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US20100093598A1 - Silicone Foam Control Agent - Google Patents

Silicone Foam Control Agent Download PDF

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Publication number
US20100093598A1
US20100093598A1 US12/445,108 US44510807A US2010093598A1 US 20100093598 A1 US20100093598 A1 US 20100093598A1 US 44510807 A US44510807 A US 44510807A US 2010093598 A1 US2010093598 A1 US 2010093598A1
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US
United States
Prior art keywords
foam control
control agent
groups
oil
water
Prior art date
Legal status (The legal status 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 status listed.)
Abandoned
Application number
US12/445,108
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English (en)
Inventor
Delphine Davio
Alain Hilberer
Jacqueline L'Hostis
Jean-Paul H. Lecomte
Andreas Stammer
Nicolas Ziolkowski
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Silicones Belgium SPRL
Original Assignee
Dow Corning Europe SA
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 Dow Corning Europe SA filed Critical Dow Corning Europe SA
Priority to US12/445,108 priority Critical patent/US20100093598A1/en
Assigned to DOW CORNING EUROPE SA reassignment DOW CORNING EUROPE SA ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DAVIO, DELPHINE, HILBERER, ALAIN, LECOMTE, JEAN-PAUL H., L'HOSTIS, JACQUELINE, STAMMER, ANDREAS
Publication of US20100093598A1 publication Critical patent/US20100093598A1/en
Assigned to DOW CORNING EUROPE SA reassignment DOW CORNING EUROPE SA ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ZIOLKOWSKI, NICOLAS
Abandoned legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M155/00—Lubricating compositions characterised by the additive being a macromolecular compound containing atoms of elements not provided for in groups C10M143/00 - C10M153/00
    • C10M155/02—Monomer containing silicon
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/06—Emulsions
    • A61K8/062—Oil-in-water emulsions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/06—Emulsions
    • A61K8/068—Microemulsions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/50—Lubricating compositions characterised by the base-material being a macromolecular compound containing silicon
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M173/00—Lubricating compositions containing more than 10% water
    • C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
    • 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
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02—Preparations containing skin colorants, e.g. pigments
    • A61Q1/10—Preparations containing skin colorants, e.g. pigments for eyes, e.g. eyeliner, mascara
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/10—Washing or bathing preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/12—Preparations containing hair conditioners
    • 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
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/0405—Siloxanes with specific structure used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/041—Siloxanes with specific structure containing aliphatic substituents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/041—Siloxanes with specific structure containing aliphatic substituents
    • C10M2229/0415—Siloxanes with specific structure containing aliphatic substituents used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/043—Siloxanes with specific structure containing carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/043—Siloxanes with specific structure containing carbon-to-carbon double bonds
    • C10M2229/0435—Siloxanes with specific structure containing carbon-to-carbon double bonds used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/045—Siloxanes with specific structure containing silicon-to-hydroxyl bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/045—Siloxanes with specific structure containing silicon-to-hydroxyl bonds
    • C10M2229/0455—Siloxanes with specific structure containing silicon-to-hydroxyl bonds used as base material

Definitions

  • This invention is concerned with silicone-based foam control agents, particularly for use in aqueous compositions, preferably detergent compositions.
  • aqueous systems which are used e.g. in food processes, textile dying, paper production, sewage treatment and cleaning applications
  • surface active agents are present either as an unwanted ingredient or as deliberately introduced materials to achieve a certain function. Due to the presence of these surface active agents foam is often generated. In certain applications, such as in dish washing by hand, this is a welcome effect but in other applications foam generation can lead to unsatisfactory results. This is for example the case in the dyeing of textiles or in the manufacture of paper. In other applications, for example the use of detergent compositions for domestic laundering, the production of foam needs to be controlled rather than avoided. It is important to keep the foam formation to an acceptable level when laundering is performed in automatic washing machines, especially front loading machines. Excessive foam would cause overflow of the washing liquor onto the floor as well as reduction in the efficiency of the laundering operation itself.
  • Silicone-based foam control agents are known and have been incorporated into, for example, heavy duty detergent powders and liquids for use in automatic washing machines. Silicone foam control agents are regarded as very effective in this application as they can be added in very small quantities and are not affected by e.g. the hardness of water, while traditional foam control compositions, such as soaps, require a certain water hardness for their effectiveness. However, they are usually not cheap, and there is a need to find ways to cheapen such formulations without compromising the cost-efficiency of the foam control agents.
  • Silicone foam control agents are mostly based on organopolysiloxane materials, which may be linear or branched, and which may contain a variety of silicon-bonded substituents. As the market for these products has developed the antifoams available have become increasingly complex and difficult and expensive to produce. The polymers used can be extremely expensive to produce because of the complex side chain technology required.
  • EP 217501 describes a foam control agent wherein a liquid siloxane component is obtained by blending two pre-prepared polymers:—
  • the post heated mixture has a viscosity in the range of 1 ⁇ 10 ⁇ 2 m 2 /s to 3 ⁇ 10 ⁇ 2 m 2 /s at 25° C.
  • the specification describes the need to control the amount of resin used in order to retain a liquid polymer, avoiding a gel structure. This indicates that some branching occurs in the siloxane component of the foam control agent.
  • U.S. Pat. No. 3,691,091 discloses a silicone emulsion for defoaming aqueous liquids, in which the silicone consists essentially of a polydimethylsiloxane fluid, silica, and an organosilicon compound or oligomer containing alkoxy and/or silanol groups.
  • EP0163541 describes a method for the preparation of a silicone defoamer by reacting a mixture of components including a pre-prepared polyorganosiloxane polymer bearing one or more hydroxyl and/or hydrocarbonoxy groups, a silicone resin, a filler, a catalyst to promote reaction.
  • the composition can contain an organopolysiloxane free of reactive groups.
  • EP 0273448 describes a process for preparing a foam suppressant composition by reacting an organopolysiloxane together with amorphous silica and a free radical initiator catalyst and optionally a vinyl monomer and/or a vinyl modified polyorganosiloxane under conditions and for a time sufficient such that free radical polymerisation occurs and a polymerisation product forms.
  • the resulting product is diluted with sufficient quantities of a polydiorganosiloxane having a viscosity of 10 to 300 cSt such that the final composition has a viscosity of 100 to 10,000 cSt.
  • GB 2257709 describes a foam control agent which is particularly useful when incorporated in detergent compositions where a high level of high foaming surfactants is present, and comprises a branched polydiorganosiloxane which is prepared through hydrosilylation of a vinyl end-blocked polydiorganosiloxane having a viscosity of from 200 to 100 000 mPa ⁇ s at 25° C., a volatile low viscosity organohydrogensiloxane having at least 3 Si—H groups and a solvent in the presence of a noble metal catalyst.
  • the solvent used was preferably a polydiorganosiloxane and was mainly present to solubilise the branched polydiorganosiloxane product.
  • GB 1224026 describes an antifoaming agent which is composed of 10 parts by weight of certain water-insoluble organic liquids and from 0.1 to 5.0 parts by weight of an organopolysiloxane which is compatible in the organic liquid and consists essentially of monovalent and tetravalent siloxane units.
  • 3,666,681 describes an antifoaming agent for aqueous systems consisting essentially of a mixture of 100 parts by weight of certain water-insoluble organic liquids, from 0.5 to 10.0 parts by weight of an organopolysiloxane, which may be a fluid or a resinous compound, and from 0.5 to 10.0 parts by weight of a filler which is selected from finely divided silica and methylsilsesquioxane gel, and from 0.002 to 5.0 parts by weight of a compound which is selected from ammonia, a disilazane and an alkali or alkaline earth metal hydroxide.
  • an organopolysiloxane which may be a fluid or a resinous compound
  • a filler which is selected from finely divided silica and methylsilsesquioxane gel
  • EP1075863 describes a foam control agent according to the invention comprises (A) a pre-prepared organopolysiloxane polymeric material having at least one silicon-bonded substituent of the formula X-Ph, wherein X denotes a divalent aliphatic hydrocarbon group and Ph denotes an aromatic group, (B) a water-insoluble organic fluid, (C) an organosilicon resin and (D) a hydrophobic filler.
  • U.S. Pat. No. 4,690,713 describes an antifoam composition comprising (a) either a hydrocarbon oil or a pre-prepared polydimethylsiloxane polymer, (b) an organosilane, (c) silica filler, and (d) a suitable catalyst.
  • U.S. Pat. No. 5,777,059 describes a silicone composition by reacting (i) a polyisobutylene compound, (ii) a pre-prepared polyorganosiloxane polymer, (iii) an organosilane or silicone resin, (iv) a suitable catalyst and optionally a silica filler. The mixture is blended and then reacted at room temperature or with heat.
  • WO2005/058454 and WO2005/058455 describe foam control compositions comprising a liquid polymer of an unsaturated hydrocarbon, a branched silicone resin and a particulate filler which is insoluble in the liquid hydrocarbon polymer.
  • WO2005/058455 further comprises a non polar organic material having a melting point of 35 to 100° C. which is miscible with the organic liquid.
  • the invention is directed to a method of making silicone-based foam control agents comprising
  • steps (iii) and (iv) may take place in any order and may, but need not, be both undertaken at the same stage in the process. Most preferably step (iv) is undertaken after step (ii) where required.
  • an inert fluid e.g. the inert organopolysiloxane and/or organic fluid
  • an inert fluid is intended to be unreactive towards any other constituent of step (i), (ii) and (iii) above. i.e. it does not chemically participate in the polymerisation reaction of step (i) and does not chemically interact with the additives introduced in steps (ii) and (iii).
  • the filler and resin of steps (ii) and (iii) respectively may be introduced into the mixture in the form of a concentrate comprising the filler and/or resin in the inert fluid, especially if this aids processing.
  • a polysiloxane containing polymer is intended to mean a polymer comprising multiple organosiloxane or polyorganosiloxane groups per molecule and is intended to include a polymer substantially containing only organosiloxane or polyorganosiloxane groups in the polymer chain and polymers where the backbone contains both organosiloxane and/or polyorganosiloxane groups and e.g. organic polymeric groups in the polymeric chain.
  • Such polymers can be homopolymers or co-polymers, including, but not limited to, block co-polymers and random co-polymers.
  • a polysiloxane containing polymer which has been prepared in the presence of an inert fluid in accordance with the present invention preferably has the general formula:
  • each R is the same or different and is an alkyl group preferably containing 1-8 carbon atoms, a substituted alkyl group preferably containing 1 to 6 carbon atoms an optionally substituted phenyl group or an optionally substituted alkylphenyl group; each R 1 is hydrogen, a hydroxy group, a hydrolysable group or an unsaturated organic group; a is zero or 1, b is an integer and c is zero or an integer and the sum of b+c is equal to a value of at least 200 preferably at least 500, more preferably at least 1500.
  • Such a polymer may comprise a degree of branching.
  • “Substituted”, when used in relation to hydrocarbon groups, means one or more hydrogen atoms in the hydrocarbon group has been replaced with another substituent.
  • substituents include, but are not limited to, halogen atoms such as chlorine, fluorine, bromine, and iodine; halogen atom containing groups such as chloromethyl, perfluorobutyl, trifluoroethyl, and nonafluorohexyl; oxygen atoms; oxygen atom containing groups such as (meth)acrylic and carboxyl; nitrogen atoms; nitrogen atom containing groups such as amines, amino-functional groups, amido-functional groups, and cyano-functional groups; sulphur atoms; and sulphur atom containing groups such as mercapto groups.
  • the polymeric chain may comprise blocks made from chains of units depicted in Formula (1) above where the two R groups or R and R 1 groups are
  • the polysiloxane containing polymer may alternatively contain a block copolymeric backbone comprising at least one block of siloxane groups and an organic component comprising any suitable organic based polymer backbone for example the organic polymer backbone may comprise, for example, polystyrene and/or substituted polystyrenes such as poly( ⁇ -methylstyrene), poly(vinylmethylstyrene), dienes, poly(p-trimethylsilylstyrene) and poly(p-trimethylsilyl- ⁇ -methylstyrene).
  • polystyrene and/or substituted polystyrenes such as poly( ⁇ -methylstyrene), poly(vinylmethylstyrene), dienes, poly(p-trimethylsilylstyrene) and poly(p-trimethylsilyl- ⁇ -methylstyrene).
  • organic components which may be incorporated in the polymeric backbone may include acetylene terminated oligophenylenes, vinylbenzyl terminated aromatic polysulphones oligomers, aromatic polyesters, aromatic polyester based monomers, polyalkylenes, polyurethanes, aliphatic polyesters, aliphatic polyamides and aromatic polyamides and the like.
  • polysiloxane containing polymer are polyoxyalkylene based blocks.
  • the oxyalkylene units are not necessarily identical throughout the polyoxyalkylene monomer, but can differ from unit to unit.
  • a polyoxyalkylene block for example, can be comprised of oxyethylene units, (—C 2 H 4 —O—); oxypropylene units (—C 3 H 6 —O—); or oxybutylene units, (—C 4 H 8 —O—); or mixtures thereof.
  • the polyoxyalkylene polymeric backbone consists essentially of oxyethylene units and/or oxypropylene units.
  • polysiloxane containing polymer may include for example units of the structure—
  • each R 2 is the same or different and is a divalent hydrocarbon group having 2 to 8 carbon atoms
  • each R 3 is the same or different and, is, an ethylene group propylene group or isopropylene group
  • each R 4 is the same or different and is a hydrogen atom or methyl group and each of the subscripts d and e is a positive integer in the range from 3 to 30.
  • the polysiloxane containing polymer is polymerised in an inert fluid.
  • inert fluid is intended to mean a substantially non-volatile fluid which is neither involved in the polymerisation process nor is removed prior to emulsification. Hence the inert fluid is substantially present in the emulsion.
  • the inert fluid is selected from an organopolysiloxane extender and/or plasticiser and/or an organic extender or plasticiser or a cyclic siloxane comprising between 3 and 20 silicon atoms.
  • the inert fluid has a viscosity of from 0.65 mPa ⁇ s at 25° C. ⁇ 10000 mPa ⁇ s at 25° C.
  • each extender and or plasticiser is miscible or at least substantially miscible with the monomeric starting materials with which they are initially mixed, and more particularly miscible with both intermediate polymerisation reaction products and the final polymerisation product.
  • Extenders and/or plasticisers which are “substantially miscible” are intended to include extenders and/or plasticisers which are completely or largely miscible with the monomer(s) and/or the reaction mixture during polymerisation and hence may include low melting point solids which become miscible liquids in a reaction mixture during the polymerisation process.
  • an extender (sometimes also referred to as a process aid or secondary plasticiser) is a compound typically used to dilute silicone based compositions to make them more economically competitive without substantially negatively affecting the properties of the formulation.
  • Suitable inert liquids include trialkylsilyl terminated polydialkylsiloxanes and derivatives thereof which may comprise a degree of substitution, with the provision that any substituted groups in the inert fluid do not participate in the polymerisation reaction.
  • the substituted groups on the inert fluid are preferably the same as those identified in the previous definition of substituted groups with respect to hydrocarbon groups.
  • each alkyl group may be the same or different and comprises from 1 to 8 carbon atoms but is preferably a methyl or ethyl group, preferably with a viscosity of from 0.65 to 100 000 mPa ⁇ s at 25° C. and most preferably from 10 to 1000 mPa ⁇ s at 25° C.
  • the inert fluid may comprise any suitable organic extender/organic plasticiser.
  • Mineral oil extenders and plasticisers are however particularly preferred.
  • examples include linear or branched mono unsaturated hydrocarbons such as linear or branched alkenes or mixtures thereof containing at least 12, e.g. from 12 to 25 carbon atoms; and/or mineral oil fractions comprising linear (e.g. n-paraffinic) mineral oils, branched (iso-paraffinic) mineral oils, cyclic (referred in some prior art as naphthenic) mineral oils and mixtures thereof.
  • the hydrocarbons utilised comprise at least 10, preferably at least 12 and most preferably greater than 20 carbon atoms per molecule.
  • mineral oil extenders include alkylcycloaliphatic compounds, low molecular weight polyisobutylenes, Phosphate esters, alkybenzenes including polyalkylbenzenes which are unreactive with the polymer.
  • any suitable mixture of mineral oil fractions may be utilised as the extender in the present invention but high molecular weight extenders (e.g. >220) are particularly preferred. Examples include:—
  • alkylcyclohexanes (molecular weight>220); paraffinic hydrocarbons and mixtures thereof containing from 1 to 99%, preferably from 15 to 80% n-paraffinic and/or isoparaffinic hydrocarbons (linear branched paraffinic) and 1 to 99%, preferably 85 to 20% cyclic hydrocarbons (naphthenic) and a maximum of 3%, preferably a maximum of 1% aromatic carbon atoms.
  • the cyclic paraffinic hydrocarbons (naphthenics) may contain cyclic and/or polycyclic hydrocarbons. Any suitable mixture of mineral oil fractions may be used, e.g. mixtures containing
  • the mineral oil based extender or mixture thereof comprises at least one of the following parameters:
  • organic extenders may include for the sake of example, fatty acids and fatty acid esters, alkylbenzene compounds suitable for use include heavy alkylate alkylbenzene or an alkylcycloaliphatic compound.
  • alkyl substituted aryl compounds useful as extenders and/or plasticisers are compounds which have aryl groups, especially benzene substituted by alkyl and possibly other substituents, and a molecular weight of at least 200.
  • alkylbenzene compounds suitable for use include heavy alkylate alkylbenzene or an alkylcycloaliphatic compound.
  • alkyl substituted aryl compounds useful as extenders and/or plasticisers are compounds which have aryl groups, especially benzene substituted by alkyl and possibly other substituents, and a molecular weight of at least 200. Examples of such extenders are described in U.S. Pat. No. 4,312,801, the content of which is incorporated herein by reference. These compounds can be represented by general formula (2), (3), (4) and (5)
  • each of R 7 through to R 16 is independently selected from hydrogen, alkyl, alkenyl, alkynyl, halogen, haloalkyl, nitrile, amine, amide, an ether such as an alkyl ether or an ester such as an alkyl ester group, and n is an integer of from 1 to 25.
  • R 7 , R 8 , R 9 , R 19 and R 11 is hydrogen and R 6 is a C 10 -C 13 alkyl group are preferred.
  • a particularly useful source of such compounds are the so-called “heavy alkylates”, which are recoverable from oil refineries after oil distillation. Generally distillation takes place at temperatures in the range of from 230 to 330° C., and the heavy alkylates are present in the fraction remaining after the lighter fractions have been distilled off.
  • alkylcycloaliphatic compounds are substituted cyclohexanes with a molecular weight in excess of 220. Examples of such compounds are described in EP 0842974, the content of which is incorporated herein by reference. Such compounds may be represented by general formula (6).
  • R 17 is a straight or branched alkyl group of from 1 to 25 carbon atoms
  • R 18 and R 19 are independently selected from hydrogen or a C 1-25 straight or branched chain alkyl group.
  • the inert fluid may comprise may comprise a suitable non-mineral based (i.e. not from petroleum or petroleum based oils) natural oil or a mixture thereof, i.e. those derived from animals, seeds and nuts such as for example almond oil, avocado oil, beef tallow, borrage oil, butterfat, canola oil, cardanol, cashew nut oil, cashew nutshell liquid, castor oil, citrus seed oil, cocoa butter, coconut oil, cod liver oil, corn oil, cottonseed oil, cuphea oil, evening primrose oil, hemp oil, jojoba oil, lard, linseed oil, macadamia oil, menhaden oil, oat oil, olive oil, palm kernel oil, palm oil peanut oil, poppy seed oil, rapeseed oil, rice bran oil, safflower oil, safflower oil (high oleic), sesame oil, soybean oil, sunflower oil, sunflower oil (high oleic), tall oil, tea tree oil, turkey
  • transesterified natural vegetable oils such as boiled natural oils such as boiled linseed oil, blown natural oils and stand natural oils.
  • An example of a suitable transesterified natural vegetable oil is known as biodiesel oil, the transesterification product produced by reacting mechanically extracted natural vegetable oils from seeds, such as rape, with methanol in the presence of a sodium hydroxide or potassium hydroxide catalyst to produce a range of esters dependent on the feed utilised. Examples might include for example methyloleate (CH 3 (CH 2 ) 7 CH ⁇ CH(CH 2 ) 7 CO 2 CH 3 ).
  • Stand natural oils which are also known as thermally polymerised or heat polymerised oils and are produced at elevated temperatures in the absence of air.
  • the oil polymerises by cross-linking across the double bonds which are naturally present in the oil.
  • the bonds are of the carbon-carbon type.
  • Stand natural oils are pale coloured and low in acidity. They can be produced with a wider range of viscosities than blown oils and are more stable in viscosity.
  • stand natural oils are produced from linseed oil and soya bean oil but can also be manufactured based on other oils. Stand natural oils are widely used in the surface coatings industry.
  • Blown oils which are also known as oxidised, thickened and oxidatively polymerised oils and are produced at elevated temperatures by blowing air through the oil. Again the oil polymerises by cross-linking across the double bonds but in this case there are oxygen molecules incorporated into the cross-linking bond. Peroxide, hydroperoxide and hydroxyl groups are also present. Blown oils may be produced from a wider range of oils than stand natural oils. In general, blown oils are darker in colour and have a higher acidity when compared to stand natural oils. Because of the wide range of raw materials used, blown oils find uses in many diverse industries, for example blown linseed oils are used in the surface coatings industry and blown rapeseed oils are often used in lubricants.
  • inert fluid which may be included in the composition will depend upon factors such as the purpose to which the composition is to be put, the molecular weight of the inert fluid(s) concerned etc.
  • Typical compositions may contain up to at least 70% w/w or even 90% w/w inert fluids(s).
  • suitable polymer products comprise from 5 to 80% w/w of inert fluid(s).
  • Such polysiloxane containing polymers as prepared in step (i) of the process in accordance with the present invention may be made by a variety of routes with the polymers produced being end-capped with compounds which will provide the required terminal groupings on the polymer and provided the polymer or its precursors and/or intermediates is/are diluted in the inert fluid described above during the polymerisation process.
  • Preferred routes to the preparation of said polymers include
  • Any suitable polycondensation reaction pathway may be utilised. Preferred are polycondensation reactions relying on the reaction schemes below:—
  • the sort of reaction envisaged between the condensable end groups of the starting materials are most preferably generally linked to the interaction of compounds having hydroxyl and/or hydrolysable end groups which can interact with the release of e.g. water or methanol or the like.
  • the following list indicates other interactions which might be considered for the cure process of the composition in accordance with the present invention:—
  • condensation reaction which occurs between monomers/oligomers and intermediates with hydroxyl and/or alkoxy end-groups thereby producing water or alcohols as a by-product.
  • a preferred method for the polymerisation process is the polymerisation of straight chain precursors and/or branched organopolysiloxanes of formula (1) including for example
  • R 5 is —OH or an alkoxy group having from 1 to 6 carbon atoms, preferably a methoxy or ethoxy group
  • f is 0 or 1
  • g is an integer from 2 to 100
  • h is from 2 to 100
  • j is an integer from 1 to 100
  • k is an integer between 1 to 100.
  • the above starting materials preferably have a viscosity of between 10 mPa ⁇ s and 5000 mPa ⁇ s at 25° C.
  • Any suitable polycondensation catalyst may be utilised including tin, lead, antimony, iron, cadmium, barium, manganese, zinc, chromium, cobalt, nickel, titanium, aluminium, gallium or germanium and zirconium based catalysts such as organic tin metal catalysts and 2-ethylhexoates of iron, cobalt, manganese, lead and zinc may alternatively be used.
  • Tin catalysts may include as triethyltin tartrate, tin octoate, tin oleate, tin naphthate, butyltintri-2-ethylhexoate, tinbutyrate, carbomethoxyphenyl tin trisuberate, isobutyltintriceroate, and diorganotin salts especially diorganotin dicarboxylate compounds such as dibutyltin dilaurate, dimethyltin dibutyrate, dibutyltin dimethoxide, dibutyltin diacetate, dimethyltin bisneodecanoate Dibutyltin dibenzoate, stannous octoate, dimethyltin dineodeconoate, dibutyltin dioctoate. Dibutyltin dilaurate, dibutyltin diacetate are particularly preferred.
  • Titanate catalysts may comprise a compound according to the general formula Ti[OR 20 ] 4 and Zr[OR 20 ] 4 respectively where each R 20 may be the same or different and represents a monovalent, primary, secondary or tertiary aliphatic hydrocarbon group which may be linear or branched containing from 1 to 10 carbon atoms.
  • the titanate may contain partially unsaturated groups.
  • R 20 include but are not restricted to methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl and a branched secondary alkyl group such as 2,4-dimethyl-3-pentyl.
  • R 20 is an isopropyl, branched secondary alkyl group or a tertiary alkyl group, in particular, tertiary butyl.
  • examples include tetrabutyltitanate, tetraisopropyltitanate, or chelated titanates or zirconates such as for example diisopropyl bis(acetylacetonyl)titanate, diisopropyl bis(ethylacetoacetonyl)titanate, diisopropoxytitanium Bis(Ethylacetoacetate) and the like.
  • suitable catalysts are described in EP1254192 and/or WO200149774 the contents of which are incorporated herein by reference. The amount of catalyst used depends on the cure system being used but typically is from 0.01 to 3% by weight of the total composition.
  • condensation catalysts which may be used, protic acids, Lewis acids, organic and inorganic bases, metal salts and organometallic complexes.
  • Lewis acid catalysts (a “Lewis acid” is any substance that will take up an electron pair to form a covalent bond).
  • suitable for the polymerisation in the present invention include, for example, boron trifluoride FeCl 3 , AlCl 3 , ZnCl 2 , and ZnBr 2 .
  • condensation specific catalysts such as acidic condensation catalysts of the formula R 21 SO 3 H in which R 21 represents an alkyl group preferably having from 6 to 18 carbon atoms such as for example a hexyl or dodecyl group, an aryl group such as a phenyl group or an alkaryl group such as dinonyl- or didoecyl-naphthyl. Water may optionally be added.
  • R 21 is an alkaryl group having an alkyl group having from 6 to 18 carbon atoms such as dodecylbenzenesulphonic acid (DBSA).
  • DBSA dodecylbenzenesulphonic acid
  • condensation specific catalysts include n-hexylamine, tetramethylguanidine, carboxylates of rubidium or caesium, hydroxides of magnesium, calcium or strontium and other catalysts as are mentioned in the art, e.g. in GB895091, GB918823 and EP 0382365. Also preferred are catalysts based on phosphonitrile chloride, for example those prepared according to U.S. Pat. No. 3,839,388, U.S. Pat. No.
  • the catalyst may comprise an oxygen-containing chlorophosphazene containing organosilicon radicals having the following general formula:—
  • Z 1 represents an organosilicon radical bonded to phosphorus via oxygen, a chlorine atom or the hydroxyl group and
  • the catalyst may also comprise condensation products of the above and/or tautomers thereof (the catalyst exists in a tautomeric form when Z 1 is a hydroxyl group).
  • a further alternative catalyst which might be used as the catalyst in the present invention is any suitable compound providing a source of anions comprising at least one quadri-substituted boron atom and protons capable of interaction with at least one silanol group as defined in WO 01/79330.
  • the activity of the catalyst is preferably quenched by using a neutralizing agent which reacts with the catalyst to render it non-active.
  • a neutralizing agent which reacts with the catalyst to render it non-active.
  • the neutralising agent is a suitable base such as an amine such as a mono/di and trialkanolamines for example monoethanolamine (MEA) and triethanolamine (TEA).
  • MEA monoethanolamine
  • TEA triethanolamine
  • alternative quenching means include aluminasilicate zeolite materials that were found to absorb DBSA and leave a stable polymer. In most cases catalyst residues remain in the polymer product or where appropriate may be removed by filtration or alternative methods.
  • the viscosity of the organosilicon compound obtained in the process can be kept constant by a procedure in which the catalyst used, or a reaction product which has been formed from this catalyst by reaction with organosilicon compound to be subjected to condensation and/or equilibration and likewise promotes the condensation and/or equilibration of organosilicon compounds, is inhibited or deactivated by addition of inhibitors or deactivators which have been employed to date in connection with phosphazenes, for example, triisononylamine, n-butyllithium, lithium siloxanolate, hexamethylcyclotrisilazane, hexamethyldisilazane and magnesium oxide.
  • inhibitors or deactivators which have been employed to date in connection with phosphazenes, for example, triisononylamine, n-butyllithium, lithium siloxanolate, hexamethylcyclotrisilazane, hexamethyldisilazane
  • the polymer obtained may be end-blocked as a means of regulating the molecular weight of the polymer and/or to add functionality. Whilst this end-blocking function can be achieved by water as discussed above, other suitable end-blocking agents include silanes having 1 group capable of reacting with the terminal groups of the resulting polymeric constituent prepared in the diluted polymer to produce the required end-groups for polymer (a).
  • a “polyaddition” or “addition polymerisation” process is a polymerisation process whereby unlike in a condensation reaction no by-products such as water or alcohols are generated from the monomeric and oligomeric co-reactants during polymerisation.
  • a preferred addition polymerisation route is a hydrosilylation reaction between an unsaturated organic group e.g. an alkenyl or alkynyl group and an Si—H group in the presence of a suitable catalyst.
  • suitable silanes may be utilised as well as siloxane containing monomers and/or oligomers.
  • the organopolysiloxane or silane (a) is selected from a silane (a) (ii) containing at least one group capable of undergoing addition type reactions and an organopolysiloxane monomer (a) (i) containing groups capable of undergoing addition type reactions.
  • the organopolysiloxane or silane (a) must contain substituents such that it is capable of undergoing an appropriate addition reaction with polymer (b).
  • the preferred addition reaction is a hydrosilylation reaction between an unsaturated group and an Si—H group.
  • silane (a) (ii) has at least 1 and preferably 2 groups capable of undergoing addition type reactions with (b).
  • the silane may contain an unsaturated constituent but preferably contains at least one Si—H group.
  • each silane contains one or more Si—H groups.
  • preferred silanes may include for example an alkyl group, an alkoxy group, an acyloxy group, a ketoximato group, an amino group, an amido group, an acid amido group, an aminoxy group, a mercapto group, an alkenyloxy group and the like.
  • alkoxy, acyloxy, ketoximato, amino, amido, aminoxy, mercapto and alkenyloxy groups are preferred.
  • halosilane tri-chlorosilane methyl dichlorosilane, dimethyl chlorosilane, and phenyl dichlorosilane
  • alkoxy silanes such as tri-methyoxy silane, tri-ethoxy silane, methyl di-ethoxy silane, methyl di-methoxy silane and phenyl-di-methoxy silane
  • acyloxy silanes such as methyl di-acetoxy silane and phenyl diacetoxy silane
  • ketoximato silanes such as bis-(dimethyl-ketoximate)-methyl silane and bis-(cyclohexyl ketoximate)methyl silane.
  • halosilanes and alkoxyl silanes are preferred.
  • Particularly preferred silanes include for example methyl dimethoxy silane (H—Si (—CH 3 ) (—OCH 3 ) 2 ).
  • silane (a) (ii) and (b) results in a polymer chain extension process or as a means of end-blocking a polymer with pre-required end groups, in which case the extender may be added in combination with silane (a) (ii), i.e. immediately prior to the addition reaction or may be present during the polymerisation of polymer (b) and as such silane (a) (ii) is added to an extended polymer (b) which has been polymerised in the presence of the extender.
  • Organopolysiloxane monomer (a) (i) is preferably in the form of a straight chain and/or branched organopolysiloxane comprising units of formula (1a)
  • each R′ may be the same or different and denotes a hydrocarbon group having from 1 to 18 carbon atoms, a substituted hydrocarbon group having from 1 to 18 carbon atoms or a hydrocarbonoxy group having up to 18 carbon atoms and a′ has, on average, a value of from 1 to 3, preferably 1.8 to 2.2.
  • each R′ is the same or different and is exemplified, by, but not limited to hydrogen, alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, undecyl, and octadecyl; cycloalkyl such as cyclohexyl; aryl such as phenyl, tolyl, xylyl, benzyl, and 2-phenylethyl; and halogenated hydrocarbon groups such as 3,3,3-trifluoropropyl, 3-chloropropyl, and dichlorophenyl.
  • Some R′ groups may be hydrogen groups.
  • the polydiorganosiloxanes are polydialkylsiloxanes, most preferably polydimethylsiloxanes.
  • said organopolysiloxane monomer must have at least one group which is reactable with at least two groups, typically the terminal groups, of (b) via an addition reaction process.
  • organopolysiloxane (a) (i) comprises at least one Si—H per molecule, preferably at least two Si—H groups per molecule.
  • organopolysiloxane (a) (i) is end-blocked with a siloxane group of the formula H(R′′) 2 SiO 1/2 , wherein each R′′ is a hydrocarbon or substituted hydrocarbon group, most preferably an alkyl group.
  • organopolysiloxane (a) (i) has a viscosity of between 10 mPa ⁇ s and 5000 mPa ⁇ s at 25° C.
  • Organopolysiloxane polymer (b) is preferably a straight chain and/or branched organopolysiloxane comprising units of formula (1b)
  • each R′′′ may be the same or different and denotes a hydrocarbon group having from 1 to 18 carbon atoms, a substituted hydrocarbon group having from 1 to 18 carbon atoms or a hydrocarbonoxy group having up to 18 carbon atoms and a′ is as previously described.
  • Preferably no R′′′ groups may be hydrogen groups.
  • each R′′′ is the same or different and are exemplified by, but not limited to alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, undecyl, and octadecyl; cycloalkyl such as cyclohexyl; aryl such as phenyl, tolyl, xylyl, benzyl, and 2-phenylethyl; and halogenated hydrocarbon groups such as 3,3,3-trifluoropropyl, 3-chloropropyl, and dichlorophenyl.
  • alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, undecyl, and octadecyl
  • cycloalkyl such as cyclohexyl
  • Organopolysiloxane polymer (b) may comprise any suitable organopolysiloxane polymeric backbone but is preferably linear or branched, and comprises at least one, preferably at least two substituent groups which will react with the aforementioned groups in the organopolysiloxane or silane (a) via an addition reaction pathway.
  • the or each addition reactive substituent group of polymer (b) is a terminal group.
  • the organopolysiloxane or silane (a) comprises at least one Si—H group
  • the preferred substituent groups on organopolysiloxane polymer (b), which are designed to interact with the Si—H groups are preferably unsaturated groups (e.g. alkenyl terminated e.g.
  • alkenyl groups are shown by the following structures; H 2 C ⁇ CH—, H 2 C ⁇ CHCH 2 —, H 2 C ⁇ C(CH 3 )CH 2 —, H 2 C ⁇ CHCH 2 CH 2 —, H 2 C ⁇ CHCH 2 CH 2 CH 2 —, and H 2 C ⁇ CHCH 2 CH 2 CH 2 CH 2 CH 2
  • alkynyl groups are shown by the following structures; HC ⁇ C—, HC ⁇ CCH 2 —, HC ⁇ CC(CH 3 )—, HC ⁇ CC(CH 3 ) 2 —, HC ⁇ CC(CH 3 ) 2 CH 2
  • the unsaturated organic group can be an organofunctional hydrocarbon such as an acrylate, methacrylate and the like such as alkenyl an/or alkynyl groups.
  • Alkenyl groups are particularly preferred.
  • the organopolysiloxane or silane (a) comprises only one addition reactable group and (b) comprises two addition reactable groups which will react with the organopolysiloxane or silane (a)
  • the resulting product will be an “ABA” type polymeric product.
  • both the organopolysiloxane or silane (a) comprises two addition reactable groups and (b) comprises two addition reactable groups which will react with the organopolysiloxane or silane (a) interaction between the two components would lead to (AB)n block copolymers in which the length of the polymer is largely determined by the relative amounts of the two constituents.
  • this hydrosilylation route may be utilised to prepare silicone-organic copolymers by using an organopolysiloxane polymer which contains organic groups in the polymer backbone or by replacing organopolysiloxane polymer (b) with, for example, alkenyl terminated polyethers.
  • linear non-hydrolysable (AB)n block copolymers in accordance with the present invention can be prepared by catalyzed hydrosilylation of alkenyl terminated polyethers with SiH-terminated dialkylsiloxane fluids.
  • the resulting copolymer being a combination of polyoxyalkylene blocks linked through silicon to carbon to oxygen linkages (i.e. a propyleneoxy group) and the end-blocking groups being selected from the group consisting of allyl, propenyl and/or hydrogen (dialkyl) siloxy groups (dependent on the relative amounts of the constituents which are present).
  • any suitable hydrosilylation catalyst may be utilised.
  • Such hydrosilylation catalysts are illustrated by any metal-containing catalyst which facilitates the reaction of silicon-bonded hydrogen atoms of the SiH terminated organopolysiloxane with the unsaturated hydrocarbon group on the polyoxyethylene.
  • the metals are illustrated by ruthenium, rhodium, palladium, osmium, iridium, or platinum.
  • Hydrosilylation catalysts are illustrated by the following; chloroplatinic acid, alcohol modified chloroplatinic acids, olefin complexes of chloroplatinic acid, complexes of chloroplatinic acid and divinyltetramethyldisiloxane, fine platinum particles adsorbed on carbon carriers, platinum supported on metal oxide carriers such as Pt(Al 2 O 3 ), platinum black, platinum acetylacetonate, platinum(divinyltetramethyldisiloxane), platinous halides exemplified by PtCl 2 , PtCl 4 , Pt(CN) 2 , complexes of platinous halides with unsaturated compounds exemplified by ethylene, propylene, and organovinylsiloxanes, styrene hexamethyldiplatinum, Such noble metal catalysts are described in U.S.
  • Karstedt's catalyst is a platinum divinyl tetramethyl disiloxane complex typically containing one weight percent of platinum in a solvent such as toluene.
  • Another preferred platinum catalyst is a reaction product of chloroplatinic acid and an organosilicon compound containing terminal aliphatic unsaturation. It is described in U.S. Pat. No. 3,419,593, incorporated herein by reference.
  • Most preferred as the catalyst is a neutralized complex of platinous chloride and divinyl tetramethyl disiloxane, for example as described in U.S. Pat. No. 5,175,325.
  • Ruthenium catalysts such as RhCl 3 (Bu 2 S) 3 and ruthenium carbonyl compounds such as ruthenium 1,1,1-trifluoroacetylacetonate, ruthenium acetylacetonate and triruthinium dodecacarbonyl or a ruthenium 1,3-ketoenolate may alternatively be used.
  • hydrosilylation catalysts suitable for use in the present invention include for example rhodium catalysts such as [Rh(O 2 CCH 3 ) 2 ] 2 , Rh(O 2 CCH 3 ) 3 , Rh 2 (C 8 H 15 O 2 ) 4 , Rh(C 5 H 7 O 2 ) 3 , Rh(C 5 H 7 O 2 )(CO) 2 , Rh(CO)[Ph 3 P](C 5 H 7 O 2 ), RhX 4 3 [(R 3 ) 2 S] 3 , (R 2 3 P) 2 Rh(CO)X 4 , (R 2 3 P) 2 Rh(CO)H, Rh 2 X 4 2 Y 4 4 , H a Rh b olefin c Cl d , Rh (O(CO)R 3 ) 3 , (OH) n where X 4 is hydrogen, chlorine, bromine or iodine, Y 4 is an alkyl group, such as methyl or ethyl, CO, C 8 H 14 or
  • Any suitable iridium catalysts such as Ir(OOCCH 3 ) 3 , Ir(C 5 H 7 O 2 ) 3 , [Ir(Z 2 )(En) 2 ] 2 , or (Ir(Z 2 )(Dien)] 2 , where Z 2 is chlorine, bromine, iodine, or alkoxy, En is an olefin and Dien is cyclooctadiene may also be used.
  • the hydrosilylation catalyst may be added to the present composition in an amount equivalent to as little as 0.001 part by weight of elemental platinum group metal, per one million parts (ppm) of the composition.
  • concentration of the hydrosilylation catalyst in the composition is that capable of providing the equivalent of at least 1 part per million of elemental platinum group metal.
  • a catalyst concentration providing the equivalent of about 3-50 parts per million of elemental platinum group metal is generally the amount preferred.
  • the process is carried out using approximately a 1:1 molar ratio of (a) to (b).
  • useful materials may also be prepared by carrying out the process with an excess of either (a) or (b) but this would be considered a less efficient use of the materials.
  • the material containing the unsaturation (b) is used in slight excess to ensure all the Si—H is consumed in the reaction.
  • end-blocking agents are not typically required when making the polymer via this route. However, they may be utilised if required.
  • a suitable hydrosilylation catalyst inhibitor may be required.
  • Any suitable platinum group type inhibitor may be used.
  • One useful type of platinum catalyst inhibitor is described in U.S. Pat. No. 3,445,420, which is hereby incorporated by reference to show certain acetylenic inhibitors and their use.
  • a preferred class of acetylenic inhibitors are the acetylenic alcohols, especially 2-methyl-3-butyn-2-ol and/or 1-ethynyl-2-cyclohexanol which suppress the activity of a platinum-based catalyst at 25° C.
  • a second type of platinum catalyst inhibitor is described in U.S. Pat. No.
  • a third type of platinum catalyst inhibitor includes polymethylvinylcyclosiloxanes having three to six methylvinylsiloxane units per molecule.
  • compositions containing these hydrosilylation catalysts typically require heating at temperatures of 70° C. or above to cure at a practical rate, particularly if an inhibitor is used.
  • Room temperature cure is typically accomplished with such systems by use of a two-part system in which the cross-linker and inhibitor are in one of the two parts and the platinum is in the other part.
  • the amount of platinum is increased to allow for curing at room temperature.
  • the optimum concentration of platinum catalyst inhibitor is that which will provide the desired storage stability or pot life at ambient temperature without excessively prolonging the time interval required to cure the present compositions at elevated temperatures. This amount will vary widely and will depend upon the particular inhibitor that is used.
  • Inhibitor concentrations as low as one mole of inhibitor per mole of platinum will in some instances yield a desirable level of storage stability and a sufficiently short curing period at temperatures above about 70° C. In other cases, inhibitor concentrations of up to 10, 50, 100, 500 or more moles per mole of platinum may be needed. The optimum concentration for a particular inhibitor in a given composition can be determined by routine experimentation.
  • Additional components can be added to the hydrosilylation reaction which are known to enhance such reactions. These components include salts such as sodium acetate which have a buffering effect in combination with platinum based catalysts.
  • the amount of hydrosilylation catalyst used is not narrowly limited as long as there is a sufficient amount to accelerate a reaction between
  • polymers obtained via a hydrosilylation route can also be cured and/or crosslinked by a hydrosilylation reaction catalyst in combination with an organohydrogensiloxane as the curing agent providing each polymer molecule produced contains at least two unsaturated groups suitable for cross-linking with the organohydrogensiloxane.
  • the organohydrogensiloxane must contain more than two silicon bonded hydrogen atoms per molecule.
  • the organohydrogensiloxane can contain, for example, from about 4-20 silicon atoms per molecule, and have a viscosity of up to about 10 Pa ⁇ s at 25° C.
  • the silicon-bonded organic groups present in the organohydrogensiloxane can include substituted and unsubstituted alkyl groups of 1-4 carbon atoms that are otherwise free of ethylenic or acetylenic unsaturation.
  • the extender is mixed into the polymer during a chain extension polymerisation step.
  • the polymeric starting material is an organopolysiloxane having end groups suitable for interaction with the chosen chain extending materials.
  • the polymer end groups are either hydrolysable or suitable for addition reaction (typically hydrosilylation) and the chain extending material is chosen on the basis of having suitable reactive groups which will chain extend the polymer.
  • Preferred chain extending materials for chain extending polymers having hydroxyl and/or hydrolysable end groups are as hereinbefore described.
  • chain extender For pre-formed polymers with alkenyl or Si—H groups (typically end groups) suitable for addition reactions via a hydrosilylation route the chain extender will contain two groups which will undergo an addition reaction with the respective addition reactive groups on the chosen polymer.
  • chain extenders may include for example:—
  • a silane comprising two alkenyl groups, a dihydrosilane, a polydialkylsiloxane having a degree of polymerisation of from 2 to 25 and at least one Si-alkenyl bond per terminal group, A polydialkylsiloxane having a degree of polymerisation of from 2 to 25 and at least one Si—H bond per terminal group and wherein each alkyl group independently comprises from 1 to 6 carbon atoms; organosilicon compounds with the general formula
  • Vi represents a vinyl group
  • Me represents a methyl group
  • Et represents an ethyl group.
  • the catalyst used to catalyse the chain extension reaction is determined by the reaction to take place.
  • any suitable condensation catalyst as hereinbefore described may be utilised.
  • any suitable hydrosilylation catalyst as hereinbefore described may be utilised.
  • the polymer contains hydrolysable terminal groups
  • end-blocking agents as described above in relation to condensation may be utilised to obtain appropriate terminal groups.
  • polymer contains addition reactable terminal groups, end-blocking agents as described above in relation to polyaddition may be utilised to obtain appropriate terminal groups.
  • the process can be carried out either batchwise or continuously on any suitable mixers.
  • generated water can either be removed by chemical drying using e.g. hydrolysable silanes like methyltrimethoxysilane or by physical separation using evaporation, coalescing or centrifuging techniques.
  • Chain extension may take place at any suitable temperature and pressure for the process concerned in batch or continuous modes of operation as preferred.
  • polymerisation may occur at temperatures of between 50° C. to 200° C., more preferably 80° C. to 160° C.
  • the condensation and/or equilibration of the organosilicon compounds may be carried out at a pressure below 80 kPa.
  • Alternative methods for the removal of condensation by-products include removal by chemical drying using e.g. hydrolysable silanes like methyltrimethoxysilane (where appropriate) or by physical separation using evaporation, coalescing or centrifuging techniques.
  • the process can be carried out either batchwise or continuously on any suitable mixers.
  • generated water may, if required, be removed by chemical drying using e.g. hydrolysable silanes like methyltrimethoxysilane or by physical separation using evaporation, coalescing or centrifuging techniques.
  • the Hydrophobic fillers of step (iii) in accordance with the method of the present invention for the preparation of foam control agents are well known and may be materials such as silica, preferably with a surface area as measured by BET measurement of at least 50 m 2 /g, titania, ground quartz, alumina, an aluminosilicate, an organic waxes e.g. polyethylene wax or microcrystalline wax, zinc oxide, magnesium oxide, a salt of an aliphatic carboxylic acids, a reaction product of an isocyanate with an amine, e.g. cyclohexylamine, or an alkyl amide such as ethylenebisstearamide or methylenebisstearamide. Mixtures of two or more of these can be used.
  • Silica fillers are particularly preferred.
  • Preferred silica materials are those which are prepared by heating, e.g. fumed silica, or precipitation, although other types of silica such as those made by gel formation are also acceptable.
  • the silica filler may for example have an average particle size of 0.5 to 50 ⁇ m, preferably 2 to 30 and most preferably 5 to 25 ⁇ m. Such materials are well known and are commercially available, both in hydrophilic form and in hydrophobic form.
  • fillers mentioned above are not hydrophobic in nature, but can be used if made hydrophobic. Such fillers may be rendered hydrophobic either in situ (i.e. by introducing a hydrophobing agent before during or after step (iii) of the process of the present invention, or by pre-treatment of the filler prior to step (iii) of the process.
  • the hydrophobing of fillers, where required may be carried out by treatment with a fatty acid, but is preferably done by the use of methyl substituted organosilicon materials.
  • Suitable hydrophobing agents include polydimethylsiloxanes, dimethylsiloxane polymers which are end-blocked with silanol or silicon-bonded alkoxy groups, hexamethyldisilazane, hexamethyldisiloxane.
  • the organosilicon resins optionally introduced in step (iv) of the process in accordance with the invention (as discussed below) may also function as filler hydrophobing agents.
  • the amount of filler in the foam control agent of the invention is preferably from 0.5 to 50% by weight based on polysiloxane containing polymer, more preferably from 1 up to 10 or 15% and most preferably 2 to 8%.
  • the ratio of the weight of organosilicon resin to filler is from 1/10 to 20/1, preferably 1/5 to 10/1, most preferably 1/2 to 6/1.
  • the manufacturing process would include a heating stage, preferably under reduced pressure, in which the filler and the treating agent are mixed together in part or all of polysiloxane containing polymer and/or all or part of fluid (B), possibly in the presence of a suitable catalyst, where required.
  • the optional organosilicon resin which may be introduced in accordance with step (iv) of the present invention is generally a non-linear siloxane resin and comprises (and most preferably consists of) siloxane units of the formula R 25 s SiO 4-s/2 wherein R 25 denotes a hydroxyl, hydrocarbon or hydrocarbonoxy group, and wherein s has an average value of from 0.5 to 2.4. It preferably consists of monovalent trihydrocarbonsiloxy (M) groups of the formula R 26 3 SiO 1/2 and tetrafunctional (O) groups SiO 4/2 wherein R 26 denotes a monovalent hydrocarbon group.
  • M monovalent trihydrocarbonsiloxy
  • R 26 tetrafunctional
  • the organosilicon resin is preferably a solid at room temperature but MQ resins having a M/Q ratio higher than 1.2, which are generally liquids, can be used successfully. For industrial foam control applications such as defoaming of black liquor in the paper and pulp industry, resins having a high M/Q ratio may be preferred.
  • the resin consists only of monovalent and tetravalent siloxy units as defined above, a resin comprising M groups, trivalent R 25 SiO 3/2 (T) units and Q units can alternatively be used. It is also acceptable that up to 20% of all units present can be divalent units R 25 2 SiO 2/2 .
  • the group R 25 is preferably an alkyl group having 1 to 6 carbon atoms, for example methyl or ethyl, or can be phenyl. It is particularly preferred that at least 80%, most preferably substantially all, R 25 groups present are methyl groups.
  • Other hydrocarbon groups may be present, e.g. alkenyl groups present for example as dimethylvinylsilyl units, preferably not exceeding 5% of all R 25 groups. Silicon bonded hydroxyl groups and/or alkoxy, e.g. methoxy groups may also be present.
  • Such organosilicon resins are well known. They can be made in solvent or in situ, e.g. by hydrolysis of certain silane materials. Particularly preferred is the hydrolysis and condensation in the presence of a solvent e.g. xylene of a precursor of the tetravalent siloxy unit (e.g. tetraorthosilicate, tetraethyl orthosilicate, polyethyl silicate or sodium silicate) and a precursor of monovalent trialkylsiloxy units (e.g. trimethylchlorosilane, trimethylethoxysilane, hexamethyldisiloxane or hexamethyldisilazane).
  • a solvent e.g. xylene of a precursor of the tetravalent siloxy unit (e.g. tetraorthosilicate, tetraethyl orthosilicate, polyethyl silicate or sodium silicate) and a precursor of monovalent trialky
  • the organosilicon resin is preferably present in the antifoam at from 0.1 to 20% by weight of the formulation, and most preferably from 0.5 to 10%.
  • the organosilicon resin may be insoluble in the inert organopolysiloxane but is generally insoluble in the organic fluid but may be soluble or insoluble in the polysiloxane containing polymer and may be soluble or insoluble in the mixture of step (i) of the process in accordance with the present invention.
  • the resin in step (iv) of the process in accordance with the present invention can be added into the foam control agent as a solution in a non-volatile solvent, for example an alcohol such as dodecanol or 2-butyl-octanol or an ester such as octyl stearate.
  • a resin solution prepared in a volatile solvent such as xylene can be mixed with the non-volatile solvent and the volatile solvent removed by stripping or other form of separation. In most cases the non-volatile solvent can be left in the foam control agent. It is preferred that the resin is dissolved in an equal amount of non-volatile solvent or less, preferably no more than half its weight of solvent. If the resin is added as a solution and is insoluble in the mixture of polysiloxane containing polymer and organic liquid, it will generally form solid particles of acceptable particle size on mixing.
  • the resin can alternatively be added into the foam control agent in the form of solid particles, for example spray dried particles or flakes etc.
  • Spray dried MQ resins are available commercially, for example of average particle size 10 to 200 microns.
  • the means by which organosilicon resin is introduced during step (iv) may be dependent on solubility of the resin. Solubility can be measured by observing a mixture of the resin of step (iv) in accordance with the invention with the polysiloxane containing and/or its precursors and/or the inert organopolysiloxane and/or organic fluid using an optical microscope.
  • the factors affecting the solubility of the resin in the mixture in step (i) of the process in accordance with the present invention include the chemical nature of the starting materials and of the resulting polymer produced.
  • the level of insolubility of the resin in the mixture of polysiloxane containing polymer and liquid (B) may affect its particle size in the composition.
  • a siloxane resin which is soluble at 1% by weight in the constituents of step (i) of the process in accordance with the present invention will tend to form smaller particles than a resin which is only soluble at 0.01% by weight.
  • Resins which are partly soluble in the mixture of step (i), that is having a solubility of at least 0.1% by weight, are preferred.
  • the molecular weight of the resin can be increased by condensation, for example by heating in the presence of a base.
  • the base can for example be an aqueous or alcoholic solution of potassium hydroxide or sodium hydroxide, e.g. a solution in methanol or propanol.
  • the MQ resins of increased molecular weight have improved resistance to loss of performance over time when stored in contact with the detergent, for example as an emulsion in liquid detergent.
  • the reaction between resin and base may be carried out in the presence of the silica, in which case there may be some reaction between the resin and the silica.
  • the reaction with base can be carried out in the presence of the polysiloxane containing polymer and/or in the presence of the non-volatile solvent and/or in the presence of a volatile solvent.
  • the reaction with base may hydrolyse an ester non-volatile solvent such as octyl stearate but we have found that this does not detract from the foam control performance.
  • the foam control agents according to the present invention may be provided as a product of the process in accordance with the present invention, but for some applications it may be preferred to make them available in alternative forms.
  • the viscosity of the mixture of the polymer and inert fluid prior to emulsifying is in the range of viscosity of from 500 to 10 000 000 mPa ⁇ s at 25° C. most preferably 1000 to 100 000 mPa ⁇ s at 25° C.
  • Emulsions may be made according to any of the known techniques, and may be macro-emulsions or micro-emulsions, however macro-emulsions are preferred.
  • the foam control agent as the disperse phase, one or more surfactants, water and standard additives, such as preservatives, viscosity modifiers and thickeners.
  • the surfactants may be selected from anionic, cationic, nonionic or amphoteric materials. Mixtures of one or more of these may also be used.
  • the surfactant can in general be a non-ionic surfactant, a cationic surfactant, an anionic surfactant, or an amphoteric surfactant, although not all procedures for carrying out the process of the invention can be used with all surfactants.
  • the amount of surfactant used will vary depending on the surfactant, but generally is up to about 30 wt. % based on the polydiorganosiloxane.
  • nonionic surfactants include condensates of ethylene oxide with long chain fatty alcohols or fatty acids such as a C 12-16 alcohol, condensates of ethylene oxide with an amine or an amide, condensation products of ethylene and propylene oxide, esters of glycerol, sucrose, sorbitol, fatty acid alkylol amides, sucrose esters, fluoro-surfactants, fatty amine oxides, polyoxyalkylene alkyl ethers such as polyethylene glycol long chain (12-14C) alkyl ether, polyoxyalkylene sorbitan ethers, polyoxyalkylene alkoxylate esters, polyoxyalkylene alkylphenol ethers, ethylene glycol propylene glycol copolymers and alkylpolysaccharides, for example materials of the structure R 24 —O—(R 25 O) s -(G) t wherein R 24 represents a linear or branched alkyl group, a linear or branched
  • non ionic surfactants additionally include polymeric surfactants such as polyvinyl alcohol (PVA) and polyvinylmethylether.
  • Suitable nonionic surfactants include silicones such as those described as Surfactants 1 to 6 in EP 638346, particularly siloxane polyoxyalkylene copolymers, condensates of ethylene oxide with a long chain (fatty) alcohol or (fatty) acid, for example C 14-15 alcohol, condensed with 7 moles of ethylene oxide (Dobanol® 45-7), condensates of ethylene oxide with an amine or an amide, condensation products of ethylene and propylene oxides, fatty acid alkylol amides, fatty amine oxides, esters of sucrose, glycerol or sorbitol and fluoro-surfactants
  • nonionic surfactants include polyoxyethylene fatty alcohols sold under the tradename BRIJ® by Uniqema (ICI Surfactants), Wilmington, Del. and. Some examples are BRIJ® 35 Liquid, an ethoxylated alcohol known as polyoxyethylene (23) lauryl ether, and BRIJ® 30, another ethoxylated alcohol known as polyoxyethylene (4) lauryl ether. polyoxyethylene fatty alcohols sold under the tradename VOLPO® by Croda Nev.; ethoxylated alcohols sold under the trademark TERGITOL® by The Dow Chemical Company, Midland, Mich.
  • TERGITOL® TMN-6 an ethoxylated alcohol known as ethoxylated trimethylnonanol
  • various of the ethoxylated alcohols i.e., C 12 -C 14 secondary alcohol ethoxylates, sold under the trademarks TERGITOL® 15-S-5, TERGITOL® 15-S-12, TERGITOL® 15-S-15, and TERGITOL® 15-S-40.
  • Surfactants containing silicon atoms can also be used.
  • amphoteric surfactants include imidazoline compounds, alkylaminoacid salts, and betaines. Specific examples include cocamidopropyl betaine, cocamidopropyl hydroxysulfate, cocobetaine, sodium cocoamidoacetate, cocodimethyl betaine, N-coco-3-aminobutyric acid and imidazolinium carboxyl compounds.
  • Suitable amphoteric organic detergent surfactants include imidazoline compounds, alkylaminoacid salts and betaines
  • suitable amphoteric surfactants include imidazoline compounds, alkylaminoacid salts, and betaines.
  • cationic surfactants include quaternary ammonium hydroxides such as octyl trimethyl ammonium hydroxide, dodecyl trimethyl ammonium hydroxide, hexadecyl trimethyl ammonium hydroxide, octyl dimethyl benzyl ammonium hydroxide, decyl dimethyl benzyl ammonium hydroxide, didodecyl dimethyl ammonium hydroxide, dioctadecyl dimethyl ammonium hydroxide, tallow trimethyl ammonium hydroxide and coco trimethyl ammonium hydroxide as well as corresponding salts of these materials, Suitable cationic organic surfactants include alkylamine salts, quaternary ammonium salts, sulphonium salts and phosphonium salts fatty amines and fatty acid amides and their derivatives, basic pyridinium compounds, quaternary ammonium bases of benzimidazolines and polypropanol
  • Suitable anionic surfactants include alkyl sulphates such as lauryl sulphate, polymers such as acrylates/C 10-30 alkyl acrylate crosspolymer alkylbenzenesulfonic acids and salts such as hexylbenzenesulfonic acid, octylbenzenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, cetylbenzenesulfonic acid and myristylbenzenesulfonic acid; the sulphate esters of monoalkyl polyoxyethylene ethers; alkylnapthylsulfonic acid; alkali metal sulforecinates, sulfonated glyceryl esters of fatty acids such as sulfonated monoglycerides of coconut oil acids, salts of sulfonated monovalent alcohol esters, amides of amino sulfonic acids, sul
  • Suitable anionic organic surfactants include alkali metal soaps of higher fatty acids, alkyl aryl sulphonates, for example sodium dodecyl benzene sulphonate, long chain (fatty) alcohol sulphates, olefin sulphates and sulphonates, sulphated monoglycerides, sulphated esters, sulphonated or sulphated ethoxylate alcohols, sulphosuccinates, alkane sulphonates, phosphate esters, alkyl isethionates, alkyl taurates and/or alkyl sarcosinates.
  • alkali metal soaps of higher fatty acids alkyl aryl sulphonates, for example sodium dodecyl benzene sulphonate, long chain (fatty) alcohol sulphates, olefin sulphates and sulphonates, sulphated monoglycerides, sulphated esters,
  • Anionic surfactants include alkali metal soaps of higher fatty acids, alkylaryl sulphonates such as sodium dodecyl benzene sulphonate, long chain fatty alcohol sulphates, olefin sulphates and olefin sulphonates, sulphated monoglycerides, sulphated esters, sulphonated ethoxylated alcohols, sulphosuccinates, alkane sulphonates, phosphate esters, alkyl isethionates, alkyl taurates, and alkyl sarcosinates.
  • a preferred anionic surfactant is sold commercially under the name Bio-Soft N-300. It is a triethanolamine linear alkylate sulphonate composition marketed by the Stephan Company, Northfield, Ill.
  • the above surfactants may be used individually or in combination.
  • the polymerisation catalyst is selected with a view to additionally being the or one of the surfactants involved in the emulsification process.
  • a particularly preferred family of catalysts which also function as surfactants when present in antifoam compositions are acidic condensation catalysts such as for example DBSA as discussed above.
  • Nonionic or anionic surfactants are preferred. Of particular interest are surfactants which are environmentally acceptable.
  • the concentration of foam control agent in an emulsion may vary according to applications, required viscosity, effectiveness of the foam control agent and addition system, and ranges on average from 5 to 80% by weight, preferably 10 to 50%, more preferably 25 to 40%.
  • a foam control emulsion may also contain a stabilising agent such as a silicone glycol copolymer or a crosslinked organopolysiloxane polymer having at least one polyoxyalkylene group as described in EP 663225.
  • a stabilising agent such as a silicone glycol copolymer or a crosslinked organopolysiloxane polymer having at least one polyoxyalkylene group as described in EP 663225.
  • Phase inversions generally occurs when the continuous phase of a dispersion becomes the dispersed phase, or vice versa.
  • Phase inversions in liquid/liquid dispersions generally are known in the art to be effected by one of two methods.
  • An inversion may be caused by changing the phase ratio until there is a high enough ratio of the dispersed phase that it becomes the continuous phase.
  • a transitional inversions may occur when the affinity of the surfactant for the two phases is altered in order to cause the inversion.
  • the inversions occurring in this invention occur due to a change in the phase ratio.
  • the inversion method used to make emulsions is carried out by forming an oil phase containing the diluted polysiloxane containing polymer and mixing and agitating the oil phase.
  • a limited and very small amount of water is added to the oil phase in a stepwise fashion, such that an inversion occurs, and an oil-in-water emulsion is formed.
  • the amount of water required is about 0.5 to 10 percent by weight based on the cumulative weight of polysiloxane containing polymer present in the oil phase.
  • the amount of water will be about 1 to 5 percent by weight based on the weight of the polysiloxane containing polymer present in the oil phase.
  • water can be added in 2 to 4 portions, addition of water in a single portion is preferred.
  • the initial addition of water can include the surfactant.
  • the emulsion is diluted with the balance of water to achieve the preferred solids content.
  • the emulsions produced by the process of this invention can have a wide variety of polysiloxane containing polymer concentrations, particle sizes and molecular weights, including novel materials having high concentrations of large particle polysiloxane containing polymer of high molecular weight.
  • the particle size can for example be chosen within the range 0.1 to 1000 micrometres.
  • the quantity of water and/or surfactant used in the initial phase inversion process may have an impact on the particle size of the final emulsion. For instance, if an emulsion is formed with the same quantity of water in two instances but in the first a large quantity of water is mixed before the phase inversion step and in the second a small quantity of water is mixed before the phase inversion step followed by mixing the remaining additional water after the phase inversion step, the first emulsion will generally have a larger particle size than the second. No matter how the water is added, the total amount of water used is generally between about 1 and 99 wt. %, preferably between about 6 and about 99 wt. %, based on the weight of the emulsion.
  • phase of the emulsions can be added to either phase of the emulsions, for example, colorants, thickeners, preservatives, freeze thaw stabilizer, inorganic salts to buffer pH, or active ingredients such as pharmaceuticals.
  • colorants for example, colorants, thickeners, preservatives, freeze thaw stabilizer, inorganic salts to buffer pH, or active ingredients such as pharmaceuticals.
  • the foam control agent can be provided as a water-dispersible composition in which the product resulting from the process in accordance with the present invention is dispersed in a water-dispersible component such as a silicone glycol or in another water-miscible liquid such as ethylene glycol, propylene glycol, polypropylene glycol, polyethylene glycol, a copolymer of ethylene glycol and propylene glycol, an alkyl polyglycoside, an alcohol alkoxylate or an alkylphenol alkoxylate.
  • a water-dispersible component such as a silicone glycol or in another water-miscible liquid
  • An alternative form of providing a foam control agent according to the present invention is in powdered or granulated form. This is particularly useful when the agent is to be used in a powdered product, e.g. a detergent powder.
  • a powdered product e.g. a detergent powder.
  • Any suitable method for the production of powdered or granulated foam control agents may be used with foam control agents produced using the method of the present invention.
  • Granulated foam control agents may, for example, be made by a variety of methods, including granulators, spray drying, emulsification followed by drying, spray mixing, spray chilling, compactors, extruders, high shear mixing, low shear mixing and flaking. Such methods have been extensively described in the patent literature and these are exemplified by an extensive list of publications in U.S. Pat. No. 6,521,587.
  • Suggested ingredients of particulate foam control agents include, in addition to the foam control agent itself, a binder or encapsulant and a carrier or support for the granule. It is preferred that any carrier or binder material should contribute to the efficiency or activity of the product in which it is to be incorporated.
  • a surfactant may be used to aid dispersion of the silicone and organic liquid in the encapsulant or binder. Sometimes other ingredients are incorporated, for example dyes, pigments, preservatives or materials to aid the dispersion in the aqueous medium in which the foam control agent is supposed to be active such as the surfactants described above in connection with foam control emulsions. Such a surfactant may help in controlling the “foam profile”, that is in ensuring that some foam is visible throughout the wash without overfoaming.
  • Binders and/or encapsulants used in particulate foam control agents may comprise waxes and/or aqueous film forming polymers.
  • Examples include dextrine, polypeptides, polyoxyalkylene polymers such as polyethylene glycol, which can be applied molten or as an aqueous solution and spray dried, reaction products of tallow alcohol and ethylene oxide, or polypropylene glycol, polycarboxylates, for example polyacrylic acid or a partial sodium salt thereof or a copolymer of acrylic acid, for example a copolymer with maleic anhydride, cellulose ethers, particularly water-soluble or water-swellable cellulose ethers such as sodium carboxymethylcellulose, gelatin, agar, microcrystalline waxes, fatty acids or fatty alcohols having 12 to 20 carbon atoms and a melting point in the range 45 to 80° C., a monoester of glycerol and such a fatty acid, a mixture of a water insoluble wax having a
  • a binder which is an organic compound having a melting point of from about 40 to 80° C. and which in its liquid form is miscible with the polysiloxane containing polymer so as to form a homogeneous liquid which upon cooling forms a monophasic wax-like substance (that is a material which is homogeneous and shows no phase separation during the process or on storage of the granules) has the advantage of producing encapsulated antifoam granules of improved storage stability.
  • the surfactant used to disperse the silicone in the binder or encapsulant can be selected from the surfactants described above in connection with foam control emulsions. Silicone glycols are preferred for many binders, or fatty alcohol ether sulphate or linear alkylbenzene sulphonate may be preferred with a polyacrylic acid binder.
  • the surfactant can be added to the silicone undiluted or in emulsion before the silicone is mixed with the binder, or the surfactant and silicone can successively be added to the binder.
  • carriers and/or supports are zeolites, for example Zeolite A or Zeolite X, other aluminosilicates or silicates, for example magnesium silicate, phosphates, for example powdered or granular sodium tripolyphosphate, sodium sulphate, sodium carbonate, sodium perborate, a cellulose derivative such as sodium carboxymethylcellulose, granulated starch, clay, sodium citrate, sodium acetate, sodium bicarbonate and native starch.
  • zeolites for example Zeolite A or Zeolite X
  • other aluminosilicates or silicates for example magnesium silicate
  • phosphates for example powdered or granular sodium tripolyphosphate
  • sodium sulphate sodium carbonate
  • sodium perborate sodium sulphate
  • a cellulose derivative such as sodium carboxymethylcellulose, granulated starch, clay, sodium citrate, sodium acetate, sodium bicarbonate and native starch.
  • the foam control agents prepared in accordance to the method of the invention are useful for reducing or preventing foam formation in aqueous systems, particularly foam generated by detergent compositions during laundering, and are particularly useful in detergent compositions which have a high foaming characteristic, for example those based on high levels of anionic surfactants, e.g. sodium dodecyl benzene sulphonate to ensure effectiveness of detergent composition at lower washing temperatures, e.g. 40° C.
  • anionic surfactants e.g. sodium dodecyl benzene sulphonate
  • a detergent composition comprises (1) 100 parts by weight of a detergent component and (2) from 0.02 to 5 parts by weight of a foam control agent according to the first aspect of the invention.
  • Suitable detergent components comprise an active detergent, organic and inorganic builder salts and other additives and diluents.
  • the active detergent may comprise organic detergent surfactants of the anionic, cationic, non-ionic or amphoteric type, or mixtures thereof.
  • Suitable anionic organic detergent surfactants are alkali metal soaps of higher fatty acids, alkyl aryl sulphonates, for example sodium dodecyl benzene sulphonate, long chain (fatty) alcohol sulphates, olefine sulphates and sulphonates, sulphated monoglycerides, sulphated esters, sulphonated or sulphated ethoxylated alcohols, sulphosuccinates, alkane sulphonates, phosphate esters, alkyl isethionates, alkyl taurates and alkyl sarcosinates.
  • Suitable cationic organic detergent surfactants are alkylamine salts, quaternary ammonium salts, sulphonium salts and phosphonium salts.
  • Suitable non-ionic organic surfactants are condensates of ethylene oxide with a long chain (fatty) alcohol or fatty acid, for example O 14-15 alcohol, condensed with 7 moles of ethylene oxide (Dobanol® 45-7), condensates of ethylene oxide with an amine or an amide, condensation products of ethylene and propylene oxides, sucrose esters, fluorosurfactants, fatty acid alkylol amides and fatty amine oxides.
  • Suitable amphoteric organic detergent surfactants are imidazoline compounds, alkylaminoacid salts and betaines.
  • inorganic components are phosphates and polyphosphates, silicates, such as sodium silicates, carbonates, sulphates, oxygen releasing compounds, such as sodium perborate and other bleaching agents and zeolites.
  • organic components are anti-redeposition agents such as carboxymethylcellulose (CMC), brighteners, chelating agents, such as ethylene diamine tetraacetic acid (EDTA) and nitrilotriacetic acid (NTA), enzymes and bacteriostats.
  • Liquid detergent compositions may contain solvents, alkanolamines, pH adjusting agents, opacifiers, perfumes, dyes, colour stabilisers, bactericides, brighteners, soil release agents and/or softening agents.
  • the foam control agents are particularly useful in detergent compositions, for e.g. domestic laundering, dishwashing applications but may also be employed in personal care type applications such as hand wash applications and no rinse softeners such processes as paper making and pulping processes, textile dyeing processes, sewage treatment applications, cutting oil, coatings and other aqueous systems where surfactants may produce foam.
  • the emulsions and/or dispersions of the present invention can generally have a silicone loading in the range of about 1 to about 94 wt. %.
  • Viscosity measurements of the polymer products were carried out using a Brookfield Viscometer, spindle 6, at 10 rpm. Unless otherwise indicated, all parts and percents are by weight and all viscosities are at 25° C.
  • a silicone-based foam control agent was prepared by polymerizing 50 parts by weight of dimethyl hydroxyl terminated polydimethylsiloxane having a viscosity of 72 mPa ⁇ s in 50 parts by weight of Hydroseal® G 250H (sold by Total Belgium of Brussels Belgium) using 2.4 parts by weight of DBSA. The polymerization was stopped once a viscosity of 52000 mPa ⁇ s was reached by the addition of 1.54 parts of triethanolamine (TEA).
  • TAA triethanolamine
  • Sipernat® D10 sold by Degussa GmbH
  • the organosilicon resin was introduced into the composition, in a trimethylsilyl terminated polydimethylsiloxane having a viscosity of 1000 mPa ⁇ s at 25° C. in a resin:siloxane ratio of 25:75.
  • Emulsified foam control compositions containing (b) alone or alternatively (b) in combination with (c) above were prepared using the following process:
  • xanthan gum used as a thickener
  • Natrosol® 250LR (a hydroxyethylcellulose sold by the Aqualon Division of Hercules Inc of USA) 0.16 parts of sorbic acid, 0.32 parts of benzoic acid, 0.77 parts of a 10% solution of sulfuric acid and 95.66 parts of water was prepared.
  • the organic acids in the composition function as preservatives and sulphuric acid is used as a preservative and as a pH controlling agent.
  • mixture [M] 45 parts was added to the receptacle and after thorough mixing, another 112 parts of mixture [M] were added and mixed in. Finally 219.5 parts of water were added resulting in a suitable emulsion of the foam control composition.
  • the bottle containing a sample prepared as described above was shaken using a commercial shaker for periods of 8, 32, 48 and 96 seconds at 400 strokes per minute. After shaking the following were observed:—
  • a granulated foam control agent was prepared using a foam control agent prepared in accordance to the method of the present invention in Example 1 which incorporated both (b) Sipernat® D10 and (c) the organosilicon resin. using the following process: 63 g of an acrylic/maleic copolymer sold as Sokalan® CP5 from BASF was initially added to 42 g of water whilst mixing. Once the resulting mixture was homogeneous 12 g of DBSA and 37 g of the foam control agent prepared above was added whilst mixing continued. The resulting mixture was then added to zeolite powder in an agglomeration mixer until a desired average granule particle size was achieved (typically 55 g of liquid on 100 g of powder). The resulting granular products were dried in a fluid bed to remove the excess water and classified to remove any undesirable fines or oversized granules.
  • the resulting granulated product was tested in a standard European style front loading washing machine (Miele®) which was loaded with 2.5 kg of clean cotton fabric.
  • the wash tests were carried out at 40° C. using 14 liters of water (hardness of 19° F.) per wash.
  • the detergent composition used comprised:
  • the granulated antifoam was added in an amount of 0.4% by weight of the detergent composition, to 90 g of the detergent powder.
  • a silicone-based foam control agent was prepared by polymerizing 50 parts by weight of dimethyl hydroxyl terminated polydimethylsiloxane having a viscosity of 72 mPa ⁇ s in 50 parts by weight of trimethylsilyl terminated polydimethylsiloxane (100 mPa ⁇ s) using 2.4 parts by weight of DBSA in the presence of 3 parts by weight of Sipernat® D10. The polymerization was stopped once a viscosity of 38000 mPa ⁇ s was reached by the addition of 1.5 g of TEA.
  • a granular form of the foam control agent produced in accordance with the present invention was prepared by the method described in Example 1.
  • a silicone-based foam control agent was prepared by polymerizing 48.5 parts by weight of dimethyl hydroxyl terminated polydimethylsiloxane having a viscosity of 72 mPa ⁇ s in 48.5 parts by weight of an organic extender (Hydroseal G250H) using 2.4 parts by weight of DBSA in the presence of 3 parts by weight of Sipernat® D10. The polymerization was stopped once a viscosity of 68000 mPa ⁇ s was reached by the addition of 1.5 parts by weight of TEA.
  • DBSA was the surfactant used in Sample 3A and the surfactant used in Sample 3B was Triton® X-100.
  • a granular form of the foam control agent produced in accordance with the present invention was prepared by the method described in Example 1.
  • Step B Foam control compositions (Samples 4a-4c) were prepared by mixing:
  • step B the ingredients were mixed (Hauschild Speedmixer) and left to react at a temperature of 60° C. for 1 hour.
  • the resulting mixture was homogenised before 200 parts of trimethyl siloxane end-blocked polydimethyl siloxane having a viscosity of 1000 mPa ⁇ s and containing 0.45% by weight of 1-ethynylcyclohexanol were added into the compound.
  • the emulsified foam control compositions were tested in a foam cell using a softwood liquor. To this effect 600 ml of softwood liquor is preheated at 90° C. and introduced in a graduated and thermostatically controlled glass cylinder having an inner diameter of 5 cm. This foamable liquid was circulated through a circulation pipe at a temperature adjusted to 89° C. The circulation flow rate is controlled using a MDR Johnson pump set up at a frequency of 50 Hz. When the foam height of 30 cm is reached, 150 ⁇ l of emulsion of the tested foam control composition is injected in the liquid jet. The evolution of the foam height was monitored and recorded. The foam height was measured in cm over a sufficient period to allow the foam control composition to have exhausted its capacity, which is when the foam height of 29 cm has been reached again in the foam cell, and the time at which this occurred was measured as it indicates the longevity of the foam control composition.
  • Table 4 is a Measure of Foam Height (FH) in Cm against Time for a (Comparative) Commercial Product and Examples 4A to 4C as Described Above.

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Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100137454A1 (en) * 2006-10-10 2010-06-03 Kathleen Barmes Silicone Polymer Emulsions
US20120020909A1 (en) * 2009-03-31 2012-01-26 Benedicte Courel Organopolysiloxane Emulsions and Their Production
US8580729B2 (en) 2009-03-31 2013-11-12 Dow Corning Corporation Organopolysiloxane compositions containing an active material
US8623958B2 (en) 2009-03-10 2014-01-07 Dow Corning Toray Co. Ltd. Oil-in-water silicone emulsion composition
US20150038388A1 (en) * 2012-02-16 2015-02-05 Dow Corning Corporation Granulated Foam Control Agent For The Rinse Cycle Using Siloxane Wax
US9029428B2 (en) 2010-07-02 2015-05-12 Dow Corning Toray Co., Ltd. Oil-in-water silicone emulsion composition
WO2015122989A1 (en) * 2014-02-14 2015-08-20 Dow Corning Corporation Emulsions of branched organopolysiloxanes
US20170218307A1 (en) * 2016-02-02 2017-08-03 The Procter & Gamble Company Antifoam molecules and compositions
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
US10144909B2 (en) 2011-06-17 2018-12-04 Dow Global Techlologies LLC Fabric care pellets and methods
US20190157518A1 (en) * 2016-03-24 2019-05-23 Nichia Corporation Method of manufacturing light emitting device
CN109942820A (zh) * 2019-03-26 2019-06-28 浙江置正有机硅有限公司 一种甲基苯基羟基硅油的制备方法及用于甲基苯基羟基硅油制备的油水分离器
US11090253B2 (en) 2016-08-03 2021-08-17 Dow Silicones Corporation Cosmetic composition comprising silicone materials
US11248119B2 (en) 2017-02-06 2022-02-15 Dow Silicones Corporation Emulsion, composition comprising same, film formed therewith, and related methods
US11254847B2 (en) 2017-05-09 2022-02-22 Dow Silicones Corporation Lamination adhesive compositions and their applications
US11332581B2 (en) 2015-01-28 2022-05-17 Dow Silicones Corporation Elastomeric compositions and their applications
CN114585427A (zh) * 2019-08-14 2022-06-03 埃肯有机硅美国公司 制备颗粒或粉末形式的泡沫控制组合物的方法
US11479022B2 (en) 2017-05-09 2022-10-25 Dow Silicones Corporation Lamination process
US11485936B2 (en) 2016-08-03 2022-11-01 Dow Silicones Corporation Fabric care composition comprising silicone materials
US12291688B1 (en) * 2023-12-12 2025-05-06 Afton Chemical Corporation Silicon-containing compounds for lubricants

Families Citing this family (51)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1866375B1 (en) 2005-04-06 2015-01-28 Dow Corning Corporation Organosiloxane compositions
US20080227679A1 (en) * 2007-03-13 2008-09-18 Elementis Specialties, Inc. Biodegradable Cleaning Compositions
CN102037088B (zh) * 2008-04-14 2014-08-06 陶氏康宁公司 胀流性有机基聚硅氧烷的乳液
KR101677123B1 (ko) * 2008-04-16 2016-11-18 다우 코닝 코포레이션 실리콘 마이크로에멀젼의 제조
GB0806900D0 (en) * 2008-04-16 2008-05-21 Dow Corning Fabric care emulsions
CN101348571B (zh) * 2008-09-02 2011-08-03 南京四新科技应用研究所有限公司 一种分散高粘度有机硅组合物于水中的方法
GB0905205D0 (en) 2009-03-26 2009-05-13 Dow Corning Preparation of organosiloxane polymer
GB0905204D0 (en) * 2009-03-26 2009-05-13 Dow Corning Preparation of organosiloxane polymers
WO2010117744A2 (en) * 2009-03-31 2010-10-14 Dow Corning Corporation Branched organopolysiloxanes
GB0905488D0 (en) * 2009-03-31 2009-05-13 Dow Corning Organopolysiloxane compositions and their production
US9587068B2 (en) * 2009-05-11 2017-03-07 Momentive Performance Materials Inc. Silicone surfactant for use in polyurethane foams prepared using vegetable oil based polyols
EP2430077B1 (en) * 2009-05-13 2018-09-12 Dow Silicones Corporation Continuous process for polymerization and emulsification of siloxane
CN101580592B (zh) * 2009-06-12 2011-07-20 南京工业大学 有机硅树脂的水性化方法
RU2012104397A (ru) 2009-08-25 2013-10-10 Доу Корнинг Корпорейшн Способ получения силиконового клея, склеивающего при надавливании
CN102199352A (zh) * 2010-03-25 2011-09-28 日照岚星化工工业有限公司 一种水溶性有机硅乳液脱模剂的制备方法
WO2012012170A1 (en) * 2010-06-30 2012-01-26 R.T. Vanderbilt Company, Inc. Silicone based lubricant compositions
CN105132205A (zh) * 2010-12-10 2015-12-09 道康宁公司 颗粒化泡沫控制组合物
KR101732412B1 (ko) * 2010-12-15 2017-05-04 주식회사 케이씨씨 실리콘 에멀젼 조성물 및 그 제조방법
CN102407033B (zh) 2011-06-29 2013-09-25 南京四新科技应用研究所有限公司 一种颗粒消泡剂的制备方法
CN103360808B (zh) * 2012-03-31 2016-01-20 攀钢集团攀枝花钢铁研究院有限公司 一种金属防护涂料及其用途和热镀金属材料
ES2707894T3 (es) 2012-10-04 2019-04-05 Ecolab Usa Inc Tecnología de remojo previo para lavar ropa y limpiar otras superficies duras
US9062282B2 (en) 2012-10-15 2015-06-23 Ecolab Usa Inc. Leather and/or vinyl cleaner and moisturizer and method of making same
CN104120624B (zh) 2013-04-28 2016-08-24 埃科莱布美国股份有限公司 生物柴油基的乳液型消泡剂及其制备方法
CN104130879B (zh) * 2014-08-08 2017-02-15 江苏四新科技应用研究所股份有限公司 一种用于液体洗涤剂的消泡剂
JP6543329B2 (ja) * 2014-09-15 2019-07-10 ユニリーバー・ナームローゼ・ベンノートシヤープ ポリジメチルシロキサンポリマーエマルジョンを含む毛髪ケア組成物
US20180193234A1 (en) * 2015-07-02 2018-07-12 Dow Corning (China) Holding Co., Ltd. Oil-in-water emulsion and method
GB2540969B (en) 2015-07-31 2017-12-27 Cambridge Display Tech Ltd Method of doping an organic semiconductor and doping composition
KR101728308B1 (ko) * 2015-09-14 2017-04-19 기초과학연구원 비전이금속 촉매법 수소규소화 반응을 이용한 규소 고분자 제조방법
DE102015222139A1 (de) * 2015-11-10 2017-05-11 Wacker Chemie Ag Verfahren zur Imprägnierung von Textilien mit Zusammensetzungen enthaltend Alkoxypolysiloxane
GB201613396D0 (en) * 2016-08-03 2016-09-14 Dow Corning Foam control compositions comprising silicone materials
CN107050935A (zh) * 2016-12-27 2017-08-18 广东中联邦精细化工有限公司 一种电厂脱硫专用消泡剂
EP3366755B1 (en) * 2017-02-22 2023-11-29 Infineum International Limited Improvements in and relating to lubricating compositions
CN107441778A (zh) * 2017-09-08 2017-12-08 宣城市聚源精细化工有限公司 一种消泡迅速的消泡剂
US11602582B2 (en) * 2018-04-10 2023-03-14 Chemsil Silicones, Inc. Intimate care lubricant compositions and methods for making same
CN109022100A (zh) * 2018-07-19 2018-12-18 芜湖维软新材料有限公司 内含有八甲基环四硅氧烷的润滑硅油
EP3837320B1 (en) 2018-08-14 2023-09-06 Basf Se Process of making silicone-in-water emulsions
JP7486505B2 (ja) 2018-10-16 2024-05-17 ファーマ イン シリカ ラボラトリーズ インコーポレイティド シリカカプセル／スフェアの調製のためのチューニング可能な方法及びそれらの使用
WO2020092983A1 (en) 2018-11-01 2020-05-07 Ppg Industries Ohio, Inc. Coating compositions containing acid functional polyol polymers and coatings formed therefrom
CN109395435A (zh) * 2018-11-06 2019-03-01 江苏赛欧信越消泡剂有限公司 一种耐高温强碱硅膏的制备方法
JP7520024B2 (ja) * 2019-02-21 2024-07-22 ファーマ イン シリカ ラボラトリーズ インコーポレイティド 球状オルガノシロキサンサブミクロン／ナノ粒子の合成のための直接ナノ乳化方法
KR102212025B1 (ko) * 2019-03-13 2021-02-04 주식회사 케이씨씨 실리콘 에멀젼 및 이의 제조방법
BR112021019500A2 (pt) 2019-04-26 2021-11-30 Unilever Ip Holdings Bv Composição para cuidados dos cabelos e uso da composição
US12264220B2 (en) * 2020-01-30 2025-04-01 Evonik Operations Gmbh Process for producing high-purity hydrosilylation products
JP7311717B2 (ja) * 2020-02-20 2023-07-19 ダウ シリコーンズ コーポレーション 泡制御組成物
CN111320967A (zh) * 2020-03-23 2020-06-23 新纳奇材料科技江苏有限公司 一种具有多级结构填料改性的高导热硅酮密封胶及其制备方法
EP4146141A4 (en) * 2020-05-07 2024-02-14 Momentive Performance Materials Inc. O/W EMULSION AND W/O EMULSION FORMED THEREFROM, AND PERSONAL CARE COMPOSITION CONTAINING THE SAME
CN113797598B (zh) * 2020-06-16 2024-04-02 江苏四新科技应用研究所股份有限公司 一种有机硅消泡组合物的制备方法
CN112293725A (zh) * 2020-10-21 2021-02-02 扬州宏远新材料股份有限公司 食品级添加剂聚二甲基硅氧烷乳液的制备工艺
IT202100032024A1 (it) * 2021-12-21 2023-06-21 Maurizio Sala Processo di preparazione di un distaccante per pressofusione.
CN119161865B (zh) * 2023-06-19 2025-09-26 中国石油化工股份有限公司 一种组合物及含有其的压裂液
CN120059710B (zh) * 2025-02-24 2025-08-08 九江蓝卓新材料科技有限公司 一种可用于高矿化度油藏的驱油用表面活性剂

Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3419593A (en) * 1965-05-17 1968-12-31 Dow Corning Catalysts for the reaction of = sih with organic compounds containing aliphatic unsaturation
US3445420A (en) * 1966-06-23 1969-05-20 Dow Corning Acetylenic inhibited platinum catalyzed organopolysiloxane composition
US3666681A (en) * 1970-03-16 1972-05-30 Dow Corning Antifoam preparation for aqueous systems
US3691091A (en) * 1969-03-22 1972-09-12 Goldschmidt Ag Th Defoaming emulsion
US3715334A (en) * 1970-11-27 1973-02-06 Gen Electric Platinum-vinylsiloxanes
US3814730A (en) * 1970-08-06 1974-06-04 Gen Electric Platinum complexes of unsaturated siloxanes and platinum containing organopolysiloxanes
US3839388A (en) * 1972-06-16 1974-10-01 Wacker Chemie Gmbh Process for the condensation and/or equilibration of organosilicon compounds
US3923705A (en) * 1974-10-30 1975-12-02 Dow Corning Method of preparing fire retardant siloxane foams and foams prepared therefrom
US3989667A (en) * 1974-12-02 1976-11-02 Dow Corning Corporation Olefinic siloxanes as platinum inhibitors
US4312801A (en) * 1979-01-16 1982-01-26 Krafft, S.A. Introduced in processes for the manufacture of silicon-based curable compositions
US4564693A (en) * 1984-08-02 1986-01-14 Wacker-Chemie Gmbh Process for stabilizing organopolysiloxanes
US4690713A (en) * 1984-01-27 1987-09-01 Shin-Etsu Chemical Co., Ltd. Antifoam composition
US4701490A (en) * 1985-09-16 1987-10-20 Wacker-Chemie Gmbh Method for stabilizing organopolysiloxanes
US5035832A (en) * 1989-05-17 1991-07-30 Kao Corporation Mild liquid aqueous detergent compositions containing an alkylsaccharide surface active agent and a silicone derivative
US5175325A (en) * 1991-02-14 1992-12-29 Dow Corning Limited Platinum complexes and use thereof
US5777059A (en) * 1996-04-19 1998-07-07 Dow Corning Corporation Silicone compositions and uses thereof
US5914362A (en) * 1996-04-19 1999-06-22 Dow Corning Corporation Silicone-based antifoam compositions cross-reference to related applications
US6521587B1 (en) * 1999-08-13 2003-02-18 Dow Corning S.A. Silicone foam control agent

Family Cites Families (86)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2891920A (en) * 1955-01-26 1959-06-23 Dow Corning Polymerization of organopolysiloxanes in aqueous emulsion
NL95962C (ru) * 1955-07-08
GB895091A (en) 1959-07-13 1962-05-02 Dow Corning Improvements in or relating to organosilicon compounds
US3094497A (en) 1960-07-28 1963-06-18 Dow Corning Condensation catalysts
GB1024024A (en) * 1963-04-08 1966-03-30 Dow Corning Improvements in or relating to polymerising or co-polymerising organosilicon compounds
US3819530A (en) * 1968-07-15 1974-06-25 Sun Oil Co Stabilized wax emulsions
US4311695A (en) * 1979-12-03 1982-01-19 Dow Corning Corporation Personal-care emulsions comprising a siloxane-oxyalkylene copolymer
JPS57153097A (en) * 1981-03-19 1982-09-21 Toray Silicone Co Ltd Organopolysiloxane composition
DE3416694A1 (de) * 1984-05-05 1985-11-07 Bayer Ag, 5090 Leverkusen Verwendung von paraffin- oder mikrowachsen fuer silikonpasten, deren konfektionierung und verwendung
CA1260795A (en) * 1985-04-02 1989-09-26 Dipak Narula Emulsification process and emulsions therefrom
US4788001A (en) * 1985-04-02 1988-11-29 Dow Corning Corporation Oil-in-water emulsion
US4725658A (en) * 1985-09-12 1988-02-16 General Electric Company Novel silicone-ester waxes
DE3836830A1 (de) * 1988-10-28 1990-05-17 Wacker Chemie Gmbh Verfahren zur herstellung waessriger emulsionen von hochmolekularen organopolysiloxanen
JPH02194001A (ja) * 1989-01-20 1990-07-31 Shin Etsu Chem Co Ltd ワックス組成物及びその製造方法
GB8902935D0 (en) 1989-02-09 1989-03-30 Dow Corning Process for producing organosilicon products
JP2739233B2 (ja) * 1989-04-19 1998-04-15 東レ・ダウコーニング・シリコーン株式会社 鉱物油含有シリコーン粒状物
DE3925846A1 (de) * 1989-08-04 1991-02-14 Huels Chemische Werke Ag Emulgatoren zur herstellung von lagerstabilen, waessrigen polysiloxan- bzw. polysiloxan-paraffinoel-emulsionen
US5189102A (en) * 1990-01-30 1993-02-23 Ricoh Company, Ltd. Method for producing a vinyl resin using a silicon oil solvent
CA2043617A1 (en) * 1990-06-01 1991-12-02 An-Li Kuo Organosilicone antifoam composition
GB9103666D0 (en) 1991-02-21 1991-04-10 Dow Corning Sa Method of making organopolysiloxanes
US5262087A (en) * 1991-05-01 1993-11-16 Kose Corporation Water-in-oil type emulsified composition
CH685392A5 (de) * 1992-09-26 1995-06-30 Sandoz Ag Wässrige Wachs- und Silicon-Dispersionen und Verfahren zu deren Herstellung.
DE4317978A1 (de) * 1993-05-28 1994-12-01 Wacker Chemie Gmbh Organosiliciumreste aufweisende Phosphazene, Verfahren zu deren Herstellung und deren Verwendung
US5403909A (en) 1993-07-15 1995-04-04 General Electric Company Catalysts for polycondensation and redistribution of organosiloxane polymers
FR2710854B1 (fr) * 1993-10-08 1995-12-01 Oreal Emulsion huile-dans-eau utilisable pour l'obtention d'une crème.
DE4405510A1 (de) * 1994-02-22 1995-08-24 Henkel Kgaa Emulsionen
US5457220A (en) * 1994-04-29 1995-10-10 General Electric Company Process for the production of crosslinked siloxanes by disproportionation
US5434215A (en) * 1994-06-14 1995-07-18 Air Products And Chemicals, Inc. Water-based polymeric emulsions incorporating wax
GB9426236D0 (en) * 1994-12-24 1995-02-22 Dow Corning Sa Particulate foam control agents and their use
JPH08245881A (ja) 1995-01-12 1996-09-24 Toray Dow Corning Silicone Co Ltd オルガノポリシロキサン生ゴムエマルジョン
US5504150A (en) * 1995-04-05 1996-04-02 Dow Corning Corporation Method of making polysiloxane emulsions
FR2744360B1 (fr) * 1996-02-07 1998-03-06 Oreal Emulsion huile-dans-eau, composition comprenant une telle emulsion et utilisation en cosmetique, en pharmacie ou en hygiene
ES2179974T3 (es) * 1996-04-19 2003-02-01 Dow Corning Composiciones dispersables de silicona.
US5861453A (en) * 1996-04-19 1999-01-19 Dow Corning Corporation Silicone compositions and uses thereof
US5908891A (en) * 1996-04-19 1999-06-01 Dow Corning Corporation Dispersible silicone compositions
GB2315757B (en) * 1996-07-31 2000-03-29 Gen Electric Dilution stable antifoam emulsion concentrates
US5973068A (en) 1996-11-07 1999-10-26 Shin-Etsu Chemical Co., Ltd. Silicone resin-containing emulsion composition, method for making same, and article having a cured film of same
ES2141458T3 (es) 1996-11-19 2000-03-16 Krafft S A Composiciones de silicona endurecibles en presencia de agua o de la humedad del aire.
GB9703552D0 (en) * 1997-02-20 1997-04-09 Dow Corning Polymerisation of cyclosiloxanes in the presence of fillers
JP4160165B2 (ja) * 1997-06-18 2008-10-01 モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 ポリオルガノシロキサンエマルジョンおよびそれを用いる化粧料
US5733533A (en) * 1997-06-25 1998-03-31 Lambent Technologies Inc. Reconstituted silicone wax esters
US5925469A (en) * 1997-12-18 1999-07-20 Dow Corning Corporation Organopolysiloxane emulsions
GB9727136D0 (en) * 1997-12-24 1998-02-25 Dow Corning Catalyst composition
JP4141003B2 (ja) 1998-02-06 2008-08-27 モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 高分子量ポリオルガノシロキサンエマルジョンおよびそれを含有する化粧料
US6362280B1 (en) * 1998-04-27 2002-03-26 Honeywell International Inc. Emulsible polyolefin wax
JP4439605B2 (ja) * 1998-07-09 2010-03-24 モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 溶媒含有ポリオルガノシロキサンエマルジョン
FR2783713B1 (fr) * 1998-09-29 2002-05-31 Oreal Utilisation d'une gomme de silicone pour stabiliser l'acide ascorbique et nouvelles compositions contenant ces composants
GB9826394D0 (en) * 1998-12-02 1999-01-27 Dow Corning Sa Method of making silicone-in-water emulsions
US6258891B1 (en) * 1998-12-03 2001-07-10 Shell Oil Company Solventless process for making polysiloxane polymers
GB9827069D0 (en) * 1998-12-09 1999-02-03 Dow Corning Polymerisation catalyst
JP2000234062A (ja) * 1999-02-16 2000-08-29 Shin Etsu Chem Co Ltd 有機ケイ素樹脂組成物及びその製造方法並びにこれを含有する化粧料
US6054548A (en) * 1999-08-26 2000-04-25 Dow Corning Limited Process for producing a silicone polymer
CA2385314C (en) 1999-10-04 2009-09-08 Unilever Plc Detergent composition comprising fragrance particle
AU2473401A (en) 2000-01-06 2001-07-16 Dow Corning Asia Limited Organosiloxane compositions
ATE272675T1 (de) 2000-01-06 2004-08-15 Dow Corning Sa Organosiloxan-zusammensetzungen
GB0003061D0 (en) * 2000-02-11 2000-03-29 Dow Corning Sa Silicone polymer emulsions
GB0009289D0 (en) 2000-04-15 2000-05-31 Dow Corning Process for the condensation of compounds having silicon bonded hydroxy or alkoxy groups
JP4548685B2 (ja) 2000-07-12 2010-09-22 信越化学工業株式会社 固形化粧料
TWI240729B (en) 2000-11-24 2005-10-01 Dow Corning Process for making silicone emulsions
FR2827191A1 (fr) 2001-06-22 2003-01-17 Rhodia Chimie Sa Composition aqueuse comprenant une emulsion directe d'une huile silicone exempte de groupement hydrophile et d'une huile comprenant au moins un groupement hydrophile et utilisation de l'emulsion
GB0120058D0 (en) * 2001-08-17 2001-10-10 Dow Corning Polysiloxanes and their preparation
US20030143176A1 (en) * 2002-01-25 2003-07-31 Yihan Liu Compositions containing silicone oil-in-water emulsions, salts, alcohols and solvents
US7311899B2 (en) * 2002-02-04 2007-12-25 L'oreal S.A. Compositions comprising at least one silicone, at least one compound comprising at least one ester group, and at least one copolymer, and methods for using the same
US6468513B1 (en) * 2002-02-19 2002-10-22 The Andrew Jergens Company Low residue liquid antiperspirant composition
GB0207647D0 (en) 2002-04-03 2002-05-15 Dow Corning Emulsions
JP5042442B2 (ja) * 2002-09-13 2012-10-03 東レ・ダウコーニング株式会社 水系エマルジョン、その製造方法および化粧料
US7041088B2 (en) * 2002-10-11 2006-05-09 Ethicon, Inc. Medical devices having durable and lubricious polymeric coating
JP4248842B2 (ja) 2002-10-16 2009-04-02 三井化学株式会社 シリコーン系室温固化組成物
US6737444B1 (en) * 2003-01-16 2004-05-18 Dow Corning Corporation Method of making silicone resin emulsions
WO2004084844A2 (en) 2003-03-27 2004-10-07 Dow Corning Corporation Controlled release compositions
US7226502B2 (en) 2003-04-10 2007-06-05 Clariant Finance (Bvi) Limited High softening temperature synthetic alkylsilicone wax
CN100500742C (zh) 2003-07-23 2009-06-17 陶氏康宁公司 制备水包硅油乳液的机械转化方法
US20070190012A1 (en) * 2004-04-15 2007-08-16 Dow Corning S.A. Low molecular weight silicone oil-in-water emulsion
DE102004027129A1 (de) * 2004-06-03 2005-12-22 Wacker-Chemie Gmbh Verfahren zur Reduzierung des Schäumens bei der wässrigen Kartoffelverarbeitung
CN1253492C (zh) * 2004-07-16 2006-04-26 南京大学 一种羧基硅油乳液的制备方法
DE102004038148A1 (de) * 2004-08-05 2006-03-16 Wacker Chemie Ag Verfahren zur Herstellung von Emulsionen von hochviskosen Organopolysiloxanen
DE102004062430A1 (de) 2004-12-20 2006-06-29 Henkel Kgaa Pigmenthaltige Wasser-in-Siliconöl-Emulsion zur Verbesserung des Erscheinungsbildes der Haut
EP1866375B1 (en) * 2005-04-06 2015-01-28 Dow Corning Corporation Organosiloxane compositions
GB0515052D0 (en) * 2005-07-22 2005-08-31 Dow Corning Organosiloxane compositions
US20100093598A1 (en) * 2006-10-10 2010-04-15 Delphine Davio Silicone Foam Control Agent
WO2008060462A1 (en) * 2006-11-09 2008-05-22 E. I. Du Pont De Nemours And Company Aqueous polymerization of fluorinated monomers using polymerization agent comprising fluoropolyether acid or salt and siloxane surfactant
GB0704871D0 (en) 2007-03-14 2007-04-18 Dow Corning Liquid laundry detergent compositions
GB0905488D0 (en) * 2009-03-31 2009-05-13 Dow Corning Organopolysiloxane compositions and their production
GB0905507D0 (en) * 2009-03-31 2009-05-13 Dow Corning Organopol Ysiloxane Compositions Containing An Active Material
US7993937B2 (en) 2009-09-23 2011-08-09 Tokyo Electron Limited DC and RF hybrid processing system
CN102666664B (zh) * 2009-10-23 2015-09-23 道康宁东丽株式会社 共改性的有机聚硅氧烷

Patent Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3419593A (en) * 1965-05-17 1968-12-31 Dow Corning Catalysts for the reaction of = sih with organic compounds containing aliphatic unsaturation
US3445420A (en) * 1966-06-23 1969-05-20 Dow Corning Acetylenic inhibited platinum catalyzed organopolysiloxane composition
US3691091A (en) * 1969-03-22 1972-09-12 Goldschmidt Ag Th Defoaming emulsion
US3666681A (en) * 1970-03-16 1972-05-30 Dow Corning Antifoam preparation for aqueous systems
US3814730A (en) * 1970-08-06 1974-06-04 Gen Electric Platinum complexes of unsaturated siloxanes and platinum containing organopolysiloxanes
US3715334A (en) * 1970-11-27 1973-02-06 Gen Electric Platinum-vinylsiloxanes
US3839388A (en) * 1972-06-16 1974-10-01 Wacker Chemie Gmbh Process for the condensation and/or equilibration of organosilicon compounds
US3923705A (en) * 1974-10-30 1975-12-02 Dow Corning Method of preparing fire retardant siloxane foams and foams prepared therefrom
US3989667A (en) * 1974-12-02 1976-11-02 Dow Corning Corporation Olefinic siloxanes as platinum inhibitors
US4312801A (en) * 1979-01-16 1982-01-26 Krafft, S.A. Introduced in processes for the manufacture of silicon-based curable compositions
US4690713A (en) * 1984-01-27 1987-09-01 Shin-Etsu Chemical Co., Ltd. Antifoam composition
US4564693A (en) * 1984-08-02 1986-01-14 Wacker-Chemie Gmbh Process for stabilizing organopolysiloxanes
US4701490A (en) * 1985-09-16 1987-10-20 Wacker-Chemie Gmbh Method for stabilizing organopolysiloxanes
US5035832A (en) * 1989-05-17 1991-07-30 Kao Corporation Mild liquid aqueous detergent compositions containing an alkylsaccharide surface active agent and a silicone derivative
US5175325A (en) * 1991-02-14 1992-12-29 Dow Corning Limited Platinum complexes and use thereof
US5777059A (en) * 1996-04-19 1998-07-07 Dow Corning Corporation Silicone compositions and uses thereof
US5914362A (en) * 1996-04-19 1999-06-22 Dow Corning Corporation Silicone-based antifoam compositions cross-reference to related applications
US6521587B1 (en) * 1999-08-13 2003-02-18 Dow Corning S.A. Silicone foam control agent

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9976105B2 (en) 2006-10-10 2018-05-22 Dow Silicones Corporation Silicone polymer emulsions
US20100137454A1 (en) * 2006-10-10 2010-06-03 Kathleen Barmes Silicone Polymer Emulsions
US8623958B2 (en) 2009-03-10 2014-01-07 Dow Corning Toray Co. Ltd. Oil-in-water silicone emulsion composition
US20120020909A1 (en) * 2009-03-31 2012-01-26 Benedicte Courel Organopolysiloxane Emulsions and Their Production
US8580729B2 (en) 2009-03-31 2013-11-12 Dow Corning Corporation Organopolysiloxane compositions containing an active material
US8597624B2 (en) * 2009-03-31 2013-12-03 Dow Corning Corporation Organopolysiloxane emulsions and their production
US9029428B2 (en) 2010-07-02 2015-05-12 Dow Corning Toray Co., Ltd. Oil-in-water silicone emulsion composition
US10005110B2 (en) 2011-02-16 2018-06-26 Dow Silicones Corporation Foam control composition
US10144909B2 (en) 2011-06-17 2018-12-04 Dow Global Techlologies LLC Fabric care pellets and methods
US9487736B2 (en) * 2012-02-16 2016-11-08 Dow Corning Corporation Granulated foam control agent for the rinse cycle using siloxane wax
US20150038388A1 (en) * 2012-02-16 2015-02-05 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
WO2015122989A1 (en) * 2014-02-14 2015-08-20 Dow Corning Corporation Emulsions of branched organopolysiloxanes
US11332581B2 (en) 2015-01-28 2022-05-17 Dow Silicones Corporation Elastomeric compositions and their applications
US10611987B2 (en) * 2016-02-02 2020-04-07 The Procter & Gamble Company Antifoam molecules containing a silica moiety and compositions
US20170218307A1 (en) * 2016-02-02 2017-08-03 The Procter & Gamble Company Antifoam molecules and compositions
US20190157518A1 (en) * 2016-03-24 2019-05-23 Nichia Corporation Method of manufacturing light emitting device
US10930822B2 (en) * 2016-03-24 2021-02-23 Nichia Corporation Method of manufacturing light emitting device
US11090253B2 (en) 2016-08-03 2021-08-17 Dow Silicones Corporation Cosmetic composition comprising silicone materials
US11485936B2 (en) 2016-08-03 2022-11-01 Dow Silicones Corporation Fabric care composition comprising silicone materials
US11248119B2 (en) 2017-02-06 2022-02-15 Dow Silicones Corporation Emulsion, composition comprising same, film formed therewith, and related methods
US11254847B2 (en) 2017-05-09 2022-02-22 Dow Silicones Corporation Lamination adhesive compositions and their applications
US11479022B2 (en) 2017-05-09 2022-10-25 Dow Silicones Corporation Lamination process
CN109942820A (zh) * 2019-03-26 2019-06-28 浙江置正有机硅有限公司 一种甲基苯基羟基硅油的制备方法及用于甲基苯基羟基硅油制备的油水分离器
CN114585427A (zh) * 2019-08-14 2022-06-03 埃肯有机硅美国公司 制备颗粒或粉末形式的泡沫控制组合物的方法
US12291688B1 (en) * 2023-12-12 2025-05-06 Afton Chemical Corporation Silicon-containing compounds for lubricants

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JP5490539B2 (ja) 2014-05-14
US20180237720A1 (en) 2018-08-23

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