WO2007045692A1 - Composition de caoutchouc de silicone presentant une meilleure resistance a la propagation du dechirement - Google Patents

Composition de caoutchouc de silicone presentant une meilleure resistance a la propagation du dechirement Download PDF

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Publication number
WO2007045692A1
WO2007045692A1 PCT/EP2006/067633 EP2006067633W WO2007045692A1 WO 2007045692 A1 WO2007045692 A1 WO 2007045692A1 EP 2006067633 W EP2006067633 W EP 2006067633W WO 2007045692 A1 WO2007045692 A1 WO 2007045692A1
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weight
parts
component
groups
polyorganosiloxane
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PCT/EP2006/067633
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German (de)
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Helmut Steinberger
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Ge Bayer Silicones Gmbh & Co. Kg
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    • 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
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups

Definitions

  • the invention relates to silicone rubber compositions which have a powdery filler for increasing the tear propagation resistance.
  • the tensile strength of crosslinked silicone rubbers can be increased from about 0.1-0.3 to 13 N / mm 2 , if fillers with a higher surface area up to 400 m 2 / g are added BET, in particular fillers with smaller primary particles 7 - 10 nm lead to higher tear propagation resistance. Such fillers are called reinforcing fillers. Values of 1 - 40 N / mm can be achieved according to ASTM 624 ("The B").
  • crosslinking structure In cases where the addition of reinforcing, ie also thickening, fillers is not permitted or desired, it is possible to tune the crosslinking structure
  • Such polymers having an increased concentration of crosslinking alkenyl groups can be linear polymers of various, almost any chain length, but also resins in liquid or solid form from 45 - 53 N / mm according to ASTM 624 "The B" and tensile strengths of 9 - 13 N / mm 2 according to DIN 53504.
  • the object of the invention was to provide compositions or materials in which an increase in the tear strength is possible at a lower cost.
  • EP 0358370 A1 discloses how, with a silicone resin consisting of trimethylsiloxy, dimethylvinylsiloxy and SiO 2, that is to say so-called Q units, it is possible to achieve an enhancement of the rubber-mechanical properties, for example the tear strength in transparent elastomers, by adding up to 40% by weight parts.
  • EP 0305 073 A2 claims a mixture for further tear-resistant silicone elastomers which i.a. 70-95 parts by weight of a component (A) of a vinyl-terminated polydimethylsiloxane having the viscosity 20-200 Pa. s (25 ° C) and 5-30 parts by weight of a component (B) of a vinyl-terminated polydimethylsiloxane of viscosity 0.1-200 Pa. s, which additionally contains 1 to 5% vinylmethylsiloxy units.
  • US Pat. No. 5,786,413 A discloses siloxane compositions in which, inter alia, vinyl-terminated polyorganosiloxanes are used together with pulverulent MDTQ powder powders with reduced particulate matter in order to compare the release forces of coatings, foam stabilization or crack propagation in RTV2 rubbers after dissolution in various solvents to evaluate resins from other manufacturing processes.
  • Example 11 discloses a concentration of about 15% by weight of a dissolved resin in a polyvinylmethylsiloxane. A lesson on how to increase the tear propagation strength with powdered resins in a small amount is not given.
  • EP 0420585 B1 discloses how to reduce the coefficient of friction in thermosetting silicone elastomers which contain vinyl-modified poly (methylvinylsilsequioxane) powders of a specific particle diameter and a vinyl group content of 0.1 to 10% by weight and reduce the tensile strength. and tear strength can improve compared to quartz powders.
  • a ratio of silsesquioxanes of 1 to 200 parts by weight to 100 parts by weight of a polyorganosiloxane having a degree of polymerization of 100 to 10,000 is given. In the specific examples, more than 25 parts by weight of the silsesquioxanes are used.
  • US Pat. No. 4,386,170 teaches how it is possible with 0.8 to 5 parts by weight of polytetrafluoroethylene powder to increase the resistance of a fluoroalkyl-containing silicone elastomer to hot oil, hot air and also its tear propagation resistance. There are disclosed increased tear propagation strengths for additions of 0, 1, 2 and 3 parts by weight of PTFE powder, the maximum tear strength being achieved with 3 parts.
  • JP 61158362 A discloses how to reinforce silicone rubber with spherical silsesquioxanes of the type Tospearl® (from GE Toshiba Silicones). Reinforcement is defined herein as abrasion resistance to cyclic loading of photocopying rollers.
  • the compositions of this invention utilize amounts greater than 5 parts by weight of silsesquioxane per 100 parts by weight of low viscosity vinyl-containing polydimethylsiloxane base polymer and other reinforcing fillers to achieve desired properties such as toner release and high abrasion resistance.
  • the examples show that the life of the photocopying rollers is prolonged with increasing silsesquioxane content.
  • the particle size distribution of the silsesquioxane powder is a range of 0.1-100 .mu.m.
  • the inventor has now surprisingly found that by the addition of very small amounts of a poly (methylsilsesquioxane) having an average particle diameter (dso) of 0.1-50 microns preferably 0.5 -15 microns and a distribution width (dgo-dio) / d 5 o of ⁇ 1, 5, which preferably has no unsaturated units, the tear propagation resistance can be significantly increased.
  • the invention thus provides a curable polyorganosiloxane composition
  • a curable polyorganosiloxane composition comprising:
  • At least one crosslinkable polyorganosiloxane (A) is At least one crosslinkable polyorganosiloxane (A),
  • powdery polyorganosilsesquioxane (C) having an average particle size (d 50) of 0.1 to 50 ⁇ m and preferably a particle size distribution width of (dg0-dio) / d 5 o of ⁇ 1.5 per 100 Parts by weight of component (A),
  • the addition-crosslinking silicone rubber mixture according to the invention comprises at least one crosslinkable polyorganosiloxane (A).
  • the crosslinkable polyorganosiloxane (A) may have a Si reactive group content of 0.03-100 mol% with respect to the Si reactive group relative to all Si units.
  • Crosslinkable polyorganosiloxanes (A) include in particular:
  • the polyorganosiloxanes (A) can be used with or without additional solvents.
  • the polyorganosiloxane (A1) preferably has the following siloxy units:
  • substituents R may be the same or different and are selected from the group consisting of a straight, branched or cyclic alkyl radical of up to 12 carbon atoms which may be optionally substituted with at least one substituent selected from the group consisting of phenyl and halogen, in particular fluorine, is - a straight-chain, branched or cyclic alkenyl radical with up to
  • the siloxy units mentioned can be randomly distributed among one another or arranged in a block.
  • a preferred straight-chain, branched or cyclic alkyl radical having up to 12 carbon atoms is methyl.
  • a preferred aryl radical is phenyl.
  • a preferred phenyl-substituted alkyl radical includes, for example, styryl (phenylethyl).
  • a preferred halogen-substituted alkyl radical includes, for example, a fluoroalkyl radical having at least one fluorine atom, such as perfluoroalkylethyl radicals such as, for example, 3,3,3-trifluoropropyl, C2-C8-perfluoroalkylethyl or perfluoroalkylether or epoxyperfluoroalkylether.
  • a fluoroalkyl radical having at least one fluorine atom such as perfluoroalkylethyl radicals such as, for example, 3,3,3-trifluoropropyl, C2-C8-perfluoroalkylethyl or perfluoroalkylether or epoxyperfluoroalkylether.
  • a preferred straight-chain, branched or cyclic alkoxy radical having up to 6 carbon atoms is, for example, methoxy and ethoxy.
  • component (A) has an average degree of polymerization of from 100 to 10,000, more preferably from 300 to 6,000, even more preferably from 500 to 1,500.
  • Straight chain or branched alkenyl radicals having from 2 to 8 carbon atoms for example: vinyl, allyl, hexenyl, octenyl, vinylphenylethyl, cyclohexenylethyl, ethylidene norbornyl or norbornenylethyl or limonyl. Particularly preferred is vinyl.
  • Preferred radicals R are thus methyl, phenyl, vinyl and 3,3,3-trifluoropropyl.
  • Preferred siloxy units are, for example, alkenyl units, such as dimethylvinylsiloxy, methylvinylsiloxy, vinylsiloxy units, alkyl units, such as trimethylsiloxy, dimethylsiloxy and methylsiloxy units, phenylsiloxy units, such as triphenylsiloxy, dimethylphenylsiloxy, diphenylsiloxy, phenylmethylsiloxy units. and phenylsiloxy units, phenyl-substituted alkylsiloxy units such as (styryl) siloxy.
  • the amount of the polyorganosiloxanes (A) may preferably be between about 20 and 99.4% by weight, based on the total amount of the curable polyorganosiloxane composition.
  • crosslinkable polyorganosiloxanes (A) there can be used, for example: (A1-1): Substantially linear alkenyl-end-stopped polyorganosiloxanes containing less than 5 mol% of T and Q units. (A1-2): Substantially linear alkenyl and / or alkyl end-capped
  • Polyorganosiloxanes additionally having alkenyl groups in the main chain (A1-3): Branched alkenyl-containing polyorganosiloxanes containing
  • the alkenyl content of the individual polyorganosiloxanes (A1-1), (A1-2) and (A1-3) used can be in the range from 0.004 mmol / g to 25 mmol / g for linear vinyl-containing polydimethylsiloxanes, ie at (0.03-100 mol. contents of 0.03-50 mol% (alkenyl-Si based on all Si units) are more preferred. Based on the totality of the polyorganosiloxanes used, the alkenyl content is expediently in total at 0.03-1.2 mol%.
  • the alkenyl content of the individual polyorganosiloxanes (A1) outside this range can also be in the range from 0.03 mmol / g to 6 mmol / g, the sum the weighted alkenyl content preferably again in the range of 0.03 - 1, 2 mol .-%.
  • the substantially linear alkenyl-endstopped polyorganosiloxanes (A1-1) preferably have an alkenyl group content of 0.03 to 1.2 mol%.
  • the substantially linear alkenyl- and / or alkylene-stopped polyorganosiloxanes (A1-2), which additionally have alkenyl groups in the main chain, preferably have an alkenyl group content of 0.03 to 50 mol%.
  • the alkenyl content is determined by H-NMR, see AL Smith (Ed.): The
  • the polyorganosiloxanes (A1) suitably have a viscosity of from 0.01 to 70,000 Pa.s, preferably from 0.3 to 30,000 Pa.s, more preferably from 1 to 100 Pa.s or 5,000 to 30,000 Pa.s.
  • the viscosity is determined according to DIN 53 019 at 25 ° C.
  • mixtures of the comparatively low-alkenyl group-rich polyorganosiloxanes (A1-1) with the comparatively alkenyl-rich polyorganosiloxanes (A1-2) and / or polyorganosiloxanes (A1-3) are used.
  • the mixing ratio of the alkenyl-rich polyorganosiloxanes (A1-2) or (A1-3) is preferably from 0.5 to 40% by weight, based on the total amount of the polyorganosiloxanes (A1).
  • the polyorganosiloxanes (A1) can be prepared by processes known per se, such as, for example, with alkaline or acid catalysts, as in US Pat. No. 5,536,803, column 4.
  • the alkenyl group-rich polyorganosiloxanes (A1-3) include, in particular, solvent-soluble solid resins or liquid resins, which preferably consist of trialkylsiloxy (M units) and silicate units (Q units), and which preferably contain vinyldimethylsiloxy units in an amount. These have a content of vinyl groups of at least 0.2 mmol / g (1, 2 mol .-%). These In addition, resins may contain up to 10 mol% of alkoxy or OH groups on the Si atoms.
  • the polyorganosiloxanes (A) are linear or branched polyorganosiloxanes (A2) having at least two alkoxy and / or SiOH groups and a viscosity of from 0.02 to 70,000 Pa s, wherein the alkoxy groups include straight or branched chain alkyl or aryl radicals of 1 to 20 carbon atoms, for example: methoxy, ethoxy, butoxy, cyclohexanol, octanol. Preferred are methoxy and ethoxy and the SiOH group.
  • crosslinkable polyorganosiloxanes (A2) it is possible to use, for example: (A2-1): Substantially linear alkoxy- and / or SiOH-end-stopped polyorganosiloxanes having a content of T and Q units of less than 5 mol%.,
  • the alkoxy or SiOH content of the individual polyorganosiloxanes (A2-1), (A2-2) and (A2-3) used may range from 0.004 mmol / g to 12 mmol / g (0.03-20 mole%). Reactive group-containing sigglig of all Si units).
  • the alkoxy or SiOH content is expediently in the sum of 0.03-2 mol%. That is, for example, if only one polyorganosiloxane (A2) is used, its alkoxy or SiOH content is desirably 0.03-2 mol%, more preferably less than 2 mol%.
  • the alkoxy or SiOH contents of the individual polyorganosiloxanes outside this range can also be in the range from 0.004 mmol / g to 3 mmol / g, the sum of the weighted alkoxy or SiOH contents preferably again in the range of 0.03 - 2 mol .-% are.
  • the substantially linear alkoxy- or SiOH-terminated polyorganosiloxanes (A2-1) preferably have an alkoxy or SiOH group content of 0.1 to 0.7 mol%.
  • the polyorganosiloxanes (A2) have a viscosity of 0.02 to 70,000 Pa s, preferably from 0.5 to 20,000 Pa. s, more preferably from 0.5 to 100 Pa.s.
  • the viscosity is determined according to DIN 53 019 at 25 ° C.
  • the alkoxy-polyorganosiloxanes (A2) are preferably reaction products of tri-or tetra-alkoxysilanes with SiOH-terminated polymers catalysed by Broenstedt acids or bases.
  • the curable polyorganosiloxane composition of the invention preferably contains the component (B) as a reinforcing filler.
  • the component (B) expediently has a specific surface area of 50-400 m 2 / g, preferably 90 to 400 m 2 / g according to BET.
  • the component (B) component is optionally surface-modified, and includes, for example: All finely divided fillers, ie with particles smaller 100 microns, so that elastomeric coatings, molded articles or extrudates with increased strength can be produced without impurities due to coarse grains of the filler.
  • the mineral fillers are selected from the group of silicates, carbonates, nitrides, oxides, carbon blacks or silicas. Preferably, they are fillers which enhance the rubber-mechanical properties, e.g. fumed or precipitated silica with BET surface areas between 50 and
  • component (A) 400 rn ⁇ / g, which may also be treated on the surface, and in amounts of 0 to 300 parts by weight, preferably 10 to 50 parts, based on 100 parts by weight of component (A) can be used.
  • Fillers with BET surface areas above 50 m 2 / g permit the preparation of silicone elastomers with improved rubber-mechanical properties, ie their use makes it possible to increase the inherently low strengths of the crosslinked silicone polymers.
  • the rubber-mechanical strength and the transparency increase with, for example, pyrogenic silicas, such as Aerosil®, HDK®, Cab-o-Sil®, with their surface.
  • extender fillers such as quartz flour, diatomaceous earths, cristobalite flours, mica, aluminum oxides, Ti, Fe, Zn oxides, chalks or carbon blacks having BET surface areas of 0.2-50 m 2 / g may additionally be used. which are different from the component (C), in particular by their shape and particle size distribution.
  • filler (B) is meant the fillers, including their surface-bound hydrophobing agents or dispersants or ' Process Aids ' , which influence the interaction of the filler with the polymer, eg the thickening effect of the filler.
  • the surface treatment of the fillers is preferably a water repellency with silanes or siloxanes. It can be carried out, for example, ' in situ ' by the addition of silazanes, such as hexamethylsilazane and / or divinyltetramethyldisilazane, and water; ' in situ ' hydrophobing is preferred.
  • Fabric treating agents such as vinylalkoxysilanes such as vinyltrimethoxysilane, polyorganosiloxanediols having average siloxane chain lengths of 2-50 to provide reactive sites for the crosslinking reaction, as well as fatty acid or fatty alcohol derivatives.
  • the fillers may be partially or completely replaced by the component (A1-2) and / or (A1-3).
  • reinforcing fillers which are those having BET surface areas above 50 m 2 / g in such a way that they are hydrophobized in-situ "before or during the mixing process.
  • the curable polyorganosiloxane composition according to the invention contains 0.3-4 parts by weight of powdered polyorganosilsesquioxane (C) with an average particle size (dso) of 0.1-50 ⁇ m and preferably a particle size distribution width of (dgo - dio) / dso of ⁇ 1 , 5 per 100 parts by weight of component (A).
  • Component (C) preferably has an average particle size (d50) in the range from 0.5 to 20 ⁇ m.
  • d10, d50 and d90 are the particle diameters for the cumulative volumes of 10%, 50% and 90% in the cumulative distribution curve.
  • D50 is the mean particle size of the particles at 50% of the total volume.
  • the determination of the mean particle sizes, or the particle size distribution is carried out by light scattering (Malvern Coulter Counter or Horiba CAPA 500 in aqueous 2% dispersion methanol: water 1: 1 and ultrasound).
  • component (C) is free of unsaturated groups.
  • the invention further relates to the use of 0.4-3.5 parts by weight of a powdery polyorganosilsesquioxane (C) having substantially spherical particles and a value d50 of 0.5-20 ⁇ m in curable silicone rubber compositions for increasing the tear propagation resistance in the corresponding cured silicone rubber compositions.
  • Preferred silsesquioxanes (C) are the polyalkyl silsesquioxanes which can be prepared by controlled hydrolysis of alkyltrialkoxysilanes.
  • silsesquioxane particles mentioned are crosslinked siloxanes which are prepared, for example, by controlled hydrolysis and condensation of methyltrimethoxysilane. They have a substantially spherical shape.
  • the illustration of such spherical methylsilsesquioxane particles has been described, for example, in US Pat. No. 4,528,390. Further disclosures can be found in US 5,352,747; US 4,769,418; US 5,620,774; US 4,895,914, US 5,204,432, which discloses the applications of these particles as abrasion resistance aids, their antiblocking properties or their ability to diffuse light in transparent thermoplastics.
  • particles with different mean particle sizes can be produced, the particle size distribution of the particles produced being very narrow.
  • the particles can be prepared by these methods with average particle diameters between 0.05 and 100 microns.
  • Particularly preferred are particle size distributions with a value d50 in the range of 0.5 to 12 microns, more preferably from 0.5 to 6 microns
  • the preferred spherical particles consist of polyorganosilsesquioxanes containing R 4 -Si ⁇ 3 / 2 groups, wherein R 4 is preferably C 1 -C 18 -alkyl, more preferably methyl, ethyl, most preferably methyl, wherein the alkyl groups may be partially replaced by phenyl, vinyl, allyl or the like. R 4 is preferably methyl.
  • the most preferred polyalkylsiloxane is a polymethylsilsesquioxane prepared by hydrolysis and condensation of methyltrialkoxysilane or a partial hydrolyzate and condensate thereof in an aqueous solution of ammonia or an amine.
  • the thus prepared product is largely free of impurities such as chlorine atoms, alkaline earth metals and has excellent flow properties and a largely spherical shape, as shown in Fig. 1 or partially in Fig. 2.
  • the spherical particles of this invention also include particles consisting of a polysiloxane core having a surface layer consisting of at least one polyalkylsiloxane containing R 4 -SiO 3/2 groups wherein R 4 is C 1 -C 18 alkyl.
  • the polysiloxane may be composed of SiO 4/2 (silica gel), or any crosslinked polyorganosiloxane.
  • Preferred polyorganosiloxanes are those containing R 5 -SiO 3/2 groups. In addition, they may contain groups selected from (R 5 ) 3 SiO , 5 units, (R 5 ) 2 SiO units, and SiO 4/2 units.
  • the amount of T units (R 5 -Si ⁇ 3 / 2) of the polyorganosiloxanes in the core is preferably more than 50 mol%, the molar proportion of the methyl groups of the groups R 5 is preferably more than 80%.
  • the content of T units (R 5 -Si ⁇ 3 / 2) is more than 60 mol .-% and the molar proportion of the methyl groups is more than 90 mol .-%.
  • R 5 is selected from R 4 and aryl, alkenyl, epoxyalkyl, aminoalkyl, haloalkyl. Preferred particles of the core-shell structure composed of a SiO 4/2
  • Core and a surface layer containing R 4 -Si ⁇ 3 / 2 groups, wherein R 4 C 1 -C 18 alkyl.
  • R 4 C 1 -C 18 alkyl.
  • Examples are CH 3 SiO 3/2 coated particles of colloidal silica produced from tetraalkoxysilanes or silicates.
  • the monoalkylpolysiloxane layer is formed after separation of the particle cores in said dispersion or subsequently by spraying or the use of an auxiliary solvent to disperse or disperse the core particles using, for example, alkyltrialkoxysilane or other alkylsilanes as precursors for silsesquioxane layers of R 4 -SiO 3/2 applied.
  • Particle surface layer consists of polyalkyl siloxane containing R 4 -Si ⁇ 3 / 2
  • Groups are by hydrolysis, condensation, polymerization and / or
  • the polyorganosiloxane in the core of the spherical particles includes, for example, R 5 -SiO 3/2 groups, wherein R 5 is as defined above.
  • Such a surface layer may have a few remaining SiOH or a minority of Si-alkoxy groups.
  • the shell of the particles is prepared by hydrolysis, condensation, polymerization or crosslinking of alkylsilanes or alkylsiloxanes resulting in particles having polyalkylsiloxane as surface layers, which predominantly comprises
  • R 4 is C 1 -C 18 alkyl, preferably methyl, ethyl, in which alkyl groups may be partially replaced by phenyl, vinyl, allyl, haloalkyl or the like.
  • the content of these groups depends on the total surface area and the heat treatment after the precipitation or condensation.
  • a part of the alkyl groups of the polyalkyl siloxanes in the surface layer of the core-shell-like particles or the particles consisting solely of polyalkyl siloxanes may be replaced by phenyl or alkenyl groups, etc. They may be present in an amount of preferably less than 20 mole percent with respect to all the aliphatic organic groups of the polyalkyl siloxanes as long as the softening point is within the desired range, as explained below.
  • the polyalkylsiloxanes on the surface of the spherical particles mainly contain only alkyl groups as organic Groups for each Si atom.
  • the alkyl groups in the polyalkylsiloxanes are preferably methyl groups.
  • the sheath of the core-shell type spherical particles and the core of polymethylsilsesquioxane are composed. This means that the proportion of T units and the content of methyl groups is about 100%.
  • the most preferred polymethylsilsesquioxanes are according to the method of US 4,528,390. They are commercially available under the name Tospearl® from GE Toshiba Silicones.
  • the term surface 'as used in the description of spherical particles is, in the present invention usually the surface of the Crystalchenkugeln that are visible in the light microscope. However, in some cases, the particles have additional porosity. In these cases of the core-shell-like particles of the invention, at least the outer shell is coated with the shell material.
  • the thickness of the surface of the core-shell particles is preferably one or two molecular layers.
  • the spherical particles have substantially no functional groups on the outer surface which are identical to the reactive groups of component (A), i.e. there is preferably no reactivity between component (A) and component (C).
  • the substantially spherical particles according to component (C) should advantageously have a softening point of at least 50 0 C higher than the curing temperature of the silicone rubber composition.
  • the softening point is measured by means of a differential scanning calorimeter as T m , ie as a glass transition equilibrium point between plastic or elastic and crystalline phase.
  • the softening point, as used in the present invention is measured at a heating rate of 5 0 K per minute.
  • the particles according to component (C) should preferably have a softening point of more than 300 ° C., more preferably more than 500 ° C., and are usually insoluble in all solvents and preferably have one Refractive index of 1, 35 - 1, 5.
  • the preferred polyalkylsiloxanes used in the particles are immiscible with component (A).
  • spherical particles ' as used in the present invention means those particles that have a nearly spherical geometry when viewed microscopically.
  • the term spherical in the meaning of the present invention also includes slight deviations from the ideal spherical shape and includes, for example, ellipsoids, wherein the ratio of minimum to maximum diameter is below 0.6 (see Figures 1 and 2).
  • the preferred spherical particles have no sharp corners or breaklines (Fig. 2c) caused by grinding processes and the like on their surface.
  • the mean particle size of the spherical particles is suitably 0.1 to 50 microns, preferably 0.1 to 20 microns. Powders more than 100 ⁇ m (microns) sometimes do not give elastomers with the necessary tear strength. Preferably, the spherical particles have an average particle size of about 0.4 to about 15 microns. If you work outside the preferred range, the maximum possible higher tear propagation resistance is no longer achieved.
  • the powdery silsesquioxane (C) is used in an amount of 0.3 to 4 parts by weight, preferably 0.5 to 3 parts by weight per 100 parts by weight of the component (A). Particular preference is given to using 0.5 to 3 parts by weight of the powdered silsesquioxane per 100 parts by weight of component (A) having an average particle size (d50) of 0.2 to 12 ⁇ m and a particle size distribution width of (dgo-1). dio) / d 5 o of ⁇ 1, 1.
  • the crosslinkable silicone rubber mixture according to the invention also contains a catalyst (D).
  • Catalyst (D 1) In one embodiment, for the polymers (A1) and crosslinker (E1), ie a crosslinking reaction which crosslinks with hydrosilylation of an alkenyl group having an SiH group to form an alkylene group, this is at least one catalyst (D1), which is preferably selected from the Pt group. and / or Rh catalysts is selected. Platinum catalysts are preferred.
  • catalysts (D1) are preferably Pt (O) complexes, Pt (II) complexes or their salts or Pt (IV) complexes or their salts with ligands, such as alkenylsiloxanes, cycloalkyldienes, alkenes, halogens or pseudohalogens, carboxyl -, S-N- or P-group-containing ligands as complexing agents in catalytic amounts of 1 to 1000 ppm preferably 1-100 ppm, more preferably 1-20 ppm, based on metal in relation to the components (A) to (F ).
  • ligands such as alkenylsiloxanes, cycloalkyldienes, alkenes, halogens or pseudohalogens, carboxyl -, S-N- or P-group-containing ligands as complexing agents in catalytic amounts of 1 to 1000 ppm preferably 1-100 ppm, more preferably 1-20 ppm, based on metal
  • Rh or Ru complexes or salts such as di- ⁇ , ⁇ '-dichloro-di (1, 5-cyclooctadiene) dirhodium.
  • Rh compounds are also in J. Appl. Polym. See, 30, 1837-1846 (1985) described compounds.
  • Inhibitors in the context of the invention are all common compounds which have hitherto been used for the delay or inhibition of the hydrosilylation. Examples of such preferred inhibitors are vinylmethylsiloxanes such as e.g.
  • the catalysts (D2) should be understood as meaning all radical initiators, including those which become part of the crosslinked product. They are suitably selected from the group consisting of organic and inorganic peroxides. Preference is given to dialkyl peroxides, alkylaryl peroxides, peroxycarbonates, diaryl peroxides, for example di-tert-butyl peroxide, dicumyl peroxide, bis-2-5-di-tert-butylperoxyhexane, benzoyl peroxide, bis-2,4-dichlorobenzyl peroxide, bis-2-methylbenzoyl peroxide, Bis-4-methyl benzoyl peroxide, etc.
  • polymers (A2) catalysts (D3) are used, which allows crosslinking with the crosslinkers (E3) in the presence of water with the escape of alcohols, amines, amides, oximes. Water can also be humidity.
  • the component (D3) of the composition according to the invention is preferably at least one tin-containing catalyst or at least one titanium chelate catalyst.
  • the tin-containing catalyst is preferably an organotin compound. Particular preference is given to at least one organic tin compound of the formula
  • R 6 is selected from the group consisting of linear or branched optionally substituted dC 3 o-alkyl groups, C 5 -C 4 -cycloalkyl groups or C 6 -C 4 -aryl groups, triorganylsilyl and diorganyl (Ci-C 3 o) alkoxysilyl groups and when a plurality of substituents R 6 are present, they may be the same or different from each other, and Y is selected from the group consisting of halogen, -OR 7 , -OC (O) R 8 , -OH, -SR 9 , -NR 10 2 , -NHR 11 , -OSiR 12 3 ,
  • n-butyl mentioned in the definition of the above-mentioned organic tin compounds, linear or branched given substituted d- C ß o-alkyl groups include those having 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, iso-propyl iso-butyl, pentyl, hexyl, heptyl, ethylhexyl, octyl, decyl, undecyl, dodecyl, tridecyl, etc.
  • Preferred is butyl, hexyl or octyl.
  • the Cs-Cu- cycloalkyl groups mentioned in the definition of the aforementioned organic tin compounds include mono- or polycyclic alkyl groups such as cylopentyl, cyclohexyl, cyclohexyl-ethyl, cyclooctyl, decalinyl, hydrindanyl, bicyclo [2.2.1] heptanyl, bicyclo [2.2.2] - octanyl, bicyclo [4.2.3] nonyl etc.
  • the C 6 -C 4 -aryl groups include, for example, phenyl and naphthenyl, fluorenyl groups.
  • Examples of C6-C3i-alkylaryl groups are ToIyI, XyIyI-, 2,4-di-tert-butylphenyl groups.
  • C 2 -C 3 -alkenyl groups include vinyl, allyl, octenyl, cyclohexenylethyl, Nornbornenyl a.
  • Examples of C 1 -C 30 -alkoxy (C 1 -C 30) -alkyl groups are methoxy- or nonyloxy-substituted ethyl, butyl or hexyl groups.
  • Polyalkenyloxy groups (polyethers) include, but are not limited to, ethyl, nonyl, or stearyl mono-end-stopped polyethyleneoxy groups having a degree of polymerization of 3-20
  • Ci-Cs-alkyl C 6 -C 4 -aryl and / or C 2 -C 8 -alkenyl groups mentioned in the definition of the abovementioned organic tin compounds, reference is made to the explanations of these substituent groups in the case of the crosslinkable polyorganosiloxanes.
  • Preferred tin compounds include dioctyltin oxide, dibutyltin oxide, dimethyltin oxide, dimethyltin dichloride, dibutyltin dichloride, tributyltin chloride, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin maleate, Dibutylzinndihexanoat, dibutyltin dioctoate, Dioctylzinndioctoat, dioctyltin Dioctyldibutoxystannan and / or Tributylethoxystannan.
  • tin-containing catalysts reaction products of the above-described organotin compounds with one or more silicic acid esters, polysilicic acid esters, organylalkoxysilane and / or their respective partial hydrolysates can be used.
  • the amount of the tin-containing catalyst in the polyorganosiloxane composition of the present invention is preferably at least about 0.2% by weight, more preferably at least about 0.3% by weight, based on (A2) to F2).
  • the proportion is about 5% by weight, preferably about 4% by weight, resulting in the following ranges of preference: from 0.2% by weight to 5% by weight, more preferably from 0.3% by weight to 4% Wt .-%, each based on the total amount of the composition of the invention.
  • the titanium chelate catalysts which can be used according to the invention are known per se and are described, for example, in US 4,680,364 US 3,689,454, US 3,334,067, DE 19 507 416 and US 4,438,039.
  • the amount of the tin-containing catalyst or titanium chelate catalyst in the polyorganosiloxane composition of the present invention is preferably at least about 0.2% by weight, more preferably at least about 0.3% by weight. At most, the proportion is about 5% by weight, preferably about 4% by weight, resulting in the following ranges of preference: from 0.2% by weight to 5% by weight, more preferably from 0.3% by weight to 4% Wt .-%, each based on the total amount of the composition of the invention.
  • Component (E) of the compositions according to the invention are crosslinkers, ie substances which, between the reactive groups on the polyorganosiloxanes (A), bring about a bond to form chemical bonds, such as Si-O-Si or Si-C-Si or CC ,
  • the crosslinkers (E) are accordingly selected from the group of polyorganohydrogensiloxanes (E1) each having at least 2 SiH unit per molecule, silanes or siloxanes (E2) which have groups which are reactive toward SiOH or Si-alkoxy.
  • the organohydrogensiloxanes according to component (E1) are preferably selected from linear, branched or cyclic polysiloxanes which may have the following siloxy units: 1
  • R 1 may be the same or different and is selected from the group consisting of
  • Hydrogen a straight-chain, branched or cyclic alkyl radical with up to 12
  • Carbon atoms which may be optionally substituted with an aromatic group, - a straight-chain, branched or cyclic alkenyl radical having up to
  • R 1 from different siloxy units together form a straight-chain, branched or cyclic alkanediyl radical having 2 to 12 carbon atoms between two silicon atoms, with the proviso that on average at least SiH groups are present per molecule.
  • the organohydrogensiloxanes (E1) are preferably linear, cyclic or branched polyorganosiloxanes of at least one of the units Q ' , T ' , D ' and M ' , which preferably contain MeHSiO or Me2HSiOo, 5 units in addition to optionally other organosiloxy units, preferably dimethylsiloxy units can.
  • These siloxanes are preferably liquid or siloxane-soluble at room temperature, ie they preferably have less than 1000 siloxy units.
  • the chain length for chains of these predominantly consisting of MeHSiO units siloxanes is preferably from 3 to 200, more preferably from 15 to 60 siloxy units.
  • the preferred representatives of component (E1) are trimethyl- or hydrogen-dimethylsiloxy-terminated poly (methylhydrogendiorganosiloxanes).
  • organohydrogensiloxanes (E1) include linear or cyclic organohydrogensiloxanes of the following formulas:
  • the polyorganosiloxane may hydrogensiloxane (E1) and [(Me 2 HSiOi / 2) 4Si ⁇ 4 / 2] or its [(Me 2 HSiO 0, 5) o 2-4 SiO 4/2] i-5oo ,
  • the organohydrogensiloxanes (E1) can be prepared by methods known per se, e.g. acid equilibration or condensation (as described, for example, in U.S. 5,536,803 column, lines 43-58).
  • the polyorganohydrogensiloxanes (E1) can also be reaction products which have arisen from a hydrosilylation of organohydrogensiloxanes with alkenyl-group-containing siloxanes in the presence of the catalysts (D1). This results in alkanediyl-bridged organohydrogensiloxanes.
  • they can also be reaction products which result from the condensation of, for example, organohydrogenalkoxysiloxanes with silicon compounds bearing organofunctional groups, as described in US Pat. No. 4,082,726, for example, column 5 u. 6 discloses.
  • the SiH content of the polyorganohydrogensiloxanes (E1) is between 0.1 and 16 mmol / g (0.67-100 mol% relative to the SiH to all Si units), preferably between 0.05 and 15 mmol / g (3.5-94 mol%).
  • SiH content is determined here by 1 H-NMR, see AL Smith (Ed.): The Analytical Chemistry of Silicones, J. Wiley & Sons 1991 Vol. 112 p. 356 et seq. In Chemical Analysis ed. By JD Winefordner.
  • the preferred amount of organohydrogensiloxanes (E1) is 0.2 to 50 parts by weight based on 100 parts by weight of component (A).
  • the organohydrogensiloxanes (E1) suitably have a viscosity of from 1 to 50,000 mPa.s at 25 ° C., preferably the viscosity is from 5 to 1000 mPa.s. or they are below 90 0 C melting solids with melt viscosities of this range or solids which are soluble in conventional solvents or siloxane polymers.
  • crosslinkers (E1) comprises polyorganosiloxanes with arylsiloxy units. These are preferably diarylsiloxy, methylaryl-siloxy or trifunctional arylsiloxy units, particular preference is given to diphenylsiloxy and 2-phenylethylenemethylsiloxy / (styryl) (methyl) siloxy units in order, for example, to improve adhesion to substrates.
  • the molar ratio of the reactive groups of (A1) to those in the component (E1) is 1: 0.8-10, more preferably 1: 1.55 Si-alkenyl to SiH. This results in a broad weight ratio for component (A) to (E1), since the concentrations of reactive groups in (A) and (E) can be chosen within wide limits.
  • the polyorganosiloxane or silane (E2) is preferably a linear, branched or cyclic polysiloxane which may have the following siloxy units:
  • Preferred polyorganosiloxanes or silanes (E2) include:
  • V is selected from methoxy, ethoxy, benzamido, butanone oximo, acetamido, mono- and di-C 1 -C -alkylamino and acetoxy
  • W is preferably alkyl, preferably methyl.
  • the alkoxysilane / siloxane crosslinker is at least one member selected from the group consisting of tetraethoxysilane, polysilicic acid esters, vinyltrialkoxysilanes, methoxyethyltrialkoxysilanes, methyltrialkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane and / or vinyltriethoxysilane.
  • the crosslinkable silicone rubber mixtures according to the invention furthermore optionally contain at least one adjuvant (F), such as, for example, the crosslinking agent.
  • adjuvant such as, for example, the crosslinking agent.
  • velocity-controlling substances such as, for example, the above-mentioned inhibitors (F1), phenylsiloxane oils which provide self-lubricating vulcanizates, for example copolymers of dimethylsiloxy and diphenylsiloxy or methylphenylsiloxy groups and polysiloxanes with methylphenylsiloxy groups having a viscosity of preferably 0.1, 10 Pa.
  • the amount of the excipients is preferably 0 to 30, more preferably 0.01 to 15 parts by weight based on 100 parts by weight of the component (A), and is preferably less than 13% by weight based on the total amount of the rubber mixture.
  • the curable polyorganosiloxane composition contains:
  • a reinforcing filler B having a specific surface area of 90-400 m 2 / g, - 0.4 - 3.5 parts by weight of a powdered polyorganosilsesquioxane (C) with spherical particles and a average particle size d50 of 0.5-15 ⁇ m and preferably a particle size distribution width of (d 9 o-dio) / d 5 o of ⁇ 1, 2,
  • auxiliaries optionally 0.001 to 30 parts by weight of auxiliaries (F1).
  • the invention further provides a process for the preparation of the crosslinkable silicone rubber mixtures, which comprises mixing the components (A), (B), (D) and optionally the components (E) to (F) and the component (C) optionally in Mixture with component (A) to produce the total mixture.
  • the mixing of the components can preferably take place with the mixers suitable for high-viscosity pastes, such as kneaders, two-roll stands, extruders, single or twin-screw mixers, dissolvers or planetary mixers under an inert gas atmosphere.
  • component (C) is preferably added in admixture with at least one part of component (A) to the mixture of the other components, this can preferably be done with a random mixer or a two-roll mill.
  • Component (C) is preferably used in the form of a so-called masterbatch, preferably in admixture with component (A), wherein component (C) is present in an amount of at least 10% by weight.
  • the invention further relates to a process for the preparation of cured polyorganosiloxane compositions which comprises curing the polyorganosiloxane composition according to the invention.
  • the invention furthermore relates to a crosslinked or cured silicone rubber mixture which is obtained by crosslinking (A1) with (E1) + (D1), or (A1) + (D2) or vulcanizing the crosslinkable silicone rubber mixtures according to the invention.
  • crosslinking or vulcanization takes place in a temperature range from 0 to 300 ° C. with or without light.
  • the subject of a second embodiment are crosslinkable silicone rubber mixtures which give crosslinked silicone elastomers by crosslinking (A2) + (E2) + (D3), (E3) or, on admission of atmospheric moisture or mixing in of water.
  • crosslinking or vulcanization takes place in a temperature range from 0 to 100 ° C. with or without light.
  • the crosslinking may optionally be carried out under normal pressure, vacuum to 20 mbar or overpressure in the presence of ambient air.
  • Overpressure in the presence of ambient air includes injection molding and crosslinking a substrate surface under spray conditions, ie up to 300 bar based on the unit area of the molding.
  • the invention further relates to the use of the curable polyorganosiloxan composition for the production of moldings and extrudates, as well as the use of the cured polyorganosiloxane compositions as
  • crosslinkable silicone rubber blends are generally linear
  • Rubbers with which elastomeric shaped bodies, extrudates or coatings can be produced Rubbers with which elastomeric shaped bodies, extrudates or coatings can be produced.
  • ECH ethynylcyclohexanol
  • E1 trimethylsilyl-terminated methylhydrogensiloxane
  • a Pt complex compound (D1) 0.0068 parts by weight of a Pt complex compound (D1) are mixed with tetramethyltetravinyl cyclotetrasiloxane ligands dissolved in a vinylendgestoppten polydimethylsiloxane viscosity 200 mPa.s (Pt content: 15 wt .-%).
  • GM 1 reactive mixture GM 1, which is processed before the end of about 7 days 25 0 C storage to elastomer parts ("pot life").
  • the data given for the elastomer test relate to the elastomer obtained, which does not require so-called post-curing, ie. a hot air treatment after vulcanization, have experienced.
  • the preparation of the basic mixture II is carried out as in the preparation of GM I, the following modified amounts were used: (A1 -1) 27 parts by weight (viscosity 10 Pa.s),
  • the mixture is then treated with the GM II as with the masterbatch GM I. After mixing the silsesquioxane powder in the amounts shown in the table, the mixtures Examples 9- 12, which were cured as described above to test plates.
  • Base mix GM III for Examples 17-19 In a kneader with Z-vanes, 73 parts by weight of dimethylvinylsiloxy end-stopped polydimethylsiloxane (A1-1) are mixed with 0.006 mmol / g of vinyl groups having a viscosity of 30,000 Pa. s (25 0 C), 1, 5 parts by weight of hexamethyldisilazane, 3 parts by weight of dimethylhydroxy endstopptes polydimethylsiloxane having a viscosity of 0.1 Pa.
  • 35 0 C is mixed - for the preparation of the following Examples 17-19 the amounts of Silsesquioxanpulver (C) specified to be of a two-roll mill in these respective parent mixture at 25th
  • the finished mixtures corresponding to the examples are converted into mold cavities for the production of elastomer test plates.
  • the silicone rubbers are cured there for 10 min at 175 0 C and about 1- 20 bar to 2 mm and 6 mm plates, from which one then punched out the standard test specimens for the rubber mechanical assessment.
  • the specified data of the elastomer test refer to elastomer, the so-called. Have experienced night annealing. Tab .1
  • Table 1 shows the influence of the various poly (methylsilsesquioxane) powders on the tear strength (WRF) and other properties.
  • the tear propagation strength increases at the latest with 0.5 parts by weight of poly (methylsilsesquioxane) powder. Above 4 parts by weight, surprisingly, a decrease in tear propagation resistance is again observed, so that the maximum effect on the tear strength ranges between approximately 0.3 to 4 parts by weight (C).
  • Table 2 shows the influence of the various poly (methylsilsesquioxane) powders on the tear strength (WRF) and other properties.
  • the tear propagation strength increases at the latest with 0.5 parts by weight of poly (methylsilsesquioxane) powder. Above 4 parts by weight, surprisingly, a decrease in tear propagation resistance is again observed, so that the maximum effect on the tear strength ranges between approximately 0.3 to 4 parts by weight (C).
  • Table 2 shows the influence of the various poly (methylsilsesquioxane) powders on the tear strength (WRF)
  • Acematt® OK 412 from Degussa Company Agglomerates of primary particles> 0.3 ⁇ m, pearl-like, non-spherical agglomerates of spherical primary particles, similar to Fig.5.
  • the comparative examples 10 V to 12 V of Table 2 show that other fillers which have no spherical particles and a different particle size distribution do not have the desired influence on the tear propagation resistance.
  • Table 3 shows on the one hand that at least 0.25 parts by weight of poly (methylsilsesquioxane) powder must be used in order to increase the tear propagation resistance.
  • Tab. 4 shows that poly (methylsilsesquioxane) powders according to the invention can increase the tear propagation resistance in other silicone rubbers with high-viscosity polymers or long polymer chains if used together in another crosslinking system with other crosslinking structures and the reactive groups with peroxide radically instead of one Platinum-catalyzed hydrosilylation be crosslinked in the presence of SiH siloxanes.

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Abstract

La présente invention concerne des compositions de caoutchouc de silicone contenant une matière de charge sous forme de poudre qui permet d'augmenter la résistance à la propagation du déchirement.
PCT/EP2006/067633 2005-10-22 2006-10-20 Composition de caoutchouc de silicone presentant une meilleure resistance a la propagation du dechirement WO2007045692A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008109865A2 (fr) * 2007-03-07 2008-09-12 Saint-Gobain Performance Plastics Corporation Articles contenant des compositions de silicone et procédés de fabrication de tels articles
WO2009006407A1 (fr) * 2007-06-29 2009-01-08 Saint-Gobain Performance Plastics Corporation Compositions de silicone, articles, et procédés de préparation de ces compositions de silicone
WO2018015816A1 (fr) * 2016-07-22 2018-01-25 Creganna Unlimited Company Gaines de câbles en silicone lubrifiantes et ensembles câbles formés à partir de celles-ci

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0420585A2 (fr) * 1989-09-28 1991-04-03 Shin-Etsu Chemical Co., Ltd. Composition de caoutchouc de silicone thermodurcissable
US5415912A (en) * 1991-09-06 1995-05-16 Toshiba Silicone Co., Ltd. Pressure-sensitive adhesive composition
US20020122946A1 (en) * 2001-03-02 2002-09-05 Kuck Valerie Jeanne Adherent silicones

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0420585A2 (fr) * 1989-09-28 1991-04-03 Shin-Etsu Chemical Co., Ltd. Composition de caoutchouc de silicone thermodurcissable
US5415912A (en) * 1991-09-06 1995-05-16 Toshiba Silicone Co., Ltd. Pressure-sensitive adhesive composition
US20020122946A1 (en) * 2001-03-02 2002-09-05 Kuck Valerie Jeanne Adherent silicones

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008109865A2 (fr) * 2007-03-07 2008-09-12 Saint-Gobain Performance Plastics Corporation Articles contenant des compositions de silicone et procédés de fabrication de tels articles
WO2008109865A3 (fr) * 2007-03-07 2009-11-05 Saint-Gobain Performance Plastics Corporation Articles contenant des compositions de silicone et procédés de fabrication de tels articles
US7939615B2 (en) 2007-03-07 2011-05-10 Saint-Gobain Performance Plastics Corporation Articles containing silicone compositions and methods of making such articles
WO2009006407A1 (fr) * 2007-06-29 2009-01-08 Saint-Gobain Performance Plastics Corporation Compositions de silicone, articles, et procédés de préparation de ces compositions de silicone
JP2010530924A (ja) * 2007-06-29 2010-09-16 サンゴバン・パフォーマンス・プラスティックス・コーポレーション シリコーン組成物、物品およびかかるシリコーン組成物を製造する方法
US7951894B2 (en) 2007-06-29 2011-05-31 Saint-Gobain Performance Plastics Corporation Silicone compositions, articles, and methods of making such silicone compositions
WO2018015816A1 (fr) * 2016-07-22 2018-01-25 Creganna Unlimited Company Gaines de câbles en silicone lubrifiantes et ensembles câbles formés à partir de celles-ci

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