IN SITU GENERATION OF PEROXYCARBOXYLIC ACIDS AT ALKALINE pH, AND METHODS OF ...

32 Pages·2015·3.3 MB·Italian

US 20150011632A1
(19) United States
(12) Patent Application Publication (10) Pub. No.: US 2015/0011632 A1
Li et al. (43) Pub. Date: Jan. 8, 2015
(54) IN SITU GENERATION OF (60) Provisional application No. 61/427,965, ?led on Dec.
PEROXYCARBOXYLIC ACIDS AT ALKALINE 29, 2010.
PH, AND METHODS OF USE THEREOF
Publication Classi?cation
(71) Applicant: Ecolab USA Inc., St. Paul, MN (US)
(51) Int. Cl.
(72) Inventors: J unzhong Li, Apple Valley, MN (US); A01N 3 7/16 (2006.01)
David D. McSherry, St. Paul, MN (US); (52) US, C],
Richard Staub, Lakeville, MN (US) CPC .................................... .. A01N 37/16 (2013.01)
USPC ......................................... .. 514/557; 514/558
(21) Appl. No.: 14/497,427
(57) ABSTRACT
(22) Flled' sep' 26’ 2014 The present disclosure is related to percarboxylic acid com
Related US. Application Data positions formed in 'situ in non-equilibrium reactions. The
peroxycarboxylic a01d composltions are formed uslng ester
(63) Continuation of application No. 13/331,486, ?led on based starting materials. Methods for using the percarboxylic
Dec. 20, 2011, now Pat. No. 8,877,254. acid compositions are also disclosed.
Patent Application Publication Jan. 8, 2015 Sheet 1 0f 6 US 2015/0011632 A1
Patent Application Publication Jan. 8, 2015 Sheet 2 0f 6 US 2015/0011632 A1
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US 2015/0011632 A1 Jan. 8, 2015
IN SITU GENERATION OF the peroxycarboxylic acids must be packed in special con
PEROXYCARBOXYLIC ACIDS AT ALKALINE tainers and shipped under the strict Department of Transpor
PH, AND METHODS OF USE THEREOF tation (DOT) guidelines. Certain improvements to peroxycar
boxylic acid stability have proved advantageous for shipping
CROSS REFERENCE TO RELATED purposes, as described in US. patent application Ser. No.
APPLICATIONS 11/847,604, entitled “Shelf Stable, Reduced Corrosion,
Ready to Use Peroxycarboxylic Acid Antimicrobial Compo
[0001] This application is a continuation application of
sitions,” the entire contents of which are hereby expressly
US. Ser. No. 13/331,486 (Attorney Docket Number
incorporated herein by reference. Most commercially avail
2757USU2), ?led Dec. 20, 2011, which is a nonprovisional
able products in an equilibrium mixture contain excess
application of US. Provisional Application No. 61/427,965
hydrogen peroxide in the presence of stabilizers and acid
(Attorney Docket Number 2757USP1), ?led Dec. 29, 2010,
catalysts, to stabilize and improve the composition’s shelf
entitled In Situ Generation of Peroxycarboxylic Acids at
life. Despite such stability improvements, excess amounts of
Alkaline pH, and Methods of Use Thereof, which is herein
reagents (e.g., acids, oxidizing agents, and stabilizers) are
incorporated by reference in its entirety.
present in the compositions during shipping to prevent
[0002] This application is related to US. patent application
decomposition. These and other disadvantages to the use of
Ser. No. 13/331,304 (Attorney Docket Number 2757USU1),
peracid compositions exist.
entitled In Situ Generation of Peroxycarboxylic Acids at
[0006] Accordingly, it is an objective of the claimed inven
Alkaline pH and Methods of Use Thereof, now US. Pat. No.
tion to develop in situ methods for generation of peroxycar
8,846,107 issued Sep. 30, 2014, US. patent application Ser.
boxylic acids at alkaline pH.
No. 13/330,915 (Attorney Docket No. 2839USU1), entitled
[0007] A further object of the invention is an in situ method
Sugar Ester Peracid On-Site Generator and Formulator, US.
for generation of stable single peracid systems that are sub
patent application Ser. No. 13/330,981 (Attorney Docket No.
stantially free of stabilizing agents and/or surfactants.
2969US01), entitled Continuous On-Line Adjustable Disin
[0008] A further object of the invention is an in situ method
fectant/ Sanitizer/ Bleach Generator, now US. Pat. No. 8,858,
for generation of stable mixed peracid systems that are sub
895 issued on Oct. 14, 2014, US. patent application Ser. No.
stantially free of stabilizing agents and/or surfactants.
13/331,104 (Attorney Docket No. 2943US01), entitled Gen
[0009] A still further object of the invention is to develop
eration of Peroxycarboxylic Acids at Alkaline pH, and Their
concentrated peracid chemistries for further dilution and/or
Use as Textile Bleaching andAntimicrobial Agents, now US.
use on site within a matter of hours to days in order to
Pat. No. 8,729,296 issued May 20, 2014, and US. patent
eliminate the need for various stabilizing agents in the com
application Ser. No. 13/331,385 (Attorney Docket No.
positions to ensure storage stability (e.g. stability for at least
2997US01), entitled Water Temperature as a Means of Con
one year as required for regulated chemistries).
trolling Kinetics of Onsite Generated Peracids. The entire
contents of these patent applications are hereby expressly
BRIEF SUMMARY OF THE INVENTION
incorporated herein by reference including, without limita
tion, the speci?cation, claims and abstract, as well as any [0010] In some aspects, the present disclosure relates to
?gures, tables or drawings thereof. peroxycarboxylic acid forming compositions. The composi
tions comprise a ?rst reagent premix comprising at least one
FIELD OF THE INVENTION ester of a polyhydric alcohol and a C1 to C18 carboxylic acid,
and one or more agents selected from the group consisting of
[0003] The present disclosure relates to compositions and
an oxidizing agent, a dispersing agent, a solvent, water and
methods for the in situ generation of peroxycarboxylic acid
mixtures thereof; wherein the solvent is an organic solvent to
compositions, at alkaline pH levels, viz. greater than about pH
solubilize the ester; wherein the dispersing agent is suf?cient
12. The present disclosure also relates to methods for the in
to create a physically meta-stable solution upon reaction with
situ generation of mixed percarboxylic acid compositions,
a source of alkalinity and the subsequent acidi?cation; and a
and methods of using the in situ generated peroxycarboxylic
second reagent source comprising the source of alkalinity;
acid compositions.
wherein said composition is not at equilibrium, has a pH
greater than about 12, and is substantially free of a stabilizing
BACKGROUND OF THE INVENTION
agent.
[0004] Peroxycarboxylic acids are known for use as anti [0011] In other aspects, the present disclosure relates a
microbials and bleaching agents. Mixed peroxycarboxylic peroxycarboxylic acid forming composition comprising a
acid systems are also known for use as antimicrobial and ?rst reagent premix comprising at least one ester of a poly
bleaching agents. However, there are disadvantages to use of hydric alcohol and a C1 to C18 carboxylic acid, an oxidizing
these antimicrobial and bleaching agents. For example, the agent and a dispersing agent; wherein the dispersing agent is
most commonly used peroxycarboxylic acid, peroxyacetic suf?cient to create a physically meta-stable solution upon
acid, is known to have a strong pungent odor. In addition, reaction with a source of alkalinity and the subsequent acidi
peracids such as peroxycarboxylic acid have known chemical ?cation; and a second reagent source comprising a source of
disadvantages, namely, they are relatively unstable in solu alkalinity; wherein said composition is not at equilibrium, has
tion and decompose to the corresponding carboxylic acids a pH greater than about 12, and is substantially free of a
and oxygen. stabilizing agent.
[0005] Conventional peroxycarboxylic acid compositions [0012] In other aspects, the present disclosure relates to
are made through an acid catalyzed equilibrium reaction. methods for delivering an antimicrobial comprising contact
Most often, the peroxycarboxylic acids are generated in a ing the surface with an antimicrobial composition formed by
chemical plant, and then shipped to customers for on-site use. diluting a composition ?rst reagent premix comprising at
Due to the limited storage stability of peroxycarboxylic acids, least one ester of a polyhydric alcohol and a C1 to C18
US 2015/0011632 A1 Jan. 8, 2015
carboxylic acid, an oxidizing agent and a dispersing agent, [0019] FIG. 4 shows a graph representing POOA produc
and a second reagent source comprising a source of alkalinity, tion at various temperatures over a period of time according to
with an aqueous acidic solution to a pH of about 1 to about 8, various embodiments of the invention.
wherein the solvent is an organic solvent to solubilize the [0020] FIG. 5 shows a graph representing POOA produc
ester; and wherein the dispersing agent is suf?cient to create tion and temperature as a function of time according to vari
a physically meta-stable solution upon reaction with a source ous embodiments of the invention.
of alkalinity. [0021] FIG. 6 shows a graph of peracid generated in a
[0013] In other aspects, the present disclosure provides a reaction solution according to the invention at varying pH.
method for forming an antimicrobial composition, compris [0022] Various embodiments of the present invention will
ing: (a) providing a peroxycarboxylic acid composition hav be described in detail with reference to the drawings, wherein
ing active peroxycarboxylic acid content from about 0.25% to like reference numerals represent like parts throughout the
about 20% comprising: (i) a ?rst reagent premix comprising several views. Reference to various embodiments does not
at least one ester of a polyhydric alcohol and a C1 to C18 limit the scope of the invention. Figures represented herein
carboxylic acid, and one or more agents selected from the are not limitations to the various embodiments according to
group consisting of an oxidizing agent, a dispersing agent, a the invention and are presented for exemplary illustration of
solvent, water and mixtures thereof; wherein the solvent is an the invention.
organic solvent to solubilize the ester; wherein the dispersing
agent is suf?cient to create a physically meta-stable solution DETAILED DESCRIPTION OF THE INVENTION
upon reaction with a source of alkalinity; and (ii) a second
[0023] The present disclosure relates to peroxycarboxylic
reagent source comprising a source of alkalinity; wherein
acid compositions generated in situ from a non-equilibrium
said composition has a pH greater than 12 and is not at
ester based reaction, as well as methods of making and using
equilibrium; (b) diluting the peroxycarboxylic acid compo
such compositions. The compositions disclosed herein have
sition to an alkaline solution having an active peroxycarboxy
many advantages over conventional, equilibrium based per
lic acid content from about 0.01% to about 1%; (c) providing
oxycarboxylic acid compositions. For example, after peroxy
an acidic aqueous solution; and (d) diluting the peroxycar
carboxylic acid formation according to methods disclosed
boxylic acid composition with the acidic aqueous solution to
herein, the compositions have signi?cantly lower levels of
a pH of about 1.0 to about 8.0 to form the antimicrobial
reactant residues compared to peroxycarboxylic acid compo
composition.
sitions generated using equilibrium reactions. Further, as the
[0014] In still yet other aspects, the present disclosure pro
compositions are generated in situ, and can be generated on
vides methods for forming an antimicrobial composition
site, the compositions can be substantially free of, or even free
comprising: (a) providing a peroxycarboxylic acid composi
of, stabilizers. Additionally, due to the ability to generate the
tion having active peroxycarboxylic acid content from about
disclosed peroxycarboxylic acid compositions on site, the
0.25% to about 20% comprising: (i) a ?rst reagent premix
step of shipping hazardous peroxycarboxylic acid composi
comprising at least one ester of a polyhydric alcohol and a C1
tions to an end user can be eliminated. This bene?cially
to C18 carboxylic acid, and one or more agents selected from
allows a user to provide diluted compositions for a particular
the group consisting of an oxidizing agent, a dispersing agent,
application without having to ship large amounts of a diluted
a solvent, water and mixtures thereof; wherein the dispersing
composition. These and other bene?ts of the present inven
agent is suf?cient to create a physically meta-stable solution
tion are disclosed herein.
upon reaction with a source of alkalinity; and (ii) a second
[0024] The embodiments of this invention are not limited to
reagent source comprising a source of alkalinity; wherein
particular peroxycarboxylic acid compositions and methods
said composition has a pH greater than 12 and is not at
for in situ generation of the same, which can vary and are
equilibrium; (b) allowing the peroxycarboxylic acid compo
understood by skilled artisans. It is further to be understood
sition to react for a suf?cient amount of time such that a C1 to
that all terminology used herein is for the purpose of describ
C18 percarboxylic acid is formed to generate an antimicro
ing particular embodiments only, and is not intended to be
bial composition; and (c) providing said composition to an
limiting in any manner or scope. For example, as used in this
application for use without an acidi?cation step.
speci?cation and the appended claims, the singular forms “a,”
[0015] While multiple embodiments are disclosed, still
“an” and “the” can include plural referents unless the content
other embodiments of the present invention will become
clearly indicates otherwise. Further, all units, pre?xes, and
apparent to those skilled in the art from the following detailed
symbols may be denoted in its SI accepted form. Numeric
description, which shows and describes illustrative embodi
ranges recited within the speci?cation are inclusive of the
ments of the invention. Accordingly, the drawings and
numbers de?ning the range and include each integer within
detailed description are to be regarded as illustrative in nature
the de?ned range.
and not restrictive.
[0025] So that the present invention may be more readily
understood, certain terms are ?rst de?ned. Unless de?ned
BRIEF DESCRIPTION OF DRAWINGS
otherwise, all technical and scienti?c terms used herein have
[0016] FIG. 1 is a graphical depiction of the stability of the same meaning as commonly understood by one of ordi
various peroxycarboxylic acid compositions formed from nary skill in the art to which embodiments of the invention
esters at an alkaline pH over time. pertain. Many methods and materials similar, modi?ed, or
[0017] FIG. 2 shows a diagram of an embodiment of meth equivalent to those described herein can be used in the prac
ods of making the peracid chemistry according to the inven tice of the embodiments of the present invention without
tion. undue experimentation, the preferred materials and methods
[0018] FIG. 3 shows a graph representing POOA concen are described herein. In describing and claiming the embodi
tration over time at various reaction temperatures according ments of the present invention, the following terminology
to various embodiments of the invention. will be used in accordance with the de?nitions set out below.
US 2015/0011632 A1 Jan. 8, 2015
[0026] As used herein, the term “about” refers to variation [0033] For the purpose of this patent application, successful
in the numerical quantity that can occur, for example, through microbial reduction is achieved when the microbial popula
typical measuring and liquid handling procedures used for tions are reduced by at least about 50%, or by signi?cantly
making concentrates or use solutions in the real world; more than is achieved by a wash with water. Larger reductions
through inadvertent error in these procedures; through differ in microbial population provide greater levels of protection.
ences in the manufacture, source, or purity of the ingredients [0034] As used herein, the term “disinfectant” refers to an
used to make the compositions or carry out the methods; and agent that kills all vegetative cells including most recognized
the like. The term “about” also encompasses amounts that pathogenic microorganisms, using the procedure described in
differ due to different equilibrium conditions for a composi A.O.A. C. Use Dilution Methods, Of?cial Methods of Analy
tion resulting from a particular initial mixture. Whether or not sis of the Association of Of?cial Analytical Chemists, para
modi?ed by the term “about”, the claims include equivalents graph 955.14 and applicable sections, 15th Edition, 1990
to the quantities. (EPA Guideline 91-2). As used herein, the term “high level
[0027] As used herein, the phrase “air streams” includes disinfection” or “high level disinfectant” refers to a com
food anti-spoilage air circulation systems. Air streams also pound or composition that kills substantially all organisms,
include air streams typically encountered in hospital, surgi except high levels of bacterial spores, and is effected with a
cal, in?rmity, birthing, mortuary, and clinical diagnosis chemical germicide cleared for marketing as a sterilant by the
rooms. Food and Drug Administration. As used herein, the term
[0028] As used herein, “agricultural” or “veterinary” “intermediate-level disinfection” or “intermediate level dis
objects or surfaces include animal feeds, animal watering infectant” refers to a compound or composition that kills
stations and enclosures, animal quarters, animal veterinarian mycobacteria, most viruses, and bacteria with a chemical
clinics (e.g. surgical or treatment areas), animal surgical germicide registered as a tuberculocide by the Environmental
areas, and the like. ProtectionAgency (EPA).As used herein, the term “low-level
[0029] As used herein, the term “alkyl” or “alkyl groups” disinfection” or “low level disinfectant” refers to a compound
refers to saturated hydrocarbons having one or more carbon or composition that kills some viruses and bacteria with a
atoms, including straight-chain alkyl groups (e.g., methyl, chemical germicide registered as a hospital disinfectant by
ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, the EPA.
etc.), cyclic alkyl groups (or “cycloalkyl” or “alicyclic” or [0035] As used herein, the phrase “food processing sur
“carbocyclic” groups) (e.g., cyclopropyl, cyclopentyl, cyclo face” refers to a surface of a tool, a machine, equipment, a
hexyl, cycloheptyl, cyclooctyl, etc.), branched-chain alkyl structure, a building, or the like that is employed as part of a
groups (e.g., isopropyl, tert-butyl, sec-butyl, isobutyl, etc.), food processing, preparation, or storage activity. Examples of
and alkyl-substituted alkyl groups (e.g., alkyl-substituted food processing surfaces include surfaces of food processing
cycloalkyl groups and cycloalkyl-substituted alkyl groups). or preparation equipment (e.g., slicing, canning, or transport
[0030] Unless otherwise speci?ed, the term “alkyl” equipment, including ?umes), of food processing wares (e. g.,
includes both “unsubstituted alkyls” and “substituted alkyls.” utensils, dishware, wash ware, and bar glasses), and of ?oors,
As used herein, the term “substituted alkyls” refers to alkyl walls, or ?xtures of structures in which food processing
groups having substituents replacing one or more hydrogens occurs. Food processing surfaces are found and employed in
food anti-spoilage air circulation systems, aseptic packaging
on one or more carbons of the hydrocarbon backbone. Such
substituents may include, for example, alkenyl, alkynyl, halo sanitiZing, food refrigeration and cooler cleaners and sani
geno, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxy tizers, ware washing sanitiZing, blancher cleaning and sani
carbonyloxy, aryloxy, aryloxycarbonyloxy, carboxylate, tiZing, food packaging materials, cutting board additives,
alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbo third-sink sanitiZing, beverage chillers and warmers, meat
nyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylthio chilling or scalding waters, auto dish sanitizers, sanitiZing
carbonyl, alkoxyl, phosphate, phosphonato, phosphinato, gels, cooling towers, food processing antimicrobial garment
cyano, amino (including alkyl amino, dialkylamino, ary sprays, and non-to-low-aqueous food preparation lubricants,
lamino, diarylamino, and alkylarylamino), acylamino (in oils, and rinse additives.
cluding alkylcarbonylamino, arylcarbonylamino, carbamoyl [0036] As used herein, the phrase “food product” includes
and ureido), imino, sulfhydryl, alkylthio, arylthio, thiocar any food substance that might require treatment with an anti
boxylate, sulfates, alkylsul?nyl, sulfonates, sulfamoyl, sul microbial agent or composition and that is edible with or
fonamido, nitro, tri?uoromethyl, cyano, aZido, heterocyclic, without further preparation. Food products include meat (e.g.
alkylaryl, or aromatic (including heteroaromatic) groups. red meat and pork), seafood, poultry, produce (e. g., fruits and
[0031] In some embodiments, substituted alkyls can vegetables), eggs, living eggs, egg products, ready to eat food,
include a heterocyclic group. As used herein, the term “het wheat, seeds, roots, tubers, leafs, stems, corns, ?owers,
erocyclic group” includes closed ring structures analogous to sprouts, seasonings, or a combination thereof. The term “pro
carbocyclic groups in which one or more of the carbon atoms duce” refers to food products such as fruits and vegetables
in the ring is an element other than carbon, for example, and plants or plant-derived materials that are typically sold
nitrogen, sulfur or oxygen. Heterocyclic groups may be satu uncooked and, often, unpackaged, and that can sometimes be
rated or unsaturated. Exemplary heterocyclic groups include, eaten raw.
but are not limited to, aZiridine, ethylene oxide (epoxides, [0037] As used herein, the term “fouling” shall be under
oxiranes), thiirane (episul?des), dioxirane, azetidine, oxet stood to mean the undesirable presence of or any deposition
ane, thietane, dioxetane, dithietane, dithiete, azolidine, pyr of any organic or inorganic material in the applicable com
rolidine, pyrroline, oxolane, dihydrofuran, and furan. position or chemistry.
[0032] The term “cleaning,” as used herein, means to per [0038] As used herein, the term “free” or “substantially
form or aid in soil removal, bleaching, microbial population free” refers to a composition, mixture, or ingredient that does
reduction, or combination thereof. not contain a particular compound or to which a particular