AROMATIC HYDROGENATION CATALYSTS AND USES THEREOF

FIELD OF THE INVENTION

This invention relates to a catalyst and use of the catalyst for processing of hydrocarbon feedstreams that contain aromatics.

BACKGROUND OF THE INVENTION

Porous inorganic solids have found great utility as catalysts and separation media for industrial application. In particular, mesoporous materials, such as silicas and aluminas, having a periodic arrangement of mesopores are attractive materials for use in catalysis processes due to their uniform and tunable pores, high surface areas and large pore volumes. Such mesoporous materials are known to have large specific surface areas (e.g., 1000 m²/g) and large pore volumes (e.g., 1 cm³/g). For these reasons, such mesoporous materials enable reactive catalysts.

For example, hydrofinishing technologies have used both base and noble metal catalysts on a mesoporous support. With noble metal catalysts, excellent color and oxidation stability can be achieved at lower pressures and temperatures with smaller reactor volumes than those required when using base metal catalysts. At higher processing temperatures, color quality is sacrificed to achieve sufficient oxidation stability. With noble metal catalysts, it is possible to get superior color stability (water-white), excellent oxidation stability, and almost complete removal of aromatics.

However, mesoporous organosilicas, which may be used as a catalyst support, are conventionally formed by the self-assembly of the silsequioxane precursor in the presence of a structure directing agent, a porogen and/or a framework element. The precursor is hydrolysable and condenses around the structure directing agent. These materials have been referred to as Periodic Mesoporous Organosilicates (PMOs), due to the presence of periodic arrays of parallel aligned mesoscale channels. For example, Landskron, K., et al. [Science, 302:266-269 (2003)] report the self-assembly of 1,3,5-tris[diethoxysila]cylcohexane[(EtO)₂SiCH₂]₃in the presence of a base and the structure directing agent, cetyltrimethylammonium bromide, to form PMOs that are bridged organosilicas with a periodic mesoporous framework, which consist of SiO₃R or SiO₂R₂building blocks, where R is a bridging organic group. In PMOs, the organic groups can be homogenously distributed in the pore walls. U.S. Pat. Pub. No. 2012/0059181 reports the preparation of a crystalline hybrid organic-inorganic silicate formed from 1,1,3,3,5,5 hexaethoxy-1,3,5trisilyl cyclohexane in the presence of NaAlO₂and base. U.S. Patent Application Publication No. 2007/003492 reports preparation of a composition formed from 1,1,3,3,5,5 hexaethoxy-1,3,5trisilyl cyclohexane in the presence of propylene glycol monomethyl ether.

However, the use of a structure directing agent, such as a surfactant, in the preparation of an organosilica material, requires a complicated, energy intensive process to eliminate the structure directing agent at the end of the preparation process. For example, calcining may be required as well as wastewater disposal steps and associated costs to dispose of the structure directing agent. This limits the ability to scale-up the process for industrial applications.

Therefore, there is a need for improved catalysts and/or processes for aromatic saturation of hydrocarbon feeds using organosilica materials that can be prepared by a method that can be practiced in the absence of a structure directing agent, a porogen or surfactant.

SUMMARY OF THE INVENTION

It has been found that catalyst supports comprising organosilica material with desirable pore diameter, pore volume, and surface area can be achieved. Further, such organosilica material supports can be successfully prepared without the need for a structure directing agent, a porogen or surfactant.

Thus, in one aspect, embodiments of the invention provide a hydrogenation catalyst for aromatic hydrogenation comprising: (i) an organosilica material support, which is a polymer comprising independent units of a monomer of Formula [Z¹OZ²OSiCH₂]₃(I), wherein each Z¹and Z²independently represent a hydrogen atom, a C₁-C₄alkyl group or a bond to a silicon atom of another monomer; and (ii) at least one catalyst metal selected from the group consisting of a Group 8 metal, a Group 9 metal, a Group 10 metal and a combination thereof.

In still another aspect, embodiments of the invention provide a method of making a hydrogenation catalyst for aromatic hydrogenation, the method comprising: a) providing an aqueous mixture that contains essentially no structure directing agent and/or porogen, (b) adding at least one compound of Formula [Z¹⁵Z¹⁶SiCH₂]₃(VII) into the aqueous mixture to form a solution, wherein each Z¹⁵represents a C₁-C₄alkoxy group and each Z¹⁶represents a C₁-C₄alkoxy group or a C₁-C₄alkyl group; (c) aging the solution to produce a gel; (d) drying the gel to obtain an organosilica material support which is a polymer comprising independent units of a monomer of Formula [Z¹OZ²OSiCH₂]₃(I), wherein each Z¹and Z²independently represent a hydrogen atom, a C₁-C₄alkyl group or a bond to a silicon atom of another monomer; and (e) impregnating the organosilica material support with at least one catalyst metal selected from the group consisting of a Group 8 metal, a Group 9 metal, a Group 10 metal and a combination thereof.

In still another aspect, embodiments of the invention provide an aromatics hydrogenation process for a hydrocarbon feedstream comprising: a) contacting a hydrocarbon feedstream comprising aromatics with a hydrogenation catalyst in the presence of a hydrogen-containing treat gas in a first reaction stage operated under effective aromatics hydrogenation conditions to produce a reaction product with reduced aromatics content, wherein the hydrogenation catalyst comprises: (i) an organosilica material support, which is a polymer comprising independent units of a monomer of Formula [Z¹OZ²OSiCH₂]₃(I), wherein each Z¹and Z²independently represent a hydrogen atom, a C₁-C₄alkyl group or a bond to a silicon atom of another monomer; and (ii) at least one catalyst metal selected from the group consisting of a Group 8 metal, a Group 9 metal, a Group 10 metal and a combination thereof.

Other embodiments, including particular aspects of the embodiments summarized above, will be evident from the detailed description that follows.

DETAILED DESCRIPTION OF THE INVENTION

In various aspects of the invention, hydrogenation catalysts, methods for preparing hydrogenation catalysts and aromatics hydrogenation processes are provided.

I. Definitions

For purposes of this invention and the claims hereto, the numbering scheme for the Periodic Table Groups is according to the IUPAC Periodic Table of Elements.

The term “and/or” as used in a phrase such as “A and/or B” herein is intended to include “A and B”, “A or B”, “A”, and “B”.

The terms “substituent”, “radical”, “group”, and “moiety” may be used interchangeably.

As used herein, and unless otherwise specified, the term “C_n” means hydrocarbon(s) having n carbon atom(s) per molecule, wherein n is a positive integer.

As used herein, and unless otherwise specified, the term “hydrocarbon” means a class of compounds containing hydrogen bound to carbon, and encompasses (i) saturated hydrocarbon compounds, (ii) unsaturated hydrocarbon compounds, and (iii) mixtures of hydrocarbon compounds (saturated and/or unsaturated), including mixtures of hydrocarbon compounds having different values of n.

As used herein, and unless otherwise specified, the term “alkyl” refers to a saturated hydrocarbon radical having from 1 to 12 carbon atoms (i.e. C₁-C₁₂alkyl), particularly from 1 to 8 carbon atoms (i.e. C₁-C₈alkyl), particularly from 1 to 6 carbon atoms (i.e. C₁-C₆alkyl), and particularly from 1 to 4 carbon atoms (i.e. C₁-C₄alkyl). Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, and so forth. The alkyl group may be linear, branched or cyclic. “Alkyl” is intended to embrace all structural isomeric forms of an alkyl group. For example, as used herein, propyl encompasses both n-propyl and isopropyl; butyl encompasses n-butyl, sec-butyl, isobutyl and tert-butyl and so forth. As used herein, “C₁alkyl” refers to methyl (—CH₃), “C₂alkyl” refers to ethyl (—CH₂CH₃), “C₃alkyl” refers to propyl (—CH₂CH₂CH₃) and “C₄alkyl” refers to butyl (e.g. —CH₂CH₂CH₂CH₃,—(CH₃)CHCH₂CH₃, —CH₂CH(CH₃)₂, etc.). Further, as used herein, “Me” refers to methyl, and “Et” refers to ethyl, “i-Pr” refers to isopropyl, “t-Bu” refers to tert-butyl, and “Np” refers to neopentyl.

As used herein, and unless otherwise specified, the term “alkylene” refers to a divalent alkyl moiety containing 1 to 12 carbon atoms (i.e. C₁-C₁₂alkylene) in length and meaning the alkylene moiety is attached to the rest of the molecule at both ends of the alkyl unit. For example, alkylenes include, but are not limited to, —CH₂—, —CH₂CH₂—, —CH(CH₃)CH₂—, —CH₂CH₂CH₂—, etc. The alkylene group may be linear or branched.

As used herein, and unless otherwise specified, the term “nitrogen-containing alkyl” refers to an alkyl group as defined herein wherein one or more carbon atoms in the alkyl group is substituted with a nitrogen atom or a nitrogen-containing cyclic hydrocarbon having from 2 to 10 carbon atoms (i.e., a nitrogen-containing cyclic C₂-C₁₀hydrocarbon), particularly having from 2 to 5 carbon atoms (i.e., a nitrogen-containing cyclic C₂-C₅hydrocarbon), and particularly having from 2 to 5 carbon atoms (i.e., a nitrogen-containing cyclic C₂-C₅hydrocarbon). The nitrogen-containing cyclic hydrocarbon may have one or more nitrogen atoms. The nitrogen atom(s) may optionally be substituted with one or two C₁-C₆alkyl groups. The nitrogen-containing alkyl can have from 1 to 12 carbon atoms (i.e. C₁-C₁₂nitrogen-containing alkyl), particularly from 1 to 10 carbon atoms (i.e. C₁-C₁₀nitrogen-containing alkyl), particularly from 2 to 10 carbon atoms (i.e. C₂-C₁₀nitrogen-containing alkyl), particularly from 3 to 10 carbon atoms (i.e. C₃-C₁₀nitrogen-containing alkyl), and particularly from 3 to 8 carbon atoms (i.e. C₁-C₁₀nitrogen-containing alkyl). Examples of nitrogen-containing alkyls include, but are not limited to,

embedded image

As used herein, and unless otherwise specified, the term “nitrogen-containing alkylene” refers to an alkylene group as defined herein wherein one or more carbon atoms in the alkyl group is substituted with a nitrogen atom. The nitrogen atom(s) may optionally be substituted with one or two C₁-C₆alkyl groups. The nitrogen-containing alkylene can have from 1 to 12 carbon atoms (i.e. C₁-C₁₂nitrogen-containing alkylene), particularly from 2 to 10 carbon atoms (i.e. C₂-C₁₀nitrogen-containing alkylene), particularly from 3 to 10 carbon atoms (i.e. C₃-C₁₀nitrogen-containing alkylene), particularly from 4 to 10 carbon atoms (i.e. C₄-C₁₀nitrogen-containing alkylene), and particularly from 3 to 8 carbon atoms (i.e. C₃-C₈nitrogen-containing alkyl). Examples of nitrogen-containing alkylenes include, but are not limited to,

embedded image

As used herein, and unless otherwise specified, the term “alkenyl” refers to an unsaturated hydrocarbon radical having from 2 to 12 carbon atoms (i.e., C₂-C₁₂alkenyl), particularly from 2 to 8 carbon atoms (i.e., C₂-C₈alkenyl), particularly from 2 to 6 carbon atoms (i.e., C₂-C₆alkenyl), and having one or more (e.g., 2, 3, etc.) carbon-carbon double bonds. The alkenyl group may be linear, branched or cyclic. Examples of alkenyls include, but are not limited to ethenyl (vinyl), 2-propenyl, 3-propenyl, 1,4-pentadienyl, 1,4-butadienyl, 1-butenyl, 2-butenyl and 3-butenyl. “Alkenyl” is intended to embrace all structural isomeric forms of an alkenyl. For example, butenyl encompasses 1,4-butadienyl, 1-butenyl, 2-butenyl and 3-butenyl, etc.

As used herein, and unless otherwise specified, the term “alkenylene” refers to a divalent alkenyl moiety containing 2 to about 12 carbon atoms (i.e. C₂-C₁₂alkenylene) in length and meaning that the alkylene moiety is attached to the rest of the molecule at both ends of the alkyl unit. For example, alkenylenes include, but are not limited to, —CH═CH—, —CH═CHCH₂—, —CH═CH═CH—, —CH₂CH₂CH═CHCH₂—, etc. —CH₂CH₂—, —CH(CH₃)CH₂—, —CH₂CH₂CH₂—, etc. The alkenylene group may be linear or branched.

As used herein, and unless otherwise specified, the term “alkynyl” refers to an unsaturated hydrocarbon radical having from 2 to 12 carbon atoms (i.e., C₂-C₁₂alkynyl), particularly from 2 to 8 carbon atoms (i.e C₂-C₈alkynyl), particularly from 2 to 6 carbon atoms (i.e., C₂-C₆alkynyl), and having one or more (e.g., 2, 3, etc.) carbon-carbon triple bonds. The alkynyl group may be linear, branched or cyclic. Examples of alkynyls include, but are not limited to ethynyl, 1-propynyl, 2-butynyl, and 1,3-butadiynyl. “Alkynyl” is intended to embrace all structural isomeric forms of an alkynyl. For example, butynyl encompassses 2-butynyl, and 1,3-butadiynyl and propynyl encompasses 1-propynyl and 2-propynyl (propargyl).

As used herein, and unless otherwise specified, the term “alkynylene” refers to a divalent alkynyl moiety containing 2 to about 12 carbon atoms (i.e. C₂-C₁₂alkenylene) in length and meaning that the alkylene moiety is attached to the rest of the molecule at both ends of the alkyl unit. For example, alkenylenes include, but are not limited to, —C≡C—, —C≡CCH₂—, —CH₂CH₂C≡CCH₂—, etc. —CH₂CH₂—, —CH(CH₃)CH₂—, —CH₂CH₂CH₂—, etc. The alkynlene group may be linear or branched.

As used herein, and unless otherwise specified, the term “alkoxy” refers to —O-alkyl containing from 1 to about 10 carbon atoms. The alkoxy may be straight-chain or branched-chain. Non-limiting examples include methoxy, ethoxy, propoxy, butoxy, isobutoxy, tert-butoxy, pentoxy, and hexoxy. “C₁alkoxy” refers to methoxy, “C₂alkoxy” refers to ethoxy, “C₃alkoxy” refers to propoxy and “C₄alkoxy” refers to butoxy. Further, as used herein, “OMe” refers to methoxy and “OEt” refers to ethoxy.

As used herein, and unless otherwise specified, the term “aromatic” refers to unsaturated cyclic hydrocarbons having a delocalized conjugated π system and having from 5 to 20 carbon atoms (aromatic C₅-C₂₀hydrocarbon), particularly from 5 to 12 carbon atoms (aromatic C₅-C₁₂hydrocarbon), and particularly from 5 to 10 carbon atoms (aromatic C₅-C₁₂hydrocarbon). Exemplary aromatics include, but are not limited to benzene, toluene, xylenes, mesitylene, ethylbenzenes, cumene, naphthalene, methylnaphthalene, dimethylnaphthalenes, ethylnaphthalenes, acenaphthalene, anthracene, phenanthrene, tetraphene, naphthacene, benzanthracenes, fluoranthrene, pyrene, chrysene, triphenylene, and the like, and combinations thereof. Additionally, the aromatic may comprise one or more heteroatoms. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, and/or sulfur. Aromatics with one or more heteroatom include, but are not limited to furan, benzofuran, thiophene, benzothiophene, oxazole, thiazole and the like, and combinations thereof. The aromatic may comprise monocyclic, bicyclic, tricyclic, and/or polycyclic rings (in some embodiments, at least monocyclic rings, only monocyclic and bicyclic rings, or only monocyclic rings) and may be fused rings.

As used herein, and unless otherwise specified, the term “aryl” refers to any monocyclic or polycyclic cyclized carbon radical containing 6 to 14 carbon ring atoms, wherein at least one ring is an aromatic hydrocarbon. Examples of aryls include, but are not limited to phenyl, naphthyl, pyridinyl, and indolyl.

As used herein, and unless otherwise specified, the term “aralkyl” refers to an alkyl group substituted with an aryl group. The alkyl group may be a C₁-C₁₀alkyl group, particularly a C₁-C₆, particularly a C₁-C₄alkyl group, and particularly a C₁-C₃alkyl group. Examples of aralkyl groups include, but are not limited to phenymethyl, phenylethyl, and naphthylmethyl. The aralkyl may comprise one or more heteroatoms and be referred to as a “heteroaralkyl.” Examples of heteroatoms include, but are not limited to, nitrogen (i.e., nitrogen-containing heteroaralkyl), oxygen (i.e., oxygen-containing heteroaralkyl), and/or sulfur (i.e., sulfur-containing heteroaralkyl).

Examples of heteroaralkyl groups include, but are not limited to, pyridinylethyl, indolylmethyl, furylethyl, and quinolinylpropyl.

As used herein, and unless otherwise specified, the term “heterocyclo” refers to fully saturated, partially saturated or unsaturated or polycyclic cyclized carbon radical containing from 4 to 20 carbon ring atoms and containing one or more heteroatoms atoms. Examples of heteroatoms include, but are not limited to, nitrogen (i.e., nitrogen-containing heterocyclo), oxygen (i.e., oxygen-containing heterocyclo), and/or sulfur (i.e., sulfur-containing heterocyclo). Examples of heterocyclo groups include, but are not limited to, thienyl, furyl, pyrrolyl, piperazinyl, pyridyl, benzoxazolyl, quinolinyl, imidazolyl, pyrrolidinyl, and piperidinyl.

As used herein, and unless otherwise specified, the term “heterocycloalkyl” refers to an alkyl group substituted with heterocyclo group. The alkyl group may be a C₁-C₁₀alkyl group, particularly a C₁-C₆, particularly a C₁-C₄alkyl group, and particularly a C₁-C₃alkyl group. Examples of heterocycloalkyl groups include, but are not limited to thienylmethyl, furylethyl, pyrrolylmethyl, piperazinylethyl, pyridylmethyl, benzoxazolylethyl, quinolinylpropyl, and imidazolylpropyl.

As used herein, the term “hydroxyl” refers to an —OH group.

As used herein, the term “mesoporous” refers to solid materials having pores that have a diameter within the range of from about 2 nm to about 50 nm.

As used herein, the term “organosilica” refers to an organosiloxane compound that comprises one or more organic groups bound to two or more Si atoms.

As used herein, the term “silanol” refers to a Si-13 OH group.

As used herein, the term “silanol content” refers to the percent of the Si-13 OH groups in a compound and can be calculated by standard methods, such as NMR.

As used herein, the terms “structure directing agent,” “SDA,” and/or “porogen” refer to one or more compounds added to the synthesis media to aid in and/or guide the polymerization and/or polycondensing and/or organization of the building blocks that form the organosilica material framework. Further, a “porogen” is understood to be a compound capable of forming voids or pores in the resultant organosilica material framework. As used herein, the term “structure directing agent” encompasses and is synonymous and interchangeable with the terms “templating agent” and “template.”

As used herein, and unless otherwise specified, the term “adsorption” includes physisorption, chemisorption, and condensation onto a solid material and combinations thereof.

II. Hydrogenation Catalyst

The invention relates to hydrogenation catalysts, particularly for aromatic hydrogenation. In a first embodiment, a hydrogenation catalyst is provided comprising: (i) an organosilica material support, which is a polymer comprising independent units of a monomer of Formula [Z¹OZ²SiCH₂]₃(I), wherein each Z¹and Z²independently can be a hydrogen atom, a C₁-C₄alkyl group or a bond to a silicon atom of another monomer; and (ii) at least one catalyst metal selected from the group consisting of a Group 8 metal, a Group 9 metal, a Group 10 metal and a combination thereof.

As used herein, and unless otherwise specified, “a bond to a silicon atom of another monomer” means the bond can advantageously displace a moiety (particularly an oxygen-containing moiety such as a hydroxyl, an alkoxy or the like), if present, on a silicon atom of the another monomer so there may be a bond directly to the silicon atom of the another monomer thereby connecting the two monomers, e.g., via a Si—O—Si linkage. For clarity, in this bonding scenario, the “another monomer” can be a monomer of the same type or a monomer of a different type.

II.A. Organosilica Material Support

1. Monomers of Formula (I)

In various embodiments, the organosilica material support can be a polymer comprising independent units of a monomer of Formula [Z¹OZ²OSiCH₂]₃(I), wherein each Z¹and/or Z²can be a hydrogen atom.

Additionally or alternatively, each Z¹and/or Z²can be a C₁-C₄alkyl group, a C₁-C₃alkyl group, a C₁-C₂alkyl group or methyl.

Additionally or alternatively, each Z¹and/or Z²can be a bond to a silicon atom of another siloxane monomer.

Additionally or alternatively, each Z¹and Z²independently can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer.

In a particular embodiment, each Z¹and Z²independently can be a hydrogen atom, ethyl or a bond to a silicon atom of another monomer.

In another particular embodiment, each Z¹and Z²independently can be a hydrogen atom or a bond to a silicon atom of another monomer.

2. Monomers of Formula (II)

In various embodiments, the organosilica material support may further comprise another monomer in combination with independent units of Formula (I), such as another monomer having at least one independent unit of Formula [Z³OZ⁴SiCH₂]₃(II), wherein each Z³represents a hydrogen atom, a C₁-C₄alkyl group or a bond to a silicon atom of another monomer and each Z⁴represents a C₁-C₆alkyl group;

In various embodiments, each Z³can be a hydrogen atom.

Additionally or alternatively, each Z³can be a C₁-C₄alkyl group, a C₁-C₃alkyl group, a C₁-C₂alkyl group or methyl.

Additionally or alternatively, each Z³can be a hydrogen atom or a C₁-C₂alkyl group.

Additionally or alternatively, each Z³can be a bond to a silicon atom of another monomer.

Additionally or alternatively, each Z³can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer.

Additionally or alternatively, each Z³can be a hydrogen atom, ethyl or a bond to a silicon atom of another monomer.

Additionally or alternatively, each Z⁴can be a C₁-C₆alkyl group, a C₁-C₅alkyl group, a C₁-C₄alkyl group, a C₁-C₃alkyl group, a C₁-C₂alkyl group or methyl. In particular, Z⁴can be a methyl.

Additionally or alternatively, each Z³can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer and each Z⁴can be a C₁-C₄alkyl group.

Additionally or alternatively, each Z³can be a hydrogen atom, ethyl or a bond to a silicon atom of another monomer and each Z⁴can be methyl.

Additionally or alternatively, each Z³can be a hydrogen atom or a bond to a silicon atom of another monomer and each Z⁴can be methyl.

In another embodiment, the organosilica material support may comprise independent units of Formula [Z³OZ⁴SiCH₂]₃(II) as described herein and not independent units of Formula (I) as described herein. In particular, each Z³can be a hydrogen atom, ethyl or a bond to a silicon atom of another monomer and each Z⁴can be methyl. Additionally or alternatively, each Z³can be a hydrogen atom or a bond to a silicon atom of another monomer and each Z⁴can be methyl.

3. Monomers of Formula (III)

In various embodiments, the organosilica material support may further comprise another monomer in combination with independent units of Formula (I) and optionally independent units of Formula (II), such as another monomer having at least one independent unit of Formula Z⁵OZ⁶Z⁷Z⁸Si (III), wherein each Z⁵can be a hydrogen atom, a C₁-C₄alkyl group or a bond to a silicon atom of another monomer; and Z⁶, Z⁷and Z⁸each independently can be selected from the group consisting of a hydroxyl group, a C₁-C₄alkyl group, a C₁-C₄alkoxy group, a nitrogen-containing C₁-C₁₀alkyl group, a nitrogen-containing heteroaralkyl group, and a nitrogen-containing optionally substituted heterocycloalkyl group, and an oxygen atom bonded to a silicon atom of another monomer.

As used herein, and unless otherwise specified, “an oxygen atom bonded to a silicon atom of another monomer” means that the oxygen atom can advantageously displace a moiety (particularly an oxygen-containing moiety such as a hydroxyl, an alkoxy or the like), if present, on a silicon atom of the another monomer so the oxygen atom may be bonded directly to the silicon atom of the another monomer thereby connecting the two monomers, e.g., via a Si—O—Si linkage. For clarity, in this bonding scenario, the “another monomer” can be a monomer of the same type or a monomer of a different type.

Additionally or alternatively, each Z⁵can be a hydrogen atom, a C₁-C₄alkyl group or a bond to a silicon atom of another monomer; and Z⁶, Z⁷and Z⁸each independently can be selected from the group consisting of a hydroxyl group, a C₁-C₄alkyl group, a C₁-C₄alkoxy group, and an oxygen atom bonded to a silicon atom of another monomer. Additionally or alternatively, Z⁶, Z⁷and Z⁸each independently can optionally be a nitrogen-containing C₁-C₁₀alkyl group, a nitrogen-containing heteroaralkyl group, and/or a nitrogen-containing optionally substituted heterocycloalkyl group.

In various aspects, each Z⁵can be a hydrogen atom.

Additionally or alternatively, each Z⁵can be a C₁-C₄alkyl group, a C₁-C₃alkyl group, a C₁-C₂alkyl group or methyl.

Additionally or alternatively, each Z⁵can be a hydrogen atom or a C₁-C₂alkyl group.

Additionally or alternatively, each Z⁵can be a bond to a silicon atom of another monomer.

Additionally or alternatively, each Z⁵can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer.

Additionally or alternatively, each Z⁵can be a hydrogen atom, ethyl, methyl or a bond to a silicon atom of another monomer.

Additionally or alternatively, Z⁶, Z⁷and Z⁸each independently can be a hydroxyl group.

Additionally or alternatively, each Z⁵can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer; and Z⁶, Z⁷and Z⁸each independently can be a hydroxyl group.

Additionally or alternatively, Z⁶, Z⁷and Z⁸each independently can be a C₁-C₄alkyl group, a C₁-C₃alkyl group, a C₁-C₂alkyl group or methyl.

Additionally or alternatively, Z⁶, Z⁷and Z⁸each independently can be a hydroxyl group or a C₁-C₂alkyl group.

Additionally or alternatively, Z⁶, Z⁷and Z⁸each independently can be a C₁-C₄alkoxy group, a C₁-C₃alkoxy group, a C₁-C₂alkoxy group or methoxy.

Additionally or alternatively, Z⁶, Z⁷and Z⁸each independently can be selected from the group consisting of a hydroxyl group, a C₁-C₂alkyl group and a C₁-C₂alkoxy group.

Additionally or alternatively, each Z⁵can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer; and Z⁶, Z⁷and Z⁸each can be selected from the group consisting of a hydroxyl group, a C₁-C₂alkyl group and a C₁-C₂alkoxy group.

Additionally or alternatively, Z⁶, Z⁷and Z⁸each independently can optionally be a nitrogen-containing C₁-C₁₀alkyl group, a nitrogen-containing C₁-C₉alkyl group, a nitrogen-containing C₁-C₈alkyl group, a nitrogen-containing C₁-C₇alkyl group, a nitrogen-containing C₁-C₆alkyl group, a nitrogen-containing C₁-C₅alkyl group, a nitrogen-containing C₁-C₄alkyl group, a nitrogen-containing C₁-C₃alkyl group, a nitrogen-containing C₁-C₂alkyl group, or a methylamine. In particular, Z⁶, Z⁷and Z⁸each independently can be a nitrogen-containing C₂-C₁₀alkyl group, a nitrogen-containing C₃-C₁₀alkyl group, a nitrogen-containing C₃-C₉alkyl group, or a nitrogen-containing C₃-C₈alkyl group. The aforementioned nitrogen-containing alkyl groups may have one or more nitrogen atoms (e.g., 2, 3, etc.). Examples of nitrogen-containing C₁-C₁₀alkyl groups include, but are not limited to,

embedded image

Additionally or alternatively, Z⁶, Z⁷and Z⁸each independently can be selected from the group consisting of a hydroxyl group, a C₁-C₂alkyl group, a C₁-C₂alkoxy group and a nitrogen-containing C₃-C₁₀alkyl group.

Additionally or alternatively, Z⁶, Z⁷and Z⁸each independently can optionally be a nitrogen-containing heteroaralkyl group. The nitrogen-containing heteroaralkyl group can be a nitrogen-containing C₄-C₁₂heteroaralkyl group, a nitrogen-containing C₄-C₁₀heteroaralkyl group, or a nitrogen-containing C₄-C₈heteroaralkyl group. Examples of nitrogen-containing heteroaralkyl groups include but are not limited to pyridinylethyl, pyridinylpropyl, pyridinylmethyl, indolylmethyl, pyrazinylethyl, and pyrazinylpropyl. The aforementioned nitrogen-containing heteroaralkyl groups may have one or more nitrogen atoms (e.g., 2, 3, etc.).

Additionally or alternatively, Z⁶, Z⁷and Z⁸each independently can be selected from the group consisting of a hydroxyl group, a C₁-C₂alkyl group, a C₁-C₂alkoxy group, nitrogen-containing C₃-C₁₀alkyl group and a nitrogen-containing heteroaralkyl group.

Additionally or alternatively, each Z⁵can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer; and Z⁶, Z⁷and Z⁸each independently can be selected from the group consisting of a hydroxyl group, a C₁-C₂alkyl group, a C₁-C₂alkoxy group, a nitrogen-containing C₃-C₁₀alkyl group and a nitrogen-containing heteroaralkyl group.

Additionally or alternatively, Z⁶, Z⁷and Z⁸each independently can optionally be a nitrogen-containing heterocycloalkyl group, wherein the heterocycloalkyl group may be optionally substituted with a C₁-C₆alkyl group, particularly a C₁-C₄alkyl group. The nitrogen-containing heterocycloalkyl group can be a nitrogen-containing C₄-C₁₂heterocycloalkyl group, a nitrogen-containing C₄-C₁₀heterocycloalkyl group, or a nitrogen-containing C₄-C₈heterocycloalkyl group. Examples of nitrogen-containing heterocycloalkyl groups include but are not limited to piperazinylethyl, piperazinylpropyl, piperidinylethyl, piperidinylpropyl. The aforementioned nitrogen-containing heterocycloalkyl groups may have one or more nitrogen atoms (e.g., 2, 3, etc.).

Additionally or alternatively, Z⁶, Z⁷and Z⁸each independently optionally can be an oxygen atom bonded to a silicon atom of another monomer.

Additionally or alternatively, each Z⁵can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer; and Z⁶, Z⁷and Z⁸each independently can be selected from the group consisting of a hydroxyl group, a C₁-C₂alkyl group, a C₁-C₂alkoxy group, a nitrogen-containing C₃-C₈alkyl group, C₄-C₁₀heteroaralkyl group, a nitrogen-containing optionally substituted C₄-C₁₀heterocycloalkyl group, and an oxygen atom bonded to a silicon atom of another monomer.

Additionally or alternatively, each Z⁵can be a hydrogen atom or a bond to a silicon atom of another monomer; and Z⁶, Z⁷and Z⁸each independently can be selected from the group consisting of a hydroxyl group, a C₁-C₂alkyl group, a nitrogen-containing C₃-C₈alkyl group, C₄-C₁₀heteroaralkyl group, a nitrogen-containing optionally substituted C₄-C₁₀heterocycloalkyl group, and an oxygen atom bonded to a silicon atom of another monomer.

In a particular embodiment, each Z⁵can be a hydrogen atom, ethyl or a bond to a silicon atom of another monomer; and Z⁶, Z⁷and Z⁸each independently can be selected from the group consisting of a hydroxyl group, ethoxy, and an oxygen atom bonded to a silicon atom of another monomer.

In another particular embodiment, each Z⁵can be a hydrogen atom, ethyl or a bond to a silicon atom of another comonomer; Z⁶and Z⁷each independently can be selected from the group consisting of a hydroxyl group, ethoxy, and an oxygen atom bonded to a silicon atom of another monomer; and Z⁸can be methyl.

In another particular embodiment, each Z⁵can be a hydrogen atom, methyl or a bond to a silicon atom of another comonomer; Z⁶and Z⁷each independently can be selected from the group consisting of a hydroxyl group, methoxy, and an oxygen atom bonded to a silicon atom of another monomer; and each Z⁸can be

embedded image

In another embodiment, the organosilica material support may comprise independent units of Formula (II) as described herein and independent units of Formula (III) as described herein and not independent units of Formula (I) as described herein. In particular, each Z³can be a hydrogen atom, ethyl or a bond to a silicon atom of another monomer, each Z⁴can be methyl; each Z⁵can be a hydrogen atom, ethyl or a bond to a silicon atom of another monomer; and Z⁶, Z⁷and Z⁸each independently can be selected from the group consisting of a hydroxyl group, ethoxy, and an oxygen atom bonded to a silicon atom of another monomer.

4. Monomers of Formula (IV)

In various embodiments, the organosilica material may further comprise another monomer in combination with independent units of Formula (I) and optionally independent units Formula (II) and/or Formula (III), such as another monomer having at least one independent unit of Formula Z⁹Z¹⁰Z¹¹Si—R—SiZ⁹Z¹⁰Z¹¹(IV), wherein each Z⁹independently can be a hydroxyl group, a C₁-C₄alkoxy group or an oxygen atom bonded to a silicon atom of another comonomer; each Z¹⁰and Z¹¹independently can a hydroxyl group, a C₁-C₄alkoxy group, a C₁-C₄alkyl group or an oxygen atom bonded to a silicon atom of another monomer; and each R can be selected from the group consisting a C₁-C₈alkylene group, a C₂-C₈alkenylene group, a C₂-C₈alkynylene group, a nitrogen-containing C₁-C₁₀alkylene group, an optionally substituted C₆-C₂₀aralkyl and an optionally substituted C₄-C₂₀heterocycloalkyl group.

Additionally or alternatively, each Z⁹independently can be a hydroxyl group, a C₁-C₄alkoxy group or an oxygen atom bonded to a silicon atom of another comonomer; each Z¹⁰and Z¹¹independently can a hydroxyl group, a C₁-C₄alkoxy group, a C₁-C₄alkyl group or an oxygen atom bonded to a silicon atom of another monomer; and each R can be selected from the group consisting a C₁-C₈alkylene group, a C₂-C₈alkenylene group, and a C₂-C₈alkynylene group. Additionally or alternatively, R optionally can be a nitrogen-containing C₁-C₁₀alkylene group, an optionally substituted C₆-C₂₀aralkyl and/or an optionally substituted C₄-C₂₀heterocycloalkyl group.

In various aspects, each Z⁹can be a hydroxyl group.

Additionally or alternatively, each Z⁹can be a C₁-C₄alkoxy group, a C₁-C₃alkoxy group, a C₁-C₂alkoxy group or methoxy.

Additionally or alternatively, each Z⁹can be a hydroxyl group or a C₁-C₂alkoxy group.

Additionally or alternatively, each Z⁹can be an oxygen atom bonded to a silicon atom of another comonomer.

Additionally or alternatively, each Z⁹can be a hydroxyl group, a C₁-C₂alkoxy group or an oxygen atom bonded to a silicon atom of another comonomer.

Additionally or alternatively, each Z⁹can be a hydroxyl group or an oxygen atom bonded to a silicon atom of another comonomer.

Additionally or alternatively, each Z¹⁰and Z¹¹independently can be a hydroxyl group.

Additionally or alternatively, each Z¹⁰and Z¹¹independently can be a C₁-C₄alkoxy group, a C₁-C₃alkoxy group, a C₁-C₂alkoxy group or methoxy.

Additionally or alternatively, each Z¹⁰and Z¹¹independently can be a hydroxyl group or a C₁-C₂alkoxy group.

Additionally or alternatively, each Z¹⁰and Z¹¹independently can be a C₁-C₄alkyl group, a C₁-C₃alkyl group, a C₁-C₂alkyl group or methyl.

Additionally or alternatively, each Z¹⁰and Z¹¹independently can be a hydroxyl group, a C₁-C₂alkoxy group, or a C₁-C₂alkyl group.

Additionally or alternatively, each Z¹⁰and Z¹¹independently can be an oxygen atom bonded to a silicon atom of another comonomer.

Additionally or alternatively, each Z¹⁰and Z¹¹independently can be a hydroxyl group, a C₁-C₂alkoxy group, a C₁-C₂alkyl group, or an oxygen atom bonded to a silicon atom of another comonomer.

Additionally or alternatively, each Z¹⁰and Z¹¹independently can be a hydroxyl group, a C₁-C₂alkyl group, or an oxygen atom bonded to a silicon atom of another comonomer.

Additionally or alternatively, each Z⁹can be a hydroxyl group, a C₁-C₂alkoxy group or an oxygen atom bonded to a silicon atom of another comonomer; and each Z¹⁰and Z¹¹independently can be a hydroxyl group, a C₁-C₂alkoxy group, a C₁-C₂alkyl group, or an oxygen atom bonded to a silicon atom of another comonomer.

Additionally or alternatively, each Z⁹can be a hydroxyl group, ethoxy, methoxy or an oxygen atom bonded to a silicon atom of another comonomer; and each Z¹⁰and Z¹¹independently can be a hydroxyl group, ethoxy, methyl, or an oxygen atom bonded to a silicon atom of another comonomer.

Additionally or alternatively, each Z⁹can be a hydroxyl group or an oxygen atom bonded to a silicon atom of another comonomer; and each Z¹⁰and Z¹¹independently can be a hydroxyl group, methyl, or an oxygen atom bonded to a silicon atom of another comonomer.

Additionally or alternatively, each R can be a C₁-C₈alkylene group, a C₁-C₇alkylene group, a C₁-C₆alkylene group, a C₁-C₅alkylene group, a C₁-C₄alkylene group, a C₁-C₃alkylene group, a C₁-C₂alkylene group or —CH₂—.

Additionally or alternatively, each R can be a C₂-C₈alkenylene group, a C₂-C₇alkenylene group, a C₂-C₆alkenylene group, a C₂-C₅alkenylene group, a C₂-C₄alkenylene group, a C₂-C₃alkenylene group, or —HC═CH—.

Additionally or alternatively, each Z⁹can be a hydroxyl group, a C₁-C₂alkoxy group or an oxygen atom bonded to a silicon atom of another comonomer; each Z¹⁰and Z¹¹independently can be a hydroxyl group, a C₁-C₂alkoxy group, a C₁-C₂alkyl group, or an oxygen atom bonded to a silicon atom of another comonomer; and each R can be selected from the group consisting of a C₁-C₄alkylene group and a C₂-C₄alkenylene group.

Additionally or alternatively, each R can be a C₂-C₈alkynylene group, a C₂-C₇alkynylene group, a C₂-C₆alkynylene group, a C₂-C₅alkynylene group, a C₂-C₄alkynylene group, a C₂-C₃alkynylene group, or —C≡C—.

Additionally or alternatively, each R can be a nitrogen-containing C₂-C₁₀alkylene group, a nitrogen-containing C₃-C₁₀alkylene group, a nitrogen-containing C₄-C₁₀alkylene group, a nitrogen-containing C₄-C₉alkylene group, a nitrogen-containing C₄-C₈alkylene group, or nitrogen containing C₃-C₈alkylene group. The aforementioned nitrogen-containing alkylene groups may have one or more nitrogen atoms (e.g., 2, 3, etc.). Examples of nitrogen-containing alkylene groups include, but are not limited to,

embedded image

Additionally or alternatively, each R can be an optionally substituted C₆-C₂₀aralkyl, an optionally substituted C₆-C₁₄aralkyl, or an optionally substituted C₆-C₁₀aralkyl. Examples of C₆-C₂₀aralkyls include, but are not limited to, phenylmethyl, phenylethyl, and naphthylmethyl. The aralkyl may be optionally substituted with a C₁-C₆alkyl group, particularly a C₁-C₄alkyl group.

Additionally or alternatively, each Z⁹can be a hydroxyl group, a C₁-C₂alkoxy group or an oxygen atom bonded to a silicon atom of another comonomer; each Z¹⁰and Z¹¹independently can be a hydroxyl group, a C₁-C₂alkoxy group, a C₁-C₂alkyl group, or an oxygen atom bonded to a silicon atom of another comonomer; and R can be selected from the group consisting of a C₁-C₄alkylene group, a C₂-C₄alkenylene group, a C₂-C₄alkynylene group, a nitrogen-containing C₄-C₁₀alkylene group and an optionally substituted C₆-C₁₀aralkyl.

Additionally or alternatively, each R can be an optionally substituted C₄-C₂₀heterocycloalkyl group, an optionally substituted C₄-C₁₆heterocycloalkyl group, an optionally substituted C₄-C₁₂heterocycloalkyl group, or an optionally substituted C₄-C₁₀heterocycloalkyl group. Examples of C₄-C₂₀heterocycloalkyl groups include, but are not limited to, thienylmethyl, furylethyl, pyrrolylmethyl, piperazinylethyl, pyridylmethyl, benzoxazolylethyl, quinolinylpropyl, and imidazolylpropyl. The heterocycloalkyl may be optionally substituted with a C₁-C₆alkyl group, particularly a C₁-C₄alkyl group.

Additionally or alternatively, each Z⁹can be a hydroxyl group, a C₁-C₂alkoxy group or an oxygen atom bonded to a silicon atom of another comonomer; each Z¹⁰and Z¹¹independently can be a hydroxyl group, a C₁-C₂alkoxy group, a C₁-C₂alkyl group, or an oxygen atom bonded to a silicon atom of another comonomer; and R can be selected from the group consisting of a C₁-C₄alkylene group, a C₂-C₄alkenylene group, a C₂-C₄alkynylene group, a nitrogen-containing C₄-C₁₀alkylene group, an optionally substituted C₆-C₁₀aralkyl and an optionally substituted C₄-C₁₀heterocycloalkyl group.

Additionally or alternatively, each Z⁹can be a hydroxyl group, ethoxy, methoxy or an oxygen atom bonded to a silicon atom of another comonomer; each Z¹⁰and Z¹¹independently can be a hydroxyl group, ethoxy, methoxy, methyl, or an oxygen atom bonded to a silicon atom of another comonomer; and R can be selected from the group consisting of —CH₂—, —CH₂CH₂—, —HC═CH—,

embedded image

Additionally or alternatively, each Z⁹can be a hydroxyl group or an oxygen atom bonded to a silicon atom of another comonomer; each Z¹⁰and Z¹¹independently can be a hydroxyl group, methyl, or an oxygen atom bonded to a silicon atom of another comonomer; and each R can be selected from the group consisting of —CH₂—,

embedded image

In a particular embodiment, each Z⁹can be a hydroxyl group, ethoxy or an oxygen atom bonded to a silicon atom of another comonomer; each Z¹⁰can be a hydroxyl group, ethoxy, and an oxygen atom bonded to a silicon atom of another monomer; each Z¹¹can be methyl; and each R can be —CH₂CH₂—.

In another particular embodiment, each Z⁹can be a hydroxyl group, ethoxy or an oxygen atom bonded to a silicon atom of another comonomer; each Z¹⁰and Z¹¹independently can be selected from the group consisting of a hydroxyl group, ethoxy, and an oxygen atom bonded to a silicon atom of another monomer; and R can be —CH₂—.

In another particular embodiment, each Z⁹can be a hydroxyl group, methoxy or an oxygen atom bonded to a silicon atom of another comonomer; each Z¹⁰and Z¹¹independently can be selected from the group consisting of a hydroxyl group, methoxy, and an oxygen atom bonded to a silicon atom of another monomer; and each R can be

embedded image

In another particular embodiment, each Z⁹can be a hydroxyl group, ethoxy or an oxygen atom bonded to a silicon atom of another comonomer; each Z¹⁰can be a hydroxyl group, ethoxy, and an oxygen atom bonded to a silicon atom of another monomer; each Z″ can be methyl; and each R can be

embedded image

In another particular embodiment, each Z⁹can be a hydroxyl group, methoxy or an oxygen atom bonded to a silicon atom of another comonomer; each Z¹⁰can be a hydroxyl group, methoxy, and an oxygen atom bonded to a silicon atom of another monomer; each Z¹¹can be methyl; and each R can be

embedded image

In another embodiment, the organosilica material support may comprise independent units of Formula (III) as described herein and independent units of Formula (IV) as described herein and not independent units of Formula (I) as described herein. In particular, each Z⁵can be a hydrogen atom, ethyl or a bond to a silicon atom of another monomer; Z⁶, Z⁷and Z⁸each independently can be selected from the group consisting of a hydroxyl group, ethoxy, and an oxygen atom bonded to a silicon atom of another monomer and each Z⁹can be a hydroxyl group, ethoxy or an oxygen atom bonded to a silicon atom of another comonomer; each Z¹⁰and Z¹¹independently can be selected from the group consisting of a hydroxyl group, ethoxy, and an oxygen atom bonded to a silicon atom of another monomer; and R can be —CH₂—.

5. Monomers of Formula (V)

Additionally or alternatively, M¹can be B, Al, Ga, IN Tl, or Uut. In particular, M¹can be Al or B.

Additionally or alternatively, each Z¹²can be a hydrogen atom.

Additionally or alternatively, M¹can be Al or B and Z³can be a hydrogen atom.

Additionally or alternatively, each Z¹²can be a C₁-C₆alkyl group, a C₁-C₅alkyl group, a C₁-C₄alkyl group, a C₁-C₃alkyl group, a C₁-C₂alkyl group or methyl. In particular, Z³can be methyl, ethyl, propyl or butyl.

Additionally or alternatively, M¹can be Al or B and Z¹²can be a hydrogen atom, methyl, ethyl, propyl or butyl.

Additionally or alternatively, each Z¹²can be a bond to a silicon atom of another monomer.

Additionally or alternatively, M¹can be Al or B and each Z¹²can be a hydrogen atom, methyl, ethyl, propyl, butyl or a bond to a silicon atom of another monomer.

Additionally or alternatively, M¹can be Al or B and each Z¹²can be a hydrogen atom or a bond to a silicon atom of another monomer.

Additionally or alternatively, M¹can be Al and each Z¹²can be a hydrogen atom, methyl, ethyl, propyl, butyl or a bond to a silicon atom of another monomer.

In a particular embodiment, M¹can be Al and each Z¹²can be a hydrogen atom, methyl or a bond to a silicon atom of another monomer.

In another particular embodiment, M¹can be Al and each Z¹²can be a hydrogen atom, ethyl or a bond to a silicon atom of another monomer.

In another particular embodiment, M¹can be Al and each Z¹²can be a hydrogen atom, propyl or a bond to a silicon atom of another monomer.

In another particular embodiment, M¹can be Al and each Z¹²can be a hydrogen atom, butyl or a bond to a silicon atom of another monomer.

In another particular embodiment, M¹can be Al or B; and each Z¹²can be a hydrogen atom or a bond to a silicon atom of another monomer.

6. Monomers of Formula (VI)

Additionally or alternatively, M²can be B, Al, Ga, IN Tl, or Uut. In particular, M²can be Al or B.

Additionally or alternatively, each Z¹³and/or Z¹⁴can be a hydrogen atom.

Additionally or alternatively, M²can be Al or B and each Z¹³and/or each Z¹⁴can be a hydrogen atom.

Additionally or alternatively, Z¹³and/or Z¹⁴each can be a C₁-C₆alkyl group, a C₁-C₅alkyl group, a C₁-C₄alkyl group, a C₁-C₃alkyl group, a C₁-C₂alkyl group or methyl. In particular, Z¹³and/or Z¹⁴can be methyl, ethyl, propyl or butyl.

Additionally or alternatively, M²can be Al or B; and Z¹³and/or Z¹⁴independently can be a hydrogen atom, methyl, ethyl, propyl or butyl.

Additionally or alternatively, each Z¹³and/or each Z¹⁴each can be a bond to a silicon atom of another monomer.

Additionally or alternatively, M²can be Al or B; and each Z¹³and each Z¹⁴independently can be a hydrogen atom, methyl, ethyl, propyl, butyl or a bond to a silicon atom of another monomer.

Additionally or alternatively, M²can be Al or B; and each Z¹³and each Z¹⁴independently can be a hydrogen atom or a bond to a silicon atom of another monomer.

Additionally or alternatively, M²can be Al; and each Z¹³and each Z¹⁴independently can be a hydrogen atom, methyl, ethyl, propyl, butyl or a bond to a silicon atom of another monomer.

In a particular embodiment, M²can be Al; and each Z¹³and each Z¹⁴independently can be a hydrogen atom, methyl or a bond to a silicon atom of another monomer.

In another particular embodiment, M²can be Al; and each Z¹³and each Z¹⁴independently can be a hydrogen atom, ethyl or a bond to a silicon atom of another monomer.

In another particular embodiment, M²can be Al; and each Z¹³and each Z¹⁴independently can be a hydrogen atom, propyl or a bond to a silicon atom of another monomer.

In another particular embodiment, M²can be Al; and each Z¹³and each Z¹⁴independently can be a hydrogen atom, butyl or a bond to a silicon atom of another monomer.

In another particular embodiment, M²can be Al or B; and each Z¹³and each Z¹⁴independently can be a hydrogen atom or a bond to a silicon atom of another monomer.

The organosilica material supports described herein can be characterized as described in the following sections.

7. X-Ray Diffraction Peaks

The organosilica material supports described herein can exhibit powder X-ray diffraction patterns with one broad peak between about 1 and about 4 degrees θ, particularly one broad peak between about 1 and about 3 degrees θ. Additionally or alternatively, the organosilica materials can exhibit substantially no peaks in the range of about 0.5 to about 10 degrees θ, about 0.5 to about 12 degrees θ range, about 0.5 to about 15 degrees θ, about 0.5 to about 20 degrees θ, about 0.5 to about 30 degrees θ, about 0.5 to about 40 degrees θ, about 0.5 to about 50 degrees θ, about 0.5 to about 60 degrees θ, about 0.5 to about 70 degrees θ, about 2 to about 10 degrees θ, about 2 to about 12 degrees θ range, about 2 to about 15 degrees θ, about 2 to about 20 degrees θ, about 2 to about 30 degrees θ, about 2 to about 40 degrees θ, about 2 to about 50 degrees θ, about 2 to about 60 degrees θ, about 2 to about 70 degrees θ, about 3 to about 10 degrees θ, about 3 to about 12 degrees θ range, about 3 to about 15 degrees θ, about 3 to about 20 degrees θ, about 3 to about 30 degrees θ, about 3 to about 40 degrees θ, about 3 to about 50 degrees θ, about 3 to about 60 degrees θ, or about 3 to about 70 degrees θ.

8. Silanol Content

The organosilica material supports described can have a silanol content that varies within wide limits, depending on the composition of the synthesis solution. The silanol content can conveniently be determined by solid state silicon NMR.

In various aspects, the organosilica material supports can have a silanol content of greater than about 5%, greater than about 10%, greater than about 15%, greater than about 20%, greater than about 25%, greater than about 30%, greater than about 33%, greater than 35%, greater than about 40%, greater than about 41%, greater than about 44%, greater than about 45%, greater than about 50%, greater than about 55%, greater than about 60%, greater than about 65%, greater than about 70%, greater than about 75%, or about 80%. In certain embodiments, the silanol content can be greater than about 30% or greater than about 41%.

Additionally or alternatively, the organosilica material supports may have a silanol content of about 5% to about 80%, about 5% to about 75%, about 5% to about 70%, about 5% to about 65%, about 5% to about 60%, about 5% to about 55%, about 5% to about 50%, about 5% to about 45%, about 5% to about 44%, about 5% to to about 41%, about 5% to about 40%, about 5% to about 35%, about 5% to about 33%, about 5% to about 30%, about 5% to about 25%, about 5% to about 20%, about 5% to about 15%, about 5% to about 10%, about 10% to about 80%, about 10% to about 75%, about 10% to about 70%, about 10% to about 65%, about 10% to about 60%, about 10% to about 55%, about 10% to about 50%, about 10% to about 45%, about 10% to about 44%, about 10% to about 41%, about 10% to about 40%, about 10% to about 35%, about 10% to about 33%, about 10% to about 30%, about 10% to about 25%, about 10% to about 20%, about 20% to about 80%, about 20% to about 75%, about 20% to about 70%, about 20% to about 65%, about 20% to about 60%, about 20% to about 55%, about 20% to about 50%, about 20% to about 45%, about 20% to about 44%, about20% to about 41%, about 20% to about 40%, about 20% to about 35%, about 20% to about 33%, about 20% to about 30%, about 20% to about 25%, about 30% to about 80%, about 30% to about 75%, about 30% to about 70%, about 30% to about 65%, about 30% to about 60%, about 30% to about 55%, about 30% to about 50%, about 30% to about 45%, about 30% to about 44%, about 30% to about 41%, about 30% to about 40%, about 30% to about 35%, about 30% to about 33%, about 40% to about 80%, about 40% to about 75%, about 40% to about 70%, about 40% to about 65%, about 40% to about 60%, about 40% to about 55%, about 40% to about 50%, about 40% to about 45%, about 40% to about 44%, or about 40% to about 41%.

9. Pore Size

The organosilica material supports described herein are advantageously in a mesoporous form. As indicated previously, the term mesoporous refers to solid materials having pores with a diameter within the range of from about 2 nm to about 50 nm. The average pore diameter of the organosilica material can be determined, for example, using nitrogen adsorption-desorption isotherm techniques within the expertise of one of skill in the art, such as the BET (Brunauer Emmet Teller) method.

The organosilica material supports can have an average pore diameter of about 0.2 nm, about 0.4 nm, about 0.5 nm, about 0.6 nm, about 0.8 nm, about 1.0 nm, about 1.5 nm, about 1.8 nm or less than about 2.0 nm.

Additionally or alternatively, the organosilica material supports can advantageously have an average pore diameter within the mesopore range of about 2.0 nm, about 2.5 nm, about 3.0 nm, about 3.1 nm, about 3.2 nm, about 3.3 nm, about 3.4 nm, about 3.5 nm, about 3.6 nm, about 3.7 nm, about 3.8 nm, about 3.9 nm about 4.0 nm, about 4.1 nm, about 4.5 nm, about 5.0 nm, about 6.0 nm, about 7.0 nm, about 7.3 nm, about 8 nm, about 8.4 nm, about 9 nm, about 10 nm, about 11 nm, about 13 nm, about 15 nm, about 18 nm, about 20 nm, about 23 nm, about 25 nm, about 30 nm, about 40 nm, about 45 nm, or about 50 nm.

Additionally or alternatively, the organosilica material supports can have an average pore diameter of 0.2 nm to about 50 nm, about 0.2 nm to about 40 nm, about 0.2 nm to about 30 nm, about 0.2 nm to about 25 nm, about 0.2 nm to about 23 nm, about 0.2 nm to about 20 nm, about 0.2 nm to about 18 nm, about 0.2 nm to about 15 nm, about 0.2 nm to about 13 nm, about 0.2 nm to about 11 nm, about 0.2 nm to about 10 nm, about 0.2 nm to about 9 nm, about 0.2 nm to about 8.4 nm, about 0.2 nm to about 8 nm, about 0.2 nm to about 7.3 nm, about 0.2 nm to about 7.0 nm, about 0.2 nm to about 6.0 nm, about 0.2 nm to about 5.0 nm, about 0.2 nm to about 4.5 nm, about 0.2 nm to about 4.1 nm, about 0.2 nm to about 4.0 nm, about 0.2 nm to about 3.9 nm, about 0.2 nm to about 3.8 nm, about 0.2 nm to about 3.7 nm, about 0.2 nm to about 3.6 nm, about 0.2 nm to about 3.5 nm, about 0.2 nm to about 3.4 nm, about 0.2 nm to about 3.3 nm, about 0.2 nm to about 3.2 nm, about 0.2 nm to about 3.1 nm, about 0.2 nm to about 3.0 nm, about 0.2 nm to about 2.5 nm, about 0.2 nm to about 2.0 nm, about 0.2 nm to about 1.0 nm, about 1.0 nm to about 50 nm, about 1.0 nm to about 40 nm, about 1.0 nm to about 30 nm, about 1.0 nm to about 25 nm, about 1.0 nm to about 23 nm, about 1.0 nm to about 20 nm, about 1.0 nm to about 18 nm, about 1.0 nm to about 15 nm, about 1.0 nm to about 13 nm, about 1.0 nm to about 11 nm, about 1.0 nm to about 10 nm, about 1.0 nm to about 9 nm, about 1.0 nm to about 8.4 nm, about 1.0 nm to about 8 nm, about 1.0 nm to about 7.3 nm, about 1.0 nm to about 7.0 nm, about 1.0 nm to about 6.0 nm, about 1.0 nm to about 5.0 nm, about 1.0 nm to about 4.5 nm, about 1.0 nm to about 4.1 nm, about 1.0 nm to about 4.0 nm, about 1.0 nm to about 3.9 nm, about 1.0 nm to about 3.8 nm, about 1.0 nm to about 3.7 nm, about 1.0 nm to about 3.6 nm, about 1.0 nm to about 3.5 nm, about 1.0 nm to about 3.4 nm, about 1.0 nm to about 3.3 nm, about 1.0 nm to about 3.2 nm, about 1.0 nm to about 3.1 nm, about 1.0 nm to about 3.0 nm or about 1.0 nm to about 2.5 nm.

In particular, the organosilica material supports can advantageously have an average pore diameter in the mesopore range of about 2.0 nm to about 50 nm, about 2.0 nm to about 40 nm, about 2.0 nm to about 30 nm, about 2.0 nm to about 25 nm, about 2.0 nm to about 23 nm, about 2.0 nm to about 20 nm, about 2.0 nm to about 18 nm, about 2.0 nm to about 15 nm, about 2.0 nm to about 13 nm, about 2.0 nm to about 11 nm, about 2.0 nm to about 10 nm, about 2.0 nm to about 9 nm, about 2.0 nm to about 8.4 nm, about 2.0 nm to about 8 nm, about 2.0 nm to about 7.3 nm, about 2.0 nm to about 7.0 nm, about 2.0 nm to about 6.0 nm, about 2.0 nm to about 5.0 nm, about 2.0 nm to about 4.5 nm, about 2.0 nm to about 4.1 nm, about 2.0 nm to about 4.0 nm, about 2.0 nm to about 3.9 nm, about 2.0 nm to about 3.8 nm, about 2.0 nm to about 3.7 nm, about 2.0 nm to about 3.6 nm, about 2.0 nm to about 3.5 nm, about 2.0 nm to about 3.4 nm, about 2.0 nm to about 3.3 nm, about 2.0 nm to about 3.2 nm, about 2.0 nm to about 3.1 nm, about 2.0 nm to about 3.0 nm, about 2.0 nm to about 2.5 nm, about 2.5 nm to about 50 nm, about 2.5 nm to about 40 nm, about 2.5 nm to about 30 nm, about 2.5 nm to about 25 nm, about 2.5 nm to about 23 nm, about 2.5 nm to about 20 nm, about 2.5 nm to about 18 nm, about 2.5 nm to about 15 nm, about 2.5 nm to about 13 nm, about 2.5 nm to about 11 nm, about 2.5 nm to about 10 nm, about 2.5 nm to about 9 nm, about 2.5 nm to about 8.4 nm, about 2.5 nm to about 8 nm, about 2.5 nm to about 7.3 nm, about 2.5 nm to about 7.0 nm, about 2.5 nm to about 6.0 nm, about 2.5 nm to about 5.0 nm, about 2.5 nm to about 4.5 nm, about 2.5 nm to about 4.1 nm, about 2.5 nm to about 4.0 nm, about 2.5 nm to about 3.9 nm, about 2.5 nm to about 3.8 nm, about 2.5 nm to about 3.7 nm, about 2.5 nm to about 3.6 nm, about 2.5 nm to about 3.5 nm, about 2.5 nm to about 3.4 nm, about 2.5 nm to about 3.3 nm, about 2.5 nm to about 3.2 nm, about 2.5 nm to about 3.1 nm, about 2.5 nm to about 3.0 nm, about 3.0 nm to about 50 nm, about 3.0 nm to about 40 nm, about 3.0 nm to about 30 nm, about 3.0 nm to about 25 nm, about 3.0 nm to about 23 nm, about 3.0 nm to about 20 nm, about 3.0 nm to about 18 nm, about 3.0 nm to about 15 nm, about 3.0 nm to about 13 nm, about 3.0 nm to about 11 nm, about 3.0 nm to about 10 nm, about 3.0 nm to about 9 nm, about 3.0 nm to about 8.4 nm, about 3.0 nm to about 8 nm, about 3.0 nm to about 7.3 nm, about 3.0 nm to about 7.0 nm, about 3.0 nm to about 6.0 nm, about 3.0 nm to about 5.0 nm, about 3.0 nm to about 4.5 nm, about 3.0 nm to about 4.1 nm, or about 3.0 nm to about 4.0 nm.

In one particular embodiment, the organosilica material supports described herein can have an average pore diameter of about 1.0 nm to about 30.0 nm, particularly about 1.0 nm to about 25.0 nm, particularly about 2.0 nm to about 25.0 nm, particularly about 2.0 nm to about 20.0 nm, particularly about 2.0 nm to about 15.0 nm, particularly about 2.0 nm to about 10.0 nm, or particularly about 3.0 nm to about 10.0 nm.

Using surfactant as a template to synthesize mesoporous materials can create highly ordered structure, e.g. well-defined cylindrical-like pore channels. In some circumstances, there may be no hysteresis loop observed from N₂adsorption isotherm. In other circumstances, for instance where mesoporous materials can have less ordered pore structures, a hysteresis loop may be observed from N₂adsorption isotherm experiments. In such circumstances, without being bound by theory, the hysteresis can result from the lack of regularity in the pore shapes/sizes and/or from bottleneck constrictions in such irregular pores.

10. Surface Area

The surface area of the organosilica material supports can be determined, for example, using nitrogen adsorption-desorption isotherm techniques within the expertise of one of skill in the art, such as the BET (Brunauer Emmet Teller) method. This method may determine a total surface area, an external surface area, and a microporous surface area. As used herein, and unless otherwise specified, “total surface area” refers to the total surface area as determined by the BET method. As used herein, and unless otherwise specified, “microporous surface area” refers to microporous surface are as determined by the BET method.

In various embodiments, the organosilica material supports can have a total surface area greater than or equal to about 100 m²/g, greater than or equal to about 200 m²/g, greater than or equal to about 300 m²/g, greater than or equal to about 400 m²/g, greater than or equal to about 450 m²/g, greater than or equal to about 500 m²/g, greater than or equal to about 550 m²/g, greater than or equal to about 600 m²/g, greater than or equal to about 700 m²/g, greater than or equal to about 800 m²/g, greater than or equal to about 850 m²/g, greater than or equal to about 900 m²/g, greater than or equal to about 1,000 m²/g, greater than or equal to about 1,050 m²/g, greater than or equal to about 1,100 m²/g, greater than or equal to about 1,150 m²/g, greater than or equal to about 1,200 m²/g, greater than or equal to about 1,250 m²/g, greater than or equal to about 1,300 m²/g, greater than or equal to about 1,400 m²/g, greater than or equal to about 1,450 m²/g, greater than or equal to about 1,500 m²/g, greater than or equal to about 1,550 m²/g, greater than or equal to about 1,600 m²/g, greater than or equal to about 1,700 m²/g, greater than or equal to about 1,800 m²/g, greater than or equal to about 1,900 m²/g, greater than or equal to about 2,000 m²/g, greater than or equal to greater than or equal to about 2,100 m²/g, greater than or equal to about 2,200 m²/g, greater than or equal to about 2,300 m²/g or about 2,500 m²/g.

Additionally or alternatively, the organosilica material supports may have a total surface area of about 50 m²/g to about 2,500 m²/g, about 50 m²/g to about 2,000 m²/g, about 50 m²/g to about 1,500 m²/g, about 50 m²/g to about 1,000 m²/g, about 100 m²/g to about 2,500 m²/g, about 100 m²/g to about 2,300 m²/g, about 100 m²/g to about 2,200 m²/g, about 100 m²/g to about 2,100 m²/g, about 100 m²/g to about 2,000 m2/g, about 100 m²/g to about 1,900 m²/g, about 100 m²/g to about 1,800 m²/g, about 100 m²/g to about 1,700 m²/g, about 100 m²/g to about 1,600 m²/g, about 100 m²/g to about 1,550 m²/g, about 100 m²/g to about 1,500 m²/g, about 100 m²/g to about 1,450 m²/g, about 100 m²/g to about 1,400 m²/g, about 100 m²/g to about 1,300 m²/g, about 100 m²/g to about 1,250 m²/g, about 100 m²/g to about 1,200 m²/g, about 100 m²/g to about 1,150 m²/g, about 100 m²/g to about 1,100 m²/g, about 100 m²/g to about 1,050 m²/g, about 100 m²/g to about 1,000 m²/g, about 100 m²/g to about 900 m²/g, about 100 m²/g to about 850 m²/g, about 100 m²/g to about 800 m²/g, about 100 m²/g to about 700 m²/g, about 100 m²/g to about 600 m²/g, about 100 m²/g to about 550m²/g, about 100 m²/g to about 500 m²/g, about 100 m²/g to about 450 m²/g, about 100 m²/g to about 400 m²/g, about 100 m²/g to about 300 m²/g, about 100 m²/g to about 200 m²/g, about 200 m²/g to about 2,500 m²/g, about 200 m²/g to about 2,300 m²/g, about 200 m²/g to about 2,200 m²/g, about 200 m²/g to about 2,100 m²/g, about 200 m²/g to about 2,000 m²/g, about 200 m²/g to about 1,900 m²/g, about 200 m²/g to about 1,800 m²/g, about 200 m²/g to about 1,700 m²/g, about 200 m²/g to about 1,600 m²/g, about 200 m²/g to about 1,550 m²/g, about 200 m²/g to about 1,500 m²/g, about 200 m²/g to about 1,450 m²/g, about 200 m²/g to about 1,400 m²/g, about 200 m²/g to about 1,300 m²/g, about 200 m²/g to about 1,250 m²/g, about 200 m²/g to about 1,200 m²/g, about 200 m²/g to about 1,150 m²/g, about 200 m²/g to about 1,100 m²/g, about 200 m²/g to about 1,050 m²/g, about 200 m²/g to about 1,000 m²/g, about 200 m²/g to about 900 m²/g, about 200 m²/g to about 850 m²/g, about 200 m²/g to about 800 m²/g, about 200 m²/g to about 700 m²/g, about 200 m²/g to about 600 m²/g, about 200 m²/g to about 550m²/g, about 200 m²/g to about 500 m²/g, about 200 m²/g to about 450 m²/g, about 200 m²/g to about 400 m²/g, about 200 m²/g to about 300 m²/g, about 500 m²/g to about 2,500 m²/g, about 500 m²/g to about 2,300 m²/g, about 500 m²/g to about 2,200 m²/g, about 500 m²/g to about 2,100 m²/g, about 500 m²/g to about 2,000 m²/g, about 500 m²/g to about 1,900 m²/g, about 500 m²/g to about 1,800 m²/g, about 500 m²/g to about 1,700 m²/g, about 500 m²/g to about 1,600 m²/g, about 500 m²/g to about 1,550 m²/g, about 500 m²/g to about 1,500 m²/g, about 500 m²/g to about 1,450 m²/g, about 500 m²/g to about 1,400 m²/g, about 500 m²/g to about ,300 m²/g, about 500 m²/g to about 1,250 m²/g, about 500 m²/g to about 1,200 m²/g, about 500 m²/g to about 1,150 m²/g, about 500 m²/g to about 1,100 m²/g, about 500 m²/g to about 1,050 m²/g, about 500 m²/g to about 1,000 m²/g, about 500 m²/g to about 900 m²/g, about 500 m²/g to about 850 m²/g, about 500 m²/g to about 800 m²/g, about 500 m²/g to about 700 m²/g, about 500 m²/g to about 600 m²/g, about 500 m²/g to about 550m²/g, about 1,000 m²/g to about 2,500 m²/g, about 1,000 m²/g to about 2,300 m²/g, about 1,000 m²/g to about 2,200 m²/g, about 1,000 m²/g to about 2,100 m²/g, about 1,000 m²/g to about 2,000 m²/g, about 1,000 m²/g to about 1,900 m²/g, about 1,000 m²/g to about 1,800 m²/g, about 1,000 m²/g to about 1,700 m²/g, about 1,000 m²/g to about 1,600 m²/g, about 1,000 m²/g to about 1,550 m²/g, about 1,000 m²/g to about 1,500 m²/g, about 1,000 m²/g to about 1,450 m²/g, about 1,000 m²/g to about 1,400 m²/g, about 1,000 m²/g to about 1,300 m²/g, about 1,000 m²/g to about 1,250 m²/g, about 1,000 m²/g to about 1,200 m²/g, about 1,000 m²/g to about 1,150 m²/g, about 1,000 m²/g to about 1,100 m²/g, or about 1,000 m²/g to about 1,050 m²/g.

In one particular embodiment, the organosilica material supports described herein may have a total surface area of about 200 m²/g to about 2,500 m²g, particularly about 400 m²/g to about 2,500 m²g, particularly about 400 m²/g to about 2,000 m²/g, particularly about 500 m²/g to about 2,000 m²/g, or particularly about 400 m²/g to about 1,500 m²/g.

11. Pore Volume

The pore volume of the organosilica material supports made by the methods described herein can be determined, for example, using nitrogen adsorption-desorption isotherm techniques within the expertise of one of skill in the art, such as the BET (Brunauer Emmet Teller) method.

In various embodiments, the organosilica material can have a pore volume greater than or equal to about 0.1 cm³/g, greater than or equal to about 0.2 cm³/g, greater than or equal to about 0.3 cm³/g, greater than or equal to about 0.4 cm³/g, greater than or equal to about 0.5 cm³/g, greater than or equal to about 0.6 cm³/g, greater than or equal to about 0.7 cm³/g, greater than or equal to about 0.8 cm³/g, greater than or equal to about 0.9 cm³/g, greater than or equal to about 1.0 cm³/g, greater than or equal to about 1.1 cm³/g, greater than or equal to about 1.2 cm³/g, greater than or equal to about 1.3 cm³/g, greater than or equal to about 1.4 cm³/g, greater than or equal to about 1.5 cm³/g, greater than or equal to about 1.6 cm³/g, greater than or equal to about 1.7 cm³/g, greater than or equal to about 1.8 cm³/g, greater than or equal to about 1.9 cm³/g, greater than or equal to about 2.0 cm³/g, greater than or equal to about 2.5 cm³/g, greater than or equal to about 3.0 cm³/g, greater than or equal to about 3.5 cm³/g, greater than or equal to about 4.0 cm³/g, greater than or equal to about 5.0 cm³/g, greater than or equal to about 6.0 cm³/g, greater than or equal to about 7.0 cm³/g, or about 10.0 cm³/g.

Additionally or alternatively, the organosilica material supports can have a pore volume of about 0.1 cm³/g to about 10.0 cm³/g, about 0.1 cm³/g to about 7.0 cm³/g, about 0.1 cm³/g to about 6.0 cm³/g, about 0.1 cm³/g to about 5.0 cm³/g, about 0.1 cm³/g to about 4.0 cm³/g, about 0.1 cm³/g to about 3.5 cm³/g, about 0.1 cm³/g to about 3.0 cm³/g, about 0.1 cm³/g to about 2.5 cm³/g, about 0.1 cm³/g to about 2.0 cm³/g, about 0.1 cm³/g to about 1.9 cm³/g, about 0.1 cm³/g to about 1.8 cm³/g, about 0.1 cm³/g to about 1.7 cm³/g, about 0.1 cm³/g to about 1.6 cm³/g, about 0.1 cm³/g to about 1.5 cm³/g, about 0.1 cm³/g to about 1.4 cm³/g, about 0.1 cm³/g to about 1.3 cm³/g, about 0.1 cm³/g to about 1.2 cm³/g, about 0.1 cm³/g to about 1.1, about 0.1 cm³/g to about 1.0 cm³/g, about 0.1 cm³/g to about 0.9 cm³/g, about 0.1 cm³/g to about 0.8 cm³/g, about 0.1 cm³/g to about 0.7 cm³/g, about 0.1 cm³/g to about 0.6 cm³/g, about 0.1 cm³/g to about 0.5 cm³/g, about 0.1 cm³/g to about 0.4 cm³/g, about 0.1 cm³/g to about 0.3 cm³/g, about 0.1 cm³/g to about 0.2 cm³/g, 0.2 cm³/g to about 10.0 cm³/g, about 0.2 cm³/g to about 7.0 cm³/g, about 0.2 cm³/g to about 6.0 cm³/g, about 0.2 cm³/g to about 5.0 cm³/g, about 0.2 cm³/g to about 4.0 cm³/g, about 0.2 cm³/g to about 3.5 cm³/g, about 0.2 cm³/g to about 3.0 cm³/g, about 0.2 cm³/g to about 2.5 cm³/g, about 0.2 cm³/g to about 2.0 cm³/g, about 0.2 cm³/g to about 1.9 cm³/g, about 0.2 cm³/g to about 1.8 cm³/g, about 0.2 cm³/g to about 1.7 cm³/g, about 0.2 cm³/g to about 1.6 cm³/g, about 0.2 cm³/g to about 1.5 cm³/g, about 0.2 cm³/g to about 1.4 cm³/g, about 0.2 cm³/g to about 1.3 cm³/g, about 0.2 cm³/g to about 1.2 cm³/g, about 0.2 cm³/g to about 1.1, about 0.5 cm³/g to about 1.0 cm³/g, about 0.5 cm³/g to about 0.9 cm³/g, about 0.5 cm³/g to about 0.8 cm³/g, about 0.5 cm³/g to about 0.7 cm³/g, about 0.5 cm³/g to about 0.6 cm³/g, about 0.5 cm³/g to about 0.5 cm³/g, about 0.5 cm³/g to about 0.4 cm³/g, about 0.5 cm³/g to about 0.3 cm³/g, 0.5 cm³/g to about 10.0 cm³/g, about 0.5 cm³/g to about 7.0 cm³/g, about 0.5 cm³/g to about 6.0 cm³/g, about 0.5 cm³/g to about 5.0 cm³/g, about 0.5 cm³/g to about 4.0 cm³/g, about 0.5 cm³/g to about 3.5 cm³/g, about 0.5 cm³/g to about 3.0 cm³/g, about 0.5 cm³/g to about 2.5 cm³/g, about 0.5 cm³/g to about 2.0 cm³/g, about 0.5 cm³/g to about 1.9 cm³/g, about 0.5 cm³/g to about 1.8 cm³/g, about 0.5 cm³/g to about 1.7 cm³/g, about 0.5 cm³/g to about 1.6 cm³/g, about 0.5 cm³/g to about 1.5 cm³/g, about 0.5 cm³/g to about 1.4 cm³/g, about 0.5 cm³/g to about 1.3 cm³/g, about 0.5 cm³/g to about 1.2 cm³/g, about 0.5 cm³/g to about 1.1, about 0.5 cm³/g to about 1.0 cm³/g, about 0.5 cm³/g to about 0.9 cm³/g, about 0.5 cm³/g to about 0.8 cm³/g, about 0.5 cm³/g to about 0.7 cm³/g, or about 0.5 cm³/g to about 0.6 cm³/g.

In a particular embodiment, the organosilica material supports can have a pore volume of about 0.1 cm³/g to about 5.0 cm³/g, particularly about 0.1 cm³/g to about 3.0 cm³/g, particularly about 0.2 cm³/g to about 3.0 cm³/g, particularly about 0.2 cm³/g to about 2.5 cm³/g, or particularly about 0.2 cm³/g to about 1.5 cm³/g.

II.B. Catalyst Metal

The hydrogenation catalyst may further comprise at least one catalyst metal. The at least one catalyst metal may be incorporated within the pores of the organosilica material support. Exemplary catalyst metals can include, but are not limited to, a Group 6 metal, a Group 8 metal, a Group 9 metal, a Group 10 metal or a combination thereof. Exemplary Group 6 metals can include, but are not limited to, chromium, molybdenum, and/or tungsten, particularly including molybdenum and/or tungsten. Exemplary Group 8 metals can include, but are not limited to, iron, ruthenium, and/or osmium. Exemplary Group 9 metals can include, but are not limited to, cobalt, rhodium, and/or iridium, particularly including cobalt. Exemplary Group 10 metals can include, but are not limited to, nickel, palladium and/or platinum.

In a particular embodiment, the catalyst metal may be selected from the group consisting of a Group 8 metal, a Group 9 metal, a Group 10 metal and a combination thereof. Additionally or alternatively, the at least one catalyst metal may be selected from the group consisting of platinum (Pt), palladium (Pd), iridium (Ir), rhodium (Rh) or a combination thereof, particularly, platinum (Pt), palladium (Pd), and a mixture thereof.

Additionally or alternatively, the catalyst metal may be present in an amount of at least about 0.010 wt. %, at least about 0.050 wt. %, at least about 0.10 wt. %, at least about 0.20 wt. %, at least about 0.40 wt. %, at least about 0.50 wt. %, at least about 0.60 wt. %, at least about 0.80 wt. %, at least about 1.0 wt. %, at least about 1.2 wt. %, at least about 1.4 wt. %, at least about 1.5 wt. %, at least about 1.6 wt. %, at least about 1.8 wt. %, at least about 2.0 wt. %, at least about 2.2 wt. %, at least about 2.4 wt. %, at least about 2.6 wt. %, at least about 2.8 wt. %, at least about 3.0 wt. %, at least about 3.5 wt. %, or at least about 4.0 wt. %. All metals weight percents are on support. By “on support” it is meant that the percents are based on the weight of the support, i.e., the organosilica material support and optionally, binder material. For example, if the support were to weigh 100 grams, then 20 wt. % catalyst metal would mean that 20 grams of the catalyst metal was on the support.

Additionally or alternatively, the catalyst metal may be present in an amount of about 0.010 wt. % to about 4.0 wt. %, about 0.010 wt. % to about 3.5 wt. %, about 0.010 wt. % to about 3.0 wt. %, about 0.010 wt. % to about 2.8 wt. %, about 0.010 wt. %

to about 2.6 wt. %, about 0.010 wt. % to about 2.4 wt. %, about 0.010 wt. % to about 2.2 wt. %, about 0.010 wt. % to about 2.0 wt. %, about 0.010 wt. % to about 1.8 wt. %, about 0.010 wt. % to about 1.6 wt. %, about 0.010 wt. % to about 1.5 wt. %, about 0.010 wt. % to about 1.4 wt. %, about 0.010 wt. % to at least about 1.2 wt. %, about 0.010 wt. % to about 1.0 wt. %, about 0.010 wt. % to about 0.80 wt. %, about 0.010 wt. % to about 0.60 wt. %, about 0.010 wt. % to about 0.50 wt. %, about 0.010 wt. % to about 0.40 wt. %, about 0.010 wt. % to about 0.20 wt. %, about 0.010 wt. % to about 0.10 wt. %, about 0.10 wt. % to about 4.0 wt. %, about 0.10 wt. % to about 3.5 wt. %, about 0.10 wt. % to about 3.0 wt. %, about 0.10 wt. % to about 2.8 wt. %, about 0.10 wt. % to about 2.6 wt. %, about 0.10 wt. % to about 2.4 wt. %, about 0.10 wt. % to about 2.2 wt. %, about 0.10 wt. % to about 2.0 wt. %, about 0.10 wt. % to about 1.8 wt. %, about 0.10 wt. % to about 1.6 wt. %, about 0.10 wt. % to about 1.5 wt. %, about 0.10 wt. % to about 1.4 wt. %, about 0.10 wt. % to at least about 1.2 wt. %, about 0.10 wt. % to about 1.0 wt. %, about 0.10 wt. % to about 0.80 wt. %, about 0.10 wt. % to about 0.60 wt. %, about 0.10 wt. % to about 0.50 wt. %, about 0.10 wt. % to about 0.40 wt. %, about 0.10 wt. % to about 0.20 wt. %, about 1.0 wt. % to about 4.0 wt. %, about 1.0 wt. % to about 3.5 wt. %, about 1.0 wt. % to about 3.0 wt. %, about 1.0 wt. % to about 2.8 wt. %, about 1.0 wt. % to about 2.6 wt. %, about 1.0 wt. % to about 2.4 wt. %, about 1.0 wt. % to about 2.2 wt. %, about 1.0 wt. % to about 2.0 wt. %, about 1.0 wt. % to about 1.8 wt. %, about 1.0 wt. % to about 1.6 wt. %, about 1.0 wt. % to about 1.5 wt. %, about 1.0 wt. % to about 1.4 wt. %, or about 1.0 wt. % to at least about 1.2 wt. %.

In particular, the catalyst metal may be present in an amount of about 0.010 wt. % to about 4.0 wt. %, about 0.05 wt. % to about 3.5 wt. %, about 0.1 wt. % to about 2.0 wt. %, or about 0.1 wt. % to about 1.4 wt. %.

The catalyst metal can be incorporated into the organosilica material support by any convenient method, such as by impregnation, by ion exchange, by complexation to surface sites or physically admixed with the organosilica material support. If the catalyst metal is to be impregnated into or exchanged onto the organosilica material support and optionally, binder, it may be done, for example, by treating the organosilica material support with a suitable ion containing the catalyst metal. If the catalyst metal is platinum, suitable platinum compounds include chloroplatinic acid, platinous chloride and various compounds containing the platinum amine complex. The catalyst metal may also be incorporated into, onto, or with the composited support and binder material by utilizing a compound(s) wherein the catalyst metal is present in the cation of the compound and/or compounds or in which it is present in the anion of the compound(s). It should be noted that both cationic and anionic compounds can be used. Non-limiting examples of suitable palladium or platinum compounds in which the metal is in the form of a cation or cationic complex are Pd(NH₃)₄Cl₂or Pt(NH₃)₄Cl₂are particularly useful, as are anionic complexes such as the vanadate and metatungstate ions. Cationic forms of other metals are also very useful since they may be exchanged onto the crystalline material or impregnated into it.

The catalyst metal so incorporated may be employed to promote any one of a number of catalytic tranformations commonly conducted in petroleum refining or petrochemicals production. Examples of such catalytic processes can include, but are not limited to, hydrogenation, dehydrogenation, aromatization, aromatic saturation, hydrodesulfurization, olefin oligomerization, polymerization, hydrodenitrogenation, hydrocracking, naphtha reforming, paraffin isomerization, aromatic transalkylation, saturation of double/triple bonds, and the like, as well as combinations thereof. In particular, the catalyst metal may be employed for aromatic hydrogenation and/or saturation.

II.C. Binder

In various aspects, the hydrogenation catalyst may further comprise a binder or be self-bound. Suitable binders, include but are not limited to active and inactive materials, synthetic or naturally occurring zeolites, as well as inorganic materials such as clays and/or oxides such as silica, alumina, zirconia, titania, silica-alumina, cerium oxide, magnesium oxide, or combinations thereof. In particular, the binder may be selected from the group consisting of active and inactive materials, inorganic materials, clays, alumina, silica, silica-alumina, titania, zirconia, or a combination thereof. Particularly, the binder may be silica-alumina, alumina and/or zirconia, particularly alumina. Silica-alumina may be either naturally occurring or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides. It should be noted it is recognized herein that the use of a material in conjunction with a zeolite binder material, i.e., combined therewith or present during its synthesis, which itself is catalytically active may change the conversion and/or selectivity of the finished catalyst. It is also recognized herein that inactive materials can suitably serve as diluents to control the amount of conversion if the present invention is employed in alkylation processes so that alkylation products can be obtained economically and orderly without employing other means for controlling the rate of reaction. These inactive materials may be incorporated into naturally occurring clays, e.g., bentonite and kaolin, to improve the crush strength of the catalyst under commercial operating conditions and function as binders or matrices for the catalyst. The catalysts described herein typically can comprise, in a composited form, a ratio of support material to binder material of about 100 parts support material to about zero parts binder material; about 99 parts support material to about 1 parts binder material; about 95 parts support material to about 5 parts binder material. Additionally or alternatively, the catalysts described herein typically can comprise, in a composited form, a ratio of support material to binder material ranging from about 90 parts support material to about 10 parts binder material to about 10 parts support material to about 90 parts binder material; about 85 parts support material to about 15 parts binder material to about 15 parts support material to about 85 parts binder material; about 80 parts support material to 20 parts binder material to 20 parts support material to 80 parts binder material, all ratios being by weight, typically from 80:20 to 50:50 support material:binder material, preferably from 65:35 to 35:65. Compositing may be done by conventional means including mulling the materials together followed by extrusion of pelletizing into the desired finished catalyst particles.

II.D. Further Metals

In some embodiments, the organosilica material support can further comprise cationic metal sites incorporated into the network structure. Such cationic metal sites may be incorporated by any convenient method, such as impregnation or complexation to the surface, through an organic precursor, or by some other method. This organometallic material may be employed in a number of hydrocarbon separations conducted in petroleum refining or petrochemicals production. Examples of such compounds to be desirably separated from petrochemicals/fuels can include olefins, paraffins, aromatics, and the like.

Additionally or alternatively, the organosilica material support can further comprise a surface metal incorporated within the pores of the organosilica material. The surface metal can be selected from a Group 1 element, a Group 2 element, a Group 13 element, and a combination thereof. When a Group 1 element is present, it can preferably comprise or be sodium and/or potassium. When a Group 2 element is present, it can include, but may not be limited to, magnesium and/or calcium. When a Group 13 element is present, it can include, but may not be limited to, boron and/or aluminum.

One or more of the Group 1, 2, 6, 8-10 and/or 13 elements may be present on an exterior and/or interior surface of the organosilica material support. For example, one or more of the Group 1, 2 and/or 13 elements may be present in a first layer on the organosilica material and one or more of the Group 6, 8, 9 and/or 10 elements may be present in a second layer, e.g., at least partially atop the Group 1, 2 and/or 13 elements. Additionally or alternatively, only one or more Group 6, 8, 9 and/or 10 elements may present on an exterior and/or interior surface of the organosilica material. The surface metal(s) can be incorporated into/onto the organosilica material by any convenient method, such as by impregnation, deposition, grafting, co-condensation, by ion exchange, and/or the like. In particular, a Group 13 metal, such as, but not limited to, aluminum may be grafted onto a surface of the organosilica material support. Additionally or alternatively, a Group 4 metal, such as, but not limited to, titanium, zirconium and hafnium, may be grafted onto a surface of the organosilica material support.

III. Methods of Making Hydrogenation Catalysts

In another embodiment, methods of producing the hydrogenation catalysts described herein for aromatic saturation are provided. The method comprises:

(a) providing an aqueous mixture that contains essentially no structure directing agent and/or porogen;

(b) adding at least one compound of Formula [Z¹⁵Z¹⁶SiCH₂]₃(VII) into the aqueous mixture to form a solution, wherein each Z¹⁵can be a C₁-C₄alkoxy group and each Z¹⁶can be a C₁-C₄alkoxy group or a C₁-C₄alkyl group;

(d) drying the pre-product to obtain an organosilica material support which is a polymer comprising independent units of a monomer of Formula [Z¹OZ²OSiCH₂]₃(I), as described herein; and

(e) impregnating the organosilica material support with at least one catalyst metal selected from the group consisting of a Group 8 metal, a Group 9 metal, a Group 10 metal and a combination thereof.

Additionally or alternatively, the at least one compound of Formula [Z¹⁵Z¹⁶SiCH₂]₃(VII) can be added in step (b) as at least partially hydroxylated and/or as at least partially polymerized/oligomerized, such that each Z¹⁵and/or Z¹⁶can more broadly represent a hydroxyl group, a C₁-C₄alkoxy group, a C₁-C₄alkyl group, or an oxygen atom bonded to a silicon atom of another siloxane. In other words, an unaged pre-product can be added in step (b), in addition to or as an alternative to the monomeric (at least one) compound of Formula [Z¹⁵Z¹⁶SiCH₂]₃(VII) and yet still form the polymer in step (d).

III.A. Aqueous Mixture

The organosilica materials described herein may be made using essentially no structure directing agent or porogen. Thus, the aqueous mixture contains essentially no added structure directing agent and/or no added porogen.

As used herein, “no added structure directing agent,” and “no added porogen” means either (i) there is no component present in the synthesis of the organosilica material that aids in and/or guides the polymerization and/or polycondensing and/or organization of the building blocks that form the framework of the organosilica material; or (ii) such component is present in the synthesis of the organosilica material in a minor, or a non-substantial, or a negligible amount such that the component cannot be said to aid in and/or guide the polymerization and/or polycondensing and/or organization of the building blocks that form the framework of the organosilica material. Further, “no added structure directing agent” is synonymous with “no added template” and “no added templating agent.”

1. Structure Directing Agent

Examples of a structure directing agent can include, but are not limited to, non-ionic surfactants, ionic surfactants, cationic surfactants, silicon surfactants, amphoteric surfactants, polyalkylene oxide surfactants, fluorosurfactants, colloidal crystals, polymers, hyper branched molecules, star-shaped molecules, macromolecules, dendrimers, and combinations thereof. Additionally or alternatively, the surface directing agent can comprise or be a poloxamer, a triblock polymer, a tetraalkylammonium salt, a nonionic polyoxyethylene alkyl, a Gemini surfactant, or a mixture thereof. Examples of a tetraalkylammonium salt can include, but are not limited to, cetyltrimethylammonium halides, such as cetyltrimethylammonium chloride (CTAC), cetyltrimethylammonium bromide (CTAB), and octadecyltrimethylammonium chloride. Other exemplary surface directing agents can additionally or alternatively include hexadecyltrimethylammonium chloride and/or cetylpyridinium bromide.

Poloxamers are block copolymers of ethylene oxide and propylene oxide, more particularly nonionic triblock copolymers composed of a central hydrophobic chain of polyoxypropylene (poly(propylene oxide)) flanked by two hydrophilic chains of polyoxyethylene (poly(ethylene oxide)). Specifically, the term “poloxamer” refers to a polymer having the formula HO(C₂H₄))a(C₃H₆O)_b(C₂H₄O)_aH in which “a” and “b” denote the number of polyoxyethylene and polyoxypropylene units, respectively. Poloxamers are also known by the trade name Pluronic®, for example Pluronic® 123 and Pluronic® F127. An additional triblock polymer is B50-6600.

Nonionic polyoxyethylene alkyl ethers are known by the trade name Brij®, for example Brij® 56, Brij® 58, Brij® 76, Brij ® 78. Gemini surfactants are compounds having at least two hydrophobic groups and at least one or optionally two hydrophilic groups per molecule have been introduced.

2. Porogen

A porogen material is capable of forming domains, discrete regions, voids and/or pores in the organosilica material. An example of a porogen is a block copolymer (e.g., a di-block polymer). As used herein, porogen does not include water. Examples of polymer porogens can include, but are not limited to, polyvinyl aromatics, such as polystyrenes, polyvinylpyridines, hydrogenated polyvinyl aromatics, polyacrylonitriles, polyalkylene oxides, such as polyethylene oxides and polypropylene oxides, polyethylenes, polylactic acids, polysiloxanes, polycaprolactones, polycaprolactams, polyurethanes, polymethacrylates, such as polymethylmethacrylate or polymethacrylic acid, polyacrylates, such as polymethylacrylate and polyacrylic acid, polydienes such as polybutadienes and polyisoprenes, polyvinyl chlorides, polyacetals, and amine-capped alkylene oxides, as well as combinations thereof.

Additionally or alternatively, porogens can be thermoplastic homopolymers and random (as opposed to block) copolymers. As used herein, “homopolymer” means compounds comprising repeating units from a single monomer. Suitable thermoplastic materials can include, but are not limited to, homopolymers or copolymers of polystyrenes, polyacrylates, polymethacrylates, polybutadienes, polyisoprenes, polyphenylene oxides, polypropylene oxides, polyethylene oxides, poly(dimethylsiloxanes), polytetrahydrofurans, polyethylenes, polycyclohexylethylenes, polyethyloxazolines, polyvinylpyridines, polycaprolactones, polylactic acids, copolymers of these materials and mixtures of these materials. Examples of polystyrene include, but are not limited to anionic polymerized polystyrene, syndiotactic polystyrene, unsubstituted and substituted polystyrenes (for example, poly(α-methyl styrene)). The thermoplastic materials may be linear, branched, hyperbranched, dendritic, or star like in nature.

Additionally or alternatively, the porogen can be a solvent. Examples of solvents can include, but are not limited to, ketones (e.g., cyclohexanone, cyclopentanone, 2-heptanone, cycloheptanone, cyclooctanone, cyclohexylpyrrolidinone, methyl isobutyl ketone, methyl ethyl ketone, acetone), carbonate compounds (e.g., ethylene carbonate, propylene carbonate), heterocyclic compounds (e.g., 3-methyl-2-oxazolidinone, dimethylimidazolidinone, N-methylpyrrolidone, pyridine), cyclic ethers (e.g., dioxane, tetrahydrofuran), chain ethers (e.g., diethyl ether, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, polyethylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether (PGME), triethylene glycol monobutyl ether, propylene glycol monopropyl ether, triethylene glycol monomethyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, dipropylene glycol methyl ether, dipropylene glycol dimethyl ether, propylene glycol phenyl ether, tripropylene glycol methyl ether), alcohols (e.g., methanol, ethanol), polyhydric alcohols (e.g., ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, dipropylene glycol), nitrile compounds (e.g., acetonitrile, glutarodinitrile, methoxyacetonitrile, propionitrile, benzonitrile), esters (e.g., ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), butyrolactone, phosphoric acid ester, phosphonic acid ester), aprotic polar substances (e.g., dimethyl sulfoxide, sulfolane, dimethylformamide, dimethylacetamide), nonpolar solvents (e.g., toluene, xylene, mesitylene), chlorine-based solvents (e.g., methylene dichloride, ethylene dichloride), benzene, dichlorobenzene, naphthalene, diphenyl ether, diisopropylbenzene, triethylamine, methyl benzoate, ethyl benzoate, butyl benzoate, monomethyl ether acetate hydroxy ethers such as dibenzylethers, diglyme, triglyme, and mixtures thereof.

3. Base/Acid

In various embodiments, the aqueous mixture used in methods provided herein can comprise a base and/or an acid.

In certain embodiments where the aqueous mixture comprises a base, the aqueous mixture can have a pH from about 8 to about 15, from about 8 to about 14.5, from about 8 to about 14, from about 8 to about 13.5, from about 8 to about 13, from about 8 to about 12.5, from about 8 to about 12, from about 8 to about 11.5, from about 8 to about 11, from about 8 to about 10.5, from about 8 to about 10, from about 8 to about 9.5, from about 8 to about 9, from about 8 to about 8.5, from about 8.5 to about 15, from about 8.5 to about 14.5, from about 8.5 to about 14, from about 8.5 to about 13.5, from about 8.5 to about 13, from about 8.5 to about 12.5, from about 8.5 to about 12, from about 8.5 to about 11.5, from about 8.5 to about 11, from about 8.5 to about 10.5, from about 8.5 to about 10, from about 8.5 to about 9.5, from about 8.5 to about 9, from about 9 to about 15, from about 9 to about 14.5, from about 9 to about 14, from about 9 to about 13.5, from about 9 to about 13, from about 9 to about 12.5, from about 9 to about 12, from about 9 to about 11.5, from about 9 to about 11, from about 9 to about 10.5, from about 9 to about 10, from about 9 to about 9.5, from about 9.5 to about 15, from about 9.5 to about 14.5, from about 9.5 to about 14, from about 9.5 to about 13.5, from about 9.5 to about 13, from about 9.5 to about 12.5, from about 9.5 to about 12, from about 9.5 to about 11.5, from about 9.5 to about 11, from about 9.5 to about 10.5, from about 9.5 to about 10, from about 10 to about 15, from about 10 to about 14.5, from about 10 to about 14, from about 10 to about 13.5, from about 10 to about 13, from about 10 to about 12.5, from about 10 to about 12, from about 10 to about 11.5, from about 10 to about 11, from about 10 to about 10.5, from about 10.5 to about 15, from about 10.5 to about 14.5, from about 10.5 to about 14, from about 10.5 to about 13.5, from about 10.5 to about 13, from about 10.5 to about 12.5, from about 10.5 to about 12, from about 10.5 to about 11.5, from about 10.5 to about 11, from about 11 to about 15, from about 11 to about 14.5, from about 11 to about 14, from about 11 to about 13.5, from about 11 to about 13, from about 11 to about 12.5, from about 11 to about 12, from about 11 to about 11.5, from about 11.5 to about 15, from about 11.5 to about 14.5, from about 11.5 to about 14, from about 11.5 to about 13.5, from about 11.5 to about 13, from about 11.5 to about 12.5, from about 11.5 to about 12, from about 12 to about 15, from about 12 to about 14.5, from about 12 to about 14, from about 12 to about 13.5, from about 12 to about 13, from about 12 to about 12.5, from about 12.5 to about 15, from about 12.5 to about 14.5, from about 12.5 to about 14, from about 12.5 to about 13.5, from about 12.5 to about 13, from about 12.5 to about 15, from about 12.5 to about 14.5, from about 12.5 to about 14, from about 12.5 to about 13.5, from about 12.5 to about 13, from about 13 to about 15, from about 13 to about 14.5, from about 13 to about 14, from about 13 to about 13.5, from about 13.5 to about 15, from about 13.5 to about 14.5, from about 13.5 to about 14, from about 14 to about 15, from about 14 to about 14.5, and from about 14.5 to about 15.

In a particular embodiment comprising a base, the pH can be from about 9 to about 15, from about 9 to about 14 or about 8 to about 14.

Exemplary bases can include, but are not limited to, sodium hydroxide, potassium hydroxide, lithium hydroxide, pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ammonia, ammonium hydroxide, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, octylamine, nonylamine, decylamine, N,N-dimethylamine, N,N-diethylamine, N,N-dipropylamine, N,N-dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, cyclohexylamine, trimethylimidine, 1-amino-3-methylbutane, dimethylglycine, 3-amino-3-methylamine, and the like. These bases may be used either singly or in combination. In a particular embodiment, the base can comprise or be sodium hydroxide and/or ammonium hydroxide.

In certain embodiments where the aqueous mixture comprises an acid, the aqueous mixture can have a pH from about 0.01 to about 6.0, from about 0.01 to about 5, from about 0.01 to about 4, from about 0.01 to about 3, from about 0.01 to about 2, from about 0.01 to about 1, 0.1 to about 6.0, about 0.1 to about 5.5, about 0.1 to about 5.0, from about 0.1 to about 4.8, from about 0.1 to about 4.5, from about 0.1 to about 4.2, from about 0.1 to about 4.0, from about 0.1 to about 3.8, from about 0.1 to about 3.5, from about 0.1 to about 3.2, from about 0.1 to about 3.0, from about 0.1 to about 2.8, from about 0.1 to about 2.5, from about 0.1 to about 2.2, from about 0.1 to about 2.0, from about 0.1 to about 1.8, from about 0.1 to about 1.5, from about 0.1 to about 1.2, from about 0.1 to about 1.0, from about 0.1 to about 0.8, from about 0.1 to about 0.5, from about 0.1 to about 0.2, about 0.2 to about 6.0, about 0.2 to about 5.5, from about 0.2 to about 5, from about 0.2 to about 4.8, from about 0.2 to about 4.5, from about 0.2 to about 4.2, from about 0.2 to about 4.0, from about 0.2 to about 3.8, from about 0.2 to about 3.5, from about 0.2 to about 3.2, from about 0.2 to about 3.0, from about 0.2 to about 2.8, from about 0.2 to about 2.5, from about 0.2 to about 2.2, from about 0.2 to about 2.0, from about 0.2 to about 1.8, from about 0.2 to about 1.5, from about 0.2 to about 1.2, from about 0.2 to about 1.0, from about 0.2 to about 0.8, from about 0.2 to about 0.5, about 0.5 to about 6.0, about 0.5 to about 5.5, from about 0.5 to about 5, from about 0.5 to about 4.8, from about 0.5 to about 4.5, from about 0.5 to about 4.2, from about 0.5 to about 4.0, from about 0.5 to about 3.8, from about 0.5 to about 3.5, from about 0.5 to about 3.2, from about 0.5 to about 3.0, from about 0.5 to about 2.8, from about 0.5 to about 2.5, from about 0.5 to about 2.2, from about 0.5 to about 2.0, from about 0.5 to about 1.8, from about 0.5 to about 1.5, from about 0.5 to about 1.2, from about 0.5 to about 1.0, from about 0.5 to about 0.8, about 0.8 to about 6.0, about 0.8 to about 5.5, from about 0.8 to about 5, from about 0.8 to about 4.8, from about 0.8 to about 4.5, from about 0.8 to about 4.2, from about 0.8 to about 4.0, from about 0.8 to about 3.8, from about 0.8 to about 3.5, from about 0.8 to about 3.2, from about 0.8 to about 3.0, from about 0.8 to about 2.8, from about 0.8 to about 2.5, from about 0.8 to about 2.2, from about 0.8 to about 2.0, from about 0.8 to about 1.8, from about 0.8 to about 1.5, from about 0.8 to about 1.2, from about 0.8 to about 1.0, about 1.0 to about 6.0, about 1.0 to about 5.5, from about 1.0 to about 5.0, from about 1.0 to about 4.8, from about 1.0 to about 4.5, from about 1.0 to about 4.2, from about 1.0 to about 4.0, from about 1.0 to about 3.8, from about 1.0 to about 3.5, from about 1.0 to about 3.2, from about 1.0 to about 3.0, from about 1.0 to about 2.8, from about 1.0 to about 2.5, from about 1.0 to about 2.2, from about 1.0 to about 2.0, from about 1.0 to about 1.8, from about 1.0 to about 1.5, from about 1.0 to about 1.2, about 1.2 to about 6.0, about 1.2 to about 5.5, from about 1.2 to about 5.0, from about 1.2 to about 4.8, from about 1.2 to about 4.5, from about 1.2 to about 4.2, from about 1.2 to about 4.0, from about 1.2 to about 3.8, from about 1.2 to about 3.5, from about 1.2 to about 3.2, from about 1.2 to about 3.0, from about 1.2 to about 2.8, from about 1.2 to about 2.5, from about 1.2 to about 2.2, from about 1.2 to about 2.0, from about 1.2 to about 1.8, from about 1.2 to about 1.5, about 1.5 to about 6.0, about 1.5 to about 5.5, from about 1.5 to about 5.0, from about 1.5 to about 4.8, from about 1.5 to about 4.5, from about 1.5 to about 4.2, from about 1.5 to about 4.0, from about 1.5 to about 3.8, from about 1.5 to about 3.5, from about 1.5 to about 3.2, from about 1.5 to about 3.0, from about 1.5 to about 2.8, from about 1.5 to about 2.5, from about 1.5 to about 2.2, from about 1.5 to about 2.0, from about 1.5 to about 1.8, about 1.8 to about 6.0, about 1.8 to about 5.5, from about 1.8 to about 5.0, from about 1.8 to about 4.8, from about 1.8 to about 4.5, from about 1.8 to about 4.2, from about 1.8 to about 4.0, from about 1.8 to about 3.8, from about 1.8 to about 3.5, from about 1.8 to about 3.2, from about 1.8 to about 3.0, from about 1.8 to about 2.8, from about 1.8 to about 2.5, from about 1.8 to about 2.2, from about 1.8 to about 2.0, about 2.0 to about 6.0, about 2.0 to about 5.5, from about 2.0 to about 5.0, from about 2.0 to about 4.8, from about 2.0 to about 4.5, from about 2.0 to about 4.2, from about 2.0 to about 4.0, from about 2.0 to about 3.8, from about 2.0 to about 3.5, from about 2.0 to about 3.2, from about 2.0 to about 3.0, from about 2.0 to about 2.8, from about 2.0 to about 2.5, from about 2.0 to about 2.2, about 2.2 to about 6.0, about 2.2 to about 5.5, from about 2.2 to about 5.0, from about 2.2 to about 4.8, from about 2.2 to about 4.5, from about 2.2 to about 4.2, from about 2.2 to about 4.0, from about 2.2 to about 3.8, from about 2.2 to about 3.5, from about 2.2 to about 3.2, from about 2.2 to about 3.0, from about 2.2 to about 2.8, from about 2.2 to about 2.5, about 2.5 to about 6.0, about 2.5 to about 5.5, from about 2.5 to about 5.0, from about 2.5 to about 4.8, from about 2.5 to about 4.5, from about 2.5 to about 4.2, from about 2.5 to about 4.0, from about 2.5 to about 3.8, from about 2.5 to about 3.5, from about 2.5 to about 3.2, from about 2.5 to about 3.0, from about 2.5 to about 2.8, from about 2.8 to about 6.0, about 2.8 to about 5.5, from about 2.8 to about 5.0, from about 2.8 to about 4.8, from about 2.8 to about 4.5, from about 2.8 to about 4.2, from about 2.8 to about 4.0, from about 2.8 to about 3.8, from about 2.8 to about 3.5, from about 2.8 to about 3.2, from about 2.8 to about 3.0, from about 3.0 to about 6.0, from about 3.5 to about 5.5, from about 3.0 to about 5.0, from about 3.0 to about 4.8, from about 3.0 to about 4.5, from about 3.0 to about 4.2, from about 3.0 to about 4.0, from about 3.0 to about 3.8, from about 3.0 to about 3.5, from about 3.0 to about 3.2, from about 3.2 to about 6.0, from about 3.2 to about 5.5, from about 3.2 to about 5, from about 3.2 to about 4.8, from about 3.2 to about 4.5, from about 3.2 to about 4.2, from about 3.2 to about 4.0, from about 3.2 to about 3.8, from about 3.2 to about 3.5, from about 3.5 to about 6.0, from about 3.5 to about 5.5, from about 3.5 to about 5, from about 3.5 to about 4.8, from about 3.5 to about 4.5, from about 3.5 to about 4.2, from about 3.5 to about 4.0, from about 3.5 to about 3.8, from about 3.8 to about 5, from about 3.8 to about 4.8, from about 3.8 to about 4.5, from about 3.8 to about 4.2, from about 3.8 to about 4.0, from about 4.0 to about 6.0, from about 4.0 to about 5.5, from about 4.0 to about 5, from about 4.0 to about 4.8, from about 4.0 to about 4.5, from about 4.0 to about 4.2, from about 4.2 to about 5, from about 4.2 to about 4.8, from about 4.2 to about 4.5, from about 4.5 to about 5, from about 4.5 to about 4.8, or from about 4.8 to about 5.

In a particular embodiment comprising an acid, the pH can be from about 0.01 to about 6.0, 0.2 to about 6.0, about 0.2 to about 5.0 or about 0.2 to about 4.5.

Exemplary acids can include, but are not limited to, inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, boric acid and oxalic acid; and organic acids such as acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid, butyric acid, mellitic acid, arachidonic acid, shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-amino-benzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, succinic acid, itaconic acid, mesaconic acid, citraconic acid, malic acid, a hydrolysate of glutaric acid, a hydrolysate of maleic anhydride, a hydrolysate of phthalic anhydride, and the like. These acids may be used either singly or in combination. In a particular embodiment, the acid can comprise or be hydrochloric acid.

III.B. Compounds of Formula (VII)

The methods provided herein comprise the step of adding at least one compound of Formula [Z¹⁵Z¹⁶SiCH₂] (VII) into the aqueous mixture to form a solution, wherein each Z¹⁵can be a C₁-C₄alkoxy group and each Z¹⁶can be a C₁-C₄alkoxy group or a C₁-C₄alkyl group.

In one embodiment, each Z¹⁵can be a C₁-C₃alkoxy or methoxy or ethoxy.

Additionally or alternatively, each Z¹⁶can be a C₁-C₄alkoxy, a C₁-C₃alkoxy or methoxy or ethoxy. Additionally or alternatively, each Z¹⁶can comprise methyl, ethyl or propyl, such as a methyl or ethyl.

Additionally or alternatively, each Z¹⁵can be a C₁-C₂alkoxy group and Z¹⁶can be a C₁-C₂alkoxy group or a C₁-C₂alkyl group.

Additionally or alternatively, each Z¹⁵can be methoxy or ethoxy and each Z¹⁶can be methyl or ethyl.

In a particular embodiment, each Z¹⁵and Z¹⁶can be ethoxy, such that the compound corresponding to Formula (VII) can be 1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane, ([(EtO)₂SiCH₂]₃).

In a particular embodiment, each Z¹⁵can be ethoxy and each Z¹⁶can be methyl, such that compound corresponding to Formula (VII) can be 1,3,5-trimethyl-1,3,5-triethoxy-1,3,5-trisilacyclohexane, ([EtOCH₃SiCH₂]₃).

As mentioned hereinabove, the at least one compound of Formula (VII) can additionally or alternatively be at least partially hydroxylated and/or polymerized/oligomerized when added into the aqueous mixture to form a solution.

Additionally or alternatively, the method can further comprise adding to the aqueous mixture a further compound Formula (VII), which may be the same or different. In the case where different compounds of Formula (VII) are added, an organosilica material support can be obtained which is a copolymer comprising at least one independent unit of Formula (I) as described herein and at least one independent unit of Formulas (II) as described herein. For example, 1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane, ([(EtO)₂SiCH₂]₃) and 1,3,5-trimethyl-1,3,5-triethoxy-1,3,5-trisilacyclohexane, ([EtOCH₃SiCH₂]₃) may be added to the aqueous mixture.

When more than one compound of Formula (VII) is used, the respective compounds may be used in a wide variety of molar ratios. For example, if two compounds of Formula (VII) are used, the molar ratio of each compound may vary from 1:99 to 99:1, such as from 10:90 to 90:10. The use of different compounds of Formula (Ia) allows to tailor the properties of the organosilica materials made by the process of the invention, as will be further explained in the examples and in the section of this specification describing the properties of the organosilicas made by the present processes.

III.D. Compounds of Formula (VIII)

In additional embodiments, the methods provided herein can further comprise adding to the aqueous solution a compound of Formula Z¹⁷OZ¹⁸Z¹⁹Z²⁰Si (VIII) to obtain an organosilica material which is a copolymer comprising at least one independent unit of Formula (I) as described herein, at least one independent unit of Formula (III) as described herein and optionally at least one independent unit of Formula (II) as described herein, wherein each Z¹⁷can be a C₁-C₆alkyl group, and Z¹⁸, Z¹⁹and Z²⁰each independently can be selected from the group consisting of a C₁-C₆alkyl group, a C₁-C₆alkoxy group, a nitrogen-containing C₁-C₁₀alkyl group, a nitrogen-containing heteroaralkyl group, and a nitrogen-containing optionally substituted heterocycloalkyl group.

Additionally or alternatively, each Z¹⁷can be a C₁-C₆alkyl group, and Z¹⁸, Z¹⁹and Z²⁰each independently can be selected from the group consisting of a C₁-C₆alkyl group and a C₁-C₆alkoxy group. Additionally or alternatively, Z¹⁸, Z¹⁹and Z²⁰each independently optionally can be a nitrogen-containing C₁-C₁₀alkyl group, a nitrogen-containing heteroaralkyl group, and a nitrogen-containing optionally substituted heterocycloalkyl group.

In various aspects, each Z¹⁷can be a C₁-C₅alkyl group, a C₁-C₄alkyl group, a C₁-C₃alkyl group, a C₁-C₂alkyl group, or methyl. In particular, Z¹⁷can be methyl or ethyl.

Additionally or alternatively, Z¹⁸, Z¹⁹and Z²⁰can be each independently a C₁-C₅alkyl group, a C₁-C₄alkyl group, a C₁-C₃alkyl group, a C₁-C₂alkyl group, or methyl.

Additionally or alternatively, each Z¹⁷can be a C₁-C₂alkyl group and Z¹⁸, Z¹⁹and Z²⁰can be each independently a C₁-C₂alkyl group.

Additionally or alternatively, Z¹⁸, Z¹⁹and Z²⁰can be each independently a C₁-C₅alkoxy group, a C₁-C₄alkoxy group, a C₁-C₃alkoxy group, a C₁-C₂alkoxy group, or methoxy.

Additionally or alternatively, each Z¹⁷can be a C₁-C₂alkyl group and Z¹⁸, Z¹⁹and Z²⁰can be each independently a C₁-C₂alkoxy group.

Additionally or alternatively, each Z¹⁷can be a C₁-C₂alkyl group and Z¹⁸, Z¹⁹and Z²⁰can be each independently a C₁-C₂alkyl group or a C₁-C₂alkoxy group.

Additionally or alternatively, Z¹⁸, Z¹⁹and Z²⁰can be each independently a nitrogen-containing C₁-C₉alkyl group, a nitrogen-containing C₁-C₈alkyl group, a nitrogen-containing C₁-C₇alkyl group, a nitrogen-containing C₁-C₆alkyl group, a nitrogen-containing C₁-C₅alkyl group, a nitrogen-containing C₁-C₄alkyl group, a nitrogen-containing C₁-C₃alkyl group, a nitrogen-containing C₁-C₂alkyl group, or a methylamine. In particular, Z¹⁸, Z¹⁹and Z²⁰can be each independently a nitrogen-containing C₂-C₁₀alkyl group, a nitrogen-containing C₃-C₁₀alkyl group, a nitrogen-containing C₃-C₉alkyl group, or a nitrogen-containing C₃-C₈alkyl group. The aforementioned nitrogen-containing alkyl groups may have one or more nitrogen atoms (e.g., 2, 3, etc.). Examples of nitrogen-containing C₁-C₁₀alkyl groups include, but are not limited to,

embedded image

Additionally or alternatively, each Z¹⁷can be a C₁-C₂alkyl group and Z¹⁸, Z¹⁹and Z²⁰can be each independently a nitrogen-containing C₃-C₈alkyl group.

Additionally or alternatively, each Z¹⁷can be a C₁-C₂alkyl group and Z¹⁸, Z¹⁹and Z²⁰can be each independently a C₁-C₂alkyl group, a C₁-C₂alkoxy group or a nitrogen-containing C₃-C₈alkyl group.

Additionally or alternatively, Z¹⁸, Z¹⁹and Z²⁰can be each independently a nitrogen-containing heteroaralkyl group. The nitrogen-containing heteroaralkyl group can be a nitrogen-containing C₄-C₁₂heteroaralkyl group, a nitrogen-containing C₄-C₁₀heteroaralkyl group, or a nitrogen-containing C₄-C₈heteroaralkyl group. Examples of nitrogen-containing heteroaralkyl groups include but are not limited to pyridinylethyl, pyridinylpropyl, pyridinylmethyl, indolylmethyl, pyrazinylethyl, and pyrazinylpropyl. The aforementioned nitrogen-containing heteroaralkyl groups may have one or more nitrogen atoms (e.g., 2, 3, etc.).

Additionally or alternatively, each Z¹⁷can be a C₁-C₂alkyl group and Z¹⁸, Z¹⁹and Z²⁰can be each independently a nitrogen-containing heteroaralkyl group.

Additionally or alternatively, each Z¹⁷can be a C₁-C₂alkyl group and Z¹⁸, Z¹⁹and Z²⁰can be each independently a C₁-C₂alkyl group, a C₁-C₂alkoxy group, a nitrogen-containing C₃-C₈alkyl group or a nitrogen-containing heteroaralkyl group.

Additionally or alternatively, Z¹⁸, Z¹⁹and Z²⁰can be each independently a nitrogen-containing heterocycloalkyl group, wherein the heterocycloalkyl group may be optionally substituted with a C₁-C₆alkyl group, particularly a C₁-C₄alkyl group. The nitrogen-containing heterocycloalkyl group can be a nitrogen-containing C₄-C₁₂heterocycloalkyl group, a nitrogen-containing C₄-C₁₀heterocycloalkyl group, or a nitrogen-containing C₄-C₈heterocycloalkyl group. Examples of nitrogen-containing heterocycloalkyl groups include but are not limited to piperazinylethyl, piperazinylpropyl, piperidinylethyl, piperidinylpropyl. The aforementioned nitrogen-containing heterocycloalkyl groups may have one or more nitrogen atoms (e.g., 2, 3, etc.).

Additionally or alternatively, each Z¹⁷can be a C₁-C₂alkyl group and Z¹⁸, Z¹⁹and Z²⁰can be each independently a nitrogen-containing optionally substituted heterocycloalkyl group.

Additionally or alternatively, each Z¹⁷can be a C₁-C₂alkyl group and Z¹⁸, Z¹⁹and Z²⁰can be each independently a C₁-C₂alkyl group, C₁-C₂alkoxy group, a nitrogen-containing C₃-C₁₀alkyl group, a nitrogen-containing C₄-C₁₀heteroaralkyl group, or a nitrogen-containing optionally substituted C₄-C₁₀heterocycloalkyl group.

In a particular embodiment, Z¹⁷can be ethyl and Z¹⁸, Z¹⁹and Z²⁰can be ethoxy, such that the compound corresponding to Formula (VIII) can be tetraethyl orthosilicate (TEOS) ((EtO)₄Si).

In another particular embodiment, a compound of Formula (VII) can be 1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane ([(EtO)₂SiCH₂]₃) and a compound of Formula (VIII) can be tetraethyl orthosilicate (TEOS) ((EtO)₄Si).

In another particular embodiment, Z¹⁷can be ethyl, Z¹⁸can be methyl and Z¹⁹and Z²⁰can be ethoxy, such that the compound corresponding to Formula (VIII) can be methyltriethoxysilane (MTES) ((EtO)₃CH₃Si).

In another particular embodiment, a compound of Formula (VII) can be 1,3,5-trimethyl-1,3,5-triethoxy-1,3,5-trisilacyclohexane ([EtOCH₃SiCH₂]₃and a compound of Formula (VIII) can be tetraethyl orthosilicate (TEOS) ((EtO)₄Si).