles include, but are not limited to, carbazole, imidazole, triazoles, benzotriazoles, quinuclidine, aziridine, azetidine, pyrrolidine, pyrazolidine, pyrrole, pyrrolidine, pyrazole, tetrazoles, piperidine, piperazine, morphimoline, pyridine, pyrrolidine. , pyridazine, triazine, dihydropyridine, indole, indolines, isoindoles, azaindoles, indazole, indolizine, benzotriazole, benzimidazole, pyrazolopyridine, azabenzimidazolyl, triazolopyridine, isoxazolopyridine, purine, Adenine, guanine, quinoline, isoquinoline, quinolizine, quinoxaline, quinazoline, phthalazine, naphthyridine, pteridine, dihydroindole, tetrahydroindole, tetrahydroindazole, tetrahydrobenzimidazole, tetrahydrobenzotriazole, tetrahydropyrrolopyrazine, tetrahydropyridine, tetrahydropyridine, tetrahydropyridine, tetrahydropyridine, tetrahydropyridine, tetrahydropyridine derivatives, tetrahydrobenzotriazole, and tetrahydropyrrolopyridoline, tetrahydropyridine, and tetrahydropyridine derivatives Suitable solvents for sulfoxidation include, but are not limited to, organic acid solvents such as HCO2H, CH3-XCLCO2H, CF3CO2H, and the like, where x is 0, 1, 2, or 3.

Fuel decontamination methods, according to some embodiments, include preparing a mixture of a sulfur and / or nitrogen contaminated fuel, a compound of formula I, an organic acid; and an oxidant; and recover the decontaminated fuel. Several examples are given below in which oils having a sulfur or nitrogen content are prepared, in the form of benzothiophenes and carbazole, and in which the present compounds are used as catalysts to decontaminate oil under experimental conditions. By such control of conditions, the effectiveness of the catalyst can be determined and monitored.

According to some embodiments, the catalyst used for desulfurization is bis (ethylene glycol) oxotitanium (IV), bis (glycerol) oxotitanium (IV), bis (erythritol) oxotitanium (IV), bis (sorbitol) oxotitanium (IV), or a mixture of any two or more such compounds or grouping compounds.

The organic acid that is used may be one that is known in the art for use with other such catalyst systems. For example, the organic acid can be HCO2H, CH3-xCClxCO2H, CF3CO2H, and mixtures of any two or more of such acids, where x is 0, 1, 2, or 3. Also the oxidant that is used can be a material such as organic nitrogen oxides, nitric acid, hydrogen peroxide, a bleach such as sodium hypochlorite, ozone, organic peroxides, oxygen, air, peracids, and mixtures of either two or more of such compounds. Depending on the fuel and other reactants, the amount of organic acid used relative to the amount of fuel can range from 1: 1 to more. In some embodiments, the acid to fuel ratio is 1: 1, 4: 1 in other embodiments, or about 10: 1 in still other embodiments.

As used herein, the term "organic peroxides" refers to organic groups having peroxide functionality of the formula RC (O) OOC (O) R ', where R and R' are individually alkyl, alkenyl, alkynyl, aryl, cyclyl, heterocyclyl, or heteroaryl. Such compounds can include, but are not limited to, benzoyl peroxide. As used herein, the term "organic nitrogen oxide" refers to organic compounds that are substituted with an NO group, such as, but not limited to, pyridine N-oxide, Morpholine noxide. As used herein, the term peracids refers to any organic acid that has a peroxo functionality for the formula R "C (O) OOH, where R" is an alkyl, alkenyl, alkynyl, aryl, cyclyl, group. heterocyclyl or heteroaryl. Such peracids are defined as carboxylic acids that have been treated with hydrogen peroxide to form a species of the general formula R "C (O) OOH. Examples of such peracids include, but are not limited to, performic acid, peracetic acid, pertrifluoro acid, and the like.

The ratios for the components used in decontamination reactions to desulfurize or denitrogenize fuels can be varied to optimize a particular catalyst, acid, oxidant, or temperature. Thus, in some embodiments, the amount of fuel in the reactant mixture can range from about 30 to 70% by weight, or from about 40 to 60% by weight in other embodiments. In some embodiments, the organic acid is present from about 20 to 60% by weight, or from about 25 to 40% in other embodiments. The organic acid reacts with the oxidant to form a peracid species that is the source of oxidation for sulfur or nitrogen contaminants, but the organic acid also acts as the extraction agent to remove sulfones or nitrogen oxide from the fuel.

The level of oxidant is normally based on the mole ratio to the sulfur or nitrogen contaminant present. The desired ratio of oxidant to sulfur can be expected to be 1: 1 on a per mole basis, however higher loadings of up to 3: 1 or even up to 8: 1 may be necessary to achieve the desired kinetic profile. In some embodiments, the oxidant is present in the mixture from about 5 to 20% by weight, or from about 10 to 18% by weight, in other embodiments.

Generally, the lower the catalyst loading to achieve the desired efficiency, the better the cost. However, the catalyst loading can vary widely. The catalyst may be present in the mixture from about 0.02 to 0.8% by weight, according to some embodiments, or from

ES 2 345 705 T3 about 0.04 to 0.4% by weight, in other embodiments. In other embodiments, the catalyst is present at a rate of 0.5 ppm or greater relative to fuel.

In a particular embodiment, the catalyst is removed and a hypochlorite, such as sodium hypochlorite, is used as the oxidant. In such a case, the action of hypochlorite on organic acid such as acetic acid produces a peracid species that can oxidize sulfur to give a sulfone, which is then removed from the fuel mixture.

Reaction temperature and time also play a role in catalyst efficiency and reaction kinetics. The temperature can range from room temperature to higher. The upper limit is limited by the desire to keep the reactant in the reactor and not lose reactants and / or products due to overheating. Thus, in some embodiments, the methods are performed at room temperature. However, in other embodiments, the reaction temperature can range from about 30 to 130 ° C, or from about 40 to 60 ° C. The reaction time is also considered. In an isolated reactor, this is simply how long the reaction takes to run before the process, however, in on-line systems, the time is determined as the residence time in the reactor. This time may vary depending on the reactants, the level of contaminant, or various other factors known to those of skill in the art. In some embodiments, the time ranges from about 5 seconds to 60 minutes. Although in other embodiments, the time ranges from about 1 minute to 30 minutes, or from about 1 minute to 10 minutes.

Figure 8 is a process flow diagram of one embodiment of a sulfoxidation process such as those described above. Source A may comprise a sulfur-rich organic fluid stream inlet into the process at mixing point 1, where the organic fluid may be a fluid such as those described above. Source Q may comprise an oxidant introduced into the system in reactor 10, where the oxidant may comprise oxidants described above, where the oxidant is mixed with the organic fluid stream at mixing point 1. Source Q may comprise an inlet electrical in embodiments where the oxidant is produced by hydrolysis.

The mixture from mixing point 1 can combine with a catalyst in reactor 2 to form a two-phase petroleum reaction mixture, resulting in the sulfoxidation of the sulfur-rich organic fluid within reactor 2, where oxidized sulfur compounds they are extracted from the organic fluid phase into an aqueous reaction phase. The catalyst can be those described above. The catalyst can enter reactor 2 as a solid or liquid, and can be transferred to reactor 2 from mixing point 11. In some embodiments, mixing performed at mixing points 1 and 11 can be performed in reactor 2.

A two-phase petroleum reaction stream B can be transferred from reactor 2 to separator 3, where a sulfur-rich polar stripped material E can be separated from a low-sulfur (or essentially sulfur-free) raffinate C. The sulfur-rich extracted material E (comprising oxidized sulfur compounds and catalysts) can be transferred from separator 3 to a distillation tower 4, where distillate surcharges F (pure extracted material, such as solvent) can be separated through the distillation of the distillate heavy materials G, where the distillate heavy materials may comprise oxidized sulfur compounds (such as organic sulfones) and catalyst. The distillate surcharges F can be returned to the mixing point 11. In some embodiments, the sulfur-rich extracted material E may account for about 15% of the two-phase petroleum reaction stream B and the low-sulfur (or essentially sulfur-free) raffinate C may account for about 85% of the Biphasic petroleum reaction current B.

Heavy distillate materials G can be transferred to extractor 5, where the catalyst can be removed via procedure H using distillation tower 6, and the solvent can be returned to extractor 5 via procedure I. Catalyst concentrate K can be returned to mixing point 11. The remaining sulfur-rich, salt-containing heavy materials J can be transferred from extractor 5 to extractor 7, where the salts can be removed via the aqueous wash outlet N and returned to reactor 10. When the oxidant is NaOCl, the The process in the extractor 7 may comprise a salt extraction. Extractor 7 may comprise a solvent wash when other oxidants are used. Water can be introduced into extractor 7 through inlet L.

Sulfur-rich heavy materials M (eg, sulfur-rich organic compounds) can be transferred from extractor 7 to reactor 8. Reactor 8 can comprise a high temperature reactor and can use a catalyst, such as a bed catalyst. solid. In reactor 8, heavy sulfur-rich materials can be catalytically fractionated to give SO2 and organic compounds, where SO2 can be removed from reactor 8 at the SO2 outlet P. The recovered organic O compounds produced in reactor 8 (e.g. oil, etc.) can be transferred from reactor 8 to mixing point 9 where the organic O compounds are mixed with the low sulfur refinement C and can be transferred Low sulfur diesel fuel outlet D.

One skilled in the art will readily see that all the intervals and all the reasons discussed

ES 2 345 705 T3 can, and indeed necessarily do, describe all sub-ranges and sub-ranges therein for all purposes and that such sub-ranges and sub-ranges are also an integral part of this invention. It can be easily recognized that any interval or ratio listed sufficiently describes and allows the same interval or ratio to be divided into at least equal halves, three parts, four parts, five parts, ten parts, etc. As a non-limiting example, each range or ratio discussed herein can easily be divided into a lower third, middle third, and upper third, and so on.

The present invention will be better understood by referring to the following example which is intended for the purpose of illustration and is not intended or should be construed in any way as limiting the scope of the present invention, which is defined in the claims appended thereto.

Experimental part

Example 1

Preparation of bis (glycerol) oxotitanium (IV). Titanium oxychloride (2 kg, Millennium Chemicals) was diluted with deionized water (2 kg) and then added to a 20 L round bottom flask containing glycerin (2 kg). The mixture was allowed to stir until a straw color was achieved. The 20 L round bottom flask was then heated to 50 ° C under vacuum (-85 kPa (-25 in Hg)) on a rotary evaporator to remove excess hydrochloric acid and water. When no additional liquid condensate was observed, the flask was recharged with water (0.65 L) and rotary evaporated to further remove excess hydrochloric acid and water. This was repeated 2 more times. After final evaporation, the viscous, straw colored liquid (2.64 kg) was weighed and diluted with methoxypropanol (0.85 kg) to reduce the viscosity. This was then neutralized with triethylamine (3.3 kg, 33% w / w in ethanol). The combined neutralized solution was then quenched over several hours producing rod-like needles of triethylamine hydrochloride. Crystalline triethylamine hydrochloride was removed by vacuum filtration. The filtrate was added slowly to acetone (70 L) causing the product to precipitate as a white solid. Acetone was then decanted and an off-white solid residue was obtained. The off-white solid residue was then vigorously washed with hexanes (20 L) to provide a fine white powder. The dust was collected by filtration (yield> 63% based on Ti). % Ti calculated: 16.98. Analysis: 16.7; mp by DSC (degrees) 273 ° C; ESI-MS (positive mode) 245 amu;¹H-NMR (DMSO-d6) 4.25 (brs, 4H), 3.45 (m, 2H),

3.38 (m, 4H), 3.31 (m, 4H).

Example 2

Preparation of bis (ethylene glycol) oxotitanium (IV). Titanium oxychloride (100.75 g, Millennium Chemicals) was diluted with deionized water (100.15 g) and then added to a 1 L round bottom flask containing ethylene glycol (59.7 g, VWR). The mixture was allowed to stir until a pale green color was achieved. The 1 L round bottom flask was then heated to 65 ° C under vacuum (-85 KPa (-25 in Hg)) on a rotary evaporator to remove excess hydrochloric acid and water. When no additional liquid condensate was observed, the flask was recharged with water (50 ml) and rotary evaporated to further remove excess hydrochloric acid and water. This was repeated 2 more times. After final evaporation, the clear, viscous liquid (90.3 g) was weighed.

Example 3

Preparation of bis (diethylene glycol monobutyl ether) oxotitanium (IV) [(BuO (CH2) 2O (CH2) 2O) 2TiO]. Titanium oxychloride (17.6 g, Millennium Chemicals) was diluted with deionized water (17.6 g) and then added to a 1 L round bottom flask containing diethylene glycol monobutyl ether (15 g, VWR). The mixture was allowed to stir until a pale orange color was achieved. The 1 L round bottom flask was then heated to 65 ° C under vacuum (85 KPa (-25 in Hg)) on a rotary evaporator to remove excess hydrochloric acid and water. When no additional liquid condensate was observed, the flask was recharged with water (50 ml) and rotary evaporated to further remove excess hydrochloric acid and water. This was repeated 2 more times. After final evaporation, the yellow, viscous oil (22 g) was weighed.¹H-NMR (DMSO-d6) 4.19 (bs, 6H), 3.45-3.39 (m, 12H), 3.37-3.34 (m, 4H), 3.31 ( m, 4H), 1.41 (m, 4H), 1.24 (m, 4H), 0.81 (t, 6H).

Example 4

Polymer preparation. Bisglycerolate-oxotitanium (IV) was dissolved in dimethylsulfoxide (DMSO) at a loading of 10% by weight of solids. 2 ml of this solution was added to 2 ml of distilled water and stirred to ensure a homogeneous starting solution. The resulting solution was placed in a quartz cuvette which had been rinsed after times with distilled water filtered through a 0.2 pm PTFE filter. The cuvette was placed on a particle size analyzer. Initially, the temperature was kept constant at 20 ° C and the particle size was measured at regular intervals. After 29 hours, the temperature was increased to 50 ° C and held constant at that value and particle size measurements were again made at regular intervals. The particle size data shows no change in particle size over time at 20 ° C, but shows a particle size

ES 2 345 705 T3 increasing steadily over time at 50 ° C.

Examples of desulfurization

The procedure of conducting sulfoxidation with the compounds of formula I which is generally described above, will be better understood by the following general methods and examples.

Example 5

Three general methods were used to prepare various samples. Each involved the preparation of a model petroleum by dissolving dibenzothiophene (DBT) in tetralin to give solutions with a sugar content of approximately 15,000 parts per million (ppm) (approximately 0.76 grams of DBT dissolved in 8.33 grams of tetralin). . A heated circulating bath was used to control the temperature (± 0.1 ° C) / (± 0.1 K) of the reactor (JKEM), at approximately 49.8 ° C (323 K), for the elevated temperature samples. . Aliquots of the oil phase were removed at various time intervals and measured by chromatographic techniques to determine the degree of conversion of the DBT. The reactions were stirred with a mixing bar speed of approximately 200 revolutions per minute (rpm).

General method A. Catalyst solutions of 40% by weight bis (glycerol) oxotitanium (IV) in methanol were prepared. Oxidative desulfurization experiments were then carried out by combining acetic acid with the model petroleum in a batch-batch glass reactor, adding a measured aliquot of the catalyst solution, and then adding an amount of the oxidant.

General Method B. Oxidative desulfurization experiments were carried out by combining acetic acid and the solid catalyst, bis (glycerol) oxotitanium (IV), with the model petroleum in a batch glass reactor, and then adding a measured amount of the oxidant.

General Method C. Oxidative desulfurization experiments were carried out combining acetic acid and a measured aliquot of a 40% by weight solution of bis (glycerol) oxotitanium (IV) in methanol with the model petroleum in a pressure reactor lined with glass. The reaction time started after pressurization with air.

Analytical methods

HPLC was carried out using an HP 1090 liquid chromatograph equipped with a column oven and a diode array detector. The system was controlled and data was collected using HP V. 5.03 Chemstation software. The column was a Luna (2) C-18 column, 250X 4.6 mm from Phenomenex. The column oven was kept at 40 ° C. Solvents contained acetonitrile (JT Baker HPLC grade acetonitrile, component # 901703) and Milli-Q water. The solvent program was 50% solvent A, remainder B, ramping up to 100% solvent A in 20 minutes and holding for 2 minutes. Returning to the starting conditions, there was an equilibration delay of 8 minutes before the injection of the next sample. The flow rate was 1.0 ml / min and the injection volume was 10 µl. The diode array detector was set at 260 nm (decalin) and 325 nm (tetralin) with 4 nm bandwidths. Identification of starting materials and reaction products was aided by comparison of retention times with commercial standards. A five-point calibration curve was used to derive analyte concentrations, describing the percent consumption yield values ​​in percent of the benzothiophene starting material.

NMR experiments were performed on a Varian VRMNS-500 device in d8-toluene unless otherwise indicated. Styrene oxide and trans-stilbene oxide spectra were obtained on commercially available materials and used for comparison with oxidation product spectra.

Desulfurization

The reactions were carried out by varying the catalyst load (cat. Vol.), The oxidant concentration (oxidant, H2O2 concentration), the acid concentration (acid, 25% acetic acid versus glacial acetic acid) and the temperature ( T) according to general method A and analyzed for percent conversion (% yield) after 1 hour. The catalyst was a 40% by weight methanol solution of bis (glycerol) oxotitanium (IV). The acid volume was between about 8.35 and about 8.37 g. The amount of oxidant was approximately 2.80 g. The results obtained are shown below in table 1 and in figure 6.

ES 2 345 705 T3

Table 1: Desulfurization results

<td>Show</td><td>Vol. Cat.</td><td>Acid</td><td>Oxidant</td><td>T</td><td>% yield</td>

<td> 1</td><td>10 ml</td><td>Acetic acid 25%</td><td>H2O2 (25%)</td><td>TA</td><td> 0</td>

<td> 2</td><td>10 ml</td><td>Acetic acid 25%</td><td>H2O2 (25%)</td><td>50 ° C</td><td> 16,6</td>

<td> 3</td><td>10 ml</td><td>Acetic acid 25%</td><td>H2O2 (50%)</td><td>TA</td><td> 0</td>

<td> 4</td><td>10 ml</td><td>Acetic acid 25%</td><td>H2O2 (50%)</td><td>50 ° C</td><td> 1,4</td>

<td> 5</td><td>100 ml</td><td>Acetic acid 25%</td><td>H2O2 (25%)</td><td>TA</td><td> 0,2</td>

<td> 6</td><td>100 ml</td><td>Acetic acid 25%</td><td>H2O2 (25%)</td><td>50 ° C</td><td> 1,9</td>

<td> 7</td><td>100 ml</td><td>Acetic acid 25%</td><td>H2O2 (50%)</td><td>TA</td><td> 0,3</td>

<td> 8</td><td>100 ml</td><td>Acetic acid 25%</td><td>H2O2 (50%)</td><td>50 ° C</td><td> 3,6</td>

<td> 9</td><td>10 ml</td><td>Glacial acetic acid</td><td>H2O2 (25%)</td><td>TA</td><td> 3,9</td>

<td> 10</td><td>10 ml</td><td>Glacial acetic acid</td><td>H2O2 (50%)</td><td>50 ° C</td><td> 96,4</td>

<td> 11</td><td>10 ml</td><td>Glacial acetic acid</td><td>H2O2 (50%)</td><td>TA</td><td> 9</td>

<td> 12</td><td>10 ml</td><td>Glacial acetic acid</td><td>H2O2 (25%)</td><td>50 ° C</td><td> 40,9</td>

<td> 13</td><td>100 ml</td><td>Glacial acetic acid</td><td>H2O2 (25%)</td><td>TA</td><td> 28,3</td>

<td> 14</td><td>100 ml</td><td>Glacial acetic acid</td><td>H2O2 (25%)</td><td>50 ° C</td><td> 100</td>

<td> 15</td><td>100 ml</td><td>Glacial acetic acid</td><td>H2O2 (50%)</td><td>TA</td><td> 89,8</td>

<td> 16</td><td>100 ml</td><td>Glacial acetic acid</td><td>H2O2 (50%)</td><td>50 ° C</td><td> 100</td>

<td> 17</td><td>100 ml</td><td>Glacial acetic acid</td><td>H2O2 (50%)</td><td>50 ° C</td><td> 100</td>

<td> 18</td><td>100 ml</td><td>Glacial acetic acid</td><td>H2O2 (50%)</td><td>50 ° C</td><td> 100</td>

Sample 19. Due to the 100% yield result of sample 16, the same conditions were repeated on aliquots withdrawn at 10 minute intervals for 40 minutes. The results obtained are shown below in table 2:

Table 2: Yield results at time t, for a catalyst volume of 100 ml, in glacial acetic acid, 50% H2O2, at 50 ° C.

<td>t (min)</td><td>% Of conversation</td>

<td> 10</td><td> 63,4</td>

<td> 20</td><td> 98,8</td>

<td> 30</td><td> 100</td>

<td> 40</td><td> 100</td>

Sample 20. The conditions of sample 19 were repeated, but with a reactor stirrer spin speed of 400 rpm. Aliquots were withdrawn for analysis at 5, 15, and 25 minutes to measure effect. The results obtained are shown below in table 3.

Table 3: Results with faster agitator spin speed

<td>t (min)</td><td>% Of conversation</td>

<td> 5</td><td> 50,6</td>

<td> 15</td><td> 99,2</td>

<td> 25</td><td> 100</td>

Sample 21. The conditions of sample 20 were repeated, however the mass ratio of glacial acetic acid to tetralin was doubled. Aliquots were withdrawn for analysis at 5, 10, and 12 minutes to measure effect. The results obtained are shown below in table 4.

Table 4: Ratio of acetic acid to higher tetralin

<td>t (min)</td><td>% Of conversation</td>

<td> 5</td><td> 99,3</td>

<td> 10</td><td> 100</td>

<td> 12</td><td> 100</td>

Sample 22. The conditions of sample 21 were repeated, however the hydrogen peroxide concentration was reduced to 3 molar equivalents relative to DBT. Aliquots were withdrawn for analysis at 5, 15, and 25 minutes to measure effect. The results obtained are shown below in table 5.

ES 2 345 705 T3

Table 5: Hydrogen peroxide at 3 equivalents

<td>t (min)</td><td>% Of conversation</td>

<td> 5</td><td> 84,4</td>

<td> 15</td><td> 100</td>

<td> 25</td><td> 100</td>

Samples 23-39. Reactions were performed by varying the amount of catalyst volume (cat. Vol.), Oxidant level (oxidant, H2O2 concentration), acid concentration (acid, 25% acetic acid vs. acid glacial acetic acid) and temperature (T) according to general method B and were analyzed to determine the conversion in percent (% yield) after 1 hour. TA is defined as an ambient temperature of approximately 20 ° C. The catalyst was solid bis (glycerol) oxotitanium (IV) (limited solubility in acetic acid). The amount of acid was between about 8.34 and about 8.38 g. The amount of oxidant was approximately 2.80 g. The results are shown below in Table 6.

Table 6: Desulfurization by general method B.

<td>Show</td><td>Acid</td><td>Weight</td><td>Ox</td><td>T</td><td>% yield</td>

<td> 23</td><td>Acetic acid 25%</td><td>8.6 mg</td><td>H2O2 (25%)</td><td>50 ° C</td><td> 0</td>

<td> 24</td><td>Glacial acetic acid</td><td>8.5 mg</td><td>H2O2 (25%)</td><td>50 ° C</td><td> 84,9</td>

<td> 25</td><td>Acetic acid 25%</td><td>84.5 mg</td><td>H2O2 (25%)</td><td>50 ° C</td><td> 3,5</td>

<td> 26</td><td>Glacial acetic acid</td><td>84.1 mg</td><td>H2O2 (25%)</td><td>50 ° C</td><td> 100</td>

<td> 27</td><td>Acetic acid 25%</td><td>8.4 mg</td><td>H2O2 (50%)</td><td>50 ° C</td><td> 1,3</td>

<td> 28</td><td>Glacial acetic acid</td><td>8.5 mg</td><td>H2O2 (50%)</td><td>50 ° C</td><td> 99,2</td>

<td> 29</td><td>Acetic acid 25%</td><td>83.7 mg</td><td>H2O2 (50%)</td><td>50 ° C</td><td> 2,7</td>

<td> 30</td><td>Glacial acetic acid</td><td>83.5 mg</td><td>H2O2 (50%)</td><td>50 ° C</td><td> 100</td>

<td> 31</td><td>Glacial acetic acid</td><td>84.0 mg</td><td>H2O2 (50%)</td><td>50 ° C</td><td> 100</td>

<td> 32</td><td>Acetic acid 25%</td><td>8.6 mg</td><td>H2O2 (50%)</td><td>TA</td><td> 0</td>

<td> 33</td><td>Glacial acetic acid</td><td>8.6 mg</td><td>H2O2 (25%)</td><td>TA</td><td> 11,6</td>

<td> 34</td><td>Acetic acid 25%</td><td>84.6 mg</td><td>H2O2 (25%)</td><td>TA</td><td> 0</td>

<td> 35</td><td>Glacial acetic acid</td><td>84.4 mg</td><td>H2O2 (25%)</td><td>TA</td><td> 92,9</td>

<td> 36</td><td>Acetic acid 25%</td><td>8.4 mg</td><td>H2O2 (25%)</td><td>TA</td><td> 0</td>

<td> 37</td><td>Glacial acetic acid</td><td>8.4 mg</td><td>H2O2 (50%)</td><td>TA</td><td> 21</td>

<td> 38</td><td>Acetic acid 25%</td><td>84.3 mg</td><td>H2O2 (50%)</td><td>TA</td><td> 0,5</td>

<td> 39</td><td>Glacial acetic acid</td><td>84.7 mg</td><td>H2O2 (50%)</td><td>TA</td><td> 95,9</td>

Effect of the catalyst on organic compounds containing nitrogen

Petroleum distillates are complex mixtures and often contain heterocycles containing nitrogen and olefin. Experiments were also carried out using styrene and trans-stilbene and carbazole to obtain a model of the effect of catalysts on heterocycles with nitrogen and olefin in fuels. The model carrier employed was d8-toluene so that analysis by NMR spectroscopy could be performed. Under the reaction conditions and times described above, no styrene oxidation products were observed. Trans-stilbene did not show any oxidation at 15 minutes and ~ 13% oxidation was observed to trans-stilbene oxide after 1 hour. Complete oxidation of carbazole was observed within 15 minutes as evidenced by the disappearance of the NH proton resonance.

A model petroleum was prepared by independently dissolving an olefin (styrene and trans-stilbene) to 10% by weight in dg-toluene (6 grams). The oxidation experiments were carried out by combining acetic acid (18 g) with the model petroleum in a batch glass reactor, adding 100 ml of a 40% by weight solution of bis (glycerol) oxotitanium (IV) in methanol and then adding 5 molar equivalents of 50% H2O2 solution (olefin base). The reactor mixed at a shaker speed of 200 rpm. A heated circulating bath was used to control the temperature (± 0.1 ° C) / (± 0.1 K) of the reactor (J-KEM), at 49.8 ° C (323 K). The experiment was carried out for one hour extracting aliquots at 15 minutes and 1 hour for their conversion. After 15 minutes no oxidation was observed for olefin by analysis of¹H-NMR and ¹³C-NMR. After 1 hour, no oxidation was observed for styrene and only partial epoxidation (13%) was observed for trans-stilbene after 1 hour.

A model petroleum was prepared by dissolving carbazole (10%) in d8-toluene (6 grams). The oxidation experiment was carried out by combining acetic acid (18 g) with the model petroleum in a batch glass reactor, adding 100 mml of a 40% by weight solution of bis (glycerol) oxotitanium (IV) in methanol and then adding 5 molar equivalents of a 50% H2O2 solution (olefin base). A heated circulating bath was used to control the temperature (± 0.1 ° C) / (± 0.1 K) of the reactor (J-KEM), at 49.8 ° C (323 K). The experiment was carried out for one hour extracting aliquots at 15 minutes and 1 hour for their conversion. After 15 minutes it was observed

ES 2 345 705 T3 complete oxidation for carbazole as evidenced by the disappearance of the NH tension by ¹H-NMR.

The reactions that occur in the process presumably involve the formation of peracetic acid catalyzed by the compounds of formula I. Peracetic acid has cross solubility in the oil phase and can react with DBT to form sulfoxides. Sulfoxides are cross-soluble with the acetic acid phase and can be further oxidized to give the sulfone which has a higher affinity for the acetic acid phase. Reactions and mass transfers are graphed in Figure 7.

Desulfurization kinetics

A model petroleum was prepared by dissolving DBT (72.4 mg, 0.39 mmol), benzothiophene (BT) (54.1 mg, 0.4 mmol),

4-methyldibenzothiophene (4-MDBT) (81.0 mg, 0.41 mmol) and 4,6-dimethyldibenzothiophene (DMDBT) (78.5 mg, 0.37 mmol) in decalin. The oxidation experiment was carried out by combining acetic acid (12 g) with the model petroleum in a batch-batch glass reactor, adding 100 µl of a 40% by weight solution of bis (glycerol) oxotitanium (IV) in methanol and then adding 2.8 grams of a 50% H2O2 solution (O: S ratio 26: 1). The reactor mixed at a shaker speed of 200 rpm. A heated circulating bath was used to control the temperature (± 0.1 ° C) / (± 0.1 K) of the reactor (J-KEM) at about 49.8 ° C (323 K). The experiment was performed for half an hour drawing aliquots at 5, 15, and 30 minute intervals (complete phase separation was allowed to occur, at which point samples were taken and time noted). The kinetic data shown in Figure 3 is plotted in comparison to the results for tungstphoric acid as determined by Yazu et al. Chemistry Letters 32 (10), 920 (2003).

As shown in Figure 5, the disappearance of DBT and its derivatives are pseudo-first order under conditions of peroxide and excess acetic acid. As can be seen, the oxidation rates follow the order DBT> BT> MDBT> DMDBT. In contrast, the rates for DBT and DMDBT observed by Yazu were identical.

The foregoing description of the invention has been presented for purposes of illustration and description. The drawings and description were chosen in order to explain the principles of the invention and its practical application.