U.S. patent application number 15/564318 was filed with the patent office on 2018-05-17 for compositions and methods of using polyamidopolyamines and non-polymeric amidoamines.
This patent application is currently assigned to Houghton Technical Corporation. The applicant listed for this patent is Houghton Technical Corporation. Invention is credited to Joseph F. Barbieri, Tom N. Demopolis, John P. Kroetz, Valarie Yvonne Pearson, Alla M. Petlyuk, Qi Wang, Joseph F. Warchol.
Application Number | 20180134846 15/564318 |
Document ID | / |
Family ID | 57125963 |
Filed Date | 2018-05-17 |
United States Patent
Application |
20180134846 |
Kind Code |
A1 |
Warchol; Joseph F. ; et
al. |
May 17, 2018 |
Compositions and Methods of Using Polyamidopolyamines and
Non-Polymeric Amidoamines
Abstract
Compositions comprising a polyamidopolyamine and/or a
non-poly-meric amidoamine are disclosed for imparting multiple
desired characteristics to a variety of industrial compositions. In
certain embodiments, these compositions are prepared by condensing
a C.sub.4 to C.sub.16 poly basic acid, monobasic acid or derivative
thereof with a polyamine comprising a primary amino group, and in
the presence of an optional organic diluent. Certain specific
polyamidopolyamine and a non-polymeric amidoamine formulae and
compositions containing same are disclosed, as are methods of use
of these compositions.
Inventors: |
Warchol; Joseph F.; (Oley,
PA) ; Barbieri; Joseph F.; (Richboro, PA) ;
Demopolis; Tom N.; (Collegeville, PA) ; Kroetz; John
P.; (Philadelphia, PA) ; Wang; Qi; (Gorham,
ME) ; Petlyuk; Alla M.; (Langhome, PA) ;
Pearson; Valarie Yvonne; (Phoenixville, PA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Houghton Technical Corporation |
Wilmington |
DE |
US |
|
|
Assignee: |
Houghton Technical
Corporation
Wilmington
DE
|
Family ID: |
57125963 |
Appl. No.: |
15/564318 |
Filed: |
April 14, 2016 |
PCT Filed: |
April 14, 2016 |
PCT NO: |
PCT/US2016/027619 |
371 Date: |
October 4, 2017 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
62147840 |
Apr 15, 2015 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08K 5/20 20130101; C08G
69/28 20130101; C08G 69/40 20130101; C08G 73/028 20130101; C21D
1/60 20130101; A01N 33/08 20130101; A01N 37/44 20130101; C08L 79/08
20130101; C08L 77/06 20130101; A01N 25/02 20130101; A01N 37/44
20130101; C07C 231/02 20130101; A01N 33/08 20130101; C07C 233/34
20130101; C07C 233/16 20130101; A01N 25/10 20130101; A01N 37/44
20130101; A01N 33/08 20130101; C08G 69/265 20130101; A01N 25/10
20130101 |
International
Class: |
C08G 73/02 20060101
C08G073/02; C08G 69/26 20060101 C08G069/26; C08G 69/28 20060101
C08G069/28; C08L 77/06 20060101 C08L077/06; C08L 79/08 20060101
C08L079/08; C07C 231/02 20060101 C07C231/02; C07C 233/16 20060101
C07C233/16; C07C 233/34 20060101 C07C233/34 |
Claims
1. A composition comprising a polyamidopolyamine produced by the
reaction of a polybasic acid and primary polyamine, which is
linear, cyclic, branched or cross-linked, said polyamidopolyamine
having a molecular weight of about 500 to about 100,000 and having
one or more repeating pendant amino groups
2. The composition according to claim 1, further comprising one or
more of: (a) a polyamidopolyamine that comprises an imide group;
(b) unreacted polyamine; (c) multiple different
polyamidopolyamines, (d) multiple different polyamidopolyamines
having an imide group, multiple different unreacted polyamines, or
any combination thereof.
3. The composition according to claim 1, wherein said
polyamidopolyamine is of the Formula I, Formula II, Formula III,
Formula IV, or Formula V.
4. The composition according to claim 1, wherein said
polyamidopolyamine is of the (a) Formula A: ##STR00032## wherein:
each polybasic acid is a dimer acid; each primary polyamine is
independently a diamine, a triamine, or a tetraamine or an amine
comprising 5 or more free amino groups; a and a' are independently
1 or 2; b is 0, 1 or 2; and r is a number between 2 to about 10,
including both endpoints of the range; or (b) Formula A':
##STR00033## wherein a is 1, 2, 3, or 4, and said reaction has a
1:1 molar ratio of polyamine to dimer acid; or (c) Formula B:
##STR00034## wherein: each polybasic acid is a trimer acid; each
primary polyamine is independently a diamine, a triamine, or a
tetraamine or an amine comprising 5 or more free amino groups; a,
c, d and e are independently 1 or 2; b is 0, 1 or 2; and r is a
number between 3 to about 10, including both endpoints of the
range; or (d) Formula C: ##STR00035## wherein: each polybasic acid
is a tetrabasic acid; each primary polyamine is independently a
diamine, a triamine, or a tetraamine or an amine comprising 5 or
more free amino groups; a, c, d, and e are independently 1 or 2; b
is 0, 1 or 2; and r is a number between 4 to 10, including both
endpoints of the range.
5. The composition according to claim 1, further comprising (i) an
organic hydroxyl containing diluent; or (ii) water as a diluent; or
(iii) a water-soluble acid to increase the solubility of the
polyamidopolyamine and non-polymeric amidoamine in water
6. (canceled)
7. The composition according to claim 1, which is characterized by
one of more of: (a) low-foaming, non-foaming, or defoaming
properties; (b) antimicrobial or bioresistant properties; (c)
lubricating properties; (d) a cloud point of about 25.degree. C. to
about 82.degree. C., or of about 77.degree. F. to about 180.degree.
F., in water; (e) a pH of about 8 to about 11: (f) water-soluble;
and (g) water dispersible.
8. A method for preparing a composition of claim 1 comprising
condensing: (a) a polyamine comprising a primary amino group, and a
C.sub.3 to C.sub.16 polybasic acid or derivative thereof,
optionally in the presence of an organic hydroxyl-containing
diluent; or (b) a polyamine comprising three primary amino groups,
and a C.sub.3 to C.sub.16 polybasic acid or derivative thereof,
optionally in the presence of an organic hydroxyl-containing
diluent; or (c) two polyamines comprising three amino groups and a
C.sub.3 to C.sub.16 polybasic acid or derivative thereof; or (d) a
polyamine comprising three amino groups and two C.sub.3 to C.sub.16
polybasic acids or derivative thereof; or (e) a polyamine
comprising three amino groups, a polyamine comprising two amino
groups, and a C.sub.3 to C.sub.16 polybasic acid or derivative
thereof.
9. A method for preparing a composition comprising a
polyamidopolyamine, wherein said method comprises: (a) reacting a
polybasic acid with a polyamine and an optional hydroxyl-containing
solvent to produce a first polyamidopolyamine as a reaction
product; (b) reacting the product (a) with the same or different a
polybasic acid and an optional hydroxyl-containing solvent to
produce another polyamidopolyamine as a subsequent reaction
product; (c) performing additional sequential condensation
reactions by reacting the polyamidopolyamine reaction product of
each preceding condensation reaction with the same or different
polybasic acid and an optional hydroxyl-containing solvent, and (d)
terminating the reaction sequence when the composition demonstrates
a desired characteristic selected from anti-foaming, defoaming,
lubricity, bioresistance, antimicrobial activity or any combination
thereof.
10. The method according to claim 9, further comprising at least
one of (e) further terminating additional free amino groups to
amide acids or salts with cyclic anhydride to cap amino groups at a
temperature below the condensation reaction temperature; (f) adding
an organic hydroxyl-containing diluent or solvent at the initiation
of the reaction; or (g) adding water or an organic
hydroxyl-containing diluent or solvent at the end of the reaction
to adjust viscosity of the composition.
11. The method according to claim 8, wherein the resulting
composition comprises a polyamidopolyamine, which is a linear,
cyclic, branched or cross-linked amide comprising multiple primary
amine groups.
12. The method according to claim 8, wherein said polybasic acid
comprises two C(O)OH groups or derivatives thereof.
13. The method according to claim 9, wherein said polyamines are
different.
14. The method according to claim 9, further comprising: (a) having
a mole ratio of polybasic acid to polyamine is equal to or greater
than about 1: (1.times.), wherein X is the number of C(O)OH groups
in the polybasic acid; or (b) having a mole ratio of the polybasic
acid to the polyamine is about is about 1:1, with an optional
organic hydroxyl-containing solvent.
15. The method according to claim 8, wherein said polyamine is: (a)
triaminononane or 4-aminomethyl-1,8-octanediamine; (b) the formula:
##STR00036## wherein: R.sup.1, R.sup.3 and R.sup.5 are
independently H, methyl, ethyl, propyl or butyl; R.sup.2, R.sup.4
and R.sup.6 are independently methyl, ethyl, propyl, or butyl; and
a, b and c are additively a number between 0 to about 90, including
both endpoints of the range; or (c) of the formula: ##STR00037##
wherein s, t and u are additively a number between 3 to about 90,
including both endpoints of the range; or (d) the formula:
##STR00038## wherein: R.sup.1, is H, methyl, ethyl, propyl or
butyl; R.sup.2, R.sup.3, and R.sup.4 are, independently, methyl,
ethyl, propyl, or butyl; and e and f are additively a number
between 0 to about 90, including both endpoints of the range; or
(e) the formula:
NH.sub.2CH(CH.sub.3)CH.sub.2--(O--CH.sub.2CF.sub.2).sub.g--(O--CH.sub.2CH-
(CH.sub.3)).sub.h--(O--CH.sub.2CH(CH.sub.3))--NH.sub.2 wherein g
and h are additively a number between 0 to about 90, including both
endpoints of the range; or (f) the formula: ##STR00039## wherein:
R.sup.1, R.sup.3, R.sup.5 and R.sup.7 are independently H, methyl,
ethyl, propyl or butyl; R.sup.2, R.sup.4, R.sup.6, and R.sup.8 are
independently is methyl, ethyl, propyl, or butyl; and w, j, k and m
are additively a number between 0 to about 90, including both
endpoints of the range; or (g) the formula: ##STR00040## wherein h,
n, o and p are additively a number between 4 to about 90, including
both endpoints of the range; or (h) the formula: ##STR00041##
wherein: R.sup.1, R.sup.3, and R.sup.5 are independently H, methyl,
ethyl, propyl or butyl; R.sup.2, R.sup.4, and R.sup.6 are
independently methyl, ethyl, propyl, or butyl; and a', b' and c'
are additively a number between 0 to 90, including both endpoints
of the range; or (i) the formula: ##STR00042## wherein e', f' and
g' are additively a number between 3 to 90.
16. A composition comprising a non-polymeric amidoamine, which is a
linear or branched amide containing a primary amine group, said
non-polymeric amidoamine having a molecular weight of about 290 to
about 5000.
17. The composition according to claim 16, wherein said composition
is produced by the reaction of a monobasic acid and a primary
amine.
18. The composition according to claim 16, further comprising an
amide comprising a diamide, a triamide or a tetraamide, or a
mixture thereof.
19. The composition according to claim 1, further comprising a
non-polymeric amidoamine, which is a linear or branched amide
containing a primary amine group, said non-polymeric amidoamine
having a molecular weight of about 290 to about 5000.
20. The composition according to claim 19, wherein said
non-polymeric amidoamine is: (a) of the Formula F: ##STR00043##
wherein x, y, and z are, are additively a number between 3 to about
90, including both endpoints of the range; and R.sup.1 is C.sub.1
to C.sub.11 alkyl or C.sub.1 to C.sub.11 substituted alkyl; or (b)
of the Formula G: ##STR00044## wherein x, y, and z are, additively
a number between 3 to about 90, including both endpoints of the
range; and R.sup.1, and R.sup.2 are, independently, C.sub.1 to
C.sub.11 alkyl or C.sub.1 to C.sub.11 substituted alkyl.
21. A composition of claim 1, produced by a condensation reaction
wherein the reactants comprise an acid and a polyamine, wherein the
acid is a polybasic acid, a monobasic acid, or both a polybasic
acid and a monobasic acid, in the optional presence of an organic
hydroxyl-containing diluent.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of the priority of US
Provisional Patent Application No. 62/147,840, filed Apr. 15, 2015,
which application is incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] Various compositions for industrial use require specific
characteristics for use, e.g., paint requires a certain amount of
rheology control and coating ability, as well as a specified amount
of bioresistance. Analogously metal working fluids require
lubricity, load carrying ability, the control of foaming during use
and microorganism growth control. Still other compositions abound
that have specific and varied requires for anti-foaming or
defoaming during use, and also bioresistance, etc. Generally to
provide a composition with multiple specific characteristics for
successful use a number of additives must be combined in
proportions appropriate to provide the characteristics. The
development of such compositions is thus expensive and
time-consuming, with the developer attempting to identify and
combine cooperative components in the correct amounts and
concentrations to achieve a useful composition that has
characteristics is as close to a specified list as possible.
[0003] Formulation of such compositions, requiring multiple
different components to achieve different end goals when in
combination is both challenging and costly. There is a need in all
of the industrial arts for compositions which may be readily
prepared using a minimal number of components to lessen the
environmental impact, and yet retaining or having desired multiple
characteristics of lubricity, low foaming, bioresistance, etc.
SUMMARY OF THE INVENTION
[0004] In one aspect, a composition is provided that comprises a
polyamidopolyamine, which is a linear, cyclic, branched or
cross-linked amide comprising a primary amine group. In still other
embodiments, the polyamidopolyamines comprises one or more primary
amine groups. In one embodiment, the polyamidopolyamine has a
molecular weight of about 500 to about 100,000. In one aspect, the
polyamidopolyamine is produced by the reaction of a polybasic acid
and primary polyamine containing at least three primary amino
groups in the optional presence of a hydroxyl-containing organic
diluent. In another aspect, the polyamidopolyamine is produced by
sequential condensation reactions of a polybasic acid and polyamine
in the optional presence of a hydroxyl-containing organic diluent.
In still another aspect, the polyamidopolyamine is produced by the
reaction of a polybasic acid, a monobasic acid, and primary
polyamine. These polyamidopolyamines or compositions containing
them surprisingly provide to a resulting composition multiple
properties selected from antimicrobial properties, bioresistant
properties, defoaming properties, anti-foaming properties,
lubricating and load-carrying properties and any combinations of
two or more of those properties.
[0005] In another aspect, a method for preparing a composition
comprising a polyamidopolyamine having a molecular weight of about
500 to about 100,000 and comprising a primary amino group is
provided. The method comprises condensing (i) a polyamine
comprising a primary amino group (e.g., one or more) and (ii) a
C.sub.3 to C.sub.16 polybasic acid or derivative thereof,
optionally in the presence of an organic hydroxyl-containing
diluent as solvent. In one embodiment, the condensation reaction
occurs in the presence of excess polyamine when the polyamine is
also used as solvent.
[0006] In still another aspect, a method for providing such
compositions containing polyamidopolyamines of molecular weights
greater than about 100,000 comprises repetitive steps. A first step
includes reacting a polybasic acid with a polyamine and an optional
hydroxyl-containing solvent to produce a first polyamidopolyamine
as a reaction product; reacting the reaction product with the same
or different a polybasic acid and an optional hydroxyl-containing
solvent to produce another polyamidopolyamine as a subsequent
reaction product. Additional sequential condensation reactions are
performed by reacting the polyamidopolyamine reaction product of
each preceding condensation reaction with the same or different
polybasic acid and an optional hydroxyl-containing solvent. The
reaction sequence may be terminated by addition of a monobasic acid
when the composition demonstrates a desired characteristic selected
from anti-foaming, defoaming, lubricity, load-carrying,
bioresistance, antimicrobial activity or any combination
thereof.
[0007] In one aspect, a composition is provided that comprises a
non-polymeric amidoamine, which is a linear or branched amide
comprising a primary amine group. In still other embodiments, the
non-polymeric amidoamine comprises two or more primary amine
groups. In one embodiment, the non-polymeric amidoamine has a
molecular weight of about 290 to about 5000.
[0008] In another aspect, the composition that comprises a
non-polymeric amidoamine also comprises a non-polymeric amide,
which is a linear or branched amide comprising no primary amine
group. In one embodiment, the non-polymeric amide has a molecular
weight of about 290 to about 5000.
[0009] In another aspect, the compositions comprising the
non-polymeric amidoamines described above are produced by the
reaction of a monobasic acid and a primary amine comprising a
primary amino group in the optional presence of a
hydroxyl-containing organic diluent. These non-polymeric
amidoamines or compositions containing them are characterized by
one, or multiple, properties selected from antimicrobial
properties, bioresistant properties, defoaming properties,
anti-foaming properties and/or lubricating and load-carrying
properties.
[0010] In still another aspect, compositions as described herein
comprising a polyamidopolyamine and a non-polymeric amidoamine are
produced by a condensation reaction comprising a polybasic acid, a
monobasic acid with a primary amine or polyamine, or multiples of
each component in the optional presence of a hydroxyl-containing
organic diluent.
[0011] Still other aspects include various methods of using the
composition and making them. These other aspects and advantages of
the invention will be readily apparent from the following detailed
description of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] FIG. 1 is a graph showing bacterial count over time measured
in colony forming units (cfu)/ml of deionized water containing a
mixed bacterial culture treated with a composition comprising
polyamidopolyamine (3533-171) described herein and in Example 1
below. FIG. 1 also indicates that the polyamidopolyamine-containing
composition 3533-171 shows marked and quick bacterial growth
inhibition rate, i.e., anti-microbial activity, at the
concentration, i.e., 0.75% by weight in deionized water. All
dilutions are in deionized water (DI).
[0013] FIG. 2 is a graph showing bacterial count over time measured
in cfu/ml of deionized water containing a mixed bacterial culture
treated with a polyamidopolyamine-containing composition 3587-17
described herein and in Example 2 below. FIG. 2 indicates that the
polyamidopolyamine-containing composition 3587-17 shows marked and
quick bacterial growth inhibition rate, i.e., anti-microbial
activity, at the concentration, i.e., 0.75% by weight in deionized
water. All dilutions are in deionized water (DI).
[0014] FIG. 3 is a graph showing bacterial count over time measured
in cfu/ml of deionized water containing a mixed bacterial culture
treated with a polyamidopolyamine-containing composition 3581-5
described herein and in Example 3 below. FIG. 3 indicates that the
polyamidopolyamine-containing composition (3581-5) shows marked and
quick bacterial growth inhibition rate, i.e., anti-microbial
activity, at the concentration, i.e., 0.75% by weight in deionized
water. All dilutions are in deionized water (DI).
[0015] FIG. 4 is a graph showing the comparative lubrication
ability of the polyamidopolyamine-containing compositions 3533-171,
3587-17 and 3581-5 of Examples 1-3 vs. that of the HOCUT.RTM. 767
commercial synthetic metal removal fluid (Houghton International
Inc.) as described in Example 4 below.
[0016] FIG. 5 is a cooling curve showing the comparison of
polyamidopolyamine reaction products with water and Aqua Quench 260
(AQ260). AQ 260 is a commercial product supplied by Houghton
International to slow down the quenching effect of water and its
curve is shown as a broken line (i.e., large dashes). The curve for
water is a solid line. The experimental polyamidopolyamine reaction
product 3587-193 has a curve formed by small dashes. Product
3587-193 is a polyamidopolyamine, the reaction of Huntsman
Jeffamine T403 (10 moles) with adipic acid (9 moles). The reaction
is performed in approximately 44% dipropylene glycol (DPG). The DPG
remains in the reaction mixture. Cloud point (1%) approximately
81.degree. F. The cooling curve measurements were made using the
IVF quenchometer.
[0017] FIG. 6 shows the curves produced by the method described in
FIG. 5 using product 3533-85-2 in the IVF method. 3533-85-2 is the
product of a condensation reaction of Huntsman Jeffamine T 403 (2
moles) with adipic acid (1 mole). Cloud point (0.75%),
approximately 86.degree. F.; weight average molecular weight,
2,240; determined by GPC. The curves are water (solid line), 260-1
(a broken line) and 3533-85-2 (line of small dashes).
[0018] FIG. 7 shows the curves produced by the method described in
FIG. 5 using product 3587-17-2 in the IVF method. 3587-17-2 is the
product of a condensation reaction of Huntsman Jeffamine T 403 (2
moles) with azelaic acid. The reaction is run in 45%
triethanolamine. The DPG and TEA are also used as solvents for the
reactions and also form the intermediate ester which is then
converted to amide, releasing that solvent. The triethanolamine
remains in the reaction mixture. Cloud point 0.75%, approximately
75.degree. F. The curves are water (solid line), 260-1 (a broken
line) and 3587-17-2 (line of small dashes).
[0019] FIG. 8 shows the curves produced by the method described in
FIG. 5 using product 3587-203-2 in the IVF method. 3587-203-2 is a
product of the condensation reaction of Huntsman Jeffamine T 403 (5
moles) with adipic acid (4 moles). Cloud point was cloudy at
ambient, about 70.degree. F., but becomes clear on cooling. The
average molecular weight by GPC is 6,240 daltons. The curves are
water (solid line), 260-1 (a broken line) and 3587-203-2 (line of
small dashes).
[0020] FIG. 9 shows the curves produced by the method described in
FIG. 5 using product 3533-171-1 in the IVF method. 3533-171-1 is
the product of the condensation reaction of Huntsman Jeffamine T
403 (2 moles) with adipic acid (1 mole) with about 12% water added
when the reaction is cooled below 90.degree. C. The water acts as a
solvent to reduce the viscosity of the neat product to make it more
flowable. Cloud point, about 88.degree. F. The curves are water
(solid line), 260-1 (a broken line) and 3533-171-1 (line of small
dashes).
DETAILED DESCRIPTION OF THE INVENTION
[0021] Described herein are compositions containing
polyamidopolyamines and/or non-polymeric amidoamines, which
compositions impart multiple desirable characteristics to the
resulting industrial composition, including one or more of
lubricity, bioresistance, anti-foaming, no-foaming, and/or
antimicrobial properties.
[0022] Various components or characteristics of the compositions
containing the polyamidopolyamines and/or non-polymeric amidoamines
are described as follows.
[0023] The term "alkyl" is used herein to refer to both straight-
and branched-chain saturated aliphatic hydrocarbon groups. In one
embodiment, an alkyl group has 1 to about 30 carbon atoms (i.e.,
C.sub.1, C.sub.2, C.sub.3, C.sub.4, C.sub.5 C.sub.6, C.sub.7,
C.sub.8, C.sub.9, or C.sub.10, C.sub.11, C.sub.12, C.sub.13,
C.sub.14, C.sub.15, C.sub.16, C.sub.17, C.sub.18, C.sub.19,
C.sub.20, C.sub.21, C.sub.22, C.sub.23, C.sub.24, C.sub.25,
C.sub.26, C.sub.27, C.sub.28, C.sub.29, or C.sub.30). In a further
embodiment, an alkyl group has 1 to about 10 carbon atoms (i.e.,
C.sub.1, C.sub.2, C.sub.3, C.sub.4, C.sub.5 C.sub.6, C.sub.7,
C.sub.8, C.sub.9, or C.sub.10). In another embodiment, an alkyl
group has 4 to about 10 carbon atoms (i.e., C.sub.4, C.sub.5,
C.sub.6, C.sub.7, C.sub.8, C.sub.9, or C.sub.10). In a further
embodiment, an alkyl group has 5 to about 10 carbon atoms (i.e.,
C.sub.5, C.sub.6, C.sub.7, C.sub.8, C.sub.9, or C.sub.10).
[0024] The term "cycloalkyl" is used herein to refer to cyclic,
saturated aliphatic hydrocarbon groups. In one embodiment, a
cycloalkyl group has 5 to about 10 carbon atoms (i.e., C.sub.5,
C.sub.6, C.sub.7, C.sub.8, C.sub.9, or C.sub.10).
[0025] The term "alkenyl" is used herein to refer to both straight-
and branched-chain alkyl groups having one or more carbon-carbon
double bonds. In one embodiment, an alkenyl group has 2 to about 30
carbon atoms (i.e., C.sub.2, C.sub.3, C.sub.4, C.sub.5 C.sub.6,
C.sub.7, C.sub.8, C.sub.9, or C.sub.10, C.sub.11, C.sub.12,
C.sub.13, C.sub.14, C.sub.15, C.sub.16, C.sub.17, C.sub.18,
C.sub.19, C.sub.20, C.sub.21, C.sub.22, C.sub.23, C.sub.24,
C.sub.25, C.sub.26, C.sub.27, C.sub.28, C.sub.29, or C.sub.30). In
a further embodiment, an alkenyl group has 2 to about 10 carbon
atoms (i.e., C.sub.2, C.sub.3, C.sub.4, C.sub.5 C.sub.6, C.sub.7,
C.sub.8, C.sub.9, or C.sub.10). In another embodiment, an alkenyl
group has 4 to about 10 carbon atoms (i.e., C.sub.4, C.sub.5,
C.sub.6, C.sub.7, C.sub.8, C.sub.9, or C.sub.10). In a further
embodiment, an alkenyl group has 5 to about 10 carbon atoms (i.e.,
C.sub.5, C.sub.6, C.sub.7, C.sub.8, C.sub.9, or C.sub.10). In
another embodiment, an alkenyl group has 1 or 2 carbon-carbon
double bonds.
[0026] The term "alkynyl" is used herein to refer to both straight-
and branched-chain alkyl groups having one or more carbon-carbon
triple bonds. In one embodiment, an alkynyl group has 2 to about 30
carbon atoms (i.e., C.sub.2, C.sub.3, C.sub.4, C.sub.5 C.sub.6,
C.sub.7, C.sub.8, C.sub.9, or C.sub.10, C.sub.11, C.sub.12,
C.sub.13, C.sub.14, C.sub.15, C.sub.16, C.sub.17, C.sub.18,
C.sub.19, C.sub.20, C.sub.21, C.sub.22, C.sub.23, C.sub.24,
C.sub.25, C.sub.26, C.sub.27, C.sub.28, C.sub.29, or C.sub.30). In
a further embodiment, an alkynyl group has 2 to about 10 carbon
atoms (i.e., C.sub.2, C.sub.3, C.sub.4, C.sub.5 C.sub.6, C.sub.7,
C.sub.8, C.sub.9, or C.sub.10). In another embodiment, an alkynyl
group has 4 to about 10 carbon atoms (i.e., C.sub.4, C.sub.5,
C.sub.6, C.sub.7, C.sub.8, C.sub.9, or C.sub.10). In a further
embodiment, an alkynyl group has 5 to about 10 carbon atoms (i.e.,
C.sub.5, C.sub.6, C.sub.7, C.sub.8, C.sub.9, or C.sub.10). In
another embodiment, an alkynyl group contains 1 or 2 carbon-carbon
triple bonds.
[0027] The term "aryl" as used herein refers to an aromatic,
carbocyclic system, e.g., of about 6 to 14 carbon atoms, which can
include a single ring or multiple aromatic rings fused or linked
together where at least one part of the fused or linked rings forms
the conjugated aromatic system. The aryl groups include, but are
not limited to, phenyl, naphthyl, biphenyl, anthryl,
tetrahydronaphthyl, phenanthryl, indene, benzonaphthyl, and
fluorenyl.
[0028] The term "heterocycle" or "heterocyclic" as used herein can
be used interchangeably to refer to a stable, saturated or
partially unsaturated 3- to 9-membered monocyclic or multicyclic
heterocyclic ring. The heterocyclic ring has in its backbone carbon
atoms and one or more heteroatoms including nitrogen, oxygen, and
sulfur atoms. In one embodiment, the heterocyclic ring has 1 to
about 4 heteroatoms in the backbone of the ring. When the
heterocyclic ring contains nitrogen or sulfur atoms in the backbone
of the ring, the nitrogen or sulfur atoms can be oxidized. The term
"heterocycle" or "heterocyclic" also refers to multicyclic rings in
which a heterocyclic ring is fused to an aryl ring of about 6 to
about 14 carbon atoms. The heterocyclic ring can be attached to the
aryl ring through a heteroatom or carbon atom provided the
resultant heterocyclic ring structure is chemically stable. In one
embodiment, the heterocyclic ring includes multicyclic systems
having 1 to 5 rings.
[0029] A variety of heterocyclic groups are known in the art and
include, without limitation, oxygen-containing rings,
nitrogen-containing rings, sulfur-containing rings, mixed
heteroatom-containing rings, fused heteroatom containing rings, and
combinations thereof. Examples of heterocyclic groups include,
without limitation, tetrahydrofuranyl, piperidinyl,
2-oxopiperidinyl, pyrrolidinyl, morpholinyl, thiamorpholinyl,
thiamorpholinyl sulfoxide, pyranyl, pyronyl, dioxinyl, piperazinyl,
dithiolyl, oxathiolyl, dioxazolyl, oxathiazolyl, oxazinyl,
oxathiazinyl, benzopyranyl, benzoxazinyl and xanthenyl.
[0030] The term "heteroaryl" as used herein refers to a stable,
aromatic 5- to 14-membered monocyclic or multicyclic
heteroatom-containing ring. The heteroaryl ring has in its backbone
carbon atoms and one or more heteroatoms including nitrogen,
oxygen, and sulfur atoms. In one embodiment, the heteroaryl ring
contains 1 to about 4 heteroatoms in the backbone of the ring. When
the heteroaryl ring contains nitrogen or sulfur atoms in the
backbone of the ring, the nitrogen or sulfur atoms can be oxidized.
The term "heteroaryl" also refers to multicyclic rings in which a
heteroaryl ring is fused to an aryl ring. The heteroaryl ring can
be attached to the aryl ring through a heteroatom or carbon atom
provided the resultant heterocyclic ring structure is chemically
stable. In one embodiment, the heteroaryl ring includes multicyclic
systems having 1 to 5 rings.
[0031] A variety of heteroaryl groups are known in the art and
include, without limitation, oxygen-containing rings,
nitrogen-containing rings, sulfur-containing rings, mixed
heteroatom-containing rings, fused heteroatom containing rings, and
combinations thereof. Examples of heteroaryl groups include,
without limitation, furyl, pyrrolyl, pyrazolyl, imidazolyl,
triazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl,
azepinyl, thienyl, dithiolyl, oxathiolyl, oxazolyl, thiazolyl,
oxadiazolyl, oxatriazolyl, oxepinyl, thiepinyl, diazepinyl,
benzofuranyl, thionapthene, indolyl, benzazolyl, purindinyl,
pyranopyrrolyl, isoindazolyl, indoxazinyl, benzoxazolyl,
quinolinyl, isoquinolinyl, benzodiazonyl, napthylridinyl,
benzothienyl, pyridopyridinyl, acridinyl, carbazolyl, and purinyl
rings.
[0032] The term "thioaryl" as used herein refers to the S(aryl)
group, where the point of attachment is through the sulfur-atom and
the aryl group can be substituted as noted herein. The term
"alkoxy" as used herein refers to the O(alkyl) group, where the
point of attachment is through the oxygen-atom and the alkyl group
can be substituted as noted herein. The term "thioalkyl" as used
herein refers to the S(alkyl) group, where the point of attachment
is through the sulfur-atom and the alkyl group can be substituted
as noted herein.
[0033] The term "hydroxyalkyl" refers to -(alkyl)OH, where the
point of attachment is group through the alkyl group and the alkyl
groups is defined above.
[0034] The term "alkylcarbonyl" or "arylcarbonyl" as used herein
refers to the group
##STR00001##
in which R is an alkyl or aryl and X' refers to the leaving
group(s), as described below. "Leaving group" refers to the group
displaced by the amine in the reactions described herein. This
includes esters, acid halides, lactones, anhydride, cyclic
anhydrides, or linear polyanhydrides, etc. Some examples are:
##STR00002##
[0035] The term "optionally substituted" as used herein refers to
the base group having one or more substituents including, without
limitation, H, halogen, CN, OH, NO.sub.2, amino, alkyl, cycloalkyl,
alkenyl, alkynyl, C.sub.1 to C.sub.3 perfluoroalkyl, C.sub.1 to
C.sub.3 perfluoroalkoxy, aryl, heterocyclic, heteroaryl, alkoxy,
aryloxy, alkylcarbonyl, alkylcarboxy, arylthio, alkylamino, or
--SO.sub.2-(optionally substituted C.sub.1 to C.sub.10 alkyl).
[0036] As referred to herein, the molecular weight of the
polyamidopolyamines and non-polymeric amidoamines are measured
using either the gel permeation column (GPC) method or by NMR and
mass spectrometry, i.e., MALDI-TOF. It is anticipated that the GPC
measurements are likely to be most accurate. "Weight average
molecular weight" as used herein means the average of the molecular
weights of all of the polyamidopolyamines present in a single
condensation reaction. The molecular weight ranges cited herein and
weight average molecular weights are expected to be understood to
be broad enough to cover measurements made by either GPC or mass
spectrometry methods or by other acceptable measurement
technologies.
[0037] The term "molar basis" or "molar ratio" as used herein
refers to the molar concentration of polybasic acid to primary
amine. For example, where the reaction is between a dibasic acid (1
mole) and a polyamine (2 moles) having at least three primary amine
groups, the molar ratio is 1:2. Where a tribasic acid is employed
in the condensation reaction with a polyamine having at least three
primary amine groups, the molar ratio is 1:3. Where a tetrabasic
acid is employed in the condensation reaction with a polyamine
having at least three primary amine groups, the molar ratio is 1:4,
and so on. This ratio can be reduced to 1:1 when the reaction
occurs in the presence of an organic hydroxyl solvent. In some
embodiments, excess polyamine allows the reaction mixtures to be
fluid. The use of organic hydroxyl solvents accomplishes the same
purpose, i.e., reduces viscosity.
[0038] If the reaction employs only monobasic acids ("capping")with
primary amine or polyamine, the term "molar basis" is alternatively
defined as follows: The moles of monobasic acid are equal to the
number of primary amino groups on the polyamine minus at least one
(1). For example, when the number of primary amino groups on the
polyamine is 2, the moles of monobasic acid is 1. When the number
of primary amino groups on the polyamine is 3, the moles of
monobasic acid are either 2 or 1. When the number of primary amino
groups on the polyamine is 4, the moles of monobasic acid are 3, 2
or 1. When the number of primary amino groups on the polyamine is
5, the moles of monobasic acid are 4, 3, 2 or 1, etc. The molar
basis employed in the reaction provides the resulting non-polymeric
amidoamine with at least one free primary amino group. The presence
of the at least one free primary amino group in the non-polymeric
amidoamine provides some degree of antimicrobial activity, which
increases with the number of free primary amino groups. Where there
are no primary amino groups left in the reactant of this reaction
between monobasic acid and primary amine or polyamine, the reactant
or composition containing the reactant does not have anti-microbial
properties, but the other properties, e.g., defoaming and/or
lubricating properties remain.
[0039] The term "polybasic acid", as used in these preparative
methods, is an acid composed of two or more C(O)OH groups or
derivatives thereof. A C(O)OH derivative includes, without
limitation, an ester, anhydride, acid halide, lactone,
polyanhydride, or lactam thereof. Among suitable polybasic acids
for the methods described herein are malonic acid, succinic acid,
glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic
acid, sebacic acid, undecanedioic acid, dodecanedioic acid,
brassylic acid, thapsic acid, phthalic acid, isophthalic acid,
terephthalic acid, hemimellitic acid, trimellitic acid, trimesic
acid, tartartic acid, malic acid, gluconic acid, citric acid,
cysteine, aspartic acid, glutamic acid, mucic acid, or combinations
thereof. Additionally, combinations of two or more of these
polybasic acids are also useful in the preparative methods for the
polyamidopolyamines.
[0040] In one embodiment, the molecular weight (MW) of the selected
polybasic acid is from about 90 to about 314 MW. In another
embodiment, the molecular weight of the selected polybasic acid is
from about 104 to about 272 MW. In still other embodiments, the MW
is 90, 104, 118, 132, 146, 160, 174, 188, 202, 216, 230, 244, 258,
272, 286, 300, 314 or more, including any numbers between and
including any two endpoints of the range selected from this
list.
[0041] The term "monobasic acid", as used herein, is an acid
composed of one C(O)OH group or derivative thereof. Monobasic acids
are useful in the condensation reactions with a primary amine to
produce the non-polymeric amidoamines. Alternatively, monobasic
acids are useful for terminating the dendrimer reaction to create
polyamidopolyamines. In another alternative, the monobasic acids
are useful in condensation reactions with other polybasic acids to
produce compositions comprising polyamidopolyamines and
non-polymeric amidoamines. Suitable monobasic acids for these
purposes include, without limitation, acetic acid, propionic acid,
butyric acid, isobutyric acid, n-valeric acid, trimethylacetic
acid, caproic acid, heptanoic acid, caprylic acid, pelargonic acid,
capric acid, lauric acid, myristic acid, palmetic acid, stearic
acid, decylenic acid, stillingic acid, palmitoleic acid, oleic
acid, ricinoleic acid, petroselinic acid, vaccenic acid, linoleic
acid, linolenic acid, eleostearic acid, punicic acid, licanic acid,
parinaric acid, glycolic acid, lactic acid, methoxyacetic acid,
thioglycoloic acid, phenylacetic acid, glucine, alanine, valine,
leucine, isoleucine, phenylalanine, tyrosine, proline,
hydroxyproline, threonine, cysteine, tryptophane, arginine, lysine,
histidine, gluconic acid, glyceric acid, or combinations thereof.
Additionally, combinations of two or more of these monobasic acids
are also useful in the preparative methods described herein.
[0042] In one embodiment, the molecular weight (MW) of the selected
monobasic acid is from about 46 to about 312 MW. In another
embodiment, the molecular weight of the selected monobasic acid is
from about 74 to about 270 MW. In still other embodiments, the MW
is 46, 60, 74, 88, 102, 116, 130, 144, 158, 172, 186, 200, 214,
228, 242, 256, 270, 284, 298, 312 or more, including any numbers
between and including any two endpoints of the range selected from
this list.
[0043] The term "amino group" as used herein means the formula
--NRR.sup.1, where in R and R' are independently H, or a C.sub.1 or
C.sub.2 alkyl. In some embodiments, the amino groups are primary,
wherein the nitrogen has two reactive hydrogens, e.g., --NH.sub.2.
In other embodiments, the amino groups are secondary, e.g.,
--NHCH.sub.3, wherein the nitrogen has a single reactive hydrogen.
In still other embodiments, the amino groups are tertiary, e.g.,
--N(CH.sub.3)CH.sub.3. Whereever in the formulae and other examples
of polyamidopolyamines, the amino group is shown as NH.sub.2, it
should be understood to include replacement thereof with secondary
or tertiary amino groups by way of alkylation with alkyl halides
(alkylation of amines) up to and including quaternary ammonium
salts. The term "pendant amino group" is meant to refer to amino
groups attached to a polymeric unit, and can repeat at regular
intervals or intermittently along the polymer chain, also including
terminal amino groups. The term "unreacted amino group" means a
primary amino group, NH.sub.2. The amino group can also be
converted to a salt with acid(s).
[0044] The term "polyamine" as used herein refers to any compound
comprising a primary amine (or amino) group. In one embodiment, the
polyamine has one or more amino groups. In another embodiment, the
polyamine has two or more amino groups. In still other embodiments,
the polyamine has at least three primary amino groups. In another
embodiment the polyamine has 5 or more primary amino groups.
[0045] The term "polyamidopolyamine" as used herein refers to a
polymeric compound having at least one primary amino group(s). In
one embodiment, the compound has at least two primary amino groups.
In another embodiment, the compound has at least three primary
amino groups. In still another embodiment, the compound has at
least four primary amino groups. When the polyamidopolyamine is one
of Formula A through E (as described herein), the number of primary
amino groups in the polymer is between 4 and 14. When the
polyamidopolyamine is prepared by the sequential (dendrimer) method
described herein, the polymer may have more than 14 primary amines,
based on the selection of polybasic acid and primary amine employed
to generate the polymer. In certain embodiments, these
polyamidopolyamine compounds are prepared by the condensation of
polyamino compounds with polybasic acids.
[0046] The term "non-polymeric amidoamine" as used herein refers to
a linear or branched non-polymeric compound having at least one
primary amino group(s). In one embodiment, the compound has at
least two primary amino groups. In another embodiment, the compound
has at least three primary amino groups. In still another
embodiment, the compound has at least four primary amino groups.
When the non-polymeric amidoamine is one of Formula F (described
herein), the number of primary amino groups in the amidoamine is 2.
When the non-polymeric amidoamine is one of Formula G, the number
of primary amino groups in the amidoamine is 1. In certain
embodiments, these non-polymeric amidoamine compounds are prepared
by the condensation of polyamino compounds with monobasic
acids.
[0047] The term "imide" as used herein refers to a compound
containing two carbonyl groups bonded to a primary amine, e.g.,
having the formula below, wherein R, R' and R'' are independently
an alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocyclic
group, aryl, heteroaryl, etc :
##STR00003##
[0048] The term "diluent" or "solvent" as used herein is a hydroxyl
containing diluent or solvent. In one embodiment, that diluent is
water. In one embodiment, when the hydroxyl containing diluent used
in the condensation reactions is water, it is added at the end of
the condensation reaction. In other embodiments, water may also be
present or added to the various use compositions or concentrates
containing the compounds described herein, such as quenching
compositions. In another embodiment, the hydroxyl containing
diluent is an organic diluent. In embodiments where the organic
diluent or solvent participates in the condensation reactions, as
described below, it is not removed from the reaction mixture. Among
suitable organic diluents are alcohols, polyols, carbitols,
CELLOSOLVE.TM. Solvents (Dow Chemical), or combinations of these
four types of diluents. In one embodiment, the organic diluent
contains a polyol, such as a glycol. One such exemplary diluent
contains a polyalkylene glycol. In another embodiment, the hydroxyl
containing diluent contains ethylene glycol or diethylene glycol.
In another embodiment the diluent comprises triethanolamine. In
still another embodiment, the diluent contains N,N,N',N'-tetrakis
(2-hydroxypropyl) ethylenediamine (also known at
tetra(2-hydroxypropyl) ethylenediamine). Another diluent component
is glycerin. Still other diluents may be prepared by combinations
of any two or more of the above noted hydroxyl-containing diluents.
One of skill in the art may readily select such diluents from among
the many diluents or solvents available.
[0049] The term "water-soluble" as used herein refers to the
ability of a chemical component to combine with, disperse, or be
emulsified, in water. Desirably, the polyamidopolyamines and/or
non-polymeric amidoamines and compositions containing them as
described herein substantially dissolve in water. More desirably,
the term "water-soluble" refers to a compound or composition that
has 100% dissolution in water.
[0050] By "water-soluble acid" is meant an acid which when added to
the compositions described and used herein enhances the water
solubility of the other components, particularly the
polyamidopolyamine, the amidopolyamines (from monobasic acid),
and/or the non-polymeric amidoamines. In one embodiment, the water
soluble acid is phosphoric acid. In another embodiment, the water
soluble acid is acetic acid or glycolic acid or lactic acid. In
still other embodiments, combinations of these water soluble acids
are used. Other acids which enhance water solubility of the
compositions described herein are intended to be incorporated by
this term.
[0051] The term "antimicrobial" as used herein means a agent,
component or composition that is destructive to, or inhibits the
growth of, microorganisms (bacteria, virus, fungus, etc.) which
come into contact with the antimicrobial agent, component or
composition.
[0052] The term "bioresistance" as used herein means that the
composition, agent or component does not support the growth of
microorganisms on or in a substrate (e.g., a surface or fluid)
treated with or containing the composition, agent or component.
[0053] The term "metal" as used herein refers to any commercial
metal that requires use of a industrial fluid for its treatment or
manufacture, e.g., metal rolling fluids, quenching fluids,
hydraulic fluid, and the like. In one embodiment, the tem refers to
any metal, metal alloy or metal substrate that can be heated to a
high temperature, e.g., up to 1600.degree. C., requiring cooling
(e.g., quenching) in a fluid. In one embodiment, the metal contains
only one metallic element. In another embodiment, the metal
contains more than one metal element, i.e., a metal alloy. For
example, the metal may contain one or more of aluminum, iron,
manganese, copper, silicon, sulfur, phosphorus, chromium, cobalt,
columbium, molybdenum, nickel, titanium, tungsten, vanadium,
zirconium, lead, tin, or zinc, among others. Specific examples of
metals that can be treated with the compositions described herein
include those described in the "Handbook of Hydraulic Fluid
Technology", 2.sup.nd ed., Totten, CRC Press, 2011, which is herein
incorporated by reference. In certain embodiments, specific
examples of metals that can be treated with certain quenching
compositions described herein include those described in "The Heat
Treater's Guide", American Society for Metals, 1982, which is
hereby incorporated by reference. Employing the methods and system
described herein, the resultant metal is not negatively impacted,
i.e., it retains its desired porosity ductility, strength such as
an excellent strength-to-weight ratio, weight, shape, corrosion
resistance mechanical properties, such as good thermal electrical
conductivity, high temperature resistance, hardness, wear
resistance, durability, and dimensional stability, among
others.
[0054] The phrase "in contact with", when utilized to refer to a
surface's interaction with the compositions described herein,
includes any point of contact of the surface with the composition.
Such contact includes, without limitation, application of the
composition to the surface (e.g., metal, polyurethane, or fibrous
surfaces, e.g., cotton or paper, etc.) using conventional
techniques. Such conventional techniques include, without
limitation, coating, spraying, contact rolling, squeegeeing,
dipping, brushing, flooding, or immersion application techniques.
In one embodiment, the surface is contacted with the composition
prior to further manipulation of the surface. In another
embodiment, the surface, e.g., metal, is contacted with the
composition during use of the surface, e.g., metal in the desired
method, e.g., rolling, stamping, etc.
[0055] The term "number" as used throughout this specification and
particularly in reference to molecular weights means a whole number
or any fraction between two other whole numbers, when applicable.
In certain embodiments, a fractional number referring to molecular
weight means molecular weights of isotopes or molecular weight
averages.
[0056] By "additively" as used herein to define substituents of a
formula, is meant that the values of the referenced subscripts,
e.g., x+y+z equal a number between, and including, two specified
endpoints of the range. Each subscript may be the same or a
different number as other subscripts forming the sum, provided that
the sum of all subscripts is between the lowest and highest point
in the range, including the endpoints of the range.
[0057] By "independently" as used herein to define substituents of
a formula, means that each substituent may be any one of a
following list of identified substituents, independent of other
substituents in a group. For example, "R1 and R2 are independently,
alkyl, aryl or alkenyl", means that R1 and R2 may be the same or
different but must be one of alkyl, aryl or alkenyl.
[0058] Various embodiments in the specification are presented using
"comprising" language, which is inclusive of features in addition
to the specifically recited features or steps. Under other
circumstances, a related embodiment is also intended to be
interpreted and described using "consisting of" or "consisting
essentially of" language. The words "consist", "consisting", and
its variants, are to be interpreted to exclude features in addition
to those features specifically recited, or to include only
additional features of minor significance.
[0059] It is to be noted that the term "a" or "an" refers to one or
more. As such, the terms "a" (or "an"), "one or more," and "at
least one" are used interchangeably herein.
[0060] As used herein, the term "about" means a variability of 10%
from the reference given, unless otherwise specified.
[0061] Unless defined otherwise in this specification, technical
and scientific terms used herein have the same meaning as commonly
understood by one of ordinary skill in the art to which this
invention belongs and by reference to published texts, which
provide one skilled in the art with a general guide to many of the
terms used in the present application.
[0062] The Compositions
[0063] The compositions described herein contain one or more of the
following components, or admixtures of various of these components.
In one embodiment, the compositions described herein contain a
polyamidopolyamine, which is a linear, cyclic, branched or
crosslinked amide comprising a primary amino group. In certain
embodiments the polyamidopolyamines comprises one or more, two or
more, three or more or 14 or more amino groups, as described
throughout this specification. In one embodiment, the compositions
of polyamidopolyamine or mixtures thereof are produced by the
reaction of a polybasic acid and polyamine in the presence of an
optional organic diluent as described below. In certain other
embodiments, the method of making the polyamidopolyamine and
mixtures thereof involves repeated cycles of condensation reactions
as described in more detail below. In still other embodiments, the
method of making the polyamidopolyamine or a composition comprising
it involves a condensation reaction employing at least one
polybasic acid and at least one polyamine.
[0064] In additional embodiments, the compositions described herein
contain a non-polymeric amidoamine, which is a linear or branched
amide comprising a primary amino group. In certain embodiments the
non-polymeric amidoamine comprises one or more, two or more, three
or more amino groups, as described throughout this specification.
In one embodiment, the compositions of non-polymeric amidoamine or
non-polymeric amide or mixtures thereof are produced by the
reaction of a monobasic acid and primary amine in the presence of
an optional organic diluent as described below. In still other
embodiments, the method of making a composition comprising a
non-polymeric amidoamine and a polyamidopolyamine involves a
condensation reaction employing at least one polybasic acid, at
least one monobasic acid and at least one polyamine or primary
amine.
[0065] The composition, in still another embodiment, contains a
mixture of multiple polyamidopolyamines and/or non-polymeric
amidoamines of different formulae. In certain embodiments, the
composition may also contain polyamidoamines and/or
polyamidopolyamides or non-polymeric amides in admixture with these
polyamidopolyamines and/or non-polymeric amidoamines. In yet a
further embodiment, the composition may contain a
polyamidopolyamine that further comprises an imide group. Still
other embodiments of the composition contain a mixture of any
number of the polyamidopolyamines, with or without imide groups,
and with unreacted polyamine. Still other embodiments of the
composition contain a mixture of any number of the non-polymeric
amidoamines, and/or non-polymeric amides, and with unreacted
polyamine. In still other embodiments, the composition may contain
multiple different non-polymeric amidoamines, multiple different
non-polymeric amides, multiple different unreacted primary amines,
multiple different monobasic acids, or any combination thereof
[0066] These compositions as described herein have a variety of
uses. Depending upon its complete formulation, the composition
containing the polyamidopolyamine and/or non-polymeric amidoamine
has antimicrobial properties. In another embodiment the composition
containing the polyamidopolyamine and/or non-polymeric amidoamine
has bioresistant properties. In another embodiment the composition
containing the polyamidopolyamine and/or non-polymeric amidoamine
has low-foaming, defoaming or anti-foaming properties. In another
embodiment the composition containing the polyamidopolyamine and/or
non-polymeric amidoamine has lubricating and/or load carrying
properties. In still other embodiments, the same composition has
bioresistant and defoaming properties. In yet other embodiments,
the same composition has bioresistant and lubricant properties. In
a further embodiment, the same composition has bioresistant,
lubricant and defoaming or anti-foaming properties. In another
embodiment, the same composition has antimicrobial properties. In
still other embodiments, the same composition has antimicrobial and
defoaming properties. In yet other embodiments, the same
composition has antimicrobial and lubricant properties. In a
further embodiment, the same composition has bioresistant,
lubricant, defoaming, deaeration, or anti-foaming properties.
[0067] In one embodiment, the composition is provided as a
concentrate. In another embodiment, the composition comprises water
or any organic diluent. In another embodiment, the composition
comprises an organic hydroxyl-containing diluent. These
compositions can be provided as additives containing the described
polyamidopolyamines for a variety of industrial fluids and uses.
Alternatively, the compositions are themselves industrial fluids
based upon the inclusion of other components. For example, the
compositions, depending upon the other components can be
lubricants, metal working fluids, metal cleaning fluids, other
industrial cleaning fluids, metal drawing fluids, metal stamping
fluids, metal rolling fluids, hydraulic fluids, metal quenching
fluids, coatings for protecting surfaces, such as polyurethane
surfaces, fibers, paper, paints, fluids for use in paper making,
fluids to decrease or eliminate biofilms, and others, in which the
polyamidopolyamines are present in amounts sufficient to add one or
more desired characteristics to the final composition. In other
embodiments, the compositions are process fluids that are dilutable
in water. See also, the uses described in detail in the Use section
below.
[0068] The Polyamidopolyamines and/or Non-Polymeric Amidoamines and
Methods for Preparing Them
[0069] In one embodiment, a polyamidopolyamine present in a
composition of this invention as described herein has the following
Formula A, in a 2:1 molar ratio of polyamine to dimer acid:
##STR00004##
[0070] According to this formula, each polybasic acid is a dimer
acid. Each polyamine is independently a primary amine, such as a
diamine, a triamine, or a tetraamine or an amine comprising 3 or
more free amino groups. The two subscripts a and a' are
independently 1 or 2; and the subscript b is 0, 1 or 2. The
subscript r represents a number between 2 to about 10, including
both endpoints of the range. The value of r can thus be 2, 3, 4, 5,
6, 7, 8, 9 or 10 including either of the included endpoints of the
range.
[0071] In another embodiment, for a 1:1 molar ratio of polyamine to
dimer acid, a compound of Formula A' exists along with a compound
of Formula A. Formula A' is:
##STR00005##
In one embodiment of this formula, (a) is a number from 1 to 4. For
example, where the polyamine has 3 amino groups, a=3-2=1. Where the
polyamine has 4 amino groups, a=4-2=2. Where the polyamine has 6
amino groups, a=6-2=4, and so on.
[0072] In another embodiment, a polyamidopolyamine present in a
composition of this invention as described herein has the following
Formula B,
##STR00006##
[0073] According to this formula, each polybasic acid is a trimer
acid. Each polyamine is independently a primary amine, such as a
diamine, a triamine, or a tetraamine or an amine comprising 5 or
more free amino groups. The four subscripts a, c, d and e are each
independently 1 or 2; and the subscript b is 0, 1 or 2. The
subscript r represents a molar percentage of different polyamines
and different polybasic acids, e.g., 75% of polyamine A plus 25% of
polyamine B with 50% polybasic acid C and 50% polybasic acid of D.
The r is thus a number between 3 to about 10, including both
endpoints of the range. The value of r can thus be at least 3, 4,
5, 6, 7, 8, 9, or 10 including the included endpoints of the
range.
[0074] In another embodiment, a polyamidopolyamine present in a
composition of this invention as described herein has the following
Formula C:
##STR00007##
[0075] According to this formula, each polybasic acid is a
tetrabasic acid. Each polyamine is independently a primary amine,
such as a diamine, a triamine, or a tetraamine or an amine
comprising 5 or more free amino groups. The four subscripts a, c,
d, and e are independently a number 1 or 2; and the subscript b is
a number 0, 1 or 2. The subscript r represents a number between 4
and about 10 (e.g., at least 4, 5, 6, 7, 8, 9 or 10, including both
endpoints of the range).
[0076] In another embodiment, a polyamidopolyamine, which contains
at least one imide group is present in a composition of this
invention. See for example Formula E, described in detail at
paragraph 00122 herein.
[0077] In a more specific embodiment, the polyamidopolyamine of the
composition has the following Formula D shown below.
##STR00008##
[0078] Compounds according to this formula are those in which
R.sup.1, R.sup.2, R.sup.3, R.sup.5, R.sup.6, R.sup.7, R.sup.8,
R.sup.9 and R.sup.10 are independently, H, methyl, ethyl, propyl or
butyl and R.sup.4, R.sup.4', and R.sup.4'' are independently
methyl, ethyl, propyl or butyl. The subscripts x, y, z, and x', y',
z', and x'', y'', and z'' are all defined additively, that is,
x+y+z equals a number from 3 to about 90; x'+y'+z' equals a number
from about 3 to about 90; and x''+y''+z'' equals a number from 3 to
about 90. This additive subscript value x, y, and z, or x', y' and
z', or x'', y'' and z'' includes both endpoints of the range and is
selected from 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17,
18, 19 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34,
35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51,
52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68,
69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85,
86, 87, 88, 89, and 90.
[0079] The formula subscript, n, is a number between 1 to 14, e.g.,
1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, and 14 including the
endpoints of the range. The formula subscript, m, represents a
number selected independently of the value of n, and is also a
whole number between 1 to 14, including e.g., 1, 2, 3, 4, 5, 6, 7,
8, 9, 10, 11, 12, 13, and 14. The formula subscript r represents a
number between 2 to about10, including both endpoints of the range.
The value of r can thus be at least 2, 3, 4, 5, 6, 7, 8, 9, or 10
and including the endpoints of the range.
[0080] In one embodiment of a polyamidopolyamine of Formula D,
R.sup.1, R.sup.2, R.sup.3, R.sup.5, R.sup.6, R.sup.7, R.sup.8,
R.sup.9 and R.sup.10 are each methyl; R.sup.4 is ethyl; and n and m
are each 4. The additive formula x+y+z is about 5; x'+y'+z' is
about 5; and x''+y''+z'' is about 5. The compound formed when r is
2 has four primary amine groups. The compound formed when r is 3
has 5 primary amine groups. The compound formed when r is 4 has six
primary amine groups. The compound formed when r is 5 has 7 primary
amino groups.
[0081] Still other polyamidopolyamines described herein are shown
below and labeled as Formula I through V. In one embodiment, the
polyamidopolyamine is of the Formula I shown below. The subscripts
x, y, z, and x', y', z', and a, b, and c are all defined
additively, that is, x+y+z equals a number from 3 to about 90 (see
para 0083); x'+y'+z' equals a number from about 3 to about 90; and
a+b+c equals a number from 3 to about 90. In another embodiment,
the polyamidopolyamine is of the Formula II shown below, wherein x,
y, z, x', y', and z' are defined additively, that is, x +y +z
equals a number from 3 to about 90 (see para 0083); and x'+y'+z'
equals a number from about 3 to about 90 (see para 0083). In
another embodiment, the polyamidopolyamine is of the Formula III
shown below, wherein x, y, z, and x', y', z', and a, b, and c are
additively 3 to about 90 (see para. 0083). In another embodiment,
the polyamidopolyamine is of the Formula IV shown below, wherein x,
y, z, x', y', z', a, b, and c are additively 3 to about 90, that
is, x+y+z equals a number from 3 to about 90 (see para 0083);
x'+y'+z' equals a number from about 3 to about 90; and a+b+c equals
a number from 3 to about 90 (see para. 0083). In another
embodiment, the polyamidopolyamine is of the Formula V shown below,
wherein x, y, z, x', y', z', a, b, and c are defined the same as
for Formula IV.
##STR00009## ##STR00010##
[0082] In some embodiments, these polyamidopolyamines are suitable
for use in quenching compositions, among other uses.
[0083] In one embodiment, a non-polymeric amidoamine present in a
composition of this invention as described herein has the following
Formula F:
##STR00011##
[0084] According to this Formula F, the subscripts x, y and z are
defined additively, that is the sum of x+y+z equals a number
between 3 to about 90, including both endpoints of the range, and
as described in para. 0083. Also according to this formula, the
monobasic acid is a carboxylic acid; and R.sup.1 is C.sub.1 to
C.sub.11 alkyl or C.sub.1 to C.sub.11 substituted alkyl, as defined
herein. Thus, R.sup.1 can be a C.sub.1, C.sub.2, C.sub.3, C.sub.4,
C.sub.5, C.sub.6, C.sub.7, C.sub.8, C.sub.9, C.sub.10 or C.sub.11
alkyl or substituted alkyl. In one embodiment of a non-polymeric
amidoamine of Formula F, R.sup.1is methyl; and x+y+z equals about 5
or 6. In this embodiment, the molar ratio of monobasic acid to
primary amine is 1:1.
[0085] In another embodiment, a non-polymeric amidoamine present in
a composition of this invention as described herein has the
following Formula G:
##STR00012##
[0086] According to this formula, x, y, and z, additively, equal a
number between 3 to about 90, including both endpoints of the range
(see para. 0083). According to this formula, R.sup.1 and R.sup.2
are, independently, C.sub.1 to C.sub.11 alkyl or C.sub.1 to
C.sub.11 substituted alkyl. Thus, R.sup.1 or R.sup.2 can
individually be a C.sub.1, C.sub.2, C.sub.3, C.sub.4, C.sub.5,
C.sub.6, C.sub.7, C.sub.8, C.sub.9, C.sub.10 or C.sub.11 alkyl or
substituted alkyl. According to this formula, the molar ratio of
acid to triamine is 2:1.
[0087] Still other polyamidopolyamines and/or non-polymeric
amidoamines and/or compositions comprising one or both such
compounds as described herein may be defined by their method of
preparation. Thus in one embodiment, the polyamidopolyamine and/or
polyamidoamine having a molecular weight of about 500 to about
100,000 and comprising at least one, or at least two, or at least
three or at least 4 or more primary amino groups or a composition
containing one or a mixture of multiple polyamidopolyamines is
prepared by a condensation reaction between a polybasic acid and a
polyamine.
[0088] In one embodiment, the composition or compound is prepared
by a method comprising condensing (i) a polyamine comprising three
primary amino groups and (ii) a C.sub.3 to C.sub.16 polybasic acid
or derivative thereof. In one embodiment, this reaction occurs in
the presence of an organic hydroxyl-containing diluent. In another
embodiment, the polyamidopolyamine having a molecular weight of
about 500 to about 100,000 and comprising at least four primary
amino groups and/or a composition containing it is prepared by a
method comprising condensing (i) two polyamines comprising three or
more primary amino groups and (ii) a C.sub.3 to C.sub.16 polybasic
acid or derivative thereof. In one embodiment, this reaction occurs
in the presence of an organic hydroxyl-containing diluent.
[0089] In another embodiment, the polyamidopolyamine having a
molecular weight of about 500 to about 100,000 and comprising four
or more primary amino groups and/or a composition containing it is
prepared by a method comprising condensing (i) a polyamine
comprising at least three primary amino groups and (ii) two C.sub.3
to C.sub.16 polybasic acids or derivative thereof. In still another
embodiment, this reaction occurs in the presence of an organic
hydroxyl-containing diluent.
[0090] In yet another embodiment, the polyamidopolyamine having a
molecular weight of about 500 to about 100,000 and comprising
multiple primary amino groups and/or a composition containing it is
prepared by a method comprising condensing (i) a polyamine
comprising three primary amino groups, (ii) a polyamine comprising
two primary amino groups, and (iii) a C.sub.3 to C.sub.16 polybasic
acid or derivative thereof. In still another embodiment, this
reaction occurs in the presence of an organic hydroxyl-containing
diluent.
[0091] Still other combinations of selected polybasic acids and
selected polyamines or primary amines comprising one or more amino
groups may participate as reactants in a suitable condensation
reaction to produce the polyamidopolyamines. One of skill in the
art given the teachings of this specification can readily select
other polybasic acids and polyamines.
[0092] In still another method, a composition comprising a
polyamidopolyamine having a molecular weight of greater than about
100,000 and comprising multiple primary amino groups and/or a
composition containing it is prepared by sequential condensation
reactions (i.e., a dendrimer process). According to this method, a
polybasic acid is reacted with a polyamine and an optional
hydroxyl-containing solvent to produce a first polyamidopolyamine
as a reaction product. The polyamidopolyamine reaction product of
the first reaction is then itself reacted with the same or
different a polybasic acid and an optional hydroxyl-containing
solvent to produce another polyamidopolyamine as a subsequent
polyamidopolyamine reaction product. Additional sequential
condensation reactions are performed by reacting the
polyamidopolyamine reaction product of each preceding condensation
reaction with the same or different polybasic acid and an optional
hydroxyl-containing solvent for a selected number of
iterations.
[0093] The reaction sequence may be terminated by addition of a
monobasic acid or polybasic acid, by a condensation reaction or a
salt reaction, or by neutralization with an acid, preferably a
water soluble acid as described above. This termination can occur
when the composition demonstrates a desired characteristic selected
from anti-foaming, low-foaming, defoaming, lubricity,
bioresistance, antimicrobial activity or any desired combination of
these characteristics.
[0094] The polyamines and polybasic acids used in the methods
described above, including the sequential (dendrimer) reaction
method, may be selected from among known compounds or those
specifically identified herein. In the sequential reaction, the
polyamines and polybasic acids may be the same in each sequential
reaction or different. The reactants for any of the above methods
can include any of the polybasic acids comprising two C(O)OH groups
or derivatives thereof, as identified above. Some of the free amino
groups can be further terminated to amide (salts) with cyclic
anhydride (such as succinic anhydride or glutamic anhydride) to cap
amino groups at a temperature which is below condensation reaction
temperature. Such a temperature is between 90 and 95.degree. C.
[0095] In still other embodiments, the non-polymeric amidoamine
having a molecular weight of about 290 to about 5000 and comprising
at least one, or at least two, or at least three or more primary
amino groups or a composition containing one or a mixture of
multiple non-polymeric amidoamines and optionally one or more of a
mixture of non-polymeric amides as described herein is prepared by
a similar condensation reaction between a selected monobasic acid
and a primary amine, or by condensation reactions between multiple
monobasic acids and one or multiple amines or polyamines, in a
manner similar to the condensation reactions described above for
the polyamidopolyamine-containing compositions.
[0096] In yet another embodiment, compositions comprising mixtures
of polyamido-polyamine(s) and non-polymeric amidoamine(s), with or
without certain amounts of the free reactants, are prepared by
condensation reactions employing a polybasic acid, a monobasic acid
and one or more polyamines or amines, in a manner similar to that
described herein.
[0097] A large number of available polyamines or primary amines are
useful in all of these described methods.
[0098] In one embodiment of the preparative methods described
above, a suitable polyamine is triaminononane. In another
embodiment, the method uses a polyamine of the formula:
##STR00013##
[0099] In this formula, R.sup.1, R.sup.3, and R.sup.5 are
independently H, methyl, ethyl, propyl or butyl; R.sup.2, R.sup.4
and R.sup.6 are independently methyl, ethyl, propyl, or butyl; and
a, b and c are additively a number between 0 to about 90, including
both endpoints of the range (see para. 0083).
[0100] A more specific suitable polyamine for use in the
preparative methods is:
##STR00014##
[0101] In this polyamine, s, t and u are additively a number
between 3 to about 90, including both endpoints of the range (see
para. 0083).
[0102] Still another suitable polyamine has the formula:
##STR00015##
[0103] For this polyamine, R.sup.1 is H, methyl, ethyl, propyl or
butyl; R.sup.2, R.sup.3, and R.sup.4 are, independently, methyl,
ethyl, propyl, or butyl; and e and f are additively a number
between 0 to about 90, including both endpoints of the range (see
para. 0083).
[0104] A more specific polyamine has the formula:
NH.sub.2CH(CH.sub.3)CH.sub.2--(O--CH.sub.2CH.sub.2).sub.g--(O--CH.sub.2C-
H(CH.sub.3)).sub.h--(O--CH.sub.2CH(CH.sub.3))--NH.sub.2
[0105] wherein g and h are additively a number between 0 to about
90, including both endpoints of the range (see para. 0083).
[0106] Still another suitable polyamine is of the formula:
##STR00016##
[0107] In this formula, R.sup.1, R.sup.3, R.sup.5 and R.sup.7 are
independently H, methyl, ethyl, propyl or butyl; R.sup.2, R.sup.4,
R.sup.6 ,and R.sup.8 are independently methyl, ethyl, propyl, or
butyl; and w, j, k and m are additively a number between 0 to about
90, including both endpoints of the range (see para. 0083).
[0108] Another more specific polyamine has the formula:
##STR00017##
[0109] In which h, n, o and p are additively a number between 4 to
about 90, including both endpoints of the range (see para.
0083).
[0110] Still another suitable polyamine for use in these methods
has the formula:
##STR00018##
[0111] In this formula, R.sup.1, R.sup.3, and R.sup.5 are
independently H, methyl, ethyl, propyl or butyl; R.sup.2, R.sup.4,
and R.sup.6 are methyl, ethyl, propyl, or butyl; and a', b' and c'
are additively a number between 0 to about 90, including both
endpoints of the range (see e.g., para 0083). Still another more
specific polyamine has the formula:
##STR00019##
[0112] in which wherein e', f' and g' are additively a number
between 3 to about 90 (see, para 0083). A specific polyamine under
this formula is marketed as Jeffamine.RTM. T403 (Huntsman
Corporation) and is used in the Examples below.
[0113] These methods of preparing the compositions and compounds
described herein involve in one embodiment, performing the
condensation reaction with the selected reactants of polyamine(s)
and polybasic acid(s) and/or monobasic acid(s) in the presence of
water (which is removed during the course of the reaction) or a
hydroxyl-containing organic diluent, described above. In certain
embodiments, the methods include the steps of adding an organic
hydroxyl-containing diluent or solvent at the initiation of the
reaction. In other embodiments, the methods include adding water or
an organic hydroxyl-containing diluent or solvent at the end of the
reaction to adjust viscosity of the composition. In still other
embodiments of these preparative methods, diluent is added at both
points of the reaction. In the condensation reactions identified
herein, the organic hydroxyl component acts as a diluent when added
at the end of the reaction to control viscosity of the resulting
polyamidopolyamine and/or non-polymeric amidoamine-containing
compositions. In another embodiment, the organic hydroxyl component
acts as a reactive intermediate in the condensation reaction (i.e.,
forms an ester). This intermediate is converted to the amide during
the reaction, regenerating the organic hydroxyl compound, and
remains in the final product.
[0114] In one embodiment of the preparative methods, the mole ratio
of the polybasic acid to polyamine is the ratio 1: (1.times.),
wherein X is the number of C(O)OH groups in the polybasic acid. In
one embodiment, in a reaction in which the polybasic acid is a
dibasic acid, the ratio of polybasic acid to polyamine is about 1
to about 2. In one embodiment of the preparative methods, the mole
ratio of the tribasic acid to polyamine is about 1 to about 3. In
one embodiment of the preparative methods, the mole ratio of the
tetrabasic acid to polyamine is about 1 to about 4, and so on. In
another embodiment, the mole ratio of the polybasic acid to the
polyamine is about is about 1:1. This ratio can be used when the
reaction is conducted in the presence of an organic hydroxyl
solvent, or without such solvents. For example, the mole ratios of
polybasic acid to polyamine can be 4 to 5, 9 to 10, 24 to 25, etc.
Where a monobasic acid is a reactant with a polyamine, the molar
ratio or molar basis is as described herein in paragraph 00125.
[0115] Generally, the temperature of the condensation reactions is
between about 150.degree. C. to about 175.degree. C. or between
about 160.degree. C. to about 165.degree. C. In another embodiment,
the temperature is about 150, 151, 152, 153, 154, 155, 156, 157,
158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170,
171, 172, 173, 174 or about 175.degree. C. The reactions can take
place from 1 to 24 hours. In one embodiment, the reactions take
place for about 8 hours. In other embodiments, the reactions take
place for between 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14,
15, 16, 17, 18, 19, 20, 21, 22, 23, or 24 hours.
[0116] In certain embodiments, the compositions resulting from
these preparative methods can contain one or more of a
polyamidopolyamine, which is a linear, cyclic, branched or
crosslinked amide containing at least one or more primary amine
groups; one or more of a non-polymeric amidoamine, which when
monobasic acid is used is a linear or branched amide containing at
least one or more primary amine groups; a polyamidopolyamine having
one or more imide groups; a mixture of any or multiple of these
polyamidopolyamine(s) or imides or non-polymeric amidoamines; or a
mixture of any of these compounds with some unreacted reactants,
such as amines, diluent, acids, etc.
[0117] There is a small possibility that the composition comprising
a polyamidopolyamine may contain a mixture of imide-containing
compounds with no primary amine. When polybasic acid carboxyls are
in the 1, 2 and or 1, 3 positions, imide formation can result
depending on reaction conditions. One exemplary imide-containing
polyamidopolyamine is shown in the following Formula E, wherein t
is a whole number from 1 to about 5:
##STR00020##
[0118] Michael addition can also result by primary amine addition
across unsaturation of double bonds in conjugation with carbonyl
groups of the polybasic acid such as maleic, itaconic, or
citraconic acids, among others.
[0119] Other Characteristics of the Compounds and/or Compositions
Containing Them
[0120] In certain embodiments, the polyamidopolyamine of these
Formulae A through D comprise from 4 to 14 amino groups. In certain
embodiments, the non-polymeric amidoamines of these Formulae F and
G comprise from 1 to 3 amino groups. Polyamidopolyamine reaction
products of the dendrimer or sequential reactions described may
have more than 14 primary amino groups, depending upon the
selection of polybasic acid and polyamines in the reaction. In some
embodiments, the number of primary amine groups in the resulting
polyamidopolyamine is calculated as (# primary amines in the
selected polyamine -1).times.the number of acid groups in the
polybasic acid. For example, the reaction of a 2:1 mole ratio of
polyamine with 3 amino groups with a dimer acid results in the
number of free amino groups in the polyamidopolyamine including
((3-1).times.2) or 4 amino groups, as one structure, among
others.
[0121] In other embodiments, the number of primary amine groups in
the non-polymeric amidoamine is calculated as (# primary amines in
the selected polyamine -1).times.the number of acid groups in the
monobasic acid. For example, the reaction of a polyamine having 3
primary amine groups with a monobasic acid in the reactions
described herein produces a non-polymeric amidoamine having
(3-1).times.1 or 2 primary amine groups etc.
[0122] In one embodiment, the polyamidopolyamine has a molecular
weight (MW) of between about 500 to about 100,000, including all
numbers therebetween and including the endpoints of the range. In
certain embodiments, the polyamidopolyamine of these compositions
can have MW of at least 500, 600, 700, 800, 900, 1000, 1100, 1200,
1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300,
2400, 2500, 2600, 2700, 2800, 2900, 3000, 3100, 3200, 3300, 3400,
3500, 3600, 3700, 3800, 3900, 4000, 4100, 4200, 4300, 4400, 4500,
4600, 4700, 4800, 4900, 5000, 6000, 7000, 8000, 9000, 10,000,
20,000, 30,000, 40,000, 50,000, 60,000, 70,000, 80,000, 90,000 and
up to 100,000 including all numbers between any two endpoints of
the range. In certain embodiments, in which the method of making
the polyamidopolyamine involves repeated cycles of reactions as
described below, the polyamidopolyamine compound can have MW of
greater than 100,000.
[0123] In one embodiment, the non-polymeric amidoamine has a
molecular weight (MW) of between about 290 to about 5000, including
all numbers therebetween and including the endpoints of the range.
In certain embodiments, the non-polymeric amidoamine of these
compositions can have MW of at least 290, 390, 490, 590, 690, 790,
800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800,
1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900,
3000, 3100, 3200, 3300, 3400, 3500, 3600, 3700, 3800, 3900, 4000,
4100, 4200, 4300, 4400, 4500, 4600, 4700, 4800, 4900, and up to
5000. In certain embodiments, the non-polymeric amidoamine compound
can have MW of greater than 5000.
[0124] In other embodiments, the polyamidopolyamine and/or
non-polymeric amidoamine and/or the composition containing that
polyamidopolyamine and/or non-polymeric amidoamine is
water-soluble. In another embodiment, the polyamidopolyamine and/or
non-polymeric amidoamine and/or the compositions containing one or
both of them is water dispersible. In another embodiment the
composition contains a water soluble acid as defined above to
enhance water solubility. Another characteristic of certain
polyamidopolyamines is that it is non-shearing in water.
[0125] Polyamidopolyamines and/or non-polymeric amidoamines and the
compositions described herein are further defined as having a cloud
point (i.e., inverse solubility) of between about 25.degree. C. to
82.degree. C. (or 77.degree. F. to 180.degree. F.) in water.
Suitable cloud points for these compositions range from about
25.degree. C. to about 82.degree. C., i.e., from 25, 30, 35, 40,
45, 50, 55, 60, 65, 70, 73, 80 to 82.degree. C. including any
degree between any two of these values. However, some embodiments
of the compounds or compositions described herein form cloud points
(i.e., appear cloudy) at ambient temperature, i.e., 25.degree. C.
These embodiments can be made clear by further cooling.
[0126] In one embodiment, the polyamidopolyamine and/or
non-polymeric amidoamine desirable for use in these compositions
and the compositions them have low-foaming properties. In other
embodiments, the polyamidopolyamine and/or non-polymeric amidoamine
and/or the composition containing the polyamidopolyamine and/or
non-polymeric amidoamines have non-foaming properties. In still
other embodiments, these compositions have defoaming properties and
the capability of releasing entrained air.
[0127] In still other embodiments the polyamidopolyamine and/or
non-polymeric amidoamine and/or the compositions them has
lubricating properties. In still other embodiments the
polyamidopolyamine and/or non-polymeric amidoamine and/or the
compositions containing them has a pH of about 8, 8.2, 8.4, 8.6,
8.8, 9.0, 9.2, 9.4, 9.6, 9.8, 10.0, 10.2, 10.4, 10.6, 10.8, 11.0,
or any number therebetween. In still other embodiments the
polyamidopolyamine or the composition has bioresistant or
antimicrobial properties, due either to the free primary amine
groups of the polyamidopolyamine, or optionally to any added
antimicrobial component added to the composition to enhance this
characteristic. In still other embodiments the non-polymeric
amidoamine or the composition containing it has bioresistant or
antimicrobial properties, due either to the free primary amine
groups of the amidoamine, or optionally to any added antimicrobial
component added to the composition to enhance this
characteristic.
[0128] Uses of the Polyamidopolyamines and/or Non Polymeric
Amidoamines and/or Compositions Containing Them
[0129] The polyamidopolyamines and/or non-polymeric amidoamines
and/or compositions containing one or both such components as
described herein can be used to introduce multiple characteristics
of lubricity, bioresistence, anti/low/no-foaming or antimicrobial
activity to a variety of industrial compositions in need of one or
more of those features. Alternatively the compositions containing
the polyamidopolyamines and other reaction products generated by
the methods may themselves be employed as the additives to other
compositions. In still other embodiments, a variety of different
additional components may be admixed with the compositions
containing the polyamidopolyamines and/or non-polymeric amidoamines
to create a variety of different use compositions.
[0130] When employed as an additive to other known compositions,
e.g., quenchants, lubricants, coatings, etc, it is anticipated that
the present polyamidopolyamine and/or non-polymeric
amidoamine--containing compositions will be employed to replace
multiple components currently in use. In one embodiment, a
composition described herein can be used simultaneously for its
characteristics as both a lubricant and a defoamer, thereby
replacing two components with a single component. Similarly, a
composition described herein which has bioresistance or
antimicrobial characteristics, as well as defoaming and/or
lubricity characteristics may replace three other components in a
suitable composition.
[0131] Based upon its intended use, or when used as a concentrate,
the composition can contain from 0.5 up to about 40% of the
polyamidopolyamine or non-polymeric amidoamine or a combination of
both. In one embodiment, the composition contains at least 0.5, 1,
2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20,
21, 22, 23, 24, 25, 26, 27, 28, 29,30,31, 32, 33, 34, 35, 36, 37,
38, 39 or at least 40%, including any whole or fractional
percentages between any two of these values.
[0132] The remainder of the concentrate, in one embodiment, can be
formed by certain selected additional components described in
detail below. Such additional components are selected based upon
the use of the resulting composition containing the
polyamidopolyamine. In certain embodiments, the composition is
dissolved in a hydroxyl-containing diluent. In one embodiment, the
concentrate is diluted with in a hydroxyl-containing diluent to
form a composition which contains about 60 to about 99% w/w, i.e.,
60, 65, 70, 75, 80, 85, 90, 95 to about 99% w/w or numbers there
between, of hydroxyl-containing diluent. The hydroxyl-containing
diluent may be included in the composition for its intended use,
thereby permitting use of the product by the customer without
addition of further diluent. Alternatively, diluent is present in
the composition in sufficient amounts to provide a stable solution
for transportation and storage, if the composition is intended to
be further diluted by the customer prior to use.
[0133] In still other embodiments, these compositions described
herein can be used in aqueous or non-aqueous systems, emulsion
systems, etc. In some embodiments, the composition is soluble or
dispersible in hydrophobic media, e.g., liquids such as mineral
oil. The compositions can also become the discontinuous phase in
water when emulsifiers are added to the compositions. The
emulsifiers, such as fatty acids, can form soaps which emulsify the
polyamidopolyamine and/or non-polymeric amidoamines.
[0134] Depending upon the intended use of the composition, a
variety of additional components may form part of the composition
containing the polyamidopolyamine and/or non-polymeric amidoamine
described herein. Whatever use for which the composition is
intended, such compositions containing the above
polyamidopolyamines and/or non-polymeric amidoamines has a pH of
between about 8 to about 11, i.e., a pH of 8.0, 8.5, 9.0, 9.5,
10.0, 10.5 and 11, including any fractional pH value between any
two endpoints of the range from 8 to 11.
[0135] In general, when use as a defoamer, the polyamidopolyamines
and/or non-polymeric amidoamines and/or compositions containing
them can desirably replace silicone defoamers. It is anticipated
that as a defoamer additive, the compositions or the compounds
isolated therefrom may be use at a concentration of between about
0.1 to 0.5% by weight of the resulting use composition, e.g., metal
working fluid. This range includes the endpoints of the range,
e.g., the present polyamidopolyamine and/or non-polymeric
amidoamine--containing compositions can be added at e.g., 0.1, 0.2,
0.3, 0.4 and 0.5% by weight of the resulting use composition.
[0136] When used primarily as an additive for its
anti-microbial/bioresistant characteristics, it is anticipated that
the compositions comprising the polyamidopolyamines and/or
non-polymeric amidoamines will be used at a concentration of
between about 1 to about 3% by weight of the resulting use
composition, e.g., a paint or polyurethane coating fluid. This
range includes the endpoints of the range, e.g., the present
polyamidopolyamine compositions can be added at e.g., 1.0, 1.3,
1.5, 1.7, 2.0, 2.2, 2.4, 2.6, 2.7, and 3.0% by weight of the
resulting use composition. Most desirably, the compositions can be
used as a formaldehyde-free anti-microbial, or as an adjuvant to
other biocides and fungicides.
[0137] When used primarily as an additive for its lubricant
characteristics and optionally its bioresistant/antimicrobial
characteristics, it is anticipated that the compositions comprising
the polyamidopolyamines and/or non-polymeric amidoamines will be
used at a concentration of between about 5 to about 30% by weight
of the resulting use composition, e.g., a lubricating fluid that
does not degrade in the presence of a microorganism. This range
includes the endpoints of the range, e.g., the present
polyamidopolyamine compositions can be added at e.g., 5.0, 5.5,
6.0, 6.5, 7.0, 8.0, 9.0, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19,
20, 21, 22, 23, 24, 25, 26, 27, 28, 29 and 30% by weight of the
resulting use composition.
[0138] In another embodiment, the composition comprising the
polyamidopolyamine and/or non-polymeric amidoamines can be used as
a quenchant that also optionally provides bioresistance and
defoaming properties, when the use composition is metal heat
quenching fluid. Suitable quenchants and other quenching components
may be selected from among many known in the art. In this
embodiment, it is anticipated that the compositions comprising the
polyamidopolyamines will be used at a concentration of between
about 10 to about 30% by weight of the resulting use composition,
and can replace or work in tandem with another quenchant, while
also replacing one or more typical quenching additives for
lubricity, bioresistance and/or foam control. Compositions
containing non-polymeric amidoamines are anticipated to work with
the polyamidopolyamines in this context, or as additives to other
known quenchant formulations. See, for example, U.S. Pat. Nos.
8,764,914; 4,486,246; 4,528,044; 4,381,205; and 4,404,044 which
describe some examples of known quenching fluids.
[0139] Thus, in certain embodiments of the heat treating (e.g.,
quenching) compositions described herein, the polyamidopolyamine
comprises a pendent amino group. Polyamidopolyamines useful in
these heat treating compositions include those described in U.S.
62/147,840, and throughout this specification, e.g., Formula I-V,
herein, as well as those described as follows:
[0140] In one embodiment, the polyamidopolyamine is of the Formula
I shown above. The subscripts x, y, z, and x', y', z', and a, b,
and c are all defined additively, that is, x+y+z equals a number
from 3 to about 90 (see para 0083); x'+y'+z' equals a number from
about 3 to about 90; and a+b+c equals a number from 3 to about
90.
[0141] In another embodiment, the polyamidopolyamine is of the
Formula II shown above, wherein x, y, z, x', y', and z' are defined
additively, that is, x+y+z equals a number from 3 to about 90 (see
para 0083); and x'+y'+z' equals a number from about 3 to about 90
(see para 0083).
[0142] In another embodiment, the polyamidopolyamine is of the
Formula III shown above, wherein x, y, z, and x', y', z', and a, b,
and c are additively 3 to about 90 (see para. 0083).
[0143] In another embodiment, the polyamidopolyamine is of the
Formula IV shown above, wherein x, y, z, x', y', z', a, b, and c
are additively 3 to about 90, that is, x+y+z equals a number from 3
to about 90 (see para 0083); x'+y'+z' equals a number from about 3
to about 90; and a+b+c equals a number from 3 to about 90 (see
para. 0083).
[0144] In another embodiment, the polyamidopolyamine is of the
Formula V shown above, wherein x, y, z, x', y', z', a, b, and c are
defined the same as for Formula IV.
[0145] In yet another embodiment, the non-polymeric amidoamines
useful in these heat treating compositions include those described
in U.S. 62/147,840, as well as those described as Formulae F and G
described herein and as follows.
[0146] Exemplary non-polymeric amidoamines have the formula:
##STR00021##
wherein x, y, and z are additively 0 to about 87, including all
numbers within that range including the endpoints of the range (see
para. 0083), and R' is C.sub.1 to C.sub.11 alkyl or C.sub.1 to
C.sub.11 substituted alkyl (see the range defined in para 0083);
or
[0147] the formula:
##STR00022##
wherein x, y, and z are additively a number between 0 to about 87,
including the endpoints of the range (see the range defined in para
0083), and R and R' are independently C.sub.1 to C.sub.11 alkyl or
C.sub.1 to C.sub.11 substituted alkyl; or
[0148] the formula:
##STR00023##
wherein w, x, y, and z are additively a number between 0 to about
86, including the endpoints of the range (see the range defined in
para 0083), and R and R' are independently C.sub.1 to C.sub.11
alkyl or C.sub.1 to C.sub.11 substituted alkyl; or
[0149] the formula:
##STR00024##
wherein w, x, y, and z are additively a number between 0 to about
86, including the endpoints of the range (see the range defined in
para 0083), and R, R' and R'' are independently C.sub.1 to C.sub.11
alkyl or C.sub.1 to C.sub.11 substituted alkyl.
[0150] In another embodiment a quenching composition containing one
such non-polymeric amidoamine can be present in a
hydroxyl-containing diluent comprising water, in which the mole
ratio of the primary polyamine to monobasic acid provides at least
one free amino group, and water is added at the end of the
condensation reaction. In another embodiment, the composition
containing the non-polymeric amidoamine has all of its amino groups
converted to amide. In this case, the condensation products retain
defoaming and lubricant properties, but do not act as antagonists
to microorganisms. In still another embodiment, the diluent lacks
water and the mole ratio of the primary amine to monobasic acid
provides at least one free amino group.
[0151] Other Components for Quenching Compositions
[0152] Still other embodiments of the quenching compositions
containing an polyamidopolyamine or non-polymeric amidoamine
described herein also contain other components. Thus other
additional components of the final use compositions comprising the
polyamidopolyamines and/or non-polymeric amidoamines described
herein include one or any combination of additional agents,
including but not limited to, coalescing/drying agent, rheology
modifier, ester, carboxylic acid, fatty acid, emulsifier, amine,
thickener, lubricant, dispersant, antioxidant, alkaline compound,
builder, solvent, amphipathic agent, carrier, preservative, buffer,
metal deactivator, dye, fragrance, caustic agent, wetting agent,
sequestering agent, fungicide, defoamer, antioxidant, die release
fluid, antiwear agent, viscosity modifier, de-emulsifier, natural
triglyceride, animal fat, vegetable oil, fatty acid ester, and/or a
phosphate ester. Still other optional components may be included in
the concentrate and/or composition and may be selected by those
skilled in the art. These additional components include, but are
not limited to, salts, buffers, pH adjustors, enzymes, surfactants,
tackifying agents, scale inhibitors, catalysts, clay control
agents, friction reducers, corrosion inhibitors, dispersants,
flocculants, H2S scavengers, CO2 scavengers, oxygen scavengers,
lubricants, gelling agent, crosslinking agent, wetting agents,
relative permeability modifiers, resins, adhesives, and coating
enhancement agents.
[0153] In one embodiment, such other components include other known
quenching polymers used in conjunction with the polyamidopolyamine
and/or non-polymeric amidoamine compound as an additional quenching
component.
[0154] Suitable polymers useful in the aqueous quenchants and
methods described herein are known in the art. Suitable polymers
include polyvinyl alcohol; polyalkylene glycol (PAG); sodium
polyacrylate (ACR); polyvinyl pyrrolidone (PVP); polyethyloxazoline
(PEOX); and hybrid polymer quenchants. See, e.g., Eshraghi-Kakhki
et al, International Journal of ISSI, 6(1):34-8 (2009). Other
suitable polymers include, for example, those described in U.S.
Pat. No. 3,220,893, which discusses a quenching medium containing
an oxyalkylene polymer having oxyethylene and higher oxyalkylene
groups which form a desirable covering over the metal substrate
surface during quenching. The polymer layer that coats the metal
permits relatively short quenching times, thereby resulting in
minimum internal stress of the metal substrate, minimum distortion
of the metal substrate, and imparts uniform hardenability of the
metal substrate. Another suitable aqueous quenching media is
described in US Patent Publication No. 2009/0095384 which contains
a polyvinylpyrrolidone/polyvinylcaprolactam copolymer; and a
non-ionic, water-soluble or water-dispersible polymer including one
or more of (a) a substituted oxazoline polymer; (b) a
poly(oxyethyleneoxyalkylene) glycol polymer; or (c) a
polyvinylpyrrolidone polymer.
[0155] Further, U.S. Pat. Nos. 3,902,929, 4,826,545, and RE 34119
discuss aqueous quenching media containing a polyvinylpyrrolidone
and U.S. Pat. No. 4,087,290 discusses an aqueous quenching medium
containing a water-soluble polyacrylate, such as a sodium
polyacrylate, which forms a vapor blanket about the metal substrate
during the quenching operation.
[0156] Suitable quenchants are known under various proprietary
names, including, without limitation, AQUA-QUENCH.RTM. 140
(Houghton Int'l); AQUA-QUENCH.RTM. 145 (Houghton Int'l);
AQUA-QUENCH.RTM. 245 (Houghton Int'l); AQUA-QUENCH.RTM. 251
(Houghton Int'l); AQUA-QUENCH.RTM. 260 (Houghton Int'l);
AQUA-QUENCH.RTM. 3699 (Houghton Int'l); AQUA-QUENCH.RTM. C
(Houghton Int'l); PARQUENCH.RTM.60 and PARQUENCH.RTM.90;
POLYQUENCH.RTM. 10, POLYQUENCH.RTM. 15, and POLYQUENCH.RTM. 20;
PLASTIQUENCH.TM.; and SPEED QUENCH.TM. 1 (all Park Metallurgical
Corporation); AQUATENSID.RTM. (Petrofer); and the UCON.TM. (DOW
Chemical Company) series of quenchants. Other suitable quenchants
are known in the art.
[0157] In certain embodiments, the aqueous quenching fluid
comprises capped polyalkylene glycols, polyvinylpyrrolidone (PVP),
polyvinylpyrrolidone copolymers, polyethyloxazoline (PEOX),
polyethyloxazoline copolymers, polyacrylate, polyacrylate
copolymers, or mixtures thereof. In certain other embodiments, the
aqueous quenching fluid comprises uncapped polyalkylene glycols,
polyvinylpyrrolidone (PVP), polyvinylpyrrolidone copolymers,
polyethyloxazoline (PEOX), polyethyloxazoline copolymers,
polyacrylate, polyacrylate copolymers, or mixtures thereof In still
other embodiments, the aqueous quenching fluid comprises capped and
uncapped polymers, such as combinations of those identified herein.
In one embodiment, the aqueous quenching fluid (bath and/or spray)
comprises polyalkylene glycol (e.g., Houghton Aqua Quench.RTM.
365). In another embodiment, the aqueous quenching fluid (bath
and/or spray) comprises a polyvinylpyrrolidone (PVP) polymer (e.g.,
Houghton Aqua Quench.RTM. C). In another embodiment, the aqueous
quenching fluid (bath and/or spray) comprises a PEOX polymer (e.g.,
Houghton Aqua Quench.RTM. 3600). In still another embodiment, the
aqueous quenching fluid (bath and/or spray) comprises PVP/PVC,
vinylpyrrolidone/vinyl caprolactam copolymer (e.g., Houghton Aqua
Quench.RTM. 4000).
[0158] In still another embodiment, the quenching fluid (bath
and/or spray) one or more additional components include a carrier.
In one example, the carrier is water. The carrier may be included
in the quenching medium, thereby permitting use of the product by
the customer without addition of further carrier. Alternatively,
the carrier is present in the quenching medium in sufficient
amounts to provide a stable solution for further dilution by the
customer prior to use. The carrier may also be added by the
customer to a concentrated quenching medium composition prior to
use. However, more water made be added to the composition to ensure
that the final quenching medium contains sufficient water for use
by the customer.
[0159] Addition components with antimicrobial activity in addition
to that activity provides by the polymeric polyamidopolyamines or
non-polymeric amideamines may optionally be added to the quenching
baths or sprays used in the processes described herein to prevent
or reduce the accumulation of microorganisms in the system. The
particular antimicrobial selected will depend on the process
parameters, including aqueous quenching fluid, hydraulic fluid, the
metal or metal alloy, the dimensions of the metal or metal
substrate being quenched, among others. Such components include,
for example biocides, bactericides or fungicides, e.g.
polyaminopropylbiguanide (obtainable from Arch under the trade name
CosmocilCQ.TM.), paraformaldehyde, glutaraldehyde, phenoxyethanol,
2,4-dichlorobenzyl alcohol, 2,3-dibromo-3-nitrilopropionamide, and
5-chloro-2-methyl-2H-isothiozol-3-one. Suitable biocides are known
in the art, including, without limitation, CONTRAM.TM. biocides
(Lubrizol); the BIOBAN.TM., DOWICIDE.TM., KATHON.TM., ROCIMA.TM.
and KORDEK.TM. brand biocides (Dow Chemical); MERGAL.RTM. brand
biocides (ECT CV Corp.); TROYSHIELD.RTM. (Troy Technical Corp)
(iodopropynyl butylcarbamate). One of skill in the art would be
able to make such a selection, taking into consideration the
teachings of this specification. In one embodiment, the
antimicrobial is the Grotan.RTM. reagent (Troy Corporation). In
another embodiment, the antimicrobial may be selected from the list
of microbicides discussed in the catalog "Metalworking", Buckman
Laboratories, Inc., 2010, which is herein incorporated by reference
in its entirety. In a further embodiment, the antimicrobial is the
Busan.RTM. 1060 reagent (Buckman Laboratories). Other examples of
suitable antimicrobials are the KATHON.TM. 886 MW product and
KATHON.TM. 893 MW product (Dow Chemical Company). Other suitable
biocides may be readily determined by one of skill in the art.
[0160] Still additional components include preservative, and also
further compounds such as ethanolamine, polyalkylene oxides,
polyethylene glycols. ethanol amine or amine soaps, buffer, metal
deactivator, dye, fragrance, caustic agent, wetting agent,
sequestering agent, among others.
[0161] Conventional antifoams/defoamers include components such as
silicone oils, fatty alcohol alkoxylates, alcohol alkoxylates,
carboxylic esters or phosphoric esters. Suitable antifoam agents
are known in the art, including, without limitation, the TEGO.RTM.
brand antifoams (Evonik Industries); XIAMETER.RTM. brand antifoams
(Dow Coming); SAF-115, SAF-125, SAF-150, SAF-151, SAF-250, SAF-251
(Silchem Inc.); SURTECH.RTM. antifoams (PMC Crystal); Additive 2901
(Quaker Chem); and TROYKYD.RTM. brand defoamers (Troy Technical
Corp). Other suitable antifoams can be readily determined by one of
skill in the art.
[0162] "Antioxidants" as described herein are useful additives for
preventing the degradation of the hydraulic fluid or quenching bath
or quenching spray through oxidation. Such antioxidants may be
selected from among an aromatic amine, quinoline, and phenolic
compounds. In one embodiment, the antioxidant is an alkylated
diphenyl amine (Vanlube.RTM. NA reagent, polymerized
trimethyl-dihydro-quinoline (Vanlube.RTM. RD reagent) or
4,4'-methylene bis(2,6-di-tert-butylphenol).
[0163] "Corrosion inhibitors" may be selected from the battery of
conventional corrosion inhibitors for both ferrous and non-ferrous
metals used in the industry. In one embodiment, the corrosion
inhibitor is tolyltriazole. Another corrosion inhibitor is sodium
nitrite, borax, amines, ammonium salts of organic acids, phosphoric
esters, alcohol alkoxylates, or 2-butyne-1,4-diol. However, other
known and commercially available corrosion inhibitors could readily
be used by one of skill in the art, taking into consideration the
teachings of this specification.
[0164] "De-emulsifiers" as described herein may also optionally be
included in the quenching baths or quenching sprays utilized
herein. This is particularly useful when high agitation rates are
utilized during the process. However, their inclusion is not
required. One of skill in the art would be able to select a
suitable de-emulsifier for use herein, taking into consideration
the teachings of this specification.
[0165] These "additional" components may be present in the
composition at about 0.05% to up to about 20% by weight. In one
example, these components are present in combination in the
quenching compositions at about 0.05, 0.1, 0.5, 1, 1.5, 2, 2.5, 3,
3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 11, 12,
13, 14, 15, 16, 17, 18, 19 or 20% by weight, or fractional
percentages therebetween.
[0166] In one exemplary embodiment, a metal quenching media
therefore advantageously comprises 60 to 99.8% by weight of water
as carrier, 0.5 to 40% polyamidopolyamine or non-polymeric
amidoamine, and 0.1 to 20% by weight of customary additives. In
still another example, an aqueous quenching medium contains a
polyamidopolyamine having a weight average molecular weight of
about 10,000 in a concentration of about 25% to about 35% by weight
and 55% water. The aqueous quenching medium may also contain about
0.05% to about 10% by weight of additives, including, without
limitation, corrosion inhibitors and defoamers.
[0167] The invention also provides a concentrate which contains the
polyamidopolyamine and/or non-polymeric amidoamine components
described above. This concentrate may be utilized by those skilled
in the art for preparing an aqueous quenching medium useful in the
heat treatment of metal substrates. In one example, the concentrate
contains water and at least about 0.5% by weight of a
polyamidopolyamine and/or non-polymeric amidoamine described above.
In another example, the concentrate contains water and about 0.5%
to 40% by weight of these polyamidopolyamine and/or non-polymeric
amidoamines. In a further example, the concentrate contains about
5% to about 20% of these polyamidopolyamine and/or non-polymeric
amidoamines described above.
[0168] In still other embodiments, the composition comprising the
polyamidopolyamines and/or non-polymeric amidoamines will be
combined with additional components, which are those necessary to
employ the composition in a final "use" composition. In one
embodiment, the composition may provide needed and multiple
properties to a metal cutting fluid. In another embodiment, the
composition may provide its multiple properties to a heat treating
fluid or hydraulic fluid. In a further embodiment, the composition
comprising the polyamidopolyamines can be used in a metal working
fluid for the purposes of application to metals for metal rolling,
metal cleaning, metal cutting, metal drawing, or metal forming. In
this embodiment, the compositions described herein are useful as
lubricants and bioresistance and defoaming components. In a further
embodiment, the composition comprising the polyamidopolyamines can
be used in a hydraulic fluid. In still other embodiments, the
additional components are those necessary to employ the composition
in a cleaning fluid, desirably for high pressure applications which
require non-foaming components. In another embodiment, the
compositions may be useful as additives to rust preventatives.
Further embodiments for use of the compositions include as
anti-microbials in oil pipelines or offshore use (e.g., blow-out
preventatives). The compositions are also useful in forming uses,
as a film-forming lubricant, or as additives or compositions used
in wire drawing, aluminum rolling, and ferrous rolling.
[0169] Still other embodiments for use of some of these
compositions are as anti-microbials to prevent the formation of
biofilms on various surfaces. Other embodiments include use as
additives to coating fluids. In still another use, the compositions
can be used in Yankee dryer coatings in the manufacture of tissue
and toweling. In still other embodiment, the additional components
are those necessary to employ the composition in a pigment-based
fluid, e.g., paints. In still other embodiment, the additional
components are those necessary to employ the composition as a
lubricant. In still other embodiment, the additional components are
those necessary to employ the composition in protective fluids for
application to porous and non-porous surfaces, e.g., e.g., metal,
plastic, polyurethane, and on fibrous substrates, e.g., paper,
wood, cardboard, wallpaper, insulation, carpeting, ceiling tiles,
textiles, wallboard and fabric, such as cotton, to discourage
microbial degradation of biofilm thereon. As one example, the
compositions may be useful in coatings that prevent microbially
induced corrosion in sprinkler pipes or other metal piping.
[0170] In another embodiment of compositions and uses, the
advantage of the polyamidopolyamine-containing composition is that
it has creping properties that are useful in adhesives (see e.g.,
U.S. Pat. No. 5,633,309 and 5,602,209). In another embodiment, the
compositions are useful to provide mold-resistance to cellulose
surfaces, such as paper, wood, wall board, ceiling tiles, and to
wood preservatives. The compositions also provide microbial
resistance to cotton fibers. Still further uses include
formulations with chitosan, a natural polymer, to protect surfaces
and fibers. As one example, nylon or similar type fibers may be
prepared with these compositions to provide built-in microbial
resistance. Still other uses of these compositions and compounds
may be determined by one of skill in the art considering the
teachings of this specification.
[0171] Thus other additional components of the final use
compositions comprising the polyamidopolyamines and/or
non-polymeric amidoamines described herein include one or any
combination of additional agents, including but not limited to,
coalescing/drying agent, rheology modifier, ester, carboxylic acid,
fatty acid, emulsifier, amine, thickener, lubricant, dispersant,
antioxidant, alkaline compound, builder, solvent, amphipathic
agent, carrier, preservative, buffer, metal deactivator, dye,
fragrance, caustic agent, wetting agent, sequestering agent,
fungicide, defoamer, antioxidant, die release fluid, antiwear
agent, viscosity modifier, de-emulsifier, natural triglyceride,
animal fat, vegetable oil, fatty acid ester, and/or a phosphate
ester. Still other optional components may be included in the
concentrate and/or composition and may be selected by those skilled
in the art. These additional components include, but are not
limited to, salts, buffers, pH adjustors, enzymes, surfactants,
tackifying agents, scale inhibitors, catalysts, clay control
agents, friction reducers, corrosion inhibitors, dispersants,
flocculants, H.sub.2S scavengers, CO.sub.2 scavengers, oxygen
scavengers, lubricants, gelling agent, crosslinking agent, wetting
agents, relative permeability modifiers, resins, adhesives, and
coating enhancement agents.
[0172] Still other additional components for admixture with the
compositions comprising the polyamidopolyamines and/or
non-polymeric amidoamines described herein are additional biocides
or antimicrobials, e.g., the biocides described in U.S. Pat. Nos.
5,332,430 and 8,276,663, which are incorporated by reference
herein. The compositions described herein with the
hydroxyl-containing diluent generally contains about 1% to about
10% w/w of an antimicrobial composition, i.e., 1, 2, 3, 4, 5, 6, 7,
8, 9, or 10% w/w or numbers therebetween of the antimicrobial
polyamidopolyamine or the same weight percent in combination with
another known antimicrobial. In one embodiment, the antimicrobial
composition contains about 3 to about 7% w/w total antimicrobial
compound (i.e., the polyamidopolyamine only or with an additional
biocide).
[0173] In still other embodiments, the compositions containing the
polyamidopolyamines and/or non-polymeric amidoamines also contain a
natural biopolymer. In one embodiment, the natural biopolymer is a
high molecular weight polyamide. In another embodiment, the natural
biopolymer is a chitosan. As one example the composition may be
used to protect a polyurethane surface when the composition
contains the polyamidopolyamine described herein and chitosan. Such
a composition may be applied directly to the surface and allowed to
dry. Furthermore, the polyamidopolyamines and non-polymeric
amidoamines (reactions with monobasic acids) can be neutralized
with fugitive acids, such as acetic acid. Compositions containing
these reaction products can be applied in water and remain as a
coating when the acetic acid and water evaporate.
[0174] Still other compositions employing the polyamidopolyamine
and/or non-polymeric amidoamines compounds and compositions
described herein may be prepared by one of skill in the art
applying the teachings of this specification.
[0175] Methods of Use of These Compositions
[0176] Various methods of heat treating metal substrates are known
and include heating a metal substrate to an elevated temperature
and then cooling. The cooling step, which is known in the art as
"quenching", typically is performed rapidly and is accomplished by
either immersion quenching or spray quenching. Immersion quenching
involves immersing the hot metal substrate in a liquid quenching
medium, i.e. a quenching bath. Spray quenching involves spraying
quenchant on the heated metal part as it travels through a quench
barrel or quench ring. The process of quenching involves the use of
certain hydraulic equipment, which requires hydraulic fluids for
performance. These quenching systems typically use large amounts of
both aqueous quenchant and hydraulic fluid. The amount of quenchant
used can be sizable depending upon the size of the metal product
that is being quenched.
[0177] Thus the polyamidopolyamine and non-polymeric amidoamines
compositions described herein can also be used in compatible
fluids, e.g. hydraulic fluids. Such compatibility is important in
circumstances in which these fluids contaminate each other during
use.
[0178] In one embodiment, a process for increasing the efficiency
of a metal quenching bath comprises the following steps, including
providing in a container or quenching tank a metal quenching bath
comprising a polyamidopolyamine and/or non-polymeric amidoamine as
described herein. Generally, metal or metal substrates enter the
quenching bath at temperatures as high as 1600.degree. C. While the
bath is being used for quenching, the bath temperature is kept
about 100.degree. F. and 120.degree. F. (i.e., 37.7.degree. C. and
48.9.degree. C.) to keep the quenching fluid at its desired
quenching temperature.
[0179] In one embodiment, a process for increasing the efficiency
of a metal spray quenching, comprises the following steps,
including spraying a metal substrate with a quenching fluid
containing a polyamidopolyamine and/or non-polymeric amidoamine as
described herein. Generally, metal or metal substrates enter the
quenching ring or quench barrel at temperatures as high as
1600.degree. C. While the spray is being used for quenching, the
spray temperature is kept between about 100.degree. F. and
120.degree. F. (i.e., 37.7.degree. C. and 48.9.degree. C.) to keep
the quenching fluid at its desired quenching temperature.
[0180] The processes of the present invention are performed using
conventional metal quenching bath equipment or quenching spray
equipment. One of skill in the art would readily be able to select
suitable quenching equipment for use in quenching the selected
metal, taking into consideration the teachings of this
specification.
[0181] When used in a quenching composition, it is anticipated that
the compositions comprising the polyamidopolyamines will be used at
a concentration of between about 10 to about 30% by weight of the
resulting use composition, and can replace or work in tandem with
another quenchant, while also replacing one or more typical
quenching additives for lubricity, bio resistance and/or foam
control. Compositions containing non-polymeric amidoamines are
anticipated to work with the polyamidopolyamines in this context,
or as additives to other known quenchant formulations. See, for
example, U.S. Pat. Nos. 8,764,914; 4,486,246; 4,528,044; 4,381,205;
and 4,404,044 which describe some examples of known quenching
fluids.
[0182] In another aspect, a method of altering surface behavior of
a liquid is provided. Foam, pockets of air that are entrapped in a
liquid, is often present in coolants and processing liquids and
causes problems. Foam can negatively influence the cooling
efficiency or lubrication properties of the metalworking fluid and
limits the visual inspection of the working process. Further
problems include reduction of pump efficiency; reduced capacity of
pumps and storage tanks; bacterial growth; dirt flotation/deposit
formation; reduced effectiveness of the fluid; and downtime to
clean tanks. In one embodiment, the liquid is an aqueous quenching
medium. In one embodiment, the method includes adding to the liquid
the polyamidopolyamine and/or non-polymeric amidoamine compound
described above. The present invention includes the use of the
polyamidopolyamine and/or non-polymeric amidoamine for altering
surface behavior, e.g., for use as an anti-foam, defoam or
low-foaming agent and/or a deaeration agent. In one embodiment,
polyamidopolyamine and/or non-polymeric amidoamine is added to an
aqueous quenching medium as an anti-foam agent. The
polyamidopolyamine and/or non-polymeric amidoamine compound
described herein can be used alone as an antifoam or low foam
component in the compositions or in conjunction with another
antifoam agent.
[0183] In another aspect, a method of providing antimicrobial or
bioresistant properties to a metalworking fluid is provided. In one
embodiment, the method includes adding a described
polyamidopolyamine to the metalworking fluid. In another
embodiment, the method includes adding a non-polymeric amidoamine
to the metalworking fluid. In another embodiment, a mixture of
these compounds can be added for enhance bioresistance in a
quenching fluid. In one embodiment, the metalworking fluid is an
aqueous quenchant. If left untreated, dangerous microorganisms are
inevitable in aqueous metalworking fluids due to the water content,
elevated temperatures, and contaminants. Good maintenance of
metalworking fluid re-circulation systems can extend the lifetime
of coolants and ensure the quality of the tools produced. In
metalworking fluids, as in the other water-based environments,
microorganisms usually live in the form of biofilms, the
communities of bacteria and fungi attached to the surface of sumps,
metal parts and also to each other. Biofilms exhibit very high
resistance to biocides.
[0184] In one embodiment a described polyamidopolyamine can be used
alone as an antimicrobial or bioresistant or in conjunction with
one or more antimicrobial or bioresistant agents in a heat
treating, e.g., quenching composition. In another embodiment, a
described non-polymeric amidoamine can be used alone as a
antimicrobial or bioresistant or in conjunction with one or more
antimicrobial or bioresistant agents in these compositions.
Non-polymeric amidoamine and polyamidopolyamine can be used
together or in conjunction with one or more antimicrobial or
bioresistant agents. In addition, polyamidopolyamine and/or
non-polymeric amidoamine may also be used in conjunction with other
anti-microbial techniques, such as the use of uv light or
ozonation.
[0185] When employed as an additive to other known heat treating
compositions, e.g., quenchants, it is anticipated that the present
polyamidopolyamine and/or non-polymeric amidoamine -containing
compositions will replace multiple components currently in use. In
one embodiment, a composition described herein can be used
simultaneously for its characteristics as both a lubricant and a
defoamer, thereby replacing two components with a single component.
Similarly, a composition described herein which has bioresistance
or antimicrobial characteristics, as well as defoaming and/or
lubricity characteristics may replace three other components in a
suitable composition.
[0186] In general, when use as a defoamer, the polyamidopolyamines
and/or non-polymeric amidoamines and/or compositions containing
them can desirably replace silicone defoamers. It is anticipated
that as a defoamer additive, the compositions or the compounds
isolated therefrom may be use at a concentration of between about
0.1 to 0.5% by weight of the resulting use composition, e.g., metal
working fluid. This range includes fractional numbers and the
endpoints of the range, e.g., the present polyamidopolyamine and/or
non-polymeric amidoamine--containing compositions can be added at
e.g., 0.1, 0.2, 0.3, 0.4 and 0.5% by weight of the resulting use
composition.
[0187] When used primarily as an additive for its
anti-microbial/bioresistant characteristics, it is anticipated that
the compositions comprising the polyamidopolyamines and/or
non-polymeric amidoamines will be used at a concentration of
between about 1 to about 3% by weight of the resulting use
composition, e.g., a paint or polyurethane coating fluid. This
range includes fractional numbers and the endpoints of the range,
e.g., the present polyamidopolyamine compositions can be added at
e.g., 1.0, 1.3, 1.5, 1.7, 2.0, 2.2, 2.4, 2.6, 2.7, and 3.0% by
weight of the resulting use composition. Most desirably, the
compositions can be used as a formaldehyde-free anti-microbial.
[0188] When used primarily as an additive for its lubricant
characteristics and optionally its bioresistant/antimicrobial
characteristics, it is anticipated that the compositions comprising
the polyamidopolyamines and/or non-polymeric amidoamines will be
used at a concentration of between about 5 to about 30% by weight
of the resulting use composition, e.g., a lubricating fluid that
does not degrade in the presence of a microorganism. This range
includes fractional numbers and the endpoints of the range, e.g.,
the present polyamidopolyamine compositions can be added at e.g.,
5.0, 5.5, 6.0, 6.5, 7.0, 8.0, 9.0, 10, 11, 12, 13, 14, 15, 16, 17,
18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 and 30% by weight of
the resulting use composition.
[0189] Methods for quenching a metal comprise immersing or spraying
a heated metal with any of the quenching compositions disclosed
herein including any of the specific embodiments described in this
specification. Use of the multi-functional polyamidopolyamine
and/or non-polymeric amidoamines to replace multiple other
components of a quenching fluid reduces the quenching costs for the
customer, and produces less waste.
Embodiments
[0190] In addition to the embodiments described above, in the
examples and in the claims, other embodiments described herein
include the following:
[0191] In one embodiment, a composition comprises a
polyamidopolyamine produced by the reaction of a polybasic acid and
primary polyamine, which is linear, cyclic, branched or
cross-linked, said polyamidopolyamine having a molecular weight of
about 500 to about 100,000 and having one or more repeating pendant
amino groups, wherein said polyamidopolyamine is of the Formula A
wherein each polybasic acid is a dimer acid; each primary polyamine
is independently a diamine, a triamine, or a tetraamine or an amine
comprising 5 or more free amino groups; a and a' are independently
1 or 2; b is 0, 1 or 2; and r is a number between 2 to about 10,
including both endpoints of the range. In another embodiment, this
composition is formed by the reaction having a 2:1 mole ratio of
polyamine to dimer acid.
[0192] In another embodiment, the composition further comprises a
polyamidopolyamine of the Formula A', wherein a is 1, 2, 3, or 4,
and said reaction has a 1:1 molar ratio of polyamine to dimer
acid.
[0193] In another embodiment, the composition further comprises a
polyamidopolyamine of the the Formula B, wherein each polybasic
acid is a trimer acid; each primary polyamine is independently a
diamine, a triamine, or a tetraamine or an amine comprising 5 or
more free amino groups; a, c, d and e are independently 1 or 2; b
is 0, 1 or 2; and r is a number between 3 to about 10, including
both endpoints of the range.
[0194] In another embodiment, the composition further comprises a
polyamidopolyamine of the Formula C, wherein each polybasic acid is
a tetrabasic acid; each primary polyamine is independently a
diamine, a triamine, or a tetraamine or an amine comprising 5 or
more free amino groups; a, c, d, and e are independently 1 or 2; b
is 0, 1 or 2; and r is a number between 4 to 10, including both
endpoints of the range.
[0195] In still another embodiment, any one of these compositions
described herein further comprises an organic hydroxyl containing
diluent. In still another embodiment, any one of these compositions
described herein further comprises water as a diluent. In still
another embodiment, any one of these compositions described herein
further comprises a water soluble acid to increase the solubility
of the polyamidopolyamine and non-polymeric amidoamine in
water.
[0196] In still another embodiment, any one of these compositions
described herein is water-soluble or water dispersible. In still
another embodiment, any one of these compositions described herein
has a cloud point of about 25.degree. C. to about 82.degree. C., or
of about 77.degree. F. to about 180.degree. F., in water. In still
another embodiment, any one of these compositions described herein
is characterized by one of more of the characteristics of
low-foaming, non-foaming, or defoaming properties and/or
antimicrobial or bioresistant properties and/or lubricating
properties. In still another embodiment, any one of these
compositions described herein has a pH of about 8 to about 11.
[0197] Use compositions containing any of the polyamidopolyamine
composition and other optional components can be a metal working
fluid, an aqueous quenchant fluid, a cleaning fluid, a hydraulic
fluid, a protective coating fluid, a lubricant, a pigment-based
fluid, or a protective coating for fibrous or metal surfaces. Other
use compositions can comprise the above described compositions and
an antimicrobial composition or a fungicide.
[0198] In still another specific embodiment, a method for preparing
a composition such as described herein that comprises a
polyamidopolyamine having a molecular weight of about 500 to about
100,000 and comprising a primary amino group involves condensing a
polyamine comprising a primary amino group, and a C.sub.3 to
C.sub.16 polybasic acid or derivative thereof, optionally in the
presence of an organic hydroxyl-containing diluent.
[0199] In still another specific embodiment, a method for preparing
a composition such as described herein that comprises a
polyamidopolyamine having a molecular weight of about 500 to about
100,000 and comprising a primary amino group involves condensing a
polyamine comprising three primary amino groups, and a C.sub.3 to
C.sub.16 polybasic acid or derivative thereof, optionally in the
presence of an organic hydroxyl-containing diluent.
[0200] In still another specific embodiment, a method for preparing
a composition such as described herein that comprises a
polyamidopolyamine having a molecular weight of about 500 to about
100,000 and comprising a primary amino group involves condensing a
two polyamines comprising three amino groups and a C.sub.3 to
C.sub.16 polybasic acid or derivative thereof.
[0201] In still another specific embodiment, a method for preparing
a composition such as described herein that comprises a
polyamidopolyamine having a molecular weight of about 500 to about
100,000 and comprising a primary amino group involves condensing a
a polyamine comprising three amino groups and two C.sub.3 to
C.sub.16 polybasic acids or derivative thereof.
[0202] In still another specific embodiment, a method for preparing
a composition such as described herein that comprises a
polyamidopolyamine having a molecular weight of about 500 to about
100,000 and comprising a primary amino group involves condensing a
a polyamine comprising three amino groups, a polyamine comprising
two amino groups, and a C.sub.3 to C.sub.16 polybasic acid or
derivative thereof.
[0203] In still another specific embodiment, a method for preparing
a composition such as described herein that comprises a
polyamidopolyamine (a) reacting a polybasic acid with a polyamine
and an optional hydroxyl-containing solvent to produce a first
polyamidopolyamine as a reaction product; (b) reacting the product
(a) with the same or different a polybasic acid and an optional
hydroxyl-containing solvent to produce another polyamidopolyamine
as a subsequent reaction product; (c) performing additional
sequential condensation reactions by reacting the
polyamidopolyamine reaction product of each preceding condensation
reaction with the same or different polybasic acid and an optional
hydroxyl-containing solvent, and (d) terminating the reaction
sequence when the composition demonstrates a desired characteristic
selected from anti-foaming, defoaming, lubricity, bioresistance,
antimicrobial activity or any combination thereof. The resulting
composition comprises a polyamidopolyamine, which is a linear,
cyclic, branched or cross-linked amide comprising multiple primary
amine groups.
[0204] In still another specific embodiment, these various methods
for generating the compositions described herein optionally include
a step for further terminating additional free amino groups to
amide acids or salts with cyclic anhydride to cap amino groups at a
temperature below the condensation reaction temperature.
[0205] In still another specific embodiment, these various methods
for generating the compositions described herein optionally include
adding an organic hydroxyl-containing diluent or solvent at the
initiation of the reaction.
[0206] In still another specific embodiment, these various methods
for generating the compositions described herein optionally include
adding water or an organic hydroxyl-containing diluent or solvent
at the end of the reaction to adjust viscosity of the
composition.
[0207] In still another specific embodiment, these various methods
for generating the compositions described herein optionally include
the use of a polybasic acid comprising two C(O)OH.
[0208] In still another specific embodiment, these various methods
for generating the compositions described herein optionally include
use of the same polyamines or different polyamines in each
condensation step.
[0209] In still another specific embodiment, these various methods
for generating the compositions described herein optionally include
having a mole ratio of polybasic acid to polyamine that is equal to
or greater than about 1: (1.times.), wherein X is the number of
C(O)OH groups in the polybasic acid.
[0210] In still another specific embodiment, these various methods
for generating the compositions described herein optionally include
having a mole ratio of the polybasic acid to the polyamine is about
is about 1:1, with an optional organic hydroxyl-containing
solvent.
[0211] In still another specific embodiment, these various methods
for generating the compositions described herein use as the
polyamine triaminononane or 4-aminomethyl-1,8-octanediamine.
[0212] In still another specific embodiment, these various methods
for generating the compositions described herein use a polyamine of
the formula (wherein R.sup.1, R.sup.3 and R.sup.5 are independently
H, methyl, ethyl, propyl or butyl; R.sup.2, R.sup.4 and R.sup.6 are
independently methyl, ethyl, propyl, or butyl; and a, b and c are
additively a number between 0 to about 90, including both endpoints
of the range):
##STR00025##
[0213] In still another specific embodiment, these various methods
for generating the compositions described herein use a polyamine of
the formula (wherein s, t and u are additively a number between 3
to about 90, including both endpoints of the range):
##STR00026##
[0214] In still another specific embodiment, these various methods
for generating the compositions described herein use a polyamine of
the formula (wherein R.sup.1 is H, methyl, ethyl, propyl or butyl;
R.sup.2, R.sup.3, and R.sup.4 are, independently, methyl, ethyl,
propyl, or butyl; and e and f are additively a number between 0 to
about 90, including both endpoints):
##STR00027##
[0215] In still another specific embodiment, these various methods
for generating the compositions described herein use a polyamine of
the formula
NH.sub.2CH(CH.sub.3)CH.sub.2--(O--CH.sub.2CH.sub.2).sub.g--(O--CH.sub.2C-
H(CH.sub.3)).sub.h--(O--CH.sub.2CH(CH.sub.3))--NH.sub.2
wherein g and h are additively a number between 0 to about 90,
including both endpoints of the range.
[0216] In still another specific embodiment, these various methods
for generating the compositions described herein use a polyamine of
the formula (wherein R.sup.1, R.sup.3, R.sup.5 and R.sup.7 are
independently H, methyl, ethyl, propyl or butyl; R.sup.2, R.sup.4,
R.sup.6 and R.sup.8 are independently is methyl, ethyl, propyl, or
butyl; and w, j, k and m are additively a number between 0 to about
90, including both endpoints of the range):
##STR00028##
[0217] In still another specific embodiment, these various methods
for generating the compositions described herein use a polyamine of
the formula (wherein h, n, o and p are additively a number between
4 to about 90, including both endpoints of the range):
##STR00029##
[0218] In still another specific embodiment, these various methods
for generating the compositions described herein use a polyamine of
the formula (wherein R.sup.1, R.sup.3, and R.sup.5 are
independently H, methyl, ethyl, propyl or butyl; R.sup.2, R.sup.4,
and R.sup.6 are independently methyl, ethyl, propyl, or butyl; and
a', b' and c' are additively a number between 0 to 90, including
both endpoints of the range):
##STR00030##
[0219] In still another specific embodiment, these various methods
for generating the compositions described herein use a polyamine of
the formula ((wherein e', f' and g' are additively a number between
3 to 90 including both endpoints):
##STR00031##
[0220] In still another specific embodiment, a composition as
described herein comprises a non-polymeric amidoamine, which is a
linear or branched amide containing a primary amine group, said
non-polymeric amidoamine having a molecular weight of about 290 to
about 5000. In one embodiment, such a composition is produced by
the reaction of a monobasic acid and a primary amine. In one
embodiment, one such composition further comprises an amide
comprising a diamide, a triamide or a tetraamide, or a mixture
thereof.
[0221] In another embodiment, one such composition further
comprises a non-polymeric amidoamine, which is a linear or branched
amide containing a primary amine group, said non-polymeric
amidoamine having a molecular weight of about 290 to about
5000.
[0222] Another specific embodiment of various compositions
described herein contain a non-polymeric amidoamine of Formula F,
wherein x, y, and z are, are additively a number between 3 to about
90, including both endpoints of the range; and R.sup.1 is C.sub.1
to C.sub.11 alkyl or C.sub.1 to C.sub.11 substituted alkyl.
[0223] Another specific embodiment of various compositions
described herein contain a non-polymeric amidoamine of Formula G,
wherein x, y, and z are, additively a number between 3 to about 90,
including both endpoints of the range; and R.sup.1 and R.sup.2 are,
independently, C.sub.1 to C.sub.11 alkyl or C.sub.1 to C.sub.11
substituted alkyl.
[0224] Another specific embodiment of various compositions
described herein are those compositions produced by a condensation
reaction wherein the reactants comprise an acid and a polyamine,
wherein the acid is a polybasic acid, a monobasic acid, or both a
polybasic acid and a monobasic acid, in the optional presence of an
organic hydroxyl-containing diluent.
[0225] The following examples are illustrative only and are not
intended to limit the present invention.
EXAMPLE 1
Antimicrobial Activity of Polyamidopolyamine Composition
3533-171
[0226] The results of this experiment are shown in FIG. 1.
[0227] A polyamidopolyamine composition of Formula A, referred to
as 3533-171, was produced by a condensation reaction of 2 moles of
the Jeffamine.RTM. T403 polyetheramine (Huntsman Corporation)
polyamine and 1 mole of adipic acid. The T403 amine is a
trifunctional primary amine having an average molecular weight of
approximately 440 with its amine groups located on secondary carbon
atoms at the ends of aliphatic polyether chains.
[0228] The reaction was conducted at 160-165.degree. C., with water
as a diluent added at the end of the reaction. The final
composition contained greater than about 73% of the
polyamidopolyamine, up to 15% by weight of free T-403 polyamine and
about 12.8% water. The composition has a cloud point (inverse
solubility) at about 31.degree. C. (88.degree. F.).
[0229] The composition was diluted to 0.75% in water and was
measured for the time in seconds that foam collapses to zero foam.
The decay was less than 15 seconds. The
polyamidopolyamine-containing composition 3533-171 was evaluated
for anti-microbial ability in the following assay. The pH for the
composition was adjusted to approximately 9.3. The composition
0.75% by weight diluted polyamidopolyamine composition 3533-171
contained 0.54% by weight polyamidopolyamine and 0.011% by weight
T403 polyamine. This composition was added to deionized water that
initially contained about 6 million Colony Forming Units (CFU)/ml
of a mixed culture of bacterial species originally cultured from
metal-working fluids. Bacterial growth measured was assessed over
time of exposure to the compositions from 0 to 120 minutes,
generating the graph of FIG. 1.
[0230] The graphical results indicate that the
polyamidopolyamine-containing composition (3533-171) has a fast
bacterial growth inhibition rate, i.e., marked anti-microbial
activity.
EXAMPLE 2
Antimicrobial Activity of Polyamidopolyamine Composition
3587-17
[0231] The results of this experiment are shown in FIG. 2.
[0232] A polyamidopolyamine composition of Formula A, referred to
as 3587-17, was produced by a condensation reaction of 2 moles of
T403 polyamine (Huntsman) with 1 mole of azelaic acid, with
triethanolamine (TEA) as a solvent. The reaction was conducted at
160-165.degree. C. The final composition contained about 46% by
weight of the polyamidopolyamine, up to 9.4% by weight of free
T-403 polyamine and about 45% by weight triethanolamine. The
composition has a cloud point (inverse solubility) at about
24.degree. C. (75.degree. F.).
[0233] The composition 3587-17, diluted to 0.75% in water was
measured for the time in seconds that foam collapses to zero foam.
The decay was less than 15 seconds.
[0234] The polyamidopolyamine-containing composition 3587-17 was
evaluated for anti-microbial ability in the following assay. The pH
for the composition was adjusted to approximately 9.3. The
composition 3587-17 at 0.75% by weight polyamidopolyamine contains
0.34% by weight polyamidopolyamine, 0.07% by weight free T403
polyamine, and 0.34% by weight TEA.
[0235] This composition was added to deionized water that initially
contained about 4.5 million CFU/ml of a mixed culture of bacterial
species originally cultured from metal-working fluids. Bacterial
growth was assessed over time of exposure to the compositions from
0 to 120 minutes, generating the graph of FIG. 2.
[0236] The graphical results of FIG. 2 indicate that the
polyamidopolyamine-containing composition 3587-17 shows marked
anti-microbial activity.
EXAMPLE 3
Antimicrobial Activity of Polyamidopolyamine Composition 3581-5
[0237] The results of this experiment are shown in FIG. 3.
[0238] A polyamidopolyamine-containing composition of Formula A,
referred to as 3581-5, was produced by a condensation reaction of 2
moles of T403 polyamine (Huntsman) with 1 mole of adipic acid, with
TEA as a solvent. The reaction was conducted at 160-165.degree. C.
The final composition contained about 44.6% by weight of the
polyamidopolyamine, up to 9.1% by weight of free T-403 polyamine
and about 46.3% by weight TEA. The composition has a cloud point
(inverse solubility) at about 50.degree. C. (122.degree. F.).
[0239] The composition 3581-5, diluted to 0.75% by weight in water,
was measured for the time in seconds that foam collapses to zero
foam, which was 60 sec.
[0240] The polyamidopolyamine-containing composition 3581-5 was
evaluated for anti-microbial ability in the following assay. The pH
for the compositions was adjusted to approximately 9.3. The 3581-5
polyamidopolyamine-containing composition at 0.75% by weight
contained 0.334% by weight of the polyamidopolyamine, 0.07% by
weight free T403 polyamine, and 0.35% by weight TEA).
[0241] This composition was added to deionized water that initially
contained about 1.8 million CFU/ml of a mixed culture of bacterial
species originally cultured from metal-working fluids. Bacterial
growth was assessed over time of exposure to the composition from 0
to 120 minutes, generating the graph of FIG. 3.
[0242] The graphical results of FIG. 3 indicate that the
polyamidopolyamine-containing composition (3581-5) shows marked
anti-microbial activity.
EXAMPLE 4
Lubrication Activity
[0243] The results of this experiment are shown in FIG. 4.
[0244] The three polyamidopolyamine-containing compositions
described in Examples 1-3 above were compared for lubrication
ability with a commercial synthetic lubricant HOCUT.RTM. 767
(Houghton International Inc.) commonly used as a metal removal
fluid. The HOCUT.RTM. 767 fluid was used as a 5% dilution in water,
which equals about 0.75% active ingredients. All dilutions
indicated are in deionized water.
[0245] The data was reported using the Falex Extreme Pressure test,
as follows: This test uses a Falex pin and vee block machine to
test the extreme pressure properties of lubricants. The pin is
Falex #8 (AISI 3135 steel, rb 87-91, 10 rms maximum) and the vee
blocks are the standard 1137 steel, Rc 2-24, 10 rms maximum,
96.degree. block angle. The vee blocks are fitted into arms that
can be closed by a ratchet wheel, putting increasing load on the
pin that is rotating at 290 rpm. Gauges allow measurement of load,
torque, and temperature. Once assembled, 70 ml of sample is poured
into the cup, which immerses the test pieces. After a break-in for
one minute at 250 pounds load, the load is increase 250 pounds at t
time and held at that load for 30 seconds. Maximum Load for this
test is 4500 pounds. Failure can occur by either of two modes:
seizure between pin and blocks causing breakage of either the brass
shear pin or steel pin; or wear is so high that at least 250 pounds
of load are lost in 30 seconds or less.
[0246] FIG. 4 and Table 1 show the lubrication data reported as
torque vs. load in pounds. Hocut 767 lubricant is used at 5% by
weight dilution. Polyamidopolyamine-containing composition 3533-171
is used at 0.75% by weight dilution. Composition 3587-17 is used at
1.38% by weight dilution. Composition 3581-5 is used at 0.75% by
weight dilution. All dilutions are in ionized water. The lower the
torque and higher the load, the better the composition operates as
a lubricant. As shown in these preliminary evaluations of FIG. 4,
all of the polyamidopolyamine-containing compositions were
comparable in lubrication with the synthetic fluid.
TABLE-US-00001 TABLE 1 LUBRICATION DATA Load/lbs. Torque applied to
pin/ Composition Composition Composition HOCUT Using Falex 3533-171
3587-17 3581-5 767 Fluid 250 28 15 25 25 500 36 23 32 28 750 40 30
35 30 1000 43 30 37 32 1250 45 35 47 34 1500 46 37 47 38 1750 48 38
52 40 2000 57 46 55 45 2250 60 51 60 48 2500 60 61 50 2750 60 61 55
3000 67 60 68 3250 69 62 80 3500 68 70 84 3750 69 67 90 4000 65 65
4250 70 4500 71
EXAMPLE 5
Defoaming, Low Foaming and Deaeration Characteristics of
Polyamidopolyamines
[0247] The product referred to as Houghto-Clean 3181 is a high
foaming cleaner used in spray wash applications. Houghto-Clean 8131
spray cleaner was modified by replacing a chlorine capped defoaming
surfactant (4%) with the polyamidopolyamine 3533-171. A second
formulation was prepared using the polyamidopolyamine 3587-17. The
results using a (a) Waring Blender Test and (b) a High Pressure
Foam Test Simulator are provided.
[0248] A polyamidopolyamine composition referred to as 3533-171,
was produced by a condensation reaction of 2 moles of the
Jeffamine.RTM. T403 polyetheramine (Huntsman Corporation) polyamine
and 1 mole of adipic acid. Water (12.8%) was added at the end of
the reaction to reduce viscosity.
[0249] 3587-17 is the condensation reaction of 2 moles of the
Jeffamine.RTM. T403 polyetheramine (Huntsman Corporation) polyamine
and 1 mole of azelaic acid. The reaction was run in 45%
triethanolamine (TEA) that was not removed.
[0250] Waring Blender Shear Test
[0251] The Waring blender test was conducted at 3% v/v dilution.
200 mL of solution was placed in the blender. The blender was
operated for 30 seconds. Solution was poured into 500 mL graduated
cylinders. Foam volume and break time were noted.
[0252] Foam Test Results are displayed in Table 2.
TABLE-US-00002 Houghto- Houghto- Houghto- Clean .TM. 8131 Clean
.TM. 8131 Clean .TM. 8131 original with 3533-171 with 3587-17 Foam
Vol (mL) 175 0 0 Foam Break Time >5 minutes NA NA
[0253] No foam was observed for the two modified formulas.
[0254] Houghto-Clean.TM. 8131 product modified with 3522-171 or
3587-17 foams significantly less than the original formula in a
Waring blender foam test.
[0255] High Pressure Foam Tests
[0256] The purpose of these experiments is to determine if 3533-171
will reduce foaming. Dilutions of each fluid to be tested were
prepared at 3% v/v using RO water. Following the procedure
described below, the solutions were tested at low pressure, then at
high pressure twice.
[0257] Temperature was monitored between foam tests. The high
pressure foam test simulator procedure involves: Filling system by
pouring 1500 mL of fluid into spray chamber. Fluid will flow
through and collect in the graduated cylinder below the fill
chamber. Then the pump is turned on and the pressure set to
approximately 80 psi. The pump is run for 30 seconds, and then foam
and foam break time are recorded. When the sample is clear and no
foam remains, the pump is turned on and pressure set to
approximately 500 psi. Pump is run for 30 seconds. Foam and foam
break time are measured. Test is repeated as necessary.
[0258] The results show that the temperature of the solutions
increased slightly throughout testing, with 3.4.degree. being the
change in temperature between initial and final foam test. This
temperature change is not likely to affect foaming or foam break
times.
[0259] In general, the foam height increased when a given solution
was subjected to a higher pressure. Houghto-Clean.TM. 8131 product
(original) foams more than the modified versions. However, cleaner
samples modified with 3533-171or 3587-17 displayed less foam
overall in comparison to the original Houghto-Clean.TM. 8131
sample. The sample of original Houghto-Clean.TM. 8131 product had
the longest foam and entrained air break times. The cleaner
modified with 3533-171 had the shortest foam and entrained air
break times. For the sample modified with 3587-17, foam and
entrained air break times were similar.
TABLE-US-00003 TABLE 3 Comparison data for high pressure foam
tests. Houghto- Houghto- Houghto- Clean .TM. Clean .TM. Clean .TM.
Pressure Other Test 8131 8131 with 8131 with Conditions Conditions
original 3533-171 3587-17 Low (80 Temp initial (.degree. F.) 72.6
71.0 71.2 psi) Temp final (.degree. F.) 73.3 71.5 71.7 Foam Ht
initial (cm) 30.3 29.5 30 Foam Break (min) 12:00 6:00 7:00
Entrained Air Break 8:30 5:30 7:00 (min) High (500 Temp initial
(.degree. F.) 73.3 71.5 71.7 psi) Run 1 Temp final (.degree. F.)
74.4 72.6 72.9 Foam Ht initial (cm) 36.5 32.3 33 Foam Break (min)
46:00 4:00 6:00 Entrained Air Break 18:30 2:00 6:00 (min) High (500
Temp initial (.degree. F.) 74.4 72.6 72.9 psi) Run 2 Temp final
(.degree. F.) 74.5 73.9 74.6 Foam Ht initial (cm) 37 33.5 31.5 Foam
Break (min) 45:00 4:00 8:00 Entrained Air Break 24:00 2:00 8:00
(min)
EXAMPLE 6
Polyamidopolyamine and Characteristics
[0260] Polyamidopolyamine 3587-203 is a condensation reaction
product of Huntsman Jeffamine T-403 (5 moles) and adipic acid (4
moles). The polyamidopolyamine was evaluated by gel permeation
chromatography analysis (GPC) and/or characterized as a diacid
product by NMR and MALDI mass spectrometry.
[0261] Polyamidopolyamine 3587-185 is a condensation reaction
product of Huntsman Jeffamine T-403 (5 moles) and adipic acid (4
moles). The reaction was run in dipropylene glycol solvent, 50% of
the charge. The polyamidopolyamine was evaluated by gel permeation
chromatography analysis (GPC) and/or characterized as a diacid
product by NMR and MALDI mass spectrometry.
[0262] Polyamidopolyamine 3533-85 is a condensation reaction
product of Huntsman Jeffamine T-403 (2 moles) and adipic acid (1
moles). The polyamidopolyamine was characterized as a diacid
product by NMR and MALDI mass spectrometry.
[0263] The following Table 4 compares the characteristics of these
polyamidopolyamines:
TABLE-US-00004 TABLE 4 Semi-quantitation distribution Mole % Mole %
Mole % by MALDI-TOF 3587-203 3587-185.sup.1 3533-85 Unreacted T-403
43.9 64.6 51 Condensation Products One T-403 + one adipic 15.3 18.2
0 Two T403 + one adipic 18.4 13.8 29 Three T403 + two adipic 12.9
2.6 12 Four T403 + three adipic 9.5 0.8 5 Five T403 + four adipic
detected Mole Ratio: T403/adipic 5:4 5:4 2:1 Avg MW measured by GPC
6,240 -- 2,240 Avg MW measured by MALDI-TOF 858 577 1,220
.sup.1Reaction run in in dipropylene glycol
[0264] The GPC measurement according to Organization for Economic
Cooperation and Development Test 118 (OECD 118) appears more
accurate in determining molecular weight for these compositions.
The MALDI-TOF is semi-quantitative for product distribution.
[0265] Approximate calculated weight % of polyamidopolyamine and
unreacted Huntsman T403 from the condensation reactions: A MW of
440 daltons was used for Huntsman T403; GPC data was used to
determine the average MW of the polyamidopolyamines. Weight % were
calculated from the mole % determined from the same quantitative
MALDI-TOF analysis. Results are as shown in Table 5.
TABLE-US-00005 TABLE 5 Condensation reaction product: 3587-203
3533-85 Mole ratio T403/adipic 5/4 2/1 Avg MW of polyamidopolyamine
by GPC 6,240 2,240 Wt % unreacted T403 5.2 17 Wt % of
polyamidopolyamine 94.8 83
[0266] The GPC measurement according to Organization for Economic
Cooperation and Development Test 118 (OECD 118) appears more
accurate in determining molecular weight for these
compositions.
EXAMPLE 7
Bioresistant Characteristics
[0267] Procedure: The test was run separately for bacteria and
fungus. The bacteria inoculum was a mixed culture grown on Houghton
fluids. The fungus test was run with the species, Aspergillus
niger. Samples were continuously stirred at room temperature for
the duration of the test. All fluids were tested at 0.75% in DI
water with pH adjusted to 9.3. Bacteria and fungi were counted as
colony forming units/ml (CFU/ml).
[0268] Test Formulations:
[0269] 30A (amide rxn): 0.75% by wt 3587-167 in water with pH
adjusted to 9.3. 3587-167 is the condensation product using
Huntsman T403 and glycolic acid at a 1:1 mole ratio. It has no
cloud point.
[0270] 30B (amide rxn): 0.75% 3587-173 in water, adjusted to pH
9.3. 3587-173 is the condensation product using Huntsman T403 and
lactic acid at 1:1 mole ratio. It has a cloud point of 142.degree.
F. (61.degree. C.), which helps in defoaming.
[0271] Results: The results presented are for comparative analysis
only. Table 6 shows the results for bacteria. Tables 7 and 8 show
the results for fungus. Different bacteria and fungus species may
give different results. % FR means % fluid resistance.
TABLE-US-00006 TABLE 6 Bacteria Inoculation: CFU/ml CFU/ml % Fluid
CFU/ml % FR CFU/ml % FR Time since Inoculation: 0 min 6 min
Resistance 30 min 2 hr % FR Total Days: 0 0 0 0 30A 2 .times.
10.sup.6 1.8 .times. 10.sup.6 10.0 6.7 .times. 10.sup.5 66.5 3.4
.times. 10.sup.5 83.0 30B 2 .times. 10.sup.6 1.3 .times. 10.sup.6
35.0 3.9 .times. 10.sup.5 80.5 0 100.0
TABLE-US-00007 TABLE 7 Fungus (part 1) Inoculation: CFU/ml CFU/ml %
CFU/ml % FR Time since 0 min 2 hrs Fluid 4 hrs Inoculation:
Resistance Total Days: 0 0 % FR 0 30A 2.1 .times. 10.sup.5 1.5
.times. 10.sup.5 28.6 1.6 .times. 10.sup.6 23.8 30B 2.1 .times.
10.sup.5 1.0 .times. 10.sup.5 52.4 6.0 .times. 10.sup.4 71.4
TABLE-US-00008 TABLE 8 Fungus (part 2) Inoculation: CFU/ml % CFU/ml
% FR Time since 8 hrs Fluid 24 hrs Inoculation: Resistance Total
Days: 0 % FR 1 30A 3.0 .times. 10.sup.4 85.7 80 100.0 30B 3.0
.times. 10.sup.4 85.7 40 100.0
EXAMPLE 8
Quenching Metal Substrates Using Aqueous Quenching Media
[0272] Experiments are conducted to determine cooling times using
quenching compositions containing a polyamidopolyamine or
non-polymeric amidoamine as described herein. The IVF Quenchotest
(The Swedish Institute of Production Engineering Research) is
utilized and includes the IVF data acquisition/recording unit, test
probe, probe handle and furnace. The test probe (600 mm in length
and 12.5 mm diameter of the Inconel.RTM. 600 probe enclosing a type
K thermocouple --NiCr/NiAl-- with a diameter of 1.5 mm) complies
with the specification for testing quenchants as established by the
International Federation for the Heat Treatment of Materials
(IFHT). The furnace thermostat controls the power supplied to the
furnace through diode rectification and is operated without a
controlled atmosphere. The furnace temperature is adjusted to about
1625.degree. F. (885.degree. C.).
[0273] In each run, the metal substrate is heated to a temperature
of about 1571.degree. F. (855.degree. C.) to about 1600.degree. F.
(870.degree. C.) and then immersed in 1.0 kilograms of an aqueous
quenching media containing a polyamidopolyamine described above
which are maintained at a temperature of about 100.degree. F.
(40.degree. C.). Data acquisition begins when the test probe
temperature of the aqueous quenching medium reaches about
1562.degree. F. (849.degree. C.) and is acquired for about 60
seconds, i.e., until the temperature reached about 300.degree.
F.
[0274] After data collection, cooling curves are obtained using the
data collected using the various polyamidopolyamine mixtures.
Cooling times are determined from the cooling curves during which
the test specimens are cooled from 1562.degree. F. (849.degree. C.)
to less than 203.degree. F. (95.degree. C.).
[0275] Results are shown in FIGS. 5-9.
[0276] FIG. 5 is a cooling curve showing the comparison of
polyamidopolyamine reaction products with water and Aqua Quench 260
(AQ260). AQ 260 is a commercial product supplied by Houghton
International to slow down the quenching effect of water. Product
3587-193 is a polyamidopolyamine, the reaction of Huntsman
Jeffamine T403 (10 moles) with adipic acid (9 moles). The reaction
is performed in approximately 44% dipropylene glycol (DPG). The DPG
remains in the reaction mixture. Cloud point (1%) approximately
81.degree. Fahrenheit. The cooling curve measurements were made
using the IVF quenchometer. Table 9 shows the parameters of the
test leading to the curves of FIG. 5.
TABLE-US-00009 TABLE 9 13% 260 PROPERTY UNIT 1.IVF 3587-193.2.IVF
WATER.IVF Max cooling rate C./s 177.43 187.03 207.67 Temp at Max C.
663.89 624.54 619.47 Cooling Rate Temp at Start of C. 844.3 815.88
844.21 Boiling Temp at Start of C. 156.28 137.64 57.68 Convection
Cooling Rate at C./s 66.26 80.83 95.22 300 C. Time to 600.degree.
C. s 2.34 3.6 1.83 Time to 400.degree. C. s 3.83 4.91 2.93 Time to
200.degree. C. s 7.25 7.81 5.31 Theta 1 C. 844.36 815.19 843.97
Theta 2 C. 287.89 237.26 250.31 HP-IVF (oils) 2311.62 2565.11
3194.38 HP-IVF (polymers) 1339.89 1603.51 1874.86 OPERATION
PARAMETERS Product Type Various Medium Temp 26 Medium concentration
Various Agitation Rate (m/s) Moderate
[0277] FIG. 6 shows similar curves produced using product 3533-85-2
in the IVF method. 3533-85-2 is the product of a condensation
reaction of Huntsman Jeffamine T 403 (2 moles) with adipic acid (1
mole). Cloud point (0.75%), approximately 86.degree. F.; weight
average molecular weight, 2,240; determined by gel permeation
column chromatography (GPC). Table 10 shows the parameters of the
test leading to the curves of FIG. 6.
TABLE-US-00010 TABLE 10 13% 260 3533-85 PROPERTY UNIT 1.IVF 2.IVF
WATER.IVF Max cooling rate C./s 177.43 229.23 207.67 Temp at Max C.
663.89 585.34 619.47 Cooling Rate Temp at Start of C. 844.3 824.16
844.21 Boiling Temp at Start of C. 156.28 139.13 57.68 Convection
Cooling Rate at C./s 66.26 92.74 95.22 300 C. Time to 600.degree.
C. s 2.34 3.03 1.83 Time to 400.degree. C. s 3.83 4.06 2.93 Time to
200.degree. C. s 7.25 6.51 5.31 Theta 1 C. 844.36 823.02 843.97
Theta 2 C. 287.89 226.32 250.31 HP-IVF (oils) 2311.62 3097.66
3194.38 HP-IVF (polymers) 1339.89 1868.75 1874.86 OPERATION
PARAMETERS Product Type Various Medium Temp 26 Medium concentration
Various Agitation Rate (m/s) Moderate
[0278] FIG. 7 shows the curves produced by the same method using
product 3587-17-2 in the IVF method. 3587-17-2 is the product of a
condensation reaction of Huntsman Jeffamine T 403 (2 moles) with
azelaic acid. The reaction is run in 45% triethanolamine. The DPG
and TEA are used as solvents for the reaction and also form the
intermediate ester which is then converted to amido, releasing that
solvent. The triethanolamme remains in the reaction mixture. Cloud
point 0.75%, approximately 75.degree. F. Table 11 shows the
parameters of the test leading to the curves of FIG. 7.
TABLE-US-00011 TABLE 11 13% 260 3587-17 PROPERTY UNIT 1.IVF 2.IVF
WATER.IVF Max cooling rate C./s 177.43 206.23 207.67 Temp at Max C.
663.89 594.26 619.47 Cooling Rate Temp at Start of C. 844.3 800.57
844.21 Boiling Temp at Start of C. 156.28 150.25 57.68 Convection
Cooling Rate at C./s 66.26 86.43 95.22 300 C. Time to 600.degree.
C. s 2.34 3.94 1.83 Time to 400.degree. C. s 3.83 5.07 2.93 Time to
200.degree. C. s 7.25 7.81 5.31 Theta 1 C. 844.36 800.35 843.97
Theta 2 C. 287.89 222.32 250.31 HP-IVF (oils) 2311.62 2782.5
3194.38 HP-IVF (polymers) 1339.89 1724.5 1874.86 OPERATION
PARAMETERS Product Type Various Medium Temp 26 Medium concentration
Various Agitation Rate (m/s) Moderate
[0279] FIG. 8 shows the curves produced by using product 3587-203-2
in the IVF method. 3587-203-2 is a product of the condensation
reaction of Huntsman Jeffamine T 403 (5 moles) with adipic acid (4
moles). Cloud point was cloudy at ambient temperature and on
cooling becomes clear. The MW (average) by GPC is 6,240 daltons.
Table 12 shows the parameters of the test leading to the curves of
FIG. 8.
TABLE-US-00012 TABLE 12 13% 260 3587-203 PROPERTY UNIT 1.IVF 2.IVF
WATER.IVF Max cooling rate C./s 177.43 195.23 207.67 Temp at Max C.
663.89 600.15 619.47 Cooling Rate Temp at Start of C. 844.3 816.1
844.21 Boiling Temp at Start of C. 156.28 144.06 57.68 Convection
Cooling Rate at C./s 66.26 82.02 95.22 300 C. Time to 600.degree.
C. s 2.34 3.47 1.83 Time to 400.degree. C. s 3.83 4.69 2.93 Time to
200.degree. C. s 7.25 7.69 5.31 Theta 1 C. 844.36 814.56 843.97
Theta 2 C. 287.89 237.98 250.31 HP-IVF (oils) 2311.62 2677.11
3194.38 HP-IVF (polymers) 1339.89 1647.1 1874.86 OPERATION
PARAMETERS Product Type Various Medium Temp 26 Medium concentration
Various Agitation Rate (m/s) Moderate
[0280] FIG. 9 shows the curves produced by using product 3533-171-1
in the IVF method. 3533-171-1 is the product of the condensation
reaction of Huntsman Jeffamine T 403 (2 moles) with adipic acid (1
mole) with about 12% water added when the reaction is cooled below
90.degree. C. The water acts as a solvent to reduce the viscosity
of the neat product to make it more flowable. Cloud point, about
88.degree. Fahrenheit. Table 13 shows the parameters of the test
leading to the curves of FIG. 9.
TABLE-US-00013 TABLE 13 13% 260 3533-171 PROPERTY UNIT 1.IVF 1.IVF
WATER.IVF Max cooling rate C./s 177.43 215.84 207.67 Temp at Max C.
663.89 595.46 619.47 Cooling Rate Temp at Start of C. 844.3 834.04
844.21 Boiling Temp at Start of C. 156.28 143.43 57.68 Convection
Cooling Rate at C./s 66.26 90.94 95.22 300 C. Time to 600.degree.
C. s 2.34 2.7 1.83 Time to 400.degree. C. s 3.83 3.82 2.93 Time to
200.degree. C. s 7.25 6.38 5.31 Theta 1 C. 844.36 832.65 843.97
Theta 2 C. 287.89 238.26 250.31 HP-IVF (oils) 2311.62 2922.34
3194.38 HP-IVF (polymers) 1339.89 1795.53 1874.86 OPERATION
PARAMETERS Product Type Various Medium Temp 26 Medium concentration
Various Agitation Rate (m/s) Moderate
[0281] All publications cited in this specification and U.S.
provisional patent application No. 62/147840, filed Apr. 15, 2015
are incorporated herein by reference. While the invention has been
described with reference to particular embodiments, it will be
appreciated that modifications can be made without departing from
the spirit of the invention. Such modifications are intended to
fall within the scope of the appended claims.
* * * * *