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WO1996009983A1 - Sols, gels, et solides a peracide stables et leur procede - Google Patents

Sols, gels, et solides a peracide stables et leur procede Download PDF

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Publication number
WO1996009983A1
WO1996009983A1 PCT/US1995/012427 US9512427W WO9609983A1 WO 1996009983 A1 WO1996009983 A1 WO 1996009983A1 US 9512427 W US9512427 W US 9512427W WO 9609983 A1 WO9609983 A1 WO 9609983A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
aqueous
gel
hydrogen peroxide
stable
Prior art date
Application number
PCT/US1995/012427
Other languages
English (en)
Inventor
Joseph C. Richards
William A. Hills
Original Assignee
Fmc Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fmc Corporation filed Critical Fmc Corporation
Priority to AU36868/95A priority Critical patent/AU3686895A/en
Publication of WO1996009983A1 publication Critical patent/WO1996009983A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C407/00—Preparation of peroxy compounds
    • C07C407/003—Separation; Purification; Stabilisation; Use of additives
    • C07C407/006—Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions

Definitions

  • the present invention is a process to form a stable aqueous polyacrylate sol or gel containing a peracid.
  • a liquid bleach be available for use as a single, stable viscous solution (sol) or a gel, although a solid would be satisfactory if it were biodegradable, easily soluble in water, and did not contain significant inorganic dissolved solids such as are provided by sodium persulfate or sodium perborate.
  • Highly viscous hydrogen peroxide sols are well known.
  • U.S. Patent 959,605 to Queisser (1910) discloses that vegetable gums were well known at that time to be useful for thickening and gelling hydrogen peroxide. The patent also teaches incorporating burnt gypsum which by hydrating further stabilizes the hydrogen peroxide and the hydrated gypsum is useful as an abrasive.
  • Patent 3,658,712 to Lindner (1972) claims a stable thickened aqueous suspension of sodium perborate of polymers containing carboxyl groups, preferably a poly ⁇ carbonate polymethacrylate.
  • the specific polymer, Carbopol 934 was cited as the thickening agent.
  • U.S. Patent 5,102,571 to Mole et al. (1992) teaches an aqueous solution or suspension of sodium perborate tetrahydrate thickened to form a mobile fluid, or a high viscosity paste or gel.
  • the thickening agents disclosed were a hydroxyalkyl cellulose, polysaccharides (that is, xanthan and galactomannan gums) , fumed silica and clays, plus a dispersing agent such as a sodium salt of polyacrylic acid.
  • a dispersing agent such as a sodium salt of polyacrylic acid.
  • U.S. Patents 3,499,844 and 4,130,501 which employ polyacrylics (the latter with an added surfactant) .
  • these sols require further compounding to increase the pH to at least 8, or must be packaged in an expensive two-compartment package.
  • thickened perhydrate suspension such as the sodium perborate composition of U.S.
  • Patent 3,658,712 contributes undesirable non- biodegradable dissolved solids to the environment, including phytotoxic borate ions.
  • Other prior attempts to provide a peroxygen-based bleach have included gelled suspensions of substantially insoluble peracids, such as diperazelic acid (U.S. Patent 3,996,152).
  • the patent discloses that the water- insoluble peracids require salt-forming alkaline conditions to provide a solution of the active oxygen bleaching species.
  • peracids themselves are effective bleaching agents even at a low pH, provided they are solubilized.
  • U.S. Patent 4,879,057 attempts to overcome some of the disadvantages of the product of U.S.
  • Patent 3,996,152 by providing pourable to pasty aqueous bleaching agent suspensions which have practically no solid/liquid phase separation and only a slight loss of available oxygen, even after two weeks of storage.
  • the patent teaches a composition comprising an aqueous carrier liquid, a particulate, practically water-insoluble peroxycarboxylic acid, an organic thickening agent (starch) and an acidifying agent, which is characterized in that it contains a xanthan polysaccharide or agar polysaccharide as thickening agent and a hydrate-forming neutral salt which desensitizes peroxycarboxylic acids, such as sodium sulfate, sodium phosphate, sodium borate or the like.
  • the bleaching agent still requires the alkaline conditions, provided by a laundry detergent to dissolve the peracid sufficiently to provide bleaching conditions.
  • the present invention overcomes the problems of the prior art by providing an aqueous colloidal peracid composition comprising stable sols, gels and solids of C2 to C6 peroxycarboxylic acids and a cross-linked polyacrylate.
  • the composition may further comprise conventional additives and gel-assisting agents for a polyacrylate.
  • the invention is also a process for forming a stable aqueous peroxycarboxylic gel by incorporating a cross-linked polyacrylate thereof into an aqueous solution to form an aqueous sol, incorporating therein a peroxycarboxylic acid and subsequently adjusting the pH to 3 or above.
  • the aqueous solution may be water or an aqueous solution of hydrogen peroxide.
  • the pH may be adjusted by adding an inorganic alkaline material, such as sodium hydroxide, potassium hydroxide, sodium carbonate, magnesium hydroxide or the like to the aqueous peroxycarboxylate sol, provided the alkaline material is not a peroxygen decomposition catalyst.
  • an inorganic alkaline material such as sodium hydroxide, potassium hydroxide, sodium carbonate, magnesium hydroxide or the like
  • the polyacrylic polymer should be one that is interpolymerized with a multi-vinyl or multi-allylic functionalized cross-linking agent.
  • the polyacrylic polymer is interpolymerized with a polyalkenyl polyether of a polyhydric compound.
  • the polyhydric compound should have at least 4 carbons and 3 hydroxy groups.
  • the thickeners are water dispersible copolymers of an alpha-beta monoolefinically unsaturated lower aliphatic acrylic acid cross-linked With a polyether of a polyol.
  • the polyol may be selected from the group consisting of oligosaccharides, reduced derivatives thereof in which the carbonyl group is converted to an alcohol group, and pentaerythritol.
  • the hydroxy groups of said polyol are etherified with allyl groups, said polyol having at least two allyl groups per polyol molecule.
  • a suitable copolymer is one of acrylic acid with low percentages (0.71 to 1.5%) poly ally sucrose.
  • Molecular weights of the cross-linked polymer may range from about 500,000 up to 10,000,000, and preferably between 600,000 and 2,000,000.
  • Examples of commercially available cross-linked polymers based upon allyl sucrose modified polyacrylic acid are the Carbopol Registered TM resins manufactured by the B.F. Goodrich Chemical Company. These materials include Carbopol 941 Registered TM (m.w. 1,250,000), Carbopol 934 Registered TM (m.w. 3,000,000) and Carbopol 940 Registered TM (m.w. 4,000,000). The optimal choice will depend on the desired and clarity and can be easily selected by consulting the manufacturers data sheets and a few simple experiments.
  • the polyacrylic polymer of this invention may be present in an amount from about 0.1 to about 10%, preferably from about 0.5 to 2%, optimally between about 0.7 and 1.5% by weight of the composition depending upon the desired viscosity and the polyacrylic polymer selected.
  • compositions are useful for delivering peracids and salts at a pH of 3.5 to 11 in applications such as surface cleaners, detergent bleach, automatic dish washing formulations and other cleaning applications.
  • compositions are particularly useful for sanitizing or bleaching at an acid or neutral pH compared with other chlorine or peroxygen bleach compounds. It was unexpected from the prior art that thickened sols, gels or solids could be made from a water-soluble peroxycarboxylic acid (peracid) such as peracetic acid. Indeed, initial experiments were unsuccessful!
  • adjusting the pH of the composition after adding the peroxycarboxylic acid has an adverse effect on the final viscosity of the composition. It is desirable that sufficient alkali be incorporated into the aqueous solution prior to adding the peroxycarboxylic acid.
  • sols or gels were stable at a pH greater than 7 in view of the known instability of both hydrogen peroxide and peracid at a pH greater than 7.
  • a “stable" sol, gel or solid peracid composition is one which maintains sufficient physical properties (viscosity) and active oxygen content long enough to be useful, at least 24 hours.
  • the sol, gel or solid peracid composition should maintain at least 90% of its viscosity and active oxygen content for one month.
  • Any C2 to C6 percarboxylic acid which is water soluble may be incorporated into the compositions.
  • Examples include peracetic acid, perproprionic acid, perbutyric acid, pervaleric acid, and percaproic acid.
  • Cross-linked polyacrylates are available in a range of molecular weights and can be derivatized (such as methacrylate) .
  • Polyacrylates are widely available under different tradenames (for example, CARBOPOL - Trademark of U.S. Goodrich Corp.).
  • Formulations of peracids were prepared by adding the peracid to an aqueous sol which was in the process of thickening.
  • the aqueous sol was prepared by adjusting 120 g of 5.0% (wt.) H202pH of about 9.5 with 50 wt. % sodium hydroxide or pellets and adding 0.61 g Carbopol 617 with vigorous stirring. If necessary, the pH was adjusted to pH 9.5 - 9.6 before the peracid was added.
  • Polyacrylic formulations were prepared in the 1% to 6% range.
  • EXAMPLE 1 A Peracetic Acid/Carbopol 941 Gel was formed by mixing the components and adjusting the pH to approximately 6.00 with dilute sodium hydroxide. A thickened solution containing 4.45% peracetic acid was obtained. This gel is stable at ambient conditions.
  • Carbopol 623, 1610, and 940 can be substituted for 941 to produce gel of similar viscosity and peracetic acid content. However, the best gel was made using Carbopol 934. Peracetic acid concentrations up to 9.78 can be obtained using 15% peracetic acid. No pH adjustment was needed to form the gel.
  • EXAMPLE 2 A gel was prepared at pH 5.1 containing 2% Carbopol 617 and 1% PAA. Initial assay was 1.69% H202 1.09% PAA. After 3 weeks the gel assayed 1.62% H202.65% PAA and had a pH of 4.5.
  • PAA 5% peracetic acid
  • Example 3A Initial: pH 4.71; 5.35% H202; 0.87% PAA. Final: 5.95% H202; 0.68% PAA.
  • Example 3B Initial: pH 5.05; 4.30% H202; 1.14% PAA. Final: 4.83% H202; 0.73% PAA.
  • Example 3C Initial pH 5.5; 2.92 H202; 0.98% PAA. Final: 3.24% H 2 0 2 ; 0.88% PAA.
  • Example 3D Initial: pH 5.55; 1.40% H202; 0.87% PAA. Final: 1.70% H202; 0.81% PAA.
  • Example 3E A sample of a gel prepared as above was vacuum dried to a solid which assayed 24.27% H202 and 1.08% PAA. After 397 days the sample assayed 17.70% H202 and 0.27% PAA.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)

Abstract

Composition stable constituée d'un sol ou d'un gel d'acide peroxycarboxylique aqueux et d'un polyacrylate réticulé présentant un pH supérieur à 3,5. L'invention porte également sur un procédé d'élaboration de cette composition.
PCT/US1995/012427 1994-09-26 1995-09-26 Sols, gels, et solides a peracide stables et leur procede WO1996009983A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU36868/95A AU3686895A (en) 1994-09-26 1995-09-26 Stable peracid sols, gels and solids and a process therefor

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US31200094A 1994-09-26 1994-09-26
US08/312,000 1994-09-26

Publications (1)

Publication Number Publication Date
WO1996009983A1 true WO1996009983A1 (fr) 1996-04-04

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1995/012427 WO1996009983A1 (fr) 1994-09-26 1995-09-26 Sols, gels, et solides a peracide stables et leur procede

Country Status (2)

Country Link
AU (1) AU3686895A (fr)
WO (1) WO1996009983A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19618674A1 (de) * 1996-05-09 1997-11-13 Solvay Interox Gmbh Kit zur Behandlung von polymeren Materialien mit Schimmelpilz-bedingten Beeinträchtigungen
US7045493B2 (en) 2004-07-09 2006-05-16 Arkema Inc. Stabilized thickened hydrogen peroxide containing compositions
US7169237B2 (en) 2004-04-08 2007-01-30 Arkema Inc. Stabilization of alkaline hydrogen peroxide
US7431775B2 (en) 2004-04-08 2008-10-07 Arkema Inc. Liquid detergent formulation with hydrogen peroxide

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3563687A (en) * 1968-03-12 1971-02-16 Dow Chemical Co Bleaching compounds and method
US4017411A (en) * 1975-03-27 1977-04-12 The Procter & Gamble Company Bleaching articles
US4879057A (en) * 1987-03-21 1989-11-07 Degussa Aktiengesellschaft Aqueous bleaching agent suspensions containing peroxycarboxylic acid, method for their preparation and use
US5091106A (en) * 1985-05-02 1992-02-25 Henkel Kommanditgesellschaft Auf Aktien Granular bleach agent: solid aliphatic peroxy-carboxylic acid, inorganic salt hydrate and organic polymer
US5160655A (en) * 1989-02-27 1992-11-03 Lever Brothers Company, Division Of Conopco, Inc. Aqueous structured liquid detergent compositions containing selected peroxygen bleach compounds
US5296239A (en) * 1989-10-05 1994-03-22 Interox Peracetic acid compositions and process for obtaining these compositions

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3563687A (en) * 1968-03-12 1971-02-16 Dow Chemical Co Bleaching compounds and method
US4017411A (en) * 1975-03-27 1977-04-12 The Procter & Gamble Company Bleaching articles
US5091106A (en) * 1985-05-02 1992-02-25 Henkel Kommanditgesellschaft Auf Aktien Granular bleach agent: solid aliphatic peroxy-carboxylic acid, inorganic salt hydrate and organic polymer
US4879057A (en) * 1987-03-21 1989-11-07 Degussa Aktiengesellschaft Aqueous bleaching agent suspensions containing peroxycarboxylic acid, method for their preparation and use
US5160655A (en) * 1989-02-27 1992-11-03 Lever Brothers Company, Division Of Conopco, Inc. Aqueous structured liquid detergent compositions containing selected peroxygen bleach compounds
US5296239A (en) * 1989-10-05 1994-03-22 Interox Peracetic acid compositions and process for obtaining these compositions

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19618674A1 (de) * 1996-05-09 1997-11-13 Solvay Interox Gmbh Kit zur Behandlung von polymeren Materialien mit Schimmelpilz-bedingten Beeinträchtigungen
US7169237B2 (en) 2004-04-08 2007-01-30 Arkema Inc. Stabilization of alkaline hydrogen peroxide
US7431775B2 (en) 2004-04-08 2008-10-07 Arkema Inc. Liquid detergent formulation with hydrogen peroxide
US7045493B2 (en) 2004-07-09 2006-05-16 Arkema Inc. Stabilized thickened hydrogen peroxide containing compositions
US7169743B2 (en) 2004-07-09 2007-01-30 Arkema Inc. Stabilized thickened hydrogen peroxide containing compositions with a mixture of stabilizers

Also Published As

Publication number Publication date
AU3686895A (en) 1996-04-19

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