US3789000A - Formulating with a non-burning chlorinated dry bleach - Google Patents

Formulating with a non-burning chlorinated dry bleach Download PDF

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Publication number
US3789000A
US3789000A US02778882*7A US3789000DA US3789000A US 3789000 A US3789000 A US 3789000A US 3789000D A US3789000D A US 3789000DA US 3789000 A US3789000 A US 3789000A
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sodium
chloride
dihydrate
bleach
bleaching
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US02778882*7A
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English (en)
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S Berkowitz
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FMC Corp
Olin Corp
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FMC Corp
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Assigned to OLIN CORPORATION, 120 LONG RIDGE ROAD, STAMFORD, CT. 06904, A CORP. OF VA. reassignment OLIN CORPORATION, 120 LONG RIDGE ROAD, STAMFORD, CT. 06904, A CORP. OF VA. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: FMC CORPORATION, 2000 MARKET STREET, PHILADELPHIA, PA., A CORP. OF DE.
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    • 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
    • C11D3/395—Bleaching agents
    • C11D3/3955—Organic bleaching agents

Definitions

  • This invention concerns bleaching, sterilizing, disinfecting and detergent compositions containing a dry bleaching compound that yields active chlorine in water and a process that reduces the precautions associated with formulating such compositions in commercial quantities.
  • Bleaching, sterilizing and disinfecting compositions employing active chlorine have been produced in liquid form using aqueous solutions of sodium hypochlorite as the bleaching chemical that yields active chlorine in water.
  • Dry bleaching compounds were substituted for aqueous solutions containing sodium hypochlorite in order to obtain increased stability (longer shelf life) and for convenience in handling, packaging, and shipping.
  • Such compounds that yield active chlorine in Water include calcium hypochlorite, lithium hypochlorite and organic compositions such as l,3-dichloro-5,S-dimethylhydantoin, trichloroisocyanuric acid, chlorinated trisodium phosphate, and dihaloisocyanuric acids and their salts.
  • chlorinated dry bleach compounds are used commercially, the problems associated with formulating bleaching, sterilizing, disinfecting and detergent compositions containing such active chlorine yielding compounds are considerable and special precautions are used commercially to minimize the problems.
  • a major commercial problem encountered during handling is due to the fact that such oxidizing chemicals can burn and evolve poisonous and noxious gases during burning.
  • oxidizing chemicals can burn and evolve poisonous and noxious gases during burning.
  • sodium, potassium and calcium dichloroisocyanurate salts and other chlorinated dry bleach compounds when exposed to a flame, spark or other high temperature source, begin to burn and continue burning after the initial heat source has been removed until all of the material is consumed. This phenomenon is referred to as self-sustaining and self-propagating clecomposition.
  • organic adjuvants for bleaching, sterilizing, disinfecting and detergent compositions are not readily compatible with chlorinated dry bleach compounds.
  • An example of such adjuvants is cationic surfactants, especially quaternary ammonium compounds which can react with and thereby inititate the burning of certain chlorinated dry bleach compounds.
  • Dust Another problem associated with formulating composi- "Ice tions containing chlorinated dry bleach compounds is known as the dust problem.
  • Fine particles comprise a portion of chlorinated dry bleach compounds which particles tend to take on electrostatic charge.
  • the charged dust particles tend to accumulate in corners and crevices of process equipment used to handle the chlorinated dry bleach. Accumulations of fine particles in and around bearings or other places where frictional heat develops is particularly undesirable because frictional heat can initiate decomposition. Precautions are taken to minimize such accumulations of dust in commercial operations.
  • hydrated calcium hypochlorite as a solution to the substantial commercial need for a non-burning chlorinated inorganic dry bleach compound.
  • hydrated calcium hypochlorite approximately the monohydrate
  • RI-7594 a satisfactory performance to the problem because it burns when mixed With certain organics as shown by its inferior performance in proposed U.S. Bureau of Mines procedure RI-7594 discussed hereafter.
  • hydrated calcium hypochlorite introduces calcium ion into solution which is undesirable because it increases the hardness level of water.
  • This invention provides an improvement in the process of formulation bleaching, sterilizing, disinfecting and detergent compositions prepared by admixing a bleaching compound that yields active chlorine in water and a compound selected from the group consisting of a detergent builder, an anionic, nonionic or cationic surfactant and a detergent filler.
  • the improvement comprises dispensing the bleaching compound from bulk storage in the form of nonburning dihydrate of sodium dichloroisocyanurate into a blending zone in which admixing of the components takes place whereby the fire hazards and dust problems during formulating are substantially diminished by employing a nonburning component having substantially reduced electrostatic charge.
  • the blending or admixing of components of bleaching, sterilizing, disinfecting, and detergent compositions can be accomplished in any of many known Ways and is typically performed in commercial blending equipment that mechanically mix components fed into the equipment.
  • the blending and feeding of components can be either continuous or intermittent. Precautions to prevent dust accumulation are not necessary because dihydrate particles have substantially reduced electrostatic charge in comparison to other chlorinated dry bleaches.
  • Dispensing means the controlled removal of material from a first zone to a second zone and can be either a continuous removal or an intermittent removal in any convenient quantity (units of material).
  • Bulk storage zone is a space where a significant quantity of material is contained in an essentially pure state. About pounds or more is a significant quantity for bulk storage of a chlorinated dry bleach because burning about 10 pounds or more results in the release of unacceptably high quantities of noxious gas requiring evacuation of even a large building.
  • Blending zone is a space where admixing of material takes place.
  • Hazardous materials as used herein refers to those materials which when tested according to US. Bureau of Mines proposed procedure RI-7594, have a flame propagation rate greater than the pure sawdust standard used in the procedure. Therefore such material enhances rather than impedes the burning of sawdust.
  • Nonburning refers to a property of a material, namely, the inability of the material to separately support flames. Specifically, when an external flame is brought into contact with a nonburning material and then removed, the
  • Detergent BuilderA material that has the ability to improve the cleansing power and detergency levels of detergent formulations.
  • Chlorinated dry bleach is a bleaching compound that yields active chlorine in water.
  • Active chlorine is chlorine of the type obtained by the hydrolysis of the chlorinecontaining composition to produce hypochlorous acid (HOCl) and/or 001- ion depending on the pH of the system.
  • Such end products of hydrolysis are composed of oxygen having two negative charges in combination with a chlorine which must be positively charged.
  • Such a positive chlorine is considered an active chlorine.
  • Active chlorine is not only obtained by the hydrolysis of inorganic hypochlorite but is also obtained from N-chloro compounds such as chlorinated cyanuric acid, and other chloro compounds containing an N-Cl bond at which site hydrolysis takes place cleaving the N-Cl bond and yielding HOCl and/ or 001* ion.
  • the best mode contemplated for dispensing the material from a bulk storage zone and then blending the components into a formulation consists of (1) storing components in individual hoppers (bulk storage zone) which can be readily filled; (2) dispensing each component from its hopper by standard means such as a conveyor belt,
  • a screw conveyor, gravity dispensing means or other similar apparatus which also transfers the material from the storage zone to a blending zone, usually a commercial mixer, in which the materials are added in their desired proportions and blended into a homogeneous mixture. The mixture is then taken from the blending zone and packaged in any convenient unit depending upon the contemplated end use.
  • Typical adjuvants for bleaching, sterilizing, disinfecting and detergent formulations used in combination with a chlorinated dry bleach compound include a detergent builder, an anionic, nonionic or cationic surfactant and a detergent filler. Selections of specific adjuvants and their concentrations in a particular formulation depends upon the specific use for the formulation. Examples of formulations employing a chlorinated dry bleach are household automatic dishwash compositions, commercial dishwasher compositions, scouring powders, household bleach, commercial laundry bleaches, sanitizers, broad spectrum biocides and general detergency sanitizing compositions. Typical formulations of detergent compositions containing a chlorinated dry bleach and typical adjuvants are as follows:
  • Chlorinated dry bleach (LS-10.0
  • Chlorinated dry bleach 0.4-4.0 Anionic surfactant 1-6 Soda ash (or other alkaline carbonates) 5-20 S o d i u m tripolyphosphate (or other builder) 0-5 Balance silica flour 55-93 4. Household bleach:
  • Chlorinated dry bleach 5-80 S o d i u m tripolyphosphate (or other builder) 0-40 Anionic surfactant 2-10 Soda ash (or other alkaline carbonates) 0-10 Balance sodium sulfate (or other filler) 10-78 5.
  • Commercial laundry bleach :
  • Chlorinated dry bleach 5-50 S o d i u m tripolyphosphate (or other builder) 0-40 Silicate (1:1 ratio, or 1.0-3.2 ratio) 10-40 Anionic surfactant 2-10 Balance sodium sulfate (or other filler such as sodium chloride or soda ash if more alkalinity desired) 0-68 TABLE-Continued Concentration 7.
  • Sanitizer range, percent Chlorinated dry bleach 5-80 Balance sodium sulfate (or other filler such as sodium chloride or soda ash if more alkalinity desired) 50-90 8. Broad spectrum biocide:
  • Chlorinated dry bleach 1 0-90 Cationic surfactant 0.4--- Balance sodium sulfate (or other filler such as sodium chloride or soda ash if more alkalinity desired) 6-90 Weight ratio of cationic surfactant to bleach must not exceed 1:24.
  • Typical detergent builders include alkali salts of nitrilotriacetic acid, ethylenediaminetetraacetic acid, gluconic acid, and citric acid.
  • Other suitable adjuvants include polycarboxylates, organic phosphonates, alkali metal carbonates, bicarbonates, borates, silicates and cyanuric acid.
  • Suitable fillers used in such compositions are well known and can be passive or actively aid the detergency function or storage by such means as pH adjustment or the like.
  • suitable detergent fillers include sodium sulfate, sodium chloride, borax, soda ash or other carbonates.
  • Suitable surfactants for use in this invention are listed in Table VI.
  • Such mixtures having greater than 11% water are referred to herein as hydrated sodium dichloroisocyanurate. Since the dihydrate contains 14.1% combined water, hydrated sodium dichloroisocyanurate having greater than 11% up to and including 14.1% average combined H O are suitable for use in this invention. Additional uncombined water up to 2% may be present (in addition to the 14.1% combined water) without altering the properties of the dihydrate.
  • sodium dichloroisocyanurate dihydrate particles possess substantially less electrostatic charge than anhydrous particles which reduces the tendency of fine particles to accumulate thereby eliminating one of the hazards of handling chlorinated dry bleach compounds.
  • EXAMPLE 1 An 18 gauge Nichrome wire was embedded in a g. sample of chlorinated dry bleach. The wire was heated by passing a current through it for several seconds until the material in contact with the wire began to decompose. The current was then shut off and the sample observed to determine the tendency for self propagated decomposition after the initial cause of decomposition was removed. This procedure was followed with samples of anhydrous and hydrated forms of both sodium dichloroisocyanurate and potassium dichloroisocyanurate. The results are listed in Table I.
  • Potassium dichloroisocyanurate 2 Anhydrous Complete and rapid. Monohydrate Complete and rapid.
  • Example 2 The procedure of Example 1 was repeated with samples of chlorinated dry bleach mixed with 2% by weight of the cationic surfactant [dimethyl benzyl di-(isobutyl phenoxy ethoxy) ethyl ammonium chloride] to demonstrate the hazard of mixing a cationic surfactant with conventional chlorinated dry bleaches.
  • the dihydrate was tested with both 2% and 4% surfactant mixtures. The results are listed in Table II.
  • EXAMPLE 3 A quantity of each of the chlorinated dry bleaches listed in Table III was placed in a bed 1" x 2 x 7 long and ignited at one end with a flame according to proposed Bureau of Mines procedures RI-7593. The horizontal rate of spread of the flame in the material was timed with the results listed in Table III.
  • EXAMPLE 4 Samples were prepared containing an :20 mixture of a chlorinated dry bleach listed in Table IV and red oak sawdust following proposed Bureau of Mines procedure RI-7594. In addition, a control sample was also prepared with pure sawdust. Each sample was placed in a bed 1" x 2" X 7 long and ignited with a flame as in Example 3, and the rate of spread of the flame was timed.
  • sodium dichloroisocyanurate dihydrate is not only nonburning but actually impedes the flame propagation rate of flammable material (dihydrate-sawdust combination burns significantly slower than sawdust alone.)
  • Oxyethylated straight chain alcohol (Plurafac RA 43- Wyandotte Chemical Corp.)
  • Anionic surfactants suitable for use in this invention include both soap and nonsoap detergent compounds.
  • suitable soaps are the sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids (C -C
  • Particularly useful are the sodium or potassium salts of the mixture of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
  • anionic organic non-soap detergent compounds are the water-soluble salts, alkali metal salts, of organic sulfuric reaction'products having in their molecular structure an alkyl radical containing from about 8 to about 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals.
  • alkyl is the alkyl portion of higher acyl radicals.
  • the synthetic detergents which form a part of the compositions of the present invention are the sodium or potassium alkyl sulfates especially those obtained by sulfating the higher alcohols (C -C carbon atoms) produced by reducing the glycerides of tallow or coconut oil; sodium or potassium alkyl benzenesulfonates, such as are described in United States Letters Pats. No. 2,220,009 and No.
  • alkyl group contains from about 9 to about 15 carbon atoms
  • alkali metal alkylbenzene sulfonates are those in which the alkyl radical is a straight chain aliphatic radical containing from about 10 to about 20 carbon atoms for instance, 2-phenyl-dodecanesulfonate and 3-pheny1-dodeoanesulfonate
  • sodium alkyl glyceryl ether sulfonates especially those ethers of the higher alcohols derived from tallow and coconut oil
  • Nonionic surfactants suitable for use in this invention may be broadly defined as compounds aliphatic or alkylaromatic in nature which do not ionize in water solution.
  • a well known class of nonionic synthetic detergents is made available on the market under the trade name of Pluronic. These compounds are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol.
  • the hydrophobic portion of the molecule which, of course, exhibits water insolubility has a molecular weight of from about 1,500 to 1,800.
  • the addition of polyoxyethylene radicals to this hydrophobic portion tends to increase the water solubility of the molecules as a whole and the liquid character of the product is retained up to the point where polyoxyethylene content is about 50% of the total weight of the condensation product.
  • nonionic synthetic detergents include: (a) The polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to 10 to 25 moles of ethylene oxide per mole of alkyl phenol.
  • the alkyl substitute in such compounds may be derived from polymerized propylene, diisobutylene, octene, or nonene, for example.
  • amine oxides corresponding to the following general formula, R R R N O, wherein R is an alkyl radical of from about 8 to 18 carbon atoms, and R and R are each methyl or ethyl radicals.
  • the arrow in the formula is a conventional representation of a semipolar bond.
  • amine oxides suitable for use in this invention include dimethyldodecylamine oxide, dimethyloctylamine oxide, dimethyldecylamine oxide, dimethyltetradecylamine oxide, dimethylhexadecylamine oxide.
  • Dimethyldodecylphosphine oxide Dimethyltetradecylphosphine oxide, Ethylmethyltetradecylphosphine oxide, Cetyldimethylphosphine oxide, Dimethylstearylphosphine oxide, Cetylethylpropylphosphine oxide, Diethyldodecylphosphine oxide,
  • suitable sulfoxide compounds are:
  • Tetradecyl methyl sulfoxide 3-hydroxytridecyl methyl sulfoxide, 2-hydroxydodecyl methyl sulfoxide, 3-hydroxy-4-decoxybutyl methyl sulfoxide, 3-hydroxy-4-dodecoxybutyl methyl sulfoxide, 2-hydroxy-3-decoxypropyl methyl sulfoxide, 2-hydroxy-3-dodecoxypropyl methyl sulfoxide, Dodecyl ethyl sulfoxide, and 2-hydroxydodecyl ethyl sulfoxide.
  • Cationic surfactants suitable for use in this invention are compounds having one of the following generic formulas where R and R are hydrophobic alkyl or alkylaryl groups containing 10 or more carbon atoms, a, b, and c are methyl, ethyl, or benzyl groups, AI is a nitrogen-containing aromatic group, and X is halide, sulfate, methosulfate or ethosulfate.
  • R and R are saturated unsaturated alkyl groups having 10 to 18 carbon atoms (cetyl, lauryl, myristyl, stearyl, oleyl) and mixtures of these such as those derived from natural products such as tallow and monoand dialkylbenzyl groups;
  • Ar is pyridine and isoquinoline and the like.
  • Typical examples of cationic surfactants are the following quaternary ammonium compounds:
  • bleaching, sterilizing, disinfecting and detergent compositions prepared by admixing a bleaching compound that yields active chlorine in water and a component selected from the group consisting of a detergent builder, an anionic, nonionic or cationic surfactant and a detergent filler wherein the improvement comprises,
  • bleaching, sterilizing, disinfecting and detergent composition is a household automatic dishwashing composition containing from 0.5 to 10% sodium dichloroisocyanurate dihydrate.
  • bleaching, sterilizing, disinfecting and detergent composition is a commercial dishwashing machine composition containing from 0.5 to 10% sodium dichloroisocyanurate dihydrate.
  • bleaching, sterilizing, disinfecting and detergent composition is a detergent-sanitizer containing from 5% to 50% sodium dichloroisocyanurate dihydrate.
  • bleaching, sterilizing, disinfecting and detergent composition is a sanitizer containing from 5% to 80% sodium dichloroisocyanurate dihydrate.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
US02778882*7A 1972-08-04 1972-08-04 Formulating with a non-burning chlorinated dry bleach Expired - Lifetime US3789000A (en)

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JPS5428283A (en) * 1977-08-05 1979-03-02 Kirisan Kasei Kk Bleaching agent

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US3035056A (en) * 1962-05-15 Potassium dichloroisocyanurate
AT212262B (de) * 1956-09-25 1960-12-12 Fmc Corp Aktives Chlor enthaltendes Präparat

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IT992836B (it) 1975-09-30
SE415194B (sv) 1980-09-15
DE2339117A1 (de) 1974-02-14
FR2194773A1 (enrdf_load_html_response) 1974-03-01
IL42678A (en) 1976-02-29
HK17077A (en) 1977-04-22
FR2194773B1 (enrdf_load_html_response) 1977-05-13
BE803084A (fr) 1974-01-31
DE2339117C3 (de) 1981-10-08
ZA734863B (en) 1974-06-26
JPS49131978A (enrdf_load_html_response) 1974-12-18
AU5782573A (en) 1975-01-09
ES417590A1 (es) 1976-08-01
IL42678A0 (en) 1973-10-25
NO144150B (no) 1981-03-23
GB1429987A (en) 1976-03-31
NO144150C (no) 1981-07-15
JPS5318189B2 (enrdf_load_html_response) 1978-06-13
BR7305934D0 (pt) 1974-05-16
AU471641B2 (en) 1976-04-29
CH581696A5 (enrdf_load_html_response) 1976-11-15
CA1004946A (en) 1977-02-08
DE2339117B2 (de) 1980-11-27
NL7310694A (enrdf_load_html_response) 1974-02-06
AR202632A1 (es) 1975-06-30

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AS Assignment

Owner name: OLIN CORPORATION, 120 LONG RIDGE ROAD, STAMFORD, C

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:FMC CORPORATION, 2000 MARKET STREET, PHILADELPHIA, PA., A CORP. OF DE.;REEL/FRAME:004467/0590

Effective date: 19850816