WO2013117490A1 - Procédé de formation de silicone sous forme de poudre - Google Patents

Procédé de formation de silicone sous forme de poudre Download PDF

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Publication number
WO2013117490A1
WO2013117490A1 PCT/EP2013/051971 EP2013051971W WO2013117490A1 WO 2013117490 A1 WO2013117490 A1 WO 2013117490A1 EP 2013051971 W EP2013051971 W EP 2013051971W WO 2013117490 A1 WO2013117490 A1 WO 2013117490A1
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WIPO (PCT)
Prior art keywords
silicone
block copolymer
poly
powder form
silicone compound
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PCT/EP2013/051971
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English (en)
Inventor
Pierre Chevalier
Francois De Buyl
Christophe Paulo
Vincent Rerat
Takeshi Yoshizawa
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Dow Corning Corporation
Dow Corning Toray Co Limited
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Application filed by Dow Corning Corporation, Dow Corning Toray Co Limited filed Critical Dow Corning Corporation
Publication of WO2013117490A1 publication Critical patent/WO2013117490A1/fr

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    • 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
    • C08J3/12—Powdering or granulating
    • 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
    • C08J3/005—Processes for mixing polymers
    • 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

Definitions

  • WO2012002571 , WO2010104186 and US201 10245374 describe a silicone emulsion composition comprising water, a silicone compound and a polyoxyethylene- polyoxypropylene copolymer-type non-ionic emulsifier.
  • the invention provides a silicone composition in powder form obtained by the above defined process.
  • the invention provides a process of forming a polymeric matrix containing silicone, characterised in that the silicone composition in powder form is incorporated into the polymeric matrix.
  • the invention further provides a process of improving mechanical, optical, or flame retardancy of a matrix by incorporating into the matrix the silicone composition in powder form.
  • the invention also provides the use of an emulsion comprising a silicone compound, water and a ethylene oxide/propylene oxide block copolymer to form a composition in powder form.
  • the silicone compound is functionalized.
  • the silicone compound contains hydroxyl, unsaturations, amino, glycidoxy or alkoxy functions. These functions can be pendant along the silicone chain or terminal at one or both ends of the chain. Alkoxies can be directly linked to the silicone atom.
  • the silicone compound is preferably a silicone gum or a silicone resin.
  • the silicone compound has preferably a kinetic viscosity greater than one million cSt at 25°C.
  • the silicone compound is preferably a polydimethylsiloxane having a viscosity of at least 500 thousand cP at 0.01 Hz at 25°C.
  • the silicone compound can be hydroxyl or alkoxy terminated polydimethylsiloxane.
  • the ethylene oxide/propylene oxide block copolymer is a
  • n may vary from 20 to 100.
  • the ethylene oxide/propylene oxide block copolymer is a tetrafunctional poly(oxyethylene)-poly(oxypropylene) block copolymer having the average formula;
  • • r may vary from 15 to 75.
  • the silicone emulsion is preferably prepared by:
  • step II admixing a sufficient amount of water to the dispersion from step I) to form an
  • Component A) can be a silicone gum.
  • Silicone gum as used herein refers to predominately linear organopolysiloxanes having sufficiently high molecular weight (Mw) to provide kinetic viscosities greater than 500 thousand cSt at 25°C. While any
  • organopolysiloxane considered as a gum may be selected as component (A), typically the silicone gum is a diorganopolysiloxane gum with a molecular weight sufficient to impart a William's plasticity number of at least about 30 as determined by the American Society for Testing and Materials (ASTM) test method 926.
  • the silicon-bonded organic groups of the diorganopolysiloxane may independently be selected from hydrocarbon or halogenated hydrocarbon groups.
  • diorganopolysiloxane can be a homopolymer, a copolymer or a terpolymer containing such organic groups. Examples include
  • homopolymers comprising dimethylsiloxy units, homopolymers comprising 3,3,3- trifluoropropylmethylsiloxy units, copolymers comprising dimethylsiloxy units and phenylmethylsiloxy units, copolymers comprising dimethylsiloxy units and 3,3,3- trifluoropropylmethylsiloxy units, copolymers of dimethylsiloxy units and diphenylsiloxy units and interpolymers of dimethylsiloxy units, diphenylsiloxy units and phenylmethylsiloxy units, among others.
  • the silicon-bonded organic groups of the diorganopolysiloxane may also be selected from alkenyl groups having 1 to 20 carbon atoms, such as vinyl, allyl, butyl, pentyl, hexenyl, or dodecenyl. Examples include; dimethylvinylsiloxy-endblocked
  • dimethylpolysiloxanes dimethylvinylsiloxy-endblocked dimethylsiloxane-methylvinylsiloxane copolymers; dimethylvinylsiloxy-endblocked methylphenylpolysiloxanes; dimethylvinylsiloxy- endblocked methylphenylsiloxane-dimethylsiloxane-methylvinylsiloxane copolymers.
  • the silicon-bonded organic groups of the diorganopolysiloxane may also be selected from various organofunctional groups such as amino, amido, mercapto, or epoxy functional groups.
  • the molecular structure is also not critical and is exemplified by straight-chain and partially branched straight-chain structures, the linear systems being the most typical.
  • the silicone gum is a hydroxy terminated polydimethylsiloxane gum having a viscosity of at least 20 million cP at 25°C at 0.01 Hz.
  • the silicone gum may be used in combination with other organopolysiloxanes.
  • Organopolysiloxanes also named silicones
  • silicones are polymers containing siloxane units independently selected from (R 3 Si0 1/2 ), (R2S1O2/2), (RSi0 3/2 ), or (Si0 4/2 ) siloxy units, where R may be any monovalent organic group.
  • R is a methyl group in the (R 3 Si0 1/2 ), (R2S1O2/2), (RS1O3/2), or (Si0 4/2 ) siloxy units of an organopolysiloxane
  • the 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 can vary. For example
  • organopolysiloxanes can be volatile or low viscosity fluids, high viscosity fluids/gums, elastomers or rubbers, and resins depending on the number and type of siloxy units in the average polymeric formula.
  • R may be any monovalent organic group, alternatively R is a hydrocarbon group containing 1 to 30 carbons, alternatively R is an alkyl group containing 1 to 30 carbon atoms, or alternatively R is methyl.
  • the amount of the additional organopolysiloxane combined with the silicone gum may vary. Typically, 0.1 parts to 1000 parts by weight, alternatively 0.1 to 100 parts by weight of the additional organopolysiloxane is added for every 100 parts of the silicone gum. [0025] In one embodiment, the silicone gum is combined with an aminofunctional
  • the aminofunctional organopolysiloxanes may be characterized by having at least one of the R groups in the formula R n SiO( 4-n )/2 be an amino functional group.
  • the amino functional group may be present on any siloxy unit having an R substituent, that is, they may be present on any (R 3 Si0 1/2 ), (R2S1O2/2), or (RSi0 3/2 ) unit, and is designated in the formulas herein as R N .
  • the amino-functional organic group R N is illustrated by groups having the formula; -R 3 NHR 4 , -R 3 NR 2 4 or -R 3 NHR 3 NHR 4 , wherein each R 3 is independently a divalent hydrocarbon group having at least 2 carbon atoms, and R 4 IS hydrogen or an alkyl group. Each R 3 is typically an alkylene group having from 2 to 20 carbon atoms. R 3 is illustrated by groups such as; -CH2CH2-, -CH2CH2CH2-, -
  • R 4 are as illustrated above for R. When R 4 is an alkyl group, it is typically methyl.
  • the amino functional group is - CH 2 CH(CH3)CH2NHCH2CH 2 NH2.
  • aminofunctional organopolysiloxane used in combination with the silicone gum may be selected from those having the average formula
  • ⁇ a is 1-1000, alternatively 1 to 500, alternatively 1 to 200,
  • R is independently a monovalent organic group
  • R is a hydrocarbon containing 1- 30 carbon atoms
  • R is a monovalent alkyl group containing 1 - 12 carbons, or • alternatively R is a methyl group;
  • the aminofunctional organopolysiloxane used I combination with the silicone gum may also be a combination of any of the aforementioned aminofunctional organopolysiloxanes.
  • Component A) can be a silicone resin.
  • silicone resin refers to any organopolysiloxane containing at least one (RS1O3/2), or (S1O4/2) siloxy unit.
  • Organopolysiloxanes are polymers containing siloxy units independently selected from (R3S1O1/2 ), (R2S1O2/2), (RS1O3/2), or (S1O4/2) siloxy units, where R may be any organic group. 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 vary depending on the number and type of siloxy units in the organopolysiloxane.
  • Linear organopolysiloxanes typically contain mostly D or (R2S1O2/2) siloxy units, which results in polydiorganosiloxanes that are fluids of varying viscosity, depending on the "degree of polymerization” or DP as indicated by the number of D units in the polydiorganosiloxane.
  • Linear organopolysiloxanes typically have glass transition temperatures (T g ) that are lower than 25°C.
  • organopolysiloxanes result when a majority of the siloxy units are selected from T or Q siloxy units.
  • T siloxy units are predominately used to prepare an organopolysiloxane
  • the resulting organosiloxane is often referred to as a "silsesquioxane resin”.
  • M and Q siloxy units are predominately used to prepare an organopolysiloxane
  • the resulting organosiloxane is often referred to as a "MQ resin”.
  • the formula for an organopolysiloxane may be designated by the average of the siloxy units in the
  • organopolysiloxane as follows; R n SiO(4- n )/2, where the R is independently any organic group, alternatively a hydrocarbon, or alternatively an alkyl group, or alternatively methyl.
  • organopolysiloxane resin refers to those
  • organopolysiloxanes having a value of n less than 1.8 in the average formula R n SiO(4 -n )/2, indicating a resin.
  • the silicone resin useful as component A) may independently comprise (i)
  • the silicone resin may also contain silanol groups ( ⁇ SiOH).
  • the amount of silanol groups present on the silicone resin may vary from 0.1 to 35 mole percent silanol groups [ ⁇ SiOH], alternatively from 2 to 30 mole percent silanol groups [ ⁇ SiOH], alternatively from 5 to 20 mole percent silanol groups [ ⁇ SiOH].
  • the silanol groups may be present on any siloxy units within the silicone resin.
  • the molecular weight of the silicone resin is not limiting.
  • the silicone resin may have an average molecular weight (M w ) of at least 1 ,000 g/mole, alternatively an average molecular weight of at least 2,000 g/mole alternatively an average molecular weight of at least 5,000 g/mole.
  • M w average molecular weight
  • the average molecular weight may be readily determined using Gel Permeation Chromatography (GPC) techniques.
  • the silicone resin is a MQ silicone.
  • the silicone resin may be a MQ resin comprising at least 80 mole% of siloxy units selected from (R 1 3 Si0 1/ 2) a and (Si0 4/2 ) d units (that is a + d ⁇ 0.8), where R 1 is an alkyl group having from 1 to 8 carbon atoms, an aryl group, a carbinol group, or an amino group, with the proviso that at least 95 mole % of the R 1 groups are alkyl groups, a and d each have a value greater than zero, and the ratio of a/d is 0.5 to 1 .5.
  • the R 1 units of the MQ resin are independently an alkyl group having from 1 to 8 carbon atoms, an aryl group, a carbinol group, or an amino group.
  • the alkyl groups are illustrated by methyl, ethyl, propyl, butyl, pentyl, hexyl, and octyl.
  • the aryl groups are illustrated by phenyl, naphthyl, benzyl, tolyl, xylyl, xenyl, methylphenyl, 2-phenylethyl, 2- phenyl-2-methylethyl, chlorophenyl, bromophenyl and fluorophenyl with the aryl group typically being phenyl.
  • MQ resins suitable for use as component (A), and methods for their preparation are known in the art.
  • U.S. Patent No. 2,814,601 to Currie et al., November 26, 1957, which is hereby incorporated by reference discloses that MQ resins can be prepared by converting a water-soluble silicate into a silicic acid monomer or silicic acid oligomer using an acid. When adequate polymerization has been achieved, the resin is end-capped with trimethylchlorosilane to yield the MQ resin.
  • Another method for preparing MQ resins is disclosed in U.S. Patent No. 2,857,356 to Goodwin, October 21 , 1958, which is hereby incorporated by reference. Goodwin discloses a method for the preparation of an MQ resin by the cohydrolysis of a mixture of an alkyl silicate and a hydrolyzable trialkylsilane
  • the MQ resins suitable as component A) in the present invention may contain D and T units.
  • the MQ resins may also contain hydroxy groups.
  • the MQ resins have a total weight % hydroxy content of 2-10 weight %, alternatively 2-5 weight %.
  • the MQ resins can also be further "capped" wherein residual hydroxy groups are reacted with additional M groups.
  • the silicone resin is a silsesquioxane resin.
  • the silsesquioxane resin may be a silsesquioxane resin comprising at least 80 mole % of R 3 Si0 3/2 units, where R 3 in the above trisiloxy unit formula is independently a Ci to C 20 hydrocarbyl, a carbinol group, or an amino group.
  • hydrocarbyl also includes halogen substituted hydrocarbyls.
  • R 3 may be an aryl group, such as phenyl, naphthyl, anthryl group.
  • R 3 may be an alkyl group, such as methyl, ethyl, propyl, or butyl.
  • R 3 may be any combination of the aforementioned alkyl or aryl groups.
  • R 3 is phenyl, propyl, or methyl.
  • at least 40 mole % of the R 3 groups are propyl, referred herein as T-propyl resins, since the majority of the siloxane units are T units of the general formula R 3 Si0 3/2 where at least 40 mole %, alternatively 50 mole %, or alternatively 90 mole % of the R 3 groups are propyl.
  • R 3 groups are phenyl, referred herein as T-phenyl resins, since the majority of the siloxane units are T units of the general formula R 3 Si0 3/2 where at least 40 mole %, alternatively 50 mole %, or alternatively 90 mole % of the R 3 groups are phenyl.
  • R 3 may be a mixture of propyl and phenyl. When R 3 is a mixture of propyl and phenyl, the amounts of each in the resin may vary, but typically the R 3 groups in the silsesquioxane resin may contain 60 - 80 mole percent phenyl and 20- 40 mole percent propyl.
  • Silsesquioxane resins are known in the art and are typically prepared by hydrolyzing an organosilane having three hydrolyzable groups on the silicon atom, such as a halogen or alkoxy group. Thus, silsesquioxane resins can be obtained by hydrolyzing
  • alkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane,
  • methyltriisopropoxysilane dimethyldimethoxysilane, and phenyltrimethoxysilane.
  • Propyltrichlorosilane can also be hydrolyzed alone, or in the presence of alcohol.
  • co-hydrolyzation can be carried out by adding methyltrichlorosilane,
  • Alcohols suitable for these purposes include methanol, ethanol, n- propyl alcohol, isopropyl alcohol, butanol, methoxy ethanol, ethoxy ethanol, or similar alcohols.
  • hydrocarbon-type solvents which can also be concurrently used include toluene, xylene, or similar aromatic hydrocarbons; hexane, heptane, isooctane, or similar linear or partially branched saturated hydrocarbons; and cyclohexane, or similar aliphatic hydrocarbons.
  • the silsesquioxane resins suitable in the present disclosure may contain M, D, and Q units, but typically at least 80 mole %, alternatively 90 mole % of the total siloxane units are T units.
  • the silsesquioxane resins may also contain hydroxy and/or alkoxy groups.
  • the silsesquioxane resins have a total weight % hydroxy content of 2-10 weight % and a total weight % alkoxy content of up to 20 weight %, alternatively 6-8 weight% hydroxy content and up to 10 weight % alkoxy content.
  • silicone resins suitable as component A2) include; silicone resins sold under the trademarks DOW CORNING® 840
  • silicone resin also encompasses silicone-organic resins.
  • silicone-organic resins includes silicone-organic copolymers, where the silicone portion contains at least one (RSi0 3/2 ), or (Si0 4/2 ) siloxy unit.
  • the silicone portion of the silicone- organic resin may be any of the silisesquioxane or MQ resins as described above.
  • the organic portion may be any organic polymer, such as those derived by free radical polymerization of one or more ethylenically unsaturated organic monomers.
  • ethylenically unsaturated and/or vinyl containing organic monomers can be used to prepare the organic portion including; acrylates, methacrylates, substituted acrylates, substituted methacrylates, vinyl halides, fluorinated acrylates, and fluorinated
  • compositions include acrylate esters and methacrylate esters such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, decyl acrylate, lauryl acrylate, isodecyl methacrylate, lauryl methacrylate, and butyl methacrylate; substituted acrylates and methacrylates such as hydroxyethyl acrylate, perfluorooctyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, and hydroxyethyl methacrylate; vinyl halides such as vinyl chloride, vinylidene chloride, and chloroprene; vinyl esters such as vinyl acetate and vinyl butyrate; vinyl pyrrolidone; conjugated dienes such as butadiene and isoprene; vinyl aromatic compounds such as styrene and divin
  • the silicone resin selected as component A) may also be a combination(s) of any of the aforementioned silicone resins.
  • Component B) is an ethylene oxide/propylene oxide block copolymer.
  • Component B) may be selected from those ethylene oxide/propylene oxide block copolymers known to have surfactant behaviour.
  • the ethylene oxide/propylene oxide block copolymers useful as component B) are surfactants having an HLB of at least 12, alternatively, at least 15, or alternatively at least 18.
  • the molecular weight of the ethylene oxide/propylene oxide block copolymer may vary, but typically is at least 4,000 g/mol, alternatively at least 8,000 g/mol, or at least 12,000 g/mol.
  • ethylene oxide (EO) and propylene oxide (PO) present in the ethylene oxide/propylene oxide block copolymer may vary, but typically, the amount of EO may vary from 50 percent to 80 percent, or alternatively from 60 percent to about 85 percent, or alternatively from 70 percent to 90 percent.
  • component B) is a poly(oxyethylene)-poly(oxypropylene)- poly(oxyethylene) tri-block copolymer.
  • Poly(oxyethylene)-poly(oxypropylene)- poly(oxyethylene) tri-block copolymers are also commonly known as Poloxamers. They are nonionic triblock copolymers composed of a central hydrophobic chain of
  • polyoxypropylene (poly(propylene oxide)) flanked by two hydrophilic chains of
  • polyoxyethylene poly(ethylene oxide)
  • Poly(oxyethylene)-poly(oxypropylene)-poly(oxyethylene) tri-block copolymers are commercially available from BASF (Florham Park, NJ) and are sold under the tradename
  • PLURONIC® Representative, non-limiting examples suitable as component (B) include; PLURONIC® F127, PLURONIC® F98, PLURONIC® F88, PLURONIC® F87, PLURONIC®
  • poly(oxyethylene)-poly(oxypropylene)- poly(oxyethylene) tri-block copolymer has the formula
  • n may vary from 20 to 100, or alternatively from 25 to 100.
  • component B) is a tetrafunctional poly(oxyethylene)- poly(oxypropylene) block copolymer derived from the sequential addition of propylene oxide and ethylene oxide to ethylene diamine. These tetra-functional block copolymers are also commonly known as Poloxamines.
  • the tetrafunctional poly(oxyethylene)- poly(oxypropylene) block copolymer may have the average formula; [HO(CH 2 CH 2 0) q (CH 2 CH(CH 3 )0) r ] 2 NCH 2 CH 2 N[(CH 2 CH(CH 3 )0) r (CH 2 CH 2 0) q H] 2
  • Tetrafunctional poly(oxyethylene)-poly(oxypropylene) block copolymers are commercially available from BASF (Florham Park, NJ) and are sold under the tradename TETRONIC®.
  • Representative, non-limiting examples suitable as component (B) include; TETRONIC® 908, TETRONIC® 1 107, TETRONIC® 1307, TETRONIC® 1508 and TETRONIC® 1504.
  • the amount of components A) and B) combined in step I) of forming the emulsion are preferably as follows;
  • the dispersion formed in step I) consists essentially of components A) and B) as described above.
  • no additional surfactants or emulsifiers are added in step I).
  • no solvents are added for the purpose of enhancing formation of an emulsion.
  • the phrase "essentially free of "solvents” means that solvents are not added to components A) and B) in order to create a mixture of suitable viscosity that can be processed on typical emulsification devices.
  • solvents as used herein is meant to include any water immiscible low molecular weight organic or silicone material added to the non-aqueous phase of an emulsion for the purpose of enhancing the formation of the emulsion, and is subsequently removed after the formation of the emulsion, such as evaporation during a drying or film formation step.
  • the phrase “essentially free of solvent” is not meant to exclude the presence of solvent in minor quantities in process or emulsions of the present invention.
  • the components A) and B) may contain minor amounts of solvent as supplied commercially. Small amounts of solvent may also be present from residual cleaning operations in an industrial process.
  • the amount of solvent present in the premix should be less than 2% by weight of the mixture, and most preferably the amount of solvent should be less than 1 % by weight of the mixture.
  • the dispersion of step (I) may be prepared by combining components A) and B) and further mixing the components to form a dispersion.
  • the resulting dispersion may be considered as a homogenous mixture of the two components.
  • the present inventors have unexpectedly found that certain ethylene oxide/propylene oxide block copolymers readily disperse with silicone gum compositions, and hence enhance the subsequent formation of emulsion compositions thereof.
  • the present inventors believe other nonionic and/or anionic surfactants, typically known for preparing silicone emulsions, do not form such dispersions or homogeneous mixtures upon mixing with a silicone gum (at least not in the absence of a solvent or other substance to act as a dispersing medium).
  • Mixing can be accomplished by any method known in the art to effect 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 mixing equipment such as those sold under the tradename Speedmixer®
  • 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.
  • components A) and B) may occur in a single step or multiple step process.
  • components A) and B) may be combined in total, and subsequently mixed via any of the techniques described above.
  • a portion(s) of components A) and B) may first be combined, mixed, and followed by combining additional quantities of either or both components and further mixing.
  • One skilled in the art would be able to select optimal portions of components A) and B) for combining and mixing, depending on the selection of the quantity used and the specific mixing techniques utilized to perform step I) to provide a dispersion of components A) and B).
  • Step II of the process involves admixing sufficient 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.
  • the emulsion formed is a water continuous emulsion.
  • the water continuous emulsion has dispersed particles of the silicone gum from step I, and having an average particle size less than 150 ⁇ .
  • the amount of water added in step II) 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 amount of silicone gum present and the specific ethylene oxide/propylene oxide block copolymer used, 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.
  • each incremental portion comprises less than 30 weight % of the mixture from step I and each incremental portion of water is added successively to the previous after the dispersion of the previous incremental portion of water, wherein sufficient incremental portions of water are added to form an emulsion.
  • a portion or all the water used in step I) may be substituted with various hydrophilic solvents that are soluble with water such as low molecular weight alcohols, ethers, esters or glycols.
  • low molecular weight alcohols such as methanol, ethanol, propanol, isopropanol and the like
  • low molecular weight ethers such as di(propyleneglycol) mono methyl ether
  • di(ethyleneglycol) butyl ether di(ethyleneglycol) methyl ether, di(propyleneglycol) butyl ether, di(propyleneglycol) methyl ether acetate, di(propyleneglycol) propyl ether, ethylene glycol phenyl ether, propylene glycol butyl ether, 1 -methoxy-2-propanol, 1-methoxy-2- propyl acetate, propylene glycol propyl ether, 1 -phenoxy-2-propanol, tri(propyleneglycol) methyl ether and tri(propyleneglycol) butyl ether, and other like glycols.
  • 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). Typically, the same equipment is used to effect mixing in steps I) and II).
  • 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 silicone gum (oil) 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.
  • Dv 50 is the particle size measured in volume corresponding to 50% of the cumulative particle population.
  • Dv 50 10 ⁇
  • 50% of the particle have an average volume particle size below 10 ⁇ and 50% of the particle have a volume average particle size above 10 ⁇ .
  • Dv 90 is the particle size measured in volume corresponding to 90% of the cumulative particle population.
  • the average volume particle size of the dispersed siloxane particles in the oil/water emulsions is between 0.1 ⁇ and 150 ⁇ ; or between 0.1 ⁇ and 30 ⁇ ; or between 0.3 ⁇ and 5.0 ⁇ .
  • Silicone gum content of the present emulsion may vary from 0.5 weight percent to 95 weight percent, alternatively from 20 weight percent to 80 weight percent, or alternatively from 40 weight percent to 60 weight percent.
  • Additional additives and components may also be included in the emulsion compositions, such as preservatives, freeze/thaw additives, and various thickeners.
  • the invention extends to a process of forming a polymeric matrix containing silicone, characterised in that the silicone composition in powder form is incorporated into the polymeric matrix.
  • the matrix pertains to thermoplastics, rubbers, any blends of the laters or thermosets.
  • the matrix is preferably organic i.e. based on carbon chemistry.
  • the matrix is filled with a filler or reinforced.
  • the invention extends to a process of improving, processability compatibility, appearance, mechanical, optical, or flame retardancy of a neat or reinforced matrix or mixture of different matrices as described above by incorporating into the matrix the silicone composition in powder form.
  • the invention extends to the use of an emulsion comprising a silicone compound, water and an ethylene oxide/propylene oxide block copolymer to form a composition in powder form as defined above.
  • polydimethylsiloxane was weighed into a Max 40 cup along with 1.5g of Pluronic ® F-88 nonionic surfactant and 10g of 3mm glass beads.
  • the cup was closed and placed inside a DAC-150 SpeedMixer ® and the cup was spun at maximum speed (3450 RPM) for 2 minutes.
  • the cup was opened and the mixture, now very warm, had become a creamy white paste that easily flowed when mixed with a spatula.
  • the walls of the cup were scraped with a spatula and the cup was spun again at maximum speed for 1 minute.
  • 0.88g of water was added to the cup and the cup was spun for 30 seconds at maximum speed.
  • An additional 1.2g of water was added and the cup was again spun for 30 seconds at maximum speed.
  • the cup was placed back in the mixer and spun for an additional 1 minute at maximum speed.
  • the mixture was diluted with 28g of deionized (Dl) water in five increments by adding aliquots of water and spinning the cup for 25 seconds after addition of each aliquot.
  • the increments of water were as follows: 2g, 3g, 5g, 8g and 10g.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un procédé de formation d'une composition de silicone sous forme de poudre, caractérisé en ce qu'une émulsion contenant le composé de silicone, de l'eau et un copolymère à blocs d'oxyde d'éthylène/oxyde de propylène est séchée pour former une composition de silicone sous forme de poudre. De préférence, le composé de silicone est fonctionnalisé.
PCT/EP2013/051971 2012-02-08 2013-01-31 Procédé de formation de silicone sous forme de poudre WO2013117490A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB201202106A GB201202106D0 (en) 2012-02-08 2012-02-08 Process of forming silicone in powder form
GB1202106.9 2012-02-08

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WO2013117490A1 true WO2013117490A1 (fr) 2013-08-15

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016014128A1 (fr) 2014-07-23 2016-01-28 Dow Corning Corporation Composition d'élastomère de silicone
WO2016164289A1 (fr) 2015-04-08 2016-10-13 Dow Corning Corporation Composition pituiteuse de fluide à base de silicone
WO2017020303A1 (fr) * 2015-08-06 2017-02-09 Dow Corning (China) Holding Co., Ltd. Émulsions de silicone pour applications de soin capillaire
US10441527B2 (en) 2015-04-08 2019-10-15 Dow Silicones Corporation Fluid compositions and personal care
US10940099B2 (en) 2015-04-08 2021-03-09 Dow Silicones Corporation Pituitous silicone emulsions

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US2857356A (en) 1954-07-08 1958-10-21 Gen Electric Organopolysiloxane compositions having pressure-sensitive adhesive properties
EP0242219A2 (fr) * 1986-04-17 1987-10-21 Toray Silicone Company, Ltd. Procédé pour préparer des poudres de caoutchouc silicone
US4761454A (en) * 1986-05-02 1988-08-02 Shin-Etsu Chemical Co., Ltd. Method for the preparation of fine spherical particles of silicone elastomer
EP0444633A2 (fr) * 1990-02-28 1991-09-04 Dow Corning Toray Silicone Company, Limited Poudre à base d'un élastomère de polyorganosiloxane et son procédé de préparation
EP0548969A1 (fr) * 1991-12-26 1993-06-30 Dow Corning Toray Silicone Company, Limited Procédé de préparation d'un mélange pulverulent constitué des microparticules réticulées de silicon et des microparticules inorganiques
US5324806A (en) * 1993-03-12 1994-06-28 General Electric Company Free flowing silicone resin powder and method for making
US5741876A (en) * 1995-07-03 1998-04-21 Dow Corning Corporation Method of preparing powdered silicone resins
US5786413A (en) * 1995-01-24 1998-07-28 Wacker-Chemie Gmbh Organopolysiloxane resin powder, process for its preparation and its use in organopolysiloxane compositions
EP1074575A2 (fr) * 1999-08-03 2001-02-07 Dow Corning Toray Silicone Co., Ltd. Particules organiques sphériques réticulées, suspensions et procédé de préparation de particules organiques sphériques réticulées et de suspensions
WO2010065712A1 (fr) * 2008-12-05 2010-06-10 Dow Corning Corporation Émulsions multiples contenant une résine de silicone
WO2010104186A2 (fr) 2009-03-10 2010-09-16 Dow Corning Toray Co., Ltd. Composition d'émulsion de silicone de type aqueux
WO2012002571A1 (fr) 2010-07-02 2012-01-05 東レ・ダウコーニング株式会社 Composition d'une émulsion de silicone d'huile dans l'eau

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2814601A (en) 1954-04-29 1957-11-26 Dow Corning Organopolysiloxane adhesive and pressure-sensitive adhesive tape containing same
US2857356A (en) 1954-07-08 1958-10-21 Gen Electric Organopolysiloxane compositions having pressure-sensitive adhesive properties
EP0242219A2 (fr) * 1986-04-17 1987-10-21 Toray Silicone Company, Ltd. Procédé pour préparer des poudres de caoutchouc silicone
US4761454A (en) * 1986-05-02 1988-08-02 Shin-Etsu Chemical Co., Ltd. Method for the preparation of fine spherical particles of silicone elastomer
EP0444633A2 (fr) * 1990-02-28 1991-09-04 Dow Corning Toray Silicone Company, Limited Poudre à base d'un élastomère de polyorganosiloxane et son procédé de préparation
EP0548969A1 (fr) * 1991-12-26 1993-06-30 Dow Corning Toray Silicone Company, Limited Procédé de préparation d'un mélange pulverulent constitué des microparticules réticulées de silicon et des microparticules inorganiques
US5324806A (en) * 1993-03-12 1994-06-28 General Electric Company Free flowing silicone resin powder and method for making
US5786413A (en) * 1995-01-24 1998-07-28 Wacker-Chemie Gmbh Organopolysiloxane resin powder, process for its preparation and its use in organopolysiloxane compositions
US5741876A (en) * 1995-07-03 1998-04-21 Dow Corning Corporation Method of preparing powdered silicone resins
EP1074575A2 (fr) * 1999-08-03 2001-02-07 Dow Corning Toray Silicone Co., Ltd. Particules organiques sphériques réticulées, suspensions et procédé de préparation de particules organiques sphériques réticulées et de suspensions
WO2010065712A1 (fr) * 2008-12-05 2010-06-10 Dow Corning Corporation Émulsions multiples contenant une résine de silicone
US20110245374A1 (en) 2008-12-05 2011-10-06 Dow Corning Corporation Multiple Emulsions Containing Silicone Resin
WO2010104186A2 (fr) 2009-03-10 2010-09-16 Dow Corning Toray Co., Ltd. Composition d'émulsion de silicone de type aqueux
WO2012002571A1 (fr) 2010-07-02 2012-01-05 東レ・ダウコーニング株式会社 Composition d'une émulsion de silicone d'huile dans l'eau

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016014128A1 (fr) 2014-07-23 2016-01-28 Dow Corning Corporation Composition d'élastomère de silicone
WO2016014127A1 (fr) 2014-07-23 2016-01-28 Dow Corning Corporation Fluide pituiteux à base de silicone
US10172781B2 (en) 2014-07-23 2019-01-08 Dow Silicones Corporation Pituitous silicone fluid
US10500151B2 (en) 2014-07-23 2019-12-10 Dow Silicones Corporation Silicone elastomer composition
WO2016164289A1 (fr) 2015-04-08 2016-10-13 Dow Corning Corporation Composition pituiteuse de fluide à base de silicone
US10441527B2 (en) 2015-04-08 2019-10-15 Dow Silicones Corporation Fluid compositions and personal care
US10940099B2 (en) 2015-04-08 2021-03-09 Dow Silicones Corporation Pituitous silicone emulsions
WO2017020303A1 (fr) * 2015-08-06 2017-02-09 Dow Corning (China) Holding Co., Ltd. Émulsions de silicone pour applications de soin capillaire

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