WO2009129175A1 - Emulsions of boron crosslinked organopolysiloxanes - Google Patents
Emulsions of boron crosslinked organopolysiloxanes Download PDFInfo
- Publication number
- WO2009129175A1 WO2009129175A1 PCT/US2009/040350 US2009040350W WO2009129175A1 WO 2009129175 A1 WO2009129175 A1 WO 2009129175A1 US 2009040350 W US2009040350 W US 2009040350W WO 2009129175 A1 WO2009129175 A1 WO 2009129175A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- emulsion
- process according
- mixture
- water
- boron
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on 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; Coating compositions based on derivatives of such polymers
- C09D183/14—Coating compositions based on 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; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
-
- 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
- C08J3/05—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on 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; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- 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
- C08J2383/06—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- 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
- C08J2383/14—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
Definitions
- This disclosure relates to a process for preparing an emulsion composition by forming a mixture of a silanol functional organopolysiloxane, a boron compound, an emulsifier, and then admixing water to the mixture to form an emulsion.
- the resulting emulsions are useful for providing a coating of a high viscosity or dilatant silicone.
- incorporation of many of these components in a silicone emulsion composition may be problematic depending on the selection of the additive component and the emulsion process (that is mechanical vs emulsion polymerization process).
- the desired silicone additive component interacts with water during the emulsification process it may be difficult or impossible to incorporate its addition into a silicone emulsion.
- the silicone emulsion art incorporating a variety of crosslinking components with organopolysiloxanes to provide high molecular weight or elastomeric silicone compositions.
- boron compounds as crosslinking additives in a silicone emulsion.
- boron crosslinked organopolysiloxanes are of particular interest because of their inherent dilatant properties.
- dilatant boron crosslinked silicones are used in active protection systems (APS) wherein a fabric is coated with a boron crosslinked silicone.
- APS active protection systems
- boron crosslinked silicone be first dispersed or dissolved in a solvent.
- Water based emulsions of boron crosslinked silicones would be easier to use and environmentally more desirable in such processes.
- there are few examples of emulsions of boron crosslinked silicones or borosiloxanes there are few examples of emulsions of boron crosslinked silicones or borosiloxanes.
- 4,863,985 discloses thixotropic silicone emulsions cross-linkable into elastomeric state upon removal of water therefrom, e.g., to fabricate elastomer seals for the construction industry, have a pH of from 4 to 8 and a solids content of at least 50%, and contain: (A) 100 parts of an oil-in-water emulsion of an ⁇ , ⁇ -(dihydroxy) polydiorganosiloxane, and a stabilizing amount of at least one anionic or nonionic surface-active agent, or mixture thereof; (B) 1 to 15 parts of a siliceous reinforcing filler in powder form; (C) 0 to 250 parts of an inorganic filler other than the siliceous filler (B); (D) 0.01 to 2 parts of a catalytic tin compound; and (E) 0.1 to 5 parts of boric oxide, a boric acid or a borate.
- A 100 parts of an oil-in-water emul
- the process provides emulsions of boron crosslinked organopolysiloxanes that yield subsequent silicone polymers of varying physical properties.
- the present process provides emulsions of boron crosslinked organopolysiloxanes that yield coatings that vary from a highly viscous silicone liquid to an elastomeric silicone having dilatant properties.
- This disclosure provides a process for preparing an emulsion composition comprising:
- the emulsions from the present process are useful in a variety of applications.
- the present process provides emulsions of high viscosity silicones for hair care applications.
- the present process further provides emulsions of dilatant silicones which are useful as fabric coatings for Active Protection Systems.
- the first step of the process of the present disclosure involves forming a mixture of; A) a silanol functional organopolysiloxane,
- Organopolysiloxanes are polymers containing siloxane units independently selected from (R 3 SiO 0 S ), (R 2 SiO), (RSiO 1 5 ), or (SiO 2 ) siloxy units, where R may independently be an organic group, OH (silanol), or H (SiH functional). These siloxy units are commonly referred to as M, D, T, and Q units respectively. These siloxy units can be combined in various manners to form cyclic, linear, or branched structures. The chemical and physical properties of the resulting polymeric structures will vary depending on the type and number of each siloxy units present in the organopolysiloxane. For example organopolysiloxanes can be volatile or low viscosity fluids, high viscosity fluids/gums, elastomers or rubbers, and resins.
- the organopolysiloxane useful as component A) in the present invention may have any combination of (R 3 SiO 0 S ), (R 2 SiO), (RSiO 1 5 ), or (SiO 2 ) siloxy units, providing the organopolysiloxane contains at least one silanol group (SiOH).
- the organopolysiloxane may have varying molecular weights and be a liquid, a gum, an elastomer, a resin, or any combination thereof.
- the organopolysiloxane may be a mixture of a higher molecular weight organopolysiloxane (such as an elastomer or resin) in a lower molecular weight liquid organopolysiloxane, providing there is at least one silanol group in the organopolysiloxane composition of component A.
- the amount of silanol groups present in the organopolysiloxane may vary.
- the amount of silanol groups in the organopolysiloxane may be designated as weight percent of SiOH.
- the weight percent of silanol groups that are typical in the organopolysiloxanes useful as component A) vary from 0.01 to 20 weight percent, alternatively from 0.05 to 10 weight percent, alternatively from 0.05 to 4 weight percent.
- the organopolysiloxane is a predominately linear polydimethylsiloxane having terminal silanol groups.
- the predominately linear polydimethylsiloxane having terminal silanol groups may have the formula;
- x is > 0, alternatively, x is 1 - 4000, alternatively 10 - 1000.
- the silanol functional organopolysiloxane may be mixed with other silane or polysiloxane components before or during mixing with components B) and C).
- the other silane or siloxane components include organofunctional silanes or organofunctional polysiloxanes that can react with the silanol functional organopolysiloxane.
- Suitable organofunctional silanes include amino functional silanes such as; aminopropyl trimethoxysilane, ethylenediaminepropyl trimethoxysilane, or ethylenediamineisobutyl trimethoxysilane.
- Suitable organofunctional polysiloxanes include amino functional organopolysiloxanes such as those having a formula
- R 2 R 2 SiO(R 2 SiO) 3 (R 1 RSiO) b SiR 2 R 2 or R 2 R 2 SiO(R 2 SiO) 3 (R 1 SiO 3/2 ) b SiR 2 R 2 wherein R is a monovalent organic group, R 1 is an aminoalkyl group having its formula selected from the group consisting of -R 3 NH 2 and -R 3 NHR 4 NH 2 wherein R 3 is a divalent hydrocarbon group having at least 3 carbon atoms and R 4 is a divalent hydrocarbon group having at least 2 carbon atoms, R 2 is R, R 1 , or OH, a has a value of 0 to 2000, and b has a value of from greater than zero to 200.
- the monovalent R groups are exemplified by alkyl groups such as the methyl, ethyl, propyl, butyl, amyl, and hexyl; alkenyl groups such as the vinyl, allyl, and hexenyl; cycloalkyl groups such as the cyclobutyl and cyclohexyl; aryl groups such as the phenyl and naphthyl; aralkyl groups such as the benzyl and 2-phenylethyl; alkaryl groups such as the tolyl, and xylyl; halohydrocarbon groups such as 3-chloropropyl, 4-bromobutyl, 3,3,3- trifluoropropyl, chlorocyclohexyl, bromophenyl, and chlorophenyl.
- alkyl groups such as the methyl, ethyl, propyl, butyl, amyl, and hexyl
- R is a monovalent hydrocarbon group having from 1 to 6 carbon atoms. Especially preferred R groups are methyl, phenyl, and vinyl.
- the group R 3 is typically an alkylene group having from 3 to 20 carbon atoms. Typically R 3 is selected from propylene, -CH 2 CHCH 3 -, butylene, -CH 2 CH(CH 3 )CH 2 -, pentamethylene, hexamethylene, 3-ethyl-hexamethylene, octamethylene, and decamethylene.
- the group R 4 is typically an alkylene group having from 2 to 20 carbon atoms.
- R 4 is selected from ethylene, propylene, -CH 2 CHCH 3 -, butylene, -CH 2 CH(CH 3 )CH 2 -, pentamethylene, hexamethylene, 3-ethyl-hexamethylene, octamethylene, and decamethylene.
- R 1 typically is -CH 2 CH 2 CH 2 NHCH 2 CH 2 NH 2 or -CH 2 CH(CH 3 )CH 2 NHCH 2 CH 2 NH 2 . Salts of these same aminofunctional groups may also be used. Examples of such salts include alkyl carboxylate salts, aryl carboxylate salts, halide salts such as chlorides and bromides, and other neutralization products of the amines with organic acids.
- the group R 2 may be R, R 1 , or -OH, typically R 2 is methyl or -OH.
- the polyorganosiloxanes may have from 0.1 to 15 molar percent of the above described amino groups and most typically from 0.2 to 10 molar percent of the above described amino groups. In the above formulas, typically a has a value of from 50 to 2000, and b has a value of 1 to 100.
- the aminofunctional polyorganosiloxanes useful in this invention can be prepared by procedures well known in the art. Many of these polyorganosiloxanes are available commercially. [0017] The amount of the silanol functional organopolysiloxane added in step I may vary.
- the amount used will depend on the type and amount of boron compound used in step I) and the extent of crosslinking desired. Typically, the amount of the silanol functional organopolysiloxane ranges from 50 to 99, alternatively from 75 to 95, alternatively from 85 to 90 weight, percent based on the total weight of the mixture in step I.
- Component B) is a boron compound.
- a "boron compound” means any compound containing boron. Any boron compound known to react with organopolysiloxanes may be selected as component B). Alternatively, the boron compound may be selected from those known to react with silanol functional groups on organopolysiloxanes. Such boron compounds include; boron or boric oxide, boric acid, borates, boric anhydride. Boric acid may be orthoboric acid, metaboric acid, or tetraboric acid.
- Borates include alkyl and allyl boric acid esters / triorganoborates that hydrolyse to boric acid in the presence of water, such as triethylborate, triphenylborate, tribenzyl borate, tricyclohexyl borate, tri(methylsilyl) borate, tri-t-butyl borate, trialkoxyboroxines such as trimethoxyboroxine and triisopropoxyboroxine, triethanolamineborate, and derivatives such as 2,2'-oxybis[4,4,6-trimethyl-1 ,3,2- dioxaboranine .
- Borates also encompass inorganic borates such as diammonium pentaborate, sodium tetraborate decahydrate (borax), potassium pentaborate, magnesium diborate, calcium monoborate, barium triborate, and zinc metaborate.
- Suitable boron compounds further includes the partial hydrolysis products of the aforementioned borates.
- the boron compound is boron oxide having the formula B 2 O 3 [CAS registry #1303-86-2], or boric acid having the formula H 3 BO 3 [CAS registry #10043-35-3].
- the boron compound may be added either alone or in combination with other ingredients in step I.
- the boron compound is boron oxide or boric acid, and is dispersed in a trimethylsiloxy terminated polydimethylsiloxane, such as
- Dow Corning ® 200 fluid having a viscosity ranging from 0.65 cS (mm 2 /s) at 25 °C to 100,000 cS (mm 2 /s) at 25 °C, alternatively from 100 to 10,000 cS (mm 2 /s) at 25 °C, or alternatively from 100 to 1 ,000 cS (mm 2 /s) at 25 °C.
- the amount of boron oxide or boric acid dispersed in the trimethylsiloxy terminated polydimethylsiloxane may vary, but typically ranges from 0.5 to 70, alternatively from 10 to 50 weight percent alternatively from 40 to 50 weight percent.
- the amount of boron compound added in step I may vary. The amount used will depend on the type and amount of organopolysiloxane used in step I) and the extent of crosslinking desired. Typically, the amount of boron compound ranges from 0.05 to 30, alternatively from 0.1 to 10 alternatively from 0.1 to 6 weight percent based on the total weight of the mixture in step I.
- Component C in the process of the present disclosure is an emulsifier.
- emulsifier refers to any compound or substance that enables the formation of an emulsion.
- the emulsion may be an oil/water emulsion, a water/oil emulsion, a multiple phase or triple emulsion.
- the emulsifier may be selected from any surface active compound or polymer capable of stabilizing emulsions. Typically, such surface active compounds or polymers stabilize emulsions by preventing coalescence of the dispersed particles.
- the surface active compounds useful as emulsifiers in the present process may be a surfactant or combination of surfactants.
- the surfactant may be an anionic surfactant, cationic surfactant, nonionic surfactant, amphoteric surfactant, or a mixture of any of these surfactants.
- Suitable 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.
- 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, sulphon
- Suitable cationic surfactants include alkylamine salts, quaternary ammonium salts, sulphonium salts, and phosphonium salts.
- suitable nonionic surfactants include condensates of ethylene oxide with long chain fatty alcohols or fatty acids such as a C-
- suitable amphoteric surfactants include imidazoline compounds, alkylaminoacid salts, and betaines.
- nonionic surfactants include polyoxyethylene fatty alcohols sold under the tradename BRIJ® by Uniqema (ICI Surfactants), Wilmington, Delaware. 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. Some additional nonionic surfactants include ethoxylated alcohols sold under the trademark TERGITOL® by The Dow Chemical Company, Midland, Michigan.
- TERGITOL® TMN-6 an ethoxylated alcohol known as ethoxylated trimethylnonanol
- various of the ethoxylated alcohols i.e., C12-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.
- Lutensol ® supplied by BASF in the series of Lutensol XP known as ethoxylated, C10-Guerbet alcohol and Lutensol TO known as ethoxylated, iso-C13 alcohol may also be used.
- one nonionic surfactant may have a low Hydrophile-Lipophile Balance (HLB) and the other nonionic surfactant may have a high HLB, such that the two nonionic surfactants have a combined HLB of 11 -15, alternatively a combined HLB of 12.5-14.5.
- HLB Hydrophile-Lipophile Balance
- the emulsifier may be a polymer or those materials consider as “thickeners” or “thickening agents".
- Such polymeric emulsifiers include polyvinyl alcohol, cellulosic polymers or xanthan gums.
- the polyvinyl alcohol includes hydrolyzed polyvinyl alcohols, such as 80 - 95 % hydrolyzed polyvinyl alcohol.
- Suitable thickening agents are exemplified by sodium alginate, gum arabic, polyoxyethylene, guar gum, hydroxypropyl guar gum, ethoxylated alcohols, such as laureth-4 or polyethylene glycol 400, cellulose derivatives exemplified by carboxy methylcellulose, methylcellulose, methylhydroxypropylcellulose, hydroxypropylcellulose, polypropylhydroxyethylcellulose, starch, and starch derivatives exemplified by hydroxyethylamylose and starch amylose, locust bean gum, electrolytes exemplified by sodium chloride and ammonium chloride, and saccharides such as fructose and glucose, and derivatives of saccharides such as PEG-120 methyl glucose diolate or mixtures of 2 or more of these.
- the thickening agent is selected from the group consisting of cellulose derivatives, saccharide derivatives, and electrolytes, or from a combination of two or more of the above thickening agents exemplified by a combination of a cellulose derivative and any electrolyte, and a starch derivative and any electrolyte.
- the emulsifier may be added either alone or in combination with varying amounts of water in step I.
- the surfactant is added in step I as a concentrated aqueous dispersion, or alternatively as an aqueous solution.
- the emulsifier is an aqueous solution containing at least 70 weight percent of two nonionic surfactants having a combined HLB of 8 -15.
- the emulsifier is an aqueous solution of 5 to 30 weight percent of nonionic surfactant having alone a HLB of 8 to 15, or the emulsifier is an aqueous solution containing at least 20 weight percent of one nonionic surfactant and a cationic surfactant, or the emulsifier is an aqueous surfactant containing 30 to 100 weight percent of a anionic surfactant.
- the amount of emulsifier added in step I may vary. The amount used will depend on the type of emulsion and the particle size desired. Typically, the amount of emulsifier added in Step I is 0.1 to 40, alternatively the amount is 0.5 to 30 weight percent of the mixture in Step I.
- step (I) can be accomplished by any method known in the art to affect mixing of high viscosity materials.
- the mixing may occur either as a batch, semi-continuous, or continuous process.
- Mixing may occur, for example using, batch mixing equipments with medium / low shear include change-can mixers, double-planetary mixers, conical-screw mixers, ribbon blenders, double-arm or sigma-blade mixers; batch equipments with high-shear and high-speed dispersers include those made by Charles Ross & Sons (NY), Hockmeyer Equipment Corp.
- NJ batch equipments with high shear actions include Banbury-type (CW Brabender Instruments Inc., NJ) and Henschel type (Henschel mixers America, TX).
- Illustrative examples of continuous mixers / compounders include extruders single- screw, twin-screw, and multi-screw extruders, co-rotating extruders, such as those manufactured by Krupp Werner & Pfleiderer Corp (Ramsey, NJ), and Leistritz (NJ); twin-screw counter-rotating extruders, two-stage extruders, twin-rotor continuous mixers, dynamic or static mixers or combinations of these equipments.
- the temperature and pressure at which the mixing of step I occurs is not critical, but generally is conducted at ambient temperature and pressures. Typically, the temperature of the mixture will increase during the mixing process due to the mechanical energy associated with shearing such high viscosity materials.
- the present inventors believe that as a result of mixing components A), B), and C) the boron compound reacts with the silanol functional organopolysiloxane to form various crosslinks.
- the inclusion of an emulsifier in the step I) mixture enhances subsequent emulsion formation in step II).
- Step Il of the process involves admixing water to the mixture of step I to form an emulsion. Typically 5 to 700 parts water are mixed for every 100 parts of the step I mixture to form an emulsion. In one embodiment the emulsion formed is a water continuous emulsion. Typically, the water continuous emulsion has dispersed particles of the boron crosslinked organopolysiloxane from step I, and having an average particle size less than 150 ⁇ m.
- the amount of water added can vary from 5 to 700 parts per 100 parts by weight of the mixture from step I.
- the water is added to the mixture from step I at such a rate so as to form an emulsion of the mixture of step I. While this amount of water can vary depending on the selection of the boron oxide crosslinked organopolysiloxane and emulsifier, generally the amount of water is from 5 to 700 parts per 100 parts by weight of the step I mixture, alternatively from 5 to 100 parts per 100 parts by weight of the step I mixture, or alternatively from 5 to 70 parts per 100 parts by weight of the step I mixture.
- step (II) can be accomplished by any method known in the art to affect mixing of high viscosity materials. The mixing may occur either as a batch, semi-continuous, or continuous process. Any of the mixing methods as described for step (I), may be used to affect mixing in step (II).
- step (III) the water continuous emulsion formed in step (II) may be further sheared according to step (III) to reduce particle size and/or improve long term storage stability. The shearing may occur by any of the mixing techniques discussed above.
- the emulsion products resulting from the present process may be an oil/water emulsion, a water/oil emulsion, a multiple phase or triple emulsion.
- the emulsion products produced by the present process are oil/water emulsions.
- the oil/water emulsion may be characterized by average volume particle of the dispersed boron crosslinked organopolysiloxane phase in a continuous aqueous phase.
- the particle size may be determined by laser diffraction of the emulsion. Suitable laser diffraction techniques are well known in the art.
- the particle size is obtained from a particle size distribution (PSD).
- PSD particle size distribution
- the PSD can be determined on a volume, surface, length basis.
- the volume particle size is equal to the diameter of the sphere that has the same volume as a given particle.
- Dv represents the average volume particle size of the dispersed particles.
- the average volume particle size of the dispersed siloxane particles in the oil/water emulsions is between 0.1 ⁇ m and 150 ⁇ m; or between 0.1 ⁇ m and 30 ⁇ m; or between 0.3 ⁇ m and 5.0 ⁇ m.
- the emulsions of the present disclosure may be further characterized by the properties of the resulting films or coatings produced after allowing a film of the emulsion to dry. Typically, such coatings are obtained by forming a film of the emulsion, and allowing the film to stand for a sufficient period of time to evaporate the water present in the emulsion. This process may be accelerated by increasing the ambient temperature of the film or coating.
- the films or coatings resulting from the present emulsions may by characterized by their rheological properties, such as with a Carri-Med rheometer to determine in the LVR at 0.2 Hz both the dynamic shear storage (G') and loss module (G").
- G' dynamic shear storage
- G' loss module
- G' ranges from 200 Pa to 10,000,000 Pa alternatively
- G' ranges from 1000 Pa to 200,000 Pa
- G" ranges from 1000 Pa to 10,000,000 Pa alternatively
- G" ranges from 1000 Pa to 200,000 Pa for the resulting silicone coating at 25 °C.
- the resulting films may be considered as high viscosity fluids as characterized by viscosity. Such viscosity measurements may be conducted using a rheometer.
- the dynamic viscosity of the resulting films may vary from 100 Pa to 10 000 000 Pa, or alternatively, from 1000 Pa to 300, 000 Pa, as measured at 25 °C.
- silica is added to the emulsion to affect subsequent properties, and in particular dilatant properties.
- the amount and type of silica added to the emulsion may vary.
- the amount of silica added to the emulsion may vary from 0.1 to 50 weight percent, alternatively, 1 to 40 weight percent, or alternatively 5 to 30 weight percent may be added to the emulsion.
- the silica may be added at any time during the processing of the emulsion, but typically is post added.
- Suitable silicas include fumed silicas such as AEROSIL® OX-50 (40 nanometer average particle diameter silica available from Evonik); stabilized silica sols such as the KLEBOSOL® Series available from Rohm and Haas), KLEBOSOL® 30H25 (25 nm average particle diameter proton stabilized waterborne colloidal silica sol having a ph of 2.2 and a 30% solids content, KLEBOSOL 30H50 (50 nm average particle diameter proton stabilized waterborne colloidal silica sol having a pH of 2.5 to 3.0 and a 30% solids content, KLEBOSOL 30N12 (12 nm average particle diameter ammonium ion stabilized waterborne colloidal silica sol having a pH of 9.5 to 10.5 and a 30% solids content, KLEBOSOL 30N25 (25 nm average particle diameter ammonium ion stabilized waterborne colloidal silica sol having a pH of 9.5 to 10.5 and a 30% solids content, K
- Suitable colloidal silicas include the LUDOX® series from W. R. Grace such as; LUDOX AM, LUDOX AM-30 (12 nm average particle diameter aqueous silica sol having a 30% solids content), LUDOX AS, LUDOX HS40, LUDOX LS, LUDOX TM and LUDOX TMA (22 nm average particle diameter aqueous silica sol having a 34% solids:content).
- Another suitable silica includes those marketed as SNOWTEX® colloidal silicas from Nissan Chemical (Houston, TX), such as SNOWTEX.
- Mean particle size was determined using a Malvern Mastersizer 2000.
- Rheological properties were determined using a TA Instruments ARES rheometer equipped with cone-and-plate geometry (Example 1 to 5) and a Carri-Med Rheometer CSL 2 with a cone-and-plate geometry (Example 6 to 10).
- the cup was spun again for 20 seconds.
- 0.75 g of lauryl alcohol (4) ethoxylate (Brij® 30) was added followed by 1.5g of a 72 % aqueous solution of lauryl alcohol (23) ethoxylate (Brij® 35L) and 0.60 g of deionized (Dl) water.
- the cup was closed and spun in the Speedmixer® for 20 seconds.
- the contents of the cup had formed a mass having a thick gel-like consistence and the walls of the cup were scraped with a spatula.
- the cup and its contents were spun again for 20 seconds.
- the thick phase composition was diluted incrementally with a total of 31 g of Dl water.
- the first increment was 5g followed by another 5g then 10 g followed with a final 1 1 g.
- the cup was spun for 18 seconds at full speed in the SpeedMixer® after each incremental addition of water.
- the resulting final composition was a milky-white liquid of low viscosity and consisted of an oil/water emulsion of approximately 60% by weight polydimethylsiloxane containing boron oxide and having a mean particle size of approximately 0.75 ⁇ m.
- a 2Og portion of the emulsion was poured into a Petri dish and allowed to evaporate and at ambient conditions for 24 hours.
- the resulting polymer from the emulsion was inspected and found to have increased in viscosity substantially from that of the starting silicone polymer.
- Viscosity of the polymer from the emulsion was determined using a rheometer and found to have a zero-shear-rate viscosity of approximately 10 7 cP (@10 "1 sec. "1 & 24 0 C), as summarized in figure 1. These results show the viscosity of the siloxane polymer from the emulsion was significantly higher than the viscosity of the starting siloxane polymer (approximately 5 x10 4 cP).
- the emulsion thick phase was diluted incrementally with a total of 31 g of Dl water using the same procedure of example 1.
- Mean particle size of the emulsion was approximately 0.75 ⁇ m
- an emulsion was prepared. This emulsion was prepared using 5Og of a Me 2 SiOH terminated dimethylpolysiloxane and 0.4Og of boron oxide/polydimethylsiloxane dispersion. Mean particle size of the emulsion was approximately 0.75 ⁇ m.
- Example 2 Using the procedure as described in Example 1 , a composition prepared from 5Og SiOH functional polydimethylsiloxane having a viscosity of approximately 50,000 mPa sec. (cP) and a number average molecular weight of approximately 61 ,000, 0.5Og of a 50% by weight dispersion of boric oxide in trimethylsiloxy-capped polydimethylsiloxane fluid having an approximate kinematic viscosity of 1000 cSt was emulsified using 1.25g of 60% by weight aqueous sodium secondary alkyl sodium sulfonate (Hostapur® SAS-60) and 5.Og of water.
- Hostapur® SAS-60 aqueous sodium secondary alkyl sodium sulfonate
- the resulting thick phase composition was diluted with 27g of Dl water incrementally as described in Example 1.
- the resulting emulsion consisted of an approximately 60% solids anionic emulsion of PDMS containing 0.5% B 2 O 3 . Removal of water from this emulsion resulted in a high viscosity polymer.
- Example 2 Using the procedure as described in Example 1 , a composition prepared from 5Og SiOH functional polydimethylsiloxane having a viscosity of approximately 50,000 mPa sec. (cP) and a number average molecular weight of approximately 61 ,000, 0.5Og of a 50% by weight dispersion of boric oxide in trimethylsiloxy-capped polydimethylsiloxane fluid having an approximate kinematic viscosity of 1000 cSt was emulsified using 3.3g of a 30% aqueous solution of cetyltrimethylammonium chloride (CETAC® 30) and Og of water. The resulting thick phase was diluted with 3Og of Dl water incrementally as described in Example 1.
- CETAC® 30 cetyltrimethylammonium chloride
- the resulting emulsion consisted of an approximately 60% cationic emulsion of PDMS containing 500ppm B 2 O 3 . Removal of water from this emulsion resulted in a film of polymer that had a rubbery consistency.
- the resulting final composition was a milky-white liquid of low viscosity and consisted of an oil/water emulsion of approximately 60% by weight polydimethylsiloxane containing boron oxide and having a mean particle size of approximately 3.8 ⁇ m.
- a 20 g portion of the emulsion was poured into an aluminum cup and allowed to evaporate and at ambient conditions for 24 hours. The resulting polymer from the emulsion was inspected and found to have formed a film.
- the resulting final composition was a milky- white liquid of low viscosity and consisted of an oil/water emulsion of approximately 60% by weight polydimethylsiloxane containing boron oxide and having a mean particle size of approximately 1.3um. As described previously, the rheology of the film was studied.
- the modulus G' was 2400 Pa and G" was 28600 Pa.
- Example 9 Using the same procedure and quantities as described in Example 6 except that 1.5 g of the ⁇ -iso-tridecyl ⁇ -hydroxyl poly(oxythylene) was replaced by the hexadecyltrimethylammonium chloride at 30% active (Arquadi 6-29). As described previously, the rheology of the film was studied. The modulus G' was 29970 Pa and G" was 1 12500 Pa. Example 9
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP09731689A EP2276818B1 (en) | 2008-04-14 | 2009-04-13 | Emulsions of boron crosslinked organopolysiloxanes |
JP2011505111A JP5536754B2 (en) | 2008-04-14 | 2009-04-13 | Boron cross-linked organopolysiloxane emulsion |
US12/937,295 US8664328B2 (en) | 2008-04-14 | 2009-04-13 | Emulsions of boron crosslinked organopolysiloxanes |
CN200980117710.XA CN102027082B (en) | 2008-04-14 | 2009-04-13 | Emulsions of boron crosslinked organopolysiloxanes |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US4459408P | 2008-04-14 | 2008-04-14 | |
US61/044,594 | 2008-04-14 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2009129175A1 true WO2009129175A1 (en) | 2009-10-22 |
Family
ID=40679637
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2009/040350 WO2009129175A1 (en) | 2008-04-14 | 2009-04-13 | Emulsions of boron crosslinked organopolysiloxanes |
Country Status (6)
Country | Link |
---|---|
US (1) | US8664328B2 (en) |
EP (1) | EP2276818B1 (en) |
JP (1) | JP5536754B2 (en) |
KR (1) | KR20110003367A (en) |
CN (1) | CN102027082B (en) |
WO (1) | WO2009129175A1 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011236421A (en) * | 2010-05-03 | 2011-11-24 | Wacker Chemie Ag | Method for preparing silicone emulsion |
WO2012119916A1 (en) | 2011-03-04 | 2012-09-13 | Dow Corning Corporation | Emulsion polymerisation method |
JP2012233039A (en) * | 2011-04-28 | 2012-11-29 | Shin-Etsu Chemical Co Ltd | Room temperature curable organopolysiloxane composition |
US9246173B2 (en) | 2012-11-16 | 2016-01-26 | Mitsubishi Chemical Corporation | Process for synthesis of hybrid siloxy derived resins and crosslinked networks therefrom |
WO2017122050A1 (en) * | 2016-01-15 | 2017-07-20 | Taghdis Porcelain Company | Anti-stain coating composition for porcelain ware |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009129175A1 (en) | 2008-04-14 | 2009-10-22 | Dow Corning Corporation | Emulsions of boron crosslinked organopolysiloxanes |
CN102037088B (en) * | 2008-04-14 | 2014-08-06 | 陶氏康宁公司 | Emulsions of dilatant organopolysiloxanes |
JP5474046B2 (en) * | 2008-04-14 | 2014-04-16 | ダウ・コーニング・コーポレイション | Boron-crosslinked organopolysiloxane emulsions and their use in personal care compositions |
CN103319719B (en) * | 2012-03-19 | 2015-07-22 | 香港纺织及成衣研发中心有限公司 | Method for preparing intelligent stress responding type silicon-boron polymer microgel |
CN105385164A (en) * | 2015-12-30 | 2016-03-09 | 中物功能材料研究院有限公司 | Smart impact-resisting material and preparation method thereof |
CN107805309B (en) * | 2016-09-09 | 2021-03-19 | 翁秋梅 | Dynamic polymer with non-covalent cross-linked structure and application thereof |
EP3655220A4 (en) * | 2017-07-19 | 2021-04-14 | Avantor Performance Materials, LLC | Curable organopolysiloxane composition containing dynamic covalent polysiloxane |
JP7212859B2 (en) * | 2019-02-28 | 2023-01-26 | 日東紡績株式会社 | Water-repellent coating composition and method of use thereof |
US11891484B2 (en) | 2019-09-17 | 2024-02-06 | Crayola Llc | Putty and putty base compounds and methods of making thereof |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4863985A (en) * | 1987-10-20 | 1989-09-05 | Rhone-Poulenc Chimie | Aqueous silicone emulsions crosslinkable into elastomeric state |
EP0446157A1 (en) * | 1990-03-08 | 1991-09-11 | Rhone-Poulenc Chimie | Aqueous dispersion of silicone oils curable to a flame-resistant elastomer by elimination of water |
Family Cites Families (93)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2431893A (en) * | 1944-08-22 | 1947-12-02 | Atlantic Coast Fisheries Co | Fish filleting machine |
US2431898A (en) | 1946-07-02 | 1947-12-02 | Witken Isadore | Work trestle |
US2798053A (en) | 1952-09-03 | 1957-07-02 | Goodrich Co B F | Carboxylic polymers |
GB890007A (en) | 1959-10-22 | 1962-02-21 | Dow Corning | Modified rubbery organopolysiloxane putty compositions |
NL277487A (en) * | 1961-04-25 | |||
DE2122066C3 (en) | 1971-05-04 | 1974-10-24 | Wacker-Chemie Gmbh, 8000 Muenchen | Preparation of compounds containing boron based on organopolysiloxanes |
US3958581A (en) | 1972-05-17 | 1976-05-25 | L'oreal | Cosmetic composition containing a cationic polymer and divalent metal salt for strengthening the hair |
CA1018893A (en) | 1972-12-11 | 1977-10-11 | Roger C. Birkofer | Mild thickened shampoo compositions with conditioning properties |
LU67061A1 (en) | 1973-02-19 | 1974-09-25 | ||
US4009256A (en) | 1973-11-19 | 1977-02-22 | National Starch And Chemical Corporation | Novel shampoo composition containing a water-soluble cationic polymer |
GB1497087A (en) | 1975-02-18 | 1978-01-05 | Foseco Int | Securing device |
DE2544180C2 (en) | 1975-10-03 | 1984-02-23 | Merck Patent Gmbh, 6100 Darmstadt | Light protection preparations for cosmetic purposes |
FR2430938A1 (en) * | 1978-07-11 | 1980-02-08 | Oreal | NOVEL BORNANONE OXYBENZYLIDENES, PROCESS FOR THEIR PREPARATION, AND COSMETIC COMPOSITIONS CONTAINING THEM |
NL190101C (en) | 1978-11-13 | 1993-11-01 | Givaudan & Cie Sa | DIBENZOYL METHANE COMPOUND AND ANTI-LIGHT PROTECTIVE PREPARATION. |
FR2528420A1 (en) | 1982-06-15 | 1983-12-16 | Oreal | NOVEL 3-BENZYLIDENE CAMPHERS, PROCESS FOR THEIR PREPARATION AND USE THEREOF FOR PROTECTION AGAINST UV RAYS |
DE3302123A1 (en) | 1983-01-22 | 1984-07-26 | Haarmann & Reimer Gmbh | NEW DIBENZOLE METHANE DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE |
US4620878A (en) * | 1983-10-17 | 1986-11-04 | Dow Corning Corporation | Method of preparing polyorganosiloxane emulsions having small particle size |
FR2557121B1 (en) * | 1983-12-21 | 1986-10-10 | Rhone Poulenc Spec Chim | HOT VULCANIZABLE ORGANOPOLYSILOXANIC ELASTOMERIC COMPOSITIONS WITH IMPROVED PHYSICAL CHARACTERISTICS |
CA1261276A (en) | 1984-11-09 | 1989-09-26 | Mark B. Grote | Shampoo compositions |
US4788006A (en) | 1985-01-25 | 1988-11-29 | The Procter & Gamble Company | Shampoo compositions containing nonvolatile silicone and xanthan gum |
US4704272A (en) | 1985-07-10 | 1987-11-03 | The Procter & Gamble Company | Shampoo compositions |
FR2592380B1 (en) | 1985-12-30 | 1988-03-25 | Oreal | NOVEL 3-BENZYLIDENE CAMPHOR DERIVATIVES CONTAINING BENZIMIDAZOLE, BENZOXAZOLE OR BENZOTHIAZOLE PATTERNS, PROCESS FOR THEIR PREPARATION AND THEIR USE IN COSMETICS FOR UV PROTECTION |
NL8801195A (en) | 1988-05-06 | 1989-12-01 | Stamicarbon | BALLISTIC STRUCTURE. |
US5973061A (en) | 1988-08-31 | 1999-10-26 | Rhone-Poulenc Chimie | Aqueous silicone dispersions crosslinkable into elastometric state by dehydration |
US5039711A (en) | 1989-09-25 | 1991-08-13 | Blount David H | Production of flame-retardant polyol-oxidated silicon-acidic boron emulsion |
TW197375B (en) | 1990-11-19 | 1993-01-01 | Hayashibara Biochem Lab | |
NL9002590A (en) | 1990-11-28 | 1992-06-16 | Stamicarbon | MULTILAYER, ANTI-BALLISTIC STRUCTURE. |
JPH04257440A (en) | 1991-02-08 | 1992-09-11 | Ube Ind Ltd | Composite material |
JPH04257439A (en) | 1991-02-08 | 1992-09-11 | Ube Ind Ltd | Composite material |
FR2677543B1 (en) | 1991-06-13 | 1993-09-24 | Oreal | COSMETIC FILTERING COMPOSITION BASED ON BENZENE 1,4-DI ACID (3-METHYLIDENE-10-CAMPHOSULFONIC) AND NANOPIGMENTS OF METAL OXIDES. |
FR2677544B1 (en) | 1991-06-14 | 1993-09-24 | Oreal | COSMETIC COMPOSITION CONTAINING A MIXTURE OF NANOPIGMENTS OF METAL OXIDES AND MELANIC PIGMENTS. |
NL9101583A (en) | 1991-09-20 | 1993-04-16 | Dsm Nv | COMPOSITE ARMOR PLATE INCLUDING A COMPOSITE LAYER AND A METAL LAYER. |
NL9200625A (en) | 1992-04-03 | 1993-11-01 | Dsm Nv | NON-WOVEN POLYOLEFINE FIBER LAYER FOR USE IN A LAYERED ANTIBALLISTIC STRUCTURE. |
JP2586285B2 (en) * | 1993-01-21 | 1997-02-26 | 信越化学工業株式会社 | Shock absorbing material |
BE1007230A3 (en) | 1993-06-23 | 1995-04-25 | Dsm Nv | COMPOSITE JOB mutually parallel fibers in a matrix. |
ES2153026T5 (en) | 1994-02-18 | 2004-05-16 | Unilever N.V. | COMPOSITIONS OF PERSONAL WASHING. |
IL112649A (en) | 1994-02-22 | 1999-12-22 | Curtis Helene Ind Inc | Topically effective compositions for application to the skin or hair |
US6893704B1 (en) | 1995-06-20 | 2005-05-17 | Dsm Ip Assets B.V. | Ballistic-resistant moulded article and a process for the manufacture of the moulded article |
NL1000598C2 (en) | 1995-06-20 | 1996-12-23 | Dsm Nv | Anti-ballistic molded part and a method of manufacturing the molded part. |
NL1001415C2 (en) | 1995-10-13 | 1997-04-15 | Dsm Nv | Anti-ballistic molded part. |
US5919441A (en) | 1996-04-01 | 1999-07-06 | Colgate-Palmolive Company | Cosmetic composition containing thickening agent of siloxane polymer with hydrogen-bonding groups |
NL1003405C2 (en) | 1996-06-24 | 1998-01-07 | Dsm Nv | Anti-ballistic molded part. |
DE69703800T2 (en) | 1996-07-11 | 2001-08-02 | Dsm Nv | METHOD FOR PRODUCING A FELT THROUGH PRODUCED FELT, AND ANTIBALLISTIC MOLDED PARTS PRODUCED ACCORDING TO THIS METHOD |
US6051216A (en) | 1997-08-01 | 2000-04-18 | Colgate-Palmolive Company | Cosmetic composition containing siloxane based polyamides as thickening agents |
US5891954A (en) | 1997-09-15 | 1999-04-06 | Dow Corning Corporation | Method of making alcohol stable emulsions ABD microemulsions |
US5981680A (en) | 1998-07-13 | 1999-11-09 | Dow Corning Corporation | Method of making siloxane-based polyamides |
NL1010399C1 (en) | 1998-10-26 | 2000-04-27 | Dsm Nv | Method for manufacturing a molded part. |
NL1010413C1 (en) | 1998-10-28 | 2000-05-01 | Dsm Nv | Highly oriented polyolefin fiber. |
US6723267B2 (en) | 1998-10-28 | 2004-04-20 | Dsm N.V. | Process of making highly oriented polyolefin fiber |
US7476889B2 (en) | 1998-12-07 | 2009-01-13 | Meridian Research And Development | Radiation detectable and protective articles |
US20030037361A1 (en) | 2000-02-10 | 2003-02-27 | Dsm N.V. | Ballistic vest |
NL1014608C2 (en) | 2000-03-10 | 2001-09-11 | Dsm Nv | Ballistic vest. |
US6709504B2 (en) | 2000-05-19 | 2004-03-23 | E. I. Du Pont De Nemours And Company | Emulsion and water-repellent composition |
JP2001329174A (en) * | 2000-05-19 | 2001-11-27 | E I Du Pont De Nemours & Co | Aqueous emulsion containing hydrolyzed fluorocarbon silane and heat-resistant water-repellent coated material |
EP1219916B1 (en) | 2000-12-19 | 2006-08-09 | DSM IP Assets B.V. | Bullet-proof vest |
EP1219915A1 (en) | 2000-12-19 | 2002-07-03 | Dsm N.V. | Ballistic vest |
FR2825916B1 (en) | 2001-06-14 | 2004-07-23 | Oreal | COMPOSITION BASED ON SILICONE OIL STRUCTURED IN RIGID FORM, PARTICULARLY FOR COSMETIC USE |
FR2825915B1 (en) | 2001-06-14 | 2006-02-03 | Oreal | COMPOSITION BASED ON STRUCTURED SILICONE OIL IN RIGID FORM, IN PARTICULAR FOR COSMETIC USE |
FR2825914B1 (en) | 2001-06-14 | 2003-09-19 | Oreal | COMPOSITION BASED ON SILICONE OIL STRUCTURED IN RIGID FORM, IN PARTICULAR FOR COSMETIC USE |
ES2346743T3 (en) | 2001-09-13 | 2010-10-20 | Daniel James Plant | FLEXIBLE ENERGY FLEXIBLE MATERIAL AND MANUFACTURING PROCEDURES OF THE SAME. |
JP3927014B2 (en) * | 2001-11-08 | 2007-06-06 | 関西ペイント株式会社 | Method for producing emulsion |
US20030114787A1 (en) | 2001-12-13 | 2003-06-19 | Victor Gura | Wearable peritoneal dialysis system |
GB0130834D0 (en) * | 2001-12-22 | 2002-02-06 | Design Blue Ltd | Energy absorbing material |
EP1336672A1 (en) | 2002-02-15 | 2003-08-20 | Dsm N.V. | Method of producing high strength elongated products containing carbon nanotubes |
US20030235553A1 (en) | 2002-06-12 | 2003-12-25 | L'oreal | Cosmetic compositions containing at least one silicone-polyamide polymer, at least one oil and at least one film-forming agent and methods of using the same |
JP2005514222A (en) * | 2002-09-13 | 2005-05-19 | プラント,ダニエル,ジェームス | Flexible energy absorbing material and manufacturing method thereof |
NL1021805C2 (en) | 2002-11-01 | 2004-05-06 | Dsm Nv | Method for the manufacture of an antiballistic molding. |
WO2004054524A1 (en) | 2002-12-17 | 2004-07-01 | L'oréal | Transparent or translucent care and/or make-up cosmetic composition structured with silicone polymers |
WO2004054523A1 (en) | 2002-12-17 | 2004-07-01 | L'oreal | Care and/or make-up cosmetic composition structured with silicone polymers |
US20040180032A1 (en) | 2003-03-15 | 2004-09-16 | Manelski Jean Marie | Long wearing cosmetic composition |
US7527854B2 (en) | 2003-10-31 | 2009-05-05 | Dsm Ip Assets B.V. | Process for the manufacture of a ballistic-resistant moulded article |
KR101237679B1 (en) | 2004-01-01 | 2013-02-26 | 디에스엠 아이피 어셋츠 비.브이. | Process for making high-performance polyethylene multifilament yarn |
DK1699954T3 (en) | 2004-01-01 | 2012-02-06 | Dsm Ip Assets Bv | Process for making high performance multifilament polyethylene yarn |
KR101088559B1 (en) | 2004-01-01 | 2011-12-05 | 디에스엠 아이피 어셋츠 비.브이. | Ballistic-resistant article |
WO2005065910A1 (en) | 2004-01-07 | 2005-07-21 | Dsm Ip Assets B.V. | Process for the manufacture of curved objects |
JP4945442B2 (en) | 2004-07-02 | 2012-06-06 | ディーエスエム アイピー アセッツ ビー.ブイ. | Flexible elastic assembly |
US7780888B2 (en) | 2004-07-27 | 2010-08-24 | Dsm Ip Assets B.V. | Process for making a carbon nanotubes/ultra-high molar mass polyethylene composite fibre |
IL224437A (en) | 2004-08-16 | 2014-05-28 | Yuval Fuchs | Ballistic resistant article comprising a plurality of polyethylene monolayers and layers of ballistic fiber |
DE102004050747A1 (en) * | 2004-10-19 | 2006-04-27 | Basf Coatings Ag | Coating compositions containing adducts with alkoxysilane functionality |
US8338155B2 (en) | 2004-12-14 | 2012-12-25 | Dsm Ip Assets B.V. | Modified mevalonate kinase with reduced feedback inhibition |
DE102005022100A1 (en) | 2005-05-12 | 2006-11-16 | Wacker Chemie Ag | Process for the preparation of dispersions of crosslinked organopolysiloxanes |
KR101289485B1 (en) | 2005-06-30 | 2013-07-24 | 디에스엠 아이피 어셋츠 비.브이. | Ballistic-resistant article |
US20090211218A1 (en) | 2005-07-15 | 2009-08-27 | Dsm Ip Assets B.V. | Polycondensate fibers |
EP1746187A1 (en) | 2005-07-18 | 2007-01-24 | DSM IP Assets B.V. | Polyethylene multi-filament yarn |
JP2007051236A (en) * | 2005-08-19 | 2007-03-01 | Shin Etsu Chem Co Ltd | Silicone emulsion composition and method for treating wood |
GB0604583D0 (en) * | 2006-03-08 | 2006-04-19 | Dow Corning | Impregnated flexible sheet material |
CA2646592C (en) | 2006-03-21 | 2015-05-26 | Dsm Ip Assets B.V. | Process for the manufacture of a shaped part and shaped part obtainable with said process |
WO2007122009A1 (en) | 2006-04-26 | 2007-11-01 | Dsm Ip Assets B.V. | Multilayered material sheet and process for its preparation |
BRPI0710768A2 (en) | 2006-04-26 | 2011-06-07 | Dsm Ip Assets Bv | composite article, a process for its manufacture and use |
KR101399260B1 (en) * | 2006-10-13 | 2014-05-27 | 니토 보세키 가부시기가이샤 | Polymeric composition comprising metal alkoxide condensation product, organic silane compound and boron compound |
WO2009129175A1 (en) | 2008-04-14 | 2009-10-22 | Dow Corning Corporation | Emulsions of boron crosslinked organopolysiloxanes |
JP5474046B2 (en) * | 2008-04-14 | 2014-04-16 | ダウ・コーニング・コーポレイション | Boron-crosslinked organopolysiloxane emulsions and their use in personal care compositions |
CN102037088B (en) * | 2008-04-14 | 2014-08-06 | 陶氏康宁公司 | Emulsions of dilatant organopolysiloxanes |
-
2009
- 2009-04-13 WO PCT/US2009/040350 patent/WO2009129175A1/en active Application Filing
- 2009-04-13 JP JP2011505111A patent/JP5536754B2/en not_active Expired - Fee Related
- 2009-04-13 US US12/937,295 patent/US8664328B2/en not_active Expired - Fee Related
- 2009-04-13 CN CN200980117710.XA patent/CN102027082B/en not_active Expired - Fee Related
- 2009-04-13 EP EP09731689A patent/EP2276818B1/en not_active Not-in-force
- 2009-04-13 KR KR1020107025401A patent/KR20110003367A/en active IP Right Grant
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4863985A (en) * | 1987-10-20 | 1989-09-05 | Rhone-Poulenc Chimie | Aqueous silicone emulsions crosslinkable into elastomeric state |
EP0446157A1 (en) * | 1990-03-08 | 1991-09-11 | Rhone-Poulenc Chimie | Aqueous dispersion of silicone oils curable to a flame-resistant elastomer by elimination of water |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011236421A (en) * | 2010-05-03 | 2011-11-24 | Wacker Chemie Ag | Method for preparing silicone emulsion |
US8575266B2 (en) | 2010-05-03 | 2013-11-05 | Wacker Chemie Ag | Preparing silicone emulsions |
WO2012119916A1 (en) | 2011-03-04 | 2012-09-13 | Dow Corning Corporation | Emulsion polymerisation method |
US9156954B2 (en) | 2011-03-04 | 2015-10-13 | Dow Corning Corporation | Emulsion polymerisation method |
JP2012233039A (en) * | 2011-04-28 | 2012-11-29 | Shin-Etsu Chemical Co Ltd | Room temperature curable organopolysiloxane composition |
US9246173B2 (en) | 2012-11-16 | 2016-01-26 | Mitsubishi Chemical Corporation | Process for synthesis of hybrid siloxy derived resins and crosslinked networks therefrom |
WO2017122050A1 (en) * | 2016-01-15 | 2017-07-20 | Taghdis Porcelain Company | Anti-stain coating composition for porcelain ware |
Also Published As
Publication number | Publication date |
---|---|
EP2276818B1 (en) | 2013-03-13 |
CN102027082A (en) | 2011-04-20 |
US8664328B2 (en) | 2014-03-04 |
US20110033627A1 (en) | 2011-02-10 |
EP2276818A1 (en) | 2011-01-26 |
KR20110003367A (en) | 2011-01-11 |
CN102027082B (en) | 2013-09-18 |
JP2011516715A (en) | 2011-05-26 |
JP5536754B2 (en) | 2014-07-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2276818B1 (en) | Emulsions of boron crosslinked organopolysiloxanes | |
US20110039087A1 (en) | Emulsions Of Dilatant Organopolysiloxanes | |
JP4932470B2 (en) | Method for producing silicone resin emulsion | |
US8865830B2 (en) | Curable organosiloxane block copolymer emulsions | |
CA1277071C (en) | Method of producing aqueous latex of crosslinked polydiorganosiloxane | |
US20030143176A1 (en) | Compositions containing silicone oil-in-water emulsions, salts, alcohols and solvents | |
US20110245374A1 (en) | Multiple Emulsions Containing Silicone Resin | |
AU759798B2 (en) | Aqueous silicone dispersion, crosslinkable into transparent elastomer | |
JP3251015B2 (en) | Silicone oil-based aqueous dispersion that can be crosslinked when water is removed | |
DK175833B1 (en) | Aqueous silicone-based dispersions which can be cross-linked to an elastomer by elimination of water | |
WO2010075244A1 (en) | Emulsions of high viscosity silicone polyethers | |
US5851594A (en) | Aqueous dispersions based on viscous silicone oils capable of cross-linking on removal of water | |
WO2013117490A1 (en) | Process of forming silicone in powder form | |
JP2009126888A (en) | Large-particle-diameter organopolysiloxane latex composition | |
KR20140135729A (en) | Substrate in powder or fibre form | |
WO2017116639A1 (en) | Aqueous silicone dispersion |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200980117710.X Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 09731689 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 12937295 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011505111 Country of ref document: JP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2009731689 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 20107025401 Country of ref document: KR Kind code of ref document: A |