U.S. patent application number 15/176402 was filed with the patent office on 2017-06-08 for nonionic surfactant compositions.
This patent application is currently assigned to Dow Global Technologies LLC. The applicant listed for this patent is Dow Global Technologies LLC. Invention is credited to Paul R. Elowe, Irina V. Graf, Arkady L. Krasovskiy, Lin Wang.
Application Number | 20170158610 15/176402 |
Document ID | / |
Family ID | 47833355 |
Filed Date | 2017-06-08 |
United States Patent
Application |
20170158610 |
Kind Code |
A1 |
Elowe; Paul R. ; et
al. |
June 8, 2017 |
NONIONIC SURFACTANT COMPOSITIONS
Abstract
The present invention provides nonionic surfactants,
compositions incorporating these surfactants, and related methods
of making and using such surfactants and compositions. The nonionic
surfactants demonstrate excellent equilibrium and dynamic surface
tension properties as well as excellent wetting properties.
Further, representative embodiments of the surfactants have, shown
low foaming characteristics, indicating that the surfactants would
be suitable in applications where resistance to foaming is desired.
The surfactants can be used singly or in combination with other
nonionic and/or ionic surfactants as desired. As an overview, the
nonionic surfactants of the present invention have a structure in
which the surfactant backbone includes one or more amine moieties.
At least one, preferably two or more branched, cyclic, fused
cyclic, and/or spyro hydrophobic moieties are pendant from at least
one of the amine moieties. Additionally, at least one, preferably
two or more hydrophilic moieties, preferably alkylene oxide (i.e.,
polyether) chains also are pendant from at least one of the amine
moieties.
Inventors: |
Elowe; Paul R.; (Midland,
MI) ; Krasovskiy; Arkady L.; (Midland, MI) ;
Graf; Irina V.; (Midland, MI) ; Wang; Lin;
(Midland, MI) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Dow Global Technologies LLC |
Midland |
MI |
US |
|
|
Assignee: |
Dow Global Technologies LLC
Midland
MI
|
Family ID: |
47833355 |
Appl. No.: |
15/176402 |
Filed: |
October 17, 2016 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14378848 |
Aug 14, 2014 |
9382192 |
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PCT/US2013/026088 |
Feb 14, 2013 |
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15176402 |
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61598469 |
Feb 14, 2012 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C07C 209/28 20130101;
C07C 2601/14 20170501; C07C 213/08 20130101; C07C 213/08 20130101;
C07C 217/08 20130101; C07C 217/08 20130101 |
International
Class: |
C07C 217/08 20060101
C07C217/08 |
Claims
1.-20. (canceled)
21. A nonionic surfactant having the formula ##STR00024## wherein R
is a divalent linking group, each R.sup.1 independently is a
branched, hydrophobic moiety; and each E independently is H or an
N-functional, monovalent moiety of the formula
--R.sup.2--(R.sup.3O).sub.x--R.sup.4 with the proviso that at least
one E is not H, wherein each R.sup.2 independently is a single bond
or a divalent linking group; each R.sup.3 is independently and
alkylene moiety containing from 1 to 5 carbon atoms; each x
independently is 1 to 100; and each R.sup.4 independently is H or a
monovalent moiety comprising from 1 to 8 carbon atoms.
22. (canceled)
23. A nonionic surfactant having the formula: ##STR00025## each E
independently is H or an N-functional, monovalent moiety of the
formula --R.sup.2--(R.sup.3O).sub.x--R.sup.4 with the proviso that
at least one E is not H, wherein R.sup.2 is a single bond; each
R.sup.3 is independently an alkylene moiety containing from 2 to 3
carbon atoms; each x independently is 1 to 100; and each R.sup.4
independently is H or a monovalent moiety comprising from 1 to 8
carbon atoms.
24.-27. (canceled)
28. A nonionic surfactant having the formula ##STR00026## wherein
each R.sup.13 and each R.sup.14 independently is a monovalent
moiety comprising 1 to 20 carbon atoms or is a co-member of a ring
structure; E is an N-functional, monovalent moiety of the formula
--R.sup.2--(R.sup.3O).sub.x--R.sup.4 wherein R.sup.2 is a single
bond or a divalent linking group; each R.sup.3 is independently and
alkylene moiety containing from 1 to 5 carbon atoms; each x
independently is 1 to 100; and R.sup.4 is H or a monovalent moiety
comprising from 1 to 8 carbon atoms; and each b independently is 1
to 20.
29.-37. (canceled)
Description
PRIORITY
[0001] This application claims priority under 35 U.S.C.
.sctn.119(e) to U.S. provisional application No. 61/598,469, titled
"NONIONIC SURFACTANT COMPOSITIONS," filed Feb. 14, 2012, wherein
the entirety of this application is incorporated herein by
reference in its entirety for all purposes.
FIELD OF THE INVENTION
[0002] The present invention relates to nonionic surfactants. More
particularly, the present invention relates to nonionic surfactants
comprising one or more amine moieties, one or more branched
hydrophobic chains pendant from the amine moieties, and one or more
hydrophilic alkylene oxide chains pendant from the amine
moieties.
BACKGROUND OF THE INVENTION
[0003] The ability to reduce the surface tension of liquid
compositions, particularly aqueous compositions, is of great
importance in a wide variety of compositions including solutions,
dispersions, gels, emulsions, latex compositions, and the like.
Such compositions are used in a wide range of applications
including paints and other coatings, stains and other coloring
agents, ink compositions, oil and gas recovery compositions, steam
assisted gravity drainage compositions, chemical flooding
compositions, cosmetics, foods, nutriceuticals, health care
products, cleaning products, etching compositions, agrochemicals,
or the like.
[0004] It is well known in the art that so-called Gemini
surfactants, which are surfactants with multiple hydrophobic tails
and multiple hydrophilic heads, or Gemini-like surfactants exhibit
superior properties compared to those of analogous conventional
surfactants. See, e.g., Gemini Surfactants: Synthesis, Interfacial
and Solution-Phase Behavior, and Applications, Vol. 117, Zana, R.;
Xia, J., Eds.; Marcel Dekker: New York, 2004. Furthermore, it is
also well known in the art that increasing branching in a
hydrophobic tail significantly improves wetting properties of a
surfactant. See, e.g., Rosen, M. J. Surfactants and Interfacial
Phenomena, 3.sup.rd ed.; John Wiley & Sons, Inc.; Hoboken, New
Jersey, 2004; pp. 243-277.
[0005] Important surfactant performance characteristics include
equilibrium surface tension properties, dynamic surface tension
properties, wetting properties, foaming properties, and the like.
Equilibrium surface tension is important when a system is at rest.
Dynamic surface tension is a fundamental property which measures
the ability of a surfactant to perform under high speed application
conditions. Many nonionic surfactants may have acceptable
equilibrium surface tension properties, but demonstrate poor
dynamic surface tension properties. Many nonionic surfactants also
tend to be foamy and make compositions too susceptible to foaming,
which can be undesirable in many applications. The importance of
improving equilibrium, dynamic, wetting and foaming performance is
well-appreciated in the art.
[0006] Accordingly, there is a strong demand for nonionic
surfactants that provide not only strong equilibrium surface
tension properties but also strong dynamic surface tension
properties and strong wetting properties with a reduced tendency to
cause foaming.
SUMMARY OF THE INVENTION
[0007] The present invention provides nonionic surfactants,
compositions incorporating these surfactants, and related methods
of making and using such surfactants and compositions. The nonionic
surfactants demonstrate excellent equilibrium and dynamic surface
tension properties as well as excellent wetting properties.
Further, representative embodiments of the surfactants have shown
low foaming characteristics, indicating that the surfactants would
be suitable in applications where resistance to foaming is desired.
The surfactants can be used singly or in combination with other
nonionic and/or ionic surfactants as desired.
[0008] As an overview, the nonionic surfactants of the present
invention have a structure in which the surfactant backbone
includes one or more amine moieties. At least one, preferably two
or more branched, cyclic, fused cyclic, and/or spyro hydrophobic
moieties are pendant from at least one of the amine moieties.
Additionally, at least one, preferably two or more hydrophilic
moieties, preferably alkylene oxide (i.e., polyether) chains also
are pendant from at least one of the amine moieties.
[0009] In one aspect, the present invention relates to a method of
making a nonionic surfactant, comprising the steps of: [0010] a)
providing an adduct comprising at least one secondary amine moiety
and at least two branched, cyclic, fused cyclic, and/or spyro
hydrophobic moieties; and [0011] b) N-functionalizing at least a
portion of the secondary amine moieties of the adduct under
conditions effective to convert at least a portion of the secondary
amine moieties to tertiary amine moieties having pendant,
hydrophilic, N-ether functionality.
[0012] In another aspect, the present invention relates to a
nonionic surfactant of the formula
(E).sub.m-A.sup.1-(R.sup.1).sub.n [0013] wherein: [0014] A.sup.1 is
an (n+m) valent moiety comprising at least one tertiary amine
moiety and optionally one or more secondary amine moieties; [0015]
each R.sup.1 independently is a branched, cyclic, fused cyclic,
and/or spyro hydrophobic moiety; [0016] each E independently is H
or an N-functional, monovalent moiety of the formula
[0016] --R.sup.2--(R.sup.3O).sub.x--R.sup.4 [0017] with the proviso
that at least one E is not H, wherein each R.sup.2 independently is
a single bond or a divalent linking group; each R.sup.3 is
independently an alkylene moiety containing from 1 to 5 carbon
atoms (e.g., each alkylene oxide chain independently may contain
one or more different kinds of alkylene oxide units used in
combination; and each alkylene oxide chain may be the same or
different than other such chains included in the molecule); each x
independently is 1 to 100; and each R.sup.4 independently is H or a
monovalent moiety comprising from 1 to 8 carbon atoms; [0018] n is
2 to 6; and [0019] m is 1 to 6.
DETAILED DESCRIPTION OF PRESENTLY PREFERRED EMBODIMENTS
[0020] The embodiments of the present invention described below are
not intended to be exhaustive or to limit the invention to the
precise forms disclosed in the following detailed description.
Rather the embodiments are chosen and described so that others
skilled in the art may appreciate and understand the principles and
practices of the present invention. All patents, pending patent
applications, published patent applications, and technical articles
cited herein are incorporated herein by reference in their
respective entireties for all purposes.
[0021] The present invention relates to nonionic surfactants of the
formula
(E).sub.m-A.sup.1-(R.sup.1).sub.n
[0022] wherein: [0023] A.sup.1 is an (n+m) valent moiety comprising
at least one, more preferably at least two tertiary amine moieties,
and optionally one or more secondary amine moieties; [0024] each
R.sup.1 independently is a branched, cyclic, fused cyclic, and/or
spyro hydrophobic moiety; [0025] each E independently is H or an
N-functional, monovalent moiety of the formula
[0025] --R.sup.2--(R.sup.3O).sub.x--R.sup.4 [0026] with the proviso
that at least one E is not H and more preferably at least two E are
not H, wherein each R.sup.2 independently is a single bond or a
divalent linking group; each R.sup.3 is independently a linear or
branched alkylene moiety containing from 1 to 5 carbon atoms (e.g.,
each alkylene oxide chain independently may contain one or more
different kinds of alkylene oxide units used in combination; and
each alkylene oxide chain may be the same or different than other
such chains included in the molecule); each x independently has an
average value of 1 to 100; and each R.sup.4 independently is H or a
monovalent moiety comprising from 1 to 8 carbon atoms; [0027] n is
2 to 6, preferably 2 to 3, more preferably 2; and [0028] m is 1 to
6, preferably 1 to 3, more preferably 1 to 2. [0029] Preferably,
each of n and m independently are 2 to 4. In some embodiments, n=m.
Even more preferably, each of n and m are 2.
[0030] As used herein, a hydrophobic moiety refers to a moiety in
which the ratio of carbon atoms to hetero atoms (such as O, P, S or
the like) in the moiety is 5:1 or greater, preferably 8:1 or
greater, more preferably 12:1 or geater. Even more preferably, a
hydrophobic moiety is a hydrocarbyl or hydrocarbylene moiety that
(1) contains at least 5 carbon atoms, (2) contains only C and H
atoms, (3) is free of hetero atoms such as O, P, and S or the like;
and (4) optionally is branched and/or has a ring, spyro, and/or
fused ring structure.
[0031] As used herein, the terminology "N-functional" means that a
moiety is pendant from a nitrogen atom.
[0032] In exemplary embodiments, each R.sup.3 moiety independently
may be ethylene, propylene, isopropylene, butylene, isobutylene, or
combinations thereof. Preferably, each R.sup.3 moiety is ethylene,
propylene, butylene or combinations thereof. More preferably,
R.sup.3 is ethylene.
[0033] As shown by the general formula, the value for x may be
selected over a wide range. In preferred embodiments, each x
independently has an average value of 1 to 20, preferably 1 to 10,
more preferably 1 to 4. When a surfactant includes 2 or more E
moieties, it is desirable that the values for x for all the E
moieties are generally matched on average. For instance, if a
surfactant embodiment has two E moieties and one of the E moieties
has an average x=4, then it is desirable that the other E has an
average x=3 to 5, more preferably x=3.5 to 4.5, more preferably
x=4.
[0034] A first, preferred class of surfactants of the present
invention may be represented by the general formula
##STR00001##
[0035] wherein E and R.sup.1 are as defined above, and R is a
divalent linking group.
[0036] One exemplary first group of surfactants according to this
first class includes surfactants according to the following
formula:
##STR00002##
[0037] wherein E and R are as defined above, wherein R preferably
is a divalent moiety that may be linear, branched, cyclic, fused
cyclic, spyro, saturated or unsaturated, aliphatic or aromatic,
substituted or unsubstituted, and more preferably is a
hydrocarbylene moiety of 1 to 20 carbon atoms; each R.sup.5 and
each R.sup.6 independently is H, a monovalent hydrocarbyl moiety
comprising 1 to 20 carbon atoms, or a co-member of a hydrocarbylene
ring structure with at least one other R.sup.5 or R.sup.6, with the
proviso that at least one R.sup.5 and at least one R.sup.6 is not
H; and each r independently is 0 to 20.
[0038] More preferably, the first group of surfactants is
exemplified by surfactants having the formula
##STR00003##
[0039] and/or of the formula
##STR00004##
[0040] wherein each E independently is as defined above, and in the
formula for E, R.sup.2 is a single bond and R.sup.3 independently
is selected from one or more of ethylene, propylene, butylene or
combinations thereof.
[0041] A particularly preferred embodiment of a surfactant of the
type shown in Paragraph 19 has the formula
##STR00005##
[0042] wherein when dynamic properties are to be favored, each of x
and y is on average independently 0 to 6, preferably independently
0 to 4, with the proviso that x+y on average is 1 to 12, preferably
1 to 8. Comparable versions of the surfactants described in
paragraphs 20 and 21 independently would have similar structures
for each E to favor dynamic properties. More generally, to favor
dynamic properties for the surfactants of the first class of
surfactants of Paragraph 16 above or the second class of
surfactants of Paragraph 29 below, each E independently generally
includes on average from 0 to 6, preferably from 0 to 4 ethylene
oxide units, with the proviso that the total number of ethylene
oxide units in all the E moieties of the surfactant on average is 1
to 12, preferably 1 to 8.
[0043] In other embodiments of the first class of surfactants of
Paragraph 16 above or the second class of surfactants of Paragraph
29 below more suitable for oil and gas applications or the like,
each E independently includes a combination comprising ethylene
oxide (EO) and optionally and preferably propylene oxide (PO)
moieties, wherein the molar ratio of EO to PO moieties (when PO
moieties are present) in each E independently is in the range from
100:1 to 1:100, desirably 20:1 to 1:20; the average number of EO
units in each E independently is in the range from 1 to 100,
preferably 1 to 50; and the average number of PO units in each E is
in the range from 0 to 100, preferably 0 to 20; and the total
number of EO and PO units in the E moieties is in the range from 1
to 200, preferably 1 to 100, more preferably 1 to 70.
[0044] An exemplary second group of surfactants according to the
first class of surfactants includes surfactants according to the
following formula:
##STR00006##
[0045] wherein each R.sup.7 and each R.sup.8 independently is a
monovalent moiety comprising 1 to 20 carbon atoms or is a co-member
of a ring structure; each R.sup.9 independently is H, a monovalent
moiety comprising 1 to 20 carbon atoms, or a co-member of a ring
structure; and each t independently is 1 to 20, preferably 1 to 6.
A particularly preferred nonionic surfactant of this type has the
formula
##STR00007##
[0046] An exemplary third group of surfactants according to the
first class of surfactants includes surfactants according to the
following formula:
##STR00008##
[0047] wherein each R.sup.10 and each R.sup.11 independently is a
monovalent moiety comprising 1 to 20 carbon atoms or is a co-member
of a ring structure; each R.sup.12 independently is H, a monovalent
moiety comprising 1 to 20 carbon atoms, or a co-member of a ring
structure; and each q independently is 1 to 20. A particularly
preferred nonionic surfactant of this type has the formula
##STR00009##
[0048] A second, representative class of surfactants of the present
invention may be represented by the general formula
##STR00010##
[0049] wherein each R.sup.13 and each R.sup.14 independently is a
monovalent moiety comprising 1 to 20 carbon atoms or is a co-member
of a ring structure; and each b independently is 0 to 20. A
particularly preferred nonionic surfactant of this type has the
formula
##STR00011##
[0050] The surfactants of the present invention have the ability to
reduce the surface tension of water. For instance, using
illustrative embodiments of the surfactants at 0.1 weight percent
concentration in water should provide solutions with an equilibrium
surface tension of less than 50 mN/m. The dynamic surface tension
of such illustrative embodiments would be less than 55 mN/m at
bubble rate of 5 bubbles/second. Desirably, the contact angle on a
Teflon film should be less than 75 degrees for more preferred
embodiments.
[0051] The surfactants of the present invention can be used singly
or in combination with other surfactants of the present invention
or with other surfactants in a wide range of applications. The
surfactants may be used in aqueous or nonaqueous compositions
including solutions, dispersions, emulsions, latex compositions,
gels, or the like. The surfactants would be particularly useful in
any application in which low foaming, nonionic wetting agents are
desired. For example, the surfactants would be useful in paint and
other coating compositions, ink compositions, adhesive
compositions, oil and gas recovery compositions, steam assisted
gravity drainage compositions, chemical flooding compositions,
cosmetics, foods, nutriceuticals, health care products, cleaning
products, staining products, etching compositions, agrochemical
compositions, or the like.
[0052] According to a preferred methodology for preparing nonionic
surfactants of the present invention, a first step involves
providing at least one adduct comprising at least one secondary
amine moiety and at least two, branched hydrophobic moieties. In a
second step, at least a portion of the secondary amine moieties of
the adduct are N-functionalized under conditions effective to
convert at least a portion of the secondary amine moieties to
tertiary amine moieties having pendant, hydrophilic, N-ether
functionality and thereby form the nonionic surfactant of the
present invention described above.
[0053] As used herein, N-functionalized means that that the
functionality is caused to be pendant from the nitrogen of the
amine moiety, converting it from a secondary amine to a tertiary
amine. N-ether means that the ether is pendant directly or
indirectly from the resultant tertiary amine.
[0054] The adduct provided in the first step generally has the
formula
A-(R.sup.1).sub.n
[0055] wherein A is an n-valent moiety comprising one or more
secondary amine moieties; each R.sup.1 independently is as defined
above such as a branched, hydrophobic moiety or is a member of a
hydrophobic ring structure with another R.sup.1; and n is 2 to 10,
preferably 2 to 6. In illustrative embodiments, the adduct
comprises a compound having a formula selected from the following
or is a combination thereof:
R.sup.1--NH--R.sup.1;
R.sup.1--NH--R--NH--R.sup.1; and/or
(R.sup.1--NH).sub.p--R.sup.15,
[0056] wherein each R.sup.1 independently is as defined above such
as a branched, hydrophobic moiety or a co-member of a hydrophobic
ring structure with another R.sup.1; R is a divalent linking moiety
as defined above; R.sup.15 is a p-valent moiety; and p is 3 to
10.
[0057] One representative class of adducts of the present invention
has the formula
##STR00012##
[0058] wherein R, R.sup.5, and R.sup.6 are independently as defined
above. One preferred adduct according to this formula has the
structure
##STR00013##
[0059] Another preferred adduct according to this formula has the
structure
##STR00014##
[0060] Another representative class of adducts of the present
invention has the formula
##STR00015##
[0061] wherein each of R.sup.7, R.sup.8, and R.sup.4 independently
is as defined above. One preferred adduct according to this formula
has the structure
##STR00016##
[0062] Another representative class of adducts of the present
invention has the formula
##STR00017##
[0063] wherein each R.sup.11, R.sup.12, and R.sup.13 independently
is as defined above. One preferred adduct according to this formula
has the structure
##STR00018##
[0064] Another representative class of adducts of the present
invention has the formula
##STR00019##
[0065] wherein each R.sup.13 and each 14 independently is as
defined above. One preferred adduct according to this formula has
the structure
##STR00020##
[0066] The adduct can be prepared by reacting ingredients
comprising first and second compounds under conditions effective to
form the adduct, wherein the first compound comprises one or more
ketone and/or aldehyde moieties and the second compound comprises
one or more primary amine moieties. Illustrative conditions for
forming the adduct from such first and second reactant compounds
include reductive amination conditions. Reductive amination
techniques are further described in (1) "The Preparation of Amines
by Reductive Alkylation", Emerson, W., Organic Reactions , Vol. 4,
174-255 (1948); (2) "Reductive Aminations of Carbonyl Compounds
with Borohydride and Borane Reducing Agents", Baxter E. W.; Reitz,
A. B., Organic Reactions, Vol 59, 1-714 (2002); (3) Abdel-Magid et
al. Org. Process Res. Dev. 2006, 10, 971-1031; (4) Abdel-Magid et
al. J. Org. Chem. 1996, 61, 3849-3862.
[0067] The hydrophobic, branched moieties may be sourced from
either the first and/or second compounds. The first and/or second
compounds can be symmetric or asymmetric. The first and/or second
compounds can be linear, branched or cyclic; aliphatic or aromatic;
and may be saturated or unsaturated. The first and/or second
compounds preferably may include from 3 to 24 carbon atoms with the
proviso that at least one of the first and second compounds
provides a source of the branched hydrophobic moiety to be
incorporated into the resultant adduct.
[0068] The first compound can include any one or more compounds
that include one or more ketone and/or one or more aldehyde
moieties. Exemplary aldehydes include 2-ethylhexanal, glyoxal,
2-ethylhex-2-enal, 2-propylhept-2-enal and 2-methylpent-2-enal,
2-propylheptanal, benzaldehyde, cinnamaldehyde, acetaldehyde; and
combinations of these. Exemplary ketones include methyl isobutyl
ketone, di-isobutyl ketone, cyclohexanone, 1,4-cyclohexanedione,
1,2-cyclohexanedione, 1,3-cyclohexanedione, acetone, methyl ethyl
ketone, di-isopropyl ketone, 2,6,8-trimethylnonan-4-one,
2-pentanone, 2-hexanone, 2-heptanone, 2-octanone, and combinations
of these.
[0069] In addition to the ketone and/or aldehyde moiety, the first
compound may optionally include one or more other kinds of
functionality that are compatible with the reductive amination and
that would not unduly compromise the subsequent alkoxylation on the
next reaction stage and/or unduly compromise performance of the
resultant surfactant. Examples of such optional functionality
include hydroxyl, alkenyl, alkynyl, secondary and tertiary amine,
amide, ether, thioether and thiol moieties.
[0070] The second compound may include any one or more compounds
including one or more primary amine moieties. Exemplary primary
amines include one or more of 1,2-ethylene diamine, 1,3-propylene
diamine, 1,2-cyclohexyldiamine, 1,3-cyclohexyldiamine,
1,4-cyclohexyldiamine, p-phenylenediamine, o-phenylenediamine,
m-phenylenediamine, 2-ethylhexyl amine, 2-propylheptyl amine,
2,4,4-trimethylpentan-2-amine, isopropylamine, isobutylamine,
isopentylamine and combinations thereof.
[0071] In addition to the primary amine moiety, the first compound
may optionally include one or more other kinds of functionality
that are compatible with the reductive amination and that would not
unduly compromise the subsequent alkoxylation on the next reaction
stage and/or unduly compromise performance of the resultant
surfactant. Examples of such optional functionality include
secondary and tertiary amine moieties, hydroxyl, alkenyl, alkynyl,
amide, ether, cyano, nitro, thioether and thiol moieties.
[0072] Reductive amination typically takes place in the presence of
one or more reducing agents. Any such agent(s) known to be useful
for reductive amination may be used in the practice of the present
invention. Exemplary reducing agents include borohydride systems
such as sodium borohydride, sodium triacetoxyborohydride and sodium
cyanoborohydride as well as hydrogenation catalysis systems such as
palladium, platinum, rhodium, ruthenium and nickel-based catalyst
systems under H.sub.2 pressure.
[0073] According to a representative reaction scheme, the first
compound and second compound are placed into a suitable reaction
vessel in a suitable solvent in the presence of the reducing agent.
The reaction may be carried out on a batch or continuous basis as
desired. The stoichiometry may be selected so that the first
compound is in excess so that the first compound end caps the
second compound. In other modes of practice, the stoichiometry is
selected so that the second compound end caps the first compound.
In some instances, the stoichiometry may be substantially 1:1. In
still other modes of practice, alternative stoichiometries may be
practiced to achieve other reaction goals.
[0074] The reaction is allowed to progress at a suitable
temperature for a suitable time period often under a protected
atmosphere. By way of example, allowing the reaction to proceed at
room temperature under a nitrogen atmosphere for 10 to 36 hours
would be suitable.
[0075] After the reaction is complete, the reaction may be
quenched, and the products may be extracted into an organic phase.
A high purity product can then be recovered from the organic phase
using any desired recovery techniques.
[0076] According to an alternative strategy, the adduct can be
provided by using reductive amination techniques to form the adduct
from one or more compounds that include at least one primary amine
moiety and at least one aldehyde and/or ketone moiety. These
compounds are multifunctional in the sense that they contain at
least two different kinds of functionality, namely a primary amine
and at least an aldehyde and/or ketone in the same. compound. In
other modes of practice, the adduct can be formed from reactants
including at least one of the first and/or second compounds
described above and at least one multifunctional reactant
compound.
[0077] To prepare a nonionic surfactant of the present invention,
one or more adducts provided in the first step are N-functionalized
via a reaction strategy that adds respective hydrophilic moieties
to one or more of the secondary amine moieties of the adduct(s).
The moieties independently may be hydrophilic ether or polyether
moieties containing, by way of example, 1 to 200 ether units, added
independently to one or more of the secondary amines of the
adduct(s). In more preferred embodiments, two or more of the
secondary amines of the adduct(s) are N-functionalized with
hydrophilic moieties. In some modes of practice, the degree of
functionalization of the secondary amines is matched as closely as
practical on average. For example, if two or more amines are
functionalized by hydrophilic groups, it is desired that the
average degree of functionality of a first a first amine moiety is
X.sub.1, then it is desired that the average degree of
functionality of the other functionalized amines is at least 50%,
or even at least 70%, or even 100% of X.sub.1.
[0078] By way of example, consider a surfactant embodiment
containing two tertiary amines functionalized with
--(CH.sub.2CH.sub.2O)-- (ethylene oxide) groups. If the first amine
moiety is functionalized with an average of 4 ethylene oxide
groups, then it is desired that the other amine also is
functionalized with 2 to 8, preferably 2.8 to 5.7, preferably 5
ethylene oxide groups.
[0079] According to one illustrative mode of practice, the
secondary amine moieties of the adduct(s) are N-functionalized
under suitable conditions to convert the secondary amine moieties
to tertiary amine moieties having directly or indirectly pendant
N-ether (or N-polyether) functionality. Representative conditions
include reacting the adduct(s) with one or more epoxy functional
compounds such as those including from 2 to 12 carbon atoms.
Examples of such compounds include one or more of ethylene oxide,
propylene oxide, butylene oxide, and combinations thereof.
[0080] The N-functionalization of the amines with these compounds
to provide pendant ether or polyether chains is known in the art as
alkoxylation. As known in the art, alkoxylation may involve
alkoxylation with more than one type of resultant alkylene oxide.
Thus, the alkylene oxide units may be the same or different. If
different, the alkylene oxide units may be random or arranged in
blocks.
[0081] An amine may be alkoxylated by any desired number of
alkylene oxide units. In representative embodiments, at least one
amine of an adduct, preferably at least two amines of each adduct
is alkoxylated with 1 to 100, preferably 1 to 20, more preferably 1
to 6 alkylene oxide units.
[0082] The alkoyxlation reaction desirably occurs in the presence
of a catalyst, optionally in a suitable solvent. The catalyst may
be any catalyst or combination of catalysts known to be useful for
carrying out alkoxylation reactions. Representative examples
include KOH, NaOH, KH, NaH and double metal cyanide (DMC)
catalysts. Suitable solvents also are widely known and any may be
used. Examples include dimethoxyethane and toluene.
[0083] According to a representative alkoxylation methodology, an
adduct, solvent and catalyst are loaded into a suitable reaction
vessel. An exemplary reaction vessel is pressurized to facilitate
the reaction. The reaction may occur on a batch or continuous
basis. The desired epoxy functional reactant may then be supplied
at the desired stoichiometric excess to achieve the desired
functionalization. For instance, 4 equivalents of epoxide can be
supplied per equivalent of amine to achieve an average
functionalization of 4 alkylene oxide units per amine. The reaction
is allowed to proceed at elevated pressure and temperature until
complete. The reaction product can then be recovered using
conventional recovery techniques.
[0084] The present invention will now be further described with
reference to the following illustrative examples.
EXAMPLE 1
[0085] Methyl isobutyl ketone (MIBK) (6.050 g, 60.403 mmol, 1
equiv.), ethylene diamine (1.815 g, 30.202 mmol, 0.5 equiv.) and
sodium triacetoxyborohydride (15.362 g, 72.484 mmol, 1.2 equiv.) in
about 175 mL CH.sub.2Cl.sub.2 were weighed into a 500 mL
three-necked flask. The mixture was stirred at room temperature
under a nitrogen atmosphere. The reaction was stopped after a total
of 20 h. The mixture was quenched with saturated aqueous
NaHCO.sub.3 and the product extracted into ethyl acetate. The
combined organic fraction was dried over sodium sulfate, filtered
and evaporated using a rotovap to yield 3.774 g of desired product.
The product, N,N'-bis(4-methylpentan-2-yl)ethane-1,2-diamine, had
high purity as determined by gas chromatography and NMR. This
adduct has the following structure:
##STR00021##
EXAMPLE 2A
[0086] N,N'-bis(4-methylpentan-2-yl)ethane-1,2-diamine (1.00 g,
4.38 mmol, 1 equiv.), 1,2-dimethoxyethane (1 mL), KH (3-5 mg,
0.3-0.5 wt. %) were loaded into a glass PPR vial (insert).
Alkoxylation was carried out in a Symyx PPR.RTM. (Parallel Pressure
Reactor) setup containing 48 reactors. Ethylene oxide (EO) was
delivered via an Isco syringe pump equipped with a
robotically-controlled needle and compressed gas microvalve
connected to the PPR, such that 4 equivalents of EO were added per
molecule of diamine initiator on average. A glass insert along with
a removable PEEK stir paddle for the cell were dried in a vacuum
oven at 125.degree. C. overnight. The insert with the diamine,
1,2-dimethoxyethane and KH was loaded into each PPR well, heated to
130.degree. C., and pressurized with nitrogen to 50 psi. EO was
introduced at 130.degree. C. and the reaction was stirred for 12 h
at that temperature. After cooling and venting, the insert was
placed in a Savant SC250EXP SpeedVac.RTM. Concentrator for 1 h at
80.degree. C. and 0.01 Torr. The resulting viscous surfactant was
tested for its properties without additional purification. The
identity of the surfactant was confirmed by NMR spectroscopy. The
ethoxylated surfactant of this Example 2A has the following
structure where the sum of x+y=4 is an average:
##STR00022##
EXAMPLE 2B
[0087] The procedure of Example 2A is repeated to prepare a
surfactant, except a catalyst is not used.
EXAMPLE 2C
[0088] The procedure of Example 2A is repeated to prepare a
surfactant, except a solvent is not used.
EXAMPLE 3
[0089] Basic surfactant properties of the surfactant from EXAMPLE
2A were characterized. The equilibrium surface tension of a 0.1 wt
% aqueous solution is reduced to 29 mN/m, and the dynamic surface
tension at 5 bubbles/second is 37 mN/m. The contact angle on a
TEFLON film is reduced to 70 degrees, and the contact angle on
polyethylene is reduced to 46 degrees. As summarized in table 1
below, the ethoxylated diamine surfactant from EXAMPLE 2A exhibits
better properties than the non-ethoxylated precursor prepared in
Example 1.
[0090] Basic surfactant properties also were characterized on the
non-ethoxylated precursor from EXAMPLE 1. The equilibrium surface
tension of a 0.1 wt % aqueous solution is reduced to 36 mN/m, the
dynamic surface tension of a 0.1 wt % aqueous solution at 5
bubbles/second is 37 mN/m, the contact angle on a Teflon film is 90
degrees, and the contact angle on polyethylene is 62 degrees. Data
is summarized in the following Table 1.
TABLE-US-00001 TABLE 1 Comparison of basic surfactant properties of
non-ethoxylated diamine- based molecule with those of the
corresponding ethoxylated version. Example 1 Precursor EXAMPLE 2
aqueous solution aqueous solution (0.1 wt %) (0.1 wt %) Equilibrium
surface tension, 36 29 mN/m Dynamic Surface Tension at 37 40 5
bbl/sec, mN/m Contact angle on polyethylene, 62 46 degree Contact
angle on Teflon, degree 90 70
EXAMPLE 4
[0091] MIBK (6.843 g, 59.93 mmol, 1 equiv.), 2-ethylhexyl amine
(7.745 g, 59.93 mmol, 1 equiv.) and sodium triacetoxyborohydride
(17.780 g, 84.37 mmol, 1.4 equiv.) were weighed into a 500 mL
three-necked flask and suspended in about 175 mL CH.sub.2Cl.sub.2.
The mixture was stirred at room temperature under a nitrogen
atmosphere for 64 h after which time the reaction was complete. The
mixture was then quenched with saturated aqueous NaHCO.sub.3 and
the product extracted into ethyl acetate. The combined organic
fraction was dried over sodium sulfate for 5 h. After filtration,
the solution was rotovaped to give 10.775 g of the desired product
as a slightly yellow liquid. GC analysis of the isolated product
showed purity of 98%.
EXAMPLE 5
[0092] 1,4-Cyclohexanedione (3.037 g, 27.08 mmol, 1 equiv.),
2-ethylhexyl amine (7.000 g, 54.16 mmol, 2 equiv.) and sodium
triacetoxyborohydride (13.775 g, 65.00 mmol, 1.2 equiv.) were
weighed into a 500 mL three-necked flask and suspended in about 160
mL CH.sub.2Cl.sub.2. The mixture was stirred at room temperature
under a nitrogen atmosphere for 22 h after which time the reaction
was complete. The mixture was then quenched with saturated aqueous
NaHCO.sub.3 and the product extracted into ethyl acetate. The
combined organic fraction was dried over magnesium sulfate for 5 h.
After filtration, the solution was rotovaped to give 7.232 g of the
desired product as a dark brown liquid. GC analysis of the isolated
product showed purity of 98%.
EXAMPLE 6
[0093] MIBK (6.130 g, 61.202 mmol, 1 equiv.),
1,2-diaminocyclohexane (3.494 g, 30.601 mmol, 0.5 equiv.) and
sodium triacetoxyborohydride (15.565 g, 73.442 mmol, 1.2 equiv.)
were weighed into a 500 mL three-necked flask and suspended in
about 175 mL CH.sub.2Cl.sub.2. The mixture was stirred at room
temperature under a nitrogen atmosphere for 19 h after which time
the reaction was complete. The mixture was then quenched with
saturated aqueous NaHCO.sub.3 and the product extracted into ethyl
acetate. The combined organic fraction was dried over magnesium
sulfate for 5 h. After filtration, the solution was rotovaped to
give 8.490 g of the desired product as an off-white paste. GC
analysis of the isolated product showed purity of 94%. .sup.1H NMR
(CD.sub.3OD, 500 MHz, RT): .delta.=0.84-0.96 (m, 12H), 1.03-1.78
(m, 14H), 1.12-1.20 (m, 6H), 2.10-2.18 (m, 1H), 2.43-2.58 (m, 1H),
2.88-3.12 (m, 2H). The following shows the structures of precursors
from EXAMPLES 4-6, respectively.
##STR00023##
EXAMPLES 7-9
[0094] The corresponding amine or diamines from Examples 4-6,
respectively, (1.00 g), 1,2-dimethoxyethane (1 mL) (the reaction
may be conducted without solvent), and KH (3-5 mg, 0.3-0.5 wt. %)
(the reaction may also be carried out without any catalyst) were
loaded into a glass PPR vial (insert). Alkoxylation was carried out
in a Symyx PPR.RTM. (Parallel Pressure Reactor) setup containing 48
reactors. Ethylene oxide (EO) was delivered via an Isco syringe
pump equipped with a robotically-controlled needle and compressed
gas microvalve connected to the PPR, such that required equivalents
of EU were added per molecule of amine precursor. A glass insert
along with a removable PEEK stir paddle for the cell were dried in
a vacuum oven at 125.degree. C. overnight. The insert with the
amine, 1,2-dimethoxyethane and KH was loaded into each PPR well,
heated to 130.degree. C., and pressurized with nitrogen to 50 psi.
EU was introduced at 130.degree. C. and the reaction was stirred
for 12 h at that temperature. After cooling and venting, the insert
was placed in a Savant SC250EXP SpeedVac.RTM. Concentrator for 1 h
at 80.degree. C. and 0.01 Torr. The resulting viscous surfactants
are identified as Examples 7-9, respectively, and were tested for
their properties without additional purification. The identity of
the surfactants was confirmed by NMR spectroscopy.
EXAMPLES 10
[0095] Basic surfactant properties were characterized on the
surfactants from EXAMPLES 7-9, where the ethylene oxide (EO)
content is 4, 3.5 and 8 equivalents, respectively. Table 2
summarizes the results obtained.
TABLE-US-00002 TABLE 2 Comparison of basic surfactant properties of
non-ethoxylated amine-based molecules from EXAMPLES 4-6 with those
of the corresponding ethoxylated versions from EXAMPLES 7-9.
COMPARATIVE COMPARATIVE COMPARTIVE EXAMPLE 7 EXAMPLE 2 EXAMPLE 8
EXAMPLE 3 EXAMPLE 9 EXAMPLE 4 Corresponding EXAMPLE 7 EXAMPLE 4
EXAMPLE 8 EXAMPLE 5 EXAMPLE 9 EXAMPLE 6 Surfactant Equilibrium 39
60 33 42 46 65 surface tension, mN/m Dynamic 54 70 50 71 37 62
Surface Tension at 5 bbl/sec, mN/m Contact angle 64 81 58 75 62 86
on polyethylene, degree Contact angle 75 91 70 101 88 102 on
Teflon, degree Note: All tests done on aqueous solutions (0.1 wt
%).
[0096] Other embodiments of this invention will be apparent to
those skilled in the art upon consideration of this specification
or from practice of the invention disclosed herein. Various
omissions, modifications, and changes to the principles and
embodiments described herein may be made by one skilled in the art
without departing from the true scope and spirit of the invention
which is indicated by the following claims.
* * * * *