U.S. patent application number 12/491673 was filed with the patent office on 2009-10-15 for surfactant compositions and associated method.
Invention is credited to Wenqing Peng, Dong Wang.
Application Number | 20090259062 12/491673 |
Document ID | / |
Family ID | 38140193 |
Filed Date | 2009-10-15 |
United States Patent
Application |
20090259062 |
Kind Code |
A1 |
Wang; Dong ; et al. |
October 15, 2009 |
SURFACTANT COMPOSITIONS AND ASSOCIATED METHOD
Abstract
A composition having a first hydrophobic moiety linked to a
spacer, which is linked to a second hydrophobic moiety to form a
Gemini surfactant is provided. Each hydrophobic moiety of the
foregoing composition may include silicon. A method for linking a
first hydrophobic moiety to a second hydrophobic moiety using a
spacer to form a Gemini surfactant is provided. A pesticide having
an active ingredient and a composition having a first hydrophobic
moiety linked to a spacer, which is linked to a second hydrophobic
moiety to form a Gemini surfactant is also provided.
Inventors: |
Wang; Dong; (Shanghai,
CN) ; Peng; Wenqing; (Shanghai, CN) |
Correspondence
Address: |
MOMENTIVE PERFORMANCE MATERIALS INC.;IP LEGAL
ONE PLASTICS AVENUE, BLDG. 51
PITTSFIELD
MA
01201-3697
US
|
Family ID: |
38140193 |
Appl. No.: |
12/491673 |
Filed: |
June 25, 2009 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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11302551 |
Dec 13, 2005 |
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12491673 |
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Current U.S.
Class: |
556/431 ;
556/443 |
Current CPC
Class: |
B01F 17/0071 20130101;
C11D 1/82 20130101; C11D 3/373 20130101 |
Class at
Publication: |
556/431 ;
556/443 |
International
Class: |
C07F 7/18 20060101
C07F007/18 |
Claims
1. A composition comprising: a first hydrophobic moiety linked to a
spacer, which is linked to a second hydrophobic moiety to form a
Gemini surfactant, wherein each hydrophobic moiety comprises
silicon.
2. The composition as defined in claim 1, wherein the spacer is a
hydrophilic moiety.
3. The composition as defined in claim 1, wherein the spacer
comprises one or more of a cationic group, an anionic group, a
polar nonionic group, or an amphoteric group.
4. The composition as defined in claim 1, wherein the spacer
comprises one or more of an ammonium group, a carboxylic acid
group, a sulfonic acid group, a sulfuric acid group, a sulfinic
acid group, a phosphonic acid group, a boronic acid group, a fatty
acid group, a fatty acid ester group, a peptide group, a
carbohydrate group, or a polyether.
5. The composition as defined in claim 1, wherein the first
hydrophobic moiety and the second hydrophobic moiety each comprises
one or more of organosilioxane groups or organosilane groups.
6. The composition as defined in claim 5, wherein one or both of
the first hydrophobic moiety or the second hydrophobic moiety
comprises an organosiloxane group having a formula (IV) or (V):
(R.sup.2R.sup.3R.sup.4SiO.sub.1/2).sub.2(R.sup.5R.sup.6SiO.sub.2/2).sub.a-
(R.sup.7SiO.sub.2/2)-- (IV)
(R.sup.8R.sup.9R.sup.10SiO.sub.1/2)(R.sup.11R.sup.12SiO.sub.2/2).sub.b(R.-
sup.13R.sup.14SiO.sub.1/2)-- (V) wherein "a" is an integer from 0
to 50, "b" is an integer from 1 to 50, and R.sup.2 to R.sup.14 are
independently at each occurrence a hydrogen atom, a
C.sub.1-C.sub.30 aliphatic radical, a C.sub.3-C.sub.30 aromatic
radical, or a C.sub.3-C.sub.30 cycloaliphatic radical.
7. The composition as defined in claim 5, wherein one or both of
the first hydrophobic moiety or the second hydrophobic moiety
comprises an organosilane group having a formula (VIII), (IX), (X)
or (XI):
(R.sup.15R.sup.16R.sup.17Si).sub.2(R.sup.18R.sup.19Si).sub.a(R.sup.20Si)--
- (VIII)
(R.sup.21R.sup.22R.sup.23Si).sub.b(R.sup.24R.sup.25Si).sub.b(R.-
sup.26R.sup.27Si)-- (IX)
(R.sup.28R.sup.29R.sup.30Si).sub.2(CR.sup.31R.sup.32).sub.a(R.sup.33Si)--
(X)
(R.sup.34R.sup.35R.sup.36Si)(CR.sup.37R.sup.38).sub.b(R.sup.39R.sup-
.40Si)-- (XI) wherein "a" is independently at each occurrence an
integer from 0 to 50, "b" is independently at each occurrence an
integer from 1 to 50, and R.sup.15 to R.sup.40 are independently at
each occurrence a hydrogen atom, a C.sub.1-C.sub.30 aliphatic
radical, a C.sub.3-C.sub.30 aromatic radical, or a C.sub.3-C.sub.30
cycloaliphatic radical.
8. The composition as defined in claim 1, wherein the first
hydrophobic moiety and the second hydrophobic moiety are the
same.
9. The composition as defined in claim 1, wherein the first
hydrophobic moiety and the second hydrophobic moiety provide steric
hindrance to a hydrolytic composition to protect the spacer from
hydrolysis.
10. The composition as defined in claim 9, wherein the spacer is
hydrolytically stable in an aqueous solution at a pH in a range of
from about pH 2 to about pH 7.
11. The composition as defined in claim 9, wherein the spacer is
hydrolytically stable in an aqueous solution at a pH in a range of
from about pH 7 to about pH 10.
12. The composition as defined in claim 1, wherein an aqueous
solution of the composition is super-spreading at a concentration
greater than about 0.1 weight percent.
13. The composition as defined in claim 12, wherein a 10 microliter
drop of the aqueous solution of the composition spreads to a
diameter greater than five times as large on a hydrophobic surface
as a 10 microliter drop of distilled water on the hydrophobic
surface, wherein the diameter is measured 30 seconds after
application of the drop to the hydrophobic surface.
14. The composition as defined in claim 1, wherein the composition
has an aqueous critical aggregation concentration in a range from
about 0.001 mM to about 100 mM.
15. The composition as defined in claim 1, wherein the composition
at a concentration greater than 0.1 weight percent has an aqueous
surface tension in a range from about 10 mN/m to about 40 mN/m.
16. A method, comprising: linking a first hydrophobic moiety to a
second hydrophobic moiety using a spacer to form a Gemini
surfactant, wherein each hydrophobic moiety comprises silicon.
17. The method as defined in claim 16, further comprising adding
water to the Gemini surfactant to form an aqueous mixture.
18. A composition comprising: a first hydrophobic moiety linked to
a spacer, which is linked to a second hydrophobic moiety to form a
Gemini surfactant, wherein each hydrophobic moiety comprises
silicon, wherein the first hydrophobic moiety and the second
hydrophobic moiety each comprise one or more organosilioxane group
or organosilane group, and wherein one or both of the first
hydrophobic moiety or the second hydrophobic moiety comprises an
organosiloxane group having a formula (IV), (V), (VIII), (IX), (X)
or (XI):
(R.sup.2R.sup.3R.sup.4SiO.sub.1/2).sub.2(R.sup.5R.sup.6SiO.sub.2/2).sub.a-
(R.sup.7SiO.sub.2/2)-- (IV)
(R.sup.8R.sup.9R.sup.10SiO.sub.1/2)(R.sup.11R.sup.12SiO.sub.2/2).sub.b(R.-
sup.13R.sup.14SiO.sub.1/2)-- (V)
(R.sup.15R.sup.16R.sup.17Si).sub.2(R.sup.18R.sup.19Si).sub.a(R.sup.20Si)--
- (VIII)
(R.sup.21R.sup.22R.sup.23Si)(R.sup.24R.sup.25Si).sub.b(R.sup.26-
R.sup.27Si)-- (IX)
(R.sup.28R.sup.29R.sup.30Si).sub.2(CR.sup.31R.sup.32).sub.a(R.sup.33Si)--
(X)
(R.sup.34R.sup.35R.sup.36Si)(CR.sup.37R.sup.38).sub.b(R.sup.39R.sup-
.40Si)-- (XI) wherein R.sup.2 to R.sup.40 are independently at each
occurrence a hydrogen atom, a C.sub.1-C.sub.30 aliphatic radical, a
C.sub.3-C.sub.30 aromatic radical, or a C.sub.3-C.sub.30
cycloaliphatic radical.
19. The composition as defined in claim 18, wherein the spacer
comprises one or more of an carboxylic acid group, a sulfonic acid
group, a sulfuric acid group, a sulfinic acid group, a phosphonic
acid group, a boronic acid group, a fatty acid group, or a fatty
acid ester group.
20. The composition as defined in claim 18, wherein the spacer
comprises one or more of an ammonium group, peptide group,
carbohydrate group, or polyether.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of application Ser. No.
11/302,551, filed Dec. 13, 2005.
BACKGROUND
[0002] The invention includes embodiments that relate to a
composition having a first hydrophobic moiety linked to a spacer,
which is linked to a second hydrophobic moiety to form a Gemini
surfactant. The invention includes embodiments that relate to
method of making and using the Gemini surfactant composition.
[0003] Organosilicone compounds may be useful because of their
unique wetting properties. These organosilicone compounds may
provide surface tension values lower than other commonly used
surfactants. A trisiloxane ethoxylate-based surfactant (TSE) may be
one example of an organosilicone surfactant that may be used as
agricultural adjuvants. These surfactants may have the property of
"super-spreading" that is the ability of a drop of the mixture to
spread to a diameter greater than a drop of distilled water on a
hydrophobic surface.
[0004] TSE surfactants may have reduced super-spreading if the
degree of ethoxylation exceeds about 12 EO units. TSE's containing
the higher EO adducts may show spreading properties similar to
conventional nonsilicone surfactants.
[0005] Conventional trisiloxane-based surfactants may have poor
hydrolytic stability and may be easily hydrolyzed under acidic or
basic conditions. Structural modifications to increase the
hydrolytic stability of the trisiloxane-based surfactants may
result in poor spreading properties. It may be desirable to have a
hydrolytically stable surfactant that shows relatively improved
super-spreading performance and adjuvant properties. It may be
desirable to have a surfactant with properties other than those
currently available for varied applications.
BRIEF DESCRIPTION
[0006] In one embodiment, the invention provides a composition
having a first hydrophobic moiety linked to a spacer, which is
linked to a second hydrophobic moiety to form a Gemini surfactant,
wherein each hydrophobic moiety comprises silicon.
[0007] In one embodiment, the invention provides a method for
linking a first hydrophobic moiety to a second hydrophobic moiety
using a spacer to form a Gemini surfactant, wherein each
hydrophobic moiety comprises silicon.
DETAILED DESCRIPTION
[0008] The invention includes embodiments that relate to a
composition having a first hydrophobic moiety linked to a spacer,
which is linked to a second hydrophobic moiety to form a Gemini
surfactant, such that the first hydrophobic moiety and the second
hydrophobic moiety may include silicon. Gemini surfactants are
surfactants having two or more hydrophobic groups and at least one
hydrophilic group attached to hydrophobic portions in the
molecule.
[0009] In the following specification and the claims which follow,
reference will be made to a number of terms have the following
meanings. The singular forms "a", "an" and "the" include plural
referents unless the context clearly dictates otherwise.
Approximating language, as used herein throughout the specification
and claims, may be applied to modify any quantitative
representation that could permissibly vary without resulting in a
change in the basic function to which it is related. Accordingly, a
value modified by a term such as "about" is not to be limited to
the precise value specified. In some instances, the approximating
language may correspond to the precision of an instrument for
measuring the value.
[0010] A composition is provided that may have a first hydrophobic
moiety linked to a spacer, which is linked to a second hydrophobic
moiety, to form a Gemini surfactant. In one embodiment, the spacer
may include a hydrophilic moiety. Suitable hydrophilic moieties may
include one or more of a cationic group, an anionic group, a polar
nonionic group, or an amphoteric group. Suitable cationic groups
may include, but are not limited to, ammonium groups or positively
charged peptide groups. Suitable anionic groups may include, but
are not limited to, carboxylic acid groups, sulfonic acid groups,
sulfuric acid groups, sulfinic acid groups, phosphonic acid groups,
boronic acid groups, fatty acid groups, or negatively charged
peptide groups. Suitable polar non-ionic groups may include, but
are not limited to, fatty acid ester groups, carbohydrate groups,
or polyether and its derivatives. Suitable amphoteric groups may
include, but are not limited to, peptide groups. In one embodiment,
a cationic group (for example an ammonium group) and an anionic
group (for example a phosphate group) may be present in the spacer
to form an amphoteric surfactant.
[0011] The terms anionic group and cationic group may encompass
both protonated and deprotonated forms of the anionic and the
cationic groups. For example, when the anionic group is described
as a "carboxylic acid group", and both the protonated form of the
carboxylic acid (CO.sub.2H) and deprotonated form of the carboxylic
acid (CO.sub.2.sup.-) may be included within the meaning of the
term "carboxylic acid group". Thus, the cationic group and the
anionic group may include salts of carboxylic acid group, a
sulfonic acid group, a sulfuric acid group, a sulfinic acid group,
a phosphoric acid group, a boronic acid group, or a fatty acid
group.
[0012] A suitable hydrophilic moiety of the spacer may include one
or more of an ammonium group, a carboxylic acid group, a sulfonic
acid group, a sulfuric acid group, a sulfinic acid group, a
phosphonic acid group, a boronic acid group, a fatty acid group, a
fatty acid ester group, a peptide group, a carbohydrate group, or a
polyether. In one embodiment, the hydrophilic moiety of the spacer
may be a nonionic polar group including one or more of a peptide
group, a carbohydrate group, or a polyether.
[0013] A peptide group for the spacer may have a linear sequence of
amino acids connected one to the other by peptide bonds between the
alpha amino and carboxyl groups of adjacent amino acids. The amino
acids may be the standard amino acids or some other non standard
amino acids. Some of the standard nonpolar (hydrophobic) amino
acids include alanine (Ala), leucine (Leu), isoleucine (Ile),
valine (Val), proline (Pro), phenylalanine (Phe), tryptophan (Trp)
and methionine (Met). The polar neutral amino acids include glycine
(Gly), serine (Ser), threonine (Thr), cysteine (Cys), tyrosine
(Tyr), asparagine (Asn) and glutamine (Gln). The positively charged
(basic) amino acids include arginine (Arg), lysine (Lys) and
histidine (His). The negatively charged (acidic) amino acids
include aspartic acid (Asp) and glutamic acid (Glu). The non
standard amino acids may be formed in body, for example by
posttranslational modification, some examples of such amino acids
being selenocysteine and pyrolysine. The peptides may be of a
variety of lengths, either in their neutral (uncharged) form or in
forms such as their salts. The peptides may be either free of
modifications such as glycosylations, side chain oxidation or
phosphorylation or comprising such modifications. Substitutes for
an amino acid within the sequence may also be selected from other
members of the class to which the amino acid belongs. A suitable
peptide group may also include peptides modified by additional
substituents attached to the amino side chains, such as glycosyl
units, lipids or inorganic ions such as phosphates as well as
chemical modifications of the chains. Thus, the term "peptide" or
its equivalent may be intended to include the appropriate amino
acid sequence referenced, subject to the foregoing modifications,
which do not destroy its functionality.
[0014] A carbohydrate group for the spacer may be a polyhydroxy
aldehyde or ketone, or a compound that can be derived from them by
any of several means including (1) reduction to give sugar
alcohols; (2) oxidation to give sugar acids; (3) substitution of
one or more of the hydroxyl groups by various chemical groups, for
example, hydrogen may be substituted to give deoxysugars, and amino
group (NH.sub.2 or acetyl-NH) may be substituted to give amino
sugars; (4) derivatization of the hydroxyl groups by various
moieties, for example, phosphoric acid to give phosphor sugars, or
sulphuric acid to give sulfo sugars, or reaction of the hydroxyl
groups with alcohols to give monosaccharides, disaccharides,
oligosaccharides, and polysaccharides. Carbohydrate group may
include monosaccharides, disaccharides, or oligosaccharides.
Suitable monosachharides may include, but are not limited to,
glucose, fructose, mannose and galactose. A disachharide, as
further defined herein, is a compound, which upon hydrolysis yields
two molecules of a monosachharide. Suitable disachharides may
include, but are not limited to, lactose, maltose, isomaltose,
trehalose, maltulose, and sucrose. Suitable oligosachharides may
include, but are not limited to, raffinose and acarbose. Also
included are the sachharides modified by additional substituents,
for example, methyl glycosides, N-acetyl-glucosamine,
N-acetyl-galactosamine and their de-acetylated forms.
[0015] A polyether group for the spacer may have structure of
formula (I).
--(CH.sub.2).sub.x--O--(C.sub.2H.sub.4O).sub.y(C.sub.2H.sub.3R.sup.1O).s-
ub.z--(CH.sub.2).sub.x-- (I)
wherein "x" is independently at each occurrence an integer from 1
to 6, "y" and "z" are independently integers from 0 to 12, with the
proviso that y+z is less than or equal to 12, and R.sup.1 is a
C.sub.1-C.sub.10 aliphatic radical. The alkyleneoxide polymers
included in structure (I) may have a broad molecular weight
distribution and the indices "y" and "z" stated above designate the
average composition only. In one embodiment, the molecular weight
distribution of alkyleneoxide polymers may be less than about 1.2.
The distribution of the different alkyleneoxide units may be random
or in blocks.
[0016] Aliphatic radical is an organic radical having at least one
carbon atom, a valence of at least one and may be a linear or
branched array of atoms. Aliphatic radicals may include heteroatoms
such as nitrogen, sulfur, silicon, selenium and oxygen or may be
composed exclusively of carbon and hydrogen. Aliphatic radical may
include a wide range of functional groups such as alkyl groups,
alkenyl groups, alkynyl groups, halo alkyl groups, conjugated
dienyl groups, alcohol groups, ether groups, aldehyde groups,
ketone groups, carboxylic acid groups, acyl groups (for example,
carboxylic acid derivatives such as esters and amides), amine
groups, nitro groups and the like. For example, the
4-methylpent-1-yl radical is a C.sub.6 aliphatic radical comprising
a methyl group, the methyl group being a functional group, which is
an alkyl group. Similarly, the 4-nitrobut-1-yl group is a C.sub.4
aliphatic radical comprising a nitro group, the nitro group being a
functional group. An aliphatic radical may be a haloalkyl group
that includes one or more halogen atoms, which may be the same or
different. Halogen atoms include, for example; fluorine, chlorine,
bromine, and iodine. Aliphatic radicals having one or more halogen
atoms include the alkyl halides: trifluoromethyl,
bromodifluoromethyl, chlorodifluoromethyl,
hexafluoroisopropylidene, chloromethyl, difluorovinylidene,
trichloromethyl, bromodichloromethyl, bromoethyl,
2-bromotrimethylene (e.g., --CH.sub.2CHBrCH.sub.2--), and the like.
Further examples of aliphatic radicals include allyl, aminocarbonyl
(--CONH.sub.2), carbonyl, dicyanoisopropylidene
--CH.sub.2C(CN).sub.2CH.sub.2--), methyl (--CH.sub.3), methylene
(--CH.sub.2--), ethyl, ethylene, formyl (--CHO), hexyl,
hexamethylene, hydroxymethyl (--CH.sub.2OH), mercaptomethyl
(--CH.sub.2SH), methylthio (--SCH.sub.3), methylthiomethyl
(--CH.sub.2SCH.sub.3), methoxy, methoxycarbonyl(CH.sub.3OCO--),
nitromethyl (--CH.sub.2NO.sub.2), thiocarbonyl,
trimethylsilyl((CH.sub.3).sub.3Si--), t-butyldimethylsilyl,
trimethoxysilylpropyl((CH.sub.3O).sub.3SiCH.sub.2CH.sub.2CH.sub.2--),
vinyl, vinylidene, and the like. By way of further example, a
"C.sub.1-C.sub.30 aliphatic radical" contains at least one but no
more than 30 carbon atoms. A methyl group (CH.sub.3--) is an
example of a C.sub.1 aliphatic radical. A decyl group
(CH.sub.3(CH.sub.2).sub.9--) is an example of a C.sub.10 aliphatic
radical.
[0017] In one embodiment, the spacer may include a polyether having
structure of formula (II).
--(CH.sub.2).sub.4--O--(C.sub.2H.sub.4O).sub.8(C.sub.3H.sub.6O).sub.4--(-
CH.sub.2).sub.4-- (II)
[0018] Structure (II) falls within generic formula (I) and
represents the case where "x" in structure (I) is 4, "y" in
structure (I) is 8, "z" in structure (I) is 4, and R.sup.1 is a
methyl radical. In another embodiment, the spacer may include a
polyether having structure of formula (III).
--(CH.sub.2).sub.3--O--(C.sub.2H.sub.4O).sub.9--(CH.sub.2).sub.3--
(III)
[0019] Structure (III) falls within generic formula (I) and
represents the case where "x" in structure (I) is 3, "y" in
structure (I) is 9, and "z" in structure (I) is 0.
[0020] In one embodiment, the first hydrophobic moiety and the
second hydrophobic moiety of the Gemini surfactant may include one
or more organosiloxane groups or organosilane groups. The first
hydrophobic group and the second hydrophobic group may be same on
either side of the spacer or different.
[0021] Suitable organosiloxane groups may have a structure of
formula (IV) or (V):
(R.sup.2R.sup.3R.sup.4SiO.sub.1/2).sub.2(R.sup.5R.sup.6SiO.sub.2/2).sub.-
a(R.sup.7SiO.sub.2/2)-- (IV)
(R.sup.8R.sup.9R.sup.10SiO.sub.1/2)(R.sup.11R.sup.12SiO.sub.2/2).sub.b(R-
.sup.13R.sup.14SiO.sub.1/2)-- (V)
wherein "a" is an integer from 0 to 50, "b" is an integer from 1 to
50, and R.sup.2 to R.sup.14 are independently at each occurrence a
hydrogen atom, a C.sub.1-C.sub.30 aliphatic radical, a
C.sub.3-C.sub.30 aromatic radical, or a C.sub.3-C.sub.30
cycloaliphatic radical. Aliphatic radical is defined hereinabove.
Aliphatic radical and aromatic radical may be defined as the
following:
[0022] An aromatic radical is an array of atoms having a valence of
at least one and having at least one aromatic group. This may
include heteroatoms such as nitrogen, sulfur, selenium, silicon and
oxygen, or may be composed exclusively of carbon and hydrogen.
Suitable aromatic radicals may include phenyl, pyridyl, furanyl,
thienyl, naphthyl, phenylene, and biphenyl radicals. The aromatic
group may be a cyclic structure having 4n+2 "delocalized" electrons
where "n" is an integer equal to 1 or greater, as illustrated by
phenyl groups (n=1), thienyl groups (n=1), furanyl groups (n=1),
naphthyl groups (n=2), azulenyl groups (n=2), anthracenyl groups
(n=3) and the like. The aromatic radical also may include
non-aromatic components. For example, a benzyl group may be an
aromatic radical, which includes a phenyl ring (the aromatic group)
and a methylene group (the non-aromatic component). Similarly a
tetrahydronaphthyl radical is an aromatic radical comprising an
aromatic group (C.sub.6H.sub.3) fused to a non-aromatic component
--(CH.sub.2).sub.4--. An aromatic radical may include one or more
functional groups, such as alkyl groups, alkenyl groups, alkynyl
groups, haloalkyl groups, haloaromatic groups, conjugated dienyl
groups, alcohol groups, ether groups, aldehyde groups, ketone
groups, carboxylic acid groups, acyl groups (for example carboxylic
acid derivatives such as esters and amides), amine groups, nitro
groups, and the like. For example, the 4-methylphenyl radical is a
C.sub.7 aromatic radical comprising a methyl group, the methyl
group being a functional group, which is an alkyl group. Similarly,
the 2-nitrophenyl group is a C.sub.6 aromatic radical comprising a
nitro group, the nitro group being a functional group. Aromatic
radicals include halogenated aromatic radicals such as
trifluoromethylphenyl,
hexafluoroisopropylidenebis(4-phen-1-yloxy)(--OPhC(CF.sub.3).sub.2PhO--),
chloromethylphenyl, 3-trifluorovinyl-2-thienyl,
3-trichloromethylphen-1-yl (3-CCl.sub.3Ph-),
4-(3-bromoprop-1-yl)phen-1-yl (BrCH.sub.2CH.sub.2CH.sub.2Ph-), and
the like. Further examples of aromatic radicals include
4-allyloxyphen-1-oxy, 4-aminophen-1-yl(H.sub.2NPh-),
3-aminocarbonylphen-1-yl (NH.sub.2COPh-), 4-benzoylphen-1-yl,
dicyanoisopropylidenebis(4-phen-1-yloxy) (--OPhC(CN).sub.2PhO--),
3-methylphen-1-yl, methylenebis(phen-4-yloxy) (--OPhCH.sub.2PhO--),
2-ethylphen-1-yl, phenylethenyl, 3-formyl-2-thienyl,
2-hexyl-5-furanyl; hexamethylene-1,6-bis(phen-4-yloxy)
(--OPh(CH.sub.2).sub.6PhO--), 4-hydroxymethylphen-1-yl
(4-HOCH.sub.2Ph-), 4-mercaptomethylphen-1-yl (4-HSCH.sub.2Ph-),
4-methylthiophen-1-yl (4-CH.sub.3SPh-), 3-methoxyphen-1-yl,
2-methoxycarbonylphen-1-yloxy (e.g., methyl salicyl),
2-nitromethylphen-1-yl(-PhCH.sub.2NO.sub.2),
3-trimethylsilylphen-1-yl, 4-t-butyldimethylsilylphenl-1-yl,
4-vinylphen-1-yl, vinylidenebis(phenyl), and the like. The term "a
C.sub.3-C.sub.30 aromatic radical" includes aromatic radicals
containing at least three but no more than 30 carbon atoms. The
aromatic radical 1-imidazolyl(C.sub.3H.sub.2N.sub.2--) represents a
C.sub.3 aromatic radical. The benzyl radical (C.sub.7H.sub.7--)
represents a C.sub.7 aromatic radical.
[0023] A cycloaliphatic radical is a radical having a valence of at
least one, and having an array of atoms, which is cyclic but which
is not aromatic. A cycloaliphatic radical may include one or more
non-cyclic components. For example, a cyclohexylmethyl group
(C.sub.6H.sub.11CH.sub.2--) is a cycloaliphatic radical, which
includes a cyclohexyl ring (the array of atoms, which is cyclic but
which is not aromatic) and a methylene group (the noncyclic
component). The cycloaliphatic radical may include heteroatoms such
as nitrogen, sulfur, selenium, silicon and oxygen, or may be
composed exclusively of carbon and hydrogen. A cycloaliphatic
radical may include one or more functional groups, such as alkyl
groups, alkenyl groups, alkynyl groups, halo alkyl groups,
conjugated dienyl groups, alcohol groups, ether groups, aldehyde
groups, ketone groups, carboxylic acid groups, acyl groups (for
example carboxylic acid derivatives such as esters and amides),
amine groups, nitro groups and the like. For example, the
4-methylcyclopent-1-yl radical is a C.sub.6 cycloaliphatic radical
comprising a methyl group, the methyl group being a functional
group, which is an alkyl group. Similarly, the 2-nitrocyclobut-1-yl
radical is a C.sub.4 cycloaliphatic radical comprising a nitro
group, the nitro group being a functional group. A cycloaliphatic
radical may include one or more halogen atoms, which may be the
same or different. Halogen atoms include, for example, fluorine,
chlorine, bromine, and iodine. Cycloaliphatic radicals having one
or more halogen atoms include 2-trifluoromethylcyclohex-1-yl,
4-bromodifluoromethylcyclooct-1-yl,
2-chlorodifluoromethylcyclohex-1-yl, hexafluoroisopropylidene
2,2-bis(cyclohex-4-yl)
(--C.sub.6H.sub.10C(CF.sub.3).sub.2C.sub.6H.sub.10--),
2-chloromethylcyclohex-1-yl; 3-difluoromethylenecyclohex-1-yl;
4-trichloromethylcyclohex-1-yloxy,
4-bromodichloromethylcyclohex-1-ylthio, 2-bromoethylcyclopent-1-yl,
2-bromopropylcyclohex-1-yloxy (e.g.
CH.sub.3CHBrCH.sub.2C.sub.6H.sub.10--), and the like. Further
examples of cycloaliphatic radicals include
4-allyloxycyclohex-1-yl,
4-aminocyclohex-1-yl(H.sub.2C.sub.6H.sub.10--),
4-aminocarbonylcyclopent-1-yl(NH.sub.2COC.sub.5H.sub.8--),
4-acetyloxycyclohex-1-yl,
2,2-dicyanoisopropylidenebis(cyclohex-4-yloxy)(--OC.sub.6H.sub.10C(CN).su-
b.2C.sub.6H.sub.10--), 3-methylcyclohex-1-yl,
methylenebis(cyclohex-4-yloxy)
(--OC.sub.6H.sub.10CH.sub.2C.sub.6H.sub.10--),
1-ethylcyclobut-1-yl, cyclopropylethenyl,
3-formyl-2-terahydrofuranyl, 2-hexyl-5-tetrahydrofuranyl;
hexamethylene-1,6-bis(cyclohex-4-yloxy)
(--OC.sub.6H.sub.10(CH.sub.2).sub.6C.sub.6H.sub.10--);
4-hydroxymethylcyclohex-1-yl (4-HOCH.sub.2C.sub.6H.sub.10--),
4-mercaptomethylcyclohex-1-yl (4-HSCH.sub.2C.sub.6H.sub.10--),
4-methylthiocyclohex-1-yl (4-CH.sub.3SC.sub.6H.sub.10--),
4-methoxycyclohex-1-yl, 2-methoxycarbonylcyclohex-1-yloxy
(2-CH.sub.3OCOC.sub.6H.sub.10--),
4-nitromethylcyclohex-1-yl(NO.sub.2CH.sub.2C.sub.6H.sub.10--),
3-trimethylsilylcyclohex-1-yl,
2-t-butyldimethylsilylcyclopent-1-yl,
4-trimethoxysilylethylcyclohex-1-yl (e.g.
(CH.sub.3O).sub.3SiCH.sub.2CH.sub.2C.sub.6H.sub.10--),
4-vinylcyclohexen-1-yl, vinylidenebis(cyclohexyl), and the like.
The term "a C.sub.3-C.sub.30 cycloaliphatic radical" includes
cycloaliphatic radicals containing at least three but no more than
10 carbon atoms. The cycloaliphatic radical
2-tetrahydrofuranyl(C.sub.4H.sub.7O--) represents a C.sub.4
cycloaliphatic radical. The cyclohexylmethyl radical
(C.sub.6H.sub.11CH.sub.2--) represents a C.sub.7 cycloaliphatic
radical.
[0024] In one embodiment, the organosiloxane group may have a
structure of formula (VI).
((CH.sub.3).sub.3SiO.sub.1/2).sub.2(CH.sub.3SiO.sub.2/2)-- (VI)
Structure (VI) falls within generic organosiloxane of formula (IV)
and represents the case where "a" in structure (IV) is 0 and
R.sup.2, R.sup.3, R.sup.4 and R.sup.7 are each a methyl
radical.
[0025] In one embodiment, the organosiloxane group may have a
structure of formula (VII).
((CH.sub.3).sub.3SiO.sub.1/2)((CH.sub.3).sub.2SiO.sub.2/2)((CH.sub.3).su-
b.2SiO.sub.1/2)-- (VII)
Structure (VII) falls within generic organosiloxane of formula (V)
and represents the case where "b" in structure (V) is 1 and
R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13 and
R.sup.14 are each a methyl radical.
[0026] Suitable organosilane groups may have a structure of formula
(VIII), (IX), (X) or (XI).
(R.sup.15R.sup.16R.sup.17Si).sub.2(R.sup.18R.sup.19Si).sub.a(R.sup.20Si)-
-- (VIII)
(R.sup.21R.sup.22R.sup.23Si)(R.sup.24R.sup.25Si).sub.b(R.sup.26R.sup.27S-
i)-- (IX)
(R.sup.28R.sup.29R.sup.30Si).sub.2(CR.sup.31R.sup.32).sub.a(R.sup.33Si)--
- (X)
(R.sup.34R.sup.35R.sup.36Si)(CR.sup.37R.sup.38).sub.b(R.sup.39R.sup.40Si-
)-- (XI)
wherein "a" is independently at each occurrence an integer from 0
to 50, "b" is independently at each occurrence an integer from 1 to
50, and R.sup.15 to R.sup.40 are independently at each occurrence a
hydrogen atom, a C.sub.1-C.sub.30 aliphatic radical, a
C.sub.3-C.sub.30 aromatic radical, or a C.sub.3-C.sub.30
cycloaliphatic radical.
[0027] In one embodiment, the organosilane group may have a
structure of formula (XII).
((CH.sub.3).sub.3Si).sub.2(CH.sub.3Si)-- (XII)
[0028] Structure (XII) falls within generic organosilane group of
formula (VIII) and represents the case where "a" in structure
(VIII) is 0 and R.sup.15, R.sup.16, R.sup.17 and R.sup.20 are each
a methyl radical. In one embodiment, the organosilane group may
have a structure of formula (XIII).
((CH.sub.3).sub.3Si)((CH.sub.3).sub.2Si)((CH.sub.3).sub.2Si)--
(XIII)
[0029] Structure (XIII) falls within generic organosilane group of
formula (IX) and represents the case where "b" in structure (IX) is
1 and R.sup.21, R.sup.22, R.sup.23, R.sup.21, R.sup.25, R.sup.26
and R.sup.27 are each a methyl radical. In one embodiment, the
organosilane group may have a structure of formula (XIV).
((CH.sub.3).sub.3Si).sub.2(CH.sub.2).sub.2(CH.sub.3Si)-- (XIV)
[0030] Structure (XIV) falls within generic organosilane group of
formula (X) and represents the case where "a" in structure X is 2;
R.sup.2, R.sup.29, R.sup.30 and R.sup.33 are each a methyl radical;
and R.sup.31 and R.sup.32 are each a hydrogen atom. In one
embodiment, the organosilane group may have a structure of formula
(XV).
((CH.sub.3).sub.3Si)(CH.sub.2).sub.2((CH.sub.3).sub.2Si)-- (XV)
[0031] Structure (XV) falls within generic organosilane group
formula XI and represents the case where "b" in structure XI is 2;
R.sup.34, R.sup.35, R.sup.36, R.sup.39 and R.sup.40 are each a
methyl radical; and R.sup.37 and R.sup.38 are each a hydrogen
atom.
[0032] In one embodiment, the first hydrophobic moiety and the
second hydrophobic moiety may be organosiloxane groups, both
represented by the structure (VI). In one embodiment, the first
hydrophobic moiety may be an organosilane group represented by the
structure (XII) and the second hydrophobic moiety may be an
organosilane group represented by the structure (XIV). In one
embodiment, the first hydrophobic moiety may be an organosiloxane
group represented by the structure (VII) and the second hydrophobic
moiety may be an organosilane group represented by the structure
(XV).
[0033] The composition including Gemini surfactants may be
characterized one or more of hydrophobic/lipophobic balance (HLB),
calorimetry, conductometry, electron spin resonance (ESR)
spectroscopy, goniometry, microscopy, light scattering, neutron
scattering, nuclear magnetic resonance (NMR) spectroscopy,
rheometry, spectrophotometry, tensiometry, gas chromatography,
atomic absorption spectroscopy, infra red (IR) spectroscopy, and
the like. Suitable properties that may be determined by one of
these techniques may include one or more of hydrolytic stability,
spreading properties, aggregation formation and structure, surface
activity, solubilization, adsorption, wetting, foaming, phase
behavior, flow, and thermotropic properties.
[0034] The hydrolytic stability of the composition may be
determined at a pH in a range from about 2 to about 10, and at a
temperature of 25 degrees Celsius for a time period greater than 24
hours. In one embodiment, the composition may be stable at a pH in
a range from about 2 to about 4, from about 4 to about 6, or from
about 6 to about 7, at a temperature of 25 degrees Celsius for a
time period greater than 24 hours. In one embodiment, the
composition may be stable at a pH in a range from about 7 to about
8, from about 8 to about 9, or from about 9 to about 10, at a
temperature of 25 degrees Celsius for a time period greater than 24
hours. Here and throughout the specification and claims, range
limitations may be combined and/or interchanged. Such ranges as
identified include all the sub-ranges contained therein unless
context or language indicates otherwise. One or both of the first
hydrophobic moiety or the second hydrophobic moiety may provide
steric hindrance to the spacer to protect it from hydrolysis.
[0035] The super-spreading properties of the composition may be
determined for an aqueous solution of the Gemini surfactant
composition to provide total wetting as measured by a contact angle
on a hydrophobic surface. In one embodiment, an aqueous solution of
the composition may be super-spreading at a concentration greater
than about 0.1 weight percent. In one embodiment, an aqueous
solution of the composition may be super-spreading at a
concentration in a range from about 0.1 weight percent to about 0.5
weight percent, from about 0.5 weight percent to about 1 weight
percent, from about 1 weight percent to about 2 weight percent,
from about 2 weight percent to about 3.5 weight percent, or from
about 3.5 weight percent to about 5 weight percent. In one
embodiment, an aqueous solution of the composition may be
super-spreading at a concentration greater than about 5 weight
percent. In one embodiment, a 10 microliter (.mu.L) drop of an
aqueous solution of the composition of concentration greater than
about 0.1 weight percent may spread to a diameter of about 5 to
about 6, of about 6 to about 7, of about 7 to about 8, or of about
8 to about 9 times or greater than a 10 microliter drop of
distilled water on the same hydrophobic surface; the diameter being
measured at 30 seconds or at 120 seconds after application of the
drop to the surface.
[0036] The critical aggregation concentration (CAC) of an aqueous
solution of the composition may be the concentration above which
monomeric surfactant molecules of the composition abruptly form
aggregates. In one embodiment, the composition may have an aqueous
critical aggregation concentration greater than about 0.001 mM. In
one embodiment, the composition may have an aqueous critical
aggregation concentration in a range from about 0.001 mM to about
0.01 mM, from about 0.01 mM to about 0.1 mM, from about 0.1 mM to
about 1 mM, from about 1 mM to about 10 mM, or from about 10 mM to
about 100 mM.
[0037] The surface tension of an aqueous solution of the
composition of a concentration greater than about 0.1 weight
percent may be in a range from about 10 mN/m to about 40 mN/m. In
one embodiment, the composition may have an aqueous surface tension
in a range from about 10 mN/m to about 20 mN/m, from about 20 mN/m
to about 30 mN/m, or from about 30 mN/m to about 40 mN/m.
[0038] The invention also includes embodiments that relate to a
method of linking a first hydrophobic moiety to a second
hydrophobic moiety by using a spacer to form a surfactant. In one
embodiment, a bifunctional spacer may be linked to the first
hydrophobic moiety and the second hydrophobic moiety
simultaneously. In one embodiment, a bifunctional spacer may be
first linked to the first hydrophobic moiety, and subsequently
linked to the second hydrophobic moiety. In one embodiment, an
initially monofunctional spacer may be linked to the first
hydrophobic moiety, subsequently functionalized, and linked to the
second hydrophobic moiety. Linking of spacer to the hydrophobic
moiety may occur by hydrosilylation reaction of a silicon
hydride-containing organosiloxane group or organosilane group and a
spacer having unsaturated carbon-carbon bonds.
[0039] Hydrosilylation reaction may be catalyzed by use of
hydrosilylation catalysts. Suitable hydrosilylation catalysts may
include one or more of rhodium, platinum, palladium, nickel,
rhenium, ruthenium, osmium, copper, cobalt or iron. Suitable
platinum catalysts may be used for the hydrosilylation reaction. A
suitable platinum compound may have the formula (PtCl.sub.2Olefin)
or H(PtCl.sub.3Olefin). Another suitable platinum catalyst may
include a cyclopropane complex or a complex formed from
chloroplatinic acid with up to 2 moles per gram of platinum and one
or more of alcohols, ethers, or aldehydes.
[0040] In one embodiment, a first hydrophobic moiety and a second
hydrophobic moiety having silicon hydride-containing organosiloxane
groups or organosilane groups may be linked by a spacer having
unsaturated polyoxyalkylene derivatives by using a hydrosilylation
catalyst. In one embodiment, two trimethylsiloxanes represented by
structure XI may be linked by hydrosilylation reaction of a silicon
hydride containing trimethylsiloxane moiety and an unsaturated
polyoxyalkylene derivative, such as a diallyl derivative, in the
presence of a platinum catalyst resulting in structure of formula
(XVI).
##STR00001##
[0041] In structure (XVI), the first hydrophobic moiety and the
second hydrophobic moiety may be organosiloxanes represented by
structure (XI) and the spacer may be a polyether represented by
structure (III). The trimethylene linkages linking the
polyoxyethylene and the siloxane may result from the
hydrosilylation reaction between the allyl groups in the
polyoxyethylene chain and the silicon hydride group. Some other
examples of Gemini surfactants exemplifying embodiments of the
invention may include structures of formulae (XVII), (XVIII),
(XIX), (XX), (XXI) and (XXII).
##STR00002##
[0042] The hydrosilylation products of SiH-containing
organosiloxanes or SiH-containing organosilanes with unsaturated
polyoxyalkylene derivatives may contain excess unsaturated
polyoxyalkylene derivative, or be an isomerization product or
derivative thereof. The linear ogranosiloxane or linear
organosilane derivatives, and their mixtures may contain up to 10
percent weight of cyclic organosiloxane or cyclic organosilane. The
hydrosilylation products of SiH-containing organosiloxanes or
SiH-containing organosilanes with unsaturated poly alkyleneoxide
derivatives may also contain unreacted cyclic organosiloxane or
cyclic organosilane.
[0043] Polar and/or non-polar solvents may be used with the Gemini
surfactant. Examples of suitable polar solvents may include water,
alcohols, fatty acids, ketones, glycols, polyethylene glycols, or
diols. Examples of suitable non-polar solvents may include aromatic
solvents, oils (e.g., mineral oil, vegetable oil, silicone oil, and
the like), lower alkyl esters of vegetable oils, or paraffinic low
molecular weight waxes.
[0044] A polar solvent, such as water, may be added to the Gemini
surfactant composition to form an aqueous mixture or an emulsion.
The aqueous mixture of the Gemini surfactants may be used to treat
a surface, which would otherwise resist the spreading of water
subsequent to treating the surface with an effective amount of the
surfactant. A coating formulation having the aqueous mixture of the
Gemini surfactants may have relatively improved spreading or
wetting of the surface.
[0045] The concentration of the Gemini surfactant composition in a
solution, emulsion, or solid may be in a range of greater than
about 0.1 weight percent, based on the weight of the total
composition. In one embodiment, the concentration of the Gemini
surfactant composition may be in a range from about 0.1 weight
percent to about 1 weight percent, from about 1 weight percent to
about 2 weight percent, from about 2 weight percent to about 5
weight percent, from about 5 weight percent to about 10 weight
percent, from about 10 weight percent to about 25 weight percent,
or from about 25 weight percent to about 50 weight percent, based
on the weight of the total composition.
[0046] Aqueous mixtures of Gemini surfactants may be used as
adjuvants; pest control agents or pesticides; flowing and leveling
agents; cosmetics; cleaners; detergents; water or fabric softeners;
wetting agents; foaming agents; anti-static agents; anti-fogging
agents; super-spreading additives; or release agents for adhesives.
The Gemini surfactants, and the aqueous mixtures formed therefrom,
may have a relatively high flash point (>93.degree. C.) and an
extended shelf life. An extended shelf life may be indefinite. A
viscosity of an aqueous mixture of one embodiment may be about 50
centipoise at about 20 degrees Celsius. Wetting may be quantified
with reference to a cotton skein test, in which the results may be
30 seconds at 0.2 percent mix or 17 seconds at 0.5 percent mix.
[0047] The aqueous mixture of the Gemini surfactant may be applied
to an agricultural field to act as an adjuvant by improving the
wetting properties of the aqueous solutions. A pesticide may be
added to the aqueous mixture of the Gemini surfactant. The
resulting mixture of the pesticide and the Gemini surfactant may be
applied to a plant. The Gemini surfactant may act like an adjuvant
and may perform a variety of functions, such as increasing spray
droplet retention on difficult to wet leaf surfaces, or may provide
penetration of an herbicide into the plant cuticle.
[0048] The Gemini surfactant compositions may be used in spray tank
mixes, pesticide formulations, adjuvant blends, and in applications
where the adjuvant is administered in a sequential addition after
the application of a pesticide. The Gemini surfactant composition
may be added directly to a spray tank along with the pesticide, or
as part of the pesticide formulation ("In Can" or "Ready to Use").
In one embodiment, the application/mixing may occur by simultaneous
spraying of the pesticide and of the Gemini surfactant aqueous
mixture.
[0049] The invention also includes embodiments that relate to a
pesticide including a Gemini surfactant composition and one or more
of an active ingredient, such as insecticide, rodenticide,
fungicide, herbicide, or the like. Illustrative examples of active
ingredients include one or more of growth regulators,
photosynthesis inhibitors, pigment inhibitors, mitotic disrupters,
lipid biosynthesis inhibitors, cell wall inhibitors, and cell
membrane disrupters.
[0050] Suitable commercially available growth regulators may
include one or more of phenoxy acetic acids, such as
2,4-dichlorophenoxyacetic acid; phenoxy propionic acids, such as
(RS)-2-(2,4-dichlorophenoxy)propionic acid or
(RS)-2-(4-chloro-o-tolyloxy)propionic acid; phenoxy butyric acids,
such as 4-(2,4-dichlorophenoxy)butyric acid; benzoic acids, such as
3,6-dichloro-o-anisic acid; or other growth regulators, such as
4-amino-3,5-dichloro-6-fluoro-2-pyridyloxy acetic acid,
4-amino-2,3,5-trichloro-2-carboxylic acid,
3,5,6-trichloro-2-pyridyloxy acetic acid, or
3,6-dichloropyridine-2-carboxylic acid.
[0051] Suitable commercially available pigment inhibitors may
include one or more of 1H-1,2,4-triazol-3-ylamine;
3-amino-1H-1,2,4-triazole;
2-(2-chlorobenzyl)-4,4-dimethyl-1,2-oxazolidin-3-one;
2-(2-chlorobenzyl)-4,4-methylisoxazolidin-3-one,
1-methyl-3-phenyl-5-(a,a,a-trifluoro-m-tolyl)-4-pyridone, or
4-chloro-5-methylamino-2-(a,a,a-trifluoro-m-tolyl)pyridazin-3(2H)-one.
[0052] Suitable commercially available mitotic disruptors may
include one or more of dinitroanilines, such as
4-isopropyl-2,6-dinitro-N,N-dipropylaniline,
3,5-dinitro-N4N4-dipropylsulfanilamide, N-(1-ethyl
propyl)-2,6-dinitro-3,4-xylidine,
5-dipropylamino-a,a,a-trifluoro-4,6-dinitro-toluidine,
2,6-dinitro-N1N1-dipropyl-4-trifluoromethyl-m-phenylene diamine, or
a,a,a-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine.
[0053] Suitable commercially available lipid biosynthesis
inhibitors may include one or more of
(.+-.)-2-((E)-3-chloroallyloxyimino)propyl)-5-(2
(ethylthio)-propyl)-3-hydroxy cyclohex-3-enone,
(RS)-2-(4-(2,4-dichlorophenoxy)phenoxy)propionic acid,
(.+-.)-2-(4-(6-chloro-1,3-benzoxazol-2-yloxy)phenoxy)propionic
acid, (.+-.)-2-(4-(5-chlorobenzoxazol-2-yloxy)phenoxy)propionic
acid, (R)-2-(4-(5-trifluoromethyl-2-pyridyloxy)phenoxy)propionic
acid, (RS)-2-(4-(3-chloro-5-trifluoro methyl
2-pyridyloxy)phenoxy)propionic acid,
(RS)-2(4-(6-chloroquinoxalin-2-yloxy)phenoxy)propionic acid, or
(O)-(EZ)-2-(1-ethoxyininobutyl)-5-(2(ethylthio)propyl)-3-hydroxycyclohex--
2-enone.
[0054] Suitable commercially available photosynthesis inhibitors
may include one or more of triazines and s-triazines, such as
3-cyclo-hexyl-6-dimethylamino-1-methyl-1,3,4-triazine-2,4-(1H,3H)
dione, 4-amino-6-tert-butyl-3-methylthio-1,2,3-triazine-5(4H)-one,
6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine,
6-chloro-N2, N4-diethyl-1,3,5-triazine-2,4-diamine,
2-(4-chloro-6-ethylamino-1,3,5-triazin-2-yl)amino-2 methyl
propanenitrile, N2,N2
4-di-isopropyl-6-methoxy-1,3,5-triazine-2,4-diamine,
N2-ethyl-N4-isopropyl-6-methylthio-1,3,5-triazine-2,4-diamine;
substituted ureas, such as 3-(3,4-dichlorophenyl)-1,1-dimethylurea,
1-dimethyl-3-(a,a,a-trifluoro-m-tolyl)urea,
3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea,
1-(5-tert-butyl-1,3,4-thiadiazol-2-yl)-1,3-dimethylurea; uracils,
such as 5-bromo-3-sec-butyl-6-methyluracil or
3-tert-butyl-5-chloro-6-methlyuracil; or other photosynthesis
inhibitors, such as
3-isopropyl-1H-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide,
ethyl-3'-phenyl carbamoyloxy carbanilate, ethyl 3-phenyl
carbamoyloxyphenyl carbamate; 3-ethoxy carbonylamino phenyl
carbamate,
2-(3,4-dichlorophenyl)-4-methyl-1,2,4-oxadiazolidine-3,5-dione,
3-(3-methyl carbaniloyloxy)carbanilate, 3-methoxy carbonyl amino
phenyl 3'-methyl carbanilate, 3',4'-dichloropropionanilide, or
6-chloro-3-phenyl pyridazin-4-yl S-octyl thiocarbonate.
[0055] Suitable commercially available amino acid synthesis
inhibitors may include one or more of glycophosphate, sulfate or
other salts of N-(phosphonomethyl)glycine; sulfonylureas, such as
a-(4,6-dimethoxypy-rimidin-2-yl carbamoyl sulfamoyl)-o-toluic acid,
2-(4-chloro-6-methoxy pyrimidin-2-yl carbamoyl sulfamoyl)benzoic
acid, 1-(2-chlorophenyl
sulfonyl)-3-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)urea,
2-(4-methoxy-6-methyl-1,3,5-triazin-2-yl carbamoyl
sulfamoyl)benzoic acid, 2-(4,6-dimethoxy pyrimidin-2-yl carbamoyl
sulfamoyl)-N,N-dimethyl nicotinamide, 1-(4,6-dimethoxy
pyrimidinyl)-3-(3-dimethyl carbamoyl-2-pyridyl sulfonyl)urea,
2-(4,6-bis(difluoro methoxy)pyrimidin-2-yl carbamoyl
sulfamoyl)benzoic acid, 2-(4,6-dimethylpyrimidin-2-yl carbamoyl
sulfamoyl)benzoic acid, 2-(3-(4,6-dimethyl pyrimidin-2-yl)ureido
sulfonyl)) benzoic acid, 3-(4-methoxy-6-methyl-1,3,5-triazin-2-yl
carbamoyl sulfamoyl)thiophen-2-carboxylic acid, 1-(2-(2-chloro
ethoxy)phenyl sulfonyl)-3
(4-methoxy-6-methyl-1,3,5-triazin-2-yl)urea, or
2-(4-methoxy-6-methyl-1,3,5-triazin-2-yl(methyl)carbamoyl
sulfamoyl)benzoic acid; or imidazolinones, such as a reaction
product comprising
(.+-.)-6-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-m-toluic
acid and
(.+-.)-2-(4-isopropyl-4-methyl-5-ox-2-imidazolin-2-yl)-p-toluic
acid, 2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinic
acid,
(RS)-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)quinoline-3-carboxyl-
ic acid, or
(RS)-5-ethyl-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinic
acid.
[0056] Suitable commercially available cell membrane disruptors may
include one or more of bipyridylium compounds, such as
9,10-dihydro-8-diazoniaphenanthrene; 6,7-dihydro dipyrido
(1,2-a:2',1'-c) pyrazine-5,8-dium;
1,1'-ethylene-2,2'-bipyridyldiylium, or
1,1'-dimethyl-4,4'-bipyridinium(I); diphenylethers, such as
A5-(2-chloro-a,a,a-trifluoro-p-tolyoxy)-2-nitrobenzoic acid,
5-(2-chloro-a,a,a-trifluoro-p-tolyloxy)-N-mesyl-2-nitrobenzamide,
5-(2-chloro-a,a,a-trifluoro-p-tolyoxy)-N-methyl
sulfonyl-2-nitrobenzamide,
5-(2-chloro-a,a,a-trifluoro-p-tolyloxy)-2-nitrobenzoyl)-DL-lactate,
or 2-chloro-a,a,a-trifluoro-p-tolyl-3-ethoxy-4-nitrophenyl
ether.
[0057] Suitable commercially available cell wall inhibitors may
include one or more of 2,6-dichloro benzonitrile,
N-(3-(1-ethyl-1-methyl propyl)-1,2-oxazol-5-yl)-2,6-dimethoxy
benzamide, or N-(3-(1-ethyl-1-methyl
propyl)isoxazol-5-yl)-2,6-dimethoxy benzamide).
[0058] The pesticide may be a liquid or a solid. If solid, the
active ingredient in the pesticide may be dissolved in a solvent
(such as a polar solvent) prior to application, and the Gemini
surfactant may act as a surfactant for such solubility, or the
Gemini surfactant may act as an emulsifier or as an emulsion
stabilizer. The amount of the active ingredient employed in a
pesticide according to an embodiment of the invention may vary
with, for example, the type of active ingredient employed, the
method of application, and the desired end concentration.
[0059] Co-adjuvants may be included in the pesticide. Suitable
co-adjuvants may include one or more of co-surfactants, stickers,
humectants, solvents, oils, drift control agents, buffers,
extenders, deposition and retention aids, defoamers, and antifoams,
compatibility agents, or herbicide activity enhancers. Herbicide
activity enhancers may include ammonium sulfate or
nitrogen-containing fertilizers.
[0060] Gemini surfactants blends with other surfactants may be used
as adjuvants. The blends may be obtained by physically mixing the
two components together as a formulation, or by adding them
separately to a spray mixture at point of use. A suitable
co-surfactant may include one or more nonionic, cationic, anionic,
amphoteric, zwitterionic, or polymeric surfactants. Suitable
co-surfactants may be hydrocarbon-based, silicone-based or
fluorocarbon-based. Suitable co-surfactants may include one or more
alkanolamides; alkyl aryl alkoxylates and their derivatives;
alkoxylated amines and their derivatives; quaternary ammonium
surfactants; alkoxylated quaternary ammonium surfactants and their
derivatives; amine oxides; betaines and their derivatives;
copolymers containing ethylene oxide, propylene oxide, butylene
oxide, styrene oxide or any combination thereof, linear alcohol
alkoxylates and their derivatives; branched alcohol alkoxylates and
their derivatives; alkoxylated amides; alkoxylated fatty acids;
alkoxylated fatty esters and oils; glycerol esters; alkoxylated
glycerol esters; imidazolines and their derivatives; propoxylated
quaternary amines; lignin and its derivatives (such as
lignosulfonate salts); mono- and di-glycerides; olefin sulfonates;
phosphate esters; alkyl polyglycosides; other siloxane surfactants,
such as alkoxylated siloxanes, alkyl siloxanes, siloxanes
containing betaine and quaternary ammonium groups, amino siloxanes,
or alkoxylated amino siloxanes; sorbitan esters; ethoxylated
sorbitan esters; sulfonate surfactants; sulfosuccinates and their
derivatives; salts of fatty acids, or sarcosinates.
[0061] In bulk powders that may not have an inherent or a desirable
flow character, the Gemini surfactant may be used as an
anti-caking, flow aid, slip modifier, and/or flowing agent. The
Gemini surfactant may perform one or more of the following
functions to affect one or more of the flow-affecting variables
listed in Table 1: agglomeration of particles to change size, shape
and/or surface texture of particulate, inter-particle interactions
for cohesivity and particle interaction, coat particles for
decreasing wear, increasing compactability by decreasing surface
friction between particles, reducing friction to reduce heat
generated by particle flow, affect moisture absorbency of the
particulate (increase or decrease depending on choice of hydrophobe
moiety), increase electrostatic dissipation, and decrease settling,
dust propensity, and/or caking.
TABLE-US-00001 TABLE 1 Variables affecting powder flow properties.
INTRINSIC PROPERTIES EXTERNAL PROPERTIES Particle size Compaction
condition Size distribution Temperature Shape Humidity Surface
texture Electro-static charge Cohesivity Container surface effects
Particle interaction Storage time Wear or attrition
characteristic
[0062] The Gemini surfactant may be useful as a leveling agent.
Leveling agents may be used in cement/concrete (and as an aeration
aid), and in paints and coatings. As a leveling agent, the Gemini
surfactant may improve the surface properties and the
adhesion/wetting of one or more of resins, plastics (particularly
composites), solvents and coatings. For coatings, interfacial
tension differentials between the coating and the substrate surface
may be problematic. Addition of the Gemini surfactant to the
coating may reduce the surface tension of the coating to more
closely match the surface tension of the substrate surface. In one
embodiment, the surface tension, measured in dynes per centimeter,
of the coating may be reduced by more than about 50 percent, or
about 25 percent, or less than about 10 percent. In one embodiment,
the interfacial tension differential of coating/substrate is less
than about five dynes per centimeter, is less than about three
dynes per centimeter, or less than about one dyne per
centimeter.
[0063] Gemini surfactants may act as dispersants in coating
formulations. That is, the material ingredients in the coating
formulations may have reduced or soft settling, enhanced
remixability, and extended shelf life. Additions of the Gemini
surfactant may affect flow of the coating during application.
Increasing the flow may reduce uneven film thickness, orange peel,
craters, and/or fat edges. Decreasing the flow may reduce
telegraphing, craters, orange peel, and/or picture framing.
Decreasing the surface tension may decrease entrapped or entrained
air, and may increase the glossiness of the finished coating.
[0064] Cosmetics may be formed from Gemini surfactants, and used,
for example, in cleaning, conditioning, coloring, moisturizing,
and/or styling products. The cosmetics may be used on keratin
materials, such as hair or nails, and on the skin. With reference
to hair treatment, the cosmetic may facilitate the disentangling of
the hair and give it softness and suppleness. The cosmetic may be
formed as a hair spray, tonic, gel, mousse, or the like.
[0065] Cleansing the skin is very important for facial care. The
cosmetic cleanser may be efficient as greasy residues such as
excess sebum, the remnants of cosmetic products used daily and
make-up products accumulate in the skin folds and can block the
pores of the skin and cause the appearance of spots. The cosmetic
may be used to cleanse the skin by foaming. The foaming cleansing
cosmetic may be in the form of foaming cakes, gels, or creams.
Foaming cosmetics may lather to form an unctuous foam (e.g., a
smooth, greasy feel); however, tightness due to excessively high
detergency may be reduced by selection of hydrophobic moieties. In
one embodiment, the cosmetic cleanser may be transparent.
[0066] The cleansing cosmetic may include one or more adjuvants
used in the cosmetic field, and in particular those used in
cleansing products. Suitable adjuvants may include one or more of
perfumes, preservatives, sequestrants (e.g., EDTA), pigments,
exfoliating fillers, soluble colorants, sunscreens, cosmetic or
dermatological active agents such as moisturizers, for instance
hyaluronic acid; ceramides; water-soluble or fat-soluble vitamins,
for example vitamin C and its derivatives such as vitamin CG;
antiseptics; antiseborrhoeic; antimicrobials such as benzoyl
peroxide, salicylic acid, triclosan, azelaic acid; optical
brighteners. The quantities of these various adjuvants may be in a
range of from about 0.01 weight percent to about 25 weight percent
of the total weight of the cosmetic composition.
[0067] The cosmetic Gemini surfactant-containing composition may be
a skin makeup product, such as a complexion product (e.g.,
foundation), eye shadow, blusher or eyeliner, a concealer product,
a body makeup product, or a lip makeup product. For example, the
cosmetic may be a foundation, eye shadow, mascara, or blusher.
Suitable complexion products may include reflective and/or tinted
particles selected from mica substrates, goniochromatic and
monochromatic coloring agents, photochromic coloring agents,
fluorescent agents, and the like.
[0068] Cosmetic complexion products may include a pulverulent base
formed from fillers and pigments. Certain fillers, however, such as
talc, owing to their opacity to light, may reduce the saturation of
the color of the pigments present in the makeup product, with the
consequence that the resulting makeup presents an apparent color,
which is less vivid than the color of the colorants alone. Other
suitable colorants may include relatively more reflective
particles, such as metal-coated glass particles, or goniochromatic
pigments having a multi-layer interference structure or with a
liquid-crystal structure. Goniochromatic pigments may produce
colored optical effects, which are original, intense, and different
from those obtained with conventional pigments such as iron oxides
or titanium dioxide. For cosmetic complexion products other than
powder, such as a cream, a gel or a cast product, for example,
whether anhydrous or aqueous, the pulverulent materials may be
present in an amount of up to about 30 weight percent.
[0069] The Gemini surfactant may clean and/or soften a soiled
article. Such articles may include hard surfaces or fabrics, and
may be porous or impermeable. The Gemini surfactant may be used as
an aqueous mixture, or as a mixture of polar liquid and the Gemini
surfactant. During cleaning, the Gemini surfactant functions to
perform one or more of emulsify oil, hold dirt in suspension, or
act as a wetting agent. In one embodiment, the Gemini surfactant
may act to disperse biofilm, may disrupt algae or fungal growth,
and may passivate reactive surfaces (such as metal rust).
[0070] The aqueous mixture of the Gemini surfactant may be foamed,
and the foam may be used to extinguish a fire. The fire fighting
applications may include house and building fires, fuel or chemical
fires, electrical fires, and may include wild fires or forest
fires. Foams produced by the Gemini surfactant may have adequate to
increased thermal insulation values relative to other commercially
available fire foam materials. For use with fuel or chemical fires,
the Gemini surfactant foam may emulsify at least a portion of the
fuel or chemical to lower the combustibility thereof. The impact of
factors such as water hardness, salinity, mix speed, temperature on
expansion, and drainage rates may be reduced using the Gemini
surfactant relative to other commercially available fire foam
materials. The aqueous mixture with the Gemini surfactant can be
used at temperatures down to the freezing point of water, and, if
frozen, can be thawed and used. Corrosion rates on aluminum, steel
and brass are less than those required under U.S. Forest Service
specifications. The L.D. 50 value according to industry standard
test measurement of Juvenile Trout at 96 hours for a concentrate of
the Gemini surfactant: greater than 40 mg per liter; and for a 0.5
weight percent dilution: greater than 8000 mg per liter.
[0071] Anti-static/electro-dissipative agents may be produced using
the Gemini surfactants. Anti-static agents alter surface properties
by reducing the tendency of the surface to acquire an electrical
charge.
[0072] Anti-fogging agents may be produced using the Gemini
surfactants. Below the dew point the air moisture condenses and
because of the low-tension surface of polymers this leads to the
formation of droplets on a substrate surface. Influencing factors
on fogging by moisture deposition may include the difference in
temperature between the air and the substrate surface, the level of
moisture in the air, and the surface tension of the substrate
surface. Because the Gemini surfactants can reduce the surface
tension at the substrate surface, a film or deposit that includes
Gemini surfactant may reduce fogging.
[0073] The examples provided are merely representative of the work
that contributes to the teaching of the present application.
Accordingly, these examples are not intended to limit the
invention, as defined in the appended claims.
EXAMPLES
[0074] Unless specified otherwise, ingredients are commercially
available from such common chemical suppliers as Aldrich Chemical
Company (Milwaukee, Wis.).
Example 1
Preparation of Allyl Capped Polyoxyethylene
[0075] Sodium hydride (NaH) is washed with dry hexane three times
to remove mineral oil and dried under nitrogen (N.sub.2) flow. NaH
(4.8 grams, 60 weight percent dispersed in mineral oil) is placed
in a three-necked round flask equipped with gas inlet and magnetic
stirrer. Dry tetrahydrofuran (THF, 50 milliliters) is charged into
the flask. Polyoxyethylene (30 grams, average M.sub.n=600)
dissolved in 100 milliliters THF is added within 1 hour. The
mixture is stirred at room temperature for 3 hours. Allyl bromide
(14.4 grams) in 30 milliliters THF is added dropwise within 30
minutes. The mixture is stirred overnight. After filtering off
solid and evaporating solvent, allyl-capped polyoxyethylene is
obtained.
Example 2
Preparation of Sample 1
[0076] Heptamethyl trisiloxane (HMTS, 1.11 grams), the allyl-capped
polyoxyethylene (1.79 grams, average M.sub.n=600) synthesized in
Example 1, and 20 microliters of Pt(0) catalyst are dissolved in 10
milliliters of dry toluene and charged into a 100 milliliters
schlenk flask. The mixture is degassed for 3 times and heated to 90
degrees Celsius with magnetic stirring for 2 hours. After cooling
to room temperature, the mixture is filtered through diatomite and
solvent removed by evaporation, to result in a Gemini surfactant,
Sample 1. Sample 1 is straw-colored oil after vacuuming at 90
degrees Celsius for 1 hour.
Example 3
Preparation of Sample 2
[0077] Heptamethyl methylene disilane (HMMDS), the allyl-capped
polyoxyethylene (average M.sub.n=600) synthesized in Example 1, and
20 microliters of Pt(0) catalyst are dissolved in 10 milliliters of
dry toluene and charged into a 100 milliliters schlenk flask. The
mixture is degassed for 3 times and heated to 90 degrees Celsius
with magnetic stirring for 2 hours. After cooling to room
temperature, the mixture is filtered through diatomite and solvent
removed by evaporation, to result in a Gemini surfactant, Sample 2.
Sample 2 is a straw colored oil after vacuuming at 90 degrees
Celsius for 1 hour.
Example 4
Preparation of Sample 3
[0078] Heptamethyl dimethylene disilane, HMDDS, the allyl-capped
polyoxyethylene (average M.sub.n=600) synthesized in Example 1, and
20 microliters of Pt(0) catalyst are dissolved in 10 milliliters of
dry toluene and charged into a 100 milliliters schlenk flask. The
mixture is degassed for 3 times and heated to 90 degrees Celsius
with magnetic stirring for 2 hours. After cooling to room
temperature, the mixture is filtered through diatomite and solvent
removed by evaporation, to result in a Gemini surfactant, Sample 3.
Sample 3 is a straw colored oil after vacuuming at 90 degrees
Celsius for 1 hour.
Example 5
Test and Results
[0079] Portions of each of Samples 1-3 are diluted with distilled
water to a first concentration of 0.1 weight percent (Samples
1A-3A), and a second concentration of 0.5 weight percent (Samples
1B-3B). Aliquots (10 microliters) of the aqueous solutions (0.1
weight percent or 0.5 weight percent) of the Gemini surfactants
(Samples 1A-3A and Samples 1B-3B), and one aliquot (10 microliter)
of distilled water (Comparative Sample 1), are applied to a surface
of a polystyrene petri dish. A hygrometer is placed next to the
petri dish, and the petri dish is covered with a recrystallization
dish. At 30 seconds and at 120 seconds the cover is removed and the
perimeter of the droplet is checked and recorded. The spread
diameter (in millimeters) of two perpendicular axes is measured 3
times for each sample. The average spread diameter is obtained from
the six measured diameters. This test is carried out under
controlled relative humidity that is selected to be between 35
percent and 70 percent, and at a temperature in a range of from
about 22 degrees Celsius to about 26 degrees Celsius. The spread
diameters and the surface tension values obtained are tabulated in
Table 2.
TABLE-US-00002 TABLE 2 Spreading test results for Samples 1-3 and
Comparative Sample 1. Spreading Spreading Surface Concentration
diameter (mm) diameter (mm) Tension Sample wt % 30 sec 120 sec
(mN/m) 1A 0.10 -- 8.8 31.54 1B 0.50 -- 17.5 -- 2A 0.10 4 13.5 32.21
2B 0.50 22.5 26.5 -- 3A 0.10 4 6 34.44 3B 0.50 9 11 -- Comparative
N/A 4 -- 72 * Sample 1 * Surface tension of distilled water in mN/m
at 25 degrees Celsius from CRC Handbook of Chemistry and Physics;
63 Edition, 1982-1983.
[0080] Results tabulated in Table 2 demonstrate that Gemini
surfactants of Samples 1-3 have spreading diameters greater than
that of pure distilled water of Comparative Sample 1. The surface
tension of aqueous solutions of Samples 1-3 is also reduced to less
than 35 N/m in comparison to that of aqueous solution of
Comparative Sample 1.
[0081] The foregoing examples are merely illustrative, serving to
illustrate only some of the features of the invention. The appended
claims are intended to claim the invention as broadly as it has
been conceived and the examples herein presented are illustrative
of selected embodiments from a manifold of all possible
embodiments. Accordingly it is Applicants' intention that the
appended claims are not to be limited by the choice of examples
utilized to illustrate features of the present invention. As used
in the claims, the word "comprises" and its grammatical variants
logically also subtend and include phrases of varying and differing
extent such as for example, but not limited thereto, "consisting
essentially of" and "consisting of." Where necessary, ranges have
been supplied, those ranges are inclusive of all sub-ranges there
between. It is to be expected that variations in these ranges will
suggest themselves to a practitioner having ordinary skill in the
art and where not already dedicated to the public, those variations
should where possible be construed to be covered by the appended
claims. It is also anticipated that advances in science and
technology will make equivalents and substitutions possible that
are not now contemplated by reason of the imprecision of language
and these variations should also be construed where possible to be
covered by the appended claims.
* * * * *