Note: Descriptions are shown in the official language in which they were submitted.
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FUNCTIONALIZED SILICATE NANOPARTICLE COMPOSITION, REMOVING AND
EXFOLIATING ASPHALTENES WITH SAME
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Application No. 14/659919,
filed
on March 17, 2015, which is incorporated herein by reference in its entirety.
BACKGROUND
[0002] Asphaltenes are a major component in crude oil, and there is general
agreement as to the deleterious effects of asphaltenes in the reduction of oil
extraction and
processing in the petrochemical industry. Asphaltenes can deposit in the pores
of formations,
blocking the flow of fluids. Additionally, asphaltenes can precipitate from a
stream of oil and
coat boreholes, production tubing, and transport lines. Moreover, in a
processing facility,
asphaltenes can foul processing equipment and poison catalysts.
[0003] Asphaltene molecules have been widely reported as having a fused
polyaromatic ring system and containing heteroatoms such as sulfur, oxygen,
nitrogen, and
the like. The heteroatoms may be part of the aromatic ring system or part of
other
carbocyclic rings, linking groups, or functional groups. Two structural motifs
for asphaltene
molecules are the so-called continental and archipelago structures. In the
continental
structure, alkyl chains connect to and branch from a central polyaromatic ring
system, which
is believed to contain several fused aromatic rings, e.g., 5 or more aromatic
rings. In the
archipelago structure, multiple polyaromatic ring systems are connected by
alkyl chains that
may contain a heteroatom, and additional alkyl chains extend freely from the
polyaromatic
rings. The number of fused aromatic rings in the continental structure can be
greater than the
number of fused aromatic rings in the archipelago structure.
[0004] In addition to the aromatic regions of the asphaltenes, heteroatoms
provide the
asphaltenes with polar regions, and the terminal alkyl chains provide
hydrophobic regions.
Consequently, it is believed that asphaltene molecules aggregate into various
micellular
structures in oil, with the alkyl chains interacting with the aliphatic oil
components. Resin
from the oil can insert between aromatic planes of neighboring asphaltene
molecules in
asphaltene aggregates, aiding in maintaining their micellular structure.
Asphaltenes can
precipitate from oil in structures where asphaltene molecules form stacked
layers having
aligned aromatic regions and aligned aliphatic regions.
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[0005] Materials and methods for treating and removal of asphaltenes from oil
environments such as a reservoir would be well received in the art.
BRIEF DESCRIPTION
[0006] The above and other deficiencies of the prior art are overcome by, in
an
embodiment, a process for removing an asphaltene particle from a substrate,
the process
comprising: contacting a silicate nanoparticle with a chemical group to form a
functionalized
silicate nanoparticle, the chemical group comprising: a first portion; and a
second portion
comprising an aromatic moiety or a nonaromatic moiety, the first portion being
directly
bonded to the silicate nanoparticle in the functionalized silicate
nanoparticle; and the second
portion comprising a moiety of a guanidine, a guanidinium salt, a biguanidine,
a
biguanidinium salt, or a sulfonium salt. contacting the asphaltene particle
with the
functionalized silicate nanoparticle, the asphaltene particle being disposed
on the substrate;
interposing the functionalized silicate nanoparticle between the asphaltene
particle and the
substrate; and separating the asphaltene particle from the substrate with the
functionalized
silicate nanoparticle to remove the asphaltene particle from the substrate.
[0007] In another embodiment, a composition comprises: a functionalized
silicate
nanoparticle comprising a reaction product of a silicate nanoparticle; and a
functionalization
compound comprising quaternary ammonium salt, quaternary phosphonium salt,
alkoxy
silane, halide, guanidine, guanidinium salt, biguanidine, biguanidinium salt,
sulfonium salt,
or a combination thereof; and a fluid, wherein the functionalization compound
includes a
chemical group comprising: a first portion, the first portion being directly
bonded to the
silicate nanoparticle in the functionalized silicate nanoparticle; and a
second portion
comprising: an aromatic moiety or a nonaromatic moiety, and the composition is
effective to
remove an aromatic compound from a substrate comprising a metal, composite,
sand, rock,
mineral, glass, formation, downhole element, or a combination thereof
[0008] A process for removing an asphaltene particle from a substrate
comprises:
contacting a silicate nanoparticle with a chemical group to form a
functionalized silicate
nanoparticle, the chemical group comprising: a first portion; and a second
portion comprising
a nonaromatic moiety, the first portion being directly bonded to the silicate
nanoparticle in
the functionalized silicate nanoparticle; and the second portion comprising a
moiety of a
guanidine, a guanidinium salt, a biguanidine, a biguanidinium salt, or a
sulfonium salt;
contacting the asphaltene particle with the functionalized silicate
nanoparticle, the asphaltene
particle being disposed on the substrate; interposing the functionalized
silicate nanoparticle
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between the asphaltene particle and the substrate; and separating the
asphaltene particle from
the substrate with the functionalized silicate nanoparticle to remove the
asphaltene particle
from the substrate.
DETAILED DESCRIPTION
[0009] A detailed description of one or more embodiments is presented herein
by way
of exemplification and not limitation.
[0010] An asphaltene particle includes any collection of asphaltene molecules,
for
example, a micelle, precipitate, layered asphaltene molecules, aggregate,
cluster, and the like.
Interactions among the asphaltene molecules in an asphaltene particle can
include hydrogen
bonding, dipole-dipole interactions, and 7C-7C interactions. Without wishing
to be bound by
theory, disruption of these interactions can lead to exfoliation of an
asphaltene molecule from
the asphaltene particle. Since asphaltenes form layered aggregates that
resemble the layered
sheet structure of graphite, perturbing the layered asphaltene structure
allows for asphaltene
production from decomposed, e.g., exfoliated asphaltene aggregates. Such
deagglomeration
is useful for extraction of oil from an oil environment, e.g., a formation, as
well as for
restoration of the permeability of a plugged or flow-constricted reservoir.
The methods and
compositions herein are applicable to a multitude of environments such as
downhole as well
as to a ground environment.
[0011] It has been found that perturbing the internal structure of asphaltene
particles,
for example, in a micelle or other aggregate, can lead to increased quality of
oil containing
asphaltenes. Further, degradation of asphaltene aggregates herein enhances
production of
petroleum fluid in a downhole, subsurface, or ground environment. Furthermore,
removal of
asphaltene from pores of a rock formation, within a reservoir, or from a
sidewall of a tubular,
production tubing, borehole, or transportation tube can improve the
permeability of such
structures, leading to increased quality of oil as well as enhanced oil
recovery from, e.g., a
reservoir.
[0012] Moreover, without wishing to be bound by theory, it is believed that
heteroatoms in the asphaltene structure interact strongly with various
materials such as
metals, minerals, and polar surfaces. Therefore, asphaltenes coat rock
formations, sand,
metal, and polymer components such as tubulars, sand screens, or packers.
These deleterious
adhesions lead to equipment malfunction, failure, or flow blockage. In order
to alleviate this
issue, a composition herein can separate and remove the asphaltene particles
that interact,
such as by adsorption or blockage, with such items or materials.
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[0013] In an embodiment, a composition includes a functionalized silicate
nanoparticle and a fluid. The functionalized silicate nanoparticle is a
reaction product of a
silicate nanoparticle and a functionalization compound. The functionalization
compound
includes a chemical group that has a first portion, e.g., a linker, and a
second portion (e.g., a
tail), which includes an aromatic or a nonaromatic moiety. The first portion
is directly
bonded to the silicate nanoparticle in the functionalized silicate
nanoparticle. The
composition is effective to remove an aromatic or olefin compound, e.g., an
asphaltene, from
a substrate. The substrate can be a metal, composite, sand, rock, mineral,
glass, formation,
downhole element, or a combination thereof
[0014] As used herein, the term "aromatic" includes an aryl or heteroaryl
group.
Thus, an aromatic compound includes an aryl moiety or heteroaryl moiety.
[0015] The functionalization compound can have a structure of formula 1,
formula 2,
formula 3, formula 4 or a salt thereof, formula 5 or a salt thereof, formula 6
or a salt thereof,
or formula 7:
(Ar¨L)¨A X-
a I
(R1)b
(1),
m a I
(R1)1u,
(2),
Ar¨L11¨X
(3),
R5
Ri
(
R2 N-R4
R3 (4)
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R8 R12
R6 N R11 N¨R13
(
R7 7¨Rio N¨Ria
R9 (5)
R17
R15 N R19
(/N¨R21
R16
R18 N¨R20 (6)
R24
R22¨
R23 (7)
R25)¨Si 10-FG
m
a /b
(8)
wherein
a is an integer from 1 to 4;
b is an integer from 0 to 3;
the sum of a and b is 4 (i.e., a + b = 4) so that the valence of A and Si is
completely
filled and not exceeded
m is 0 or 1, n is independently an integer from 0 to 20;
Ar is an aromatic moiety or a nonaromatic moiety, wherein each Ar is the same
or
different, and when Ar is an aromatic moiety, Ar is independently a C6 to C30
aryl group, C3
to C30 heteroaryl, or combination thereof;
L is a linker group, wherein each L is the same or different, and L is
independently a
bond, C1 to C30 alkylene, C3 to C30 cycloalkenylene, C1 to C30 fluoroalkylene,
C3 to C30
cycloalkylene, C3 to C30 heterocycloalkylene, C6 to C30 arylene, C6 to C40
aralkylene, C6
to C30 aryleneoxy, C3 to C30 heteroarylene, C6 to C40 heteroaralkylene, C2 to
C30
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alkenylene, C2 to C30 alkynylene, C1 to C30 amide, amine, C1 to C30
oxyalkylene, C1 to
C30 oxyarylene, oxygen (0), sulfur (S), or a combination thereof L can be
substituted or
unsubstituted (with the exception of 0 and S). Moreover, L can be linear or
branched, with
the exception of 0 and S.
A is nitrogen (N) or phosphorous (P);
X- is an anion of a halogen;
R' is a substituent on A or Si, wherein each le is the same or different, and
le
independently is hydrogen, C1 to C30 alkyl group, C1 to C30 alkenyl group, C1
to C30
alkoxy group, C1 to C30 alkynyl group, C1 to C30 aryloxy, halogen, C6 to C30
aryl group,
C1 to C30 amide, amino, C3-C30 cycloalkenyl, C3-C30 cycloalkyl, C3-C30
fluoroalkyl, C1-
C30 heteroalkyl, C3-C30 heteroaryl, hydroxy, C1-C30 oxyalkyl, or a combination
thereof,
and each foregoing group can be substituted or unsubstituted or can be linear
or branched;
R1-R9 and R,,-R24 are independently hydrogen atom, alkyl, heterocyclic,
carbonyl,
amino, amide, sulfonamide, phosphoramide, imide moiety, an aromatic moiety, or
a
combination thereof;
R10 is a bond, alkylene, heterocyclic biradical, carbonyl, amino, amide,
sulfonamide,
phosphoramide, imide biradical, an aromatic moiety, or a combination thereof;
R25 is a halogen or an alkoxy group; and
G is of formulas (4)-(7), wherein at least one of R1-R9 and 1-R24 is a
divalent group
attached to oxygen atom or silicon atom.
[0016] As used herein, "alkenyl" refers to a straight or branched chain,
monovalent
C2-C10 hydrocarbon group having at least one carbon-carbon double bond (e.g.,
ethenyl (-
HC=CH2)). As used herein, "alkenylene" refers to a straight or branched chain,
divalent C2-
C30 hydrocarbon group having at least one carbon-carbon double bond (e.g.,
ethenylene (-
HC=CH-)). As used herein, "alkoxy" refers to an alkyl group that is linked via
an oxygen
(i.e., -0-alkyl). Non-limiting examples of Cl to C30 alkoxy groups include
methoxy groups,
ethoxy groups, propoxy groups, isobutyloxy groups, sec-butyloxy groups,
pentyloxy groups,
iso-amyloxy groups, and hexyloxy groups.
[0017] As used herein, "alkyl" refers to a straight or branched chain
saturated
aliphatic hydrocarbon having the specified number of carbon atoms,
specifically 1 to 12
carbon atoms, more specifically 1 to 6 carbon atoms. Alkyl groups include, for
example,
groups having from 1 to 50 carbon atoms (C1 to C50 alkyl).
[0018] As used herein, "alkylene' refers to a straight, branched or cyclic
divalent
aliphatic hydrocarbon group, and can have from 1 to about 18 carbon atoms,
more
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specifically 2 to about 12 carbons. Exemplary alkylene groups include
methylene (-CH2-),
ethylene (-CH2CH2-), propylene (-(CH2)3-), cyclohexylene (-C6H10-),
ethyleneoxy (-
CH2CH20-), methylenedioxy (-0-CH2-0-), or ethylenedioxy (-0-(CH2)2-0-).
[0019] As used herein, "alkynyl" refers to a straight or branched chain,
monovalent
hydrocarbon group having at least one carbon-carbon triple bond (e.g.,
ethynyl). As used
herein, "alkynylene" refers to a straight or branched chain divalent aliphatic
hydrocarbon that
has one or more unsaturated carbon-carbon bonds, at least one of which is a
triple bond (e.g.,
ethynylene). As used herein, "amide" refers to a group of the formula ¨C(0)-
N(Rx)(Ry) or ¨
N-C(0)-Rx, wherein Rx is an alkyl, an alkenyl, an alkynyl, a cycloalkyl, an
aryl group, or
heteroaryl group; and Ry is hydrogen or any of the groups listed for Rx. As
used herein, "C1
to C15 amine group" is a group of the formula ¨N(Rw)(Rz), wherein Rw is a C1
to C15
alkyl, a C1 to C15 alkenyl, a C1 to C15 alkynyl, a C3 to C15 cycloalkyl, a C6
to C15 aryl, or
C3 to C15 heteroaryl group; and Rz is hydrogen or any of the groups listed for
Rw.
[0020] As used herein, "aryl" refers to a cyclic moiety in which all ring
members are
carbon and at least one ring is aromatic, the moiety having the specified
number of carbon
atoms, specifically 6 to 24 carbon atoms, more specifically 6 to 12 carbon
atoms. More than
one ring may be present, and any additional rings may be independently
aromatic, saturated
or partially unsaturated, and may be fused, pendant, spirocyclic or a
combination thereof
[0021] As used herein, "arylalkylene" group is an aryl group linked via an
alkylene
moiety. The specified number of carbon atoms (e.g., C7 to C30) refers to the
total number of
carbon atoms present in both the aryl and the alkylene moieties.
Representative arylalkyl
groups include, for example, benzyl groups.
[0022] As used herein, "arylene" refers to a divalent radical formed by the
removal of
two hydrogen atoms from one or more rings of an aromatic hydrocarbon, wherein
the
hydrogen atoms may be removed from the same or different rings (preferably
different rings),
each of which rings may be aromatic or nonaromatic. As used herein, "aryloxy"
refers to an
aryl moiety that is linked via an oxygen (i.e., -O-aryl). As used herein,
"cycloalkenyl" refers
to a monovalent group having one or more rings and one or more carbon-carbon
double bond
in the ring, wherein all ring members are carbon (e.g., cyclopentyl and
cyclohexyl).
[0023] As used herein, "cycloalkyl" refers to a group that comprises one or
more
saturated and/or partially saturated rings in which all ring members are
carbon, such as
cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl,
adamantyl and
partially saturated variants of the foregoing, such as cycloalkenyl groups
(e.g., cyclohexenyl)
or cycloalkynyl groups. Cycloalkyl groups do not include an aromatic ring or a
heterocyclic
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ring. When the numbers of carbon atoms is specified (e.g., C3 to C15
cycloalkyl), the
number refers to the number of ring members present in the one or more rings.
[0024] As used herein, "cycloalkenylene" refers to a stable aliphatic 5-15-
membered
monocyclic or polycyclic, divalent radical having at least one carbon-carbon
double bond,
which comprises one or more rings connected or bridged together. Unless
mentioned
otherwise, the cycloalkenylene radical can be linked at any desired carbon
atom provided that
a stable structure is obtained. If the cycloalkenylene radical is substituted,
this may be so at
any desired carbon atom, once again provided that a stable structure is
obtained. Examples
thereof are cyclopentenylene, cyclohexenylene, cycloheptenylene,
cyclooctenylene,
cyclononenylene, cyclodecenylene, norbornenylene, 2-methylcyclopentenylene, 2-
methylcyclooctenylene.
[0025] As used herein, "cycloalkylene" refers to a divalent radical formed by
the
removal of two hydrogen atoms from one or more rings of a cycloalkyl group (a
nonaromatic
hydrocarbon that comprises at least one ring).
[0026] As used herein, "fluoroalkyl" refers to an alkyl group in which at
least one
hydrogen is replaced with fluorine. "Fluoroalkylene" refers to an alkylene
group in which at
least one hydrogen is replaced with fluorine.
[0027] As used herein, "halogen" refers to one of the elements of group 17 of
the
periodic table (e.g., fluorine, chlorine, bromine, iodine, and astatine).
[0028] As used herein, the prefix "hetero" means that the compound or group
includes a heteroatom (e.g., 1, 2, or 3 heteroatom(s)), wherein the
heteroatom(s) is each
independently N, 0, S, Si, or P.
[0029] As used herein, "heteroalkyl" group is an alkyl group that comprises at
least
one heteroatom covalently bonded to one or more carbon atoms of the alkyl
group. Each
heteroatom is independently chosen from nitrogen (N), oxygen (0), sulfur (S),
and
phosphorus (P).
[0030] As used herein, "heteroaryl" refers to a monovalent carbocyclic ring
group
that includes one or more aromatic rings, in which at least one ring member
(e.g., one, two or
three ring members) is a heteroatom. In a C3 to C30 heteroaryl, the total
number of ring
carbon atoms ranges from 3 to 30, with remaining ring atoms being heteroatoms.
Multiple
rings, if present, may be pendent, spiro or fused. The heteroatom(s) are
generally
independently selected from nitrogen (N), oxygen (0), phosphorus (P), and
sulfur (S).
[0031] As used herein, "heteroarylene" refers to a divalent radical formed by
the
removal of two hydrogen atoms from one or more rings of a heteroaryl moiety,
wherein the
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hydrogen atoms may be removed from the same or different rings (preferably the
same ring),
each of which rings may be aromatic or nonaromatic.
[0032] As used herein, "oxyalkyl" refers to an alkyl group to which at least
one
oxygen atom is covalently attached (e.g., via a single bond, forming a
hydroxyalkyl or ether
group, or double bond, forming a ketone or aldehyde moiety). As used herein,
"oxyalkylene"
refers to a divalent radical comprising an alkylene group to which at least
one oxygen atom is
covalently attached (e.g., via a single bond, forming a hydroxyalkylene or an
ether group, or
double bond, forming a ketone or aldehyde moiety). As used herein,
"oxyarylene" moiety is
an aromatic group in which all ring members are independently chosen from
carbon and
oxygen.
[0033] As used herein, "substituted" means that the compound or group is
substituted
with at least one (e.g., 1, 2, 3, or 4) substituent independently selected
from a hydroxyl
(-OH), a C1-9 alkoxy, a C1-9 haloalkoxy, an oxo (=0), a nitro (-NO2), a cyano
(-CN), an
amino (-NH2), an azido (-N3), an amidino (-C(=NH)NH2), a hydrazino (-NHNH2), a
hydrazono (-C(=NNH2)-), a carbonyl (-C(=0)-), a carbamoyl group (-C(0)NH2), a
sulfonyl (-
S(=0)2-), a thiol (-SH), a thiocyano (-SCN), a tosyl (CH3C6H4S02-), a
carboxylic acid (-
C(=0)0H), a carboxylic C1 to C6 alkyl ester (-C(=0)OR wherein R is a C1 to C6
alkyl
group), a carboxylic acid salt (-C(=0)0M) wherein M is an organic or inorganic
anion, a
sulfonic acid (-503H2), a sulfonic mono- or dibasic salt (-S03MH or -503M2
wherein M is an
organic or inorganic anion), a phosphoric acid (-P03H2), a phosphoric acid
mono- or dibasic
salt (-P03MH or -P03M2 wherein M is an organic or inorganic anion), a C1 to
C12 alkyl, a
C3 to C12 cycloalkyl, a C2 to C12 alkenyl, a C5 to C12 cycloalkenyl, a C2 to
C12 alkynyl, a
C6 to C12 aryl, a C7 to C13 arylalkylene, a C4 to C12 heterocycloalkyl, and a
C3 to C12
heteroaryl instead of hydrogen, provided that the substituted atom's normal
valence is not
exceeded.
[0034] The aromatic moiety of the functionalization compound can include an
aryl
group or heteroaryl group. Exemplary aryl groups include anthracyl, azulenyl,
benzocyclooctenyl, benzocycloheptenyl, biphenylyl, chrysenyl, fluorenyl,
indanyl, indenyl,
naphthyl, pentalenyl, phenalenyl, phenanthrenyl, phenanthryl, phenyl, pyrenyl,
tetrahydronaphthyl, a derivative thereof, or a combination thereof
[0035] Exemplary heteroaryl groups include acridinyl, benzimidazolyl,
benzofuranyl,
benzofurazanyl, benzothiazolyl, benzothiophenyl, benzoxazolyl, carbazolyl.
chromanyl,
cinnolinyl, dibenzofuranyl, furazanyl, furopyridinyl, furyl, imidazolyl,
indazolyl, indolinyl,
indolizinyl, indolyl, isochromanyl, isoindolinyl, isoindolyl, isoquinolinyl,
isothiazolyl,
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isoxazolyl, naphthyridinyl, oxadiazolyl, oxazolyl, perimidinyl,
phenanthridinyl,
phenanthrolinyl, phenazinyl, phenoxathiinyl, phenothiazinyl, phenoxazinyl,
phthalazinyl,
pteridinyl, purinyl, pyrazinyl, pyrazolyl, pyridazinyl, pyridinyl,
pyrimidinyl, pyrrolyl,
quinazolinyl, quinolinyl, quinoxalinyl, tetrazolyl, thiadiazolyl, thiazolyl,
thienyl, triazinyl,
triazolyl, a derivative thereof, or a combination thereof The heteroaryl group
may be
attached at any heteroatom or carbon atom of the ring such that the result is
a stable structure.
Thus, for example, pyridyl represents 2-, 3-, or 4-pyridyl, thienyl represents
2- or 3-thienyl,
and quinolinyl represents 2-, 3-, or 4-quinolinyl, and the like.
[0036] According to an embodiment, a substituent of the aromatic moiety (e.g.,
the
aryl group or heteroaryl group) includes halogen, hydroxy, lower alkyl, lower
alkoxy, lower
aralkyl, -NR22 (wherein R2 is a lower alkyl), R3CONH (wherein R3 is phenyl or
a lower
alkyl), and -0C(0)R4 (wherein R4 is hydrogen, alkyl, or aralkyl). Other
substituents for the
aromatic moiety can be -0R5, -0C(0)R5, -NR5R6, -SR5, -R5, -CN, -NO2, -
CO2R5, -CONR5R6, -C(0)R5, -0C(0)NR5R6, -NR6C(0)R5, -NR6C(0)2R5, -NR5-
C(0)NR6R7, -NH-C(NH2)=NH, -NR5C(NH2)=NH, -NH-C(NH2)=NR5, -S(0)R5,
-S(0)2R5, -S(0)2NR5R6, -N3, -CH(Ph)2, perfluoro(Ci-C4)alkoxy, and perfluoro(Ci-
C4)alkyl, in a number ranging from zero to the total number of open valences
on the aromatic
moiety ring system; and where R5, R6, and R7 are independently selected from
hydrogen, C I-
C8 alkyl or heteroalkyl, unsubstituted aryl and heteroaryl, (unsubstituted
aryl)-(C1-C4)alkyl,
(unsubstituted aryl)oxy-(C1-C4)alkyl, (unsubstituted heteroaryl)-(C1-C4)alkyl,
or
(unsubstituted heteroaryl)oxy-(C1-C4)alkyl.
[0037] In a specific embodiment, a substituent for the aromatic moiety of the
aromatic compound includes, for example, an alkyl group (having 1 to 20 carbon
atoms,
specifically 1 to 12 carbon atoms, and more specifically 1 to 8 carbon atoms
and including,
e.g., methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl,
cyclopropyl,
cyclopentyl, cyclohexyl, and the like), an aryl group (having 6 to 30 nuclear
carbon atoms,
specifically 6 to 20 nuclear carbon atoms and including, for example, phenyl,
naphthyl,
biphenylyl, anthranyl, phenanthryl, pyrenyl, chrysenyl, fluorenyl, and the
like), an alkenyl
group (having 2 to 20 carbon atoms, specifically 2 to 12 carbon atoms, and
more specifically
2 to 8 carbon atoms and including, for example, vinyl, allyl, 2-butenyl, 3-
pentenyl, and the
like), an alkynyl group (having 2 to 20 carbon atoms, specifically 2 to 12
carbon atoms, and
more specifically 2 to 8 carbon atoms and including, for example, propargyl, 3-
pentynyl, and
the like), an amino group (having 0 to 20 carbon atoms, specifically 0 to 12
carbon atoms,
and more specifically 0 to 6 carbon atoms and including, for example, amino,
methylamino,
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dimethylamino, diethylamino, diphenylamino, dibenzylamino, and the like), an
alkoxy group
(having 1 to 20 carbon atoms, specifically 1 to 12 carbon atoms, and more
specifically 1 to 8
carbon atoms and including, for example, methoxy, ethoxy, butoxy, and the
like), an aryloxy
group (having 6 to 20 carbon atoms, specifically 6 to 16 carbon atoms, and
more specifically
6 to 12 carbon atoms and including, for example, phenyloxy, 2-naphthyloxy, and
the like), an
acyl group (having 1 to 20 carbon atoms, specifically 1 to 16 carbon atoms,
and more
specifically 1 to 12 carbon atoms and including, for example, acetyl, benzoyl,
formyl,
pivaloyl, and the like), an alkoxycarbonyl group (having 2 to 20 carbon atoms,
specifically 2
to 16 carbon atoms, and more specifically 2 to 12 carbon atoms and including,
for example,
methoxycarbonyl, ethoxycarbonyl, and the like), an aryloxycarbonyl group
(having 7 to 20
carbon atoms, specifically 7 to 16 carbon atoms, and more specifically 7 to 10
carbon atoms
and including, for example, phenyloxycarbonyl and the like), an acyloxy group
(having 2 to
20 carbon atoms, specifically 2 to 16 carbon atoms, and more specifically 2 to
10 carbon
atoms and including, for example, acetoxy, benzoyloxy, and the like), an
acylamino group
(having 2 to 20 carbon atoms, specifically 2 to 16 carbon atoms, and more
specifically 2 to 10
carbon atoms and including, for example, acetylamino, benzoylamino, and the
like), an
alkoxycarbonylamino group (having 2 to 20 carbon atoms, specifically 2 to 16
carbon atoms,
and more specifically 2 to 12 carbon atoms and including, for example,
methoxycarbonylamino and the like), an aryloxycarbonylamino group (having 7 to
20 carbon
atoms, specifically 7 to 16 carbon atoms, and more specifically 7 to 12 carbon
atoms and
including, for example, phenyloxycarbonylamino and the like), a sulfonylamino
group
(having 1 to 20 carbon atoms, specifically 1 to 16 carbon atoms, and more
specifically 1 to 12
carbon atoms and including, for example, methanesulfonylamino,
benzenesulfonylamino, and
the like), a sulfamoyl group (having 0 to 20 carbon atoms, specifically 0 to
16 carbon atoms
and more specifically 0 to 12 carbon atoms and including, for example,
sulfamoyl,
methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl, and the like), a
carbamoyl group
(having 1 to 20 carbon atoms, specifically 1 to 16 carbon atoms and more
specifically 1 to 12
carbon atoms and including, for example, carbamoyl, methylcarbamoyl,
diethylcarbamoyl,
phenylcarbamoyl, and the like), an alkylthio group (having 1 to 20 carbon
atoms, specifically
1 to 12 carbon atoms, and more specifically 1 to 8 carbon atoms and including,
for example,
methylthio, ethylthio, and the like), an arylthio group (having 6 to 20 carbon
atoms,
specifically 6 to 16 carbon atoms, and more specifically 6 to 12 carbon atoms
and including,
for example, phenylthio and the like), a sulfonyl group (having 1 to 20 carbon
atoms,
specifically 1 to 16 carbon atoms and more specifically 1 to 12 carbon atoms
and including,
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for example, mesyl, tosyl, and the like), a sulfinyl group (having 1 to 20
carbon atoms,
specifically 1 to 16 carbon atoms, and more specifically 1 to 12 carbon atoms
and including,
for example, methanesulfinyl, benzenesulfinyl, and the like), a ureido group
(having 1 to 20
carbon atoms, specifically 1 to 16 carbon atoms, and more specifically 1 to 12
carbon atoms
and including, for example, ureido, methylureido, phenylureido, and the like),
a
phosphoramide group (having 1 to 20 carbon atoms, specifically 1 to 16 carbon
atoms, and
more specifically 1 to 12 carbon atoms and including, for example,
diethylphosphoramide,
phenylphosphoramide, and the like), a hydroxy group, a mercapto group, a
halogen atom (for
example, a fluorine atom, chlorine atom, bromine atom, iodine atom, and the
like), a cyano
group, a sulfo group, a carboxyl group, a nitro group, a hydroxamic acid, a
sulfino group, a
hydrazine group, an imino group, a heterocyclic group (having 1 to 30 carbon
atoms,
specifically 1 to 12 carbon atoms, including, for example, a nitrogen atom, an
oxygen atom
and a sulfur atom as a heteroatom and including, for example, imidazolyl,
pyridyl, quinolyl,
furyl, thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl,
benzothiazolyl and
carbazolyl), a silyl group (having 3 to 40 carbon atoms, specifically 3 to 30
carbon atoms,
and more specifically 3 to 24 carbon atoms and including, for example,
trimethylsilyl,
triphenylsilyl, and the like), and the like.
[0038] In an embodiment, the R group of formula (1), (2), or (3) is one of the
preceding substituents mentioned with the respect to the aromatic moiety.
[0039] In an embodiment, the linking groups of formula (1), (2), or (3)
include groups
obtained by converting the preceding substituents mentioned above with the
respect to the
aromatic moiety into divalent groups. Exemplary linking groups are a hetero
atom, a
substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, a
substituted or
unsubstituted cycloalkylene group having 3 to 30 carbon atoms, a substituted
or unsubstituted
arylene group having 6 to 30 nuclear carbon atoms, or a substituted or
unsubstituted
heteroarylene group having 5 to 30 nuclear carbon atoms. The heteroatom can
be, for
example, an oxygen atom, a sulfur atom, a nitrogen atom and a silicon atom.
The alkylene
group can be, for example, methylene, ethylene, propylene, butylene,
pentylene, hexylene,
heptylene, octylene, dimethylmethylene, diphenylmethylene, and the like. The
cycloalkylene
group can be, for example, cyclopropylene, cyclobutylene, cyclopentylene and
cyclohexylene, 1,1-cyclohexylene, and the like. The arylene group can be, for
example,
phenylene, biphenylene, terphenylene, naphthylene, anthracenylene,
phenathrylene,
chrysenylene, pyrenylene, fluorenylene, 2,6-diphenylnaphthalene-4',4"-ene, 2-
phenylnaphthalene-2,4'-ene, fluorenylene, and the like. The heteroarylene
group can be, for
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example, a divalent residue of imidazole, benzimidazole, pyrrole, furan,
thiophene,
benzothiophene, oxadiazoline, indoline, carbazole, pyridine, quinoline,
isoquinoline,
benzoquinone, pyrrolidine, imidazolidine, piperidine, pyridylene, and the
like.
[0040] According to an embodiment, the functionalization compound can be a
quaternary ammonium salt, quaternary phosphonium salt, alkoxy silane, halide,
a guanidine,
a guanidinium salt, a biguanidine, a biguanidinium salt, a sulfonium salt, or
the like.
[0041] Non-limiting examples of the aryl quaternary ammonium salt include
benzylammonium chloride, benzyldimethyldecylammonium chloride,
benzyldimethyldodecylammonium chloride, benzyldimethylhexadecylammonium
chloride,
benzyldimethylhexylammonium chloride, benzyldimethyl(2-hydroxyethyl)ammonium
chloride, benzyldimethyl(2-hydroxymethyl)ammonium chloride,
benzyldimethyloctylammonium chloride, benzyldimethylstearylammonium chloride
monohydrate, benzyldimethyltetradecylammonium chloride,
benzyldodecyldimethylammonium bromide, benzyltributylammonium bromide,
benzyltributylammonium chloride, benzyltributylammonium iodide,
benzyltriethylammonium bromide, benzyltriethylammonium chloride,
benzyltrimethylammonium bromide, benzyltrimethylammonium dichloroiodate,
bis(triphenylphosphoranylidene)ammonium chloride, (dodecyldimethy1-2-
phenoxyethyl)ammonium bromide,
(diisobutylphenoxyethoxyethyl)dimethylbenzylammonium chloride, (4-
nitrobenzyl)trimethylammonium chloride, trimethylphenylammonium bromide,
trimethylphenylammonium chloride, (vinylbenzyl)trimethylammonium chloride, 3-b
enzy1-5-
(2-hydroxyethyl)-4-methylthiazolium chloride, 1,1-dimethy1-4-
phenylpiperazinium iodide,
and the like. In an embodiment, the aryl compound is an aryl phosphine such as
one of the
aforementioned phosphines and the like. In an embodiment, the heteroaryl
quaternary
ammonium salt includes a heteroaryl group instead of the aryl group in the
aryl quaternary
ammonium salt here. Exemplary heteroaryl quaternary ammonium salts include
pyridyl(methyl)ammonium chloride (bromide, iodide), chinolinyl(methyl)ammonium
chloride (bromide, iodide), benzothiophenyl(methyl)ammonium chloride (bromide,
iodide),
and the like.
[0042] Exemplary aryl quaternary phosphonium salts include
benzyltriphenylphosphonium chloride, dimethyldiphenylphosphonium iodide,
ethyltriphenylphosphonium iodide, methyltriphenoxyphosphonium iodide,
tetraphenylphosphonium bromide, and the like. additional quaternary
phosphonium salts
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includes those derived from commercially available (Sigma Aldrich co.)
phosphines such as
substituted or unsubstituted triphenylphosphine, naphthyldiphenylphosphine,
dinaphthylphenylphosphine, trinaphthylphosphine, 9-anthryldiphenylphosphine, 9-
anthryldinaphthylphosphine, diphenylpyrenylphosphine,
dinaphthylpyrenylphosphine,
bis(pentafluorophenyl)phenylphosphine, (4-bromophenyl)diphenylphosphine, 4-
(dimethylamino)phenyldiphenylphosphine, dipheny1(2-methoxyphenyl)phosphine,
diphenyl(pentafluorophenyl)phosphine, 2-(diphenylphosphino)benzaldehyde,
dipheny1-2-
pyridylphosphine, diphenyl(p-tolyl)phosphine, tri-2-furylphosphine, tris(4-
chlorophenyl)phosphine, tris(2,6-dimethoxyphenyl)phosphine, tris(4-
fluoropheny1)-
phosphine, tris(3-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine,
tris(pentafluoro-phenyl)phosphine, tris(2,4,6-trimethoxyphenyl)phosphine,
tris(2,4,6-
trimethylphenyl)phosphine, 2-(diphenylphosphino)benzoic acid, 4-
(diphenylphosphino)benzoic acid, 4,4'-(phenyl-
phosphinidene)bis(benzenesulfonic acid),
3,3',3"-phosphinidynetris(benzenesulfonic acid), tri-m-tolylphosphine, tri-o-
tolylphosphine,
tri-p-tolylphosphine, (1,2-bis(diphenyl-phosphino)benzene), (2,2'-
bis(diphenylphosphino)-
1,1'-binaphthyl, and the like. These phosphines can be processed to produce
aryl quaternary
phosphonium salts as described in U.S. Patent Application No. 10/553,307, the
disclosure of
which is incorporated herein in its entirety. In an embodiment, the heteroaryl
quaternary
phosphonium salt includes a heteroaryl group instead of the aryl group in the
aryl quaternary
phosphonium salts here. Exemplary heteroaryl quaternary phosphonium salts
include
pyridyl(methyl)phosphonium chloride (bromide, iodide),
chinolinyl(methyl)phosphonium
chloride (bromide, iodide), benzothiophenyl(methyl)phosphonium chloride
(bromide, iodide),
and the like.
[0043] The anion X- of the aromatic compound of formula (1) (e.g., the aryl
quaternary ammonium salt, heteroaryl quaternary ammonium salt, aryl quaternary
phosphonium salt, or heteroaryl quaternary phosphonium salt) can be a halide,
triflate,
sulfate, nitrate, hydroxide, carbonate, bicarbonate, acetate, phosphate,
oxalate, cyanide,
aklylcarboxylate, N-hydroxysuccinimide, N-hydroxybenzotriazole, alkoxide,
thioalkoxide,
alkane sulfonyloxide, halogenated alkane sulfonyloxide, arylsulfonyloxide,
heteroarylsulfonyloxide bisulfate, valerate, oleate, palmitate, stearate,
laurate, borate,
benzoate, lactate, citrate, maleate, fumarate, succinate, tartrate,
naphthylate, mesylate,
glucoheptonate, lactobionate, and the like.
[0044] Exemplary aryl alkoxy silanes includes tert-
butoxy(chloro)diphenylsilane,
aminophenyltrimethoxysilane, 2-(4-pyridylethyl)triethoxysilane, 2-
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(trimethoxysilylethyl)pyridine, n-(3-trimethoxysilylpropyl)pyrrole, 3-(m-
aminophenoxy)propyltrimethoxy-silane, n-phenylaminopropyltrimethoxy-silane,
(phenylaminomethyl)methyl-dimethoxysilane, n-phenylaminomethyltriethoxysilane,
3-(n-
styrylmethy1-2-aminoethylamino)-propyltrimethoxysilane hydrochloride, (2-n-
benzylaminoethyl)-3-aminopropyl-trimethoxysilane hydrochloride, n-(3-
triethoxysilylpropy1)-4,5-dihydroimidazole, 2-(2-
pyridylethyl)thiopropyltrimethoxysilane, 2-
(4-pyridylethyl)thiopropyltrimethoxysilane, benzoyloxypropyltrimethoxysilane,
((chloromethyl)phenylethyl)-trimethoxysilane, (p-
chloromethyl)phenyltrimethoxysilane,
((chloromethyl)phenylethyl)-methyldimethoxysilane, bis(2-
diphenylphosphinoethyl)-
methylsilylethyltriethoxysilane, diphenylphosphinoethyldimethyl-ethoxysilane,
2-
(diphenylphosphino)ethyl-triethoxysilane, 2-(2-
pyridylethyl)thiopropyltrimethoxysilane, 2-
(4-pyridylethyl)thiopropyltri-methoxysilane, 2-(3-trimethoxysilylpropylthio)-
thiophene, 3-(n-
styrylmethy1-2-aminoethylamino)-propyltrimethoxysilane, (3-
cyclopentadienylpropyl)triethoxysilane, styrylethyltrimethoxysilane, 3-(2,4-
dinitrophenylamino)propyl-triethoxysilane, 2-hydroxy-4-(3-methyldiethoxysilyl-
propoxy)diphenylketone, 2-hydroxy-4-(3-triethoxysilylpropoxy)-diphenylketone,
o-4-
methylcoumarinyl-n-[3-(triethoxy-silyl)propyl]carbamate, 7-
triethoxysilylpropoxy-5-
hydroxy-flavone, 5-dimethylamino-n-(3-triethoxysilylpropy1)-napthalene-1-
sulfonamide, 2-
(2-triethoxysilylpropoxy-5-methyl-p henyl)benzotriazole, 3-
(triethoxysilylpropy1)-p-nitro-
benzamide, (R)-n-triethoxysilylpropyl-o-quinine-urethane, (R)-n-l-phenylethyl-
n'-
triethoxysilyl-propylurea, (S)-n-l-phenylethyl-n'-triethoxysilyl-propylurea,
and the like
available from Gelest Inc, Morrisville, PA. In an embodiment, the heteroaryl
alkoxy silanes
include a heteroaryl group instead of the aryl group in the aryl alkoxy silane
compounds here.
Exemplary heteroaryl alkoxy silanes include pyridylmethyltriethoxy silane,
furylethyltriethoxysilane, thiophenylethyltriethoxy silane, and the like.
[0045] Exemplary aryl halides include phenyl chloride, 2-chlorotoluene, 2-
bromotoluene, 4-chlorotoluene, 4-bromotoluene, 2-chloro-4-methylnaphthalene, 2-
bromo-4-
methylnaphthalene, 4-chloroanisole, 4-bromoanisole, 2-chlorobenzyl(2-
methoxy)ethyl ether,
2-bromobenzyl(2-methoxy)ethyl ether, 2-chlorobenzyl methyl ether, 2-
bromobenzyl methyl
ether, 2-chlorobenzyl ethyl ether, 2-bromobenzyl ethyl ether, chlorobenzene,
bromobenzene,
iodobenzene, fluorobenzene, dichlorobenzene, trichlorobenzene, chlorotoluene,
2,4-
dichlorotoluene, chloronaphthalene, bromonaphthalene, iodotoluenes,
iodonaphthalene, 2-
bromo-6-methoxynaphthalene, 4-bromo-isobutylbenzene, triphenylmethane
chloride,
iodobenzene, bromotoluene, iodonaphthalene, chlorobenzene, phenylphosphine
dichloride,
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diphenylphosphine mono chloride, (o-chlorophenyl)phosphine dichloride, bis(o-
chlorophenyl)phosphine monochloride, 1-naphthylphosphine bromides,
chlorotolylphosphine
chlorides, dichlorotolylphosphine chlorides, and the like. In an embodiment,
the heteroaryl
halide includes a heteroaryl group instead of the aryl group in the aryl
halide compounds
here, e.g., 2,6- dichloropyridine. Exemplary heteroaryl halides include
pyridylethyl chloride,
furylethyl chloride, thiophenylethyl chloride, and the like.
[0046] In the composition, the functionalized silicate nanoparticle includes a
silicate
nanoparticle. The silicate nanoparticle contains silicon and oxygen that can
be arranged in
various structures such as a tetrahedral configuration and can have a shape
such as a platelet,
sphere, polyhedron, rod, cylinder, a combination thereof, and the like.
According to an
embodiment, the silicate nanoparticle comprises a silsesquioxane,
cyclosilicate, inosilicate,
nesosilicate, phyllosilicate, sorosilicate, tectosilicate, or a combination
thereof
[0047] The silicate nanoparticles, from which the composition is formed, are
generally particles having an average particle size, in at least one
dimension, of less than one
micrometer ( m). As used herein "average particle size" refers to the number
average
particle size based on the largest linear dimension of the particle (sometimes
referred to as
"diameter"). Particle size, including average, maximum, and minimum particle
sizes, may be
determined by an appropriate method of sizing particles such as, for example,
static or
dynamic light scattering (SLS or DLS) using a laser light source. Silicate
nanoparticles can
include both particles having an average particle size of 250 nm or less, and
particles having
an average particle size of greater than 250 nm to less than 1 i_tm (sometimes
referred in the
art as "sub-micron sized" particles). In an embodiment, a silicate
nanoparticle can have an
average particle size of about 0.1 nanometers (nm) to about 500 nm,
specifically 0.5 nm to
250 nm, more specifically about 1 nm to about 150 nm, more specifically about
1 nm to
about 125 nm, and still more specifically about 1 nm to about 75 nm. The
silicate
nanoparticles may be monodisperse, where all particles are of the same size
with little
variation, or polydisperse, where the particles have a range of sizes and are
averaged.
Generally, polydisperse silicate nanoparticles are used. Silicate
nanoparticles of different
average particle size may be used, and in this way, the particle size
distribution of the silicate
nanoparticles can be unimodal (exhibiting a single size distribution), bimodal
(exhibiting two
size distributions), or multi-modal (exhibiting more than one particle size
distribution).
[0048] The minimum particle size for the smallest 5 percent of the silicate
nanoparticles can be less than 2 nm, specifically less than or equal to 1 nm,
and more
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specifically less than or equal to 0.5 nm. Similarly, the maximum particle
size for 95% of the
silicate nanoparticles can be greater than or equal to 900 nm, specifically
greater than or
equal to 750 nm, and more specifically greater than or equal to 500 nm. The
silicate
nanoparticles can have a high surface area of greater than 300 m2/g, and in a
specific
embodiment, 300 m2/g to 1800 m2/g, specifically 500 m2/g to 1500 m2/g. In a
particular
embodiment, the silsesquioxane has a size from 0.5 nm to 10 nm.
[0049] According to an embodiment, the silicate nanoparticle is a
silsesquioxane.
Silsesquioxanes, also referred to as polysilsesquioxanes,
polyorganosilsesquioxanes, or
polyhedral oligomeric silsesquioxanes (POSS), are polyorganosilicon oxide
compounds of
general formula RSiOi 5 (where R is a hydrogen, inorganic group, or organic
group) having
defined closed or open cage structures (closo or nido structures, which are
called respectively
completely condensed or incompletely condensed structures). Silsesquioxanes
can be
prepared by acid and/or base-catalyzed condensation of functionalized silicon-
containing
monomers such as tetraalkoxysilanes including tetramethoxysilane and
tetraethoxysilane,
alkyltrialkoxysilanes such as methyltrimethoxysilane and
methyltrimethoxysilane, as well as
other groups.
[0050] In an embodiment, the silsesquioxane has a closed cage structure, an
open
cage structure, or a combination thereof The silsesquioxane can have any shape
of cage
structure such as cubes, hexagonal prisms, octagonal prisms, decagonal prisms,
dodecagonal
prisms, and the like. Additionally, the cage structure of the silsesquioxane
comprises from 4
to 30 silicon atoms, specifically, 4 to 20 silicon atoms, and more
specifically 4 to 16 silicon
atoms, with each silicon atom in the cage structure being bonded to oxygen. It
should be
noted that the term "cage structure" is meant to include the SiOi 5 portion of
the general
silsesquioxane formula RSi01.5, and not the R-group.
[0051] According to an embodiment, the silsesquioxane comprises a functional
group
bonded to a silicone atom of the silsesquioxane. In a specific embodiment, the
functional
group bonded to the silicon atom comprises an alkyl, alkoxy, haloakyl,
cycloalkyl,
heterocycloalkyl, cycloalkyloxy, aryl, aralkyl, aryloxy, aralkyloxy,
heteroaryl, heteroaralkyl,
alkenyl, alkynyl, amine, alkyleneamine, aryleneamine, alkenyleneamine,
hydroxy, carboxyl,
ether, epoxy, ketone, halogen, hydrogen, or a combination thereof Thus, the
silsesquioxane
derivatized with a functional group includes a group such as an alcohol,
amine, carboxylic
acid, epoxy, ether, fluoroalkyl, halide, imide, ketone, methacrylate,
acrylate, silica, nitrile,
norbornenyl, olefin, polyethylene glycol (PEG), silane, silanol, sulfonate,
thiol, and the like.
Furthermore, the silsesquioxane can have from one functional group to as many
functional
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groups as there are silicon atoms in the cage structure of the silsesquioxane.
In a specific
embodiment, the silsesquioxane is a derivatized octasilsesquioxane
R8Eln(Si01.5)8 (where 0
n 8, and R can be a same or different functional group), and the number of
functional
groups varies with the number of silicon atoms in the cage structure, i.e.,
from 0 to 8
functional groups.
[0052] Exemplary silsesquioxanes having a closed cage structure include 1-
ally1-
3,5,7,9,11,13,15-
heptacyclopentylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane; 1-
ally1-3,5,7,9,11,13,15-
heptaisobutylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane; 1-
[3-(2-aminoethyl)amino]propy1-3,5,7,9,11,13,15-
isobutylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane; 1-
chlorobenzylethy1-
3,5,7,9,11,13,15-
heptaisobutylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane; 1-(4-
chlorobenzy1)-3,5,7,9,11,13,15-
heptacyclopentylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane; 1-
chloropropyl-
3,5,7,9, 11,13,15-isobutylpentacyclo
[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane;
(cyanopropyldimethylsilyloxy)heptacyclopentylpentacyclooctasiloxane; 1-(2-
trans-
cyclohexanediopethy1-3,5,7,9,11,13,15-
isobutylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane; 1-(3-cyclohexen-
1-y1)-
3,5,7,9,11,13,15-
heptacyclopentylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane;
dodecaphenyl-dodecasiloxane; 1-[2-(3,4-epoxycyclohexyl)ethy1]-3,5,7,9,11,13,15-
isobutylpentacyclo [9.5.1. 1(3,9).1(5,15).1(7,13)]octasiloxane;
1,3,5,7,9,11,13-
heptacyclopenty1-15-
glycidylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane; 1-(3-
glycidyl)propoxy-3,5,7,9,11,13,15-
isobutylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane;
octakis(tetramethylammonium)
pentacyclo [9.5.1. 1(3,9). 1(5,15).1(7,13)]octasiloxane-1,3,5,7,9,11,13,15-
octakis(yloxide)
hydrate; 3-hydroxypropylheptaisobutyl-octasiloxane; 1-(3-mercapto)propy1-
3,5,7,9,11,13,15-
isobutylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane;
octacyclohexenylethyldimethylsilyloxy-octasiloxane; 1,3,5,7,9,11,13,15-
octacyclohexylpentacyclooctasiloxane; octa[(1,2-epoxy-4-
ethylcyclohexyl)dimethylsiloxy]octasiloxane; octa[(3-
glycidyloxypropyl)dimethylsiloxy]octasiloxane; octa[(3-
hydroxypropyl)dimethylsiloxy]octasiloxane; 1,3,5,7,9,11,13,15-octakis[2-
(chlorodimethylsilyl)ethyl]pentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane
;
1,3,5,7,9,11,13,15-
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octakis(dimethylsilyloxy)pentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane;
1,3,5,7,9,11,13,15-octamethylpentacyclo [9.5.1.1(3,9).
1(5,15).1(7,13)]octasiloxane;
1,3,5,7,9,11,13,15-
octaphenylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane;
1,3,5,7,9,11,13,15-octa(2-
trichlorosilyl)ethyl)pentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane;
1,3,5,7,9,11,13,15-
octavinylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane; 1-(2,3-
propanediol)propoxy-
3,5,7,9, 11,13,15-isobutylpentacyclo-[9.5.1.1(3,9).
1(5,15).1(7,13)]octasiloxane; 3-
(3,5,7,9,11,13,15-heptaisobutylpentacyclo [9.5.1.
1(3,9).1(5,15).1(7,13)]octasiloxan-1-
yl)propylmethacrylate; (3-tosyloxypropy1)-heptaisobutyloctasiloxane; 1-
(trivinylsilyloxy)-
3,5,7,9,11,13,15-
heptacyclopentylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane; 1-
viny1-3,5,7,9,11,13,15-
isobutylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane,(3-(2,2-
bis(hydroxymethyl)butoxy)propyl)dimethylsiloxy-3,5,7,9,11,13,15-
isobutylpentacyclo[9.5.1.1.(3,9).1(5,15).1(7,13)]octasiloxane; octa(3-hydroxy-
3-
methylbutyldimethylsiloxy)octasiloxane; 1-(3-amino)propy1-3,5,7,9,11,13,15-
isobutylpentacyclo[9.5.1.1.(3,9).1(5,15).1(7,13)]octasiloxane; 1-(3-
amino)propyl-
3,5,7,9, 11,13,15-isooctylpentacyclo [9.5.1.1. (3,9).1(5,15).1(7,13)]
octasiloxane;
1,3,5,7,9,11,13,15-
octaaminophenylpentacyclo[9.5.1(3,9).1(5,15).1(7,13)]octasiloxane; octa-
n-phenylaminopropy1)-octasiloxane; n-methylaminopropyl-heptaisobutyl-
octasiloxane;
octaethylammoniumoctasiloxane chloride; 1-(4-amino)pheny1-3,5,7,9,11,13,15-
cyclohexlpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane; 1-(amino)pheny1-
3,5,7,9,11,13,15-
cyclohexlpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane; 1-(4-
amino)pheny1-3,5,7,9,11,13,15-
heptaisobutylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane; 1-
(amino)phenyl-
3,5,7,9, 11,13,15-heptaisobutylpentacylco [9.5.1.1(3,9).
1(5,15).1(7,13)]octasiloxane; 1-[(3-
maleamic acid)propy1]-3,5,7,9,11,13,15-
heptacyclohexylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]-octasiloxane; 1-[(3-
maleamic
acid)propy1]-3,5,7,9,11,13,15-
heptaisobutylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]-
octasiloxane; octamaleamic acid octasiloxane; trimethoxy42-(7-
oxabicyclo[4.1.0]hept-3-
yl)ethyl]silane, hydrolyzed; 2-[[3-(trimethoxysilyl)propoxy]methy1]-oxirane,
hydrolyzed;
ethyl 3,5,7,9, 11,13,15-heptaethylpentacyclo
[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane-1-
undecanoate; 1-(3-glycidyl)propoxy-3,5,7,9,11,13,15-
isooctylpentacyclo [9.5.1. 1(3,9).1(5,15).1(7,13)]octasiloxane; 3,7,14-tris{
[3-
(epoxypropoxy)propyl]dimethylsilyloxy}-1,3,5,7,9,11,14-
heptacyclohexyltricyclo [7. 3 .3 .1(5,11)]heptasiloxane; 3,7,14-tris{ [3 -
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(epoxypropoxy)propyl]dimethylsilyloxy}-1,3,5,7,9,11,14-
heptaisobutyltricyclo[7.3.3.1(5,11)]heptasiloxane;
octatrifluoropropyloctasiloxane; endo-
3,7,14-trifluoropropy1-1,3,5, 7,9, 11,14-heptaisobutyltricyclo
[7.3.3.1(5,11)]heptasiloxane; 1-
chlorobenzy1-3,5,7,9,11,13,15-
heptaisobutylpentacyclo [9.5.1. 1(3,9).1(5,15).1(7,13)]octasiloxane;
1,3,5,7,9,11,13,15-
octakis(1,2-dibromoethyl)-pentacyclo [9.
5.1.1(3,9).1(5,15).1(7,13)]octasiloxane; 1-[(3-
maleimide)propy1]-3,5,7,9,11,13,15-
heptacyclohexylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]-
octasiloxane; 1-[(3 -maleimide)propy1]-3,5,7,9,11,13,15-
heptaisobutylpentacyclo [9.5.1. 1(3,9).1(5,15).1(7,13)]-octasiloxane; 3-
(3,5,7,9,11,13,15-
heptaisobutylpentacyclo [9. 5.1.1(3,9).1(5,15).1(7,13)]octasiloxan-1-
yl)propylacrylate; 3-
[3,5,7,9,11,13,15-heptacyclohexylpentacyclo
[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxan-1-
yl]methylmethacrylate; 3-[3,5,7,9,11,13,15-
heptaisobutylpentacyclo [9. 5.1.1(3,9).1(5,15).1(7,13)]octasiloxan-1-
yl]methylmethacrylate; 3-
[3,5,7,9,11,13,15-heptaethylpentacyclo [9.5.1.
1(3,9).1(5,15).1(7,13)]octasiloxan-1-
yl]methylmethacrylate; 3-[3,5,7,9,11,13,15-
heptaethylpentacyclo [9. 5.1. 1(3,9).1(5,15).1(7,13)]octasiloxan-1-
yl]propylmethacrylate; 3-
[3,5,7,9,11,13,15-heptaisooctylpentacyclo
[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxan-
lyl]methylmethacrylate; 3-(3,5,7,9,11,13,15-
heptaisooctylpentacyclo [9. 5.1.1(3,9).1(5,15).1(7,13)]octasiloxan-1-
yl)propylmethacrylate; 3-
(3,5,7,9,11,13,15-heptaphenylpentacyclo [9.5.1.
1(3,9).1(5,15).1(7,13)]octasiloxan-1-
yl)propylmethacrylate; octasiloxa-octapropylmethacrylate; octasiloxa-
octapropylacrylate;
dodecaphenyldecasiloxane; octaisooctyloctasiloxane;
phenylheptaisobutyloctasiloxane;
phenylheptaisooctyloctasiloxane; isooctylhetpaphenyloctasiloxane;
octaisobutyloctasiloxane;
octamethyloctasiloxane; octaphenyloctasiloxane;
octakis(tetramethylammonium)pentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxan
e
1,3,5,7,9,11,13,15-octakis(cyloxide)hydrate;
octakis(trimethylsiloxy)pentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane;
3,5,7,9, 11,13,15-heptaisobutylpentacyclo
[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane-1-
butyronitrile; 142-(5-norbornen-2-yl)ethyl]-3,5,7,9,11,13,15-
heptaethylpentacyclo [9. 5.1.1(3,9).1(7,13)]octasiloxane; 1-[2-(5-norbornen-2-
ypethy1]-
3,5,7,9, 11,13,15-heptaisobutylpentacyclo [9. 5.1.1(3,9).1(7,13)]octasiloxane;
1-allyl-
3,5,7,9, 11,13,15-heptaisobutylpentacyclo [9.5.1.1(3,9).1(7,13)]octasiloxane;
1,3,5,7,9,11,13-
heptaisobuty1-15-vinylpentacyclo [9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane;
1,3,5,7,9,11,13,15-octa[2-(3-
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cyclohexenyl)ethyldimethylsiloxy]pentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasi
loxane;
1,3,5,7,9,11,13,15-
octavinylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane;
1,3,5,7,9,11,13,15-
octa[vinyldimethylsiloxy]pentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane;
1,3,5,7,9,11,13,15-
octakis(dimethylsilyloxy)pentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane;
1,3,5,7,9,11,13,15-
octahydropentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane; 1-(3-
mercapto)propy1-3,5,7,9,11,13,15-
isobutylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane; 1-(3-
mercapto)propy1-
3,5,7,9,11,13,15-isooctylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane;
and the like.
[0053] Exemplary silsesquioxanes having an open cage structure include
1,3,5,7,9,11,14-heptacyclohexyltricyclo[7.3.3.1(5,11)]heptasiloxane-endo-
3,7,14-triol;
1,3,5,7,9,11,14-heptacyclopentyltricyclo[7.3.3.1(5,11)]heptasiloxane-endo-
3,7,14-triol;
1,3,5,7,9,11-octaisobutyltetracyclo[7.3.3.1(5,11)]octasiloxane-endo-3,7-diol;
1,3,5,7,9,11,14-
heptaethyltricyclo[7.3.3.1(5,11)]heptasiloxane-endo-3,7,14-triol;
1,3,5,7,9,11,14-
heptaisobutyltricyclo[7.3.3.1(5,11)]heptasiloxane-endo-3,7,14-triol;
1,3,5,7,9,11,14-
heptaisooctyltricyclo[7.3.3.1(5,110]heptasiloxane-endo-3,7,14-triol;
1,3,5,7,9,11,14-
heptaphenyltricyclo [7. 3 .3 . 1(5, 11)]heptasiloxane-endo-3 , 7,14-triol;
tricyclo[7.3.3.3(3,7)]octasiloxane-5,11,14,17-tetrao1-1,3,5,7,9,11,14,17-
octaphenyl; 9-
{ dimethyl[2-(5-norbornen-2-yl)ethyl] silyloxy } -1,3,5, 7, 9, 11,14-
heptaisobutyltricyclo [7.3 .3 . 1
5,11 ]heptasiloxane-1,5-diol; endo-3,7,14-tris{dimethyl[2-(5-norbornen-2-
yl)ethyl]silyloxy}-
1,3,5,7,9,11,14-heptaisobutyltricyclo[7.3.3.1(5,11)]heptasiloxane;
Rdimethyl(trifluoromethyl)ethyl]silyloxy]heptacyclopentyltricycloheptasiloxaned
iol;
1,3,5,7,9,11,14-heptacyclohexyltricyclo[7.3.3.1(5,11)]heptasiloxane-3,7,14-
triol;
1,3,5,7,9,11,14-heptaisobutyltricyclo[7.3.3.1(5,11)]heptasiloxane-endo-3,7,14-
triol;
1,3,5,7,9,11-octacyclopentyltetracyclo[7.3.3.1(5,11)]octasiloxane-endo-3,7-
diol;
1,3,5,7, 9,11,14-hepta-isooctyltricyclo [7.3 .3 .1(5,11)]heptasiloxane-endo-
3,7,14-triol; endo-
3,7,14-trifluoro-1,3,5,7,9,11,14-
heptacyclopentyltricyclo[7.3.3.1(5,11)]heptasiloxane; endo-
3,7,14-tris{dimethyl[2-(5-norbornen-2-yl)ethyl]silyloxy}-1,3,5,7,9,11,14-
heptacyclopentyltricyclo[7.3.3.1(5,11)]heptasiloxane;
tris((dimethyl(trifluoromethyl)ethyl)silyloxy)heptacyclopentyltricycloheptasilo
xane; 3,7,14-
tris { [3 -(epoxypropoxy)propyl]dimethylsilyloxy} -1,3,5,7,9,11,14-
heptacyclopentyltricyclo[7.3.3.1(5,11)]heptasiloxane, and the like.
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[0054] A combination of the silsesquioxanes with an open cage structure or
closed
cage structure can be used as the silsesquioxane in conjunction with a
combination of any of
the other silicate nanoparticles.
[0055] In an embodiment, the silicate nanoparticle is a silicate mineral such
as
cyclo silicate, inosilicate, nesosilicate, phyllo silicate, sorosilicate,
tectosilicate, or a
combination thereof
[0056] Cyclosilicates are silicates with tetrahedrons that can link to form
rings of
three (Si309)-6, four (Si4012)-8, six (Si6018)-12 or nine (Si9027)-18 units.
Exemplary
cyclosilicates include benitoite, axinite, beryl, cordierite, tourmaline,
papagoite, eudialyte,
milarite, and the like.
[0057] The inosilicate can have a crystalline structure in the form of a chain
such as
pyroxenes and pyroxenoids (with a crystalline structure of single chains
(SiO3)-2) or
amphiboles (with a crystalline structure of double chains (Si4011)-6). Non-
limiting examples
of pyroxenes and pyroxenoids include diopside, spodumene, wollastonite,
enstatite,
hypersthene, hedenbergite, augite, pectolite, diallage, fassaite, spodumene,
jeffersonite,
aegirine, omphafacite, hiddenite, and the like. Non-limiting examples of
amphiboles are
calcium amphiboles such as tremolite, actinote, and hornblende; iron-magnesium
amphiboles
such as grunerite and cummingtonite; and sodium amphiboles such as
glaucophane,
arfvedsonite and riebeckite; and the like.
[0058] Non-limiting examples of nesosilicates are alite, almandine,
andalousite,
andalusite, andradite, belite, chloritoid, chondrodite, clinohumite, datolite,
dumortierite,
fayalite, forsterite, grossular, humite, hydrogrossular, kyanite, norbergite,
olivine, phenakite,
pyrope, sillimanite, spessartine, staurolite, thaumasite, thorite, titanite,
topaz, uvarovite,
zircon, and the like.
[0059] The phyllosilicate can be a clay, mica, serpentine, chlorite, or a
combination
thereof Exemplary phyllosicates include antigorite, biotite, chlorite,
chrysotile, glauconite,
halloysite, illite, kaolinite, lepidolite, lizardite, margarite,
montmorillonite, muscovite,
palygorskite, phlogopite, pyrophyllite, talc, vermiculite, and the like.
[0060] The sorosilicate can be allanite, clinozoisite, dollaseite, epidote,
hemimorphite, ilvaite, lawsonite, prehnite, tanzanite, vesuvianite, zoisite,
and the like.
[0061] The tectosilicate can be, for example, albite, alkali-feldspars,
analcime,
andesine, anorthite, anorthoclase, bytownite, cancrinite, celsiane, chabazite,
coesite,
cristobalite, feldspar, feldspathoid, hauyne, heulandite, labradorite,
lazurite, leucite, marialite,
meionite, microcline, mordenite, natrolite, nepheline, nosean, oligoclase,
orthoclase, petalite,
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plagioclase, quartz, sanidine, scapolite, scolecite, silica, sodalite,
stilbite, tridymite, zeolite,
and the like.
[0062] Exemplary zeolites include naturally occurring zeolites such as
amicite,
analcime, barrerite, bellbergite, bikitaite, boggsite, brewsterite, chabazite,
clinoptilolite,
cowlesite, dachiardite, edingtonite, epistilbite, erionite, faujasite,
ferrierite, garronite,
gismondine, gmelinite, gobbinsite, gonnardite, goosecreekite, harmotome,
herschelite,
heulandite, laumontite, levyne, maricopaite, mazzite, merlinoite, mesolite,
montesommaite,
mordenite, natrolite, offretite, paranatrolitem, paulingite, pentasil,
perlialite, phillip site,
pollucite, scolecite, sodium dachiardite, stellerite, stilbite,
tetranatrolite, thomsonite,
tschernichite, wairakite, wellsite, willhendersonite, and yugawaralite. In
some embodiments,
the zeolite is analcime, chabazite, clinoptilolite, heulandite, natrolite,
phillipsite, stilbite, or a
combination thereof A synthetic zeolite also can be used as the tectosilicate
of the silicate
nanoparticle. The synthetic zeolites can be selected from Zeolite A, Zeolite
B, Zeolite F,
Zeolite H, Zeolite L, Zeolite T, Zeolite W, Zeolite X, Zeolite Y, Zeolite
Omega, Zeolite
ZSM-5, Zeolite ZSM-4, Zeolite P, Zeolite N, Zeolite D, Zeolite 0, Zeolite S,
and Zeolite Z.
[0063] In an embodiment, the silicate nanoparticle can include other elements
or
components in addition to silicon and oxygen. The silicate nanoparticle can
include an oxide,
for example, silicon dioxide (Si02), aluminum oxide (A1203), barium oxide
(BaO), bismuth
trioxide (Bi203), boron oxide (B203), calcium oxide (CaO), cesium oxide (Cs0),
lead oxide
(Pb0), strontium oxide (Sr0), rare earth oxides (e.g., lanthanum oxide
(La203), neodymium
oxide (Nd203), samarium oxide (5m203), cerium oxide (Ce02)), and the like. An
exemplary
silicate nanoparticle containing 5i02 includes quartz, cristobalite,
tridymite, and the like. The
other elements can be, for example, aluminum, antimony, arsenic, barium,
beryllium, boron,
calcium, cerium, cesium, chromium, cobalt, copper, gallium, gold, iron,
lanthanum, lead,
lithium, magnesium, manganese, molybdenum, neodymium, nickel, niobium,
palladium,
phosphorus, platinum, potassium, praseodymium, silver, sodium, tantalum,
thorium, titanium,
vanadium, zinc, zirconium, and the like. The other elements can occur in the
silicate
nanoparticle in the form of oxides, carbonates, nitrates, phosphates,
sulfates, or halides.
Furthermore, the other element can be a dopant in the silicate nanoparticle.
[0064] It is contemplated that the silicate nanoparticle is functionalized
with the
functionalization compound or a chemical group from the functionalization
compound.
Functionalization of the silicate nanoparticle to form the functionalized
silicate nanoparticle
can be achieved by a cation exchange reaction, substitution, condensation,
alkoxysilane
chemistry, and the like. Without wishing to be bound by the theory, the
silicate nanoparticle
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can have a group such as a hydroxy group on its surface that interacts with
and can react with
the functionalization compound or chemical group thereof As used herein, the
bond of the
first portion of the chemical group includes covalent bonds as well as ionic
bonds.
[0065] As noted above, the functionalization compound includes a chemical
group
that has a first portion and a second portion, which includes an aromatic
moiety or a
nonaromatic moiety. The first portion is directly bonded to the silicate
nanoparticle in the
functionalized silicate nanoparticle. In terms of formulas (1), (2), and (3),
the second portion
includes the aromatic or nonaromatic moiety Ar. Also, the first portion can
include the A
group (e.g., nitrogen or phosphorous), Si, oxygen (-0-), or linker group L in
formulas (1), (2),
and (3). As used herein, the bond of the first portion of the chemical group
includes
covalent bonds as well as ionic bonds.
[0066] The compounds of formulas (4)-(7) can be attached to the silicate
nanoparticles through an ionic bond via "N" or "S." In this instant, the first
portion of the
chemical group which functionalizes the silicate nanoparticle is an ionic bond
and the second
portion of the chemical group is a cation of formula (4), formula (5), formula
(6) or formula
(7). The compounds of formula (8) can be attached to the silicate nanoparticle
through Si
when R25 is halide or when R25 is an alkoxy group.
[0067] In an embodiment, the functionalization compound is a compound of
formula
(2) in which the central silicon atom is bonded to the silicate nanoparticle.
In an
embodiment, the aromatic compound of formula (1) is bonded to the silicate
nanoparticle via
directly bonding the A group to the silicate nanoparticle.
[0068] In another embodiment, the chemical group is derived from a compound of
formula (1), (2), (3), (4), (5), (6), (7), or (8). In a specific embodiment,
the chemical group is
derived from a quaternary ammonium salt, quaternary phosphonium salt, alkoxy
silane,
halide, a guanidine, a guanidinium salt, a biguanidinium salt, or a sulfonium
salt. Here, the
chemical group can be derived from the functionalization compound (e.g., by
hydrolysis,
photolytic cleavage, thermal decomposition, elimination, substitution, etc.)
to produce the
chemical group including the aromatic or nonaromatic moiety Ar with or without
the linker
group L, such that the chemical group is bonded to the silicate nanoparticle.
In formula (1),
the bond between the A group and linker group, moiety Ar, or R group is
broken. In formula
(2), the bond between the Si atom and oxygen atom (-0-), linker group L,
moiety Ar, or R
group is broken. In formula (3), the bond between the halogen X and linker
group or moiety
Ar is broken. Thus, in an embodiment, the moiety Ar is directly bonded to the
silicate
nanoparticle. Alternatively, the linker group L can remain attached to the
moiety Ar such
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that the linker group L is directly bonded to the silicate nanoparticle with
the moiety Ar
indirectly bonded to the silicate nanoparticle via the linker group L. In an
embodiment, the R
group is directly bonded to the silicate nanoparticle. Consequently, it is
contemplated that the
linker group L can be disposed between the silicate nanoparticle and the
second portion of the
chemical group in the functionalized silicate nanoparticle. Thus, the
functionalized silicate
nanoparticle can be a reaction product of the silicate nanoparticle with the
aromatic or
nonaromatic compound, chemical group derived from the aromatic or nonaromatic
compound, or a combination thereof
[0069] In an embodiment, the functionalized silicate nanoparticle can be
prepared by
contacting the silicate nanoparticle with the functionalization compound or
chemical group
thereof under conditions effective to functionalize the silicate nanoparticle.
The chemical
group can be prepared by subjecting the functionalization compound to
conditions effective
to break bonds within the functionalization compound with a product fragment
being the
chemical group comprising the first and second portions herein. Conditions
include those of
temperature, pressure, catalysis (e.g., acid catalysis, metal catalysis,
support (e.g., zeolite)
promotion, and the like), and the like. After contact of the silicate
nanoparticle with the
aromatic compound or chemical group, the aromatic compound or chemical group
is bonded
to the silicate nanoparticle to form the functionalized silicate nanoparticle.
[0070] In a particular embodiment, an aryl alkoxy silane (e.g., trimethyl(2-
phenylethoxy)silane contacts a silicate nanoparticle clay (e.g.,
montmorillonite), and the
silicon of the trimethyl(2-phenylethoxy)silane bonds to the montmorillonite to
form a
functionalized silicate nanoparticle, having a phenyl ring extending from the
surface of the
montmorillonite to form a phenyl terminated functionalization. In another
embodiment, the
trimethyl(2-phenylethoxy)silane is subjected to a lysis condition to produce
an aromatic
moiety of a (2-phenylethyl)oxidanyl radical, which subsequently bonds to the
montmorillonite to form the functionalized silicate nanoparticle, having a
phenyl ring
extending from the surface of the montmorillonite to form a phenyl terminated
functionalization. Here, the linker group is ¨CH20-, which is directly bonded
to the silicate
nanoparticle via oxygen (0) and directly bonded to the phenyl ring by the
methylene (-CH2-).
[0071] In another embodiment, a heteroaryl quaternary ammonium salt (e.g., N,N-
dimethyl-N-(pyridine-3-ylmethyl)ethanaminium chloride (DIVIPME)) contacts a
silicate
nanoparticle silsesquioxane (e.g., 1-ally1-3,5,7,9,11,13,15-
heptacyclopentylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane). The
resulting
functionalized silicate nanoparticle includes the silsesquioxane directly
bonded to the amino
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nitrogen of the DMPME with the pyridinyl ring extending (via the methylene
amino
(-CH2N-) linker group) from the surface of the DMPME to form a pyridinyl
terminated
functionalization.
[0072] The composition is effective to remove an asphaltene particle from a
substrate
such as a metal, composite, sand, rock, mineral, glass, formation, downhole
element, or a
combination thereof Without wishing to be bound by theory, it is believed that
the
functionalized silicate nanoparticle is an amphiphile (i.e., having
hydrophilic and lipophilic
portions) and interacts with both the substrate and the asphaltene particle.
It is contemplated
that, within the functionalized silicate nanoparticle, the silicate
nanoparticle is hydrophilic
with a greater affinity for the substrate than the asphaltene particle, and
the aromatic or
nonaromatic functionalization (either aryl or heteroaryl terminated
functionalization) is
lipophilic with a greater affinity for the asphaltene particle than the
substrate. Moreover, the
asphaltene particle has a greater affinity for the aromatic or nonaromatic
functionalization of
the functionalized silicate nanoparticle than the silicate nanoparticle
portion of the
functionalized silicate nanoparticle or the substrate.
[0073] In an embodiment, in addition to the functionalized silicate
nanoparticle, the
composition also includes a fluid. The fluid can be present in an amount to
increase a
separation and aid removal of the asphaltene particle from the substrate. That
is, while the
functionalized silicate nanoparticle separates or removes the asphaltene
particle from the
substrate, the fluid can sweep the removed asphaltene particle (which has been
desorbed from
the substrate) away from a location proximate to the substrate. In an
embodiment, the fluid
can also aid in separating the asphaltene particle from the substrate. In an
embodiment, the
asphaltene particle has a greater affinity for the fluid than the substrate or
the silicate
nanoparticle portion of the functionalized silicate nanoparticle.
[0074] Exemplary fluids include water (liquid or steam), oil, carbon dioxide,
C1-C6
alkane (e.g., gaseous or liquefied at a temperature or pressure of the
surrounding environment
of the composition), tetrahydrofuran, 1,4-dioxane; diglyme, triglyme,
acetonitrile,
propionitrile, benzonitrile, N,N-dimethylformamide, N,N-dimethylacetamide,
dimethylsulfoxide, nitrobenzene, sulfolane, acetone, butanone, cyclohexanone,
diethyl
ketone, methyl isobutyl ketone, 2-pentanone, 2-hexanone, 2-heptanone, 3-
heptanone, 4-
heptanone, 3-pentanone, brine, completion fluid, acid, base, gas, polar
solvent, nonpolar
solvent, or a combination thereof Additional exemplary fluids also include
those typically
encountered downhole, such as hydrocarbons, solvents, or an aqueous
environment that
includes formation water, seawater, salt (i.e., brine, including formates and
inorganic salts,
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e.g., NaC1, KC1, CaC12, MgC12, CaBr2, ZnBr2, NaBr, and the like), completion
brine,
stimulation treatment fluid, remedial cleanup treatment fluid, acidic or
corrosive agent such
as hydrogen sulfide, hydrochloric acid, or other such corrosive agents, or a
combination
thereof Solvents include an inorganic solvent, organic solvent, or a
combination thereof
Exemplary solvents include water, alcohols (e.g., methanol, ethanol, and the
like), polyhydric
alcohols (e.g., diethylene glycol, dipropylene glycol, 1,2-propanediol, 1,4-
butanediol, 1,3-
butanediol, glycerol, 1,5-pentanediol, 2-ethyl-1-hexanol, and the like),
ketones (e.g.,
acetophenone, methyl-2-hexanone, and the like), ethers (e.g., ethylene glycol
monobutyl
ether, triethylene glycol monomethyl ether, and the like), carboxylic acid
esters (e.g., [2,2-
butoxy(ethoxy)]ethyl acetate and the like), esters of carbonic acid (e.g.,
propylene carbonate
and the like), inorganic acids (e.g., hydrofluoric acid, hydrochloric acid,
phosphoric acid,
sulfuric acid, nitric acid, and the like), organic acids (e.g., those having
an C1-C10 alkyl
chain, which is a straight or branched chain and can be substituted), or a
combination thereof
[0075] The brine can be, for example, seawater, produced water, completion
brine, or
a combination thereof The properties of the brine can depend on the identity
and
components of the brine. Seawater, as an example, contains numerous
constituents such as
sulfate, bromine, and trace metals, beyond typical halide-containing salts. On
the other hand,
produced water can be water extracted from a production reservoir (e.g.,
hydrocarbon
reservoir), produced from the ground. Produced water is also referred to as
reservoir brine
and often contains many components such as barium, strontium, and heavy
metals. In
addition to the naturally occurring brines (seawater and produced water),
completion brine
can be synthesized from fresh water by addition of various salts such as NaC1,
CaC12, or KC1
to increase the density of the brine, such as 10.6 pounds per gallon of CaC12
brine.
Completion brines typically provide a hydrostatic pressure optimized to
counter the reservoir
pressures downhole. The above brines can be modified to include an additional
salt. In an
embodiment, the additional salt included in the brine is NaC1, KC1, NaBr,
MgC12, CaC12,
CaBr2, ZnBr2, NH4C1, sodium formate, cesium formate, and the like. The salt
can be present
in the brine in an amount from about 0.5 wt.% to about 50 wt.%, specifically
about 1 wt.% to
about 40 wt.%, and more specifically about 1 wt.% to about 25 wt.%, based on
the weight of
the composition
[0076] The density, polarity, hydrophilicity, lipophilicity, and the like of
the fluid can
be achieved by selection of the foregoing fluids. The selection of the fluid
can depend on, for
example, a desired density for the composition. In an embodiment, fluid is
present in the
composition in an amount from about 1 weight percent (wt.%) to about 99 wt.%,
specifically
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about 10 wt.% to about 90 wt.%, and more specifically about 20 wt.% to about
80 wt.%,
based on the weight of the composition.
[0077] The composition can be prepared by combining the fluid with the
functionalized silicate nanoparticle. In an embodiment, the fluid is combined
with the
functionalization compound and silicate nanoparticle with subsequent formation
of the
functionalized silicate nanoparticle. According to an embodiment, the
functionalized silicate
nanoparticle can contact an asphaltene particle prior to addition of the
fluid. In an
embodiment, the silicate nanoparticle is contacted with the chemical group
(which includes
the aromatic moiety) derived from the functionalization compound, such as by
breaking a
bond between the chemical group and the rest of the functionalization
compound.
Consequently, it will be appreciated that the functionalized silicate
nanoparticle is a reaction
product of the silicate nanoparticle and the functionalization compound or
chemical group
thereof
[0078] In an embodiment, a method for making the functionalized silicate
nanoparticle includes contacting the silicate nanoparticle with a chemical
group to form the
functionalized silicate nanoparticle. The chemical group includes a first
portion and a second
portion comprising an aromatic or nonaromatic moiety. In forming the
functionalized silicate
nanoparticle, the first portion is directly bonded to the silicate
nanoparticle in the
functionalized silicate nanoparticle. The aryl or nonaromatic moiety extends
from the surface
of the functionalized silicate nanoparticle by the first portion.
[0079] The functionalized silicate nanoparticle herein has many uses and
beneficial
properties. In an embodiment, the functionalized silicate nanoparticle is
effective to remove
an asphaltene particle or other aromatic species from a substrate comprising a
metal,
composite, sand, rock, mineral, glass, formation, downhole element, or a
combination
thereof
[0080] According to an embodiment, an asphaltene particle, which is disposed
on a
substrate, can be removed from the substrate by contacting the asphaltene
particle with the
functionalized silicate nanoparticle. The functionalized silicate nanoparticle
can be
interposed between the asphaltene particle and the substrate. The asphaltene
particle can be
separated from the substrate with the functionalized silicate nanoparticle and
removed from
the substrate.
[0081] In an embodiment, the asphaltene particle can be exfoliated using the
functionalized silicate nanoparticle. Without wishing to be bound by theory,
it is believed the
aromatic moiety of the functionalized silicate nanoparticle can intercalate in
a gallery of the
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asphaltene particle. The functionalized silicate nanoparticle can be heated to
a temperature
effective to exfoliate the functionalized silicate nanoparticle, asphaltene
particle, or a
combination thereof According to an embodiment, the functionalized silicate
nanoparticle
expands upon heating. As a result of the expansion, a distance increases
between
neighboring aromatic moieties that are tethered to the functionalized silicate
nanoparticle.
The asphaltene particles expand and exfoliate in response to the increased
distance between
the neighboring aromatic moieties of the functionalized silicate nanoparticle
that are
intercalated in the gallery of asphaltene molecules of the asphaltene
particle. Exfoliation of
the asphaltene particle can occur for asphaltene particles attached to the
substrate or for those
asphaltene particles that are not attached to a substrate.
[0082] The removal of the asphaltene particle from the substrate can also
include
contacting the asphaltene particle with a fluid. Here, contact of the fluid
can increase a
distance of separation between the asphaltene particle and the substrate
before or after
separating the asphaltene particle from the substrate.
[0083] Beneficially, the methods herein, e.g., contacting the silicate
nanoparticle with
the chemical group to form the functionalized silicate nanoparticle, can be
performed in-situ
in an environment such as a pipeline, downhole, formation, tubular, frac
feature (e.g., a vein
or pore), production zone, reservoir, refinery, transport tube, production
tube, or a
combination thereof Moreover, the asphaltene particle or exfoliated asphaltene
can be
removed from the environment after separating the asphaltene particle from the
substrate.
[0084] Furthermore, it has been found that perturbing the internal structure
of
asphaltene particles, for example, in a micelle or other aggregate, can lead
to increased
quality of oil containing asphaltenes. Additionally, degradation of asphaltene
aggregates
herein enhances production of petroleum fluid in a downhole, subsurface, or
ground
environment. Furthermore, removal of asphaltene from pores of a rock
formation, within a
reservoir, or from a sidewall of a tubular, production tubing, borehole, or
transportation tube
can improve the permeability of such structures, leading to increased quality
of oil as well as
increased or prolonged lifetime for oil production.
[0085] In an embodiment, a method for decomposing an asphaltene particle
includes
contacting the asphaltene particle with the functionalized silicate
nanoparticle and causing the
intercalating agent to increase a distance between asphaltene molecules in the
asphaltene
particle to decompose the asphaltene particle. As above, the aromatic moiety
or nonaromatic
moiety of the functionalized silicate nanoparticle can be disposed in the
gallery between
adjacent asphaltene molecules or disposed at the periphery of an asphaltene
molecule such as
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proximate to an edge of an aromatic plane or terminal chain attached to an
aromatic portion
of an asphaltene molecule in the asphaltene particle. During the exfoliation
of the asphaltene
particle, the functionalized silicate nanoparticle portion in the gallery
forces the adjacent
asphaltene molecules away from one another, thereby separating the asphaltene
molecules.
In this manner, an asphaltene molecule can be exfoliated from the asphaltene
particle.
[0086] As used herein, "decomposition" refers to an increased separation
distance
between asphaltene molecules in an asphaltene particle, expansion of the
volume of the
asphaltene particle, complete removal of an asphaltene molecule from an
asphaltene particle,
or a change in the electronic structure or bonding in an asphaltene molecule
in an asphaltene
particle. Thus, decomposition includes, for example, deagglomeration,
exfoliation,
disaggregation, and the like. An example of a change in the electronic
structure or bonding in
an asphaltene molecule in an asphaltene particle includes converting a bond
(e.g., converting
a it bond to a bond or vice versa), breaking a bond, or forming a bond.
[0087] Thus, according to an embodiment, the method includes exfoliating an
asphaltene particle. In an embodiment, exfoliating includes removing an
asphaltene molecule
from the asphaltene particle. Exfoliation of an asphaltene particle, in an
embodiment,
decreases the number of asphaltene molecules in the asphaltene particle. It
will be
appreciated that exfoliation of asphaltene particles can provide exfoliated
asphaltene as a
single asphaltene molecule or as a micelle or layered particle containing
fewer asphaltene
molecules than the non-exfoliated asphaltene particle.
[0088] In a further embodiment, the method includes increasing the temperature
of
the functionalized silicate nanoparticle, asphaltene particle, or substrate.
Increasing the
temperature includes techniques that can elevate the temperature to about 60 C
to about
1200 C, specifically about 100 C to about 1000 C, and more specifically about
100 C to
about 800 C. Such techniques involve, for example, in-situ combustion, steam
introduction,
heated fluid injection, or a combination comprising at least one of the
foregoing. In an
embodiment, a downhole environment is heated by introducing steam in an
injection well
with the steam propagating through the formation and heating the
functionalized silicate
nanoparticle, asphaltene particle, or substrate. It is contemplated that
increasing the
temperature can cause reaction, including decomposition of the functionalized
silicate
nanoparticle, substrate, or asphaltene particle. In addition, the asphaltene
particles can be
heated to expand, decreasing the mutual attraction among asphaltene molecules
therein.
Depending on the amount of expansion of the asphaltene particle, asphaltene
molecules can
exfoliate from the asphaltene particles. In one embodiment, the heating of a
functionalized
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silicate nanoparticle associated with the asphaltene particle can lead to
exfoliation of an
asphaltene molecule therefrom.
[0089] Heated fluid injection can include heating a fluid (e.g., a solvent)
and
subsequently disposing the heated fluid downhole to increase the temperature
of the
asphaltene particles. In a non-limiting embodiment, in-situ combustion
increases the
temperature of the functionalized silicate nanoparticle by injecting a gas
containing oxygen,
for example air, downhole and igniting oil in the reservoir. The combustion
releases heat,
which can be absorbed by the functionalized silicate nanoparticle or
asphaltene particle, in
order to exfoliate an asphaltene molecule from the asphaltene particle.
[0090] In certain embodiments, the method further includes applying sonic
frequencies to the intercalating agent. The sonic frequencies can be from
about 400 hertz
(Hz) to about 400 megahertz (MHz), specifically about 800 Hz to about 350 MHz,
and more
specifically about 1 kilohertz (kHz) to about 300 MHz. A transducer placed
near the
asphaltene particle can produce the sonic frequency, which can destructively
interact with the
asphaltene particle or functionalized silicate nanoparticle. Sonic frequencies
may induce
chemical reactions or expansion of the functionalized silicate nanoparticle
and disrupt
interparticle bonding in the asphaltene particle, leading to exfoliation of an
asphaltene
molecule. The sonic frequencies can detach neighboring polyaromatic planes of
adjacent
asphaltene molecules. Without wishing to be bound by any particular theory,
such
deterioration of the asphaltene particle may be induced by short-lived,
localized disturbances
(e.g., a hot spot) produced by the implosion of bubbles in the course of
acoustic cavitation.
[0091] In some embodiments, the functionalized silicate nanoparticle is
dispersed in a
fluid. Such dispersion can occur before or after contacting the asphaltene
particle with the
functionalized silicate nanoparticle. The fluid can be an organic solvent,
inorganic solvent, or
a combination comprising at least one of the foregoing. Exemplary fluids are
those above
and can include CH3NO2, CH2C12, CHC13, CC14, C2H4C12, H20, SOC12, 502C12,
53N3C13,
benzene, toluene, o-xylene, dimethyl sulfoxide, furan, tetrahydrofuran, o-
dioxane, m-dioxane,
p-dioxane, dimethoxyethane, n-methyl-pyrrolidone, n,n-dimethylacetamide, y-
butyrolactone,
1,3-dimethy1-2-imidazolidinone, benzyl benzoate, hexafluorobenzene,
octafluorotoluene,
pentafluorobenzonitrile, pentafluoropyridine, pyridine, dimethylformamide,
hexamethylphosphoramide, nitromethane, benzonitrile, or the like. In an
embodiment, the
fluid can react with the functionalized silicate nanoparticle to produce
product compounds
that decompose the asphaltene particle.
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[0092] In another embodiment, after contact with the functionalized silicate
nanoparticle, the asphaltene particle can be heated. The heat is absorbed by
the asphaltene
molecule, causing high amplitude vibrational motion of the non-polar groups,
e.g.,
hydrocarbon tails that terminate an asphaltene molecule. In this manner,
exfoliation of
asphaltene molecules can occur by vibrationally-mediated dissociation or
further increased
spacing among the asphaltene molecules in the asphaltene particle.
Additionally, the heated
asphaltene particles can be more miscible with the fluid. Here, the fluid can
be as before and
can include, for example, an alkane, aromatic solvent, carbon dioxide, carbon
disulfide, resin,
oil, or a combination thereof Particular fluids include, 2,2-dimethylpropane,
butane, 2,2-
dimethylbutane, pentane, hexane, heptane, octane, nonane, decane, unedecane,
cyclopentane,
cyclohexane, benzene, toluene, o-xylene, dimethyl sulfoxide, furan,
tetrahydrofuran, o-
dioxane, m-dioxane, p-dioxane, dimethoxyethane, n-methyl-pyrrolidone, n,n-
dimethylacetamide, y-butyrolactone, 1,3-dimethy1-2-imidazolidinone, benzyl
benzoate,
hexafluorobenzene, octafluorotoluene, pentafluorobenzonitrile,
pentafluoropyridine, pyridine,
dimethylformamide, hexamethylphosphoramide, nitromethane, benzonitrile, and
the like.
[0093] In another embodiment, a fluid or surfactant can contact the exfoliated
asphaltene particle and allow dispersion of the asphaltene particle, for
example, in an oil.
Exemplary fluids include solvent such as a polar solvent, aromatic solvent, or
a combination
comprising at least one of the foregoing. The polar solvent can be an alcohol
(e.g., ethanol,
propanol, glycol, and the like), amine (e.g., methylamine, diethyl amine,
tributyl amine, and
the like), amide (e.g., dimethylformamide), ether (e.g., diethyl ether,
polyether,
tetrahydrofuran, and the like), ester (e.g., ethyl acetate, methyl butyrate,
and the like), ketone
(e.g., acetone), acetonitrile, dimethylsulfoxide, propylene carbonate, and the
like. The
aromatic solvent can be, for example, benzene, toluene, xylene, pyridine,
hexafluorobenzene,
octafluorotoluene, pentafluoropyridine, and the like.
[0094] The methods and materials herein can be used to enhance oil recovery in
a
reservoir, borehole, downhole, production zone, formation, or a combination
thereof
Additionally, the methods and materials can be used to increase flow velocity
of oil in a
processing facility, refinery, pre-refinery facility, tubular, reactor, or a
combination thereof
Removal of the asphaltene molecules from the substrate by the functionalized
silicate
nanoparticle herein can be used to extract asphaltene deposits that constrict
flow in, for
example, a tubular, and can restore flow in a plugged reservoir. Additionally,
exfoliation of
asphaltenes can increase permeability in porous media (e.g., a sand screen
that can be
deformable such as a polymeric open-cell foam) and flow channels (e.g., a
crack in a
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formation filled with proppant such as obtained in a fracking process). As a
result of
exfoliation to decrease the number of asphaltene molecules in an asphaltene
particle, oil
viscosity also decreases. Lowering the viscosity of the oil improves
production efficiency.
Additionally, the detrimental effects of asphaltene can be diminished or
eliminated, including
alleviation of flocculates of asphaltenes that can plug a reservoir or
production tubing, restrict
flow in a transport line, stabilize water-in-oil emulsions, foul a production
facility, alter
wettability of porous rock in the reservoir, or poison a refinery catalyst.
[0095] Thus, in an embodiment, a method for producing decomposed asphaltene
includes disposing a functionalized silicate nanoparticle in an oil
environment and contacting
an asphaltene particle in the oil environment with the functionalized silicate
nanoparticle.
The embodiment also includes decomposing the asphaltene particle to produce
decomposed
asphaltene. In a certain embodiment, the method also includes breaking a water-
in-oil
emulsion in response to decomposing the asphaltene particle. Here the oil-in-
water emulsion
can be a Pickering emulsion that is stabilized by asphaltene particles at the
water-oil
interface. Upon decomposing the asphaltene particles, the emulsion is
destabilized and thus
broken.
[0096] In addition, water can be introduced by methods such as hot water
injection,
steam stimulation, or a combination comprising at least one of the foregoing.
It is believed
that, in this way, the asphaltene particles decompose as exfoliation of
asphaltene molecules in
the asphaltene particles occurs. As a result, the viscosity of oil in the oil
environment is
reduced. Moreover, increasing the mobility of the asphaltene particles by
removing them
from the substrate is advantageous as noted above. Therefore, the method can
be used to
enhance oil recovery. In a further embodiment, the method includes increasing
a
permeability of a reservoir of the oil environment. According to another
embodiment, the
method further includes producing the oil including the decomposed or removed
asphaltene
from the oil environment, wherein decomposing the asphaltene particle occurs
prior to
producing the oil. Alternatively or in addition, decomposing the asphaltene
particle can
occur subsequent to producing the oil.
[0097] While one or more embodiments have been shown and described,
modifications and substitutions may be made thereto without departing from the
spirit and
scope of the invention. Accordingly, it is to be understood that the present
invention has been
described by way of illustrations and not limitation. Embodiments herein can
be used
independently or can be combined.
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[0098] All ranges disclosed herein are inclusive of the endpoints, and the
endpoints
are independently combinable with each other. The ranges are continuous and
thus contain
every value and subset thereof in the range. The suffix "(s)" as used herein
is intended to
include both the singular and the plural of the term that it modifies, thereby
including at least
one of that term (e.g., the colorant(s) includes at least one colorants).
"Optional" or
"optionally" means that the subsequently described event or circumstance can
or cannot
occur, and that the description includes instances where the event occurs and
instances where
it does not. As used herein, "combination" is inclusive of blends, mixtures,
alloys, reaction
products, and the like.
[0099] As used herein, "a combination thereof' refers to a combination
comprising at
least one of the named constituents, components, compounds, or elements,
optionally
together with one or more of the same class of constituents, components,
compounds, or
elements.
[0100] The use of the terms "a" and "an" and "the" and similar referents in
the
context of describing the invention (especially in the context of the
following claims) are to
be construed to cover both the singular and the plural, unless otherwise
indicated herein or
clearly contradicted by context. "Or" means "and/or." It should further be
noted that the
terms "first," "second," and the like herein do not denote any order,
quantity, or importance,
but rather are used to distinguish one element from another. The modifier
"about" used in
connection with a quantity is inclusive of the stated value and has the
meaning dictated by the
context (e.g., it includes the degree of error associated with measurement of
the particular
quantity). The conjunction "or" is used to link objects of a list or
alternatives and is not
disjunctive; rather the elements can be used separately or can be combined
together under
appropriate circumstances.
34
