Functionalized colloidal silicon dioxide and preparation method thereof

Abstract

The present disclosure relates to a composition comprising water and a functionalized colloidal silica, wherein the functionalized colloidal silica comprises silica particles, wherein each silica particle comprises a surface, and a structural unit according to Formula I and / or a structural unit according to Formula II # imgabs0 #. The present disclosure also relates to a method of preparing a composition of the present technology.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of priority to U.S. Provisional Patent Application No. 63 / 430,618, filed on December 6, 2022, the contents of which are incorporated herein by reference in their entirety. Background of the Invention

[0003] The present technology generally relates to functionalized colloidal silica and methods useful for synthesizing such functionalized colloidal silica, including compositions that are stable to aging at a temperature of 80° C. for 24 hours or longer when the compositions comprise a salt solution at an ionic strength of 0.5 to 3.0. SUMMARY OF THE INVENTION

[0004] In one aspect, the present technology provides a composition comprising water and functionalized colloidal silica. The functionalized colloidal silica comprises silica particles (wherein each silica particle comprises a surface) and a structural unit according to formula I and / or a structural unit according to formula II

[0005]

[0006] in

[0007] R 1 is H, unsubstituted alkyl, hydroxy-substituted alkyl, alkoxy-substituted alkyl, hydroxy-substituted cycloalkyl, aryl, or heteroaryl;

[0008] R 2 is a hydroxy-substituted alkyl group, an alkoxy-substituted alkyl group, or a hydroxy-substituted cycloalkyl group;

[0009] or R 1 and R 2 Together they are a C4-C6 alkylene group substituted with a hydroxy group;

[0010] R 3 is hydroxy, alkoxy, aryloxy or G 2 ;

[0011] R 4 is hydroxy, alkoxy, aryloxy or G 3 ;

[0012] R 5 is hydroxy, alkoxy, aryloxy or G 5 ;

[0013] R 6 is hydroxy, alkoxy, aryloxy or G 6 ;

[0014] G 1 , G 2 , G3 , G 4 , G 5 and G 6 are each independently an oxygen atom on the surface of the silica particle, wherein G 1 , G 2 , G 3 , G 4 , G 5 and G 6 are not the same oxygen atom; and

[0015] Y 1 It is an anion.

[0016] In another aspect, the present technology provides a method for preparing functionalized colloidal silica (e.g., a method for preparing a composition of any embodiment herein). The method comprises contacting colloidal silica with a silane according to Formula IV to produce the functionalized colloidal silica.

[0017]

[0018] in

[0019] R 1 is H, unsubstituted alkyl, hydroxy-substituted alkyl, alkoxy-substituted alkyl, hydroxy-substituted cycloalkyl, aryl, or heteroaryl;

[0020] R 2 is a hydroxy-substituted alkyl group, an alkoxy-substituted alkyl group, or a hydroxy-substituted cycloalkyl group;

[0021] or R 1 and R 2 Together they are a C4-C6 alkylene group substituted with a hydroxy group;

[0022] R 9 is hydroxy, alkoxy or aryloxy;

[0023] R 10 is hydroxy, alkoxy or aryloxy; and

[0024] L 1 is an alkoxy group or an aryloxy group.

[0025] In additional aspects, the present technology provides functionalized silica prepared according to the method of any embodiment described herein.

[0026] It should be understood that all combinations of the foregoing concepts and the additional concepts discussed in more detail below (provided such concepts are not mutually inconsistent) are considered to be 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 to be part of the subject matter disclosed herein. Summary of the Figures

[0027] Figure 1 Provided are the tests performed on the compositions of the present technology as described in the working examples. 13 C-NMR spectral results.

[0028] Figure 2 Depicts the zeta titration results of LUDOX HS-40 according to the working examples

[0029] Figure 3 Depicted are the zeta titration results of diethanolamine functionalized LUDOX HS-40 according to the working examples.

[0030] Figure 4 Depicted is a comparison of particle surface zeta potentials of functionalized colloidal silica according to Examples 1-6 of the present technology, according to working examples.

[0031] Figure 5 The zeta potential curves of unmodified LUDOX AM and Example 9 (Example 9 is a composition of the present technology) according to the working examples were compared. Detailed Description of the Invention

[0032] Various embodiments are described below. It should be noted that the specific embodiments are not intended to be exhaustive descriptions or limitations on the broader aspects discussed herein. An aspect described in conjunction with a specific embodiment is not necessarily limited to that embodiment and can be implemented with any other embodiment.

[0033] As used herein and in the appended claims, unless otherwise stated herein or clearly contradicted by context, in the context of describing an element (especially in the context of the following claims), singular articles such as "a" and "an" and "the" and similar indicators should be interpreted as covering both the singular and the plural. Unless otherwise stated herein, the description of a numerical range herein is intended only to be used as a shorthand method for individually referring to each individual value falling within the range, and each individual value is incorporated into this specification as if it were individually stated herein. Unless otherwise stated herein or clearly contradicted by context, all methods described herein can be performed in any suitable order. Unless otherwise stated, the use of any and all examples or exemplary language (e.g., "such as") provided herein is intended only to better illustrate the embodiment and is not intended to limit the scope of the claims. Any language in the specification should not be interpreted as indicating that any unclaimed element is essential.

[0034] As used herein, "about" will be understood by one of ordinary skill in the art and will vary to some extent depending on the context in which it is used. If there is a use of a term that is unclear to one of ordinary skill in the art, given the context in which it is used, "about" will mean up to plus or minus 10% of the particular term, e.g., "about 10% by weight" will be understood to mean "9% to 11% by weight." It should be understood that when "about" precedes a term, the term should be interpreted as disclosing "about" the term as well as the term not modified by "about"—e.g., "about 10% by weight" discloses "9% to 11% by weight" as well as disclosing "10% by weight."

[0035] The phrase "and / or" as used in this disclosure will be understood to refer to any of the recited members individually or in any combination of two or more - for example, "A, B and / or C" will mean "A or B or C; A and B; A and C; B and C; or a combination of A, B and C."

[0036] Generally, reference to an element such as hydrogen or H is meant to include all isotopes of that element. For example, if an R group is defined to include hydrogen or H, it also includes deuterium and tritium. Radioactive isotopes such as tritium, C 14 、P 32 and S 35 Compounds of the invention are thus within the scope of the present technology. The procedures for inserting such labels into the compounds of the present technology will be apparent to those skilled in the art based on the disclosure herein.

[0037] Typically, "substituted" refers to an organic group (e.g., an alkyl group) as defined below, wherein one or more bonds contained therein to a hydrogen atom are replaced by bonds to a non-hydrogen or non-carbon atom. Substituted groups also include groups in which one or more bonds to a carbon or hydrogen atom are replaced by one or more bonds to a heteroatom (including double or triple bonds). Thus, unless otherwise indicated, a substituted group is substituted by one or more substituents. In some embodiments, a substituted group is substituted by 1, 2, 3, 4, 5, or 6 substituents. Examples of substituents include: halogen (i.e., F, Cl, Br, and I); hydroxy; alkoxy, alkenyloxy, aryloxy, aralkyloxy, heterocyclyl, heterocyclylalkyl, heterocyclyloxy, and heterocyclylalkoxy; carbonyl (oxo); carboxylate; ester; carbamate; oxime; hydroxylamine; alkoxyamine; aralkyloxyamine; thiol; sulfide; sulfoxide; sulfone; sulfonyl; pentafluorosulfanyl (i.e., SF5), sulfonamide; amine; N-oxide; hydrazine; hydrazide; hydrazone; azide; amide; urea; amidine; guanidine; enamine; imide; isocyanate; isothiocyanate; cyanate; thiocyanate; imine; nitro; and nitrile (i.e., CN).

[0038] Substituted ring groups such as substituted cycloalkyl, aryl, heterocyclyl and heteroaryl also include rings and ring systems in which the bond to a hydrogen atom is replaced by a bond to a carbon atom. Thus, substituted cycloalkyl, aryl, heterocyclyl and heteroaryl may also be substituted with substituted or unsubstituted alkyl, alkenyl and alkynyl groups as defined below.

[0039] Alkyl comprises the straight chain and branched chain alkyl with 1 to 12 carbon atoms and is generally 1 to 10 carbon atoms or in some embodiments 1 to 8, 1 to 6 or 1 to 4 carbon atoms.Alkyl can be substituted or unsubstituted.The example of straight chain alkyl comprises the group such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl and n-octyl.The example of branched chain alkyl includes but is not limited to isopropyl, isobutyl, sec-butyl, the tert-butyl, neopentyl, isopentyl and 2,2-dimethylpropyl.Representational substituted alkyl can be substituted once or many by substituent group (such as those listed above), and includes but is not limited to haloalkyl (for example trifluoromethyl), hydroxyalkyl, thioalkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, alkoxyalkyl, carboxyalkyl etc.

[0040] Cycloalkyl includes 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, or 3 to 4, 5 or 6 carbon atoms. Cycloalkyl groups can 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 both bridged cycloalkyl groups and fused rings, such as, but not limited to, bicyclo[2.2.1]hexane, adamantyl, decalinyl and the like. Substituted cycloalkyl groups can be substituted one or more times by non-hydrogen and non-carbon groups as defined above. However, substituted cycloalkyl groups also include rings substituted by straight or branched chain alkyl groups as defined above. Representative substituted cycloalkyl groups may be monosubstituted or substituted more than once, such as, but not limited to, 2,2-, 2,3-, 2,4-, 2,5-, or 2,6-disubstituted cyclohexyl groups, which may be substituted with substituents such as those listed above.

[0041] Cycloalkylalkyl is alkyl as defined above, wherein the hydrogen or carbon bond of alkyl is replaced with the key of cycloalkyl as defined above.Cycloalkylalkyl can be substituted or unsubstituted.In some embodiments, cycloalkylalkyl has 4 to 16 carbon atoms, 4 to 12 carbon atoms and usually 4 to 10 carbon atoms.The cycloalkylalkyl of replacement can be substituted at the alkyl, cycloalkyl or alkyl and cycloalkyl part of this group.Representational substituted cycloalkylalkyl can be monosubstituted or replace more than once, such as but not limited to by those substituent monosubstituted, disubstituted or trisubstituted as enumerated above.

[0042] Alkenyl includes straight and branched chain alkyl as defined above, except that there is at least one double bond between two carbon atoms.Alkenyl can be substituted or unsubstituted.Alkenyl has 2 to 12 carbon atoms, and typically 2 to 10 carbons, or in some embodiments 2 to 8, 2 to 6, or 2 to 4 carbon atoms. In some embodiments, alkenyl has one, two, or three carbon-carbon double bonds. Examples include, but are not limited to, vinyl, allyl, -CH=CH(CH 3 ), -CH=C(CH 3 ) 2 , -C(CH 3 )=CH 2 , -C(CH 3 )=CH (CH 3 ), -C(CH 2 CH 3 )=CH 2 and the like. Representative substituted alkenyl can be monosubstituted or substituted more than once, such as, but not limited to, monosubstituted, disubstituted, or trisubstituted by those substituents listed above.

[0043] Cycloalkenyl is included in the cycloalkyl as defined above with at least one double bond between two carbon atoms.Cycloalkenyl can be substituted or unsubstituted.In some embodiments, cycloalkenyl can have one, two or three double bonds, but does not include aromatic compounds.Cycloalkenyl has 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.The example of cycloalkenyl includes cyclohexenyl, cyclopentenyl, cyclohexadienyl, cyclobutadienyl and cyclopentadienyl.

[0044] Cycloalkenylalkyl is an alkyl as defined above, wherein the hydrogen or carbon bond of the alkyl is replaced with the key of the cycloalkenyl as defined above.Cycloalkenylalkyl can be substituted or unsubstituted.The cycloalkenylalkyl of substitution can be substituted at the alkyl, cycloalkenyl or alkyl and cycloalkenyl moiety of this group.Representational substituted cycloalkenylalkyl can be substituted once or many by those substituents as listed above.

[0045] Alkynyl includes straight and branched chain alkyl as defined above, except that there is at least one triple bond between two carbon atoms.Alkynyl can be substituted or unsubstituted.Alkynyl has 2 to 12 carbon atoms and is typically 2 to 10 carbons or in some embodiments 2 to 8, 2 to 6 or 2 to 4 carbon atoms.In some embodiments, alkynyl has one, two or three carbon-carbon triple bonds.Examples include but are not limited to-C≡CH ,-C≡CCH ,-CH 2 C≡CCH 3 and-C≡CCH 2 CH (CH 2 CH 3 ) 2 and the like.Representative substituted alkynyl can be monosubstituted or substituted more than once, such as but not limited to those substituents monosubstituted, disubstituted or trisubstituted as listed above.

[0046] Aryl is a cyclic aromatic hydrocarbon that does not contain heteroatoms. Aryl herein includes monocyclic, bicyclic and tricyclic ring systems. Aryl can be substituted or unsubstituted. Thus, aryl includes but is not limited to phenyl, azulenyl, heptalenyl, biphenyl, fluorenyl, phenanthrenyl, anthracenyl, indenyl, indanyl, pentalenyl and naphthyl. In some embodiments, aryl contains 6-14 carbons in the ring portion of the group, and in other embodiments contains 6 to 12 or even 6-10 carbon atoms. In some embodiments, aryl is phenyl or naphthyl. The phrase "aryl" includes groups containing fused rings, such as fused aromatic-aliphatic ring systems (e.g., indanyl, tetrahydronaphthyl, etc.). Representative substituted aryl can be monosubstituted (e.g., tolyl) or substituted more than once. For example, monosubstituted aryl includes but is not limited to 2-, 3-, 4-, 5- or 6-substituted phenyl or naphthyl, which can be substituted by those substituents listed above.

[0047] Aralkyl is alkyl as defined above, wherein the hydrogen or carbon bond of alkyl is replaced with the key of aryl as defined above.Aralkyl can be substituted or unsubstituted.In some embodiments, aralkyl contains 7 to 16 carbon atoms, 7 to 14 carbon atoms or 7 to 10 carbon atoms.The aralkyl of replacement can be substituted at the alkyl, aryl or alkyl and aryl moiety of this group.Representational aralkyl includes but is not limited to benzyl and phenethyl and fused (cycloalkylaryl) alkyl, such as 4-indanyl ethyl.Representational substituted aralkyl can be substituted once or many by those substituents as listed above.

[0048] Heterocyclic radical comprises aromatic (also referred to as heteroaryl) and non-aromatic cyclic compounds containing 3 or more ring members, one or more of which are heteroatoms, such as but not limited to N, O and S. Heterocyclic radical can be substituted or unsubstituted. In some embodiments, heterocyclic radical contains 1,2,3 or 4 heteroatoms. In some embodiments, heterocyclic radical groups comprise monocycles, dicycles and tricycles with 3 to 16 ring members, and other such groups have 3 to 6, 3 to 10, 3 to 12 or 3 to 14 ring members. Heterocyclic radical encompasses aromatic, partially unsaturated and saturated ring systems, such as for example imidazolyl, imidazolinyl and imidazoline pyridinyl (imidazolidinyl). The phrase "heterocyclyl" includes fused ring species, including those containing fused aromatic and non-aromatic groups, such as, for example, benzotriazolyl, 2,3-dihydrobenzo[1,4]dioxinyl, and benzo[1,3]dioxolyl. The phrase also includes bridged polycyclic ring systems containing heteroatoms, such as, but not limited to, quinuclidine. The phrase includes heterocyclyl groups having other groups, such as alkyl, oxo, or halo groups, bonded to one of the ring members, termed "substituted heterocyclyls." Heterocyclyl groups include, but are not limited to, aziridinyl, azetidinyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, thiazolidinyl, tetrahydrothiophenyl, tetrahydrofuranyl, dioxolyl, furanyl, thienyl, pyrrolyl, pyrrolinyl, imidazolyl, imidazolinyl, pyrazolyl, pyrazolinyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiazolyl, thiazolinyl, isothiazolyl, thiadiazolyl, oxadiazolyl, piperidinyl, piperazinyl, morpholinyl, thio Morpholinyl, tetrahydropyranyl, tetrahydrothiopyranyl, oxathiane, dioxy, dithianyl, pyranyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, dihydropyridyl, dihydrodithiinyl, dihydrodisulfinyl, homopiperazinyl, quinuclidinyl, indolyl, dihydroindolyl, isoindolyl, azaindolyl (pyrrolopyridinyl), indazolyl, indolizinyl, benzotriazolyl, benzimidazolyl, benzofuranyl, benzo thienyl, benzothiazolyl, benzoxadiazolyl, benzoxazinyl, benzodithiinyl, benzoxathiinyl, benzothiazinyl, benzoxazolyl, benzothiazolyl, benzothiadiazolyl, benzo[1,3]dioxolyl, pyrazolopyridinyl, imidazopyridinyl (azabenzimidazolyl), triazolopyridinyl, isoxazolopyridinyl, purinyl, xanthinyl, adeninyl, guanosine Purinyl, quinolyl, isoquinolyl, quinolizinyl, quinoxalinyl, quinazolinyl, cinnolinyl, phthalazinyl, naphthyridinyl, pteridinyl, thiazinyl, dihydrobenzothiazinyl, dihydrobenzofuranyl, dihydroindolyl, dihydrobenzodioxinyl, tetrahydroindolyl, tetrahydroindazolyl, tetrahydrobenzimidazolyl, tetrahydrobenzotriazolyl, tetrahydropyrrolopyridinyl, tetrahydropyrazolopyridinyl, tetrahydroimidazopyridinyl, tetrahydrotriazolopyridinyl and tetrahydroquinolinyl.Representative substituted heterocyclyl groups can be monosubstituted or substituted more than once, such as, but not limited to, pyridyl or morpholinyl, which are 2-, 3-, 4-, 5-, or 6-substituted, or disubstituted with various substituents such as those listed above.

[0049] Heteroaryl groups are aromatic ring compounds containing 5 or more ring members, one or more of which is a heteroatom such as, but not limited to, N, O, and S. Heteroaryl groups can be substituted or unsubstituted. Heteroaryl groups include, but are not limited to, groups such as pyrrolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiazolyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, thienyl, benzothienyl, furanyl, benzofuranyl, indolyl, azaindolyl(pyrrolopyridinyl), indazolyl, benzimidazolyl, azaindolyl(pyrrolopyridinyl), pyrazolopyridinyl, triazolopyridinyl, benzotriazolyl, benzoxazolyl, benzothiazolyl, benzothiadiazolyl, imidazopyridinyl, isoxazolopyridinyl, thiazolyl, purinyl, xanthinyl, adeninyl, guaninyl, quinolinyl, isoquinolinyl, tetrahydroquinolinyl, quinoxalinyl, and quinazolinyl. Heteroaryl includes fused ring compounds in which all rings are aromatic, such as indolyl, and includes fused ring compounds in which only one ring is aromatic, such as 2,3-dihydroindole. Representative substituted heteroaryl can be substituted one or more times by various substituents, such as those listed above.

[0050] Heterocyclylalkyl is an alkyl as defined above, wherein the hydrogen or carbon bond of the alkyl is replaced with the key of the heterocyclyl as defined above.Heterocyclylalkyl can be substituted or unsubstituted.The substituted heterocyclylalkyl can be substituted at the alkyl, heterocyclyl or alkyl and heterocyclyl moiety of the group.Representative heterocyclylalkyl includes but is not limited to morpholin-4-yl-ethyl, furans-2-base-methyl, imidazole-4-base-methyl, pyridin-3-yl-methyl, tetrahydrofuran-2-base-ethyl and indol-2-base-propyl group.Representative substituted heterocyclylalkyl can be substituted once or many by those substituents as listed above.

[0051] Heteroaralkyl is an alkyl as defined above, wherein the hydrogen or carbon bond of the alkyl is replaced by a key of a heteroaryl as defined above. Heteroaralkyl can be substituted or unsubstituted. The substituted heteroaralkyl can be substituted at the alkyl, heteroaryl or alkyl and heteroaryl moieties of the group. Representational substituted heteroaralkyl can be substituted once or many by those substituents as listed above.

[0052] Groups described herein that have two or more points of attachment (i.e., divalent, trivalent, or multivalent) within the compounds of the present technology are indicated by using the suffix "sub". For example, a divalent alkyl group is an alkylene group, a divalent aryl group is an arylene group, a divalent heteroaryl group is a divalent heteroarylene group, and so on. Substituted groups that have a single point of attachment to the compounds of the present technology are not referred to using the "sub" designation. Thus, for example, a chloroethyl group is not referred to herein as a chloroethylene group.

[0053] Alkoxy is hydroxyl (-OH), wherein the bond with hydrogen atom is replaced by the bond with the carbon atom of substituted or unsubstituted alkyl as defined above.Alkoxy can be substituted or unsubstituted.The example of straight chain alkoxy includes but is not limited to methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy etc.The example of branched alkoxy includes but is not limited to isopropoxy, sec-butoxy, tert-butoxy, isopentyloxy, isohexyloxy etc.The example of cycloalkoxy includes but is not limited to cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy etc.Representational substituted alkoxy can be substituted once or many by those substituents as listed above.

[0054] As used herein, the terms "alkanoyl" and "alkanoyloxy" may refer to -C(O)-alkyl and -OC(O)-alkyl, respectively, each containing 2-5 carbon atoms. Similarly, "aroyl" and "aroyloxy" refer to -C(O)-aryl and -OC(O)-aryl.

[0055] The terms "aryloxy" and "aralkyloxy" refer to a substituted or unsubstituted aryl group bonded to an oxygen atom and a substituted or unsubstituted aralkyl group bonded to an oxygen atom at the alkyl position, respectively. Examples include, but are not limited to, phenoxy, naphthoxy, and benzyloxy. Representative substituted aryloxy and aralkoxy groups may be substituted one or more times with substituents such as those listed above.

[0056] As used herein, the term "carboxylate" refers to a -COOH group.

[0057] As used herein, the term "ester" refers to -COOR 70 and -C(O)OG groups. 70G is a carboxylate protecting group. Carboxylate protecting groups are well known to those of ordinary skill in the art. A broad 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 can be added or removed using the procedures described therein, and which is incorporated herein by reference in its entirety and for any and all purposes as if fully described herein.

[0058] The term "amide" (or "amido") includes both C- and N-amide groups, i.e., -C(O)NR 71 R 72 and -NR 71 C(O)R 72 Group. R 71 and R 72 is independently hydrogen, or a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heterocyclylalkyl, or heterocyclyl as defined herein. Amide groups therefore include, but are not limited to, carbamoyl (-C(O)NH2) and formamide groups (-NHC(O)H). In some embodiments, the amide is -NR 71 C(O)-(C 1-5 alkyl), and the group is termed a "carbonylamino," and in other cases the amide is -NHC(O)-alkyl, and the group is termed an "alkanoylamino."

[0059]

[0046] The term "nitrile" or "cyano" as used herein refers to a -CN group.

[0060] Urethane groups include N- and O-urethane groups, namely -NR 73 C(O)OR 74 and -OC(O)NR 73 R 74 Group. R 73 and R 74 R is independently a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heterocyclylalkyl or heterocyclyl group as defined herein. 73 It can also be H.

[0061] As used herein, the term "amine" (or "amino") refers to a -NR 75 R 76 Group, where R 75 and R76 is independently hydrogen, or a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heterocyclylalkyl, or heterocyclyl as defined herein. In some embodiments, the amine is alkylamino, dialkylamino, arylamino, or alkylarylamino. In other embodiments, the amine is NH2, methylamino, dimethylamino, ethylamino, diethylamino, propylamino, isopropylamino, phenylamino, or benzylamino.

[0062] The term "sulfonamide" includes both S- and N-sulfonamide groups, namely -SO2NR 78 R 79 and -NR 78 So2R 79 Group. R 78 and R 79 is independently hydrogen, or a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heterocyclylalkyl or heterocyclyl as defined herein. Sulfonamido therefore includes but is not limited to sulfamoyl (-SO2NH2). In some embodiments herein, sulfonamido is -NHSO2-alkyl and is referred to as an "alkylsulfonylamino" group.

[0063] The term "thiol" refers to a -SH group, while "sulfide" includes -SR 80 The group "sulfoxide" includes -S(O)R 81 The group "sulfone" includes -SO2R 82 group, 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, heterocyclyl or heterocyclylalkyl as defined herein. In some embodiments, the sulfide is an alkylthio (-S-alkyl).

[0064] The term "urea" refers to -NR 84 -C(O)-NR 85 R 86 Group. R 84 、R 85 and R 86 The groups are independently hydrogen, or substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heterocyclyl or heterocyclylalkyl as defined herein.

[0065] The term "amidine" refers to -C(NR 87 )NR 88 R 89 and -NR 87 C(NR88 )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, heterocyclyl or heterocyclylalkyl group as defined herein.

[0066] 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, heterocyclyl or heterocyclylalkyl group as defined herein.

[0067] 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 、R 96 and R 97 Each is independently hydrogen, substituted or unsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl, heterocyclyl or heterocyclylalkyl as defined herein.

[0068] As used herein, the term "halogen" or "halo" refers to bromine, chlorine, fluorine, or iodine. In some embodiments, halogen is fluorine. In other embodiments, halogen is chlorine or bromine.

[0069] As used herein, the term "hydroxy" may refer to -OH or its ionized form -O-. A "hydroxyalkyl" group is an alkyl group substituted with a hydroxy group, such as HO-CH2-.

[0070] 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, heterocyclyl or heterocyclylalkyl group as defined herein.

[0071] The term "imine" refers to -CR 100 (NR101 ) and -N(CR 100 R 101 ) group, wherein R 100 and R 101 are each independently hydrogen or a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl, heterocyclyl or heterocyclylalkyl group as defined herein, provided that R 100 and R 101 Different are hydrogen.

[0072] As used herein, the term "nitro" refers to a -NO2 group.

[0073] As used herein, the term "trifluoromethyl" refers to -CF3.

[0074] As used herein, the term "trifluoromethoxy" refers to -OCF3.

[0075] The term "azido" refers to -N3.

[0076] The term "trialkylammonium" refers to an -N(alkyl)3 group. The trialkylammonium group is positively charged and, as such, typically has an associated anion, such as a halide anion.

[0077] The term "isocyano" refers to -NC.

[0078] The term "isothiocyanato" refers to -NCS.

[0079] The term "pentafluorosulfanyl" refers to -SF5.

[0080] As will be understood by those skilled in the art, for any and all purposes, particularly in providing written description, all scopes disclosed herein also encompass any and all possible sub-ranges and combinations thereof.Any enumerated scope can be easily understood to fully describe and can decompose the same scope into at least equal half, one-third, one-quarter, one-fifth, one-tenth, etc. As non-limiting examples, each scope discussed herein can be easily decomposed into lower one-third, middle one-third, and upper one-third, etc. As will be understood by those skilled in the art, all languages ​​such as "at most," "at least," "greater than," "less than," etc. include enumerated numbers, and refer to the scope that can subsequently be decomposed into the sub-ranges discussed above. Finally, as will be understood by those skilled in the art, scope includes each individual member. Thus, for example, a group with 1-3 atoms refers to a group with 1, 2, or 3 atoms. Similarly, a group with 1-5 atoms refers to a group with 1, 2, 3, 4, or 5 atoms, etc.

[0081] As understood by those of ordinary skill in the art, "molecular weight" (also known as "relative molar mass") is a dimensionless quantity, but is converted to molar mass by multiplying by 1 gram / mole or by multiplying 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.

[0082] It will be understood by those skilled in the art that the compounds of the present technology may exhibit tautomerism, conformational isomerism, geometric isomerism and / or stereoisomerism. Since the formulae in the specification and claims can only represent one of the possible tautomeric, conformational, stereochemical or geometric isomeric forms, it should be understood that the present technology covers any tautomeric, conformational, stereochemical and / or geometric isomeric forms of the compounds having one or more of the utilities described herein, as well as mixtures of these various forms.

[0083] "Tautomers" refer to isomeric forms of a compound that are in equilibrium with each other. The presence and concentration of isomeric forms will depend on the environment in which the compound exists and may differ depending on, for example, whether the compound is a solid or in an organic solution or aqueous solution. For example, in aqueous solution, quinazolinone may exhibit the following isomeric forms, which are referred to as tautomers of each other:

[0084]

[0085] As another example, guanidine can exhibit the following isomeric forms, also known as tautomers of one another, in protic organic solutions:

[0086]

[0087] Due to the limitation of representing compounds by structural formulae, it should be understood that all formulae of compounds depicted herein represent all tautomeric forms of the compounds and are within the scope of the present technology.

[0088] Stereoisomers (also referred to as optical isomers) of a compound include all chiral, diastereomeric, and racemic forms of the structure, unless a specific stereochemistry is explicitly indicated. Thus, the compounds used in the present technology include optical isomers enriched or resolved at any or all asymmetric atoms, as apparent from the depiction. Racemic and diastereomeric mixtures, as well as individual optical isomers, can be separated or synthesized so as to be substantially free of their enantiomers or diastereomeric partners, and all such stereoisomers are within the scope of the present technology.

[0089] The compounds of the present technology may exist as solvates, especially hydrates. Hydrates may be formed during the manufacture of the compound or a composition comprising the compound, or may be formed over time due to the hygroscopicity of the compound. The compounds of the present technology may also exist as organic solvates, including DMF, ether and alcohol solvates, and the like. The identification and preparation of any particular solvate is within the skill of a person of ordinary skill in synthetic organic chemistry.

[0090] This technology

[0091] For colloidal silica to be used under extreme conditions (e.g., high divalent metal salt solutions, high trivalent metal salt solutions, low pH, and / or high temperatures) in applications such as enhanced oil recovery, metal surface treatment, and electroplating formulations, colloidal stability is an even more stringent requirement. Indeed, as shown in the comparative examples disclosed herein, functionalized colloidal silica available prior to the present disclosure suffered from stability issues under such extreme conditions.

[0092] The present technology addresses the deficiencies discussed above, including those associated with metal surface treatment and electroplating formulations, and provides additional advantages. Thus, in one aspect, the present technology provides a composition comprising water and functionalized colloidal silica. The functionalized colloidal silica comprises silica particles (wherein each silica particle comprises a surface) and a structural unit according to Formula I and / or a structural unit according to Formula II,

[0093]

[0094] in

[0095] R 1 is H, unsubstituted alkyl, hydroxy-substituted alkyl, alkoxy-substituted alkyl, hydroxy-substituted cycloalkyl, aryl, or heteroaryl;

[0096] R 2 is a hydroxy-substituted alkyl group, an alkoxy-substituted alkyl group, or a hydroxy-substituted cycloalkyl group;

[0097] or R 1 and R 2 Together they are a C4-C6 alkylene group substituted with a hydroxy group;

[0098] R 3 is hydroxy, alkoxy, aryloxy or G 2 ;

[0099] R 4 is hydroxy, alkoxy, aryloxy or G 3 ;

[0100] R 5is hydroxy, alkoxy, aryloxy or G 5 ;

[0101] R 6 is hydroxy, alkoxy, aryloxy or G 6 ;

[0102] G 1 , G 2 , G 3 , G 4 , G 5 and G 6 are each independently an oxygen atom on the surface of the silica particle, wherein G 1 , G 2 , G 3 , G 4 , G 5 and G 6 are not the same oxygen atom; and

[0103] Y 1 It is an anion.

[0104] In any embodiment herein, the composition can comprise a pH of about 8.5 or less; thus, the composition of any embodiment herein can comprise a pH of about 8.5, about 8.0, about 7.5, about 7.0, about 6.5, about 6.0, about 5.5, about 5.0, about 4.5, about 4.0, about 3.5, about 3.0, about 2.5, about 2.0, about 1.5, about 1.0, a range less than any of these values, or any range including any two of these values ​​and / or between any two of these values. In any embodiment wherein the composition comprises a pH of about 8.5 or less, the functionalized colloidal silica can comprise a positive zeta potential. The positive zeta potential of any such embodiments herein can be about +1 millivolt ("mV"), about +2 mV, about +3 mV, about +4 mV, about +5 mV, about +6 mV, about +7 mV, about +8 mV, about +9 mV, about +10 mV, about +15 mV, about +20 mV, about +25 mV, about +30 mV, about +35 mV, about +40 mV, about +45 mV, about +50 mV, about +55 mV, about +60 mV, about +65 mV, about +70 mV, a range greater than any of these values, or any range including and / or between any two of these values. In any embodiment wherein the composition comprises a pH of about 8.5 or less, the composition can comprise a molar ratio of structural units according to Formula I to structural units according to Formula II (i.e., [number of moles of structural units according to Formula I] / [number of moles of structural units according to Formula II]) of about 1:1 or greater. Thus, in any embodiment wherein the composition comprises a pH of about 8.5 or less, the composition can comprise a molar ratio of structural units according to Formula I to structural units according to Formula II 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 any range including and / or between any two of these values. In any of the embodiments herein, the silica particles can have a median diameter (volume-based D50) of about 1 nm to about 100 nm as determined by dynamic light scattering.Thus, the silica particles, as determined by dynamic light scattering, can have a median diameter of 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 range including and / or between any two of these values.

[0105] In any of the embodiments herein, the silica particles may have a particle size of about 25 m 2 / g to about 1,200m 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 of any embodiment herein may have a surface area of ​​about 25 m 2 / g、26m 2 / g、27m 2 / g、28m 2 / g、29m 2 / g、30m 2 / g、35m 2 / g, 40m 2 / g、45m 2 / g, 50m 2 / g、55m 2 / g, 60m 2 / g、70m 2 / g、80m 2 / g、90m 2 / g、100m 2 / g, 150m 2 / g, 200m 2 / g, 250m 2 / g、300m 2 / g、350m 2 / g, 400m 2 / g, 450m 2 / g、500m 2 / g、550m 2 / g、600m 2 / g、650m 2 / g、700m 2 / g、750m 2 / g、800m 2 / g、850m 2 / g、900m 2 / g、950m 2 / g、1,000m 2 / g、1,100m 2 / g、1,200m 2 / g, or any range comprising any two of these values ​​and / or between any two of these values.

[0106] The composition of any embodiment herein may include from about 0.8 to about 3.5 nanoparticles per nm. 2 The number of structural units according to Formula I and / or Formula II per nm of surface area. Thus, the composition of any embodiment herein may comprise about 0.8, about 0.9, about 1.0, about 1.1, about 1.2, about 1.3, about 1.4, about 1.5, about 1.6, about 1.7, about 1.8, about 1.9, about 2.0, about 2.1, about 2.2, about 2.3, about 2.4, about 2.5, about 2.6, about 2.7, about 2.8, about 2.9, about 3.0, about 3.1, about 3.2, about 3.3, about 3.4, about 3.5, or any range of any two of these values ​​and / or between any two of these values ​​per nm. 2 The surface area is determined by the number of structural units according to formula I and / or formula II.

[0107] In any of the embodiments herein, it is possible that R 1 is H, unsubstituted alkyl, hydroxy-substituted alkyl, alkoxy-substituted alkyl, hydroxy-substituted cycloalkyl, amine-substituted aryl, hydroxy-substituted aryl, or heteroaryl. In any embodiment herein, it is possible that R 3 is hydroxy, methoxy, ethoxy, propoxy, phenoxy or G 2 In any of the embodiments herein, it is possible that R 4 is hydroxy, methoxy, ethoxy, propoxy, phenoxy, or G 3 In any of the embodiments herein, it is possible that R 5 is hydroxy, methoxy, ethoxy, propoxy, phenoxy or G 5 In any of the embodiments herein, it is possible that R 6 is hydroxy, methoxy, ethoxy, propoxy, phenoxy or G6 In any of the embodiments herein, it is possible that R 1 R is H, methyl, ethyl, hydroxy-substituted C2-C6 alkyl, or alkoxy-substituted C2-C6 alkyl; 2 is a hydroxy-substituted C2-C6 alkyl group or an alkoxy-substituted C2-C6 alkyl group; or R 1 and R 2 Together they are hydroxy-substituted C4-C6 alkylene groups. In any embodiment herein, it is possible that R 3 It's G 2 In any of the embodiments herein, it is possible that R 4 In any embodiment herein, the silica particles may comprise at least one structural unit according to Formula Ia, Ib, Ic, Id, Ie, If or Ig

[0108]

[0109]

[0110] where Y 2 、Y 3 、Y 4 、Y 5 、Y 6 、Y 7 and Y 8 is independently an anion at each occurrence.

[0111] In any of the embodiments herein, Y 1 、Y 2 、Y 3 、Y 4 、Y 5 、Y 6 、Y 7 and Y 8 Can be Cl independently at each occurrence - 、NO3 - or SO4 2- In any of the embodiments herein, it is possible that the silicon dioxide particles further comprise at least one structural unit according to formula III

[0112]

[0113] in

[0114] R 7 is hydroxy, alkoxy, aryloxy or G 8 ;

[0115] R 8 is hydroxy, alkoxy, aryloxy or G 9 ;

[0116] G 7 , G 8 and G 9 are each independently an oxygen atom on the surface of the silica particle, wherein G 7 , G 8 and G 9 Not the same oxygen atom.

[0117] In any of the embodiments herein, it is possible that R 7 is hydroxy, methoxy, ethoxy, propoxy, phenoxy or G 8 In any of the embodiments herein, it is possible that R 8 is hydroxy, methoxy, ethoxy, propoxy, phenoxy or G 9 .

[0118] The composition of any embodiment herein can include about 0.1% to about 50% by weight of the functionalized colloidal silica. Thus, in any embodiment herein, the composition can include 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%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50% by weight, or any range of any two of these values ​​and / or between any two of these values. For example, in any of the embodiments herein, the composition can comprise the functionalized colloidal silica in an amount from about 0.1 wt % to about 30 wt %, from about 5 wt % to about 30 wt %, from about 10 wt % to about 30 wt %, or from about 0.1 wt % to about 5 wt %.

[0119] When the composition of any embodiment herein comprises a salt solution having an ionic strength of 0.5 to 3.0, the composition can be stably aged at a temperature of 80° C. for 24 hours or longer. The salt solution of any embodiment herein can comprise NaCl, CaCl 2 , MgSO 4 , or a combination of any two or more thereof. In any embodiment herein, the ionic strength can be 0.5, 1.0, 2.0, 3.0, or any range including and / or between any two of these values. When the composition comprises a salt solution having an ionic strength of 0.5 to 3.0, in any such embodiment, the composition can be at a pH of about 5.0, about 5.1, about 5.2, about 5.3, about 5.4, about 5.5, about 5.6, about 5.7, about 5.8, about 5.9, about 6.0, about 6.1, about 6.2, about 6.3, about 6.4, about 6.5, about 6.6, about 6.7, about 6.8, about 6.9, about 7.0, or any range including and / or between any two of these values.

[0120] In another aspect, the present technology provides a method for preparing functionalized colloidal silica (e.g., a method for preparing a composition of any embodiment herein). The method comprises contacting colloidal silica with a silane according to Formula IV to produce the functionalized colloidal silica.

[0121]

[0122] in

[0123] R 1 is H, unsubstituted alkyl, hydroxy-substituted alkyl, alkoxy-substituted alkyl, hydroxy-substituted cycloalkyl, aryl, or heteroaryl;

[0124] R 2 is a hydroxy-substituted alkyl group, an alkoxy-substituted alkyl group, or a hydroxy-substituted cycloalkyl group;

[0125] or R 1 and R 2 Together they are a C4-C6 alkylene group substituted with a hydroxy group;

[0126] R 9 is hydroxy, alkoxy or aryloxy;

[0127] R 10 is hydroxy, alkoxy or aryloxy; and

[0128] L 1 is an alkoxy group or an aryloxy group.

[0129] The colloidal silica may be aqueous colloidal silica. In any embodiment herein, it is possible that R 7 、R 8 and L 1 Each independently is an alkoxy or aryloxy group. In any embodiment herein, it is possible that R 7 、R 8 and L 1 Each independently is an alkoxy or aryloxy group. In any embodiment herein, it is possible that R 1 is H, unsubstituted alkyl, hydroxy-substituted alkyl, alkoxy-substituted alkyl, hydroxy-substituted cycloalkyl, amine-substituted aryl, hydroxy-substituted aryl, or heteroaryl. In any embodiment herein, it is possible that R 9 is hydroxy, methoxy, ethoxy, propoxy or phenoxy. In any embodiment herein, it is possible that R 10 Is hydroxy, methoxy, ethoxy, propoxy or phenoxy. In any embodiment herein, it is possible that L 1 is methoxy, ethoxy, propoxy or phenoxy. In any embodiment herein, it is possible that R 1 R is H, methyl, ethyl, hydroxy-substituted C2-C6 alkyl, or alkoxy-substituted C2-C6 alkyl; 2 is a hydroxy-substituted C2-C6 alkyl group or an alkoxy-substituted C2-C6 alkyl group; or R 1 and R 2 Together they are a C4-C6 alkylene group substituted with a hydroxy group.

[0130] In any embodiment of the method herein, the functionalized colloidal silica may include a surface and a structural unit according to formula I and / or a structural unit according to formula II

[0131]

[0132] in

[0133] R 3 is hydroxy, alkoxy, aryloxy or G 2 ;

[0134] R 4 is hydroxy, alkoxy, aryloxy or G 3 ;

[0135] R 5 is hydroxy, alkoxy, aryloxy or G 5 ;

[0136] R 6 is hydroxy, alkoxy, aryloxy or G 6 ;

[0137] G 1 , G 2 , G 3 , G 4 , G 5 and G 6 are each independently an oxygen atom on the surface of the silica particle, wherein G 1 , G 2 , G 3 , G 4 , G 5 and G 6 are not the same oxygen atom; and

[0138] Y 1 It is an anion.

[0139] In any of the embodiments herein, it is possible that R 3 is hydroxy, methoxy, ethoxy, propoxy, phenoxy or G 2 In any of the embodiments herein, it is possible that R 4 is hydroxy, methoxy, ethoxy, propoxy, phenoxy, or G 3 In any of the embodiments herein, it is possible that R 5 is hydroxy, methoxy, ethoxy, propoxy, phenoxy or G 5 In any of the embodiments herein, it is possible that R 6 is hydroxy, methoxy, ethoxy, propoxy, phenoxy or G 6 .

[0140] In any embodiment of the method herein, the functionalized colloidal silica can include a surface and at least one structural unit according to Formula Ia, Ib, Ic, Id, Ie, If, or Ig

[0141]

[0142]

[0143]

[0144] where Y 2 、Y 3 、Y 4 、Y 5 、Y 6 、Y 7 and Y 8 is independently an anion at each occurrence.

[0145] In any of the embodiments herein of the method, Y 1 、Y 2 、Y3 、Y 4 、Y 5 、Y 6 、Y 7 and Y 8 Can be Cl independently at each occurrence - 、NO3 - or SO4 2- In any embodiment herein of the method, it is possible that the functionalized colloidal silica further comprises at least one structural unit according to formula III

[0146]

[0147] in

[0148] R 7 is hydroxy, alkoxy, aryloxy or G 8 ;

[0149] R 8 is hydroxy, alkoxy, aryloxy or G 9 ;

[0150] G 7 , G 8 and G 9 are each independently an oxygen atom on the surface of the silica particle, wherein G 7 , G 8 and G 9 Not the same oxygen atom.

[0151] In any embodiment herein of the method, it is possible that R 7 is hydroxy, methoxy, ethoxy, propoxy, phenoxy or G 8 In any embodiment herein of the method, it is possible that R 8 is hydroxy, methoxy, ethoxy, propoxy, phenoxy or G 9 .

[0152] The method of any embodiment herein may comprise 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 wherein the medium comprises a polar organic solvent, the polar organic solvent may comprise methanol, ethanol, propanol, ethylene glycol, acetone, dimethylformamide, N-methylpyrrolidone, or a combination of any two or more thereof.

[0153] The method of any of the embodiments herein may comprise contacting every 1 nm 2The colloidal silica surface area is about 1.5 to about 3.0 molecules of silane. Thus, in any embodiment herein, the method may include contacting every 1 nm 2 The colloidal silica can be prepared by adding molecular silane in an amount having a surface area of ​​about 1.5, about 1.6, about 1.7, about 1.8, about 1.9, about 2.0, about 2.1, about 2.2, about 2.3, about 2.4, about 2.5, about 2.6, about 2.7, about 2.8, about 2.9, about 3.0, or any range including and / or between any two of these values.

[0154] The method of any embodiment herein can provide a composition comprising water and the functionalized colloidal silica (e.g., a composition of any embodiment of the composition aspect of the present technology). In such embodiments, when the composition comprises a salt solution having an ionic strength of 0.5 to 3.0, the composition can be stably aged at a temperature of 80° C. for 24 hours or longer. The salt solution of any embodiment herein may include NaCl, CaCl 2 , MgSO 4 or a combination of any two or more thereof. In any embodiment herein, the ionic strength may be 0.5, 1.0, 2.0, 3.0, or any range including any two of these values ​​and / or between any two of these values. When the composition comprises a salt solution having an ionic strength of 0.5 to 3.0, in any such embodiment, the composition can be at a pH of about 5.0, about 5.1, about 5.2, about 5.3, about 5.4, about 5.5, about 5.6, about 5.7, about 5.8, about 5.9, about 6.0, about 6.1, about 6.2, about 6.3, about 6.4, about 6.5, about 6.6, about 6.7, about 6.8, about 6.9, about 7.0, or any range including and / or between any two of these values.

[0155] The method of any embodiment herein can include contacting colloidal silica with a silane according to Formula IV to produce an initial mixture comprising functionalized colloidal silica and unreacted silane, silane not bonded to the colloidal silica, impurities, or a combination of any two or more thereof; and purifying the functionalized colloidal silica by ultrafiltering the initial mixture to separate the functionalized colloidal silica from the unreacted silane, silane not bonded to the colloidal silica, impurities, or a combination of any two or more thereof.

[0156] In another aspect, the present technology provides functionalized silica prepared according to the method of any embodiment described herein.

[0157] The present technology thus generally described will be understood more readily by reference to the following examples, which are provided by way of illustration and are not intended to be limiting of the present technology. Example

[0158] Commercially available LUDOX colloidal silica grades were used in these examples. These products were supplied by WR Grace & Co. Similar products such as LEVASIL (available from Nouryon), AMSOL (available from Applied Material Solutions), KOSTROSOL 1540 (available from CWK Chemiewerk Bad GmbH), NALCO 1140 (from Nalco Water), SNOWTEX (from Nissan Chemical).

[0159] All chemicals used in these examples were obtained from common suppliers such as Sigma Aldrich, Fisher Scientific, TCI America, and Gelest, Inc. These chemicals were purchased and used without further purification.

[0160] To calculate the silane treatment level of colloidal silica particles, as shown in Table 1 below, we use 345m 2 / g surface area, for 12nm grade colloidal silica (such as LUDOX HS-40 or LUDOX AM or LUDOX CL), use 220m 2 / g surface area, for 22nm grade colloidal silica (such as LUDOX TM-40), use 140m 2 / g surface area, and for 40nm grade colloidal silica (such as LUDOX PW-50(X), a colloidal silica grade with polydisperse, different sized silica particles) use 75nm 2 / g surface area. The treatment level (TL) is defined as the number of molecules per square nanometer of solid particle surface area, or NM / nm 2 .

[0161] Table 1

[0162]

[0163]

[0164] In a typical procedure for the purification of functionalized colloidal silica, a SPECTRUM MIDIKROS hollow fiber membrane (e.g., with a surface area of ​​75 cm2 The colloidal silica sample was passed through the membrane via TYGON tubing with a peristaltic pump at a pressure of less than 25 psi. The permeate was collected and the total volume was measured. Typical solids for colloidal silica ranged from 5% to 25%, and fresh deionized water was added to compensate for the volume loss of the permeate. Typically, 5-10 volumes of permeate accumulated relative to the initial total volume of the colloidal sample before the ultrafiltration process was complete.

[0165] General method for elemental analysis of functionalized particles for carbon (C%), hydrogen (H%), and nitrogen (N%): A small amount of purified colloid sample was placed in a glass vial and the vial was dried overnight in an oven at 90° C. The dried solid was collected and subjected to elemental analysis using a LECO G4 ICARUS Series 2 analyzer or a PerkinElmer 2400 series.

[0166] Titration method: for ζ titration, use the Colloid Dynamics AcoustoSizer IIX that is connected to the automatic titrator device to measure the ζ potential that changes with pH by electroacoustic method.For typical operation, by diluting the original sample with 5% colloidal solids with deionized water, prepare sol.Begin to carry out potentiometric titration under the sol nascent pH, and rise to pH 9 (sol on the acid side for nascent pH) or be down to pH 3 (sol on the alkali side for nascent pH), and return to pH 9 or 3 subsequently.Use SiO2 (silicon dioxide, amorphous-typical) and the preload instrument parameter of water by software.Titrate with 0.1N HCl and 0.1NNaOH.

[0167] For dynamic light scattering (DLS) particle size measurements, a Malvern Zetasizer Nano-S90 model ZEN1690 was used. A 2 wt% colloidal solids solution was prepared by diluting the original sol with deionized water. Once diluted, the sol was filtered into a measuring cuvette using a 0.45 micron syringe filter. Measurements were accumulated for 60 seconds. The reported value is the volume-based D50.

[0168] Method for characterizing the surface groups of functionalized colloidal particles: After purification by ultrafiltration to remove unreacted species, functionalized colloidal silica at approximately 20% solids was subjected to NMR analysis. The samples were diluted to approximately 10% with D2O and analyzed on a Bruker Avance III 400 MHz nuclear magnetic resonance (NMR) instrument.

[0169] Example 1 (1.7 NM / nm 2 TL's DEA)

[0170] In a 20 ml vial, 2.95 g (12.5 mmol) of 3-glycidyloxypropyltrimethoxysilane (glycidylsilane) and 1.31 g (12.5 mmol) of diethanolamine (DEA) were mixed using a stirring rod. Initially, the two liquid compounds were immiscible with each other and existed in two phases. After approximately 1 hour of reaction, a single phase formed, and a new silane having the following structure was formed:

[0171]

[0172] In a 250 ml beaker, 50 g of LUDOX HS-40 (40% solids, 20 g neat SiO solids) was diluted to 30% by adding 16.6 g of deionized water. Fresh silane was added dropwise to the stirred colloidal silica over 10 minutes. After addition, the mixture was stirred at room temperature for 1 hour and then heated to 70° C. for another hour. The mixture was then allowed to cool to room temperature and the resulting mixture was purified by ultrafiltration with 5 volumes of DI water as described above.

[0173] A small amount of sample was taken from the purified sample and dried in an oven at 90°C overnight. The dried sample was subjected to elemental analysis.

[0174] The functionalized sample was run at approximately 10% solids (20% solids after ultrafiltration and subsequent dilution with an equal volume of D2O). 13 C-NMR spectrum test. Figure 1 As shown, the signals indicate the bonding of a new silane bearing a diethanolamine moiety as well as a diol functionality. While not wishing to be bound by theory, the presence of two silane groups suggests that the reaction of the diethanolamine with the glycidyl silane is incomplete or that the glycidyl silane undergoes partial hydrolysis (to yield a diol group) upon reaction with the diethanolamine.

[0175] It is well known that available colloidal silica is almost always stabilized with sodium hydroxide at the time of its manufacture (see "Colloidal Silica: Fundamentals and Applications", edited by Bergna and Roberts, Taylor & Francis, CRC Press 2006, page 139), and carries a negative charge at pH 7 due to deprotonation of surface silanol groups. Figure 2 Shown are the zeta potentials of LUDOX HS-40 (starting material of Example 1), a colloidal silica stabilized by NaOH, at different pH values.

[0176] Figure 3Depicted are the results of zeta titration of functionalized colloidal silica from Example 1 of the present technology. As shown, unlike the starting sample LUDOX HS-40, which carries a negative charge from pH 4 to pH 10, the particle surface of the functionalized sample carries a positive charge when the aqueous colloidal system has a pH below 8.5. Therefore, the isoelectric point of the sample is approximately 8.5.

[0177] Example 2 (2.0 NM / nm 2 TL's DEA)

[0178] The same procedure as in Example 1 was followed, except that the amounts of glycidylsilane and diethanolamine used were 3.47 g (14.6 mmol) and 1.54 g (14.6 mmol), respectively.

[0179] Example 3 (2.0 NM / nm 2 TL of DEA, where methanol is used as a co-solvent in the silane formation reaction)

[0180] In a 50 ml beaker, 3.47 g (14.6 mmol) of glycidylsilane, 1.54 g (14.6 mmol) of DEA, and 10 ml of methanol were mixed with a stirring rod. A uniform solution was obtained from the start, and mixing was continued at room temperature for 1 hour. Afterwards, the methanol solution of the silane was added dropwise to 66.7 g of 30% colloidal silica (diluted HS-40). The mixture was stirred at room temperature for 1 hour and then heated to 70° C. for another hour, during which time most of the methanol evaporated from the heat. The mixture was then allowed to cool to room temperature. The resulting mixture was purified by ultrafiltration through 5 volumes of DI water.

[0181] Example 4 (1.7 NM / nm 2 TL of TRIS base, where methanol is used as a co-solvent)

[0182] In a 50 ml beaker, mix 2.95 g (12.5 mmol) of glycidylsilane, 1.51 g (12.5 mmol) of TRIS base (tris(hydroxymethyl)aminomethane), and 20 ml of methanol using a stir bar. Heat the mixture to 55°C in a water bath until a clear solution forms. The structure of the newly formed silane is as follows:

[0183]

[0184] Afterwards, the methanol solution of the new silane was added dropwise to 66.7 g of 30% colloidal silica (diluted HS-40). The mixture was stirred at room temperature for 1 hour and then heated to 70° C. for another 1 hour and then allowed to cool to room temperature. The resulting mixture was purified by ultrafiltration with 5 volumes of DI water.

[0185] Example 5 (2.1 NM / nm 2 TL's DIPA, diisopropanolamine)

[0186] In a 20 ml vial, 3.64 g (15.4 mmol) of 3-glycidoxypropyltrimethoxysilane and 2.05 g (15.4 mmol) of diisopropanolamine (DIPA, or bis(2-hydroxypropyl)amine) were mixed overnight with a stirring bar to form a transparent, single-phase new silane. The structure of the newly formed silane is as follows:

[0187]

[0188] The new silane was then added dropwise to 66.7 g of 30% colloidal silica (diluted HS-40). The mixture was stirred at room temperature for 1 hour and then heated to 70° C. for another hour and then allowed to cool to room temperature. The resulting mixture was purified by ultrafiltration with 5 volumes of DI water.

[0189] Example 6 (1.7 NM / nm 2 TL's MEG, meglumine)

[0190] In a 50 ml beaker, mix 2.95 g (12.5 mmol) of glycidylsilane, 2.43 g (12.5 mmol) of meglumine (MEG, or N-methylglucamine), and 20 ml of methanol using a stir bar. Heat the mixture to 55°C in a water bath until a clear solution forms (2-3 hours). The structure of the newly formed silane is as follows:

[0191]

[0192] After obtaining the new silane, the methanol solution of the new silane was added dropwise to 66.7 g of diluted 30% colloidal silica (HS-40). The mixture was stirred at room temperature for 1 hour and then heated to 70° C. for another 1 hour and then allowed to cool to room temperature. The resulting mixture was purified by ultrafiltration with 5 volumes of DI water.

[0193] Figure 4 Depicted is a comparison of the particle surface zeta potential of colloidal silica functionalized with different types of surface functional groups from the above examples. As shown, a similar pattern of positively charged surface vs. pH was found with these types of surface groups.

[0194] Example 7 (2.5 NM / nm 2 TL EAE, 2-(ethylamino)ethanol)

[0195] The same procedure as in Example 1 was followed for the formation of the new silane, except that the amounts of glycidylsilane and 2-(ethylamino)ethanol used were 4.33 g (18.3 mmol) and 1.63 g (18.3 mmol), respectively. The newly formed silane had the following structure:

[0196]

[0197] The reaction of this silane with 50 g of HS-40 was carried out similarly to that described in Example 1.

[0198] Example 8 (2.5n / nm 2 TL's BMEA, bis(methoxyethyl)amine)

[0199] The same procedure for the formation of the new silane was followed as in Example 1, except that the amounts of glycidylsilane and bis(methoxyethyl)amine used were 4.33 g (18.3 mmol) and 2.44 g (18.3 mmol), respectively. The newly formed silane had the following structure:

[0200]

[0201] The reaction of this silane with 50 g of HS-40 was carried out similarly to that described in Example 1.

[0202] Table 2 lists the elemental analysis results of Examples 1-8.

[0203]

[0204] In Table 1, the found C, H, N values ​​for the analyzed samples are reported in columns D, E, and F. Based on the nitrogen number, the density of bound alkylamine groups can be calculated (column H). The corresponding "theoretical" carbons calculated from the nitrogen content (column F) and based on the molecular formula of the bound silane (column G) always appear to be less than the total carbons measured (column D). The difference is believed to come from the diol-silane groups generated by hydrolysis of the epoxy groups (which do not react with the hydroxyalkylamine molecules), and the calculated diol-silane density is reported in column I. These results are consistent with the results from 13 The findings were consistent with those from the C-NMR data.

[0205] Example 9 (DEA on LUDOX AM, 1.7 TL)

[0206] The same treatment silane and procedure as in Example 1 was used to functionalize LUDOX AM (12 nm grade, where colloidal silica was functionalized with negatively charged aluminates). After the DEA silane was formed, it was used to functionalize LUDOX AM at approximately 30% solids and approximately pH 9.

[0207] Figure 5The zeta potential curves of unmodified LUDOX AM and the bonded samples are compared. As shown, functionalization significantly changes the zeta potential of many of the colloidal particles from the starting material, as they have a similar curve to DEA silane functionalized HS-40, i.e., a positive charge at pH less than 8.5.

[0208] Example 10 (DEA on LUDOX SM, 2.5 TL)

[0209] As described in Example 1, 6.8 g (28.7 mmol) of 3-glycidoxypropyltrimethoxysilane and 3.83 g (28.7 mmol) of diethanolamine were reacted in a 20 ml vial to form a new silane. The new silane was used to treat 66.6 g of LUDOX SM (30%, neat 20 g of SiO2, 7 nm particles with a surface area of ​​approximately 345 m 2 / g). After purification, the dried sample obtained a carbon content of 13.77%.

[0210] Example 11 (DEA on LUDOX TM-40, 1.7 TL)

[0211] DEA silane, formed by reacting 1.88 g (7.9 mmol) of glycidylsilane and 0.83 g (7.9 mmol) of diethanolamine, was used to react with 50 g of 40% TM-40 (22 nm, with a surface area of ​​approximately 140 m 2 / g) and 16.6g of DI water.

[0212] Example 12 (DEA on LUDOX PW-50(X), 1.7 TL)

[0213] DEA silane, formed by reacting 1.0 g (4.2 mmol) of glycidylsilane and 0.45 g (4.2 mmol) of diethanolamine, was used to react with 40 g of 50% PW-50X (mixed particle size grade with an average particle size of approximately 40 nm and a surface area of ​​approximately 75 m 2 / g) and 20g of DI water.

[0214] Example 13 (DEA on LUDOX CL, 1.7 TL)

[0215] As previously described, DEA silane was first formed by reacting 2.95 g (12.5 mmol) of glycidylsilane with 1.31 g (12.5 mmol) of DEA. The new silane was then dissolved in a mixture of 10 ml of water and 12.5 ml of 1 M HCl (final pH approximately 4.0), and the silane solution was slowly added to a stirred 66.6 g of LUDOX CL (12 nm grade, positively charged polyaluminum chlorohydrate). After mixing for 1 hour at room temperature and an additional hour at 70° C., the functionalized particles were purified by ultrafiltration through 5 volumes of DI water. The carbon content of the dried, purified sample was measured to be 1.78%, indicating a lower amount of surface functional groups than the similarly modified sample in Example 1. This is likely due to the fact that most of the particle surface was covered with cationic aluminum ions.

[0216] Comparative Example 1 (APS or 3-aminopropylsilane, 1.7TL)

[0217]

[0218] 2.76 g (12.5 mmol) of aminopropyltrimethoxysilane was dissolved in 25 ml of 0.5 M HCl to a pH of 4.0. 50 g of LUDOX HS-40 (diluted to 20% solids with 50 mL of DI water) was acidified to pH 4.0 with the gradual addition of 1 M HCl. To this dispersion was added the silane solution from the APS silane solution. After the addition was complete, the mixture was stirred at room temperature for 1 hour and then heated to 70° C. for an additional hour. After cooling to room temperature, the modified colloidal sample was purified by ultrafiltration through 5 volumes of DI water. Elemental analysis of carbon on the dried sample gave a value of 1.27%.

[0219] Comparative Example 2 (Sample Preparation According to Prior Art Procedure)

[0220] U.S. Patent No. 5,464,900 discloses a water-soluble organosiloxane comprising an oligomer of an addition product of at least two reactants, one of which is at least one 3-glycidyloxypropyl alkoxysiloxane and the other is at least one secondary hydroxyalkylamine, and optionally colloidal silica may be added to the mixture. U.S. Patent No. 5,464,900 discloses that the resulting mixture can be used in a coating composition and applied to a coating film. A procedure similar to that described in Examples 1 and 3 of U.S. Patent No. 5,464,900 (on a 1 / 10 scale) was performed to prepare a mixture containing both a silane and colloidal silica.

[0221] Therefore, 2.36g of glycidyl silane, 1.05g of DEA and 0.5g of isopropyl alcohol were placed in a flask and stirred rapidly at room temperature. Initially, the reaction was heterogeneous, but after about 5-10 minutes, a clear, single-phase, viscous liquid was formed. After the mixture was stirred for about 30 minutes, the mixture was heated in a hot water bath at 45°C for another 30 minutes. After the mixture was removed from the hot water bath, the liquid was stirred for an additional 30 minutes, followed by the addition of 11g of water to hydrolyze the methoxy groups. This will produce a coupling agent with a 20% solid content. 1 gram of LUDOX HS-30 (12nm grade, 30% solids, a product similar to NALCO 1030 in particle size and concentration) was diluted with 2 grams of DI water in a vial. This was mixed with 2g of a 10% solution of the silane just described to provide a 3:2 silica / oligomer solution. The salt stability of this mixture was tested as described below.

[0222] Comparative Example 3

[0223] US Pat. No. 6,015,843 discloses a method for preparing silanized colloidal silica. Specifically, bis(2-hydroxyethyl)-2-aminoethyltrimethoxysilane is listed, although its preparation is not discussed. Nevertheless, bis(2-hydroxyethyl)-2-aminoethyltrimethoxysilane was prepared and used to produce functionalized colloidal silica to allow for comparison with Example 1.

[0224]

[0225] Thus, 3.62g of 3-iodopropyltrimethoxysilane, 1.31g of DEA, and 1.26g of triethylamine were mixed in 5g of N,N-dimethylformamide at room temperature for 3 days. The mixture was then slowly added to 20ml of 1M HCl (pH 1.0). 50g of LUDOX HS-40 and 16.6g of DI water were acidified to pH 2.0 with 1M HCl. The two were then mixed at room temperature for 30 minutes and then heated to 70°C for 1 hour. After purification by ultrafiltration with 10 volumes of DI water, a functionalized colloid was formed. Elemental analysis of the dried sample revealed a carbon content of 1.56%.

[0226] Comparative Example 4

[0227] In US Pat. No. 7,544,726, glycidylsilane-functionalized colloidal silica is disclosed. The resulting surface functional groups were determined to be diols (derived from the hydrolysis of the epoxide of the glycidylsilane). Comparative Example 4 was prepared following a procedure similar to that described in Examples 1-8 and in a literature report (Greenwood and Gevert, "Aqueous silica modified silica sols: theory and preparation", Pigment & Resin Technology, 40 / 5 (2011) 275-284).

[0228]

[0229] Mix 2.95 g of glycidylsilane with 5 ml of DI water for 2 hours. A clear solution forms after 2 hours. Dilute 50 g of HS-40 to 20% solids with 50 g of DI water. Heat the stirred colloidal silica to 60°C in a water bath. Slowly add the aqueous silane solution to the colloidal silica over 1 hour. After addition, continue heating for an additional hour. Purify with 5 volumes of DI water to obtain the corresponding functionalized colloidal silica. A small dried sample was determined to have a C% content of 3.78%.

[0230] Example 14 Salt stability test

[0231] It is well known that colloidal systems composed of charged nanoparticles stabilized by electrostatic repulsion are sensitive to high ionic strength or high salt concentration solutions due to the significantly reduced Debye length in a high salt environment. For example, NaCl in water at 25 °C and a concentration of 1 × 10 -3 The solution of M has λ D = 9.6 nm, corresponding to about 40 water diameters; and at a concentration of 0.1 M, the Debye length is λ D =0.96 nm, which is 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. Without intending to be bound by theory, it is believed that the bound surface organic groups on the colloidal particles can introduce steric effects and contribute to the salt tolerance of the colloidal system containing the functionalized colloidal nanoparticles. Here, we compare the colloidal stability with selected functional groups and starting materials from the examples and comparative examples 1-4.

[0232] To standardize the salt concentration in the stability tests, we used the same ionic strength of 0.5, 1.0, 2.0, and 3.0 with a monovalent salt solution (NaCl), a 2 / 1 divalent salt solution (CaCl2), and a 2 / 2 divalent salt solution (MgSO4). The molar ionic strength, I, is a function of the concentrations of all ions present in the solution and is defined as:

[0233]

[0234] Where Ci is the molar concentration of ion i, Zi is the charge of i, and the sum is calculated for all ions (cations and anions) in solution. Therefore, the molar concentrations of the three different salt systems mentioned are:

[0235] Ionic strength NaCl(M) <![CDATA[CaCl2(M)]]> <![CDATA[MgSO4(M)]]> I＝0.5 0.5 0.17 0.12 I＝1.0 1.0 0.32 0.24 I＝2.0 2.0 0.65 0.50 I＝3.0 3.0 1.0 0.74

[0236] For all colloidal samples and at a final colloidal silica concentration of 2%, the pH of the diluted colloidal samples was pre-adjusted to 4.0 (adjusted with HCl or NaOH solution). Thus, equal volumes of the salt solutions in the table (natural pH 5-8, depending on the pH of the DI water used) (at twice the concentration in the table) were mixed with 4% of the colloidal samples and their colloidal stability was visually observed at room temperature (20°C), 40°C, and 80°C for 4 hours and 24 hours. Arrhenius chemical reaction kinetics indicate that higher temperatures accelerate reactions, generally doubling the rate for every 10 degrees increase. Thus, 24 hours at 40°C (2×10 degrees) is equivalent to approximately 24×2 hours at 20°C. 2 = 96 hours (or 4 days), and 24 hours at 80°C (6×10 degrees) is equivalent to approximately 24×2 at 20°C. 6 =1536 hours (or 64 days).

[0237] The colloidal stability of the samples was determined by visually observing the test samples in the experiment after aging at three different temperatures. The term "stable" means that no visual or physical changes were observed in the colloidal dispersion after aging. The term "turbid" means that the colloidal dispersion became whiter in color and decreased in clarity, but no visible sedimentation was observed in the sample. The term "sedimentation" means that the silica solids separated and settled to the bottom of the sample vial after aging. The term "gelled" means that the viscosity of the colloidal dispersion increased to the point that the entire sample could no longer flow like a liquid.

[0238] Table 3-10 provides a summary of the colloidal stability results for the samples tested in these experiments:

[0239]

[0240]

[0241]

[0242]

[0243]

[0244]

[0245]

[0246]

[0247] As shown in Tables 3-10, examples according to the present technology (Examples 1, 4, and 6) exhibit excellent stability and are significantly more stable than the HS-40 starting material and Comparative Examples 1-4.

[0248] While certain embodiments have been illustrated and described, it will be understood that changes and modifications may be made therein in accordance with one skilled in the art without departing from the technology in its broader aspects as defined in the appended claims.

[0249] The embodiments exemplarily described herein may be suitably implemented in the absence of any one or more elements, one or more limitations not specifically disclosed herein. Thus, for example, the terms "comprising," "including," "containing," etc. should be understood broadly and without limitation. In addition, the terms and expressions employed herein have been used as terms of description rather than limitation, and in the use of such terms and expressions, there is no intention to exclude any equivalents of the features shown and described, or portions thereof, but it should be recognized that various modifications may be made within the scope of the claimed technology. In addition, the phrase "consisting essentially of..." will be understood to include those elements specifically recited and those additional elements that do not materially affect the basic and novel characteristics of the claimed technology. The phrase "consisting of..." excludes any element not specified. Finally, it will be understood that the disclosure of one of the aforementioned terms also discloses embodiments using either of the other two terms or their equivalents.

[0250] The present disclosure is not limited to the specific embodiments described in this application. Without departing from its spirit and scope, many modifications and changes can be made, which will be apparent to those skilled in the art. Based on the foregoing description, in addition to those enumerated herein, functionally equivalent methods and compositions within the scope of the present disclosure will be apparent to those skilled in the art. These modifications and changes are intended to fall within the scope of the appended claims. The present disclosure is only subject to the terms of the appended claims and the full scope of equivalents granted by such claims. It should be understood that the present disclosure is not limited to specific methods, reagents, compounds, compositions or biological systems, which can of course vary. It should also be understood that the terms used herein are only used to describe the purpose of specific embodiments and are not intended to be restrictive.

[0251] In addition, where features or aspects of the disclosure are described in terms of Markush groups, those skilled in the art will recognize that the disclosure is also thereby described in terms of any individual member or subgroup of members of the Markush group.

[0252] As will be understood by those skilled in the art, for any and all purposes, particularly in terms of providing a written description, all ranges disclosed herein also encompass any and all possible subranges and combinations of subranges thereof. Any enumerated range can be readily understood to fully describe and be capable of decomposing the same range into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each range discussed herein can be readily decomposed into a lower third, a middle third, and an upper third, etc. As will be understood by those skilled in the art, all language such as "at most," "at least," "greater than," "less than," etc. includes the cited number and refers to a range that can subsequently be decomposed into the subranges discussed above. Finally, as will be understood by those skilled in the art, a range includes each individual member.

[0253] All publications, patent applications, issued patents, and other documents mentioned in this specification are incorporated herein by reference to the same extent as if each individual publication, patent application, issued patent, or other document was specifically and individually indicated to be incorporated herein by reference in its entirety. Definitions contained in text incorporated by reference are excluded to the extent they are inconsistent with definitions in this disclosure.

[0254] The present technology may include, but is not limited to, the features and combinations of features set forth in the following lettered paragraphs, with the understanding that the following paragraphs shall not be construed as limiting the scope of the appended claims or mandating that all such features must be included in such claims:

[0255] A. A composition comprising water and functionalized colloidal silica, wherein the functionalized colloidal silica comprises:

[0256] silica particles comprising a surface, and

[0257] Structural units according to formula I and / or structural units according to formula II

[0258]

[0259] in

[0260] R 1 is H, unsubstituted alkyl, hydroxy-substituted alkyl, alkoxy-substituted alkyl, hydroxy-substituted cycloalkyl, aryl, or heteroaryl;

[0261] R 2 is a hydroxy-substituted alkyl group, an alkoxy-substituted alkyl group, or a hydroxy-substituted cycloalkyl group;

[0262] or R 1 and R 2 Together they are a C4-C6 alkylene group substituted with a hydroxy group;

[0263] R 3 is hydroxy, alkoxy, aryloxy or G 2 ;

[0264] R 4 is hydroxy, alkoxy, aryloxy or G 3 ;

[0265] R 5 is hydroxy, alkoxy, aryloxy or G 5 ;

[0266] R 6 is hydroxy, alkoxy, aryloxy or G 6 ;

[0267] G 1 , G 2 , G 3 , G 4 , G 5 and G 6 are each independently an oxygen atom on the surface of the silica particle, wherein G 1 , G 2 , G 3 , G 4 , G 5 and G 6 are not the same oxygen atom; and

[0268] Y 1 It is an anion.

[0269] B. The composition of paragraph A, wherein the composition comprises a pH of about 8.5 or less.

[0270] C. The composition of paragraph B, wherein the composition comprises a molar ratio of structural units according to Formula I to structural units according to Formula II greater than 1:1.

[0271] D. The composition of any of paragraphs AC, wherein the silica particles have a median diameter of about 1 nm to about 100 nm as determined by dynamic light scattering.

[0272] E. The composition of any of paragraphs A to D, wherein the silica particles have a diameter of about 25 m 2 / g to approximately 1,200m 2 / g of Sears surface area.

[0273] F. The composition of any of paragraphs AE, wherein each nm 2 The number of structural units according to formula I and / or formula II per surface area is from about 0.8 to about 3.5.

[0274] G. The composition of any of paragraphs AF, wherein:

[0275] R 1 is H, methyl, ethyl, hydroxy-substituted C2-C6 alkyl, or alkoxy-substituted C2-C6 alkyl;

[0276] R 2 is a hydroxy-substituted C2-C6 alkyl group or an alkoxy-substituted C2-C6 alkyl group;

[0277] or R 1 and R 2 Together they are a C4-C6 alkylene group substituted with a hydroxy group.

[0278] H. The composition of any of paragraphs AG, wherein R 3 It's G 2 .

[0279] I. The composition of any of paragraphs AH, wherein R 4 It is a hydroxyl group.

[0280] J. The composition of any of paragraphs A to I, wherein the silica particles comprise at least one structural unit according to Formula Ia, Ib, Ic, Id, Ie, If, or Ig.

[0281]

[0282]

[0283] where Y 2 、Y 3 、Y 4 、Y 5 、Y 6、Y 7 and Y 8 is independently an anion at each occurrence.

[0284] K. The composition of any of paragraphs A to J, wherein the silica particles further comprise at least one structural unit according to Formula III

[0285]

[0286] in

[0287] R 7 is hydroxy, alkoxy, aryloxy or G 8 ;

[0288] R 8 is hydroxy, alkoxy, aryloxy or G 9 ;

[0289] G 7 , G 8 and G 9 are each independently an oxygen atom on the surface of the silica particle, wherein G 7 , G 8 and G 9 Not the same oxygen atom.

[0290] L. The composition of any of paragraphs A to K, wherein the composition comprises from about 0.1 wt.% to about 50 wt.% of the functionalized colloidal silica.

[0291] M. The composition of any of paragraphs AL, wherein when the composition comprises a salt solution having an ionic strength of 0.5 to 3.0, the composition is stable upon aging at a temperature of 80°C for 24 hours or more.

[0292] N. A method for preparing functionalized colloidal silica, the method comprising:

[0293] Contacting colloidal silica with a silane according to formula IV to produce the functionalized colloidal silica

[0294]

[0295] in

[0296] R 1 is H, unsubstituted alkyl, hydroxy-substituted alkyl, alkoxy-substituted alkyl, hydroxy-substituted cycloalkyl, aryl, or heteroaryl;

[0297] R 2 is a hydroxy-substituted alkyl group, an alkoxy-substituted alkyl group, or a hydroxy-substituted cycloalkyl group;

[0298] or R1 and R 2 Together they are a C4-C6 alkylene group substituted with a hydroxy group;

[0299] R 9 is hydroxy, alkoxy or aryloxy;

[0300] R 10 is hydroxy, alkoxy or aryloxy; and

[0301] L 1 is an alkoxy group or an aryloxy group.

[0302] O. The method of paragraph N, wherein R 7 、R 8 and L 1 Each is independently an alkoxy group or an aryloxy group.

[0303] P. The method of paragraph N or paragraph O, wherein R 7 、R 8 and L 1 Each is independently an alkoxy group or an aryloxy group.

[0304] Q. The method of any of paragraphs NP, wherein the functionalized colloidal silica comprises a surface and a structural unit according to formula I and / or a structural unit according to formula II

[0305]

[0306] in

[0307] R 3 is hydroxy, alkoxy, aryloxy or G 2 ;

[0308] R 4 is hydroxy, alkoxy, aryloxy or G 3 ;

[0309] R 5 is hydroxy, alkoxy, aryloxy or G 5 ;

[0310] R 6 is hydroxy, alkoxy, aryloxy or G 6 ;

[0311] G 1 , G 2 , G 3 , G 4 , G 5 and G 6 are each independently an oxygen atom on the surface of the silica particle, wherein G 1 , G 2 , G 3 , G4 , G 5 and G 6 are not the same oxygen atom; and

[0312] Y 1 It is an anion.

[0313] R. The method of any of paragraphs NQ, wherein the method comprises contacting the colloidal silica with the silane in a medium comprising a polar organic solvent.

[0314] S. The method of paragraph R, wherein the polar organic solvent comprises methanol, ethanol, propanol, ethylene glycol, acetone, dimethylformamide, N-methylpyrrolidone, or a combination of any two or more thereof.

[0315] T. The method of any of paragraphs NS, wherein the method comprises contacting every 1 nm 2 The surface area of ​​colloidal silica is about 1.5 to about 3.0 molecules of silane.

[0316] U. The method of any of paragraphs NT, wherein the method comprises:

[0317] contacting the colloidal silica with the silane to produce an initial mixture comprising functionalized colloidal silica and one or more of unreacted silane, silane not bonded to the colloidal silica, or impurities; and

[0318] The functionalized colloidal silica was purified by ultrafiltration of the initial mixture.

[0319] V. The method of any of paragraphs NU, wherein the method provides a composition comprising water and the functionalized colloidal silica.

[0320] W. The method of paragraph V, wherein when the composition comprises a salt solution having an ionic strength of 0.5 to 3.0, the composition is stable upon aging at a temperature of 80°C for 24 hours or more.

[0321] X. The method of any of paragraphs NW, wherein the method provides a composition according to any of paragraphs AM.

[0322] Y. A functionalized silica prepared according to any of paragraphs NW.

[0323] 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: silica particles comprising a surface, and Structural units according to formula I and / or structural units according to formula II in R 1 is H, unsubstituted alkyl, hydroxy-substituted alkyl, alkoxy-substituted alkyl, hydroxy-substituted cycloalkyl, aryl, or heteroaryl; R 2 is a hydroxy-substituted alkyl group, an alkoxy-substituted alkyl group, or a hydroxy-substituted cycloalkyl group; or R 1 and R 2 Together they are a C4-C6 alkylene group substituted with a hydroxy group; R 3 is hydroxy, alkoxy, aryloxy or G 2 ; R 4 is hydroxy, alkoxy, aryloxy or G 3 ; R 5 is hydroxy, alkoxy, aryloxy or G 5 ; R 6 is hydroxy, alkoxy, aryloxy or G 6 ; G 1 , G 2 , G 3 , G 4 , G 5 and G 6 are each independently an oxygen atom on the surface of the silica particle, wherein G 1 , G 2 , G 3 , G 4 , G 5 and G 6 are not the same oxygen atom; and Y 1 It is an anion.

2. The composition of claim 1, wherein the composition comprises a pH of about 8.5 or less.

3. The composition of claim 2, wherein the composition comprises a molar ratio of structural units according to formula I to structural units according to formula II greater than 1:

1.

4. The composition of any one of claims 1-3, wherein the silica particles have a median diameter of about 1 nm to about 100 nm as determined by dynamic light scattering.

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

6. The composition of any one of claims 1 to 5, wherein each nm 2 The number of structural units according to formula I and / or formula II per surface area is from about 0.8 to about 3.

5.

7. The composition of any one of claims 1 to 6, wherein R 1 is H, methyl, ethyl, hydroxy-substituted C2-C6 alkyl, or alkoxy-substituted C2-C6 alkyl; R 2 is a hydroxy-substituted C2-C6 alkyl group or an alkoxy-substituted C2-C6 alkyl group; or R 1 and R 2 Together they are a C4-C6 alkylene group substituted with a hydroxy group.

8. The composition of any one of claims 1 to 7, wherein R 3 It's G 2 .

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

10. The composition of any one of claims 1 to 9, wherein the silica particles comprise at least one structural unit according to formula Ia, Ib, Ic, Id, Ie, If or Ig where Y 2 、Y 3 、Y 4 、Y 5 、Y 6 、Y 7 and Y 8 is independently an anion at each occurrence.

11. The composition of any one of claims 1 to 10, wherein the silicon dioxide particles further comprise at least one structural unit according to formula III in R 7 is hydroxy, alkoxy, aryloxy or G 8 ; R 8 is hydroxy, alkoxy, aryloxy or G 9 ; G 7 , G 8 and G 9 are each independently an oxygen atom on the surface of the silica particle, wherein G 7 , G 8 and G 9 Not the same oxygen atom.

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

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

14. A method for preparing functionalized colloidal silica, the method comprising: Contacting colloidal silica with a silane according to formula IV to produce the functionalized colloidal silica in R 1 is H, unsubstituted alkyl, hydroxy-substituted alkyl, alkoxy-substituted alkyl, hydroxy-substituted cycloalkyl, aryl, or heteroaryl; R 2 is a hydroxy-substituted alkyl group, an alkoxy-substituted alkyl group, or a hydroxy-substituted cycloalkyl group; or R 1 and R 2 Together they are a C4-C6 alkylene group substituted with a hydroxy group; R 9 is hydroxy, alkoxy or aryloxy; R 10 is hydroxy, alkoxy or aryloxy; and L 1 is an alkoxy group or an aryloxy group.

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

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

17. The method of any one of claims 14 to 16, wherein the functionalized colloidal silica comprises a surface and a structural unit according to formula I and / or a structural unit according to formula II in R 3 is hydroxy, alkoxy, aryloxy or G 2 ; R 4 is hydroxy, alkoxy, aryloxy or G 3 ; R 5 is hydroxy, alkoxy, aryloxy or G 5 ; R 6 is hydroxy, alkoxy, aryloxy or G 6 ; G 1 , G 2 , G 3 , G 4 , G 5 and G 6 are each independently an oxygen atom on the surface of the silica particle, wherein G 1 , G 2 , G 3 , G 4 , G 5 and G 6 are not the same oxygen atom; and Y 1 It is an anion.

18. The method of any one of claims 14-17, wherein the method comprises contacting the colloidal silica with the silane in a medium comprising a polar organic solvent.

19. The method of claim 18, wherein the polar organic solvent comprises methanol, ethanol, propanol, ethylene glycol, acetone, dimethylformamide, N-methylpyrrolidone, or a combination of any two or more thereof.

20. The method of any one of claims 13 to 19, wherein the method comprises contacting every 1 nm 2 The surface area of ​​colloidal silica is about 1.5 to about 3.0 molecules of silane.

21. The method of any one of claims 13 to 20, wherein the method comprises: contacting the colloidal silica with the silane to produce an initial mixture comprising functionalized colloidal silica and one or more of unreacted silane, silane not bonded to the colloidal silica, or impurities; and The functionalized colloidal silica was purified by ultrafiltration of the initial mixture.

22. The method of any one of claims 13-21, wherein the method provides a composition comprising water and the functionalized colloidal silica.

23. The method of claim 22, wherein when the composition comprises a salt solution having an ionic strength of 0.5 to 3.0, the composition is stable upon aging at a temperature of 80°C for 24 hours or more.

24. The method of any one of claims 13-23, wherein the method provides a composition according to any one of claims 1-13.

25. A functionalized silica prepared according to the method of any one of claims 13 to 23.

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