WO2004063265A1 - Procédé de préparation d'une suspension de silice dans une matiere silicone eventuellement réticulable - Google Patents
Procédé de préparation d'une suspension de silice dans une matiere silicone eventuellement réticulable Download PDFInfo
- Publication number
- WO2004063265A1 WO2004063265A1 PCT/FR2003/003815 FR0303815W WO2004063265A1 WO 2004063265 A1 WO2004063265 A1 WO 2004063265A1 FR 0303815 W FR0303815 W FR 0303815W WO 2004063265 A1 WO2004063265 A1 WO 2004063265A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- pos
- silica
- functions
- optionally
- suspension
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- 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
- C08J3/20—Compounding polymers with additives, e.g. colouring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions 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; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side 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
Definitions
- the field of the invention is that of charged silicones and in particular silicone elastomers crosslinkable by polyaddition or polycondensation and silicone anti-foam compositions.
- the present invention relates to the preparation of an intermediate product useful for obtaining these elastomers and these anti-foam silicone compositions.
- This intermediate product consists of a fine charge suspension (as defined below): m in a polyorganosiloxane (POS) not carrying reactive functions, "or in a polyorganosiloxane carrying Si-alkenyl functions - preferably Si-Vi - capable of reacting by polyaddition with the Si-H crosslinking functions of another POS, " or in a polyorganosiloxane carrying Si-OR ° functions (preferably
- the fillers considered are reinforcing fillers, to be distinguished from non-reinforcing fillers.
- the most commonly used reinforcing fillers are preferably fumed silicas having a BET surface area> 50 m 2 / g. They owe their reinforcing effect on the one hand, to their morphology and on the other hand, to the hydrogen bonds which form between the silanol groups on the surface of the silicas and the polyorganosiloxane chains. These interactions between the filler and the polymer increase the viscosity and modify the behavior of the polymer in the vicinity of the solid surface of the fillers. Furthermore, the connections between polymer and filler improve the mechanical properties but can also cause a prejudicial premature hardening ("structuring") of the precursor compositions of the elastomers.
- the non-reinforcing fillers have an extremely weak interaction with the silicone polymer. These include, for example, chalk, quartz powder, diatomaceous earth, mica, kaolin, aluminas or iron oxides. Their effect is often to increase the viscosity of the unvulcanized precursors of the elastomers, as well as the Shore hardness and the elastic modulus of the latter.
- the silicone elastomers can also contain, inter alia, catalysts, inhibitors, crosslinkers, pigments, non-stick agents, plasticizers and adhesion promoters.
- elastomers which can be crosslinked by polyaddition or polycondensation, are shaped before crosslinking by casting, extrusion, calendering, coating, with a brush or with a gun, or by compression molding, injection or transfer.
- Cold-crosslinkable silicone compositions in elastomers by polyaddition at room temperature or at higher temperatures ( ⁇ generally at 200 ° C.), are conventionally packaged in the form of two-component systems, that is to say comprising two parts packaged separately. and to be mixed at the time of use.
- one of the components comprises the catalyst for the polyaddition reaction.
- This catalyst is preferably platinum in nature. It may, for example, be a platinum complex such as that prepared from chloroplatinic acid and divinyl-1,3-tetramethyl-l-, l-, 3-, 3-disiloxane, according to the patent US-B-3,814,730 (Karstedt catalyst). Other platinum complexes are described in US Pat. Nos. 3,159,601, 3,159,662 and 3,220,972.
- This component comprising the catalyst generally also comprises a type A POS with Fa: Si-alkenyl, preferably Si-vinyl, crosslinking functions.
- the other component, without catalyst, comprises at least one type B POS with Fb: Si-H crosslinking functions.
- POS type A and POS type B comprise at least two groups Si-Vi and Si-H respectively per molecule, preferably in ⁇ , ⁇ for POS type A; at least one of the two must comprise at least three crosslinking functions per molecule.
- These two-component systems can also include a platinum inhibitor allowing the components to crosslink only when mixed together, possibly having been heated.
- a platinum inhibitor allowing the components to crosslink only when mixed together, possibly having been heated.
- inhibitors include:
- polyorganosiloxanes advantageously cyclic, substituted with at least one alkenyl, tetramethylvinyltetrasiloxane being particularly preferred,
- compositions can also be presented in the form of single-component systems which crosslink only after being heated.
- the silicone compositions which can be crosslinked or curable into elastomers by polycondensation at room temperature or at higher temperatures are conventionally packaged in the form of systems. single-component (that is to say comprising a single package) or two-component systems (that is to say comprising two parts packed separately and which must be mixed at the time of use).
- one of the components comprises in particular a type C POS having reactive ends Fc, in particular hydroxydimethylsiloxy, the other component comprising the catalyst of the polycondensation reaction.
- This catalyst can be a metallic compound, such as for example an organic tin compound.
- This component comprising the catalyst can also comprise a crosslinking agent D carrying Fd functions capable of reacting with the reactive functions Fc of POS C.
- compositions can also be presented in the form of single-component systems which crosslink at room temperature, in the presence of moisture.
- the fillers used are particulate fillers of the type of those mentioned above for the elastomeric compositions. These charges act through their non-deformable nature, their geometry and their dimensions as well as through the interactions they exchange with the surrounding environment.
- the preparation of concentrated suspensions (mashings) of reinforcing particulate fillers in reactive or non-reactive silicone oils, intended to produce crosslinkable elastomers or anti-foam silicone compositions, is a step in the processes for preparing elastomeric compositions widely used in the field. silicone elastomers.
- the best known reinforcing particulate fillers are based on pyrogenic silica, but substances such as precipitation silica, titanium oxide, for example, can also be used in certain cases.
- These charges have a BET specific surface of at least 1 m 2 / g up to generally 400 m 2 / g.
- These are ultra-fine powders that can be dispersed in silicone oils. This dispersion poses problems of mixing the powdery charge with the oil and particular care must be taken to obtain a uniform distribution of the charge in the suspension.
- fluid compositions are generally sought after; the use of a manufacturing intermediate consisting of a concentrated suspension in accordance with the invention described below, is a means of achieving this objective.
- compatibilizers There are mainly two types of compatibilizers:
- This compatibilization treatment can take place before and / or during and / or after the incorporation of the filler (e.g. silica) in the polyorganosiloxane oils.
- the filler e.g. silica
- French patent application FR-A-2 320 324 describes a homogeneous distribution process in polyorganosiloxane oils, of a filler based on highly dispersed pyrogenic silica and with a BET specific surface of at least 50 m 2 / g .
- This process is characterized in that the filler is treated during the incorporation, in the presence of water, with a compatibilizing agent (hexamethyldisilazane).
- This accounting treatment of the silica with the silicone oil can be described as "early" since the HMDZ is present as soon as the reinforcing combustion silica is brought into contact with this silicone oil.
- EP-A-0 462 032 describes a process for preparing a pasting which can be used in particular in compositions which can be crosslinked by polyaddition reaction.
- the compatibilization treatment using hexamethyldisilazane takes place after the incorporation of the silica into the silicone oil. This processing method is here called "late”.
- PCT patent application WO-A-02/44259 discloses the preparation of a suspension of precipitation silica in a silicone oil, this suspension being usable for producing crosslinkable silicones by polyaddition or by polycondensation (RTN elastomers).
- the precipitated silica is treated using hexamethyldisilazane (HMDZ) introduced in two fractions (15 and 85%) in a crosslinkable silicone oil. The first fraction is first brought into contact with the precipitation silica and water.
- HMDZ hexamethyldisilazane
- Document OA-01/14480 teaches the presence of a coupling agent (a) (egMeViSiCl 2 ) and a hydrophobic organometallic compound (b) (egMe SiCl 2 ).
- a coupling agent egMeViSiCl 2
- b egMe SiCl 2
- Isopropyl alcohol, THexaMethylDiSiloxane (HMDS or M 2 ) or toluene are also part of the reagents in addition to the aqueous silica slurry.
- the temperature is also increased (65 ° C).
- the content of document WO-A-01/12730 is comparable to that of document WO-A-01/14480.
- Hydrophobization of silica in the form of an aqueous slurry is carried out at acidic pH (H 2 S0 or HCl), in the presence of isoprapanol, of HMDS with heating at 60-70 ° C.
- the aforementioned hydrophobized silica particles are then transferred into an organic phase based on hexane for example.
- the goal is to have 2 to 15 OH / nm 2 , a methanol wettability of 15 to 45% and, after neutralization, a reduced carbon content (close to 0) and a pH between 3 and 10 and a lower whiteness Mi at 0.4%.
- HDMS can be replaced by Me 2 SiCl 2 .
- one of the essential objectives of the present invention is to provide an economical process for preparing a suspension of a particulate charge treated with a compatibilizing agent based on halosilanes, in a silicone oil, this suspension can be useful as a raw material for the preparation of:> two-component or even one-component silicone compositions, crosslinkable in particular by polyaddition, polycondensation or dehydrogenocondensation, in silicone elastomers, or silicone anti-foam compositions.
- This process must meet the following specifications: - coupling in a single production sequence of the silica compatibilization treatment in particular using halosilanes and mixing the silica with a polysiloxane silicone material capable of be used directly as a raw material for the preparation of crosslinkable silicone compositions, - uniformization and homogenization of the distribution of the charge in the silicone oil, optimization of the dispersion, viscosity suitable for the handling and transformation of the suspension, - properties mechanical properties of the elastomers resulting from an acceptable level, or quality anti-foam properties, reduced cost.
- Another essential objective of the invention is to provide a process for the preparation of a reinforcing filler / silicone oil suspension for elastomers, which is simple to implement and applicable on an industrial scale.
- Another essential objective of the invention is to provide an efficient and direct process for obtaining a suspension of reinforcing filler in a silicone oil for elastomers, this process being of the type of that aimed for in the abovementioned objectives.
- Another essential objective of the invention is to provide a process for obtaining a silicone composition, crosslinkable by polyaddition or polycondensation to form an elastomer and comprising as constituent element the suspension as obtained by the process referred to above.
- Another essential objective of the invention is to provide a process for obtaining a silicone anti-foam composition and comprising as a constituent element the suspension as obtained by the process referred to above.
- this suspension being, in particular, usable for producing crosslinkable compositions by polyaddition and / or by polycondensation and / or by dehydrogenocondensation or silicone anti-foam compositions; this process being of the kind in which an aqueous suspension of silica particulate filler is made hydrophobic by treatment with at least one halogenated reagent, this treatment comprising a transfer of the silica rendered hydrophobic in a non-aqueous phase and at the at least one step of at least partial elimination of the water; characterized in that: a) an aqueous suspension of silica is prepared or used, comprising:
- hydrophobic dried silica is understood within the meaning of the present invention and throughout the present description, a hydrophobic silica comprising less than 10% of extractables not attached to the hydrophobic silica.
- extractables designating:
- step e) of drawing off the aqueous phase is interpreted as follows:
- step e) is compulsory and it is even completed by devolatilization (distillation) to completely eliminate volatiles, including water;
- an anti-foam silicone composition it is optionally possible to dispense with eliminating the volatile species including water, with a view to subsequent emulsification.
- the invention also relates to a treatment intended to make the silica hydrophobic, which treatment being capable of being implemented in the process for the preparation of a suspension of a filler (eg silica) in a silicone.
- a ' there is brought into contact: "an aqueous suspension of silica comprising 100 parts by dry weight of silica, optionally acidified using 20 to 60 (preferably 30 to 50) parts by weight of at least one acid, knowing that the pH of the non-aqueous phase is preferably ⁇ 2, preferably ⁇ 1;
- a silicone resin precursor preferably sodium silicate
- the water represents 2 to 8000, preferably 200 to 1000 parts by weight per 100 parts by weight of dry silica.
- silicone resin is meant, within the meaning of the invention, a resin comprising siloxy units Q and / or T and optionally siloxy units M and / or D and / or Q 0Rq ' and / or T 0Rt' and / or M 0Rm and / or D 0Rd ' .
- Rq ' H or radical of the same definition as R m .
- the precursor of such silicone resins (preferably a sodium silicate) is transformed into polysilicic acid in the presence of acidified water preferably at a pH ⁇ 2.
- This acid forms a network of Q units which aggregate on the silica initially set artwork.
- the functionalization (“hydrophobation") of the network using AC II then occurs.
- a silicone phase is thus obtained containing MQ resin with a large Q core.
- the aqueous phase is devoid of any trace of silica.
- the precursor of such resins is preferably a sodium silicate (Si ⁇ 2 ,
- the precursor of silicone resins can be used in the form of an aqueous solution.
- silicone resin for example MQ
- functional units other than hydrophobic units are grafted onto the silica, by placing the latter in the presence of halosilane precursors of these functional grafts.
- the functions that can be provided to silica by these motifs are for example the following: bactericidal, bacteriostatic, chromophore, fluorescence, "anti-fouling", refractive index modifier, coupling with the silicone network (eg haloalkoxy) -alkenyl-silane, ... and their associations.
- one or more precipitating silica preferably present essentially in the form of a slurry and whose specific surface
- BET is between 50 and 400 m 2 / g, "and mixing conditions such that the dynamic viscosity at 25 ° C. of the suspension is less than or equal to 300 Pa.s, preferably less than or equal to 150 Pa.s.
- a precipitation silica results from a succession of operations which can be for example: - precipitation of the silica in the aqueous phase by acidification, by addition of acid on a silicate base stock or by total or partial simultaneous addition of acid and silicate on the base of a water tank or silicate solution, filtration making it possible to recover a phase enriched in silica, optionally disintegrating the precipitated silica filtrate to prepare an easily manipulated aqueous suspension, optionally drying the silica precipitated, - optionally grinding and / or compacting the precipitated silica powder, and optionally bagging the precipitated silica powder thus obtained.
- the preparation of precipitated silica used in the context of the invention is described in documents EP-A-0 520 862, WO-A-95/09127 and WO-A-95/09128.
- the precipitated silica used in the process according to the invention can be in the form of powder or in the form of an aqueous slurry taken at the filtration or disintegration stage.
- the term "powder” used to qualify precipitated silica denotes precipitated silica in the solid state, generally in powder form or in the form of granules or substantially spherical beads.
- one or more precipitation silica are chosen whose BET specific surface is between 50 and 400 m 2 / g and mixing conditions such as the dynamic viscosity at 25 ° C. the suspension (pasting) is less than or equal to 300 Pa.s, preferably less than or equal to 150 Pa.s.
- the BET specific surface is determined according to the method of BRUNAUER, EMMET, TELLER described in "The Journal of the American Chemical Society, vol. 80, page 309 (1938)" corresponding to standard NFT 45007 of November 1987.
- the silica filler preferably (precipitation) represents from 10 to 50% by weight of the suspension. In practice, this charge is of the order of 30 + 10% by weight.
- the stabilizer / initiator of hydrogen bonds is chosen from organic solvents, preferably from the group comprising alcohols (in particular isopropyl alcohol, ethanol and butanol), ketones (in particular MethyllsoButylKetone: MIBK), amides (in particular DiMethylACetamide: DMAC), alkanes (in particular tetrahydrofuran: THF) and their mixtures.
- the acidification of the aqueous suspension (aqueous phase) which optionally occurs in the process according to the invention, is rather carried out using an acid, preferably a mineral acid, and more preferably another acid is chosen from the group comprising: HC1, H 2 S0 4 , H 3 PO and their mixtures.
- Another means than the external supply of acid to keep the pH of the aqueous suspension (aqueous phase) below the required limit, consists in the in situ formation of acid - preferably HCl - by reaction of l halosilane precursor of hydrophobic units, with water.
- the MS silicone material comprises at least one oligoorganosiloxane, preferably a diorganosiloxane, and more preferably still hexamethyldisiloxane (HMDS or M 2 ).
- oligoorganosiloxane preferably a diorganosiloxane, and more preferably still hexamethyldisiloxane (HMDS or M 2 ).
- the oligoorganosiloxane (s) of the MS can can (can) be associated (s) with one or more polyorganosiloxanes (POS) of all types, in particular A, B, C, D, E as referred to above and defined in more detail below.
- POS polyorganosiloxanes
- oligoorganosiloxane denotes a siloxane oligomer comprising from 2 to 10 siloxy units of type M, D, or T as defined above, while a polyorganosiloxane denotes a polymer comprising from 11 to 10000 , preferably from 100 to 5000.
- the silicone material MS of oligoorganosiloxane nature preferably corresponds to the first fraction optionally used, during step b) of the process according to the invention for the preparation of a suspension of silica in a silicone oil.
- the halosilane precursor of hydrophobic units is an alkyl halogenated, nnoossiillaannee ,, ddee preferably an alkylchlorosilane, and more preferably still a methylch hlloorroossiillaannee .
- This alkylhalosilane is very advantageously a blocker of the monosilane type, for example (CH 3 ) SiCl. This blocker limits the growth of silica, or even of the silicone resin obtained from the sodium silicate, preferably used in step a) or a ').
- halosilane (s) in the group comprising: "dialkyldihalogenonosilanes for example (CH 3 ) 2 SiCl 2 ,” dialkylhydrogenohalogenonosilanes for example (CH 3 ) 2 SiCl 2 , "alkylhydrogenodihalogenonosilanes for example CH 3 S1HCI 2 ,
- alkylalcényldihalogénomonosilanes for example (CH 3) ViSiCl 2 "the dialkylalcénylhalogénomonosilanes for example (CH 3) 2 ViSiCl, 1 the alkyltrihalogénomonosilanes for example (CH 3) SiCl 3," the hydrogénotrihalogénomonosilanes e.g. HSiCl 3, "lesalcényltrihalogénomonosilanes e.g. ViSiCl 3 ,
- the alkyl may be a C 1 -C 30 alkyl, the alkenyl a C 2 -C 3 alkenyl.
- the alkyl, alkenyl or hydrogen substituents can be combined or replaced by an aryl.
- These alkyl, alkenyl or aryl groups can be optionally substituted (preferably halogen).
- the preferred alkyl and halogen are methyl and chlorine respectively and the alkenyl is preferably Vi-vinyl.
- the method according to the invention essentially consists in using a precipitated silica powder and in implementing the following operations: • the products concerned are introduced into the agitated preparation enclosure '' following order:
- the stabilizer / initiator of hydrogen bonds preferably consisting of isopropyl alcohol-, optionally an acid-preferably HC1-;
- this non-aqueous phase is washed with an aqueous liquid and then the aqueous washing phase is eliminated;
- the proportions of the various ingredients are as follows (in parts by dry weight for all that is not water):
- - acid e.g. HC1: 20 to 60, preferably 30 to 50;
- - stabilizer / initiator of H bonds eg isopranol: 0 to 20, preferably from 1 to 10;
- - MS oil 40 to 2000, consisting exclusively or not of oligoorganosiloxane - preferably M 2 ;
- - water 2 to 8000, preferably 200 to 1000.
- the silica used is essentially in the form of a precipitated silica slurry (s).
- s precipitated silica slurry
- the dryness of the silica slurry is generally between 1 and 50% by weight, preferably between 10 and 40% by weight.
- This new preparation process proves to be particularly economical and allows easy incorporation of the ingredients with tools that consume little energy. Indeed, the composition remains easily malleable throughout the process without that it doesn't require a lot of power for mixing. This process also results, in the case of crosslinkable silicone elastomers, in the use properties of the elastomers that are entirely up to the expected specifications, compared to the conventional processes using combustion silica. The same applies with regard to pastings intended for preparing anti-foam compositions.
- the different stages of the process can be of variable duration and accomplished in separate apparatus.
- silicone oils used in the process according to the invention preferably, linear or cyclic, and preferably linear, polydiorganosiloxanes will be chosen.
- the silicone material can be, first of all, a polyaddition MSj comprising:
- POS B reactive silicone oil whose crosslinking functions Fb are hydrogen functions, this POS B comprising at least two Si-H groups per molecule (preferably at least three when the POS A comprises only two Si- Ni per molecule), these Si-H being advantageously located in the chain,
- a catalytic system comprising a metal polyaddition catalyst (preferably of platinum nature) and optionally an inhibitor; "possibly one or more semi-reinforcing, non-reinforcing or tamping filler (s); * possibly water;
- additive chosen from pigments, plasticizers, other rheology modifiers, stabilizers and / or adhesion promoters.
- POS A can be, for example, a polydialkyl- (methyl) -siloxane ⁇ , ⁇ -divinylated oil.
- the POS A used for the preparation of the suspension is a vinylated POS A carrying at least two Si-Vi units per molecule, preferably at least three per molecule, when the POS B comprises only two Si- Vi units H per molecule.
- POS B is for example polyalkyl (methyl) hydrogenosiloxane or alternatively a branched hydrogenated POS comprising tri or tetrafunctional units and units carrying SiH.
- POS E can be a polydiorganosiloxane, such as a polyalkyl, preferably polydimethylsiloxane with trimethylsilyl ends.
- the preferred silicone oils (A, B, E) essentially comprise R ' 2 SiO units, the symbols R 1 , which are identical or different, representing optionally halogenated (cyclo) C 1 -C 30 alkyl groups, (cyclo) groups optionally halogenated C 2 -C 30 alkenyls, or optionally substituted or halogenated aryl groups.
- R 1 which are identical or different, representing optionally halogenated (cyclo) C 1 -C 30 alkyl groups, (cyclo) groups optionally halogenated C 2 -C 30 alkenyls, or optionally substituted or halogenated aryl groups.
- alkyl mention may in particular be made of methyl, ethyl propyl and butyl groups,
- - halogenated alkyl mention may be made of 3-3-trifluoropropyl
- - cyclo-alkyl mention may be made of cyclo-hexyl
- the silicone material can be an MS? polycondensation comprising: "at least one POS C reactive silicone oil whose Fc crosslinking functions react by polycondensation, these POS C corresponding to the following formula (1):
- additive chosen from pigments, plasticizers, other rheology modifiers, stabilizers and / or adhesion promoters.
- radicals R are methyl radicals
- the other radicals can generally be phenyl radicals.
- POS C hydroxyls of formula (1) a mixture consisting of several hydroxyl polymers which differ from each other by the value of the viscosity and / or the nature of the substituents linked to silicon atoms. It should also be indicated that the hydroxylated polymers of formula (1) may optionally comprise, alongside the D units, T units and / or Q units in the proportion of at most 1% (these% expressing the number of T and / or Q units for 100 silicon atoms).
- This MS polycondensation can also comprise a non-reactive silicone oil comprising non-reactive POS E corresponding to the following formula (2):
- R " which are identical or different, represent monovalent hydrocarbon radicals, preferably C 1 -C 30 alkyl, C 2 -C 30 alkenyl, aryl, optionally substituted (preferably halogen),
- radicals R As examples of radicals R ", mention may be made of alkyl radicals having from 1 to 8 carbon atoms such as methyl, ethyl, propyl, butyl, hexyl and octyl, phenyl radicals.
- substituted R radicals
- the hydroxylated polymers of formula (2) may optionally comprise, alongside the units D of formula R " 2 SiO, T units of formula R" Si0 3/2 and / or SiO units, in the proportion of at most 1% (these percentages expressing the number of T and / or Q units per 100 silicon atoms).
- the latter is preferably chosen from: the silanes of general formula: R 3 4.a If (OR) a (3) in which:
- crosslinking agents D selected from monomeric silanes
- polyacyloxysilanes there may be mentioned more particularly polyacyloxysilanes, polyalkoxysilanes, polyketiminoxysilanes and polyiminoxysilanes, and in particular the following silanes: CH 3 Si (OCOCH 3 ) 3 ; C, H 5 Si (OCOCH 3 ) 3 ;
- CH 2 CHSi (OCH.) 3 ;
- Partial hydrolysis products for example, polyalkoxysilanes, usually called alkyl polysilicates, are well known products.
- the most commonly used product is ethyl polysilicate 40® resulting from the partial hydrolysis of Si (OC 2 H 5 ) 4 .
- crosslinking agents D preferably used in the case of the preferred use of POS ⁇ , co-dihydroxylates of formula (1), are the alkyltrialkoxysilanes and the tetraalkoxysilanes of formula (3) where R represents an alkyl radical having from 1 to 4 carbon atoms, and the partial hydrolysis products of these preferred silanes.
- the silicone material can be a MS 3 polydhydrogenocondensation comprising:
- the purpose of the reinforcing filler / silicone oil suspension prepared in accordance with the invention is to be used in obtaining liquid or pasty silicone compositions which can be crosslinked by polyaddition or polycondensation, preferably in silicone elastomer in the ambient atmosphere at temperature. normal or at a higher temperature, or non-reactive liquid or pasty silicone compositions (anti-foam).
- the present invention relates to a process for obtaining a crosslinkable silicone composition by polyaddition, consisting in incorporating in particular into the suspension as prepared according to the process as defined above, the following products:
- a catalytic system comprising a catalyst, preferably of a platinum nature, and optionally an inhibitor.
- composition is produced in the form of two-component systems Pi and
- compositions which can be crosslinked by polyaddition of elastomers can also comprise one or more functional additives ⁇ , such as for example a non-reinforcing filler formed by chalk, quartz powder, diatomaceous earth, mica, kaolin, aluminas or iron oxides.
- functional additives ⁇ can also consist of pigments, non-stick agents, plasticizers or rheology modifiers, stabilizers or adhesion promoters.
- the invention also relates to a process for obtaining a crosslinkable silicone composition by polycondensation, characterized in that it consists in incorporating, in particular, into the suspension as prepared according to the process as defined above, the following products:
- POS E as defined above and useful (s) as diluent (s);
- additive chosen from pigments, plasticizers, other rheology modifiers, stabilizers and / or adhesion promoters.
- the charges v ′ generally have a particle diameter greater than 0.1 ⁇ m and are preferably chosen from ground quartz, zirconates, calcined clays, diatomaceous earth, calcium carbonate, aluminas .
- a single-component composition (that is to say a single package) is produced intended to crosslink in the presence of moisture, in particular humidity provided by the ambient air or by the water present and / or added within the composition, at ambient temperature and / or under the effect of the temperature which can range, for example from 25 ° C. to a value of less than 100 ° C.
- the crosslinking catalyst ⁇ 'used is a metal catalyst which is chosen in particular from tin monocarboxylates, diorgano tin dicarboxylates, a valence IV tin chelate, a hexacoordinated valence IV tin chelate, amino silanes, an organic derivative of titanium, an organic derivative of zirconium.
- each composition is produced in the form of a two-component system (or two packages) P 1 and P2, intended to be brought into contact with one another to result in a polycondensation elastomer,
- the polycondensation catalyst ⁇ 'used is preferably an organic derivative of tin as defined above, an amine or a mixture of these species or an organic derivative of titanium.
- the invention also relates to a process for the preparation of a silicone composition which can be crosslinked by polydhydrogenoconsidation, characterized in that in that a polydhydroxyondondensation MSs is used comprising:
- At least one type C POS carrying hydroxyl crosslinking functions Fc 'and / or OR' functions R- C 1 -C 30 alkyl, C 2 -C 30 alkenyl, aryl, optionally substituted (preferably halogen )) precursor of the functions Fc ', these crosslinking functions Fc' being capable of reacting with other crosslinking functions Fb '(SiH) of at least one POS of type B', this POS C "being taken alone or in mixing with at least one non-reactive POS (E),
- POS B at least one POS B 'reactive silicone oil, whose crosslinking functions Fb' are hydrogen functions, this POS B 'comprising at least two ⁇ Si-H groups per molecule (preferably at least three when the POS A does not comprise than two ⁇ Si-Vi per molecule), these ⁇ Si-H being advantageously located in the chain,
- a catalytic system comprising a metal polydhydrogenocondensation catalyst (preferably of a platinum nature) and optionally an inhibitor; o optionally one or more charge (s) semi-reinforcing, non-reinforcing or stuffing; o possibly water; o optionally one or more additive (s) chosen from pigments, plasticizers, other rheology modifiers, stabilizers and / or adhesion promoters.
- the mixtures involved in these processes can be produced using known and appropriate devices. It can be for example:
- the mixing operation is carried out at normal temperature and pressure and preferably under an inert atmosphere (N 2 ). It should moreover that, under these conditions, the silicone oil, the water but also the accounting agent are in liquid form to facilitate mixing.
- Z160 type silica slurry i.e. a precipitated silica slurry, surface
- Z160 type silica slurry i.e. a precipitated silica slurry, surface
- a 3 L reactor fitted with impeller type agitation and two counter blades.
- 317 g of propan-2-ol (stabilizer / initiator of bonds H) and 217 g of 36% hydrochloric acid specific ⁇ 160 m 2 / g, not ground, at 23% of dry extract by weight in water and consisting of an intermediate product for the production of silica), 317 g of propan-2-ol (stabilizer / initiator of bonds H) and 217 g of 36% hydrochloric acid.
- the reaction medium is stirred and a mixture of 272.5 g of trimethychlorosilane (halogenosilane precursor of hydrophobic grafts for silica) and 133 g of hexamethyldisiloxane (M 2 : silicone material.
- MS constituting the silicone oil in which the treated silica is suspended
- the reaction mixture is heated and left to reflux for 2 hours.
- the agitation is then stopped and the medium is left to settle.
- the aqueous phase is drawn off and the silicone phase is washed three times with a total of 1538 g of a sodium bicarbonate solution at 5% by weight. 580 g of silica suspension are recovered in a MS made of hexamethyldisiloxane with 7% of aqueous phase.
- aqueous phase is drawn off and the silicone phase is washed three times with a total of 1581 g of a sodium bicarbonate solution at 5% by weight. 580 g of silica suspension are recovered in an MS made of hexamethyldisiloxane with 7% of aqueous phase.
- aqueous phase is drawn off and the silicone phase is washed three times with a total of 1591 g of a sodium bicarbonate solution at 5% by weight. 571 g of silica suspension are recovered in an MS made of hexamethyldisiloxane with 5% of aqueous phase.
- HC1 not important at the start and is generated during the reaction.
- Primordial propan-2-ol present.
- hexamethyldisiloxane not important for carrying out the reaction but necessary for decantation and serving as MS Silicone Material in which the hydrophobic silica is suspended.
- the aqueous phase is drawn off and the MQ resin with a silica core is reextracted by adding 329.19 g of hexamethyldisiloxane and washing twice with 806.18 g of water. After concentration by evaporation of the volatiles, 486.60 g of a suspension of MQ resin with a silica core in a silicone oil (MS) constituted by
Landscapes
- 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)
- Silicon Polymers (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP03799646A EP1578859A1 (fr) | 2002-12-30 | 2003-12-19 | Procede de preparation d'une suspension de silice dans une matiere silicone eventuellement reticulable |
AU2003299363A AU2003299363A1 (en) | 2002-12-30 | 2003-12-19 | Method for preparing a silica suspension in a potentially crosslinkable silicone material |
US10/541,161 US20060258780A1 (en) | 2002-12-30 | 2003-12-19 | Method for preparing a silica suspension in a potentially crosslinkable silicone material |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0216854A FR2849444B1 (fr) | 2002-12-30 | 2002-12-30 | Procede de preparation d'un suspension de silice dans une matiere silicone eventuellement reticulable |
FR0216854 | 2002-12-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2004063265A1 true WO2004063265A1 (fr) | 2004-07-29 |
Family
ID=32480284
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR2003/003815 WO2004063265A1 (fr) | 2002-12-30 | 2003-12-19 | Procédé de préparation d'une suspension de silice dans une matiere silicone eventuellement réticulable |
Country Status (8)
Country | Link |
---|---|
US (1) | US20060258780A1 (fr) |
EP (1) | EP1578859A1 (fr) |
KR (1) | KR100689685B1 (fr) |
CN (1) | CN1745133A (fr) |
AU (1) | AU2003299363A1 (fr) |
FR (1) | FR2849444B1 (fr) |
TW (1) | TWI308165B (fr) |
WO (1) | WO2004063265A1 (fr) |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102007035952A1 (de) * | 2007-07-30 | 2009-04-09 | Evonik Degussa Gmbh | Oberflächenmodifizierte, pyrogen hergestellte Kieselsäuren |
US20100135949A1 (en) | 2008-12-01 | 2010-06-03 | Becton, Dickinson And Company | Antimicrobial compositions |
US8821455B2 (en) | 2009-07-09 | 2014-09-02 | Becton, Dickinson And Company | Antimicrobial coating for dermally invasive devices |
EP2714949A4 (fr) * | 2011-05-25 | 2015-06-24 | Cidra Corporate Services Inc | Récupération de minerais dans les résidus grâce à des polymères fonctionnalisés |
US9352119B2 (en) | 2012-05-15 | 2016-05-31 | Becton, Dickinson And Company | Blood control IV catheter with antimicrobial properties |
US9579486B2 (en) | 2012-08-22 | 2017-02-28 | Becton, Dickinson And Company | Blood control IV catheter with antimicrobial properties |
US9750928B2 (en) | 2013-02-13 | 2017-09-05 | Becton, Dickinson And Company | Blood control IV catheter with stationary septum activator |
US9695323B2 (en) | 2013-02-13 | 2017-07-04 | Becton, Dickinson And Company | UV curable solventless antimicrobial compositions |
US9750927B2 (en) | 2013-03-11 | 2017-09-05 | Becton, Dickinson And Company | Blood control catheter with antimicrobial needle lube |
US9327095B2 (en) | 2013-03-11 | 2016-05-03 | Becton, Dickinson And Company | Blood control catheter with antimicrobial needle lube |
EP2832690A1 (fr) * | 2013-08-02 | 2015-02-04 | EMPA Eidgenössische Materialprüfungs- und Forschungsanstalt | Procédé de fabrication d'un matériau aérogel |
US10376686B2 (en) | 2014-04-23 | 2019-08-13 | Becton, Dickinson And Company | Antimicrobial caps for medical connectors |
US9789279B2 (en) | 2014-04-23 | 2017-10-17 | Becton, Dickinson And Company | Antimicrobial obturator for use with vascular access devices |
US9675793B2 (en) | 2014-04-23 | 2017-06-13 | Becton, Dickinson And Company | Catheter tubing with extraluminal antimicrobial coating |
US10232088B2 (en) | 2014-07-08 | 2019-03-19 | Becton, Dickinson And Company | Antimicrobial coating forming kink resistant feature on a vascular access device |
US10493244B2 (en) | 2015-10-28 | 2019-12-03 | Becton, Dickinson And Company | Extension tubing strain relief |
CN111072037B (zh) * | 2020-02-10 | 2023-04-28 | 赢胜节能集团股份有限公司 | 一种二氧化硅气凝胶的制备方法 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0778307A2 (fr) * | 1995-11-29 | 1997-06-11 | Dow Corning Corporation | Méthode de préparation d'un mélange de polydiorganosiloxane-silice, le mélange ainsi obtenu et joint silicone réticulable à température ambiante |
US5750610A (en) * | 1997-02-24 | 1998-05-12 | Dow Corning Corporation | Hydrophobic organosilicate-modified silica gels |
EP0475132B1 (fr) * | 1990-08-27 | 1998-06-10 | Idemitsu Kosan Company Limited | Sol de dioxide de silicium hydrofuge et procédé pour sa préparation |
WO2000037549A1 (fr) * | 1998-12-22 | 2000-06-29 | Rhodia Chimie | Procede de preparation d'une suspension de silice dans une matrice silicone reticulable par polycondensation pour former des elastomeres |
EP0900829B1 (fr) * | 1997-09-03 | 2001-11-14 | Dow Corning Corporation | Procédé de préparation de silice précipitée hydrophobe |
FR2817262A1 (fr) * | 2000-11-30 | 2002-05-31 | Rhodia Chimie Sa | Procede de preparation d'une suspension de silice dans une matrice silicone eventuellement reticulable |
EP1217042A1 (fr) * | 2000-12-20 | 2002-06-26 | General Electric Company | Préparation de caoutchouc de silicone liquide en continu |
EP0982268B1 (fr) * | 1998-08-24 | 2003-04-16 | Dow Corning Corporation | Procédé de préparation de silice colloidale non aggrégée hydrophobe |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2184006A (en) * | 1937-10-27 | 1939-12-19 | Lon C Spencer | Trolley splicer |
US2676182A (en) * | 1950-09-13 | 1954-04-20 | Dow Corning | Copolymeric siloxanes and methods of preparing them |
US3122520A (en) * | 1959-10-05 | 1964-02-25 | Dow Corning | Method of making silicone rubber fillers |
US3159601A (en) * | 1962-07-02 | 1964-12-01 | Gen Electric | Platinum-olefin complex catalyzed addition of hydrogen- and alkenyl-substituted siloxanes |
US3159662A (en) * | 1962-07-02 | 1964-12-01 | Gen Electric | Addition reaction |
US3220972A (en) * | 1962-07-02 | 1965-11-30 | Gen Electric | Organosilicon process using a chloroplatinic acid reaction product as the catalyst |
US3814730A (en) * | 1970-08-06 | 1974-06-04 | Gen Electric | Platinum complexes of unsaturated siloxanes and platinum containing organopolysiloxanes |
DE2535334B2 (de) * | 1975-08-07 | 1978-09-28 | Bayer Ag, 5090 Leverkusen | Verfahren zur homogenen Verteilung hochdisperser aktiver Füllstoffe in Poly organosiloxanen |
US4581411A (en) * | 1983-11-17 | 1986-04-08 | Phillips Petroleum Company | Rubbery compounds as modifiers for poly(arylene sulfide) |
US4785047A (en) * | 1987-07-30 | 1988-11-15 | Dow Corning Corporation | Method for preparing clear polyorganosiloxane elastomers |
FR2663340B1 (fr) * | 1990-06-13 | 1994-04-08 | Rhone Poulenc Chimie | Procede de preparation d'empatage en extrudeuse double-vis pour compositions rtv sih/sivi. |
FR2678259B1 (fr) * | 1991-06-26 | 1993-11-05 | Rhone Poulenc Chimie | Nouvelles silices precipitees sous forme de granules ou de poudres, procedes de synthese et utilisation au renforcement des elastomeres. |
FR2710630B1 (fr) * | 1993-09-29 | 1995-12-29 | Rhone Poulenc Chimie | Nouvelles silices précipitées, leur procédé de préparation et leur utilisation au renforcement des élastomères. |
US6169135B1 (en) * | 1993-09-29 | 2001-01-02 | Rhone Poulenc Chimie | Precipitated silica |
US5942590A (en) * | 1997-02-24 | 1999-08-24 | Dow Corning Corporation | Process for making hydrophobic silica with reduced surface area under neutral conditions |
FR2764894B1 (fr) * | 1997-06-24 | 1999-09-24 | Rhodia Chimie Sa | Procede de preparation d'une suspension de silice dans une matrice silicone vulcanisable a temperature ambiante et a chaud pour former des elastomeres |
US5919298A (en) * | 1998-01-12 | 1999-07-06 | Dow Corning Corporation | Method for preparing hydrophobic fumed silica |
US6184408B1 (en) * | 1999-04-28 | 2001-02-06 | Dow Corning Corporation | Method for preparation of hydrophobic precipitated silica |
-
2002
- 2002-12-30 FR FR0216854A patent/FR2849444B1/fr not_active Expired - Fee Related
-
2003
- 2003-12-19 AU AU2003299363A patent/AU2003299363A1/en not_active Abandoned
- 2003-12-19 WO PCT/FR2003/003815 patent/WO2004063265A1/fr not_active Application Discontinuation
- 2003-12-19 US US10/541,161 patent/US20060258780A1/en not_active Abandoned
- 2003-12-19 KR KR1020057012468A patent/KR100689685B1/ko not_active IP Right Cessation
- 2003-12-19 CN CNA2003801094699A patent/CN1745133A/zh active Pending
- 2003-12-19 EP EP03799646A patent/EP1578859A1/fr not_active Withdrawn
- 2003-12-29 TW TW092137353A patent/TWI308165B/zh not_active IP Right Cessation
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0475132B1 (fr) * | 1990-08-27 | 1998-06-10 | Idemitsu Kosan Company Limited | Sol de dioxide de silicium hydrofuge et procédé pour sa préparation |
EP0778307A2 (fr) * | 1995-11-29 | 1997-06-11 | Dow Corning Corporation | Méthode de préparation d'un mélange de polydiorganosiloxane-silice, le mélange ainsi obtenu et joint silicone réticulable à température ambiante |
US5750610A (en) * | 1997-02-24 | 1998-05-12 | Dow Corning Corporation | Hydrophobic organosilicate-modified silica gels |
EP0900829B1 (fr) * | 1997-09-03 | 2001-11-14 | Dow Corning Corporation | Procédé de préparation de silice précipitée hydrophobe |
EP0982268B1 (fr) * | 1998-08-24 | 2003-04-16 | Dow Corning Corporation | Procédé de préparation de silice colloidale non aggrégée hydrophobe |
WO2000037549A1 (fr) * | 1998-12-22 | 2000-06-29 | Rhodia Chimie | Procede de preparation d'une suspension de silice dans une matrice silicone reticulable par polycondensation pour former des elastomeres |
FR2817262A1 (fr) * | 2000-11-30 | 2002-05-31 | Rhodia Chimie Sa | Procede de preparation d'une suspension de silice dans une matrice silicone eventuellement reticulable |
EP1217042A1 (fr) * | 2000-12-20 | 2002-06-26 | General Electric Company | Préparation de caoutchouc de silicone liquide en continu |
Also Published As
Publication number | Publication date |
---|---|
AU2003299363A1 (en) | 2004-08-10 |
KR100689685B1 (ko) | 2007-03-12 |
FR2849444A1 (fr) | 2004-07-02 |
US20060258780A1 (en) | 2006-11-16 |
CN1745133A (zh) | 2006-03-08 |
EP1578859A1 (fr) | 2005-09-28 |
FR2849444B1 (fr) | 2006-07-28 |
KR20050093815A (ko) | 2005-09-23 |
TW200508322A (en) | 2005-03-01 |
TWI308165B (en) | 2009-04-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2004063265A1 (fr) | Procédé de préparation d'une suspension de silice dans une matiere silicone eventuellement réticulable | |
AU615122B2 (en) | Process for rendering hydrophobic a particulate solid containing si-oh groups and the use of the resulting hydrophobic particulate solid in a process for preparing compositions, based on diorganopolysiloxanes, which can be cured to form elastomers | |
EP0991712B1 (fr) | Procede de preparation d'une suspension de silice dans une matrice silicone vulcanisable pour former des elastomeres | |
CN102027074B (zh) | 表面改性的二氧化硅颗粒 | |
US7790829B2 (en) | Curable and cured silicone rubber compositions and methods therefor | |
EP1877470B1 (fr) | Compositions organopolysiloxanes durcissant en elastomeres des la temperature ambiante en presence d' humidite | |
JPH02281041A (ja) | オルガノシロキサン樹脂の製造方法 | |
JP2986746B2 (ja) | 低分子有機珪素化合物及び架橋性材料 | |
CN101180355A (zh) | 用于生产含有微细填料的硅氧烷组合物的方法 | |
EP2744855B1 (fr) | Procédé de préparation d'une silice greffée par un composé organosilicié | |
WO2003037987A1 (fr) | Composition silicone adhesive reticulable comprenant comme agent thixotropant un compose a fonction amine cyclique portee par une chaine siloxanique | |
CA2352124A1 (fr) | Compositions organopolysiloxanes durcissant en elastomeres translucides des la temperature ambiante en presence d'humidite | |
EP1141108B1 (fr) | Procede de preparation d'une suspension de silice dans une matrice silicone reticulable par polycondensation pour former des elastomeres | |
EP1578860A1 (fr) | Proc d de pr paration d'une suspension de silice dans une matiere silicone eventuellement r ticulable | |
FR2659658A1 (fr) | Silice traitee par un organosilicone et composition la contenant. | |
EP1337581A1 (fr) | Procede de preparation d'une suspension de silice dans une matrice silicone eventuellement reticulable | |
FR2639950A1 (fr) | ||
WO2012084992A1 (fr) | Composition silicone reticulable par hydrosilylation et procede de revetement ou de fabrication d'objets a partir de cette composition | |
EP1697454A1 (fr) | Composition polyorganosiloxane monocomposante reticulant en elastomere silicone |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): BW GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2003799646 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020057012468 Country of ref document: KR |
|
WWE | Wipo information: entry into national phase |
Ref document number: 20038A94699 Country of ref document: CN |
|
WWP | Wipo information: published in national office |
Ref document number: 1020057012468 Country of ref document: KR |
|
WWP | Wipo information: published in national office |
Ref document number: 2003799646 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2006258780 Country of ref document: US Ref document number: 10541161 Country of ref document: US |
|
WWP | Wipo information: published in national office |
Ref document number: 10541161 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: JP |
|
WWW | Wipo information: withdrawn in national office |
Country of ref document: JP |