Anionically functionalized colloidal silica and method of making

Abstract

This disclosure relates to compositions comprising water and functionalized colloidal silica, wherein the functionalized colloidal silica comprises silica particles (each silica particle comprising a surface) and structural units according to formulas I, II, III and / or IV (I)(II)(III)(IV). This disclosure also discloses methods for manufacturing the compositions of this technology.

Description

Technical Field

[0001] This technology generally relates to functionalized colloidal silica and methods for synthesizing such functionalized colloidal silica, including compositions that are stable for aging at 80°C for 24 hours or longer when the composition contains a salt solution with an ionic strength of 0.5 to 3.0. Summary of the Invention

[0002] In one aspect, this technology provides a composition comprising water and functionalized colloidal silica. The functionalized colloidal silica comprises silica particles (each silica particle including a surface) and structural units according to Formula I, Formula II, Formula III, or Formula IV. in R 1 It is -S-(CH2) n R 2 Or -NH-NH-C(O)-(CH2) m -C(O)NH-NH2, where n It is 1, 2, 3, 4, 5 or 6 and m It can be 1, 2, 3, 4, 5, 6, 7, or 8; R 2 It is independently -SO3Y each time it appears. 1 -SO3H, -SO3 - -CO2Y 2 -CO2H or -CO2 - ; R 2’ and R 2’’ Each is independently H, -SO3Y 1 -SO3H, -SO3 - -CO2Y 2 -CO2H or -CO2 - ; R 3 It is hydroxyl, alkoxy, aryloxy, or G 2 ; R 4 It is hydroxyl, alkoxy, aryloxy, or G 3 ; G 1 G 2 and G 3 Each is an oxygen atom on the surface of the silica particle, wherein G 1 G 2 and G 3 Not the same oxygen atom; Y1 It is an independent cation each time it appears; and Y 2 It is an independent cation each time it appears.

[0003] On the other hand, this technology provides a method for manufacturing functionalized colloidal silica (e.g., a method for manufacturing the composition of any embodiment herein). The method includes contacting the colloidal silica with a silane according to formula VI, formula VII, formula VIII, or formula IX to produce the functionalized colloidal silica. in R 1 It is -S-(CH2) n R 2 Or -NH-NH-C(O)-(CH2) m -C(O)NH-NH2, where n It is 1, 2, 3, 4, 5 or 6 and m It can be 1, 2, 3, 4, 5, 6, 7, or 8; R 2 It is independently -SO3Y each time it appears. 1 -SO3H, -SO3 - -CO2Y 2 -CO2H or -CO2 - ; R 2’ and R 2’’ Each is independently H, -SO3Y 1 -SO3H, -SO3 - -CO2Y 2 -CO2H or -CO2 - ; R 7 It is a hydroxyl, alkoxy, or aryl group; R 8 It is a hydroxyl, alkoxy, or aryl group; L 1 It is an alkoxy or aryloxy group; Y 1 It is an independent cation each time it appears; and Y 2 It is an independent cation each time it appears.

[0004] In another aspect, this technology provides functionalized silica prepared according to any embodiment described herein.

[0005] It should be understood that all combinations of the foregoing concepts and the additional concepts discussed in more detail below (assuming these concepts do not contradict each other) are considered part of the subject matter disclosed herein. In particular, all combinations of the claimed subject matter appearing at the end of this disclosure are considered part of the subject matter disclosed herein.

[0006] Overview of the attached figures Figure 1 A graph of the zeta potential of colloidal silica samples functionalized with different sulfonate groups at pH is provided and compared with that of unmodified colloidal silica.

[0007] Figure 2 A graph of the zeta potential of pH-modified and isophthalic acid-modified colloidal silica is provided and compared with that of unmodified HS-40.

[0008] Figure 3 A graph of the zeta potential of pH vs. hydrazide-modified colloidal silica is provided and compared with that of unmodified HS-40. Invention Details Various implementation schemes are described below. It should be noted that the specific implementation schemes are not intended as an exhaustive description or as a limitation on the broader aspects discussed herein. An aspect described in conjunction with a particular implementation scheme is not necessarily limited to that scheme and can be implemented with any other implementation scheme.

[0010] As used herein and in the appended claims, unless otherwise stated herein or obviously contradictory to the context, in the context of describing elements (especially in the context of the following claims), singular articles such as “an,” “a,” and “the,” and similar indicators, shall be construed as covering both the singular and plural. Unless otherwise stated herein, the description of numerical ranges herein is intended only as a convenient way to individually refer to each individual value falling within that range, and each individual value is incorporated into this specification as if it were individually described herein. Unless otherwise stated herein or obviously contradictory to the context, all methods described herein may be performed in any suitable order. Unless otherwise stated, the use of any and all instances or exemplary language (e.g., “such”) provided herein is intended only to better illustrate the embodiments and does not constitute a limitation on the scope of the claims. No language in the specification should be construed as indicating that any unclaimed element is essential.

[0011] As used herein, “about” will be understood by those skilled in the art and will vary to some extent depending on the context in which it is used. Where there is use of terms that are not readily apparent to those skilled in the art, “about” will, in light of the context in which it is used, mean at most 10% plus or minus a particular term; for example, “about 10% by weight” will be understood to mean “9% to 11% by weight”. It is to be understood that when “about” precedes a term, that term should be interpreted as disclosing both the term described by “about” and terms not modified by “about”—for example, “about 10% by weight” discloses both “9% to 11% by weight” and “10% by weight”.

[0012] The phrase “and / or” as used in this disclosure shall be understood to mean any one of the stated members alone or any combination of two or more thereof—for example, “A, B and / or C” means “A or B or C; A and B; A and C; B and C; or a combination of A, B and C”.

[0013] Generally, mentioning an element such as hydrogen or H means including all isotopes of that element. For example, if the R group is defined as including hydrogen or H, it also includes deuterium and tritium. This includes radioactive isotopes such as tritium and carbon. 14 P 32 and S 35 The compounds are thus within the scope of this technology. Based on the disclosure herein, the procedures for inserting such markings into the compounds of this technology will be apparent to those skilled in the art.

[0014] Generally, "substituted" refers to an organic group (e.g., an alkyl group) as defined below, wherein one or more bonds therein with hydrogen atoms are replaced by bonds with non-hydrogen or non-carbon atoms. Substituted groups also include groups in which one or more bonds with carbon or hydrogen atoms are replaced by one or more bonds with heteroatoms (including double or triple bonds). Thus, unless otherwise stated, a substituted group is substituted by one or more substituents. In some embodiments, the substituted group is substituted by 1, 2, 3, 4, 5, or 6 substituents. Examples of substituents include: halogens (i.e., F, Cl, Br, and I); hydroxyl groups; alkoxy, alkenoxy, aryloxy, arylalkoxy, heterocyclic, heterocyclic alkyl, heterocyclic and heterocyclic alkoxy groups; carbonyl (oxo); carboxyl groups; esters; carbamates; oximes; hydroxylamines; alkoxyamines; arylalkoxyamines; thiols; sulfides; sulfoxides; sulfones; sulfonyl groups; pentafluorothioalkyl (i.e., SF5); sulfonamides; amines; N-oxides; hydrazines; acyl hydrazides; hydrazones; azides; amides; ureas; amidines; guanidines; enamines; imides; isocyanates; isothiocyanates; cyanates; thiocyanates; imines; nitro groups; and nitriles (i.e., CN).

[0015] Substituted cyclic groups, such as substituted cycloalkyl, aryl, heterocyclic, and heteroaryl groups, also include rings and ring systems in which the bond to a hydrogen atom is replaced by a bond to a carbon atom. Therefore, substituted cycloalkyl, aryl, heterocyclic, and heteroaryl groups can also be substituted or unsubstituted alkyl, alkenyl, and alkynyl groups as defined below.

[0016] Alkyl groups include straight-chain and branched alkyl groups having 1 to 12 carbon atoms, and typically 1 to 10 carbon atoms, or in some embodiments 1 to 8, 1 to 6, or 1 to 4 carbon atoms. Alkyl groups may be substituted or unsubstituted. Examples of straight-chain alkyl groups include groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl. Examples of branched alkyl groups include, but are not limited to, isopropyl, isobutyl, sec-butyl, tert-butyl, neopentyl, isopentyl, and 2,2-dimethylpropyl. Representative substituted alkyl groups may be substituted once or multiple times with substituents (such as those listed above), and include, but are not limited to, haloalkyl (e.g., trifluoromethyl), hydroxyalkyl, thioalkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, alkoxyalkyl, carboxylalkyl, etc.

[0017] Cycloalkyl groups include monocyclic, bicyclic, or tricyclic alkyl groups having 3 to 12 carbon atoms in the ring, or in some embodiments 3 to 10, 3 to 8, 3 to 4, 5, or 6 carbon atoms. Cycloalkyl groups may be substituted or unsubstituted. Exemplary monocyclic cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. In some embodiments, the cycloalkyl group has 3 to 8 ring members, while in other embodiments, the number of ring carbon atoms is 3 to 5, 3 to 6, or 3 to 7. Bicyclic and tricyclic ring systems include bridged cycloalkyl groups and fused rings, such as, but not limited to, bicyclic [2.2.1]hexane, adamantyl, decahydronaphthyl, etc. Substituted cycloalkyl groups may be substituted once or multiple times with non-hydrogen and non-carbon groups as defined above. However, substituted cycloalkyl groups also include rings substituted with straight-chain or branched alkyl groups as defined above. Representative substituted cycloalkyl groups can be monosubstituted or substituted more than once, such as, but not limited to, 2,2-, 2,3-, 2,4-, 2,5- or 2,6-disubstituted cyclohexyl groups, which can be substituted by, for example, those substituents listed above.

[0018] A cycloalkyl group is an alkyl group as defined above, wherein the hydrogen or carbon bond of the alkyl group is replaced by a bond with the cycloalkyl group as defined above. The cycloalkyl group may be substituted or unsubstituted. In some embodiments, the cycloalkyl group has 4 to 16 carbon atoms, 4 to 12 carbon atoms, and typically 4 to 10 carbon atoms. A substituted cycloalkyl group may be substituted at the alkyl, cycloalkyl, or alkyl-to-cycloalkyl moiety of the group. Representative substituted cycloalkyl groups may be monosubstituted or substituted more than once, for example, but not limited to monosubstituted, disubstituted, or trisubstituted substituents such as those listed above.

[0019] Alkenyl groups include straight-chain and branched alkyl groups as defined above, differing in that at least one double bond exists between two carbon atoms. Alkenyl groups can be substituted or unsubstituted. Alkenyl groups have 2 to 12 carbon atoms, and typically 2 to 10 carbon atoms, or in some embodiments 2 to 8, 2 to 6, or 2 to 4 carbon atoms. In some embodiments, the alkenyl group has one, two, or three carbon-carbon double bonds. Examples include, but are not limited to, vinyl, allyl, -CH=CH(CH3), -CH=C(CH3)2, -C(CH3)=CH2, -C(CH3)=CH(CH3), -C(CH2CH3)=CH2, and so on. Representative substituted alkenyl groups can be monosubstituted or substituted more than once, for example, but not limited to monosubstituted, disubstituted, or trisubstituted substituents such as those listed above.

[0020] Cycloalkenyl groups include cycloalkyl groups as defined above that have at least one double bond between two carbon atoms. Cycloalkenyl groups can be substituted or unsubstituted. In some embodiments, the cycloalkenyl group may have one, two, or three double bonds, but does not include aromatic compounds. Cycloalkenyl groups have 4 to 14 carbon atoms, or in some embodiments 5 to 14 carbon atoms, 5 to 10 carbon atoms, or even 5, 6, 7, or 8 carbon atoms. Examples of cycloalkenyl groups include cyclohexenyl, cyclopentenyl, cyclohexadienyl, cyclobutadienyl, and cyclopentadienyl.

[0021] A cycloalkenylalkyl group is an alkyl group as defined above, wherein the hydrogen or carbon bond of the alkyl group is replaced by a bond with a cycloalkenyl group as defined above. A cycloalkenylalkyl group can be substituted or unsubstituted. A substituted cycloalkenylalkyl group can be substituted at the alkyl, cycloalkenyl, or alkyl-cycloalkenyl moiety of the group. Representative substituted cycloalkenylalkyl groups can be substituted once or multiple times, for example, by the substituents listed above.

[0022] The alkynyl group includes straight-chain and branched alkyl groups as defined above, differing in that there is at least one triple bond between two carbon atoms. The alkynyl group can be substituted or unsubstituted. The alkynyl group has 2 to 12 carbon atoms, and typically 2 to 10 carbon atoms, or in some embodiments 2 to 8, 2 to 6, or 2 to 4 carbon atoms. In some embodiments, the alkynyl group has one, two, or three carbon-carbon triple bonds. Examples include, but are not limited to, -C≡CH, -C≡CCH3, -CH2C≡CCH3, and -C≡CCH2CH(CH2CH3)2, etc. Representative substituted alkynyl groups can be monosubstituted or substituted more than once, for example, but not limited to monosubstituted, disubstituted, or trisubstituted groups as listed above.

[0023] Aromatic groups are cyclic aromatic hydrocarbons that do not contain heteroatoms. Aryl groups as used herein include monocyclic, bicyclic, and tricyclic ring systems. Aryl groups can be substituted or unsubstituted. Thus, aryl groups include, but are not limited to, phenyl, azulel, heptatenyl, biphenyl, fluorenyl, phenanthryl, anthraceneyl, indene, indanyl, cyclopentadienyl, and naphthyl. In some embodiments, the aryl group contains 6-14 carbon atoms in the ring moiety of the group, and in other embodiments, it contains 6 to 12 or even 6-10 carbon atoms. In some embodiments, the aryl group is phenyl or naphthyl. The phrase “aryl” includes groups containing a fused ring, such as fused aromatic-aliphatic ring systems (e.g., indene, tetrahydronaphthyl, etc.). Representative substituted aryl groups can be monosubstituted (e.g., tolyl) or substituted more than once. For example, monosubstituted aryl groups include, but are not limited to, 2-, 3-, 4-, 5-, or 6-substituted phenyl or naphthyl groups, which can be substituted with, for example, those substituents listed above.

[0024] Aryl alkyl groups are alkyl groups as defined above, wherein the hydrogen or carbon bonds of the alkyl group are replaced by bonds with aryl groups as defined above. Aryl alkyl groups can be substituted or unsubstituted. In some embodiments, the aryl alkyl group contains 7 to 16 carbon atoms, 7 to 14 carbon atoms, or 7 to 10 carbon atoms. Substituted aryl alkyl groups may be substituted at the alkyl, aryl, or alkyl-aryl moiety of the group. Representative aryl alkyl groups include, but are not limited to, benzyl and phenethyl, as well as fused (cycloalkylaryl)alkyl groups, such as 4-indenylethyl. Representative substituted aryl alkyl groups may be substituted once or multiple times with the substituents listed above.

[0025] Heterocyclic groups include aromatic (also called heteroaryl) and non-aromatic cyclic compounds containing three or more ring members, one or more of which are heteroatoms, such as, but not limited to, N, O, and S. Heterocyclic groups can be substituted or unsubstituted. In some embodiments, the heterocyclic group contains 1, 2, 3, or 4 heteroatoms. In some embodiments, the heterocyclic group includes monocyclic, bicyclic, and tricyclic groups having 3 to 16 ring members, while other such groups have 3 to 6, 3 to 10, 3 to 12, or 3 to 14 ring members. Heterocyclic groups encompass aromatic, partially unsaturated, and saturated cyclic systems such as imidazolyl, imidazolinyl, and imidazolinidyl. The phrase "heterocyclic group" includes fused cyclic compounds, including those containing fused aromatic and non-aromatic groups, such as benzotriazolyl, 2,3-dihydrobenzo[1,4]dioxane-hexenyl, and benzo[1,3]dioxane-pentenyl. This phrase also includes bridged polycyclic ring systems containing heteroatoms, such as, but not limited to, quinine ring groups. This phrase includes heterocyclic groups having other groups bonded to one of the ring members, such as alkyl, oxygen, or halogen groups, referred to as "substituted heterocyclic groups." Heterocyclic groups include, but are not limited to, aziridinyl, acridineyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, tetrahydrothiopheneyl, tetrahydrofuranyl, dioxacyclopentenyl, furanyl, thiopheneyl, pyrrolyl, pyrrololinyl, imidazolyl, imidazolinyl, pyrazolyl, pyrazolyl, triazolyl, tetraazolyl, oxazolyl, isoxazolyl, thiazolyl, thiazolinyl, isothiazolyl, thiazolinyl, isothiazolyl, thiadiazolyl, oxadiazolyl, piperidinyl, piperazine, morphoyl, etc. Phospholinyl, thiomorpholinyl, tetrahydropyranyl, tetrahydrothiopyranyl, oxothiacyclohexane, dioxy, dithiaalkyl, pyranyl, pyridyl, pyrimidinyl, pyridazinyl, triazinyl, dihydropyridinyl, dihydrodithiocyclohexenyl, dihydrodithionyl, peripetaazinyl, quininyl, indoleyl, dihydroindoleyl, isoindoleyl, azaindoleyl (pyrrolopyridyl), indazoleyl, inazinyl, benzotriazolyl, benzimidazoleyl Benzofuranyl, benzothiopheneyl, benzothiazolyl, benzoxadiazolyl, benzoxazinyl, benzodithiacyclohexenyl, benzoxazinyl, benzothiazolyl, benzothiazolyl, benzothiazolyl, benzothiazolyl, benzo[1,3]dioxacyclopentenyl, pyrazolopyridyl, imidazopyridyl (azabenzimidazolyl), triazolopyridyl, isoxazolopyridyl, purine, xanthine, adenine, guanine Quinolinyl, isoquinolinyl, quinazinyl, quinoxalinyl, quinazolinyl, cinolinyl, phthalazinyl, naphridinyl, pteridinyl, thionaphthyl, dihydrobenzothiazinyl, dihydrobenzofuranyl, dihydroindolyl, dihydrobenzodioxinyl, tetrahydroindolyl, tetrahydroindolyl, tetrahydrobenzimidazolyl, tetrahydrobenzotriazolyl, tetrahydropyrrolopyridinyl, tetrahydropyrazolopyridinyl, tetrahydroimidazopyridinyl, tetrahydrotriazolopyridinyl, and tetrahydroquinolinyl.Representative substituted heterocyclic groups can be monosubstituted or substituted more than once, such as, but not limited to, pyridyl or morpholino, which are 2-, 3-, 4-, 5- or 6-substituted, or disubstituted by various substituents (such as those listed above).

[0026] A heteroaryl group is an aromatic ring compound containing five or more ring members, one or more of which are heteroatoms, such as, but not limited to, N, O, and S. The heteroaryl group can be substituted or unsubstituted. Heteroaryl groups include, but are not limited to, groups such as pyrroloyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiazolyl, pyridinyl, pyridinyl, pyrazinyl, thiophenyl, benzothiophene, furanyl, benzofuranyl, indolyl, azaindolyl (pyrrolopyridinyl), inzolyl, benzimidazolyl, imidazopyridinyl (azabenzimidazolyl), pyrazolopyridinyl, triazolopyridinyl, benzotriazolyl, benzooxazolyl, benzothiazolyl, benzothiadiazolyl, imidazopyridinyl, isoxazolopyridinyl, thianaphthyl, purine, xanthine, adenine, guanine, quinolinyl, isoquinolinyl, tetrahydroquinolinyl, quinoxolinyl, and quinazolinyl. Heteroaryl groups include fused-ring compounds in which all rings are aromatic, such as indole, and fused-ring compounds in which only one ring is aromatic, such as 2,3-dihydroindole. Representative substituted heteroaryl groups can be substituted once or multiple times by various substituents (such as those listed above).

[0027] Heterocyclic alkyl groups are alkyl groups as defined above, wherein the hydrogen or carbon bond of the alkyl group is replaced by a bond with a heterocyclic group as defined above. Heterocyclic alkyl groups can be substituted or unsubstituted. Substituted heterocyclic alkyl groups can be substituted at the alkyl, heterocyclic, or alkyl-and-heterocyclic moiety of the group. Representative heterocyclic alkyl groups include, but are not limited to, morpholino-4-yl-ethyl, furan-2-yl-methyl, imidazol-4-yl-methyl, pyridin-3-yl-methyl, tetrahydrofuran-2-yl-ethyl, and indol-2-yl-propyl. Representative substituted heterocyclic alkyl groups can be substituted once or multiple times with the substituents listed above.

[0028] A heteroaryl group is an alkyl group as defined above, wherein the hydrogen or carbon bond of the alkyl group is replaced by a bond with a heteroaryl group as defined above. A heteroaryl group can be substituted or unsubstituted. A substituted heteroaryl group can be substituted at the alkyl, heteroaryl, or alkyl-and-heteraryl moiety of the group. Representative substituted heteroaryl groups can be substituted once or multiple times by the substituents listed above.

[0029] In compounds of this technology, groups having two or more linkage sites (i.e., divalent, trivalent, or polyvalent) described herein are indicated by the prefix "alkylene". For example, divalent alkyl is alkylene, divalent aryl is arylene, divalent heteroaryl is divalent heteroarylene, and so on. Substituted groups having a single linkage site with compounds of this technology are not referred to by the name "alkylene". Thus, for example, chloroethyl is not referred to herein as chloroethylene.

[0030] An alkoxy group is a hydroxyl group (-OH) in which the bond with a hydrogen atom is replaced by a bond with a carbon atom of a substituted or unsubstituted alkyl group as defined above. Alkoxy groups can be substituted or unsubstituted. Examples of straight-chain alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, pentoxy, and hexoxy. Examples of branched-chain alkoxy groups include, but are not limited to, isopropoxy, sec-butoxy, tert-butoxy, isopentoxy, and isohexoxy. Examples of cycloalkoxy groups include, but are not limited to, cyclopropoxy, cyclobutoxy, cyclopentoxy, and cyclohexoxy. Representative substituted alkoxy groups can be substituted once or multiple times by the substituents listed above.

[0031] As used herein, the terms “alkanoyl” and “alkanoyloxy” can refer to –C(O)–alkyl and –O–C(O)–alkyl, respectively, each containing 2–5 carbon atoms. Similarly, “aromaticyl” and “aromaticoxy” refer to –C(O)–aryl and –O–C(O)–aryl.

[0032] The terms "aryloxy" and "arylalkoxy" refer to a substituted or unsubstituted aryl group bonded to an oxygen atom and a substituted or unsubstituted aryl group bonded to an oxygen atom at an alkyl group, respectively. Examples include, but are not limited to, phenoxy, naphthoxy, and benzyloxy. Representative substituted aryloxy and arylalkoxy groups may be substituted once or multiple times by the substituents listed above.

[0033] The term "carboxylate group" as used in this article refers to the -COOH group.

[0034] The term "ester" as used in this article refers to -COOR 70 And -C(O)OG group. R 70G is a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl, heterocyclic alkyl, or heterocyclic group as defined herein. G is a carboxylate protecting group. Carboxylate protecting groups are well known to those skilled in the art. A comprehensive list of protecting groups for carboxylate functional groups can be found in Protective Groups in Organic Synthesis, Greene, TW; Wuts, PGM, John Wiley & Sons, New York, NY (3rd edition, 1999), which may be added or removed using the procedures set forth therein, and which are incorporated herein by reference in their entirety, and are as fully set forth herein for any and all purposes.

[0035] The term "amide" (or "amide group") includes C- and N-amide groups, namely -C(O)NR, respectively. 71 R 72 and -NR 71 C(O)R 72 R 71 and R 72 Independently hydrogen, or a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heterocyclic alkyl, or heterocyclic group as defined herein. The amide group therefore includes, but is not limited to, carbamoyl (-C(O)NH2) and formamide (-NHC(O)H). In some embodiments, the amide is -NR. 71 C(O)-(C 1-5 The amide is an alkyl group, and the group is referred to as "carbonylamino". In other cases, the amide is -NHC(O)-alkyl, and the group is referred to as "alkanoylamino".

[0036] The terms “nitrile” or “cyano” as used in this article refer to the –CN group.

[0037] Carbamate groups include N- and O-carbamate groups, namely -NR and -NR respectively. 73 C(O)OR 74 and -OC(O)NR 73 R 74 Group. R 73 and R 74 Independently defined herein, it is a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heterocyclic alkyl, or heterocyclic group. 73 It can also be H.

[0038] The term "amine" (or "amino group") used in this article refers to -NR 75 R 76 Group, wherein R 75 and R76 The amine is independently hydrogen, or a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heterocyclic alkyl, or heterocyclic group as defined herein. In some embodiments, the amine is an alkylamino, dialkylamino, arylamino, or alkylarylamino. In other embodiments, the amine is NH2, methylamino, dimethylamino, ethylamino, diethylamino, propylamino, isopropylamino, phenylamino, or benzylamino.

[0039] The term "sulfonamide group" includes S- and N-sulfonamide groups, namely -SO2NR and -SO2NR, respectively. 78 R 79 and –NR 78 SO2R 79 Group. R 78 and R 79 Independently hydrogen, or a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heterocyclic alkyl, or heterocyclic group as defined herein. The sulfonamide group therefore includes, but is not limited to, aminosulfonyl (-SO2NH2). In some embodiments herein, the sulfonamide group is –NHSO2-alkyl and is referred to as an “alkylsulfonylamino” group.

[0040] The term "thiol" refers to the -SH group, while "sulfide" includes -SR. 80 Groups, "sulfoxide" include –S(O)R 81 Groups, sulfones include -SO2R 82 Groups, and "sulfonyl" includes –SO2OR 83 R 80 R 81 R 82 and R 83 Each is independently a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl, heterocyclic, or heterocyclic alkyl group as defined herein. In some embodiments, the sulfide is an alkylthio (-S-alkyl). The term "sulfonic acid" as used herein refers to the -SO3H group, and "sulfonate" as used herein refers to -SO3 - Group (the deprotonated form of sulfonic acid).

[0041] The term "urea" refers to –NR 84 -C(O)-NR 85 R 86 Group. R 84 R 85 and R 86 Independently hydrogen, or substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heterocyclic or heterocyclic alkyl groups as defined herein.

[0042] The term "ammonia" refers to –C(NR)87 )NR 88 R 89 and –NR 87 C(NR 88 )R 89 , where R 87 R 88 and R 89 Each is independently hydrogen, or a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl, heterocyclic or heterocyclic alkyl group as defined herein.

[0043] The term "guanidine" refers to –NR 90 C(NR 91 )NR 92 R 93 , where R 90 R 91 R 92 and R 93 Each is independently hydrogen, or a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl, heterocyclic or heterocyclic alkyl group as defined herein.

[0044] The term "enamine" refers to –C(R 94 )=C(R 95 )NR 96 R 97 and –NR 94 C(R 95 )=C(R 96 )R 97 , where R 94 R 95 R96 and R 97 Each of these can be hydrogen, substituted or unsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl, heterocyclic or heterocyclic alkyl, as defined herein.

[0045] As used herein, the term "halogen" or "halogenated" refers to bromine, chlorine, fluorine, or iodine. In some embodiments, the halogen is fluorine. In other embodiments, the halogen is chlorine or bromine.

[0046] The term "hydroxyl" as used in this article can refer to –OH or its ionized form –O–. A "hydroxyalkyl" group is an alkyl group substituted with a hydroxyl group, such as HO-CH2-.

[0047] The term "imide" refers to –C(O)NR 98 C(O)R 99 , where R 98 and R 99 Each is independently hydrogen, or a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl, heterocyclic or heterocyclic alkyl group as defined herein.

[0048] The term "imine" refers to –CR 100 (NR 101 ) and –N(CR 100 R 101 ) group, wherein R 100 and R 101 Each is independently hydrogen or a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, ynyl, aryl, aralkyl, heterocyclic, or heterocyclic alkyl group as defined herein, provided that R 100 and R 101 Both are hydrogen at different times.

[0049] The term "nitro" as used in this article refers to the –NO2 group.

[0050] The term “trifluoromethyl” as used in this article refers to –CF3.

[0051] The term “trifluoromethoxy” as used in this article refers to –OCF3.

[0052] The term "azido group" refers to –N3.

[0053] The term "trialkylammonium" refers to the –N(alkyl)3 group. Trialkylammonium groups are positively charged and thus usually have associated anions, such as halide anions.

[0054] The term "isocyanate" refers to –NC.

[0055] The term "isothiocyanate" refers to –NCS.

[0056] The term "pentafluorosulfuryl" refers to –SF5.

[0057] As those skilled in the art will understand, for any and all purposes, particularly in providing a written description, all scopes disclosed herein also encompass any and all possible subscopes and combinations thereof. Any enumerated scope can be readily understood as sufficiently descriptive and capable of being decomposed into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each scope discussed herein can be readily decomposed into a lower third, a middle third, and an upper third, etc. As those skilled in the art will also understand, all language such as “at most,” “at least,” “greater than,” “less than,” etc., includes the referenced numbers and refers to a scope that can subsequently be decomposed into subscopes as discussed above. Finally, as those skilled in the art will understand, a scope includes each individual member. Thus, for example, a group having 1-3 atoms means a group having 1, 2, or 3 atoms. Similarly, a group having 1-5 atoms means a group having 1, 2, 3, 4, or 5 atoms, and so on.

[0058] As understood by those skilled in the art, “molecular weight” (also known as “relative molar mass”) is a dimensionless quantity, but it is converted to molar mass by multiplying by 1 g / mol or by 1 Da – for example, a compound with a weight-average molecular weight of 5,000 has a weight-average molar mass of 5,000 g / mol and a weight-average molar mass of 5,000 Da.

[0059] Those skilled in the art will understand that the compounds of this technology can exhibit tautomerism, conformational isomerism, geometric isomerism, and / or stereoisomerism. Since the diagrams in the specification and claims only represent one possible tautomerism, conformational isomerism, stereochemical isomerism, or geometric isomerism, it should be understood that this technology covers any tautomerism, conformational isomerism, stereochemical isomerism, and / or geometric isomerism of compounds having one or more of the effects described herein, as well as mixtures of these various forms.

[0060] "Tautomers" refer to the isomers of compounds that are in equilibrium with each other. The presence and concentration of isomers will depend on the environment in which the compound is present and can vary depending on, for example, whether the compound is a solid or in an organic solution or an aqueous solution. For example, in aqueous solution, quinazolinones can exhibit the following isomers, which are referred to as tautomers of each other: .

[0061] As another example, guanidine can exhibit the following isomers in protonated organic solutions, also known as tautomers of each other: .

[0062] Due to the limitations of representing compounds by structural formulas, it should be understood that all chemical formulas of the compounds described herein represent all tautomer forms of the compounds and are within the scope of this art.

[0063] Stereoisomers of a compound (also known as optical isomers) include all chiral, diastereomeric, and racemic forms of the structure, unless the specific stereochemistry is explicitly specified. Thus, compounds used in this technique include optical isomers enriched or resolved at any or all asymmetric atoms, as is evident from the description. Racemic and diastereomeric mixtures, as well as individual optical isomers, can be isolated or synthesized to be substantially free of their enantiomers or diastereomeric counterparts, and all such stereoisomers are within the scope of this technique.

[0064] The compounds of this technique can exist as solvates, especially hydrates. Hydrates can form during the preparation of the compound or a composition containing the compound, or they can form over time due to the hygroscopic nature of the compound. The compounds of this technique can also exist as organic solvates, including DMF, ether, and alcohol solvates. The identification and preparation of any particular solvate are within the skill of a person generally skilled in synthetic organic chemistry.

[0065] This technology For colloidal silica used in applications such as enhanced crude oil recovery, metal surface treatment, and electroplating formulations under extreme conditions (e.g., high divalent metal salt solutions, high trivalent metal salt solutions, wide pH ranges, and / or high temperatures), colloidal stability is a more stringent requirement. Indeed, as the comparative examples disclosed herein demonstrate, functionalized colloidal silica available prior to this disclosure suffers from stability issues under such extreme conditions.

[0066] Furthermore, colloidal silica particles have been used in paint formulations, as described in U.S. Patent Nos. 8,436,088, 9,598,557, and 10,487,240. In paint formulations, particularly in aqueous systems containing latex binder particles, various components are present, and components such as surfactants, coalescing agents, defoamers, and thickeners may undesirably interact with unmodified colloidal silica and affect the stability of the colloidal system.

[0067] This technology addresses the aforementioned deficiencies—including those related to crude oil enhanced recovery, metal surface treatment (e.g., corrosion-resistant metal surface treatment), electroplating, and coatings—and provides additional advantages. Thus, in one aspect, this technology provides a composition comprising water and functionalized colloidal silica. The functionalized colloidal silica comprises silica particles (each silica particle comprising a surface) and structural units according to Formula I, Formula II, Formula III, or Formula IV. in R 1 It is -S-(CH2) n R 2 Or -NH-NH-C(O)-(CH2) m -C(O)NH-NH2, where n is 1, 2, 3, 4, 5 or 6 and m It can be 1, 2, 3, 4, 5, 6, 7, or 8; R 2 It is independently -SO3Y each time it appears. 1 -SO3H, -SO3- -CO2Y 2 -CO2H or -CO2 - ; R 2’ and R 2’’ Each is independently H, -SO3Y 1 -SO3H, -SO3 - -CO2Y 2 -CO2H or -CO2 - ; R 3 It is hydroxyl, alkoxy, aryloxy, or G 2 ; R 4 It is hydroxyl, alkoxy, aryloxy, or G 3 ; G 1 G 2 and G 3 Each is an oxygen atom on the surface of the silica particle, wherein G 1 G 2 and G 3 Not the same oxygen atom; Y 1 It is an independent cation each time it appears; and Y 2 It is an independent cation each time it appears.

[0068] The composition may include a pH of about 2 to about 11 or a pH of about 3.5 to about 11. The composition may include a pH of 11 or lower; thus, the composition herein may include a pH of about 3.5, about 4.0, about 4.5, about 5.0, about 5.5, about 6.0, about 6.5, about 7.0, about 7.5, about 8.0, about 8.5, about 9.0, about 9.5, about 10.0, about 10.5, about 11.0, or any two of these values ​​and / or any range between any two of these values.

[0069] In any embodiment where the composition comprises a pH of approximately 3.5 to 11, the functionalized colloidal silica may include a negative zeta potential. The negative zeta potential of any such embodiment herein may be approximately -1 mV (“mV”), approximately -2 mV, approximately -3 mV, approximately -4 mV, approximately -5 mV, approximately -6 mV, approximately -7 mV, approximately -8 mV, approximately -9 mV, approximately -10 mV, approximately -15 mV, approximately -20 mV, approximately -25 mV, approximately -30 mV, approximately -35 mV, approximately -40 mV, approximately -45 mV, approximately -50 mV, approximately -55 mV, approximately -60 mV, approximately -65 mV, approximately -70 mV, or any two of these values ​​and / or any range between any two of these values. In any embodiment where the composition comprises a pH of about 3.5 to 11, the functionalized colloidal silica may comprise a zeta potential of about -50 mV to about -60 mV.

[0070] In any embodiment where the composition comprises a pH of about 11 or lower, the composition may comprise a molar ratio of any one of the structural units of formulas I-IV to any of the remaining structural units of formulas I-IV of about 1:1 or greater (i.e., [moles of structural units according to one formula] / [moles of structural units according to another formula]). Thus, in any embodiment where the composition comprises a pH of about 11 or lower, the composition may comprise a molar ratio of any one of the structural units of formulas I-IV to any of the remaining structural units of formulas I-IV of about 1:1, about 2:1, about 3:1, about 4:1, about 5:1, about 6:1, about 7:1, about 8:1, about 9:1, about 10:1, about 20:1, about 30:1, about 40:1, about 50:1, about 100:1, about 1,000:1, a range greater than any of these values, or including any two of these values ​​and / or any range between any two of these values.

[0071] In any embodiment herein, the silica particles may have a median diameter (D50 based on volume) of about 1 nm to about 100 nm as determined by dynamic light scattering or disc centrifugation analysis. Thus, the median diameter of the silica particles determined by dynamic light scattering may be about 1 nm, about 5 nm, about 10 nm, about 15 nm, about 20 nm, about 25 nm, about 30 nm, about 35 nm, about 40 nm, about 45 nm, about 50 nm, about 55 nm, about 60 nm, about 65 nm, about 70 nm, about 75 nm, about 80 nm, about 85 nm, about 90 nm, about 95 nm, about 100 nm, or any two of these values ​​and / or any range between any two of these values.

[0072] In any embodiment described herein, the silica particles may have a diameter of approximately 25 μm. 2 / g to approximately 1,200 m 2 / g Sears surface area. See Sears, “Determination of Specific Area of ​​Colloidal Silica by Titration with Sodium Hydroxide”, Analytical Chemistry 1956, 28(12), 1981-1983 https: / / doi.org / 10.1021 / ac60120a048. Thus, the silica particles in any embodiment described herein can have approximately 25 m² / g. 2 / g、26 m 2 / g、27 m 2 / g、28 m 2 / g、29 m 2 / g、30 m 2 / g、35 m 2 / g、40 m 2 / g、45 m 2 / g、50 m 2 / g、55 m 2 / g、60 m 2 / g、70 m 2 / g、80 m 2 / g、90 m 2 / g, 100 m 2 / g, 150m 2 / g、200 m 2 / g、250 m 2 / g、300 m 2 / g、350 m 2 / g、400 m 2 / g、450 m 2 / g、500 m 2 / g、550 m 2 / g、600m 2 / g、650 m 2 / g、700 m 2 / g、750 m 2 / g、800 m 2 / g、850 m 2 / g、900 m 2 / g、950 m 2 / g、1,000 m 2 / g、1,100 m 2 / g、1,200 m 2 / g, or the Sears surface area including any two of these values ​​and / or any range between any two of these values.

[0073] The composition of any embodiment described herein may include approximately 0.8 to approximately 3.5 per nm. 2 The number of structural units according to Formula I, Formula II, Formula III, and / or Formula IV in terms of surface area. Therefore, the composition of any embodiment herein may comprise approximately 0.8, approximately 0.9, approximately 1.0, approximately 1.1, approximately 1.2, approximately 1.3, approximately 1.4, approximately 1.5, approximately 1.6, approximately 1.7, approximately 1.8, approximately 1.9, approximately 2.0, approximately 2.1, approximately 2.2, approximately 2.3, approximately 2.4, approximately 2.5, approximately 2.6, approximately 2.7, approximately 2.8, approximately 2.9, approximately 3.0, approximately 3.1, approximately 3.2, approximately 3.3, approximately 3.4, approximately 3.5, or any two of these values ​​and / or any range between any two of these values ​​per nm. 2 The number of structural units according to Formula I, Formula II, Formula III and / or Formula IV for the surface area.

[0074] The composition of any embodiment described herein may comprise a mass percentage composition of carbon determined by elemental analysis of about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, or any two of these values ​​and / or any range between any two of these values.

[0075] Compositions comprising any embodiment having a sulfur-containing structural unit may include a percentage composition of sulfur determined by elemental analysis of about 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, or any two of these values ​​and / or any range between any two of these values.

[0076] Compositions comprising any embodiment having nitrogen-containing structural units may include a percentage composition of nitrogen determined by elemental analysis of about 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, or any two of these values ​​and / or any range between any two of these values.

[0077] In any embodiment described herein, it is possible that the composition comprises a structural unit according to Formula I and R 1 -(CH2)2SO3Na and / or R 1 The composition is -(CH2)3SO3Na. In any embodiment described herein, it is possible that the composition comprises a structural unit according to Formula I and R 1 The composition is -NH-NH-C(O)-(CH2)4-C(O)NH-NH2. In any embodiment described herein, it is possible that the composition comprises a structural unit according to Formula II and RR 2 The value is -SO3Na. In any embodiment described herein, it is possible that the composition comprises a structural unit according to Formula III, wherein R 2 It is -SO3Na and R 2’ and R 2’’ Each is independently H. In any embodiment herein, it is possible that the composition comprises a structural unit according to Formula III, wherein R 2 For -CO2H, R 2’ Let H be the number of 'R', and R be the number of 'R'. 2’’ -CO2H. In any embodiment described herein, it is possible that the composition comprises a structural unit according to Formula III, wherein R 2 For -CO2H, R 2’ It is -CO2H, and R 2’’ For H. In any embodiment herein, it is possible that the composition comprises a structural unit according to Formula III, wherein R 2 For -CO2H, R 2’ It is -CO2H, and R 2’’-CO2H. In any embodiment described herein, it is possible that the composition comprises a structural unit according to Formula IV. In any embodiment described herein, it is possible that R 3 It can be hydroxyl, methoxy, ethoxy, propoxy, phenoxy, or G. 2 In any implementation described herein, R is possible. 4 It can be hydroxyl, methoxy, ethoxy, propoxy, phenoxy, or G. 3 In any implementation described herein, R is possible. 3 For G 2 In any implementation described herein, R is possible. 4 The silica particles are hydroxyl groups. In any embodiment herein, the silica particles may contain at least one structural unit according to formula Ia or Ib. Where Y 3 and Y 4 It is an independent cation each time it appears.

[0078] In any of the implementations described herein, Y 1 Y 2 Y 3 and Y 4 Each occurrence can be independently represented as, for example, NH4. + Na + Li + K + Ag + Ca 2+ Mg 2+ or Zn 2+ .

[0079] In any embodiment described herein, it is possible that the silica particles further comprise at least one structural unit according to Formula V. in R 5 It is hydroxyl, alkoxy, aryloxy, or G 5 ; R 6 It is hydroxyl, alkoxy, aryloxy, or G 6 ; G 4 G 5 and G 6 Each is an oxygen atom on the surface of the silica particle, wherein G 4 G 5 and G 6 They are not the same oxygen atom.

[0080] In any implementation described herein, R is possible. 4 It can be hydroxyl, methoxy, ethoxy, propoxy, phenoxy, or G. 5 In any implementation described herein, R is possible. 5 It can be hydroxyl, methoxy, ethoxy, propoxy, phenoxy, or G. 6 .

[0081] The composition of any embodiment herein may comprise from about 0.1 wt% to about 50 wt% of the functionalized colloidal silica. Thus, in any embodiment herein, the composition may comprise the functionalized colloidal silica in amounts of about 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, or any two of these values ​​and / or any range between any two of these values. For example, in any embodiment herein, the composition may contain the functionalized colloidal silica in amounts from about 0.1% to about 30% by weight, from about 5% to about 30% by weight, from about 10% to about 30% by weight, or from about 0.1% to about 5% by weight.

[0082] When the composition of any embodiment herein comprises a salt solution with an ionic strength of 0.5 to 3.0, the composition is aging stable at 80°C for 24 hours or longer. The salt solution of any embodiment herein may comprise NaCl, CaCl2, MgSO4, or any combination of two or more thereof. In any embodiment herein, the ionic strength may be 0.5, 1.0, 2.0, 3.0, or any two of these values ​​and / or any range between these values. When the composition comprises a salt solution with an ionic strength of 0.5 to 3.0, in any such embodiment, the composition may be at a pH of about 2 to about 11, or about 11 or lower; including about 3.5, about 4.0, about 4.5, about 5.0, about 5.5, about 6.0, about 6.5, about 7.0, about 7.5, about 8.0, about 8.5, about 9.0, about 9.5, about 10.0, about 10.5, about 11.0, or any two of these values ​​and / or any range between any two of these values.

[0083] On the other hand, this technology provides a method for manufacturing functionalized colloidal silica (e.g., a method for manufacturing the composition of any embodiment herein). The method includes contacting the colloidal silica with a silane having at least one structural unit according to Formula VI, at least one structural unit according to Formula VII, at least one structural unit according to Formula VIII, or at least one structural unit according to Formula IX to produce the functionalized colloidal silica. in R 1 It is -S-(CH2) n R 2 Or -NH-NH-C(O)-(CH2) m -C(O)NH-NH2, where n It is 1, 2, 3, 4, 5 or 6 and m It can be 1, 2, 3, 4, 5, 6, 7, or 8; R 2 It is independently -SO3Y each time it appears. 1 -SO3H, -SO3 - -CO2Y 2 -CO2H or -CO2 - ; R 2’ and R 2’’ Each is independently H, -SO3Y 1 -SO3H, -SO3 - -CO2Y 2 -CO2H or -CO2 - ; R 7 It is a hydroxyl, alkoxy, or aryl group; R 8 It is a hydroxyl, alkoxy, or aryl group; L 1 It is an alkoxy or aryloxy group; Y 1 It is an independent cation each time it appears; and Y 2 It is an independent cation each time it appears.

[0084] The colloidal silica may be aqueous colloidal silica.

[0085] In any implementation described herein, R is possible. 7 R 8 and L 1 Each is independently alkoxy or aryloxy. In any embodiment described herein, R is possible. 7It can be hydroxyl, methoxy, ethoxy, propoxy, or phenoxy. In any embodiment described herein, R is possible. 8 It can be hydroxyl, methoxy, ethoxy, propoxy, or phenoxy. In any embodiment described herein, L is possible. 1 It can be methoxy, ethoxy, propoxy, or phenoxy.

[0086] In any embodiment of the method described herein, it is possible that the method comprises structural units according to Equation VI and R 1 -(CH2)2SO3Na and / or R 1 The value is -(CH2)3SO3Na. In any embodiment herein, the method may include structural units according to Formula I and R 1 The form is -NH-NH-C(O)-(CH2)4-C(O)NH-NH2. In any embodiment herein, it is possible that the method comprises a structural unit according to formula VII and R 2 For -SO3Na. In any embodiment herein, it is possible that the method comprises a structural unit according to formula VIII, wherein R 2 It is -SO3Na and R 2’ and R 2’’ Each is independently H. In any embodiment herein, it is possible that the composition comprises a structural unit according to Formula VIII, wherein R 2 For -CO2H, R 2’ Let H be the number of 'R', and R be the number of 'R'. 2’’ -CO2H. In any embodiment described herein, it is possible that the composition comprises a structural unit according to Formula VIII, wherein R 2 For -CO2H, R 2’ It is -CO2H, and R 2’’ For H. In any embodiment herein, it is possible that the composition comprises a structural unit according to Formula VIII, wherein R 2 For -CO2H, R 2’ It is -CO2H, and R 2’’ The value is -CO2H. In any embodiment herein, the method may include structural units according to Formula IX.

[0087] In any embodiment of the method herein, the functionalized colloidal silica of the method may include a surface and structural units according to Formula I, Formula II, Formula III, and / or Formula IV. in R 1It is -S-(CH2) n R 2 Or -NH-NH-C(O)-(CH2) m -C(O)NH-NH2, where n It is 1, 2, 3, 4, 5 or 6 and m It can be 1, 2, 3, 4, 5, 6, 7, or 8; R 2 It is independently -SO3Y each time it appears. 1 -SO3H, -SO3 - -CO2Y 2 -CO2H or -CO2 - ; R 2’ and R 2’’ Each is independently H, -SO3Y 1 -SO3H, -SO3 - -CO2Y 2 -CO2H or -CO2 - ; R 3 It is hydroxyl, alkoxy, aryloxy, or G 2 ; R 4 It is hydroxyl, alkoxy, aryloxy, or G 3 ; G 1 G 2 and G 3 Each is an oxygen atom on the surface of the silica particle, wherein G 1 G 2 and G 3 Not the same oxygen atom; Y 1 It is an independent cation each time it appears; and Y 2 It is an independent cation each time it appears.

[0088] In any embodiment of the method described herein, it is possible that the method comprises structural units according to Equation VI and R 1 -(CH2)2SO3Na and / or R 1 The value is -(CH2)3SO3Na. In any embodiment herein, the method may include structural units according to Formula I and R 1 The form is -NH-NH-C(O)-(CH2)4-C(O)NH-NH2. In any embodiment herein, it is possible that the method comprises a structural unit according to Formula II and R 2The value is -SO3Na. In any embodiment described herein, the method may include structural units according to Formula III, where R... 2 It is -SO3Na and R 2’ and R 2’’ Each is independently H. In any embodiment herein, it is possible that the composition comprises a structural unit according to Formula III, wherein R 2 For -CO2H, R 2’ Let H be the number of 'R', and R be the number of 'R'. 2’’ -CO2H. In any embodiment described herein, it is possible that the composition comprises a structural unit according to Formula III, wherein R 2 For -CO2H, R 2’ It is -CO2H, and R 2’’ For H. In any embodiment herein, it is possible that the composition comprises a structural unit according to Formula III, wherein R 2 For -CO2H, R 2’ It is -CO2H, and R 2’’ -CO2H. In any embodiment herein, the method may include structural units according to Formula IV. In any embodiment herein, R may be... 3 It can be hydroxyl, methoxy, ethoxy, propoxy, phenoxy, or G. 2 In any implementation described herein, R is possible. 4 It can be hydroxyl, methoxy, ethoxy, propoxy, phenoxy, or G. 3 In any implementation described herein, R is possible. 3 For G 2 In any implementation described herein, R is possible. 4 The hydroxyl group is present. In any embodiment of the method described herein, the functionalized colloidal silica may comprise at least one structural unit according to formula Ia or Ib. Where Y 3 and Y 4 It is an independent cation each time it appears.

[0089] In any implementation of the method herein, Y 1 Y 2 Y 3 and Y 4 Each occurrence can be independently represented as, for example, NH4. + Na + Li + K + Ag + Ca 2+ Mg2+ or Zn 2+ .

[0090] In any embodiment of the method described herein, it is possible that the functionalized colloidal silica further comprises at least one structural unit according to Formula V. in R 4 It is hydroxyl, alkoxy, aryloxy, or G 5 ; R 5 It is hydroxyl, alkoxy, aryloxy, or G 6 ; G 4 G 5 and G 6 Each is an oxygen atom on the surface of the silica particle, wherein G 4 G 5 and G 6 They are not the same oxygen atom.

[0091] In any implementation of the method described herein, R is possible. 4 It can be hydroxyl, methoxy, ethoxy, propoxy, phenoxy, or G. 5 In any implementation of the method described herein, R is possible. 5 It can be hydroxyl, methoxy, ethoxy, propoxy, phenoxy, or G. 6 .

[0092] Any method described in any embodiment herein may include contacting the colloidal silica with a silane in a medium, wherein the medium comprises water and / or a polar organic solvent (e.g., a polar organic solvent miscible with water). In any embodiment where the medium comprises a polar organic solvent, the polar organic solvent may include methanol, ethanol, propanol, ethylene glycol, acetone, tetrahydrofuran, 1,4-dioxane, dimethylformamide, N-methylpyrrolidone, or any combination of two or more thereof.

[0093] Any implementation method described herein may include contact per 1 nm 2 The surface area of ​​colloidal silica is approximately 1.5 to approximately 3.0 molecular weights of silane. Therefore, in any embodiment herein, the method may include contact per 1 nm 2A molecular weight of silane in amounts of approximately 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, or any range between any two of these values ​​and / or any two of these values, on a colloidal silica surface.

[0094] The methods of any embodiment herein can provide a composition comprising water and the functionalized colloidal silica (e.g., a composition of any embodiment of the compositional aspect of this technology). In such embodiments, when the composition comprises a salt solution with an ionic strength of 0.5 to 3.0, the composition is aging stable at 80°C for 24 hours or longer. The salt solution of any embodiment herein may comprise NaCl, CaCl2, MgSO4, or any combination of two or more thereof. In any embodiment herein, the ionic strength may be 0.5, 1.0, 2.0, 3.0, or any two of these values ​​and / or any range between these values. When the composition comprises a salt solution with an ionic strength of 0.5 to 3.0, in any such embodiment, the composition may be at a pH of about 2 to about 11, or about 3.5 to about 11; including about 3.5, about 4.0, about 4.5, about 5.0, about 5.5, about 6.0, about 6.5, about 7.0, about 7.5, about 8.0, about 8.5, about 9.0, about 9.5, about 10.0, about 10.5, about 11.0, or any two of these values ​​and / or any range between any two of these values.

[0095] Any method according to any embodiment herein may include contacting colloidal silica with a silane according to Formula V to produce an initial mixture comprising functionalized colloidal silica and unreacted silane, silane not bonded to the colloidal silica, impurities, or any combination of two or more thereof; and purifying the functionalized colloidal silica by ultrafiltration of the initial mixture to separate the functionalized colloidal silica from the unreacted silane, silane not bonded to the colloidal silica, impurities, or any combination of two or more thereof.

[0096] On the other hand, this technology provides functionalized silica prepared according to any embodiment described herein.

[0097] The present technology, which is generally described herein, will be more readily understood by referring to the following embodiments, which are provided by way of example and are not intended to limit the present technology. Example

[0098] In these embodiments, commercially available LUDOX colloidal silica grades were used. These products were supplied by WR Grace & Co. Similar products may also be used, such as Levasil from Nouryon, AMSol from Applied Material Solutions, Köstrosol 1540 from CWK Chemiewerk Bad Köstritz GmbH, Nalco 1140 from Nalco Water, Snowtex from Nissan Chemical, and so on.

[0099] All chemicals used in these examples were sourced from common suppliers such as SigmaAldrich, Fisher Scientific, TCI America, and Gelest, Inc. These chemicals were purchased and can be used without further purification.

[0100] To calculate the silane treatment level of colloidal silica particles, 345 nm was used for 7 nm grade colloidal silica (e.g., LUDOX SM). 2 / g surface area, using 220 m for 12 nm grade colloidal silica (e.g., LUDOX HS-40, LUDOX AM, or LUDOX CL). 2 / g surface area, using 140 m for 22 nm grade colloidal silica (e.g., LUDOX™-40). 2 / g surface area, for 40 nm grade colloidal silica (e.g., LUDOX PW-50(X), a grade of colloidal silica with polydisperse silica particles of different sizes) using 75 m 2 / g surface area. Treatment level (TL) is defined as the number of molecules per square nanometer of solid particle surface area, or NM / nm. 2 .

[0101] The process for purifying functionalized colloidal silica includes using Spectrum MidiKros hollow fiber membranes (e.g., with a surface area of ​​75 cm²). 2The membrane used is a D02-E050-10-S mPES / 50 kD molecular weight cutoff (MWCO) membrane (other types of membranes with suitable MWCO membranes may also be used). The colloidal silica sample is passed through the membrane via a Tygon tube equipped with a peristaltic pump at a pressure less than 25 psi. The permeate containing impurities such as salts and unbound free organic molecules is collected, and the total volume is measured. The typical solids content of the colloidal silica is 5-25%, and fresh deionized (DI) water is added to replenish the volume lost due to permeate loss. Typically, 5-10 volumes of permeate accumulate relative to the initial total volume of the colloidal sample before the ultrafiltration process is complete.

[0102] A general method for elemental analysis of functionalized particles containing carbon (C%), hydrogen (H%), nitrogen (N%), and sulfur (S%) involves placing a small amount of purified colloidal sample in a glass vial. The vial is then dried overnight in an oven at 90°C. The dried solid is collected and subjected to elemental analysis using a LECO G4 ICARUS Series 2 analyzer or a PerkinElmer 2400 Series analyzer.

[0103] Titration was employed. For zeta titration, the pH-dependent zeta potential was measured using an electroacoustic method with the Colloid Dynamics AcoustoSizer IIX connected to the automatic titrator. For a typical run, a colloidal solution was prepared by diluting the original sample with DI water to a 5% colloidal solids concentration. Potentiometric titration was initiated at the nascent pH of the colloidal solution and proceeded to pH 9 (for nascent colloidal solutions with a pH less than 7) or pH 3 (for nascent colloidal solutions with a pH greater than 7), and subsequently returned to pH 9 or 3. Preloaded instrument parameters for SiO2 (silica, amorphous - typical) and water were used by the software. Titrations were performed with 0.1N HCl and 0.1N NaOH.

[0104] For dynamic light scattering (DLS) particle size measurements, a Malvern Zetasizer Nano-S90 model ZEN1690 was used. A solution of 2 wt% colloidal solids was prepared by diluting the original colloidal solution with DI water. Once diluted, the colloidal solution was filtered into measuring cuvettes using a 0.45-micron syringe filter. Measurements were accumulated over 60 seconds. Reported values ​​are based on volume D50.

[0105] Example 1 (Sodium mercaptoethanesulfonate at 2.0 NM / nm) 2 TL on LUDOX HS-40 3.61 g of sodium 2-mercaptoethanesulfonate (98% purity, available from Aldrich) was dissolved in 30 mL of DI water. The pH of the solution was approximately 5.3. 5.20 g of (3-glycidoxypropyl)trimethoxysilane (glycidylsilane) was added dropwise to the stirred solution. The mixture was stirred at room temperature for approximately 1 hour. In a 250 mL beaker, 75 g of LUDOX HS-40 (approximately 30 g of dry SiO2) was weighed and diluted with 30 mL of DI water. While mixing, the silane solution was slowly added dropwise to the colloidal silica at room temperature. Once added, the solution was allowed to mix at room temperature for 1 hour. After 1 hour, the sample was heated at 60–70 °C and the solution was allowed to mix at this temperature for another 1 hour. After the reaction, the mixture was cooled to room temperature and percolated with 6 volumes of DI water. A small amount of the sample was removed and dried overnight at 90 °C for elemental analysis to determine the carbon content of the dried sample.

[0106] The following reaction scheme I illustrates the reaction scheme of this embodiment.

[0107] Example 2 (Sodium mercaptopropanesulfonate at 2.0 NM / nm) 2 TL on LUDOX HS-40 4.61 g of sodium 3-mercapto-1-propanesulfonate (>85% purity, available from TCI America) was dissolved in 30 mL of DI water. The pH of the solution was approximately 1.7. 5.20 g of (3-glycidoxypropyl)trimethoxysilane (glycidylsilane) was added dropwise to the stirred solution. The mixture was stirred at room temperature for approximately 1 hour. In a 250 mL beaker, 75 g of LUDOX HS-40 (~30 g of dry SiO2) was weighed and diluted with 30 mL of DI water. While mixing, the silane solution was slowly added dropwise to the colloidal silica at room temperature. Once added, the solution was allowed to mix at room temperature for 1 hour. After 1 hour, the sample was heated at 60–70 °C and the solution was allowed to mix at this temperature for another 1 hour. After the reaction, the mixture was cooled to room temperature and percolated with 6 volumes of DI water. A small amount of the sample was removed and dried overnight at 90 °C for elemental analysis to determine the carbon content of the dried sample.

[0108] The reaction scheme of this embodiment is shown in Reaction Scheme II below.

[0109] Comparative Example 1 (commercially available 3-(trihydroxysilyl)-1-propanesulfonic acid at 2.0 NM / nm) 2 TL on LUDOX HS-40 Add 75 g of LUDOX HS-40 to a 250 mL beaker and dilute with 30 g of DI water. Add 12.71 g of commercially available 3-(trihydroxysilyl)-1-propanesulfonic acid (30-35% concentration, available from Gelest, Inc.) dropwise to the stirred colloidal silica. During the addition, when the pH drops to approximately 6.0, add 1 M NaOH to bring the pH back to 8.0, then continue adding the silane solution. Repeat this process until all the silane has been added and the final pH of the mixture is approximately 7.5. Once added, allow the solution to mix at room temperature for 1 hour. After 1 hour, heat the sample at 60-70°C and allow the solution to mix at this temperature for another 1 hour. After the reaction, allow the mixture to cool to room temperature and percolate the sample with 6 volumes of DI water. Remove a small amount of the sample and dry it overnight at 90°C for elemental analysis to determine the carbon content of the dried sample.

[0110] The following reaction scheme III illustrates the reaction scheme of Comparative Example 1.

[0111] Table 1 shows the carbon and sulfur content of the corresponding dried samples in Examples 1 and 2 and Comparative Example 1.

[0112] Table 1

[0113] As shown, at the same treatment level, the samples of Examples 1 and 2 have higher amounts of carbon and sulfur, but the calculated SO3Na groups based on S content are relatively similar for the three samples in these examples.

[0114] Figure 1 This is a graph showing the pH vs. zeta potential of a colloidal silica sample modified with one of the three sulfonate groups from Example 1, Example 2, or Comparative Example 1, and unmodified HS-40. (See figure) Figure 1 As shown, when compared with unmodified HS-40 (which exhibits typical ionization of surface silanol groups relative to solution pH), all three sulfonate-functionalized modified colloidal samples showed negative zeta potentials throughout the pH titration range, with almost no change in surface charge.

[0115] Examples 1-2, Comparative Examples, and Salt Stability Tests of HS-40 Starting Materials Colloidal systems composed of charged nanoparticles stabilized by electrostatic repulsion are sensitive to high ionic strength or high-concentration salt solutions due to the significantly reduced Debye length in high-salt environments. For example, NaCl in water at 25°C and a concentration of 1×10⁻⁶... -3The solution of M has a Debye length of λD = 9.6 nm, corresponding to approximately 40 water diameters; while at a concentration of 0.1 M, the Debye length is λD = 0.96 nm, equivalent to only four water diameters. (Smith, Lee, and Perkin, “The electrostatic screening length in concentrated electrolytes increases with concentration”, J. Phys. Chem. Lett. 2016, 7, 12, 2157–2163). While not bound by any theory, the surface organic groups bound on colloidal particles can introduce steric effects and contribute to the salt tolerance of colloidal systems containing functionalized colloidal nanoparticles. Here, the colloidal stability is compared with the selected functionality from the described examples, for both the starting materials and samples from the comparative examples.

[0116] To standardize the salt concentration in the stability test, sodium chloride at two different concentrations (1 M and 2 M) was used for the salt compatibility test of these samples.

[0117] Table 2 lists the results of the salt stability tests. These tests were conducted at pH 7–10 (the natural pH of these samples) and at pH 3, a 2% colloidal silica concentration, and at elevated temperatures. Equal volumes of the salt solutions from Table 2 (2 × the concentrations in Table 2) and 4% colloidal samples were mixed, and their colloidal stability was visually observed at 80°C for 4 hours and 24 hours. Arrhenius chemical reaction kinetics indicate that higher temperatures accelerate the reaction, typically doubling the reaction rate for every 10°C increase. Therefore, 24 hours at 80°C (6 × 10°C) is approximately 24 × 2 at 20°C (room temperature). 6 = 1536 hours (or 64 days). Colloidal stability is defined as stable, cloudy (less stable), or gelled (unstable) after aging at this high temperature. The term "stable" means that no visual or physical changes are observed in the colloidal dispersion after aging. The term "cloudy" means that the colloidal dispersion becomes whiter and less transparent, but no visible sedimentation or increase in viscosity is observed in the sample. The term "gelled" means that the viscosity of the colloidal dispersion increases to the point that the entire sample does not flow like a liquid.

[0118] As shown in Table 2, the comparative examples show improved stability beyond that of the unmodified HS-40, but the two samples from Examples 1 and 2 showed excellent stability at both salt concentrations with no visual changes after thermal aging.

[0119] Example 3 (Sodium mercaptopropanesulfonate at 1.7 NM / nm)2 TL on LUDOX HS-40, adding order changes) 22.10 g of glycidyl silane was mixed with 40 mL of DI water at room temperature until a clear solution was obtained (~3 hours). In a 500 mL beaker, 150 g of LUDOX HS-40 (~60 g of dried SiO2) was weighed and diluted with 50 mL of DI water. 18.52 g of sodium 3-mercapto-1-propanesulfonate (>85% purity, available from TCI America) was dissolved in 50 mL of DI water, and this solution was slowly added to the stirred colloidal silica. The pH of the mixture was maintained at approximately 9.5 with dilute NaOH solution. Subsequently, the stirred colloidal mixture was heated in a water bath at 55°C. The prepared virgin glycidyl silane solution was added dropwise to the stirred solution after 1 hour. After addition, the reaction was maintained at 55-60°C for another 1 hour. After the reaction, the mixture was cooled to room temperature, and the sample was percolated with 6 volumes of DI water. A small sample was taken out and dried at 90°C overnight. Elemental analysis was then performed to determine the carbon content of the dried sample.

[0120] The following reaction scheme IV illustrates the reaction scheme of Example 3.

[0121] Elemental analysis of the dried sample showed C% = 3.72% and S% = 0.94%. This result indicates that even at lower processing levels (1.7 vs. 2.0 in Example 2), there was a greater decrease in S% in this example, suggesting that this in-situ method has fewer sulfonate group attachments compared to the standalone silane preparation method described in Example 2.

[0122] Example 4 (2.0 NM / nm) 2 (P-aminobenzenesulfonic acid modification under TL) 11.4 g of p-aminobenzenesulfonic acid was dissolved in 60 mL of DI water, and the pH of the solution was adjusted to approximately 6.0 with 5 M NaOH. 10.4 g of glycidyl silane was added to the stirred solution. The mixture was stirred at room temperature for 1 hour, followed by heating at 60 °C for 2 hours. In a 300 mL beaker, 150 g of LUDOX HS-40 (approximately 60 g of dry SiO2) was mixed with 50 mL of DI water, and the silane solution was slowly added to the stirred colloidal mixture over 10 minutes. The resulting mixture was stirred at room temperature for 1 hour, followed by stirring at 70 °C for 2 hours. The sample was percolated with 6 volumes of DI water. Elemental analysis of a small amount of dried sample showed C% = 4.28%, N% = 0.40%, and S% = 0.63%. The sample was stable (without visual change) overnight (24 hours) at 80 °C in 2% solids and in 2 M NaCl at pH 9.1 and at pH 2.0.

[0123] The following reaction scheme V illustrates the reaction scheme of Example 4.

[0124] Example 5 (1.5 NM / nm) 2 isophthalic acid modification under TL 2.99 g of 5-aminoisophthalic acid was slurried in 80 mL of DI water. The pH of the solution was adjusted to approximately 6.0 with 1M NaOH. 3.90 g of glycidyl silane was added to the stirred solution. The mixture was stirred overnight at room temperature (approximately 15 hours), and the pH was maintained at approximately 6.0 by adding 1M NaOH. The mixture was then heated at 50°C until all solids dissolved. In a 300 mL beaker, 75 g of LUDOX HS-40 (approximately 30 g of dried SiO2) was mixed with 30 mL of DI water, and the silane solution was slowly added to the stirred colloidal mixture over 10 minutes. The resulting mixture was stirred at room temperature for 1 hour and then at 70°C for 2 hours. The sample was percolated with 5 volumes of DI water. Elemental analysis of a small amount of dried sample showed C% = 3.45% and N% = 0.22%.

[0125] The following reaction scheme VI illustrates the reaction scheme of Example 5.

[0126] The percolated sample had a pH of approximately 10.1 and was stable (without visual change) for approximately 15 hours at 80°C in 2% solids and in 2M NaCl.

[0127] Figure 2This is a graph showing the pH vs. zeta potential of the colloidal silica samples modified according to Examples 4 and 5, compared to unmodified HS-40. Figure 2 As shown, when compared with unmodified HS-40 (which exhibits typical ionization of surface silanol groups relative to solution pH), the modified samples in Examples 4 and 5 exhibit a greater negative charge in the pH range of 3 to 8.

[0128] Example 6 (1.7 NM / nm) 2 Taurine modification under TL Mix 81.0 g of glycidyl silane with 135 g of DI water until the silane is completely dissolved (over approximately 2 hours). In a separate beaker, dissolve 65.0 g of taurine in 250 mL of DI water. Adjust the pH of the solution to 9.5 with 1 M NaOH. In a 3 L beaker, mix 1375 g of LUDOX HS-40 (approximately 550 g of dried SiO2) with 825 mL of DI water, and first add the taurine solution to the stirred colloidal silica, followed by the silane solution slowly. Gradually heat the mixture to 70 °C and maintain this temperature for 2 hours. Percolate the sample with 5 volumes of DI water. Elemental analysis of a small amount of dried sample showed C% = 3.43% and S% = 0.36%.

[0129] The following reaction scheme VII illustrates the reaction scheme of Example 6.

[0130] Example 7 (Acylhydrazide Modification) 122 g of adipic acid dihydrazide (available from Aldrich) was dissolved in 1 L of DI water. The solution was adjusted to pH 6 with NaOH. 73.7 g of glycidyl silane was added to the solution. The mixture was stirred at room temperature for 3 hours. In a separate 3 L beaker, 1250 g of LUDOX HS-40 (~500 g of dry SiO2) was stirred. The silane solution was slowly added to the stirred colloidal silica. The mixture was gradually heated to 70 °C and maintained for 2 hours. The sample was percolated with 5 volumes of DI water. Elemental analysis of a small amount of dried sample showed C% = 5.101% and N% = 1.475%.

[0131] The following reaction scheme VIII illustrates the reaction scheme of Example 7.

[0132] Figure 3 The graph shows the pH vs. zeta potential of hydrazide-modified colloidal silica (Example 7) compared to unmodified HS-40.

[0133] While certain embodiments have been described and illustrated, it should be understood that changes and modifications may be made therein by those skilled in the art without departing from the broader aspects of the technology as defined in the appended claims.

[0134] The embodiments exemplified herein may be suitably implemented in the absence of any one or more elements or limitations not specifically disclosed herein. Thus, terms such as “comprising,” “including,” and “containing” should be understood broadly and without limitation. Furthermore, the terms and expressions used herein are used as descriptive rather than limiting terms, and the use of such terms and expressions is not intended to exclude any equivalents or portions thereof of the features shown and described, but it should be recognized that various modifications may be made within the scope of the claimed technology. Additionally, the phrase “consistently composed of” will be understood to include those specifically described elements and those additional elements that do not materially affect the essential and novel features of the claimed technology. The phrase “consisting of” excludes any unspecified elements. Finally, it should be understood that disclosure of one of the foregoing terms also discloses embodiments using any one of the other two terms or their equivalents.

[0135] This disclosure is not limited to the specific embodiments described herein. Many modifications and alterations can be made without departing from its spirit and scope, as will be apparent to those skilled in the art. Based on the foregoing description, functionally equivalent methods and compositions within the scope of this disclosure, other than those listed herein, will be apparent to those skilled in the art. These modifications and alterations are intended to fall within the scope of the appended claims. This disclosure is limited only by the terms of the appended claims and the full scope of their equivalents. It is to be understood that this disclosure is not limited to specific methods, reagents, compounds, compositions, or biological systems, which can, of course, be varied. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

[0136] Furthermore, when features or aspects of this disclosure are described in the form of the Markush group, those skilled in the art will recognize that this disclosure is also described in the form of any single member or subgroup of the Markush group.

[0137] As those skilled in the art will understand, for any and all purposes, particularly in providing a written description, all scopes disclosed herein also encompass any and all possible subscopes and combinations thereof. Any enumerated scope can be readily understood as sufficiently descriptive and capable of being decomposed into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each scope discussed herein can be readily decomposed into a lower third, middle third, and upper third, etc. As those skilled in the art will also understand, all language such as “at most,” “at least,” “greater than,” “less than,” etc., includes the referenced numbers and refers to a scope that can subsequently be decomposed into subscopes as discussed above. Finally, as those skilled in the art will understand, a scope includes each individual member.

[0138] All publications, patent applications, granted patents, and other documents mentioned in this specification are incorporated herein by reference, as if each individual publication, patent application, granted patent, or other document specifically and individually indicated that it is incorporated herein in its entirety. Definitions contained in the incorporated text are excluded to the extent that they contradict the definitions in this disclosure.

[0139] Other embodiments are set forth in the following claims.

Claims

1. A composition comprising water and functionalized colloidal silica, wherein the functionalized colloidal silica comprises Includes silica particles on the surface, and Structural units according to Equation I, Equation II, Equation III, or Equation IV in R 1 It is -S-(CH2) n R 2 Or -NH-NH-C(O)-(CH2) m -C(O)NH-NH2, where n It is 1, 2, 3, 4, 5 or 6 and m It can be 1, 2, 3, 4, 5, 6, 7, or 8; R 2 It is independently -SO3Y each time it appears. 1 -SO3H, -SO3 - -CO2Y 2 -CO2H or -CO2 - ; R 2’ and R 2’’ Each is independently H, -SO3Y 1 -SO3H, -SO3 - -CO2Y 2 -CO2H or -CO2 - ; R 3 It is hydroxyl, alkoxy, aryloxy, or G 2 ; R 4 It is hydroxyl, alkoxy, aryloxy, or G 3 ; G 1 G 2 and G 3 Each is an oxygen atom on the surface of the silica particle, wherein G 1 G 2 and G 3 Not the same oxygen atom; Y 1 It is an independent cation each time it appears; and Y 2 It is an independent cation each time it appears.

2. The composition of claim 1, wherein the composition comprises a pH of about 10.5 or lower, and the functionalized colloidal silica has a negative surface charge.

3. The composition of claim 2, wherein the functionalized colloidal silica comprises a structural unit according to formula I, R 1 It is -S-(CH2) n R 2 ,and n It can be 2 or 3.

4. The composition of any one of claims 1-3, wherein the median diameter of the silica particles, as determined by dynamic light scattering or disc centrifugation analysis, is from about 1 nm to about 100 nm.

5. The composition of any one of claims 1-4, wherein the silica particles have a density of approximately 25 μm. 2 / g to approximately 1,200m 2 / g Sears surface area.

6. The composition of any one of claims 1-5, wherein each nm 2 The number of structural units according to Formula I, Formula II, Formula III and Formula IV is approximately 0.8 to approximately 3.

5.

7. The composition of any one of claims 1-6, wherein R 1 It is -(CH2)2SO3Na.

8. The composition of any one of claims 1-7, wherein R 3 For G 2 .

9. The composition of any one of claims 1-8, wherein R 4 It is a hydroxyl group.

10. The composition of any one of claims 1-9, wherein the silica particles comprise at least one structural unit according to formula Ia or Ib. Where Y 3 and Y 4 It is an independent cation each time it appears.

11. The composition of any one of claims 1-10, wherein the silica particles further comprise at least one structural unit according to formula V. in R 5 It is hydroxyl, alkoxy, aryloxy, or G 5 ; R 6 It is hydroxyl, alkoxy, aryloxy, or G 6 ; G 4 G 5 and G 6 Each is an oxygen atom on the surface of the silica particle, wherein G 4 G 5 and G 6 They are not the same oxygen atom.

12. The composition of any one of claims 1-11, wherein the composition comprises about 0.1% by weight to about 50% by weight of the functionalized colloidal silica.

13. The composition of any one of claims 1-12, wherein when the composition comprises a salt solution with an ionic strength of 0.5 M to 3.0 M, the composition is aging stable for 24 hours or longer at a temperature of 80°C.

14. A method for manufacturing functionalized colloidal silica, the method comprising: The functionalized colloidal silica is produced by contacting colloidal silica with a silane according to formula VI, formula VII, formula VIII, or formula IX. in R 1 It is -S-(CH2) n R 2 Or -NH-NH-C(O)-(CH2) m -C(O)NH-NH2, where n It is 1, 2, 3, 4, 5 or 6 and m It can be 1, 2, 3, 4, 5, 6, 7, or 8; R 2 It is independently -SO3Y each time it appears. 1 -SO3H, -SO3 - -CO2Y 2 -CO2H or -CO2 - ; R 2’ and R 2’’ Each is independently H, -SO3Y 1 -SO3H, -SO3 - -CO2Y 2 -CO2H or -CO2 - ; R 7 It is a hydroxyl, alkoxy, or aryl group; R 8 It is a hydroxyl, alkoxy, or aryl group; L 1 It is an alkoxy or aryloxy group; Y 1 It is an independent cation each time it appears; and Y 2 It is an independent cation each time it appears.

15. The method of claim 14, wherein R 7 R 8 and L 1 Each can be an alkoxy or aryloxy group independently.

16. The method of claim 14 or claim 15, wherein R 7 R 8 and L 1 Each is an alkoxy group independently.

17. The method of any one of claims 14-16, wherein R 2 -SO3H or -SO3 - And R 2’ and R 2’’ Each is independently represented by H.

18. The method of any one of claims 14-17, wherein the method comprises contacting the colloidal silica with a silane in a medium containing water.

19. The method of claim 18, wherein the method comprises contacting the colloidal silica with a silane according to formula VI or a silane according to formula VII, and the medium having a pH of about 4 to about 6.

20. The method of claim 18, wherein the method comprises contacting the colloidal silica with a silane according to formula VIII, and the medium having a pH of about 2 to about 11.

21. The method of any one of claims 14-20, wherein the method comprises contacting every 1 nm 2 Colloidal silica has a surface area of ​​approximately 1.5 to approximately 3.0 molecules of silane.

22. The method of any one of claims 14-21, wherein the method provides a composition according to any one of claims 1-13.

23. Functionalized silica prepared by the method according to any one of claims 14-22.

24. A formulation for use in crude oil enhanced recovery, metal surface treatment, electroplating, coatings and / or paints, wherein the formulation comprises a composition according to any one of claims 1-13.

25. A formulation for use in crude oil enhanced recovery, metal surface treatment, electroplating, coatings and / or paints, wherein the formulation comprises functionalized silica prepared by the method of any one of claims 14-22.

Images