U.S. patent application number 12/150922 was filed with the patent office on 2008-11-13 for stabilized fluids.
Invention is credited to Terry Michael Williams.
Application Number | 20080280792 12/150922 |
Document ID | / |
Family ID | 39642733 |
Filed Date | 2008-11-13 |
United States Patent
Application |
20080280792 |
Kind Code |
A1 |
Williams; Terry Michael |
November 13, 2008 |
Stabilized Fluids
Abstract
There is provided a fluid composition comprising (a) one or more
non-chlorinated 3-isothiazolone, (b) 0.7% to 10% by weight, based
on the weight of said fluid composition, one or more primary
alkanolamine, (c) 2% to 30% by weight, based on the weight of said
fluid composition, one or more tertiary alkanolamine, (d) one or
more stabilizer selected from the group consisting of
iodine-containing stabilizers, mercaptobenzothiazole, and mixtures
thereof, wherein the molar ratio of said stabilizer to said
non-chlorinated 3-isothiazolone is from 0.3:1 to 3:1.
Inventors: |
Williams; Terry Michael;
(Lower Gwynedd, PA) |
Correspondence
Address: |
ROHM AND HAAS COMPANY;PATENT DEPARTMENT
100 INDEPENDENCE MALL WEST
PHILADELPHIA
PA
19106-2399
US
|
Family ID: |
39642733 |
Appl. No.: |
12/150922 |
Filed: |
May 1, 2008 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60928230 |
May 8, 2007 |
|
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|
Current U.S.
Class: |
508/154 ;
508/271; 508/276 |
Current CPC
Class: |
C10M 2201/081 20130101;
C10M 2219/066 20130101; C10M 2219/068 20130101; C10M 141/08
20130101; C10M 2219/104 20130101; C10N 2040/20 20130101; C10M
2215/042 20130101; C10N 2030/24 20200501; A01N 43/80 20130101; C10N
2010/02 20130101; C10M 173/02 20130101; C10M 2207/126 20130101;
C10M 2207/127 20130101; A01N 43/80 20130101; A01N 25/02 20130101;
A01N 25/22 20130101; A01N 33/08 20130101; A01N 43/78 20130101; A01N
47/12 20130101; A01N 59/12 20130101; A01N 43/80 20130101; A01N
2300/00 20130101 |
Class at
Publication: |
508/154 ;
508/271; 508/276 |
International
Class: |
C10M 125/18 20060101
C10M125/18; C10M 135/36 20060101 C10M135/36 |
Claims
1. A fluid composition comprising (a) one or more non-chlorinated
3-isothiazolone, (b) 0.7% to 10% by weight, based on the weight of
said fluid composition, one or more primary alkanolamine, (c) 2% to
30% by weight, based on the weight of said fluid composition, one
or more tertiary alkanolamine, (d) one or more stabilizer selected
from the group consisting of iodine-containing stabilizers,
mercaptobenzothiazole, and mixtures thereof, wherein the weight
ratio of said stabilizer to said non-chlorinated 3-isothiazolone is
from 0.2:1 to 5:1.
2. The fluid composition of claim 1, wherein said primary
alkanolamine has a primary hydroxyl group, and wherein said
alkanolamine has 4 or more carbon atoms.
3. The fluid composition of claim 1, wherein said primary
alkanolamine comprises one or more compound selected from the group
consisting of 2-amino-2-methyl-1-propanol, 2-(2-aminoethyl)ethanol,
and mixtures thereof.
4. The fluid composition of claim 1, wherein said tertiary
alkanolamine has two or more --CH.sub.2CH.sub.2OH groups.
5. The fluid composition of claim 1, wherein said tertiary
alkanolamine comprises one or more compound selected from the group
consisting of triethanolamine, bis(hydroxyethyl)methylamine, and
mixtures thereof.
6. The fluid composition of claim 1, wherein said stabilizer
comprises one or more compound selected from the group consisting
of iodic acid, periodic acid, iodate salts, periodate salts,
iodopropynylbutylcarbamate, mercaptobenzothiazole, and mixtures
thereof.
7. The fluid composition of claim 1, wherein said stabilizer
comprises one or more iodine-containing stabilizer.
8. The fluid composition of claim 1, wherein said stabilizer
comprises one or more compound selected from the group consisting
of iodic acid, periodic acid, iodate salts, periodate salts,
iodopropynylbutylcarbamate, and mixtures thereof.
9. The fluid composition of claim 1, further comprising one or more
metalworking additive selected from the group consisting of one or
more fatty acid, one or more surfactant, and mixtures thereof.
10. A dilute fluid composition formed by a process comprising
diluting the fluid composition of claim 1 by a factor of 10 to 50,
wherein said dilute fluid composition is suitable as a metalworking
fluid.
Description
[0001] This application claims the benefit of priority under 35
U.S.C. .sctn. 19(e) of U.S. Provisional Patent Application No.
60/928,230 filed on May 8, 2007.
BACKGROUND
[0002] A variety of useful fluids contain one or more
3-isothiazolone and contain a relatively high concentration of one
or more alkanolamine. Some 3-isothiazolones are not stable during
storage in some of such fluids, and it is desired to also include a
stabilizer in the fluid. One example of such a fluid is a
metalworking fluid concentrate, which is a fluid that, after
dilution by a factor of at least 10, is useful as a metalworking
fluid.
[0003] U.S. Pat. No. 5,210,094 discloses metalworking fluids and
metalworking fluid concentrates that contain 3-isothiazolones and a
sulfur-containing compound.
[0004] It is desired to provide fluids that contain one or more
3-isothiazolone and that contain a relatively high concentration of
certain alkanolamines, in which the one or more 3-isothiazolone is
stable on storage.
STATEMENT OF THE INVENTION
[0005] In one aspect of the present invention, there is provided a
fluid composition comprising [0006] (a) one or more non-chlorinated
3-isothiazolone, [0007] (b) 0.7% to 10% by weight, based on the
weight of said fluid composition, one or more primary alkanolamine,
[0008] (c) 1% to 30% by weight, based on the weight of said fluid
composition, one or more tertiary alkanolamine, [0009] (d) one or
more stabilizer selected from the group consisting of
iodine-containing stabilizers, mercaptobenzothiazole, and mixtures
thereof, wherein the weight ratio of said stabilizer to said
non-chlorinated 3-isothiazolone is from 0.2:1 to 5:1.
DETAILED DESCRIPTION
[0010] A fluid composition is a composition that is liquid from
15.degree. C. to 60.degree. C. or possibly over a broader
temperature range.
[0011] A 3-isothiazolone is a compound of the formula
##STR00001##
wherein R.sup.1, R.sup.2, and R.sup.3 is each independently a
hydrogen or a halogen or a substituted or unsubstituted organic
radical. R.sup.1 and R.sup.2 may or may not be connected to each
other to form a ring structure. If any one or more of R.sup.1,
R.sup.2, and R.sup.3 has one or more chlorine atom, the compound is
known as a chlorinated 3-isothiazolone. If any one or more of
R.sup.1, R.sup.2, and R.sup.3 has one or more halogen atom, the
compound is known as a halogenated 3-isothiazolone. If none of
R.sup.1, R.sup.2, and R.sup.3 has any chlorine atoms, the compound
is known as a non-chlorinated 3-isothiazolone. If none of R.sup.1,
R.sup.2, and R.sup.3 has any halogen atoms, the compound is known
as a non-halogenated 3-isothiazolone.
[0012] A non-chlorinated 3-isothiazolone suitable for use in the
present invention is, for example, a compound of the above formula,
where R.sup.3 is (C.sub.1-C.sub.18) alkyl or (C.sub.3-C.sub.12)
cycloalkyl, each optionally substituted with one or more of
hydroxy, cyano, alkylamino, dialkylamine, arylamino, carboxy,
carbalkoxy, alkoxy, aryloxy, alkylthio, arylthio, cycloalkylamino,
carbamoxy, or isothiazolonyl; an unsubstituted (C.sub.2-C.sub.8)
alkenyl or alkynyl; a (C.sub.7-C.sub.10) aralkyl optionally
substituted with one or more of (C.sub.1-C.sub.4) alkyl or
(C.sub.1-C.sub.4) alkoxy; or an aryl optionally substituted with
one or more of, nitro, (C.sub.1-C.sub.4) alkyl, (C.sub.1-C.sub.4)
alkyl-acylamino, carb(C.sub.1-C.sub.4)alkoxy or sulfamyl; and
wherein R.sup.1 and R.sup.2 are each independently H,
(C.sub.1-C.sub.4) alkyl, (C.sub.4-C.sub.8) cycloalkyl, or joined to
form a benzyl.
[0013] In some embodiments, the fluid composition contains any one
of or any mixture of the non-chlorinated 3-isothiazolones defined
herein above. It is contemplated that the fluid composition of the
present invention contains at least one 3-isothiazolone that has no
chlorine atom. In some embodiments, the fluid composition contains
no 3-isothiazolone that has a chlorine atom.
[0014] In some embodiments, the fluid composition of the present
invention contains one or more of 2-methyl-3-isothiazolone,
2-n-octyl-3-isothiazolone, 1,2-benzisothiazolone, or a mixture
thereof. In some embodiments, the fluid composition contains one or
more of 2-methyl-3-isothiazolone or 2-n-octyl-3-isothiazolone or a
mixture thereof. Independently, in some embodiments, the fluid
composition contains no halogenated 3-isothiazolones.
Independently, in some embodiments, the fluid composition contains
no 3-isothiazolone other than 2-methyl-3-isothiazolone,
2-n-octyl-3-isothiazolone, and 1,2-benzisothiazolone.
Independently, in some embodiments, the fluid composition contains
no 3-isothiazolone other than 2-methyl-3-isothiazolone and
2-n-octyl-3-isothiazolone.
[0015] Independent of the type of non-chlorinated 3-isothiazolone
used, the amount of non-chlorinated 3-isothiazolone may vary
widely. It is contemplated that a specific fluid composition, used
under specific conditions, will have greater or lesser tendency to
form biological growth, and thus a larger or smaller amount of
non-chlorinated 3-isothiazolone, which is generally considered to
be an effective biocide, will be used. In some embodiments, the
amount of non-chlorinated 3-isothiazolone, by weight based on the
weight of fluid composition, is 200 ppm or more; or 500 ppm or
more, or 900 ppm or more. Independently, in some embodiments, the
amount of non-chlorinated 3-isothiazolone, by weight based on the
weight of fluid composition, is 20,000 ppm or less; or 10,000 ppm
or less, or 5,000 ppm or less.
[0016] An alkanol group is a group with the structure
HO--R.sup.7--, wherein R.sup.7 is an alkyl or alkoxyalkyl group.
R.sup.7 may be straight, branched, cyclic, or a combination
thereof. Some suitable alkanol groups are, for example,
--CH.sub.2OH, --CH.sub.2CH.sub.2OH, --CH.sub.2CH.sub.2CH.sub.2OH,
--C(CH.sub.3).sub.2CH.sub.2OH,
--CH.sub.2CH.sub.2--O--CH.sub.2CH.sub.2OH,
##STR00002##
In some embodiments, alkanol groups include --CH.sub.2CH.sub.2OH,
--C(CH.sub.3).sub.2CH.sub.2OH, and
--CH.sub.2CH.sub.2--O--CH.sub.2CH.sub.2OH.
[0017] An alkanolamine is a compound with the structure
##STR00003##
wherein R.sup.4 an alkanol group, and wherein R.sup.5 and R.sup.6
is each independently a hydrogen or a substituted or unsubstituted
organic radical.
[0018] A primary alkanolamine is an alkanolamine in which R.sup.5
and R.sup.6 is each a hydrogen. In some embodiments, a primary
alkanolamine is used in which the alkanol group has four or five
carbon atoms. In some embodiments, a primary alkanolamine is used
in which the alkanol group has four carbon atoms. Independently,
some embodiments, a primary alkanolamine is used in which the
alkanol group is --CH.sub.2CH.sub.2OH,
--C(CH.sub.3).sub.2CH.sub.2OH,
--CH.sub.2CH.sub.2--O--CH.sub.2CH.sub.2OH, or
##STR00004##
Independently, in some embodiments, a primary alkanolamine is used
in which the alkanol group is --C(CH.sub.3).sub.2CH.sub.2OH or
--CH.sub.2CH.sub.2--O--CH.sub.2CH.sub.2OH. In some embodiments, no
primary alkanolamine is used that has an alkanol group other than
--C(CH.sub.3).sub.2CH.sub.2OH or
--CH.sub.2CH.sub.2--O--CH.sub.2CH.sub.2OH.
[0019] A tertiary alkanolamine is an alkanolamine in which neither
R.sup.5 nor R.sup.6 is a hydrogen. Each of R.sup.5 and R.sup.6 may,
for example, be a substituted or unsubstituted alkyl group
(straight, branched, cyclic, or a combination thereof), a
substituted or unsubstituted aryl group, or a combination thereof.
In some embodiments, at least one of R.sup.5 and R.sup.6 is an
unsubstituted alkyl group or an alkanol group. In some embodiments,
both of R.sup.5 and R.sup.6 are selected from unsubstituted alkyl
groups, alkanol groups, and mixtures thereof. In some embodiments,
no tertiary alkanolamine is used other than those in which both of
R.sup.5 and R.sup.6 are selected from unsubstituted alkyl groups,
alkanol groups, and mixtures thereof. Independently, in some
embodiments, at least one of R.sup.5 and R.sup.6 is an alkanol
group.
[0020] Among embodiments in which at least one of R.sup.5 and
R.sup.6 is an unsubstituted alkyl group, some suitable
unsubstituted alkyl groups are, for example, C.sub.1 to C.sub.4
alkyl groups that are straight or branched. In some embodiments, at
least one of R.sup.5 and R.sup.6 is a methyl group. Independently,
among embodiments in which at least one of R.sup.5 and R.sup.6 is
an alkanol group, suitable alkanol groups include, for example,
--CH.sub.2OH, --CH.sub.2CH.sub.2OH, --CH.sub.2CH.sub.2CH.sub.2OH,
and
##STR00005##
In some embodiments, at least one of R.sup.5 and R.sup.6 is
--CH.sub.2CH.sub.2OH.
[0021] Some suitable tertiary alkanolamines include, for example,
triethanolamine, bis(hydroxyethyl)methylamine (also called
N-methyldiethanolamine), 2-dimethylamino-2-methylpropanol, and
mixtures thereof. In some embodiments, the tertiary alkanolamine
includes triethanolamine, bis(hydroxyethyl)methylamine, or mixtures
thereof. In some embodiments, no tertiary alkanolamine is used
other than triethanolamine or bis(hydroxyethyl)methylamine.
[0022] The fluid compositions of the present invention contain one
or more primary alkanolamine in an amount chosen so that the amount
of all primary alkanolamines is 0.7% or more by weight, based on
the weight of the fluid composition. In some embodiments, the
amount of all primary alkanolamines is, by weight based on the
weight of the fluid composition, 1.5% or more, or 3% or more.
[0023] Independently, the fluid compositions of the present
invention contain one or more primary alkanolamine in an amount
chosen so that the amount of all primary alkanolamines is 10% or
less by weight, based on the weight of the fluid composition. In
some embodiments, the amount of all primary alkanolamines is, by
weight based on the weight of the fluid composition, 7% or less, or
5% or less.
[0024] The fluid compositions of the present invention contain one
or more tertiary alkanolamine in an amount chosen so that the
amount of all tertiary alkanolamines is 2% or more by weight, based
on the weight of the fluid composition. In some embodiments, the
amount of all tertiary alkanolamines is, by weight based on the
weight of the fluid composition, 4% or more, or 8% or more.
[0025] Independently, the fluid compositions of the present
invention contain one or more tertiary alkanolamine in an amount
chosen so that the amount of all tertiary alkanolamines is 30% or
less by weight, based on the weight of the fluid composition. In
some embodiments, the amount of all tertiary alkanolamines is, by
weight based on the weight of the fluid composition, 20% or less,
or 15% or less.
[0026] In some embodiments, the fluid composition of the present
invention contains no secondary alkanolamine. A secondary
alkanolamine is an alkanolamine in which exactly one of R.sup.5 and
R.sup.6 is a hydrogen.
[0027] The fluid composition of the present invention contains one
or more stabilizer selected from iodine-containing stabilizers,
mercaptobenzothiazole, and mixtures thereof. Iodine-containing
stabilizers are compounds that contain at least one iodine atom per
molecule and that are effective at stabilizing non-chlorinated
3-isothiazolones when used in fluid compositions of the present
invention. Suitable iodine-containing stabilizers include, for
example, iodic acid, periodic acid, iodate salts, periodate salts,
and iodopropynylbutylcarbamate. Iodate salts include, for example,
alkali metal salts. One suitable iodate salt is potassium iodate.
Periodate salts include, for example, alkali metal salts. One
suitable periodate salt is potassium periodate.
[0028] In some embodiments, the fluid composition contains one or
more iodine-containing stabilizer. Independently, in some
embodiments, the fluid composition contains one or more stabilizer
selected from iodic acid, iodate salts, periodic acid, periodate
salts, iodopropynylbutylcarbamate, mercaptobenzothiazole, and
mixtures thereof. Independently, in some embodiments, the fluid
composition contains one or more stabilizer selected from iodic
acid, iodate salts, periodic acid, periodate salts,
iodopropynylbutylcarbamate, and mixtures thereof. Independently, in
some embodiments, the fluid composition contains one or more
stabilizer selected from iodic acid, iodate salts, periodic acid,
periodate salts, and mixtures thereof. Independently, in some
embodiments, the fluid composition contains one or more stabilizer
selected from iodic acid, potassium iodate,
iodopropynylbutylcarbamate, mercaptobenzothiazole, and mixtures
thereof. Independently, in some embodiments, the fluid composition
contains one or more stabilizer selected from iodic acid, potassium
iodate, iodopropynylbutylcarbamate, and mixtures thereof.
Independently, in some embodiments, the fluid composition contains
one or more stabilizer selected from iodic acid, potassium iodate,
and mixtures thereof.
[0029] Independent of the type of stabilizer that is used, the
amount of stabilizer is chosen according to the weight ratio of
stabilizer to non-chlorinated 3-isothiazolone. In the practice of
the present invention, that weight ratio is from 0.2:1 to 5:1. In
some embodiments, that weight ratio is 0.5 or larger, or 0.75 or
larger, or 0.9 or larger. Independently, in some embodiments, that
weight ratio is 2 or lower, or 1.5 or lower. As used herein, when a
ratio is said to be "X or larger," it is meant that the ratio is
Y:1, where Y is equal to or greater than X. Similarly, when a ratio
is said to be "W or lower," it is meant that the ratio is Z:1,
where Z is equal to or less than W.
[0030] In some embodiments, the fluid composition of the present
invention contains no pyridine-N-oxide, pyridine, 2-pyrrolidone,
1-methyl-2-pyrrolidone, s-triazine, or dimethyl oxime. In some
embodiments, the fluid composition contains no nitrogen-based
heterocyclic compounds. In some embodiments, the fluid composition
contains no nitrogen-containing compounds that are not
alkanolamines and that are capable of reversibly forming an adduct
with any of the non-chlorinated 3-isothiazolones described herein
above.
[0031] In some embodiments, the fluid composition of the present
invention contains no 2-mercaptopyridine, 4-mercaptopyridine,
sodium salt of 2-mercaptopyridine-N-oxide, 2-mercaptobenzothiazole,
4-methyl-4-H-1,2,4-triazole-3-thiol, 2-methylthiobenzothiazole,
2-thiohydantoin, methylenebisthiocyante, L-cystin, or
4-R(thiazolidene-thione-4-carbonic acid). In some embodiments, the
fluid composition contains no nitrogen-based heterocyclic thiols.
In some embodiments, the fluid composition contains no compounds
having a sulfur atom attached to a nitrogen-containing aromatic
ring. In some embodiments, the fluid composition contains no
sulfur-containing compound or salt thereof capable of reversibly
forming an adduct with any of the non-chlorinated 3-isothiazolones
described herein above.
[0032] In some embodiments, the fluid composition of the present
invention contains no aromatic disulfide.
[0033] The fluid compositions of the present invention may be used
for any purpose. For example, the fluid compositions, optionally
diluted and/or optionally mixed with additional ingredients, may
form preparations that are useful for any of a wide variety of
purposes. In some cases, such preparations are subject to
contamination by bacteria, fungi, yeast, or algae, and it is
contemplated that non-chlorinated 3-isothiazolone may provide
useful biocide properties. Independently, in some cases, such
preparations may be useful as one or more of metalworking fluid,
industrial process water, laundry rinse water, coatings, adhesives,
lubricants, process additives, cosmetics, caulks, and personal care
products.
[0034] In some embodiments, a fluid composition of the present
invention further contains one or more metalworking additive.
Metalworking additives include, for example, fatty acids,
surfactants, soluble oils, emulsifiable oils, and mixtures thereof.
In some embodiments, a fluid composition of the present invention
contains one or more surfactant, one or more fatty acid, or a
mixture thereof.
[0035] Independently, in some embodiments, a fluid composition of
the present invention is suitable as a metalworking fluid
concentrate. That is, diluting the fluid composition of the present
invention by a factor of at least 10 produces a preparation that is
suitable as a metalworking fluid, or in some cases, a preparation
that becomes suitable as a metalworking fluid after addition of
additional ingredients. In some of such embodiments, the fluid
composition of the present invention, prior to dilution, is not
suitable as a metalworking fluid.
[0036] As used herein, diluting the fluid composition by a factor
of F means mixing the fluid composition with a solvent, where the
ratio of weight of solvent to weight of fluid composition is F.
[0037] In some embodiments, the fluid composition of the present
invention is used to produce a preparation suitable as a
metalworking fluid by dilution with an aqueous solvent. An aqueous
solvent is a solvent that contains 50% or more water by weight,
based on the weight of the solvent. In some embodiments, an aqueous
solvent is used that has water, by weight based on the weight of
the solvent, of 75% or more, or 90% or more, or 95% or more.
[0038] In some embodiments, a preparation suitable as a
metalworking fluid is made by diluting a fluid composition of the
present invention by a factor of 15 or more. Independently, in some
embodiments, a preparation suitable as a metalworking fluid is made
by diluting a fluid composition of the present invention by a
factor of 50 or less, or 25 or less.
EXAMPLES
[0039] In the following examples, the non-chlorinated
3-isothiazolones were methylisothiazolone (MIT), octylisothiazolone
(OIT) and benzisothiazolone (BIT). The primary alkanolamines used
were monoethanolamine (MEA), 2-amino-2-methyl-1-propanol (AMP),
monoisopropanolamine (MIPA), and 2-(2-aminoethoxy)-ethanol (AEE).
Secondary alkanolamine used was 2-butylaminoethanol (BAE). Tertiary
alkanolamines were triethanolamine (TEA) and
bis(hydroxyethyl)methylamine (BHEMA).
Test Formulation
[0040] The formulation used for these tests was prepared in 2
stages. The following amounts were used to prepare 100 grams of the
formulation. For stage one, the following was added: distilled
water, 2.7 g; tertiary or secondary amine, 10.1 g; primary amine,
2.6 g; boric acid, 2.0 g; Corfree.TM. M1, 1.2 g; pelargonic acid,
0.2 g; caprylic acid, 0.2 g; citric acid, 0.1 g; and glycerin, 0.2
g. Each of the above components was added individually and in order
with heating (50.degree. C.) and mixing. Each ingredient was
allowed to thoroughly dissolve before adding the next component.
Heating of the mixture was discontinued after all ingredients were
added. The following ingredients were added to the stage one
mixture: distilled water, 65.7 g; primary amine, 1.0 g;
Pluronic.TM. 25R (100% polyoxypropylene-polyoxyethylene block
copolymer), 10.0 g; caprylic acid, 2.0 g; sodium tolyltriazole-50%
solution, 1.0 g; and biocide, 0.3-0.6 g. The ingredients were added
individually and in the above order at room temperature with
mixing. Each ingredient was allowed to thoroughly dissolve before
adding the next component.
[0041] It is contemplated that this formulation would be suitable
as a metalworking fluid if it were diluted with water by a factor
of 20.
[0042] Each formulation received an addition of one of the
following stabilizers, at a 1:1 ratio to the biocide active
ingredient to stabilizer. Stabilizers tested were potassium iodate,
iodic acid, iodopropynylbutylcarbamate (IPBC) and
mercaptobenzothiazole (MBZ). A sample without stabilizer served as
a control. Biocide additions (by weight of active ingredient) to
formulations were as follows: 2,000 ppm MIT, 1,000 ppm OIT, and
4,000 ppm BIT. The biocides used in this study were Kordek.TM. LX
5000 (50% MIT), Kathon.TM. 893 MW (45% OIT), and Rocima.TM. BT 2S
(19% BIT).
[0043] Samples were aged at 50.degree. C. for 30 days to determine
the percent biocide remaining over time. The 3-isothiazolone
content was measured by high pressure liquid chromatography (HPLC)
at time zero (initial, prior to aging) and after 30 days. The %
remaining of the biocides are reported for each amine combination
and in the presence or absence of 4 stabilizers. The initial pH of
the various formulations was pH 10-11.
[0044] Corfree.TM. M1 is a registered trademark of INVISTA, and is
a mixture containing dibasic acids, primarily dodecanedioic acid
(38-49%) and undecanedioic acid (31-38%), sebacic acid (5-7%),
other dibasic acids (9-19%), other organics (7-11%), nitrogen
(0.5%), and water (0.3%).
[0045] Pluronic.TM. is a registered trademark of BASF
Corporation.
[0046] Kordek, Kathon, and Rocima are registered trademarks of the
Rohm and Haas Company.
Example 1
Results for MIT
TABLE-US-00001 [0047] % MIT Remaining Secondary Potas- Sample
Primary or Tertiary No sium Iodic # Amine Amine Stabilizer Iodate
Acid IPBC MBZ 1 MEA TEA 4 68 67 3 5 2 AEE TEA 3 92 92 0 3 3 MIPA
TEA 3 86 95 83 5 4 AMP TEA 6 93 98 85 0 5 MEA BHEMA 8 72 7 6 8 6
AEE BHEMA 10 71 78 7 9 7 MIPA BHEMA 16 97 98 5 8 8 AMP BHEMA 12 100
100 100 100 9 MEA BAE 5 1 2 3 5 10 AEE BAE 4 2 1 3 5 11 MIPA BAE 2
2 0 2 5 12 AMP BAE 2 2 1 2 4
[0048] In the absence of a stabilizer, MIT degraded significantly.
None of the stabilizers were effective (no increased stability of
MIT) with any of the combinations using BAE as the secondary amine.
Combinations with TEA or BHEMA as the tertiary amine provided
greatly improved stability of the MIT (from 67 to 100% remaining)
with one or more of the stabilizers. The AMP/BHEMA amine
combination (#8) was most effective with no measurable loss of
biocide with all stabilizers tested (100% remaining). Combinations
#3 (MIPA/TEA) and #4 (AMP/TEA) also showed excellent stability with
three of the four stabilizers. Overall, iodate and iodic acid
demonstrated the best improvement in stability of MIT with 8 amine
combinations showing greater than 60% of the biocide remaining.
IPBC and MBZ were effective stabilizers with three and one amine
combination, respectively.
Example 2
Results for OIT
TABLE-US-00002 [0049] % OIT Remaining Secondary Potas- Sample
Primary or Tertiary No sium Iodic # Amine Amine Stabilizer Iodate
Acid IPBC MBZ 1 MEA TEA 0 87 80 0 0 2 AEE TEA 0 85 78 15 17 3 MIPA
TEA 13 96 78 0 0 4 AMP TEA 0 77 83 83 80 5 MEA BHEMA 0 57 68 0 0 6
AEE BHEMA 13 45 49 12 0 7 MIPA BHEMA 0 72 80 0 0 8 AMP BHEMA 0 94
100 85 96 9 MEA BAE 0 5 0 0 0 10 AEE BAE 0 0 0 0 0 11 MIPA BAE 0 0
0 0 0 12 AMP BAE 0 0 0 0 0
[0050] In the absence of a stabilizer, OIT degraded completely in
10 fluids and only 13% remaining in two combinations. None of the
stabilizers were effective (no increased stability of OIT) with any
of the combinations using BAE as the secondary amine. Combinations
with TEA or BHEMA as the tertiary amine provided greatly improved
stability of the OIT (from 45 to 100% remaining) with one or more
of the stabilizers. Amine combinations #8 (AMP/BHEMA) and #4
(AMP/TEA) were most effective with 77-100% of the biocide remaining
with the four stabilizers tested. Iodate and iodic acid
demonstrated the best overall improvement in stability of OIT with
8 amine combinations showing greater than 60% of the biocide
remaining. IPBC and MBZ were effective stabilizers with two amine
combinations.
Example 3
Results with BIT
TABLE-US-00003 [0051] % BIT Remaining Secondary Potas- Sample
Primary or Tertiary No sium Iodic # Amine Amine Stabilizer Iodate
Acid IPBC MBZ 1 MEA TEA 100 91 96 58 100 2 AEE TEA 93 91 90 93 98 3
MIPA TEA 100 100 100 100 89 4 AMP TEA 100 100 97 98 99 5 MEA BHEMA
82 99 91 97 81 6 AEE BHEMA 94 85 100 90 99 7 MIPA BHEMA 100 99 94
100 102 8 AMP BHEMA 99 100 100 100 81 9 MEA BAE 77 88 94 97 88 10
AEE BAE 87 94 98 96 100 11 MIPA BAE 88 92 100 100 100 12 AMP BAE
100 89 100 100 89
[0052] BIT showed very good stability without addition of a
stabilizer in all of the fluids, with 77-100% of the biocide
remaining. Several combinations provided improved stability of the
BIT using one or more stabilizers, compared to the controls with no
stabilizer added.
* * * * *