WO2012135463A2 - Compositions de tensioactif et procédés de fabrication - Google Patents

Compositions de tensioactif et procédés de fabrication Download PDF

Info

Publication number
WO2012135463A2
WO2012135463A2 PCT/US2012/031158 US2012031158W WO2012135463A2 WO 2012135463 A2 WO2012135463 A2 WO 2012135463A2 US 2012031158 W US2012031158 W US 2012031158W WO 2012135463 A2 WO2012135463 A2 WO 2012135463A2
Authority
WO
WIPO (PCT)
Prior art keywords
surfactant
composition
alcohol
liquid detergent
alcohol ethoxylate
Prior art date
Application number
PCT/US2012/031158
Other languages
English (en)
Other versions
WO2012135463A3 (fr
Inventor
Paul Theodore SHARKO
Julian Richard Barnes
Elizabeth Elaine ENDLER
Original Assignee
Shell Oil Company
Shell Internationale Research Maatschappij B.V.
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 Shell Oil Company, Shell Internationale Research Maatschappij B.V. filed Critical Shell Oil Company
Publication of WO2012135463A2 publication Critical patent/WO2012135463A2/fr
Publication of WO2012135463A3 publication Critical patent/WO2012135463A3/fr

Links

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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • This invention relates to surfactant compositions for use in detergent applications and methods for manufacture of those compositions.
  • the invention provides a composition
  • a composition comprising an alcohol ethoxylate having a formula R 1 -0-(CH 2 CH 2 0) m -H where R 1 is one or more substantially straight-chain alkyl groups having Y carbon atoms; a salt of an alcohol ethoxysulfate having a formula R 2 -0- (CH 2 CH 2 0) n -S0 3 X where R 2 is one or more substantially straight-chain alkyl groups having Z carbon atoms, X is a cation selected from an alkali metal ion, an ammonium ion, and mixtures thereof; and less than 20 wt% water wherein Z is at least 9, Y may be less than, greater than, or equal to Z, and m is greater than or equal to n.
  • the invention further provides a method of preparing a surfactant blend comprising reacting an alcohol ethoxylate of the formula R 1 -0-(CH 2 CH 2 0) m -H with gaseous S0 3 to produce the acid form of an alcohol ethoxysulfate; and neutralizing the acid form of the ethoxysulfate with an alkaline solution of alcohol ethoxylate of the formula R 2 -0-(CH 2 CH 2 0) n -H where R 1 is one or more substantially straight-chain alkyl groups, R 2 is one or more substantially straight-chain alkyl groups, m is less than or equal to n, and n is at least 4.
  • the invention further provides a method of preparing a surfactant blend comprising reacting an alcohol ethoxylate of the formula R 1 -0-(CH2CH 2 0) m -H with gaseous S0 3 at a mole ratio of S0 3 to alcohol ethoxylate of less than 1 to produce the acid form of an alcohol ethoxysulfate in a solution of unreacted alcohol ethoxylate; and neutralizing the acid/unreacted ethoxylate mixture with an alkaline aqueous solution where R 1 is one or more substantially straight-chain alkyl groups, and m is at least 4.
  • Figure 1 depicts the chemical reactions involved in two embodiments of the manufacture of the surfactant compositions.
  • Figures 2a-2b depict the viscosity of various surfactant blends.
  • Figure 3 depicts the gel regions of surfactant blends formed using different neutralization agents.
  • Figure 4 depicts the solution time of surfactant blends.
  • Figure 5 depicts the detergency performance as determined by reflectance detergency of surfactant blends in combination with selected detergent components.
  • Figure 6 depicts the detergency performance as determined by radiotracer detergency of surfactant blends in combination with selected detergent components.
  • Figure 7 depicts the detergency performance as determined by reflectance detergency of surfactant blends in combination with selected detergent components.
  • Figure 8 depicts the detergency performance as determined by reflectance detergency of surfactant blends in combination with selected detergent components.
  • Figure 9 depicts the detergency performance as determined by a soil titration method of surfactant blends.
  • Liquid product formulations have increased in popularity as consumer cleaning products have evolved. Compact formulas have gained acceptance as a means to produce more sustainable formulations, as packaging and transportation footprints are reduced. Also, as washing temperatures have declined globally, the improved dissolution of liquids in low temperature wash water has become an attractive attribute compared to less soluble powders.
  • surfactants are selected for their performance and handling characteristics. For household laundry, a blend of anionic and nonionic surfactants is typically most effective against a wide variety of soils.
  • AEOS alcohol ethoxysulfate
  • AE alcohol ethoxylates
  • the properties of AEOS in liquid detergents include relatively high-foaming, low sensitivity to water hardness, and excellent enzyme stability relative to linear alkylbenzene sulfonate (LAS).
  • LAS linear alkylbenzene sulfonate
  • Mixed surfactant systems have been used for a number of years, since these systems often exhibit synergism or antagonism.
  • This invention provides surfactant blends of alcohol ethoxylates and alcohol ethoxysulfates that provide excellent performance and demonstrate excellent handling characteristics.
  • Surfactants provide the primary soil removal capability of a detergent, with enzymes, builders, and antiredeposition agents often added to the detergent formulation to assist with soil removal. Additionally, a surface is often judged to be clean through visual inspection, and optical brighteners may be added to a detergent to improve the appearance of fabrics. Further, detergent compositions may also be designed to impart a secondary benefit, such as antimicrobial activity or skin
  • the surfactant blends described by the invention may be used to prepare liquid detergents that may be used for cleaning a variety of surfaces.
  • a detergent formulation containing the surfactant composition described in the invention may also contain water, additional surfactants, enzymes, antiredeposition agents, optical brighteners, builders, foam boosters or reducers, rheology modifiers, pH adjustment materials, preservatives, antimicrobial agents, skin conditioners, or fragrances.
  • the nomenclature to be used herein for the alcohol ethoxylates is depicted in Table 1 along with the pour points of the respective alcohol ethoxylates.
  • the name with a "S" designation indicates an alcohol ethoxysulfate formed by sulfating the alcohol ethoxylate, e.g., AE 91-8S.
  • the surfactant blends comprise an alcohol ethoxylate component, an alcohol ethoxysulfate component and less than 20 wt% of water.
  • the composition is preferably free of organic solvents, particularly low molecular weight organic solvents, such as, lower alcohols having from 1 to 5 carbon atoms.
  • R 1 is a straight-chain or branched-chain alkyl group having in the range of from about 8 to about 18 carbon atoms, preferably 9 to 15 carbon atoms, and m represents the average number of oxyethylene groups per molecule and is in the range of from about 1 to about 12.
  • Ethoxylates within this class are conventionally prepared by the sequential addition of ethylene oxide to the corresponding alcohol (R 1 OH) in the presence of a catalyst.
  • the general class of alcohol ethoxysulfates suitable for use in the surfactant blends described herein is characterized by the chemical formula
  • R 2 is a straight-chain or branched-chain alkyl group having in the range of from about 8 to about 18 carbon atoms
  • n represents the average number of oxyethylene groups per molecule and is in the range of from about 1 to about 12
  • X is a cation selected from an alkali metal ion, an ammonium ion, and mixtures thereof.
  • Ethoxysulfates within this class are typically prepared by one of two methods, which are depicted in Figure 1.
  • the first method for producing the surfactant blends is termed "neutralization".
  • an alcohol ethoxylate generally containing an average of three or fewer EO groups, is fed to a falling-film sulfation reactor and reacted with gaseous S0 3 at a mole ratio of about 0.98 - 1.02 to produce the acid form of an alcohol ethoxysulfate.
  • this acid is then immediately neutralized in an alkaline solution of nonionic surfactant, generally an alcohol ethoxylate which generally contains an average of four or more EO groups.
  • the alcohol groups are designated Ri and R 2 in the figure, where R may be selected from C 8 to Ci 8 .
  • Sodium hydroxide (NaOH) or triethanolamine (TEA) is typically combined with the nonionic surfactant to produce a solution that is used for neutralization of the alcohol ethoxysulfate acid.
  • an alcohol ethoxylate generally containing an average of four or more EO groups, is fed to a falling-film sulfation reactor, reacted with gaseous S0 3 at a mole ratio significantly under 1 to produce an acid form of an alcohol
  • Both methods can be used to produce surfactant blends with total active surfactant content (AEOS and AE) greater than 70%, preferably greater than 85%, and more preferably greater than 90%.
  • AEOS and AE total active surfactant content
  • the high active products are typically transparent and fluid at reasonably low temperatures.
  • Viscosities of surfactants and surfactant blends were measured using a temperature-controlled Brookfield viscometer. Solution times were determined by preparing 50 mL of deionized water at 25°C in a flat bottom pour point tube stirred at 500 rpm with a 1.5 x 0.5 cm magnetic stir bar and adding 0.20 mL of ethoxylate below the water line. The solution time was judged as the time at which the ethoxylate was completely dissolved. Gel curves were obtained for selected systems by studying desired ratios of surfactant concentrate and deionized water in test tubes. The samples were heated to approximately 70°C and thoroughly mixed manually. After observation at the maximum test temperature, the solutions were cooled in 10°C intervals and observed under polarized light at each temperature.
  • Figures 2a-2b illustrate viscosity data for different surfactant blends measured at
  • gel is used here to indicate the collection of micelle structures that do not flow, such as hexagonal and bicontinuous phases. Adding co- solvents, such as propylene glycol, can also help narrow the gel regions.
  • Figure 4 also helps demonstrate how alcohol ethoxylates based on alcohols of lighter molecular weight improve fluidity and rate of dissolution in water. The latter is important to insure good cleaning performance in a wash cycle.
  • AE 91-8 and AE 23-6.5 are shown for reference relative to the surfactant blends.
  • the dissolution test (a spinning stir bar in a volume of liquid) is rather mild and solution times will likely be long relative to solution times achieved through high shear mixing. Solution times of ⁇ 5 minutes are considered acceptable, since more rigorous mixing conditions would likely be used during the preparation of a formulation.
  • the surface tension of deionized water is 72 dynes/cm.
  • the surfactant blends generally reduce the surface tension of water to values of 28-32 dynes/cm, behavior which is consistent with data for single component alcohol ethoxylates.
  • An exception to this trend is the single component alcohol ethoxysulfate AE 91-8S, which only reduces surface tension to 39 dynes/cm. Therefore, it is likely that alcohol ethoxysulfates based on AE 91-8 are highly soluble in water and are not as active at the air-water interface as are alcohol ethoxysulfates based on higher molecular weight alcohols.
  • CMC critical micelle concentration
  • AE 91-8 has a CMC approximately one order of magnitude higher than AE 23-6.5 or AE 25-7. This difference is most likely due to the lighter molecular-weight alcohol used as the surfactant hydrophobe.
  • Table 2b compare the CMCs for surfactant blends containing different anionic: nonionic surfactant ratios, as well as different counter ions used for neutralization.
  • Soil removal was measured by reflectance or by radiotracer methods, and the methods have previously been correlated. Soils, wash temperatures, and water hardness 5 were selected to match consumer-relevant conditions. No enzymes or optical brighteners were used. For reflectance measurements, pre-soiled swatches were washed in a Terg-o- tometer for a 10 minute wash cycle. The soil used exclusively in this method was a
  • AE 23- 2S/AE 91-8 is a good candidate for detergent formulations, since it was previously shown to have promising physical properties.
  • Selection of the proper surfactant blend for a formulation is a function of desired performance, desired formulation appearance, and logistics and handling capacity.
  • Figure 8 shows that a targeted level of cleaning performance can be achieved at similar total surfactant loading with different neutralization agents and different ratios of anionic: nonionic surfactant.
  • Alcohol ethoxysulfates are the primary components of liquid dish formulations, and additional surfactants are commonly used to boost performance.
  • Figure 9 shows that an anionic: nonionic surfactant blend is nearly as effective at cleaning food soil as a standard blend of linear alkylbenzene sulfonate (LAS) and alcohol ethoxysulfate.
  • LAS linear alkylbenzene sulfonate
  • Figure 9 shows that an anionic: nonionic surfactant blend is nearly as effective at cleaning food soil as a standard blend of linear alkylbenzene sulfonate (LAS) and alcohol ethoxysulfate.
  • LAS linear alkylbenzene sulfonate
  • AE 23-2S/AE 91-8 is relatively fluid at high concentrations and is a candidate for the concentration of liquid dish products.

Landscapes

  • 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)

Abstract

L'invention concerne des mélanges de tensioactifs qui sont utiles dans une composition de détergent, en particulier des mélanges de tensioactifs comprenant des éthoxylates d'alcool, des éthoxysulfates d'alcool et moins de 20 % d'eau. En outre, elle concerne des procédés de fabrication de ces mélanges de tensioactifs.
PCT/US2012/031158 2011-03-31 2012-03-29 Compositions de tensioactif et procédés de fabrication WO2012135463A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201161470068P 2011-03-31 2011-03-31
US61/470,068 2011-03-31

Publications (2)

Publication Number Publication Date
WO2012135463A2 true WO2012135463A2 (fr) 2012-10-04
WO2012135463A3 WO2012135463A3 (fr) 2012-12-27

Family

ID=46932337

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2012/031158 WO2012135463A2 (fr) 2011-03-31 2012-03-29 Compositions de tensioactif et procédés de fabrication

Country Status (1)

Country Link
WO (1) WO2012135463A2 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0431653A2 (fr) * 1989-08-31 1991-06-12 Shell Internationale Researchmaatschappij B.V. Composition liquide tensio-active
US5209874A (en) * 1989-04-26 1993-05-11 Shell Oil Company Liquid surface active compositions
US6284724B1 (en) * 1995-05-09 2001-09-04 Church & Dwight Co., Inc. Powder laundry detergent product with improved cold water residue properties
US20060183655A1 (en) * 2005-02-14 2006-08-17 Thorsten Bastigkeit Surface active composition containing alcoholethoxy sulfate for use in laundry detergents and process for making it
US20080312121A1 (en) * 2005-09-08 2008-12-18 Kirk Herbert Raney Liquid Surface Active Compositions

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5209874A (en) * 1989-04-26 1993-05-11 Shell Oil Company Liquid surface active compositions
EP0431653A2 (fr) * 1989-08-31 1991-06-12 Shell Internationale Researchmaatschappij B.V. Composition liquide tensio-active
US6284724B1 (en) * 1995-05-09 2001-09-04 Church & Dwight Co., Inc. Powder laundry detergent product with improved cold water residue properties
US20060183655A1 (en) * 2005-02-14 2006-08-17 Thorsten Bastigkeit Surface active composition containing alcoholethoxy sulfate for use in laundry detergents and process for making it
US20080312121A1 (en) * 2005-09-08 2008-12-18 Kirk Herbert Raney Liquid Surface Active Compositions

Also Published As

Publication number Publication date
WO2012135463A3 (fr) 2012-12-27

Similar Documents

Publication Publication Date Title
EP3152286B1 (fr) Détergents pour nettoyage à l'eau froide
JP4275723B2 (ja) 界面活性剤組成物
JP5133083B2 (ja) 液体洗浄剤組成物
JP5686638B2 (ja) 衣料用液体洗浄剤組成物
JP5186493B2 (ja) 洗浄剤組成物
US4668423A (en) Liquid biodegradable surfactant and use thereof
JP5571367B2 (ja) 界面活性剤組成物
EP3574067A1 (fr) Composition de tensioactif concentrée
JPH05132699A (ja) 軽質液体洗剤組成物
JP2009540025A5 (fr)
EP3971274B1 (fr) Composition de nettoyage liquide pour laver la vaisselle à la main
NZ240394A (en) Liquid detergent comprising alkylbenzene sulphonate, a magnesium salt and
JP5439205B2 (ja) 液体洗浄剤組成物
EP1589093B1 (fr) Composition de detergent liquide
JP2001131579A (ja) 脂肪酸ｎ−アルキルポリヒドロキシアミドと脂肪酸アミドアルコキシレートとよりなる界面活性剤混合物
JP2008156589A (ja) 液体洗浄剤組成物
CN111492045B (zh) 包含烷基乙氧基化硫酸盐表面活性剂的液体洗涤剂组合物
JP2017078098A (ja) 食器用液体洗浄剤
JP2018035269A (ja) 台所用洗浄剤組成物
WO2012135463A2 (fr) Compositions de tensioactif et procédés de fabrication
JP4361052B2 (ja) 液体洗浄剤組成物
JP2022063462A (ja) 食器用洗浄剤
JP2020519754A (ja) 全炭素数１４のアルキル鎖長を有するａｅｓ界面活性剤を含む洗剤組成物
JP7381534B2 (ja) 液体食器手洗い用洗浄組成物
EP3971271B1 (fr) Composition de nettoyage liquide pour laver la vaisselle à la main

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12765922

Country of ref document: EP

Kind code of ref document: A2

NENP Non-entry into the national phase in:

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12765922

Country of ref document: EP

Kind code of ref document: A2