U.S. patent number RE29,473 [Application Number 05/744,113] was granted by the patent office on 1977-11-15 for chemical composition.
This patent grant is currently assigned to DHP Corporation. Invention is credited to Walter P. Fitzgerald, Jr..
United States Patent |
RE29,473 |
Fitzgerald, Jr. |
* November 15, 1977 |
Chemical composition
Abstract
A chemical composition comprising a mixture of alkali and/or
alkaline earth metal hypochlorites and, as a stabilizing and/or
reinforcing agent, alkali and/or alkaline earth metal
pyrosulfates.
Inventors: |
Fitzgerald, Jr.; Walter P. (San
Diego, CA) |
Assignee: |
DHP Corporation (Wilmington,
DE)
|
[*] Notice: |
The portion of the term of this patent
subsequent to February 8, 1989 has been disclaimed. |
Family
ID: |
27537573 |
Appl.
No.: |
05/744,113 |
Filed: |
November 22, 1976 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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828710 |
May 28, 1969 |
3640879 |
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791512 |
Jan 15, 1969 |
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Reissue of: |
120327 |
Mar 2, 1971 |
03755179 |
Aug 28, 1973 |
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Current U.S.
Class: |
510/370; 510/108;
510/116; 510/254; 510/380; 510/513; 8/109; 252/186.25; 252/187.26;
252/187.28; 424/665; 424/709 |
Current CPC
Class: |
C11D
3/046 (20130101); C11D 3/3953 (20130101); D21C
9/12 (20130101) |
Current International
Class: |
C11D
3/02 (20060101); C11D 3/395 (20060101); D21C
9/12 (20060101); D21C 9/10 (20060101); C11D
007/54 () |
Field of
Search: |
;252/95,99,186,187
;8/109 ;424/149 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Weinblatt; Mayer
Attorney, Agent or Firm: Connolly and Hutz
Parent Case Text
REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of application Ser. No.
828,710 filed May 28, 1969, now U.S. Pat. No. 3,640,879 issued Feb.
8, 1972 which in turn is a continuation-in-part of application Ser.
No. 791,512, filed Jan. 15, 1969, now abandoned.
Claims
I claim:
1. A chemical composition consisting essentially of a mixture of
(a) a member selected from the group consisting of an alkali metal
pyrosulfate, an alkaline earth metal pyrosulfate or mixtures
thereof.Iadd., .Iaddend..[.and.]. (b) a member selected from the
group consisting of an alkali metal hypochlorite, an alkaline earth
metal hypochlorite or mixtures thereof .Iadd.and (c) an agent
rendering the pH of the chemical composition alkaline.Iaddend.,
component (a) being present in from about 1 to about 99 parts by
weight.Iadd., .Iaddend..[.and.]. component (b) being present in
from about 99 to 1 parts by weight.Iadd., and component (c) being
present in an amount sufficient to render the pH of the composition
in excess of 8.Iaddend..
2. The chemical composition according to claim 1 wherein component
(b) is an alkali or alkaline earth metal hypochlorite and component
(a) is present in an amount of from about 0.5 to 50 percent by
weight.
3. The chemical composition according to claim 1 wherein component
(b) is an alkali or alkaline earth metal hypochlorite.
4. An aqueous medium containing the composition according to claim
2.
Description
BACKGROUND OF THE INVENTION
In the aforementioned applications I disclosed and claimed a
chemical composition well suited as a cleaning agent, for example,
as a dental prostheses cleaner. This composition, comprising the
combination of lithium hypochlorite, an alkali metal pyrosulfate,
alkali metal bisulfate and/or mixtures thereof, preferably
potassium pyrosulfate, and an alkali metal hydroxide was found to
be highly effective as a cleaner because, particularly in its
preferred embodiments, it combined the features of solid chemicals
highly stable in admixture with outstanding and long-term cleaning
ability for plastics, metals, porcelains, glass and the like.
SUMMARY OF THE INVENTION
The present invention relates to the combination of alkali and/or
alkaline earth metal hypochlorites, which are alone strong
oxidizing agents, with alkali and/or alkaline earth metal
pyrosulfates, which appear to act as a stabilizer and/or
reinforcing agent for the hypochlorite, alone or in combination
with supplemental agents such as surface active agents, pH
adjusting agents and the like. The pyrosulfate and hypochlorite are
admixed in widely varying proportions depending upon the ultimate
end use desired. These proportions can range broadly from about 1
to 99 parts by weight of pyrosulfate to 99 to 1 parts by weight
hypochlorite.
DETAILED DESCRIPTION OF THE INVENTION
The terms alkali metal and alkaline earth metal as used herein are
meant in their normal sense to include such metals as sodium,
potassium, lithium, magnesium, calcium and barium. As might be
expected by the chemical relationship of these metals, mixtures of
two or more hypochlorites and pyrosulfates are equally
possible.
Some pyrosulfates of such metals are commercially available, such
as potassium pyrosulfate, also known as fused potassium bisulfate.
Normally this product as obtained commercially is made up of a
mixture of pyrosulfate and bisulfate, the latter being the
accidental hydrolysis product of the pyrosulfate since the former
is obtained by driving off water from the bisulfate usually by the
application of heat. The term "pyrosulfate" as employed herein is
intended to mean the grades and purities of pyrosulfate
commercially available although, in general, an assay of at least
40 percent pyrosulfate is advisable to obtain the full benefits of
the invention.
Methods of producing the metal pyrosulfates are well known and for
a particular metal can follow the analogous procedure for preparing
potassium pyrosulfate. Lithium pyrosulfate can be prepared for
example by the manner described by Arnold and Lehmann, Z. Anorg.
Allg. Chem., 354, 56-59 (1967); Chem. Abs. 67, 104662 (1967).
Potassium pyrosulfate can be prepared by numerous chemical methods
such as described in Chem. Abs. 47, 9840 (1953); 57, 16005 (1962)
and 58, 12158 (1963). The production of sodium pyrosulfate is
described at Chem. Abs., 69, 102597 (1968) and of calcium
pyrosulfate at Chem. Abs., 68, 45844 (1968).
The pyrosulfate, regardless of the specific metal, is characterized
by the .sup.- S.sub.2 O.sub.7 ion and has the general formula
M.sub.x S.sub.2 O.sub.7 wherein M stands for the particular metal
and x stands for one or two, depending on the valency of the
metal.
The metal hypochloride is, per se, a well-known compound whose
methods of manufacture were well established many years ago, such
as by electrolysis of a sodium chloride solution or chlorination of
a slurry of .[.line.]. .Iadd.lime .Iaddend.and caustic soda with
subsequent precipitation of calcium hypochlorite dihydrate which is
then dried under vacuum. Since those methods are well known in the
literature, they will not be repeated here. It may be solid (such
as lithium and calcium hypochlorite) or liquid (such as sodium
hypochlorite which is unstable in air and is normally stored and
used in solution with sodium hydroxide as a stabilizer). As with
the pyrosulfate, it may be employed in its commercially available
grades such as technical, analytical or reagent. Because of
differing physical characteristics as between the metal
hypochlorites, selection depends primarily on cost, intended use,
stability and the liquid or solid nature desired of the ultimate
product.
While I do not wish to be bound by any theory underlying the action
of this unique chemical combination, it appears that the
hypochlorite, itself a strong oxidizing agent, may be stabilized by
the action of the pyrosulfate. Particularly in the presence of
water, either as a solution or ambient moisture picked up by the
chemicals from the air, the release of active oxidizing agent from
the hypochlorite appears to be attenuated by the pyrosulfate to
preserve and/or obtain slow release of the oxidizing power of the
hypochlorite. This factor can be advantageously utilized to either
prolong the activity of the hypochlorite in aqueous solutions or to
prevent loss in potency during storing of the dry hypochlorite,
that is, increase its storage stability.
Alternatively, the pyrosulfate (e.g., potassium pyrosulfate) and
hypochlorite (e.g., lithium hypochlorite) may undergo, particularly
in the presence of water at ambient temperatures, the following
reaction:
The reaction product itself may be a new product.
Regardless of the precise mechanism involved, the mixture of the
two ingredients, alone or in combination with supplemental
ingredients, later defined, provides a novel combination with many
advantageous properties.
Supplemental ingredients include thickening agents, inert or even
active supports (as in the case of catalysts), surface active
agents (as in the case of cleaning uses), indicators, chelating
agents, dyes, free-flowing agents, masking agents, perfumes,
fragrances, bonding agents (as in shaping tablets) and the like.
The product, in its commercial state, may partake of liquid,
powder, pellet, bread, wafer or other physical form suitable for
the particular end use desired. Moreover, agents to provide varying
pH are sometimes desired. Such agents include alkali and alkaline
earth metal hydroxides such as lithium and sodium hydroxide which
can be employed to raise the pH of an aqueous solution containing
the chemicals to the alkaline side, say in excess of 8, generally 9
to 14 and preferably from 10 to 12.
Supplemental agents, their nature and use are more fully described
in my aforesaid-mentioned applications when the combination is
intended for cleaning purposes, the disclosures of which are
incorporated herein by reference.
The relative amounts of pyrosulfate and hypochlorite can vary
widely depending on the end use intended. Broadly speaking this may
vary from about 1 to 99 parts by weight hypochlorite for 99 to 1
parts by weight pyrosulfate. In cleaning applications, particularly
with an alkaline pH, the proportions may vary on a weight ratio of
from about 1:3.5 to 3.5:1 preferably on an equal weight basis. For
other applications such as in stabilizing bulk hypochlorite used on
an industrial scale or in the disinfecting and purification of
water (e.g., in swimming pools where it also acts to kill algae)
relatively small amounts of pyrosulfate based on hypochlorite may
be employed (for illustration purposes from 0.25 to 5 percent by
weight, preferably 0.5 to 2.5 percent.
The composition according to the present invention should find
utility in a number of potential areas. These include as an
initiator of vinyl polymerization, oxidative treatment of
polyethylene film surfaces to render same printable, bactericide
and algaecide in water treatment and general bleaching of paper,
fabric, wood and the like.
In the catalytic field, mixtures of metal pyrosulfate and metal
hypochlorite alone or with co-catalysts, with or without suitable
supports, may be used in various fields such as replacing the
pyrosulfate employed in admixture with bis(1,5-cyclo-octadienyl)
nickel to prepare poly(butadiene) rubber with essentially cis
structure as disclosed, for example, by Dawans and Teyssie, C.R.
Acad. Sci., Paris, Ser. C-263 (25), 1512 (1966) (cf. Chem. Abs., 66
47063 (1967). Other catalytic uses for the mixture according to the
claimed invention may be obtained by replacement of pyrosulfate in
various processes such as those disclosed in French Pat. No.
1,447,472, July 29, 1966 (Chem. Abs. 66 P 66051 (1967); Netherlands
application 6,406,764 (Chem. Abs. 64 PC 17432 (1966); Chem. Abs.,
68, 117462 (1963); Chem. Abs. 69, 70633 (1968); Chem. Abs., 65, P
20068 (1966); Chem. Abs., 55, 18033 (1961) and Chem. Abs. 64, 6488
(1966), all of which references are incorporated herein by
reference.
The following examples serve to further illustrate the nature of
the invention and are not intended to impliedly or expressly
restrict the nature thereof.
EXAMPLE 1
A mixture consisting of 5.0 grams of potassium pyrosulfate, 5.0
grams of lithium hypochlorite, 2.0 grams of lithium hydroxide, and
1.0 gram of Duponol C (E. I. du Pont de Nemours' brand of sodium
lauryl sulfate) was prepared by grinding the ingredients separately
to remove lumps or large particles and mixing the resulting dry
powders. The resulting mixture was a white, free-flowing powder and
was packaged in various dosages for further use.
An 8.0 gram quantity of the mixture described above was disclosed
in 100 milliliters of hot water (approximately 140.degree. F. tap
water). With slight swirling of the mixture, solution was rapid and
complete, giving a pH of 11. A solid denture (complete upper or
lower plate) was immersed in the solution for 15 minutes. Upon
removal and rinsing with water, all tar and nicotine stains had
been removed together with the calculus, food debris, and other
solid materials. The porecelain, acrylic, and metal portions of the
denture were bright and shining and resembled those of a freshly
manufactured, unused denture.
EXAMPLE 2
A mixture is prepared by grinding together with a mortar and pestle
5.0 grams potassium pyrosulfate, 3.0 grams lithium hypochlorite,
2.0 grams lithium chloride, 2.0 grams lithium hydroxide and 1.0
grams sodium lauryl sulfate. The article to be cleaned, in this
case a denture, is covered with about 100 ml of hot tap water
(70.degree. C.). To this is added 10 grams of the above mixture
with sufficient agitation to promote dissolution.
Soaking is accomplished for 30 minutes and the denture is then
removed, rinsed with warm water and dried. The denture is restored
to a clean, lustrous, tasteless condition.
EXAMPLES 3-9
In a manner similar to Example 1, the following dry formulations
are prepared:
______________________________________ Ingredients, percent by
Example weight 3 4 5 6 7 8 9 ______________________________________
Potassium pyrosulfate 40 45 42 30 38 25 30 Lithium hypochlorite 40
35 33 44 25 55 20 Lithium chloride -- -- -- 15 -- 5 20 Lithium
hydroxide 14 7 17 -- 25 10 20 Surface active agent .sup.1 6 .sup.2
6 .sup.1 8 .sup.2 2 .sup.2 12 .sup.1 5 .sup.1 10 Sodium hydroxide
-- 7 -- 9 -- -- -- ______________________________________ .sup.1
Sodium lauryl sulfate. .sup.2 Sodium dodecyl benzene sulfonate.
When the above compositions are dissolved in 100 ml of water in an
amount ranging from 1 to 15 grams per 100 ml, they effectively
clean a variety of dentures in a short period of time without
adverse effect on the denture material.
EXAMPLE 10
A mixture consisting of 4.0 grams of potassium pyrosulfate, 5.5
grams of lithium hypochlorite, 2 grams of lithium hydroxide and 2
grams of sodium lauryl sulfate is ground together and the resulting
dry composition is added in an amount of 5 grams to 100 milliliters
of tap water (room temperature).
Various articles such as small gold jewelry pieces, a heating aid
ear piece and a denture when immersed in the resulting solution are
cleaned and restored to a bright and shining appearance after from
25 to 60 minutes of soaking.
In the above formulations, the potassium pyrosulfate can be
replaced by equivalent amounts of other pyrosulfates such as
sodium, lithium and/or calcium pyrosulfate and the lithium
hypochlorite can be replaced by equivalent amounts of calcium
and/or sodium hypochlorite, the resulting compositions varying in
physical form depending upon the liquid and solid form of the base
chemicals.
In other applications, such as the use of metal hypochlorite in
bulk form for industrial (e.g., bleaching) and sterilization
purposes, the metal pyrosulfate can be added in relatively minor
amounts say from 0.5 to 50 percent by weight based on metal
hypochlorite and, as illustration, in 0.5, 2.5, 5 and 10 percent by
weight. In such instances, the metal pyrosulfate should serve to
preserve the activity of the metal hypochlorite during storage and
after addition to aqueous liquids. Such admixtures, with or without
the usual supplemental agents commonly used in industrial or
household applications (e.g., common household bleaching and
washing applications) find many applications wherein prolonged
stability and activity are desired.
In the above-mentioned uses it is sometimes advisable to
incorporate surface active agents which may vary widely depending
upon the use, acidity and alkalinity of the ultimate product. When
employed as an alkaline cleaning agent, alkaline stable agents such
as sulfates of long chain alcohols such as dodecanol up to
octadecanol (e.g., sodium lauryl sulfate), sulfonated amide and
ester derivatives, and alkyl aryl sulfonates (e.g., dodecyl benzene
sodium sulfonate) may be used. Both cationic and anionic agents
come under consideration in the alkaline field. Of course,
non-ionic agents, if sufficiently stable may be employed .
* * * * *