WO1991000763A1 - Formulations desemulsifiantes/antiemulsifiantes a faible viscosite - Google Patents

Formulations desemulsifiantes/antiemulsifiantes a faible viscosite Download PDF

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Publication number
WO1991000763A1
WO1991000763A1 PCT/US1990/003886 US9003886W WO9100763A1 WO 1991000763 A1 WO1991000763 A1 WO 1991000763A1 US 9003886 W US9003886 W US 9003886W WO 9100763 A1 WO9100763 A1 WO 9100763A1
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WO
WIPO (PCT)
Prior art keywords
composition
weight
mixture
liquid
value
Prior art date
Application number
PCT/US1990/003886
Other languages
English (en)
Inventor
Manilal S. Dahanayake
Original Assignee
Rhone-Poulenc Surfactants And Specialties, L.P.
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 Rhone-Poulenc Surfactants And Specialties, L.P. filed Critical Rhone-Poulenc Surfactants And Specialties, L.P.
Publication of WO1991000763A1 publication Critical patent/WO1991000763A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D19/00—Degasification of liquids
    • B01D19/02—Foam dispersion or prevention
    • B01D19/04—Foam dispersion or prevention by addition of chemical substances
    • B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
    • C08J2333/12—Homopolymers or copolymers of methyl methacrylate

Definitions

  • polypropylene glycols and polyoxyethylene-polyoxypropylene copolymers which have been employed individually as antifoaming agents have several drawbacks. Primarily, they have limited water solubility and dispersibility so that large amounts of these antifoamers must be employed and, even then, the defoa ing action is relatively low. Generally, a foam head of less than 2 cm on a 60 square cm surface area is the upper limit of tolerance for commercial defoaming applications and for certain uses not more than 0.3 cm is required. Secondly, formulations containing these compounds are somewhat viscous which presents pumping difficulties in antifoaming processing. Several solid non-foaming dispersing formulations have also been proposed as in U.S. 3,959,176; however these present problems of dispersibility and cannot be pumped into foamable solutions.
  • Another object of this invention is to provide a liquid mixture which is capable of defoaming an aqueous system at a greatly increased rate.
  • Another object is to provide a liquid antifoaming/defoaming composition having significantly reduced viscosity which can be most economically incorporated into a foamable liquid or added to a foam.
  • Still another object is to prepare a composition which, in addition to its antifoaming and defoaming properties, provides antiswelling in solutions of various polymers.
  • liquid antifoaming/defoaming mixture or blend of components having a cloud point less than 35 and comprising:
  • R is linear or branched chain alkyl having from 4 to 22 carbon atoms or a mixture thereof and is hydrophobic in character; x has a value of from 2 to 20; y has a value of from 0 to 15 and z has a value of from 10 to 200; with the proviso that when the number of carbon atoms in R, is less than 11, the value of x exceeds the value of y. It is to be understood that the values of x and y represent the total number of units in component (a) and do not define the order in which they appear; accordingly the formula of component (a) can also be written as
  • the cloud point of instant mixtures can vary, from about 1 to about 35, although a cloud point of from about 1 to 25 in distilled water is preferred.
  • Preferred blends of the present composition are those wherein component (a) and component (b) are each present in an amount between about 35% and about 65% by weight; most preferred are those having about equal proportions of component (a) and component (b) and wherein R is C 8 to C 22 alkyl and mixtures of said alcohol alkoxylates.
  • the moles propylene oxide units, with respect to ethylene oxide units is at least 50%.
  • the hydrophobic silica is preferably employed at concentrations between about 0.5 and about 8% by weight, most desirably, when a liquid mixture having a viscosity of not more than 500 centipoises (cps) is required, the concentration of the silica is not greater than 5% by weight.
  • the viscosity of the liquid mixture can vary between about 100 and about 3,000 cps, depending upon its intended use, lower viscosities of less than 550 are usually desired for processing purposes. While increased hydrophobic silica content materially raises the viscosity, such increased amounts do not provide any antifoaming benefit. Accordingly, the amount of hydrophobic silica above 10% by weight is not desirable.
  • the hydrophobic silica component of the composition is prepared from hydrophilic silica which is treated to render the silica hydrophobic.
  • One suitable method for rendering the silica hydrophobic is to permanently affix a liquid hydrophobic polysiloxane oil onto the silica particles.
  • Hydrophobic silica is well known in the art and, accordingly, no detailed description thereof is deemed necessary for a complete understanding of the present invention.
  • the preparation and use of hydrophobic silica is described in U.S. Patent Nos. 3,207,698; 3,408,306; and 3,076,768, as well as the refeences referred to in such patents, all of which are hereby incorporated by reference.
  • a preferred silica is a precipitated silica, such as the precipitated silica sold as Quso-G30 or Quso WR-83.
  • the above blend of components provides a hydrophobic/hydrophilic balance which allows faster diffusion of the antifoamer composition into the liquid/air interface and rapidly transports silica to the interface where a small amount efficiently performs defoaming action.
  • the components of the above mixture also interact to effect destructurization of the monomolecular foamed layer by increasing the free energy of interaction between the foam forming molecules which leads to liberation of air and collapse of bubbles.
  • the present composition has greater affinity for and faster action in aqueous systems which are subject to foaming.
  • the present blend is capable of reducing the foam head of a foamed liquid by at least 70% upon contact and in less than 1.5 minutes completely destroys the foam.
  • the present composition provides antiswelling properties to certain polymers such as polyvinyl halides, polypropylenes , polyethylenes, polytetrafluoroethylene, polychlorotrifluoroethylene and the like.
  • foamed solutions to which the present composition is applied include the alkali and alkaline earth metal salts, as well as ammonium salts, of alkyl benzene sulfonates and lauryl sulfates, lauryl ether sulfates, alkoxylated alkyl phenols, urethane polymers, phosphate ester surfactants, salts of fatty acids employed in the paper making industry and photopolymers such as methacrylic alkyl esters and their carboxylic salts employed for printed board circuits in the electronic industry.
  • the present blends are useful as defoamers or antifoamers for laundry detergents, dishwashing formulations, paper making processes, metal working processes and many others.
  • the blend is needed to provide the desired result.
  • a small amount of the blend is needed to provide the desired result.
  • a small amount of the blend is needed to provide the desired result.
  • the present mixture is economically and conveniently prepared by merely mixing components (a) , (b) and (c) in any order at a temperature between about 10°C. and about 100 ⁇ C. under atmospheric conditions for a period of up to 3 hours depending upon the volume and the mixing equipment employed.
  • the formulation is prepared within a 1 hour mixing period at ambient temperature.
  • the resulting mixture is preferably used in undiluted condition; although in certain cases where desired it can be diluted to a desired concentration with an inert solvent such as water, PEG, PPG, benzene, heptane, hydrocarbons and the like before contact with a foamed layer or before admixture wit a foamable liquid prior to agitation.
  • an inert solvent such as water, PEG, PPG, benzene, heptane, hydrocarbons and the like.
  • composition A was mixed for 5 minutes at ambient temperature under atmospheric conditions in a 200 ml glass beaker.
  • the antifoaming property of the above composition was tested as follows. As a control, 200 g. of 0.1% anionic dodecyl benzene sulfonate in water was stirred at ambient temperature in a glass measuring column for 1 minute at 1000 rpm and developed a foam head of 10 cm. Stirring was then discontinued and the liquid left to stand for 1 minute. The foam head was unchanged after 1 minute standing time. The above procedure was repeated except that 0.1 % of the above liquid composition was added to the sulfonate before stirring. After stirring this mixture for 1 minute, only 1.5 cm of foam head developed and after 1 minute standing time, the aqueous sulfonate solution was completely defoa ed. EXAMPLE 2
  • Example 2 The antifoaming test of Example 1 was repeated except that a methacrylic acid methyl ester photopolymer in 0.85% Na 2 C0 3 , was substituted for the foamable sulfonate.
  • the results were as follows cm
  • Example 1 was repeated except that ethoxylated (9 moles) nonyl phenol was substituted as the foamable liquid.
  • the results were as follows.
  • composition X was mixed for 5 minutes at ambient temperature under atmospheric conditions in a 200 ml glass beaker.
  • the antifoaming property of the above composition was tested as follows. As a control, 200 g. of 0.1% anionic dodecyl benzene sulfonate in water was stirred at ambient temperature in a glass measuring column for 1 minute at 1000 rpm and developed a foam head of 10 cm. Stirring was then discontinued and the liquid left to stand for 1 minute. The foam head was unchanged after 1 minute standing time. The above procedure was repeated except that 0.1 % of the above liquid composition X was added to the sulfonate before stirring. After stirring this mixture for 1 minute, only 1.8 cm of foam head developed and after 1 minute standing time, the foam head of the aqueous sulfonate solution was 0.4. COMPARATIVE EXAMPLE 5
  • composition B was mixed for 5 minutes at ambient temperature under atmospheric pressure in a 200 ml glass beaker.
  • the viscosity of this composition was 700 cps.
  • the hydrophobic silica was increased to 10% and component (i) reduced to 40%, the viscosity of the mixture increased to 2000 SUS which made pumping of the liquid composition difficult and led to deposits on the equipment.
  • dispersibility in the foamable liquid solution of dodecyl benzene sulfonate was markedly reduced.
  • the foam head of the aqueous sulfonate solution was reduced only 35% (to 3.5 cm) using composition B.
  • Example 1 The procedure in Example 1 is repeated except that components (b) and (c) are omitted.
  • Example 1 The procedure in Example 1 is repeated except that components (a) and (c) are omitted.
  • the results of the antifoaming test are as follows.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Toxicology (AREA)
  • Degasification And Air Bubble Elimination (AREA)

Abstract

L'invention concerne des formulations liquides hydrophobes/hydrophiles équilibrées comprenant: a) entre environ 10 % et environ 90 % en poids d'alkoxylate d'alcool dont la formule est (I), b) entre environ 90 % et environ 10 % en poids de polypropylèneglycol dont la formule est (II), et c) entre environ 0,3 % et environ 10 % en poids de dioxyde de silicium hydrophobe à base de (a) et (b). L'invention se rapporte également à l'utilisation du mélange précité dans les liquides moussés ou dans un liquide susceptible de mousser.
PCT/US1990/003886 1989-07-12 1990-07-11 Formulations desemulsifiantes/antiemulsifiantes a faible viscosite WO1991000763A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US37931289A 1989-07-12 1989-07-12
US379,312 1989-07-12

Publications (1)

Publication Number Publication Date
WO1991000763A1 true WO1991000763A1 (fr) 1991-01-24

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Family Applications (1)

Application Number Title Priority Date Filing Date
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Country Status (3)

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AU (1) AU6063590A (fr)
IL (1) IL95029A0 (fr)
WO (1) WO1991000763A1 (fr)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0544303A2 (fr) * 1991-11-27 1993-06-02 Union Carbide Chemicals & Plastics Technology Corporation Suspensions des polymères solubles dans l'eau
WO1994003251A1 (fr) * 1992-07-30 1994-02-17 Henkel Kommanditgesellschaft Auf Aktien Agents antimousse fermes au niveau du groupe terminal
EP1018354A1 (fr) * 1999-01-04 2000-07-12 Halliburton Energy Services, Inc. Compositions anti-mousse pour fluides de traitement de puits de forage
US6417142B1 (en) 2001-10-02 2002-07-09 Halliburton Energy Services, Inc. Defoaming methods and compositions
US7273103B2 (en) 2005-06-03 2007-09-25 Halliburtoncenergy Services, Inc. Cement compositions comprising environmentally compatible defoaming agents and methods of use
US7670423B2 (en) 2005-06-03 2010-03-02 Halliburton Energy Services, Inc. Cement composition comprising environmentally compatible defoaming agents and methods of use
WO2010108858A1 (fr) 2009-03-26 2010-09-30 Dr. W. Kolb Ag Agent de désaération d'une eau de traitement, en particulier lors de la fabrication de papier
US9487736B2 (en) 2012-02-16 2016-11-08 Dow Corning Corporation Granulated foam control agent for the rinse cycle using siloxane wax
US9913795B2 (en) 2013-08-09 2018-03-13 Dow Corning Corporation Cosmetic compositions containing silicones
US10005110B2 (en) 2011-02-16 2018-06-26 Dow Silicones Corporation Foam control composition
WO2020227056A1 (fr) * 2019-05-03 2020-11-12 Sasol Performance Chemicals Gmbh Mélanges d'alcoxylate d'alcool en tant qu'agents anti-mousse aqueux concentrés
JP2021023891A (ja) * 2019-08-06 2021-02-22 サンノプコ株式会社 消泡剤及び塩化ビニル系樹脂の製造方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA724623A (en) * 1965-12-28 E. Sullivan Robert Foam control agents ii
JPS53134785A (en) * 1977-04-30 1978-11-24 Nippon Oil & Fats Co Ltd Deforming agent
DD200024A1 (de) * 1981-07-27 1983-03-09 Wolfgang Thuemmler Verfahren zur restmonomerenentfernung aus waessrigen vinylchloridpolymerisat-dispersionen
CA1143244A (fr) * 1979-10-22 1983-03-22 Robert E. Gansser Composition de repression des ecumes
JPS607909A (ja) * 1983-06-25 1985-01-16 Toho Chem Ind Co Ltd 発泡液用消泡剤
JPS63232808A (ja) * 1987-03-19 1988-09-28 Meisei Kagaku Kogyo Kk 製紙工業において使用される消泡剤

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA724623A (en) * 1965-12-28 E. Sullivan Robert Foam control agents ii
JPS53134785A (en) * 1977-04-30 1978-11-24 Nippon Oil & Fats Co Ltd Deforming agent
CA1143244A (fr) * 1979-10-22 1983-03-22 Robert E. Gansser Composition de repression des ecumes
DD200024A1 (de) * 1981-07-27 1983-03-09 Wolfgang Thuemmler Verfahren zur restmonomerenentfernung aus waessrigen vinylchloridpolymerisat-dispersionen
JPS607909A (ja) * 1983-06-25 1985-01-16 Toho Chem Ind Co Ltd 発泡液用消泡剤
JPS63232808A (ja) * 1987-03-19 1988-09-28 Meisei Kagaku Kogyo Kk 製紙工業において使用される消泡剤

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Choosing the Right Polyglycol, Technical Service and Development, DOW CHEMICAL COMPANY, MIDLAND, MICHIGAN, 3rd Ed., 1959, see entire document. *
Information on Applications of Pluronics Wayndotte, WAYNDOTTE, MICHIGAN, 01 March 1952, see pages 8, 10 & 12. *

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0544303A2 (fr) * 1991-11-27 1993-06-02 Union Carbide Chemicals & Plastics Technology Corporation Suspensions des polymères solubles dans l'eau
EP0544303A3 (en) * 1991-11-27 1993-09-29 Union Carbide Chemicals & Plastics Technology Corporation Slurries of water-soluble polymers
WO1994003251A1 (fr) * 1992-07-30 1994-02-17 Henkel Kommanditgesellschaft Auf Aktien Agents antimousse fermes au niveau du groupe terminal
EP1018354A1 (fr) * 1999-01-04 2000-07-12 Halliburton Energy Services, Inc. Compositions anti-mousse pour fluides de traitement de puits de forage
US6156808A (en) * 1999-01-04 2000-12-05 Halliburton Energy Services, Inc. Defoaming compositions and methods
US6297202B1 (en) 1999-01-04 2001-10-02 Halliburton Energy Services, Inc. Defoaming compositions and methods
US6417142B1 (en) 2001-10-02 2002-07-09 Halliburton Energy Services, Inc. Defoaming methods and compositions
US7670423B2 (en) 2005-06-03 2010-03-02 Halliburton Energy Services, Inc. Cement composition comprising environmentally compatible defoaming agents and methods of use
US7273103B2 (en) 2005-06-03 2007-09-25 Halliburtoncenergy Services, Inc. Cement compositions comprising environmentally compatible defoaming agents and methods of use
WO2010108858A1 (fr) 2009-03-26 2010-09-30 Dr. W. Kolb Ag Agent de désaération d'une eau de traitement, en particulier lors de la fabrication de papier
US10005110B2 (en) 2011-02-16 2018-06-26 Dow Silicones Corporation Foam control composition
US9487736B2 (en) 2012-02-16 2016-11-08 Dow Corning Corporation Granulated foam control agent for the rinse cycle using siloxane wax
US9913795B2 (en) 2013-08-09 2018-03-13 Dow Corning Corporation Cosmetic compositions containing silicones
WO2020227056A1 (fr) * 2019-05-03 2020-11-12 Sasol Performance Chemicals Gmbh Mélanges d'alcoxylate d'alcool en tant qu'agents anti-mousse aqueux concentrés
CN114126735A (zh) * 2019-05-03 2022-03-01 萨索尔化学品有限公司 作为浓缩的水性消泡剂的醇烷氧化物混合物
JP2021023891A (ja) * 2019-08-06 2021-02-22 サンノプコ株式会社 消泡剤及び塩化ビニル系樹脂の製造方法

Also Published As

Publication number Publication date
IL95029A0 (en) 1991-06-10
AU6063590A (en) 1991-02-06

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