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WO2025122370A1 - Silice colloïdale à fonction polyol et procédés de production - Google Patents

Silice colloïdale à fonction polyol et procédés de production Download PDF

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WO2025122370A1
WO2025122370A1 PCT/US2024/057083 US2024057083W WO2025122370A1 WO 2025122370 A1 WO2025122370 A1 WO 2025122370A1 US 2024057083 W US2024057083 W US 2024057083W WO 2025122370 A1 WO2025122370 A1 WO 2025122370A1
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composition
groups
colloidal silica
silica
substituted
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Feng Gu
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WR Grace and Co Conn
WR Grace and Co
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WR Grace and Co Conn
WR Grace and Co
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/146—After-treatment of sols
    • C01B33/149—Coating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/19—Oil-absorption capacity, e.g. DBP values
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/90—Other properties not specified above

Definitions

  • the present technology relates generally to functionalized colloidal silica as well as methods useful for synthesizing such functionalized colloidal silica, including compositions that are stable to aging for 24 hours or longer at temperature of 80 °C when the composition includes a salt solution at an ionic strength of 0.5 to 3.0.
  • the present technology provides a composition that includes water and a functionalized colloidal silica.
  • the functionalized colloidal silica includes silica particles (where each silica particle includes a surface) and a structural unit according to Formula I where R 1 is -CH 2 (CHOH) x CH 2 OH where x is 1, 2, 3, 4, 5, or 6, R 2 is hydroxyl, alkoxy, aryloxy, or G 2 ; R 3 is hydroxyl, alkoxy, aryloxy, or G 3 ; and G 1 , G 2 , and G 3 are each independently an oxygen atom of the surface of the silica particle, where G 1 , G 2 , and G 3 are not the same oxygen atom.
  • the present technology provides a method of making a functionalized colloidal silica (for example, a method of making a composition of any embodiment herein).
  • the method includes contacting a colloidal silica with a silane according to Formula III to yield the functionalized colloidal silica where R 1 is -CH 2 (CHOH) x CH 2 OH where x is 1, 2, 3, 4, 5, or 6, where y + z is 0, 1, 2, 3, 4, or 5,
  • R 6 is hydroxyl, alkoxy, or aryloxy
  • R 7 is hydroxyl, alkoxy, or aryloxy
  • L 1 is alkoxy or aryloxy.
  • FIG.1 provides a reaction scheme for functionalizing silica with sugar alcohols.
  • FIG.2 depicts 13 C-NMR spectra of sorbitol silane-functionalized colloidal silica dispersion (top spectrum), sorbitol solution in a mixture of H 2 O and D 2 O (middle spectrum), and dispersion of colloidal silica functionalized with diol silane (bottom spectrum), according to the working examples.
  • FIG.3 depicts the zeta titration results of alcohol-functionalized LUDOX HS-40, according to the working examples.
  • FIG.4 depicts titration results of alcohol-functionalized LUDOX HS-40, according to the working examples.
  • DETAILED DESCRIPTION [0010] Various embodiments are disclosed and described hereinafter. It should be noted that the specific embodiments are not intended as an exhaustive description or as a limitation to the broader aspects discussed herein. One aspect described in conjunction with a particular embodiment is not necessarily limited to that embodiment and can be practiced with any other embodiment(s).
  • an R group is defined to include hydrogen or H, it also includes deuterium and tritium.
  • Compounds comprising radioisotopes such as tritium, C 14 , P 32 and S 35 are thus within the scope of the present technology. Procedures for inserting such labels into the compounds of the present technology will be readily apparent to those skilled in the art based on the disclosure herein.
  • substituted refers to an organic group as defined below (e.g., an alkyl group) in which one or more bonds to a hydrogen atom contained therein are replaced by a bond to non- hydrogen or non-carbon atoms.
  • Substituted groups also include groups in which one or more bonds to a carbon(s) or hydrogen(s) atom are replaced by one or more bonds, including double or triple bonds, to a heteroatom.
  • a substituted group is substituted with one or more substituents, unless otherwise specified.
  • a substituted group is substituted with 1, 2, 3, 4, 5, or 6 substituents.
  • substituent groups include: halogens (i.e., F, Cl, Br, and I); hydroxyls; alkoxy, alkenoxy, aryloxy, aralkyloxy, heterocyclyl, heterocyclylalkyl, heterocyclyloxy, and heterocyclylalkoxy groups; carbonyls (oxo); carboxylates; esters; urethanes; oximes; hydroxylamines; alkoxyamines; aralkoxyamines; thiols; sulfides; sulfoxides; sulfones; sulfonyls; pentafluorosulfanyl (i.e., SF 5 ), sulfonamides; amines; N-oxides; hydrazines; hydrazides; hydrazones; azides; amides; ureas; amidines; guanidines; enamines; imides; isocyanates; isothi
  • Substituted ring groups such as substituted cycloalkyl, aryl, heterocyclyl and heteroaryl groups also include rings and ring systems in which a bond to a hydrogen atom is replaced with a bond to a carbon atom. Therefore, substituted cycloalkyl, aryl, heterocyclyl and heteroaryl groups may also be substituted with substituted or unsubstituted alkyl, alkenyl, and alkynyl groups as defined below.
  • Alkyl groups include straight chain and branched chain alkyl groups having from 1 to 12 carbon atoms, and typically from 1 to 10 carbons or, in some embodiments, from 1 to 8, 1 to 6, or 1 to 4 carbon atoms.
  • Alkyl groups may be substituted or unsubstituted.
  • straight chain alkyl groups include groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl groups.
  • branched alkyl groups include, but are not limited to, isopropyl, iso-butyl, sec-butyl, tert-butyl, neopentyl, isopentyl, and 2,2-dimethylpropyl groups.
  • substituted alkyl groups may be substituted one or more times with substituents such as those listed above, and include without limitation haloalkyl (e.g., trifluoromethyl), hydroxyalkyl, thioalkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, alkoxyalkyl, carboxyalkyl, and the like.
  • Cycloalkyl groups include mono-, bi- or tricyclic alkyl groups having from 3 to 12 carbon atoms in the ring(s), or, in some embodiments, 3 to 10, 3 to 8, or 3 to 4, 5, or 6 carbon atoms. Cycloalkyl groups may be substituted or unsubstituted.
  • Exemplary monocyclic cycloalkyl groups include, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups.
  • the cycloalkyl group has 3 to 8 ring members, whereas in other embodiments the number of ring carbon atoms range from 3 to 5, 3 to 6, or 3 to 7.
  • Bi- and tricyclic ring systems include both bridged cycloalkyl groups and fused rings, such as, but not limited to, bicyclo[2.1.1]hexane, adamantyl, decalinyl, and the like.
  • Substituted cycloalkyl groups may be substituted one or more times with non-hydrogen and non- carbon groups as defined above. However, substituted cycloalkyl groups also include rings that are substituted with straight or branched chain alkyl groups as defined above. Representative substituted cycloalkyl groups may be mono-substituted or substituted more than once, such as, but not limited to, 2,2-, 2,3-, 2,4- 2,5- or 2,6-disubstituted cyclohexyl groups, which may be substituted with substituents such as those listed above.
  • Cycloalkylalkyl groups are alkyl groups as defined above in which a hydrogen or carbon bond of an alkyl group is replaced with a bond to a cycloalkyl group as defined above. Cycloalkylalkyl groups may be substituted or unsubstituted. In some embodiments, cycloalkylalkyl groups have from 4 to 16 carbon atoms, 4 to 12 carbon atoms, and typically 4 to 10 carbon atoms. Substituted cycloalkylalkyl groups may be substituted at the alkyl, the cycloalkyl or both the alkyl and cycloalkyl portions of the group.
  • Alkenyl groups include straight and branched chain alkyl groups as defined above, except that at least one double bond exists between two carbon atoms. Alkenyl groups may be substituted or unsubstituted. Alkenyl groups have from 2 to 12 carbon atoms, and typically from 2 to 10 carbons or, in some embodiments, from 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.
  • Representative substituted alkenyl groups may be mono-substituted or substituted more than once, such as, but not limited to, mono-, di- or tri-substituted with substituents such as those listed above.
  • Cycloalkenyl groups include cycloalkyl groups as defined above, having at least one double bond between two carbon atoms.
  • Cycloalkenyl groups may 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 from 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.
  • Cycloalkenylalkyl groups are alkyl groups as defined above in which a hydrogen or carbon bond of the alkyl group is replaced with a bond to a cycloalkenyl group as defined above. Cycloalkenylalkyl groups may be substituted or unsubstituted. Substituted cycloalkenylalkyl groups may be substituted at the alkyl, the cycloalkenyl or both the alkyl and cycloalkenyl portions of the group. Representative substituted cycloalkenylalkyl groups may be substituted one or more times with substituents such as those listed above.
  • Alkynyl groups include straight and branched chain alkyl groups as defined above, except that at least one triple bond exists between two carbon atoms. Alkynyl groups may be substituted or unsubstituted. Alkynyl groups have from 2 to 12 carbon atoms, and typically from 2 to 10 carbons or, in some embodiments, from 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 ⁇ CCH 3 , -CH 2 C ⁇ CCH 3 , and -C ⁇ CCH 2 CH(CH 2 CH 3 ) 2 , among others.
  • Aryl groups are cyclic aromatic hydrocarbons that do not contain heteroatoms.
  • Aryl groups herein include monocyclic, bicyclic, and tricyclic ring systems.
  • Aryl groups may be substituted or unsubstituted.
  • aryl groups include, but are not limited to, phenyl, azulenyl, heptalenyl, biphenyl, fluorenyl, phenanthrenyl, anthracenyl, indenyl, indanyl, pentalenyl, and naphthyl groups.
  • aryl groups contain 6-14 carbons, and in others from 6 to 12 or even 6-10 carbon atoms in the ring portions of the groups.
  • the aryl groups are phenyl or naphthyl.
  • aryl groups includes groups containing fused rings, such as fused aromatic-aliphatic ring systems (e.g., indanyl, tetrahydronaphthyl, and the like).
  • Representative substituted aryl groups may be mono-substituted (e.g., tolyl) or substituted more than once.
  • monosubstituted aryl groups include, but are not limited to, 2-, 3-, 4-, 5-, or 6-substituted phenyl or naphthyl groups, which may be substituted with substituents such as those listed above.
  • Aralkyl groups are alkyl groups as defined above in which a hydrogen or carbon bond of an alkyl group is replaced with a bond to an aryl group as defined above.
  • Aralkyl groups may be substituted or unsubstituted.
  • aralkyl groups contain 7 to 16 carbon atoms, 7 to 14 carbon atoms, or 7 to 10 carbon atoms.
  • Substituted aralkyl groups may be substituted at the alkyl, the aryl or both the alkyl and aryl portions of the group.
  • Representative aralkyl groups include but are not limited to benzyl and phenethyl groups and fused (cycloalkylaryl)alkyl groups such as 4-indanylethyl.
  • Heterocyclyl groups include aromatic (also referred to as heteroaryl) and non-aromatic ring compounds containing 3 or more ring members, of which one or more is a heteroatom such as, but not limited to, N, O, and S. Heterocyclyl groups may be substituted or unsubstituted. In some embodiments, the heterocyclyl group contains 1, 2, 3 or 4 heteroatoms. In some embodiments, heterocyclyl groups include mono-, bi- and tricyclic rings having 3 to 16 ring members, whereas other such groups have 3 to 6, 3 to 10, 3 to 12, or 3 to 14 ring members.
  • Heterocyclyl groups encompass aromatic, partially unsaturated, and saturated ring systems, such as, for example, imidazolyl, imidazolinyl and imidazolidinyl groups.
  • the phrase “heterocyclyl group” includes fused ring species including those comprising 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 a heteroatom such as, but not limited to, quinuclidyl.
  • heterocyclyl groups that have other groups, such as alkyl, oxo or halo groups, bonded to one of the ring members, referred to as “substituted heterocyclyl groups.”
  • Heterocyclyl groups include, but are not limited to, aziridinyl, azetidinyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, thiazolidinyl, tetrahydrothiophenyl, tetrahydrofuranyl, dioxolyl, furanyl, thiophenyl, pyrrolyl, pyrrolinyl, imidazolyl, imidazolinyl, pyrazolyl, pyrazolinyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiazolyl, thiazolinyl, isothiazolyl, thiadiazolyl, o
  • substituted heterocyclyl groups may be mono-substituted or substituted more than once, such as, but not limited to, pyridyl or morpholinyl groups, which are 2-, 3-, 4-, 5-, or 6-substituted, or disubstituted with various substituents such as those listed above.
  • Heteroaryl groups are aromatic ring compounds containing 5 or more ring members, of which, one or more is a heteroatom such as, but not limited to, N, O, and S. Heteroaryl groups may 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, thiophenyl, benzothiophenyl, furanyl, benzofuranyl, indolyl, azaindolyl (pyrrolopyridinyl), indazolyl, benzimidazolyl, imidazopyridinyl (azabenzimidazolyl), pyrazolopyridinyl, triazolopyridinyl, benzotriazolyl, benzoxazolyl, benzothiazolyl, benzothiadiazolyl, imidazopyridinyl, isoxazolopyridinyl, thianaphthyl, purinyl,
  • Heteroaryl groups include fused ring compounds in which all rings are aromatic such as indolyl groups and include fused ring compounds in which only one of the rings is aromatic, such as 2,3-dihydro indolyl groups. Representative substituted heteroaryl groups may be substituted one or more times with various substituents such as those listed above. [0028] Heterocyclylalkyl groups are alkyl groups as defined above in which a hydrogen or carbon bond of an alkyl group is replaced with a bond to a heterocyclyl group as defined above. Heterocyclylalkyl groups may be substituted or unsubstituted.
  • Substituted heterocyclylalkyl groups may be substituted at the alkyl, the heterocyclyl or both the alkyl and heterocyclyl portions of the group.
  • Representative heterocyclyl alkyl groups include, but are not limited to, morpholin-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 heterocyclylalkyl groups may be substituted one or more times with substituents such as those listed above.
  • Heteroaralkyl groups are alkyl groups as defined above in which a hydrogen or carbon bond of an alkyl group is replaced with a bond to a heteroaryl group as defined above. Heteroaralkyl groups may be substituted or unsubstituted. Substituted heteroaralkyl groups may be substituted at the alkyl, the heteroaryl or both the alkyl and heteroaryl portions of the group. Representative substituted heteroaralkyl groups may be substituted one or more times with substituents such as those listed above.
  • Groups described herein having two or more points of attachment i.e., divalent, trivalent, or polyvalent
  • divalent alkyl groups are alkylene groups
  • divalent aryl groups are arylene groups
  • divalent heteroaryl groups are divalent heteroarylene groups
  • Substituted groups having a single point of attachment to the compound of the present technology are not referred to using the “ene” designation.
  • chloroethyl is not referred to herein as chloroethylene.
  • Alkoxy groups are hydroxyl groups (-OH) in which the bond to the hydrogen atom is replaced by a bond to a carbon atom of a substituted or unsubstituted alkyl group as defined above. Alkoxy groups may be substituted or unsubstituted. Examples of linear alkoxy groups include but are not limited to methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, and the like. Examples of branched alkoxy groups include but are not limited to isopropoxy, sec-butoxy, tert- butoxy, isopentoxy, isohexoxy, and the like.
  • cycloalkoxy groups include but are not limited to cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, and the like.
  • Representative substituted alkoxy groups may be substituted one or more times with substituents such as those listed above.
  • alkanoyl and alkanoyloxy as used herein can refer, respectively, to –C(O)– alkyl groups and –O–C(O)–alkyl groups, each containing 2–5 carbon atoms.
  • aryloyl and “aryloyloxy” refer to –C(O)–aryl groups and –O–C(O)–aryl groups.
  • aryloxy and arylalkoxy refer to, respectively, a substituted or unsubstituted aryl group bonded to an oxygen atom and a substituted or unsubstituted aralkyl group bonded to the oxygen atom at the alkyl. Examples include but are not limited to phenoxy, naphthyloxy, and benzyloxy. Representative substituted aryloxy and arylalkoxy groups may be substituted one or more times with substituents such as those listed above. [0034] The term “carboxylate” as used herein refers to a -COOH group.
  • esters refers to –COOR 70 and –C(O)O-G groups.
  • R 70 is a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl, heterocyclylalkyl or heterocyclyl group as defined herein.
  • G is a carboxylate protecting group.
  • Carboxylate protecting groups are well known to one of ordinary skill in the art. An extensive list of protecting groups for the carboxylate group functionality may be found in Protective Groups in Organic Synthesis, Greene, T.W.; Wuts, P. G.
  • amide includes C- and N-amide groups, i.e., -C(O)NR 71 R 72 , and –NR 71 C(O)R 72 groups, respectively.
  • R 71 and R 72 are independently hydrogen, or a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heterocyclylalkyl or heterocyclyl group as defined herein.
  • Amido groups therefore include but are not limited to carbamoyl groups (-C(O)NH 2 ) and formamide groups (-NHC(O)H).
  • the amide is – NR 71 C(O)-(C 1-5 alkyl) and the group is termed "carbonylamino," and in others the amide is – NHC(O)-alkyl and the group is termed "alkanoylamino.”
  • the term “nitrile” or “cyano” as used herein refers to the –CN group.
  • Urethane groups include N- and O-urethane groups, i.e., -NR 73 C(O)OR 74 and -OC(O)NR 73 R 74 groups, respectively.
  • R 73 and R 74 are independently a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heterocyclylalkyl, or heterocyclyl group as defined herein.
  • R 73 may also be H.
  • amine or “amino” as used herein refers to –NR 75 R 76 groups, wherein R 75 and R 76 are independently hydrogen, or a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heterocyclylalkyl or heterocyclyl group as defined herein.
  • the amine is alkylamino, dialkylamino, arylamino, or alkylarylamino. In other embodiments, the amine is NH 2 , methylamino, dimethylamino, ethylamino, diethylamino, propylamino, isopropylamino, phenylamino, or benzylamino.
  • sulfonamido includes S- and N-sulfonamide groups, i.e., -SO 2 NR 78 R 79 and – NR 78 SO 2 R 79 groups, respectively.
  • R 78 and R 79 are independently hydrogen, or a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heterocyclylalkyl, or heterocyclyl group as defined herein.
  • Sulfonamido groups therefore include but are not limited to sulfamoyl groups (-SO 2 NH 2 ).
  • the sulfonamido is –NHSO 2 -alkyl and is referred to as the "alkylsulfonylamino" group.
  • thiol refers to —SH groups
  • sulfides include —SR 80 groups
  • sulfoxides include –S(O)R 81 groups
  • sulfones include -SO 2 R 82 groups
  • sulfonyls include –SO 2 OR 83 .
  • R 80 , R 81 , R 82 , and R 83 are each independently a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl aralkyl, heterocyclyl or heterocyclylalkyl group as defined herein.
  • the sulfide is an alkylthio group, -S-alkyl.
  • urea refers to –NR 84 -C(O)-NR 85 R 86 groups.
  • R 84 , R 85 , and R 86 groups are independently hydrogen, or a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heterocyclyl, or heterocyclylalkyl group as defined herein.
  • amidine refers to –C(NR 87 )NR 88 R 89 and –NR 87 C(NR 88 )R 89 , wherein R 87 , R 88 , and R 89 are each independently hydrogen, or a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl aralkyl, heterocyclyl or heterocyclylalkyl group as defined herein.
  • guanidine refers to –NR 90 C(NR 91 )NR 92 R 93 , wherein R 90 , R 91 , R 92 and R 93 are each independently hydrogen, or a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl aralkyl, heterocyclyl or heterocyclylalkyl group as defined herein.
  • halogen or “halo” as used herein refers to bromine, chlorine, fluorine, or iodine.
  • the halogen is fluorine. In other embodiments, the halogen is chlorine or bromine.
  • hydroxyl as used herein can refer to –OH or its ionized form, –O – .
  • a “hydroxyalkyl” group is a hydroxyl-substituted alkyl group, such as HO-CH 2 -.
  • imide refers to –C(O)NR 98 C(O)R 99 , wherein R 98 and R 99 are each independently hydrogen, or a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl aralkyl, heterocyclyl or heterocyclylalkyl group as defined herein.
  • the term “imine” refers to –CR 100 (NR 101 ) and –N(CR 100 R 101 ) groups, 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, with the proviso that R 100 and R 101 are not both simultaneously hydrogen.
  • nitro as used herein refers to an –NO 2 group.
  • the term “trifluoromethyl” as used herein refers to –CF 3 .
  • trifluoromethoxy refers to –OCF 3 .
  • zido refers to –N 3 .
  • trifluoromethoxy refers to –N 3 .
  • zido refers to –N 3 .
  • trimhexo refers to –N 3 .
  • trimhexo refers to a –N(alkyl)3 group. A trialkylammonium group is positively charged and thus typically has an associated anion, such as halogen anion.
  • isocyano refers to –NC.
  • isothiocyano refers to –NCS.
  • penentafluorosulfanyl refers to –SF 5 .
  • a range includes each individual member.
  • a group having 1-3 atoms refers to groups having 1, 2, or 3 atoms.
  • a group having 1-5 atoms refers to groups having 1, 2, 3, 4, or 5 atoms, and so forth.
  • molecular weight 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.
  • compounds of the present technology may exhibit the phenomena of tautomerism, conformational isomerism, geometric isomerism, and/or stereoisomerism.
  • Tautomers refers to isomeric forms of a compound that are in equilibrium with each other. The presence and concentrations of the isomeric forms will depend on the environment the compound is found in and may be different depending upon, for example, whether the compound is a solid or is in an organic or aqueous solution.
  • quinazolinones may exhibit the following isomeric forms, which are referred to as tautomers of each other: .
  • guanidines may exhibit the following isomeric forms in protic organic solution, also referred to as tautomers of each other:
  • Stereoisomers of compounds also known as optical isomers
  • compounds used in the present technology include enriched or resolved optical isomers at any or all asymmetric atoms as are apparent from the depictions. Both racemic and diastereomeric mixtures, as well as the individual optical isomers can be isolated or synthesized so as to be substantially free of their enantiomeric or diastereomeric partners, and these stereoisomers are all within the scope of the present technology.
  • the compounds of the present technology may exist as solvates, especially hydrates. Hydrates may form during manufacture of the compounds or compositions comprising the compounds, or hydrates may form over time due to the hygroscopic nature of the compounds.
  • colloidal silica may exist as organic solvates as well, including DMF, ether, and alcohol solvates, among others.
  • the identification and preparation of any particular solvate is within the skill of the ordinary artisan of synthetic organic chemistry.
  • colloidal stability is a more stringent requirement. Indeed, as shown by the Comparative Examples disclosed herein, functionalized colloidal silica available prior to the present disclosure suffers stability issues in such extreme conditions.
  • colloidal silica particles have been used in coating or paint formulations, such as described in U.S. Pat. Nos.8,436,088, 9,598,557, and 10,487,240.
  • paint formulations especially in aqueous systems that contain latex binder particles, various components are present and the components such as surfactants, coalescent agents, defoamers, thickeners, etc., may undesirably interact with unmodified colloidal silica and affect the stability of the colloidal system.
  • Silanized colloidal silicas for example, as disclosed in U.S. Pat. No.9,249,317) have been discussed as useful in paint formulations too, but the colloidal stability may still be an issue.
  • the present technology addresses the above-discussed deficiencies-including in relation to enhanced oil recovery, metal surface treatments (e.g., anticorrosion metal surface treatments), electroplating, and coatings-as well as provides additional advantages.
  • the present technology provides a composition that includes water and a functionalized colloidal silica.
  • the functionalized colloidal silica includes silica particles (where each silica particle includes a surface) and a structural unit according to Formula I
  • R 1 is -CH 2 (CHOH) x CH 2 OH where x is 1, 2, 3, 4, 5, or 6, where y + z is 0, 1, 2, 3, 4, or 5,
  • the composition may include a pH of about 2 to about 11.
  • the composition may include a pH of about 3.5 to about 11 or about 7 to about 10.
  • the composition may include a pH of about 11 or lower; thus, the composition herein may include a pH of about 6.5 to about 10.5, 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 range including and/or in-between any two of these values.
  • the functionalized colloidal silica may include a neutral or negative zeta potential.
  • the negative zeta potential of any such embodiment herein may 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, or any range including and/or in-between any two of these values.
  • mV millivolt
  • the functionalized colloidal silica may include a zeta potential of about 0 mV to about ⁇ 60 mV.
  • the silica particles may have a median diameter as determined by dynamic light scattering or disc centrifuge analysis of about 1 nm to about 100 nm (D50 on a volume basis).
  • the median diameter of the silica particles as 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 range including and/or in-between any two of these values.
  • the silica particles may have a Sears surface area of about 25 m 2 /g to about 1,200 m 2 /g. 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.
  • the silica particles of any embodiment herein may have a Sears surface area of about 25 m 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, 150 m 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, 600 m 2 /g, 650 m 2 /g, 700 m 2 /g, 750 m 2
  • the composition of any embodiment herein may include a number of structural units according to Formula I per nm 2 surface area of about 0.8 to about 3.5. Accordingly, the composition of any embodiment herein may include a number of structural units according to Formula I per nm 2 surface area of 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 including and/or in-between any two of these values.
  • composition of any embodiment herein may include mass percentage composition of carbon as determined by elemental analysis of about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, or any range including and/or between any two of these values.
  • R 1 is -CH 2 (CHOH) x CH 2 OH where x is 1, 2, 3, 4, 5, or 6, .
  • R 1 may be -CH 2 (CHOH) x CH 2 OH where x is 1, 2, 3, 4, 5, or 6-for example, x may be 1 (arising from glycerol), x may be 2 (e.g., arising from erythritol), x may be 3 (e.g., arising from xylitol), x may be 4 (e.g., arising from sorbitol or mannitol), or x may be 5.
  • x may be 1 (arising from glycerol)
  • x may be 2 (e.g., arising from erythritol)
  • x may be 3 (e.g., arising from xylitol)
  • x may be 4 (e.g., arising from sorbitol or mannitol)
  • x may be 5.
  • R 1 may alternatively be where y + z is 0, 1, 2, 3, 4, or 5-for example, y may be 0 and z may be 0, y may be 0 and z may be 1, 2, 3, 4, or 5, y may be 1 and z may be 1, 2, 3, or 4, or y may be 2 and z may be 1, 2, or 3.
  • R 1 may alternatively ; thus, for example, R 1 may arising from D-glucose), H (e.g., arising from D-mannose), or (e.g., arising from D-galactose).
  • R 1 may alternatively b where q + r is 2-for example, q may be 0 and r may be 2, q may be 1 and r may be 1, or q may be 2 and r may be 0.
  • R 1 may alternatively such as (e.g., arising from D-fructose).
  • R 1 may alternatively be -24-
  • R 2 is hydroxyl, methoxy, ethoxy, propoxy, phenoxy, or G 2 .
  • R 3 is hydroxyl, methoxy, ethoxy, propoxy, phenoxy, or G 3 .
  • R 2 is G 2 .
  • R 3 is hydroxyl.
  • the silica particles may include at least one structural unit according to Formula Ia, Ib, Ic, Id, or Ie
  • the silica particles further include at least one structural unit according to Formula II wherein R 4 is hydroxyl, alkoxy, aryloxy, or G 5 ; R 5 is hydroxyl, alkoxy, aryloxy, or G 6 ; G 4 , G 5 , and G 6 are each independently an oxygen atom of the surface of the silica particle, where G 4 , G 5 , and G 6 are not the same oxygen atom. [0079] In any embodiment herein, it may be that R 4 is hydroxyl, methoxy, ethoxy, propoxy, phenoxy, or G 5 .
  • composition of any embodiment herein may include about 0.1 wt% to about 50 wt% of the functionalized colloidal silica.
  • the composition may include the functionalized colloidal silica in an amount 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 range including and/or in-between any two of these values.
  • the composition may include the functionalized colloidal silica in an amount of about 0.1 wt% to about 30 wt%, about 5 wt% to about 30 wt%, about 10 wt% to about 30 wt%, or about 0.1 wt% to about 5 wt%.
  • the composition of any embodiment herein may be stable to aging for 24 hours or longer at temperature of 80 °C when the composition comprises a salt solution at an ionic strength of 0.5 to 3.0.
  • the salt solution of any embodiment herein may include NaCl, CaCl 2 , MgSO 4 , or a combination of any two or more thereof.
  • the ionic strength may be 0.5, 1.0, 2.0, 3.0, or any range including and/or in-between any two of these values.
  • the composition may be at a pH of about 2 to about 11 or about 7 to about 10; including about 7.0, about 7.1, about 7.2, about 7.3, about 7.4, about 7.5, about 7.6, about 7.7, about 7.8, about 7.9, about 8.0, about 8.1, about 8.2, about 8.3, about 8.4, about 8.5, about 8.6, about 8.7, about 8.8, about 8.9, about 9.0, about 10.1, about 10.2, about 10.3, about 10.4, about 10.5, about 10.6, about 10.7, about 10.8, about 10.9, about 11.0, or any range including and/or in-between any two of these values.
  • the present technology provides a method of making a functionalized colloidal silica (for example, a method of making a composition of any embodiment herein).
  • the method includes contacting a colloidal silica with a silane according to Formula III to yield the functionalized colloidal silica where R 1 is -CH 2 (CHOH) x CH 2 OH where x is 1, 2, 3, 4, 5, or 6, where y + z is 0, 1, 2, 3, 4, or 5,
  • the colloidal silica may be an aqueous colloidal silica.
  • the method may include contacting the colloidal silica with a silane according to Formula III in the presence of an acid catalyst.
  • the acid catalyst may include sulfuric acid, hydrochloric acid, nitric acid, and/or methanesulfonic acid.
  • the acid catalyst may be present in a concentration of about 0.01 M, 0.1 M, 0.5 M, 1.0 M, 1.5 M, 2.0 M, or any range including and/or in-between any two of these values.
  • R 6 , R 7 , and L 1 are each independently alkoxy or aryloxy.
  • R 1 is -CH 2 (CHOH) x CH 2 OH where x is 1, 2, 3, 4, 5, or 6,
  • R 1 may be -CH 2 (CHOH) x CH 2 OH where x is 1, 2, 3, 4, 5, or 6-for example, x may be 1 (arising from glycerol), x may be 2 (e.g., arising from erythritol), x may be 3 (e.g., arising from xylitol), x may be 4 (e.g., arising from sorbitol or mannitol), or x may be 5.
  • R 1 may alternatively be
  • R 1 may alternatively ; thus, for example, R 1 may , arising from D-glucose),
  • R 1 may alternatively where q + r is 2-for example, q may be 0 and r may be 2, q may be 1 and r may be 1, or q may be 2 and r may be 0.
  • R 1 may alternatively such as , arising from D-fructo 1 se). R may alternatively be
  • R 2 is hydroxyl, methoxy, ethoxy, propoxy, phenoxy, or G 2 .
  • R 3 is hydroxyl, methoxy, ethoxy, propoxy, phenoxy, or G 3 .
  • R 2 is G 2 .
  • R 3 is hydroxyl.
  • R 6 is hydroxyl, methoxy, ethoxy, propoxy, or phenoxy.
  • R 7 is hydroxyl, methoxy, ethoxy, propoxy, or phenoxy.
  • L 1 is methoxy, ethoxy, propoxy, or phenoxy.
  • the functionalized colloidal silica may include a surface as well as a structural unit according to Formula I where R 1 is -CH 2 (CHOH) x CH 2 OH where x is 1, 2, 3, 4, 5, or 6, where y + z is 0, 1, 2, 3, 4, or 5,
  • R 2 is hydroxyl, alkoxy, aryloxy, or G 2 ;
  • R 3 is hydroxyl, alkoxy, aryloxy, or G 3 ;
  • G 1 , G 2 , and G 3 are each independently an oxygen atom of the surface of the silica particle, where G 1 , G 2 , and G 3 are not the same oxygen atom.
  • R 2 is hydroxyl, methoxy, ethoxy, propoxy, phenoxy, or G 2 .
  • R 3 is hydroxyl, methoxy, ethoxy, propoxy, phenoxy, or G 3 .
  • the functionalized colloidal silica may include at least one structural unit according to Formula Ia, Ib, Ic, Id, or Ie
  • the functionalized colloidal silica further includes at least one structural unit according to Formula II wherein R 4 is hydroxyl, alkoxy, aryloxy, or G 5 ; R 5 is hydroxyl, alkoxy, aryloxy, or G 6 ; G 4 , G 5 , and G 6 are each independently an oxygen atom of the surface of the silica particle, where G 4 , G 5 , and G 6 are not the same oxygen atom.
  • R 4 is hydroxyl, methoxy, ethoxy, propoxy, phenoxy, or G 5 .
  • the method of any embodiment herein may include contacting the colloidal silica with the silane in a medium, where the medium includes water and/or a polar organic solvent (e.g., a polar organic solvent miscible with water).
  • a polar organic solvent e.g., a polar organic solvent miscible with water
  • the polar organic solvent may include methanol, ethanol, propanol, ethylene glycol, acetone, tetrahydrofuran, 1,4-dioxane, dimethylformamide, N- methylpyrrolidone, or a combination of any two or more thereof.
  • the method of any embodiment herein may include contacting about 1.5 to about 3.0 molecules silane per 1 nm 2 colloidal silica surface area.
  • the method may include contacting an amount of molecules silane per 1 nm 2 colloidal silica 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 in-between any two of these values.
  • the method of any embodiment herein may provide a composition comprising water and the functionalized colloidal silica (e.g., of any embodiment of the composition aspect of the present technology).
  • the composition may be stable to aging for 24 hours or longer at temperature of 80 °C when the composition comprises a salt solution at an ionic strength of 0.5 to 3.0.
  • the salt solution of any embodiment herein may include NaCl, CaCl 2 , MgSO 4 , or a combination of any two or more thereof.
  • the ionic strength may be 0.5, 1.0, 2.0, 3.0, or any range including and/or in-between any two of these values.
  • the composition may be at a pH of about 2 to about 11 or about 7 to about 10; including about 7.0, about 7.1, about 7.2, about 7.3, about 7.4, about 7.5, about 7.6, about 7.7, about 7.8, about 7.9, about 8.0, about 8.1, about 8.2, about 8.3, about 8.4, about 8.5, about 8.6, about 8.7, about 8.8, about 8.9, about 9.0, about 10.1, about 10.2, about 10.3, about 10.4, about 10.5, about 10.6, about 10.7, about 10.8, about 10.9, about 11.0, or any range including and/or in-between any two of these values.
  • the method of any embodiment herein may include contacting a colloidal silica with a silane according to Formula III to yield an initial mixture, the initial mixture including the functionalized colloidal silica as well as unreacted silane, a silane not bonded to the colloidal silica, an impurity, or a combination of any 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, the silane not bonded to the colloidal silica, impurity, or a combination of any two or more thereof.
  • the present technology provides a functionalized silica prepared according to a method of any embodiment disclosed herein, such as a functionalized colloidal silica of any embodiment disclosed herein.
  • a formulation for use in enhanced oil recovery, metal surface treatment, electroplating, coating, and/or paint wherein the formulation includes a composition according to any embodiment disclosed herein, a functionalized colloidal silica of any embodiment disclosed herein, and/or a functionalized silica prepared according to a method of any embodiment disclosed herein.
  • a composition, a functionalized colloidal silica, and/or a functionalized silica of the present technology may be reactive with other components included in a coating and/or paint formulation (e.g., with isocyanates in a polyurethane coating formulation and/or polyurethane paint formulation) and thus may provide improved performance and/or mechanical properties in layers formed from the formulation.
  • a coating and/or paint formulation e.g., with isocyanates in a polyurethane coating formulation and/or polyurethane paint formulation
  • 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.
  • EXAMPLES [0098] Commercially available LUDOX colloidal silica grades were used in these examples. These products were supplied by W.R. Grace &Co.
  • LUDOX SM a value of 220 m 2 /g surface area for the 12 nm grades of colloidal silica (e.g. LUDOX HS-40 or LUDOX AM or LUDOX CL), a value of 140 m 2 /g surface area for the 22 nm grade of colloidal silica (e.g. LUDOX TM-40), and a value of 75 m 2 /g surface area for the 40 nm grade (e.g. LUDOX PW-50 (X), a colloidal silica grade with polydispersed, different sized silica particles).
  • colloidal silica e.g. LUDOX HS-40 or LUDOX AM or LUDOX CL
  • 140 m 2 /g surface area for the 22 nm grade of colloidal silica e.g. LUDOX TM-40
  • 75 m 2 /g surface area for the 40 nm grade e.g. LUDOX PW-50 (X
  • the treatment level is defined as Number of Molecules (NM) per square nanometer of solid particle surface area, or NM/nm 2 .
  • NM Number of Molecules
  • the procedure for purifying the functionalized colloidal silica included using Spectrum MidiKros hollow fiber membranes (e.g. D02-E050-10-S mPES/50 kD molecular weight cut-off (MWCO) with surface area of 75 cm 2 ), though other types of membranes with suitable molecular weight cutoff may also be used).
  • the colloidal silica samples were passed through the membranes via Tygon tubing with a peristaltic pump under a pressure of less than 25 psi.
  • the typical solids for the colloidal silica were between 5- 25%, and fresh deionized water was added to make up the volume lost in the permeates.
  • 5-10 volumes of permeates were accumulated against the initial total volume of the colloidal samples before the completion of the ultrafiltration process.
  • Potentiometric titrations were performed starting at the sol nascent pH and run either up to pH 11 (for sols with nascent pH on the acid side) or down to pH 3 (for sols with nascent pH on the alkaline side) and then back to either pH 11 or 3, respectively.
  • the pre-loaded instrument parameters for SiO 2 (silica, amorphous-typical) and water were used by the software. Titrations were done with 0.1 N HCl and 0.1 N NaOH.
  • DLS dynamic light scattering
  • Solutions of 2% wt colloidal solids were prepared by dilution of the original sols with deionized water. Once diluted, the sols were filtered with 0.45-micron syringe filter into the measurement cuvette. Measurements were accumulated for 60 seconds. Values reported are D50 on a volume basis.
  • Nuclear magnetic resonance (NMR) was used to characterize surface groups of the functionalized colloidal particles. The functionalized colloidal silica samples had approximately 20% solids. Prior to the analysis, the samples were subjected to an ultrafiltration purification procedure to remove unreacted species. The samples were diluted to around 10% with D 2 O and they were analyzed on a Bruker Avance III 400 MHz NMR instrument.
  • FIG.1 provides a generalized reaction scheme for functionalizing silica with sugar alcohols.
  • Example 1 (Glycerol modification on LUDOX SM at 1.5 NM/nm 2 TL)
  • MSA 2 M methanesulfonic acid
  • Reaction Scheme I illustrates the chemical transformation from the example.
  • glycidylsilane and glycerol in water with catalytic amount of MSA acid, since both water molecule and glycerol molecule would compete and react with epoxy ring of the glycidylsilane, it was expected that the formation of glycerol silane (from the reaction with glycerol) and diol silane (from the reaction with water) could happen, and the ratio of the two new silanes might depend on the amount of the water in the system, and the reaction conditions.
  • Example 2 (Erythritol modification on LUDOX SM at 1.5 NM/nm 2 TL) [0111] In a 50ml beaker with a stir bar, slowly added the 4.08 g of 2 M MSA and 4.08 g of deionized water. The beaker was heat to around 55-60°C with a water bath. Then, while stirring, 10.19 g of meso-erythritol were added in small portions. Once the solids were dissolved and the solution is clear, stopped the heating of the water bath. Slowly added 6.12 g of (3- glycidyloxypropyl)trimethoxysilane dropwise with vigorous mixing (the reaction was strongly exothermic).
  • Reaction Scheme II illustrates the chemical transformation from the example. As shown, during the reaction of glycidylsilane and erythritol in water with catalytic amount of MSA acid, since both water molecule and erythritol molecule would compete and react with epoxy ring of the glycidylsilane, it was expected that the formation of erythritol silane (from the reaction with erythritol) and diol silane (from the reaction with water) could happen, and the ratio of the two new silanes might depend on the amount of the water in the system, and the reaction conditions.
  • Example 3 (Sorbitol modification on LUDOX SM at 1.5 NM/nm 2 TL) [0114] In a 50 mL beaker with a stir bar, slowly added the 4.08 g of 2 M MSA and 1.22 g of deionized water. The beaker was heat to around 55-60°C with a water bath. Then, while stirring, 10.19 g of D-sorbitol were added in small portions. Once the solids are dissolved and the solution was clear, stopped the heating of the water bath. Slowly added 6.12 g of (3- glycidyloxypropyl)trimethoxysilane dropwise with vigorous mixing (the reaction is strongly exothermic).
  • Reaction Scheme III illustrates the chemical transformation from the example. As shown, during the reaction of glycidylsilane and sorbitol in water with catalytic amount of MSA acid, since both water molecule and glycerol molecule would compete and react with epoxy ring of the glycidylsilane, it was expected that the formation of sorbitol silane (from the reaction with sorbitol) and diol silane (from the reaction with water) could happen, and the ratio of the two new silanes might depend on the amount of the water in the system, and the reaction conditions.
  • Reaction Scheme IV illustrates the chemical reaction from this example.
  • Table 1 shows the carbon contents of the corresponding dried samples in Examples 1-3 and Comparative Example 1. Table 1. [0120] As shown, at the same treatment level, samples in Examples 1-3 had higher amounts of organic groups, indicated by increased carbon content (C%), than the sample in Comparative Example 1. Larger sugar molecules had a higher C%: Example 3 > Example 2 > Example 1 > Comparative Example 1.
  • FIG.2 shows 13 C-NMR spectra of a dispersion of the sorbitol-functionalized colloidal silica of Example 3 (top spectrum), sorbitol solution in D 2 O (middle spectrum), and a dispersion of the diol-functionalized colloidal silica of Comparative Example 1 (bottom spectrum) in the region of 60 ppm to 80 ppm. Carbon atoms assigned numbers in the middle spectrum were connected to OH groups. As shown, since the “free”, unbonded sorbitol had been removed through ultrafiltration, the top spectrum showed a similar pattern to the molecule sorbitol, indicating the presence of bonded surface functional groups.
  • Colloidal stability is defined stable, turbid (less stable) or gelled (not stable) after aging at these 3 different temperatures.
  • stable means no visual or physical changes was observed in the colloidal dispersion after aging.
  • turbid means that the colloidal dispersion became more whitish in color and less transparent but with no visible settlement or viscosity increase observed in the samples.
  • gelled means that the viscosity of the colloidal dispersion increased to the extent that the whole sample did not flow as a liquid. Table 2 lists the salt stability test results.
  • Example 4 (Glycerol modification on LUDOX HS-40 at 1.7 NM/nm 2 TL) [0128] A similar procedure was followed as in Example 2, except that reagent amounts were: Glycerol: 7.5 g 2 M MSA: 1.5 g Glycidylsilane: 4.5 g HS-40: 75 g (net of 30 g of SiO 2 ) [0129]
  • Example 5 (Erythritol modification on LUDOX HS-40 at 1.7 NM/nm 2 TL) [0130] A similar procedure was followed as in Example 1, except that reagent amounts were: Erythritol: 7.5 g 2M MSA: 3.0 g Deionized water: 3.0 g Glycidylsilane: 4.5 g HS-40: 75 g (net of 30 g of SiO 2 ) [0131]
  • Example 6 (Sorbitol modification on LUDOX HS-40 at 1.7 NM/nm 2 TL)
  • Table 3 shows the carbon contents of the corresponding dried samples in Examples 4-6 and Comparative Example 2. Table 3.
  • samples in Examples 4-6 had higher amounts of organic groups, indicated by higher C% contents, than the sample in Comparative Example 2, and larger sugar molecules had higher C%: Example 6 > Example 5 > Example 4 > Comparative Example 2.
  • FIG.3 shows the plots of zeta titrations vs. pH for unfunctionalized HS-40 starting colloidal sample and Examples 4-6 and Comparative Example 2. As shown, these samples have similar surface charge pattern as that of HS-40, except that the net charges were less negative than that of HS-40.
  • the sugar alcohol modified HS-40 samples have exact the same pattern as that of the diol sample (Comparative Example 2) These modifications are based on neutral molecules, and they do not affect the particle surface charge properties. On the other hand, since some of the surface silanols are bonded with these new silanes, the net ionizable/titratable groups are reduced. Thus, these surface modified samples exhibit less negative charge than that of the HS-40 at the same pHs.
  • FIG.4 shows the plots of acid-base titration results for unfunctionalized HS-40 starting colloidal sample and Examples 4-6 and Comparative Example 2. As shown, the samples in Examples 4-6 have similar natural pH.
  • Example 7 (Sorbitol modification on LUDOX HS-40 at 1.7 NM/nm 2 TL, 100 g net SiO2 scale) [0140] A procedure similar to what were described in Examples 1 and 4 were followed, except the larger size beakers were used. The amounts of reagents were listed in Table 4. After purification, the sample had a carbon content of 4.83% in its dried form. Table 4. [0141]
  • Example 8 (Sorbitol modification on LUDOX HS-40 at 1.7 NM/nm 2 TL, 500 g net SiO2 scale) [0142] A procedure similar to what were described in Examples 1 and 4 were followed, except that larger amounts and large size beakers were used. The amounts of reagents were listed in Table 5.
  • Example 9 (Sugar modification on LUDOX HS-40 at 1.7 NM/nm 2 TL) [0144] To a 20 mL vial containing a magnetic stir bar and 0.9 g of deionized water was added 3 g of 2M methanesulfonic acid with continuous magnetic stirring. The vial was then warmed to 50 °C via water bath, whereafter 7.5 grams of sucrose was added with continuous magnetic stirring and maintained until disappearance of all solids.
  • Reaction Scheme V illustrates the expected reaction (but does not depict the stereochemistry). As shown, sucrose is expected to undergo acidic hydrolysis into D-glucose and D-fructose in the 20 mL vial.
  • Reaction Scheme V only depicts one product of D-glucose reacting with the glycidylsilane and only depicts one product of D-fructose reacting with the glycidylsilane.
  • Example 10 D-glucose modification on LUDOX HS-40 at 1.7 NM/nm 2 TL
  • the procedure of Example 9 was repeated using D-glucose instead of sucrose. After purification, the sample had a carbon content of 4.75% in its dried form.
  • Salt Stability Test of Samples from Examples 9 and 10 [0150] The colloidal stability of samples of Examples 9 and 10 was then evaluated in accordance with the procedure described above in “Salt Stability Test of Examples 1-3, Comparative Example 1 and HS-40 Starting Material” at 80 °C overnight, and using similar protocols also evaluated at pH 2 at 80 °C overnight (where samples were acidified via addition of dilute aqueous hydrochloric acid to pH 2 and any NaCl indicated was added after such acidification). Table 6 below summarizes the stability test results. Table 6.

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Abstract

La présente divulgation concerne des compositions qui comprennent de l'eau et une silice colloïdale à fonction polyol, la silice colloïdale à fonction polyol comprenant des particules de silice (chaque particule de silice comprenant une surface) ainsi que des unités structurales selon la formule (I). La présente divulgation concerne également des procédés de fabrication de compositions de la présente technologie.
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