WO2020132846A1 - Compositions de caoutchouc de fluorosilicone - Google Patents

Compositions de caoutchouc de fluorosilicone Download PDF

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WO2020132846A1
WO2020132846A1 PCT/CN2018/123335 CN2018123335W WO2020132846A1 WO 2020132846 A1 WO2020132846 A1 WO 2020132846A1 CN 2018123335 W CN2018123335 W CN 2018123335W WO 2020132846 A1 WO2020132846 A1 WO 2020132846A1
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composition
amount
accordance
fluorosilicone rubber
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PCT/CN2018/123335
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Shaohui Wang
Yusheng CHENG
Rui Wang
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Dow Silicones Corporation
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Priority to PCT/CN2018/123335 priority Critical patent/WO2020132846A1/fr
Priority to CN201880099764.7A priority patent/CN113166547B/zh
Publication of WO2020132846A1 publication Critical patent/WO2020132846A1/fr

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    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica

Definitions

  • This disclosure relates to fluorosilicone elastomeric materials which may be used in damping applications and to the fluorosilicone rubber compositions from which they are cured.
  • Silicone elastomeric materials are well known as such damping materials for use in systems and applications requiring vibration damping and/or noise reduction, e.g. to decrease vibrations and noise transmitted from engines and/or machinery e.g. power and suspension devices and/or other machine/engine parts. They may also be used to limit the effect of shocks transmitted from foundations in buildings.
  • silicone elastomeric materials can be used to dampen vibrations in macro situations e.g. in automotive applications, e.g. road vehicles and trains, aircraft applications, industrial machinery applications, construction applications, i.e. building and bridge structures and/or they can be used in “micro” situations e.g. electronics and music/acoustic systems.
  • automotive applications e.g. road vehicles and trains, aircraft applications, industrial machinery applications, construction applications, i.e. building and bridge structures and/or they can be used in “micro” situations e.g. electronics and music/acoustic systems.
  • vibration absorbers e.g. in automotive applications, e.g. road vehicles and trains, aircraft applications, industrial machinery applications, construction applications, i.e. building and bridge structures and/or they can be used in “micro” situations e.g. electronics and music/acoustic systems.
  • vibration absorbers e.g. in automotive applications, e.g. road vehicles and trains, aircraft applications, industrial machinery applications, construction applications, i.e. building and
  • Silicone elastomeric materials suitable to function as vibration dampers need to have the ability to support weight, e.g. of an engine/machine part, imparting heat resistance to high temperatures (>100°C. ) generated in and around engines during e.g. the running of a vehicle or machine whilst providing durability against repetitive loading.
  • Silicone elastomeric materials are used in anti-vibration systems for e.g. automotive engine mounts, because of their excellent strength, fatigue resistance, high resilience and low level of strain sensitivity particularly at low temperatures but one of the most important aspects is that they can function over wide temperature ranges whilst e.g. vulcanized natural rubbers tends to degrade when used in high temperature environments (>100°C. ) which is a critical failing in the case of the latter given many of today’s engines etc. seek to function in environments at significantly greater temperatures than 100°C in order to improve engine efficiency.
  • SBR styrene butadiene rubber
  • BR polybutadiene rubber
  • CR chloroprene rubber
  • NBR nitrile butadiene rubber
  • IIR isobutylene isopropylene rubber
  • EPDM ethylene propylene diene monomer
  • silicone rubber since when the silicone rubber is mixed with the above-mentioned rubbers, the silicone rubber shows excellent physical properties such as a heat-resisting property, ageing resistance and durability in comparison with other rubbers.
  • Known methods for improving the vibration damping characteristics of a fluorosilicone elastomeric material obtained by hydrosilylation-induced curing in the presence of a platinum catalyst include those in which the content of silicon atom-bonded alkenyl groups in an alkenyl group-containing polydiorganosiloxane is reduced, an uncross-linked polydiorganosiloxane is added, and the content of the cross-linking agent in this composition is reduced or the like, yielding a slightly cured, low-hardness silicone gel.
  • Such low-hardness silicone gels tend to have poor shape retention properties because the gel material is very soft with having a very low mechanical strength.
  • a lack of shape retention in the case of many vibration damping applications is clearly a major problem and as such these gel materials are only suitable for limited applications and/or situations. Whilst a gel has viscoelastic properties it is it’s viscous behaviour which is the main contributor when used in damping applications and as such whilst it has acceptable damping properties it does not provide the elastic support needed and as such can’t be used in many if not most damping situations. Hence, for many applications alternative damping materials are required.
  • a fluorosilicone-based vibration damping rubber composition which, upon cure, provides a fluorosilicone elastomeric material having excellent physical properties for damping vibration.
  • a fluorosilicone rubber damping material having a tan delta in the tensile mode of > 0.12 in a temperature range of from -30°C to +80°C, which material is the cured product of a composition comprising
  • a curing agent selected from either (i) a peroxide curing agent in an amount of from 0.3 to 3%wt. or (ii) a hydrosilylation cure package comprising an organohydrogenpolysiloxane having 3 or more silicon-bonded hydrogen atoms per molecule and a hydrosilylation catalyst or a mixture thereof;
  • a fluorosilicone rubber damping material having a tan delta in the tensile mode of > 0.12 in a temperature range of from -30°C to +80°C, obtainable or obtained by curing a composition comprising
  • a curing agent selected from either (i) a peroxide curing agent in an amount of from 0.3 to 3%wt. or (ii) a hydrosilylation cure package comprising an organohydrogenpolysiloxane having 3 or more silicon-bonded hydrogen atoms per molecule and a hydrosilylation catalyst or a mixture thereof; and optionally
  • the total weight %of the composition is always 100%wt. Tan delta was measured in the tensile mode using an RSA-G2 dynamic mechanical analysis testing apparatus from TA Instruments at a frequency of 1Hz and at 0.05%dynamic strain over a range of temperatures at a 2°C per minute rate. Values of vinyl content are the cumulative totals of the weight %of vinyl groups in the composition, i.e. typically in gums/polymers, determined using quantitative infra-red spectroscopy in accordance with ASTM E168. Values of silicon bonded hydrogen atoms in weight %of the composition were also determined by infra-red spectroscopy in accordance with ASTM E168.
  • a curing agent selected from either (i) a peroxide curing agent in an amount of from 0.3 to 3%wt. or (ii) a hydrosilylation cure package comprising an organohydrogenpolysiloxane having 3 or more silicon-bonded hydrogen atoms per molecule and a hydrosilylation catalyst or a mixture thereof;
  • a dilatant material in an amount of from 5 to 40%wt, which upon cure provides high damping performance fluorosilicone rubber damping material having a tan delta in the tensile mode of > 0.12 in a temperature range of from -30°C to +80°C.
  • a curing agent selected from either (i) a peroxide curing agent in an amount of from 0.3 to 3%wt. or (ii) a hydrosilylation cure package comprising an organohydrogenpolysiloxane having 3 or more silicon-bonded hydrogen atoms per molecule and a hydrosilylation catalyst or a mixture thereof;
  • a structure comprising or consisting of a fluorosilicone rubber damping material having a tan delta in the tensile mode of > 0.12 in a temperature range of from -30°C to +80°C, obtainable or obtained by curing a composition comprising
  • a curing agent selected from either (i) a peroxide curing agent in an amount of from 0.3 to 3%wt. or (ii) a hydrosilylation cure package comprising an organohydrogenpolysiloxane having 3 or more silicon-bonded hydrogen atoms per molecule and a hydrosilylation catalyst or a mixture thereof;
  • a fluorosilicone rubber composition which cures to form a fluorosilicone damping material having a tan delta in the tensile mode of > 0.12 in a temperature range of from -30°C to +80°C, the composition comprising
  • a curing agent selected from either (i) a peroxide curing agent in an amount of from 0.3 to 3%wt. or (ii) a hydrosilylation cure package comprising an organohydrogenpolysiloxane having 3 or more silicon-bonded hydrogen atoms per molecule and a hydrosilylation catalyst or a mixture thereof;
  • the fluorosilicone rubber material shows significant higher tan delta (otherwise referred to as damping factor or loss factor) than non-fluorinated silicone rubber over the wide temperature range of from -30°C to +80°C, the tan delta of general silicone rubber is in the range of 0.05 ⁇ 0.1, whereas the fluorosilicone rubber material described herein has a tan delta value of ⁇ 0.12, alternatively ⁇ 0.14, alternatively from 0.14 to 0.5, alternatively 0.14 to 0.4.
  • the composition described above is considered to provide a fluorosilicone rubber material which has a high damping performance i.e. it not only yields the above but also a rubber with comparatively higher hardness (i.e. Shore A hardness > 10) and generally a higher tensile strength (>4MPa in most cases) than is usually seen with damping gel materials. Furthermore the fluorosilicone rubber material is vibration damping whilst possessing high shape retention capabilities.
  • the viscoelastomeric product of the above composition provides excellent physical properties such as heat-resistance, ageing and durability in comparison with organic based rubber materials, as well as being sufficiently elastomeric to retain its shape, unlike previously discussed silicone gel.
  • the present composition once cured provides viscoelastomeric characteristics but is far more elastomeric and far less viscous in nature compared to the gels and as such has additional tensile strength compared to the gels enabling the cured product of the present composition to be sufficiently strong and resistant to damaging stress in real applications. Whilst not being bound by current theories it is the viscous properties that provide damping while the elasticity of the product will resist permanent deformation and retain its original shape. The crosslinking degree of gel is much lower than a cured rubber.
  • Fluorinated polydiorganosiloxane gum (a) comprises units having the formula
  • each R may be the same or different and denotes a branched or linear fluoroalkyl radical having from 1 to 8 carbon atoms;
  • each Z may be the same or different and denotes a divalent alkylene group containing at least two carbon atoms, a hydrocarbon ether or a hydrocarbon thioether.
  • Each R” radical is linked to a silicon atom via a Z group,
  • each R' is the same or different and denotes an optionally substituted saturated or unsaturated silicon-bonded, monovalent hydrocarbon group
  • Each gum (a) contains at least two alkenyl groups per molecule.
  • Substituted means one or more hydrogen atoms in a hydrocarbon group has been replaced with another substituent.
  • substituents include, but are not limited to, halogen atoms such as fluorine, chlorine, bromine, and iodine; halogen atom containing groups such as perfluorobutyl, trifluoroethyl, nonafluorohexyl and chloromethyl; oxygen atoms; oxygen atom containing groups such as (meth) acrylic and carboxyl; nitrogen atoms; nitrogen atom containing groups such as amino-functional groups, amido-functional groups, and cyano-functional groups; sulphur atoms; and sulphur atom containing groups such as mercapto groups.
  • saturated R' radicals include alkyl radicals, such as methyl, ethyl, propyl, isopropyl, butyl, hexyl, 2-ethylhexyl, octyl, isooctyl and decyl.
  • alkyl radicals such as methyl, ethyl, propyl, isopropyl, butyl, hexyl, 2-ethylhexyl, octyl, isooctyl and decyl.
  • all of the R' radicals in the fluorosilicone polymer are methyl radicals.
  • a when a is 0, on average about at least one R’ per unit contains at least one carbon –fluorine bond alternatively when a is 0, at least one R’ per unit is CF 3 –.
  • R denotes a fluoroalkyl radical having at least one carbon atom, alternatively having from 1 to 8 carbon atoms, over the complete range of from 5 to 100 mol%fluorinated siloxane units.
  • Each fluoroalkyl radical present has at least one –C-F bond.
  • the R” radicals can be identical or different and can have a normal or a branched structure.
  • at least some, most preferably at least 50%of the fluoroalkyl groups are perfluoroalkyl groups.
  • Examples thereof include CF 3 -, C 2 F 5 -, C 3 F 7 -, such as CF 3 CF 2 CF 2 -or (CF 3 ) 2 CF-, C 4 F 9 -, such as CF 3 CF 2 CF 2 -, (CF 3 ) 2 CFCF 2 -, (CF 3 ) 3 C-and CF 3 CF 2 (CF 3 ) CF-; C 5 F 11 such as CF 3 CF 2 CF 2 CF 2 -, C 6 F 13 -, such as CF 3 (CF 2 ) 4 CF 2 -; C 7 F 14 -, such as CF 3 (CF 2 CF 2 ) 3 -; and C 8 F 17 -.
  • Each perfluoroalkyl radical is bonded to a silicon atom by way of Z, a divalent spacing radical containing carbon, hydrogen and, optionally, oxygen and/or sulphur atoms which are present as ether and thioether linkages, respectively.
  • the sulphur and oxygen atoms, if present, must be bonded to only carbon atoms.
  • Each Z radical can have any structure containing the elements listed; however, each is preferably an alkylene radical (i.e. an acyclic, branched or unbranched, saturated divalent hydrocarbon group) .
  • alkylene radicals include -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH (CH 3 ) CH 2 -, (CH 2 CH 2 ) 2 -and -CH (CH 3 ) CH 2 CH 2 -.
  • each fluorinated radical, R” Z preferably has the formula R” CH 2 CH 2 –, i.e. Z is an ethylene group.
  • the fluorinated polydiorganosiloxane gum (a) additionally comprises a proportion, preferably of less than 25%, more preferably less than 15%of the total number of units per molecule of non-fluorinated siloxane units having the formula
  • Each R”’ contains no fluorine (and therefore R”’ cannot contain any of the fluoro containing substituents mentioned in the general definition of “substituted groups” above.
  • R denotes an optionally substituted saturated or unsaturated silicon-bonded, monovalent hydrocarbon group.
  • each R may be the same or different and are selected from C1 to C10 alkyl groups; alkenyl groups such as vinyl or allyl groups; and/or aryl groups such as such as phenyl, tolyl, benzyl, beta-phenylethyl, and styryl.
  • at least two R”’ substituents per molecule are alkenyl groups, most preferably vinyl groups.
  • the fluorinated polydiorganosiloxane gum (a) contains at least two alkenyl groups per molecule, each having from 2 to 8 carbon atoms, preferably vinyl groups.
  • fluorinated polydiorganosiloxane gum (a) examples include copolymers of dimethylsiloxy units and (3, 3, 3-trifluoropropyl) methylsiloxy units; copolymers of dimethylsiloxy units, (3, 3, 3-trifluoropropyl) methylsiloxy units, and vinylmethylsiloxy units; copolymers of (3, 3, 3-trifluoropropyl) methylsiloxy units and vinylmethylsiloxy units; and poly (3, 3, 3-trifluoropropyl) methylsiloxane.
  • the terminal group on the molecular chains thereof being selected from a trimethylsiloxy group, vinyldimethylsiloxy group, dimethylhydroxysiloxy group, and (3, 3, 3-trifluoropropyl) methylhydroxysiloxy group.
  • fluorinated polydiorganosiloxane gum (a) may be chain extended.
  • Any suitable form of chain extender may be utilised but one particularly preferred for component (A) herein is a chain extended polymer having pendant alkenyl groups only at the location of the chain extension.
  • the alkenyl groups are preferably vinyl groups.
  • Such polymers can be prepared by polymerizing a hydroxyl end-blocked trifluoropropylmethylsiloxane in the presence of an alkylalkenyldi (N-alkylacetamido) silane such as described in EP 0542471, the contents of which are hereby incorporated.
  • the fluorinated polydiorganosiloxane gum (a) typically has a viscosity of at least 1,000,000 mPa. s at 25°C. However, because of the difficulty in measuring viscosity above these values, gums tend to be described by way of their Williams plasticity values in accordance with ASTM D-926-08 as opposed to by viscosity.
  • the fluorinated polydiorganosiloxane gum (a) has a viscosity resulting in a Williams plasticity of at least 30mm/100 measured in accordance with ASTM D-926-08, alternatively at least 50mm/100 measured in accordance with ASTM D-926-08, alternatively alternatively at least 100mm/100 measured in accordance with ASTM D-926-08, alternatively at least 125mm/100, alternatively from 125mm/100 to 400mm/100measured in accordance with ASTM D-926-08.
  • Component (b) of the composition is a reinforcing filler such as finely divided silica.
  • Silica and other reinforcing fillers (b) are often treated with one or more known filler treating agents to prevent a phenomenon referred to as “creping” or “crepe hardening" during processing of the curable composition.
  • Finely divided forms of silica are preferred reinforcing fillers (b) .
  • Colloidal silicas are particularly preferred because of their relatively high surface area, which is typically at least 50 m 2 /g (BET method in accordance with ISO 9277: 2010) .
  • Fillers having surface areas of from 50 to 450 m 2 /g (BET method in accordance with ISO 9277: 2010) , alternatively of from 50 to 300 m 2 /g (BET method in accordance with ISO 9277: 2010) are typically used.
  • colloidal silicas as described herein may be can be provided in the form of precipitated silica and/or fumed silica. Both types of silica are commercially available.
  • the amount of reinforcing filler (b) e.g. finely divided silica in the composition herein is from 5 to 40%wt, alternatively of from 5 to 30%wt. In some instances, the amount of reinforcing filler may be of from 7.5 to 30%wt alternatively from 10 to 30%wt. based on the weight of the composition.
  • reinforcing filler (b) When reinforcing filler (b) is naturally hydrophilic (e.g. untreated silica fillers) , it is typically treated with a treating agent to render it hydrophobic. These surface modified reinforcing fillers (b) do not clump, and can be homogeneously incorporated into fluorinated polydiorganosiloxane gum (a) as the surface treatment makes the fillers easily wetted by fluorinated polydiorganosiloxane gum (a) . This results in improved room temperature mechanical properties of the compositions and resulting cured materials cured therefrom.
  • fluorinated polydiorganosiloxane gum (a) This results in improved room temperature mechanical properties of the compositions and resulting cured materials cured therefrom.
  • the surface treatment may be undertaken prior to introduction in the composition or in situ (i.e. in the presence of at least a portion of the other ingredients of the composition herein by blending these ingredients together at room temperature or above until the filler is completely treated.
  • untreated reinforcing filler (b) is treated in situ with a treating agent in the presence of fluorinated polydiorganosiloxane gum (a) , whereafter mixing a silicone rubber base composition is obtained, to which other ingredients may be added.
  • reinforcing filler (b) may be surface treated with any low molecular weight organosilicon compounds disclosed in the art applicable to prevent creping of organosiloxane compositions during processing.
  • organosilanes, polydiorganosiloxanes, or organosilazanes e.g. hexaalkyl disilazane, short chain siloxane diols or fatty acids or fatty acid esters such as stearates to render the filler (s) hydrophobic and therefore easier to handle and obtain a homogeneous mixture with the other ingredients.
  • silanol terminated trifluoropropylmethyl siloxane examples include but are not restricted to silanol terminated trifluoropropylmethyl siloxane, silanol terminated ViMe siloxane, tetramethyldi (trifluoropropyl) disilazane, tetramethyldivinyl disilazane, silanol terminated MePh siloxane, liquid hydroxyl-terminated polydiorganosiloxane containing an average from 2 to 20 repeating units of diorganosiloxane in each molecule, hexaorganodisiloxane, hexaorganodisilazane.
  • a small amount of water can be added together with the silica treating agent (s) as processing aid.
  • composition as described herein is cured using a curing agent selected from either (i) a peroxide curing agent in an amount of from 0.3 to 3%wt. and/or (ii) a hydrosilylation cure package comprising an organohydrogenpolysiloxane having 3 or more silicon-bonded hydrogen atoms per molecule and a hydrosilylation catalyst.
  • a curing agent selected from either (i) a peroxide curing agent in an amount of from 0.3 to 3%wt. and/or (ii) a hydrosilylation cure package comprising an organohydrogenpolysiloxane having 3 or more silicon-bonded hydrogen atoms per molecule and a hydrosilylation catalyst.
  • the curing agent may be (i) a peroxide curing agent or mixtures of different types of peroxide curing agents.
  • the or each peroxide curing agent (i) may be any of the well-known commercial peroxides used to cure fluorosilicone elastomer compositions.
  • the amount of organic peroxide used is determined by the nature of the curing process, the organic peroxide used, and the fluorosilicone elastomer base used. These considerations are well-known to those skilled in the art of fluorosilicone elastomers.
  • the amount of peroxide curing agent utilised in a composition as described herein is from 0.3 to 3%wt., alternatively 0.3 to 2%wt. in each case based on the weight of the composition.
  • organic peroxide Any suitable organic peroxide may be utilized.
  • Some commonly used organic peroxides include benzoyl peroxide, 1 , 4-dichlorobenzyl peroxide, 2, 4-dichlorobenzyl peroxide, 2, 4-dichlorobenzoyl peroxide, 1 , 4-dimethylbenzyl peroxide, 2, 4-dimethylbenzyl peroxide, di-i-butyl peroxide, dicumyl peroxide, tertiary butyl-perbenzoate, monochlorobenzoyl peroxide, ditertiary-butyl peroxide, 2, 5-bis- (tertiarybutyl-peroxy) -2, 5-dimethylhexane, 1 , 1-bis (t-butylperoxy) -3, 3, 5-trimethylcyclohexane, tertiary-butyl-trimethyl peroxide, n-butyl-4, 4-bis (t-butylperoxy) valerate,
  • the curing agent may be (ii) a hydrosilylation cure package comprising an organohydrogenpolysiloxane having 3 or more silicon-bonded hydrogen atoms per molecule and a hydrosilylation catalyst.
  • organohydrogenpolysiloxane (s) which, when present, operate (s) as cross-linker (s) for fluorinated polydiorganosiloxane gum (a) will undergo a hydrosilylation (addition) reaction by way of its silicon-bonded hydrogen atoms with the alkenyl groups in fluorinated polydiorganosiloxane gum (a) catalysed by one or more hydrosilylation catalysts discussed below.
  • the organohydrogenpolysiloxane normally contains 3 or more silicon-bonded hydrogen atoms per molecule so that the hydrogen atoms of this ingredient can sufficiently react with the alkenyl groups of fluorinated polydiorganosiloxane gum (a) to form a network structure therewith and thereby cure the composition.
  • the molecular configuration of the organohydrogenpolysiloxane is not specifically restricted, and it can be straight chain, branch-containing straight chain, or cyclic. While the molecular weight of this ingredient is not specifically restricted, the viscosity is typically from 0.001 to 50 Pa. s at 25 °C using a Brookfield DV-III Ultra Programmable Rheometer for viscosities ⁇ 50,000 mPa. s, and a Brookfield DV 3T Rheometer for viscosities less than 50,000 mPa. s, unless otherwise indicated.
  • the organohydrogenpolysiloxane is typically added in an amount such that when part A and part B of a formulation are mixed together, the molar ratio of the total number of the silicon-bonded hydrogen atoms in the composition to the total number of all alkenyl groups in the composition herein is from 0.5: 1 to 5: 1. When this ratio is less than 0.5: 1, a well-cured composition will not be obtained.
  • organohydrogenpolysiloxane examples include but are not limited to:
  • copolymers composed of (CH 3 ) 3 SiO 1/2 units, (CH 3 ) 2 HSiO 1/2 units, and SiO 4/2 units.
  • cross-linkers When present such cross-linkers will be present in an amount of from 2 to 10%by weight of the composition.
  • the composition may be cured using hydrosilylation cure package (ii) catalysed by a hydrosilylation (addition cure) catalyst that is a metal selected from the platinum metals, i.e. platinum, ruthenium, osmium, rhodium, iridium and palladium, or a compound of such metals.
  • a hydrosilylation (addition cure) catalyst that is a metal selected from the platinum metals, i.e. platinum, ruthenium, osmium, rhodium, iridium and palladium, or a compound of such metals.
  • the metals include platinum, palladium, and rhodium but platinum and rhodium compounds are preferred due to the high activity level of these catalysts for hydrosilylation reactions.
  • Example of preferred hydrosilylation catalysts for package (ii) include but are not limited to platinum black, platinum on various solid supports, chloroplatinic acids, alcohol solutions of chloroplatinic acid, and complexes of chloroplatinic acid with ethylenically unsaturated compounds such as olefins and organosiloxanes containing ethylenically unsaturated silicon-bonded hydrocarbon groups.
  • the catalyst (e) can be platinum metal, platinum metal deposited on a carrier, such as silica gel or powdered charcoal, or a compound or complex of a platinum group metal.
  • Suitable platinum based catalysts include
  • a platinum-containing catalyst which is obtained by a method comprising reacting chloroplatinic acid with an aliphatically unsaturated organosilicon compound, such as divinyltetramethyldisiloxane;
  • alkene-platinum-silyl complexes as described in US Pat. No. 6,605,734 such as (COD) Pt (SiMeCl 2 ) 2 where “COD” is 1, 5-cyclooctadiene; and/or
  • the hydrosilylation catalyst when present, is present in the total composition in a catalytic amount, i.e., an amount or quantity sufficient to promote a reaction or curing thereof at desired conditions. Varying levels of the hydrosilylation catalyst can be used to tailor reaction rate and cure kinetics.
  • the catalytic amount of the hydrosilylation catalyst is generally between 0.01 ppm, and 10,000 parts by weight of platinum-group metal, per million parts (ppm) , based on the combined weight of the components (a) , (b) , and (d) and/or (e) if the latter is/are present; alternatively between 0.01 and 5000ppm; alternatively between 0.01 and 3,000 ppm, and alternatively between 0.01 and 1,000 ppm.
  • the catalytic amount of the catalyst may range from 0.01 to 1,000 ppm, alternatively 0.01 to 750 ppm, alternatively 0.01 to 500 ppm and alternatively 0.01 to 100 ppm of metal based on the weight of the composition.
  • the ranges may relate solely to the metal content within the catalyst or to the catalyst altogether (including its ligands) as specified, but typically these ranges relate solely to the metal content within the catalyst.
  • the catalyst may be added as a single species or as a mixture of two or more different species. Typically, dependent on the form/concentration in which the catalyst package is provided the amount of catalyst present will be within the range of from 0.001 to 3.0%by weight of the composition.
  • the composition may be a dual cure composition, wherein the cure composition may include both the peroxide curing agent and the hydrosilylation cure package comprising organohydrogenpolysiloxane cross-linkers, hydrosilylation catalysts in combination.
  • the present disclosure may also comprises at least one of
  • Non-reinforcing filler (d) may comprise, for example, crushed quartz, diatomaceous earths, barium sulphate, iron oxide, titanium dioxide and carbon black, talc, wollastonite.
  • Other non-reinforcing fillers (d) which might be used alone or in addition to the above include aluminite, calcium sulphate (anhydrite) , gypsum, calcium sulphate, magnesium carbonate, clays such as kaolin, aluminium trihydroxide, magnesium hydroxide (brucite) , graphite, copper carbonate, e.g. malachite, nickel carbonate, e.g. zarachite, barium carbonate, e.g. witherite and/or strontium carbonate e.g. strontianite.
  • aluminium oxide silicates from the group consisting of olivine group; garnet group; aluminosilicates; ring silicates; chain silicates; and sheet silicates may be utilised.
  • the olivine group comprises silicate minerals, such as but not limited to, forsterite and Mg 2 SiO 4 .
  • the garnet group comprises ground silicate minerals, such as but not limited to, pyrope; Mg 3 Al 2 Si 3 O 12 ; grossular; and Ca 2 Al 2 Si 3 O 12 .
  • Aluninosilicates comprise ground silicate minerals, such as but not limited to, sillimanite; Al 2 SiO 5 ; mullite; 3Al 2 O 3 .2SiO 2 ; kyanite; and Al 2 SiO 5.
  • the ring silicates group comprises silicate minerals, such as but not limited to, cordierite and Al 3 (Mg, Fe) 2 [Si 4 AlO 18 ] .
  • the chain silicates group comprises ground silicate minerals, such as but not limited to, wollastonite and Ca [SiO 3 ] .
  • the sheet silicates group comprises silicate minerals, such as but not limited to, mica; K 2 AI 14 [Si 6 Al 2 O 20 ] (OH) 4 ; pyrophyllite; Al 4 [Si 8 O 20 ] (OH) 4 ; talc; Mg 6 [Si 8 O 20 ] (OH) 4 ; serpentine for example, asbestos; Kaolinite; Al 4 [Si 4 O 10 ] (OH) 8 ; and vermiculite.
  • the non-reinforcing filler is present in a in a cumulative amount of from 1 to 50%wt. of the composition.
  • the non-reinforcing filler may be a plate/sheet like filler selected from the group of such as talc, mica, clay, graphite and mixtures thereof.
  • the non-reinforcing filler (d) may be present in a range of from 5 to 50 %by weight of the composition.
  • the non-reinforcing filler (d) may also be treated as described above with respect to the reinforcing fillers (b) to render them hydrophobic and thereby easier to handle and obtain a homogeneous mixture with the other components.
  • surface treatment of the non-reinforcing fillers (d) makes them easily wetted by fluorinated polydiorganosiloxane gum (a) which may result in improved properties of the uncured compositions, such as better processability (e.g. lower viscosity, better mold releasing ability and/or less sticky in processing equipment, such as two roll mills) . They may also improve physical properties of the resulting cured elastomers e.g. heat resistance, and/or mechanical properties.
  • Dilatant material (e) is a non-Newtonian fluid wherein its shear viscosity increases with applied shear stress, i.e. a fluid whose viscosity is temporarily or permanently increased upon application of a shear force.
  • Dilatant material (e) may alternatively be referred to as a “shear thickening fluid. ”
  • molecules of a dilatant compound are weakly bonded and can move around with ease, but the pressure shock from an impact results in strengthening of the chemical bonds, thereby locking the molecules into place and hardening the material. Once the impact force dissipates, the bonds weaken and the material returns to its flexible state.
  • Dilatant material (e) may be any suitable dilatant material which is compatible with the present composition, such as silicone based dilatant materials.
  • the dilatant material herein may be the reaction product of a polydiorganosiloxane and a boron compound, selected from boric oxide, a boric acid or boric acid precursor, a borate or a partially hydrolysed borate.
  • the polydiorganosiloxane which is reacted with the boron compound is preferably a polydimethylsiloxane (PDMS) and can be a hydroxy-end-blocked polydimethylsiloxane ranging from a disiloxane to a “high” polymer gum having a viscosity of at least 1000000 mPa. at 25°C., optionally used together with a cyclic polydimethylsiloxane.
  • Some trimethylsiloxane, monomethylsiloxane and SiO 2 units can be present but only in such proportions that the ratio of methyl radicals to silicon atoms is about 2, e.g. from 1.95 to 2.05.
  • the boron compound can be boric oxide, sometimes referred to as boric anhydride, boric acids such as orthoboric acid, metaboric acid and tetraboric acid, a boric acid precursor, for example a compound which hydrolyses to boric acid such as trimethoxy boroxine, and borates such as triethyl borate, tricyclohexyl borate, tritolyl borate, tribenzyl borate, triphenyl borate, triphenyl borate, triallyl borate, tridodecyl borate, trictadecyl borate, tri-tertiary butyl borate, phenyl ethylene borate, cyclohexyl ethylene borate, cyclohexyl ophenylene borate, glycerol borate, tris-trimethylsilyl borate, diammonium tetraborate, ammonium pentaborate, diammonium octaborate, sodium
  • the dilatant silicone composition can be formed by heating a mixture of the polydiorganosiloxane and the boron compound, for example at temperatures of up to 250°C., for various periods of time, if necessary with milling to break up any gels formed.
  • the preferred method is merely heating 100 parts by weight of a hydroxyl-end-blocked dimethylpolysiloxane containing from 20 to 175 silicon atoms per molecule, preferably from 40 to 100 silicon atoms per molecule, with e.g. 2 to 6 parts of boric oxide at a temperature between 150°C. and 200°C.
  • the reaction product of the polydiorganosiloxane and the boron compound is made up, almost entirely, of dimethylpolysiloxane chains which average from 20 to 175 silicon atoms and which are silanol-end-blocked or joined together by -OBO-linkages or both.
  • Additives may be present in the composition depending on the intended use of the curable fluorosilicone elastomer composition.
  • the curing agent is a hydrosilylation cure package inhibitors designed to inhibit the reactivity of the hydrosilylation catalysts may be utilised.
  • optional additives include electrical conductive fillers, thermally conductive fillers, non-conductive filler, pot life extenders, flame retardants, pigments, colouring agents, adhesion promoters, chain extenders heat stabilizers, compression set improvement additives and mixtures thereof .
  • a suitable inhibitor may be incorporated into the composition in order to retard or suppress the activity of the catalyst.
  • Inhibitors of platinum metal based catalysts generally a platinum metal based catalyst are well known in the art.
  • Hydrosilylation or Addition-reaction inhibitors include hydrazines, triazoles, phosphines, mercaptans, organic nitrogen compounds, acetylenic alcohols, silylated acetylenic alcohols, maleates, fumarates, ethylenically or aromatically unsaturated amides, ethylenically unsaturated isocyanates, olefinic siloxanes, unsaturated hydrocarbon monoesters and diesters, conjugated ene-ynes, hydroperoxides, nitriles, and diaziridines. Alkenyl-substituted siloxanes as described in US 3,989,887 may be used, of which cyclic methylvinylsiloxanes are preferred.
  • Another class of known inhibitors of platinum catalysts includes the acetylenic compounds disclosed in US 3,445,420.
  • Acetylenic alcohols such as 2-methyl-3-butyn-2-ol constitute a preferred class of inhibitors that will suppress the activity of a platinum-containing catalyst at 25 °C.
  • Compositions containing these inhibitors typically require heating at temperature of 70 °C or above to cure at a practical rate.
  • acetylenic alcohols and their derivatives include 1-ethynyl-1-cyclohexanol (ETCH) , 2-methyl-3-butyn-2-ol, 3-butyn-1-ol, 3-butyn-2-ol, propargylalcohol, 2-phenyl-2-propyn-1-ol, 3, 5-dimethyl-1-hexyn-3-ol, 1-ethynylcyclopentanol, 1-phenyl-2-propynol, 3-methyl-1-penten-4-yn-3-ol, and mixtures thereof.
  • ECH 1-ethynyl-1-cyclohexanol
  • 2-methyl-3-butyn-2-ol 3-butyn-1-ol
  • 3-butyn-2-ol propargylalcohol
  • 2-phenyl-2-propyn-1-ol 3, 5-dimethyl-1-hexyn-3-ol
  • 1-ethynylcyclopentanol 1-phen
  • inhibitor concentrations as low as 1 mole of inhibitor per mole of the metal of catalyst (e) will in some instances impart satisfactory storage stability and cure rate. In other instances inhibitor concentrations of up to 500 moles of inhibitor per mole of the metal of catalyst (e) are required.
  • the optimum concentration for a given inhibitor in a given composition is readily determined by routine experimentation. Dependent on the concentration and form in which the inhibitor selected is provided/available commercially, when present in the composition, the inhibitor is typically present in an amount of from 0.0125 to 10%by weight of the composition. Mixtures of the above may also be used.
  • electrical conductive fillers examples include metal particles, metal oxide particles, metal-coated metallic particles (such as silver plated nickel) , metal coated non-metallic core particles (such as silver coated talc, or mica or quartz) and a combination thereof.
  • Metal particles may be in the form of powder, flakes or filaments, and mixtures or derivatives thereof.
  • thermally conductive fillers examples include boron nitride, aluminium nitride, metal oxides such as zinc oxide, magnesium oxide, aluminium oxide, aluminium trihydrate; as well as graphite, diamond, and mixtures or derivatives thereof.
  • non-conductive fillers examples include quartz powder, diatomaceous earth, talc, clay, alumina, mica, calcium carbonate, magnesium carbonate, hollow glass, glass fibre, hollow resin and plated powder, and mixtures or derivatives thereof.
  • Pot life extenders such as triazole, may be used, but are not considered necessary in the scope of the present invention.
  • the liquid curable silicone elastomer composition may thus be free of pot life extender.
  • flame retardants examples include aluminium trihydrate, magnesium hydroxide, calcium carbonate, zinc borate, wollastonite, mica, chlorinated paraffins, hexabromocyclododecane, triphenyl phosphate, dimethyl methylphosphonate, tris (2, 3-dibromopropyl) phosphate (brominated tris) , and mixtures or derivatives thereof.
  • Further additives include silicone fluids, such as trimethylsilyl or OH terminated siloxanes. Such trimethylsiloxy or OH terminated polydimethylsiloxanes typically have a viscosity ⁇ 150 mPa. s. When present such silicone fluid may be present in the liquid curable silicone elastomer composition in an amount ranging of from 0.1 to 5%weight, based on the total weight of the composition.
  • Other additives include silicone resin materials, which may or may not contain alkenyl or hydroxyl functional groups.
  • pigments include carbon black, iron oxides, titanium dioxide, chromium oxide, bismuth vanadium oxide and mixtures or derivatives thereof.
  • colouring agents examples include vat dyes, reactive dyes, acid dyes, chrome dyes, disperse dyes, cationic dyes and mixtures thereof.
  • adhesion promoters include silane coupling agents, alkoxysilane containing methacrylic groups or acrylic groups such as methacryloxymethyl-trimethoxysilane, 3-methacryloxypropyl-tirmethoxysilane, 3-methacryloxypropyl-methyldimethoxysilane, 3-methacryloxypropyl-dimethylmethoxysilane, 3-methacryloxypropyl-triethoxysilane, 3-methacryloxypropyl-methyldiethoxysilane, 3-methacryloxyisobutyl-trimethoxysilane, or a similar methacryloxy-substituted alkoxysilane; 3-acryloxypropyl-trimethoxysilane, 3-acryloxypropyl-methyldimethoxysilane, 3-acryloxypropyl-dimethyl-methoxysilane, 3-acryloxypropyl-triethoxysilane, or a similar acryloxy-substituted alk
  • chain extenders examples include disiloxane or a low molecular weight polyorganosiloxane containing two silicon-bonded hydrogen atoms at the terminal positions.
  • the chain extender typically reacts with the alkenyl groups of ingredient (a) , thereby linking two molecules of ingredient together and increasing its effective molecular weight and the distance between potential cross-linking sites.
  • a disiloxane is typically represented by the general formula (HR a 2 Si) 2 O.
  • the chain extender is a polyorganosiloxane, it has terminal units of the general formula HR a 2 SiO 1/2 and non-terminal units of the formula R b 2 SiO.
  • R a and R b individually represent unsubstituted or substituted monovalent hydrocarbon groups that are free of ethylenic unsaturation, which include, but are not limited to alkyl groups containing from 1 to 10 carbon atoms, substituted alkyl groups containing from 1 to 10 carbon atoms such as chloromethyl and 3, 3, 3-trifluoropropyl, cycloalkyl groups containing from 3 to 10 carbon atoms, aryl containing 6 to 10 carbon atoms, alkaryl groups containing 7 to 10 carbon atoms, such as tolyl and xylyl, and aralkyl groups containing 7 to 10 carbon atoms, such as benzyl.
  • chain extenders include tetramethyldihydrogendisiloxane or dimethylhydrogen-terminated polydimethylsiloxane.
  • the optional additives may be used for more than one reason e.g. as a non-reinforcing filler and flame retardant, when present they may function in both roles.
  • the aforementioned additional ingredients are cumulatively present in an amount of from 0.1 to 30%wt, alternatively of from 0.1 to 20%wt based on the weight of the composition.
  • the composition may be mixed and/or processed using any suitable mixing/processing equipment, such as any suitable mixer e.g kneader mixers, internal mixers, extruders, calendering or on a two roll mill.
  • any suitable mixer e.g kneader mixers, internal mixers, extruders, calendering or on a two roll mill.
  • the gum/polymers and fillers are initially mixed together to form a base before the other ingredients are introduced into the composition.
  • the filler may have been pre-treated with a hydrophobing treating or alternatively the filler (s) may be treated in situ during mixing into the fluorinated polydiorganosiloxane gum (a) .
  • composition as hereinbefore described may comprise
  • a reinforcing filler in an amount of 5 to 40%wt., alternatively from 5 to 30%wt, alternatively from 7.5 to 30%wt., alternatively, 10 to 30%wt. of the composition;
  • a curing agent selected from either (i) a peroxide curing agent in an amount of from 0.3 to 3%wt. of the composition or (ii) a hydrosilylation cure package comprising an organohydrogenpolysiloxane having 3 or more silicon-bonded hydrogen atoms per molecule and a hydrosilylation catalyst;
  • the composition When the composition is cured via a hydrosilylation process the composition is typically stored in two parts prior to use.
  • the hydrosilylation catalyst is placed in one part, often referred to as Part A and the cross-linker and if present the inhibitor, is placed in the second part, often referred to as Part B.
  • the other ingredients may typically be present in either or both compositions.
  • the part A and Part B compositions are then mixed immediately prior to use.
  • the mixing ratios by weight will depend on the level of ingredients in each part and can vary for part A to part B from about 15 : 1 to 1 to 1, typically dependent on whether components (a) and/or (b) are in both components and indeed the amounts in each.
  • part A Part B will be in a ratio of from 5 : 1 to 1 : 1, alternatively from 3 : 1 to 1 : 1.
  • the fluorosilicone rubber composition may be cured by way of a compression molding press, a transfer molding press, an injection machine, by hot air oven, by autoclave or even by way of a salt bath.
  • the composition may be cured at any suitable temperature e.g. from 80°C to 250°C, typically dependent on the curing agent (s) being used.
  • a peroxide curing agent cure will take place at a temperature between about 150°C to 250°C alternatively 150°C to 225°C, alternatively from 150°C to 200°C.
  • the temperature for curing via hydrosilylation however is typically from 80°C to 150°C, alternatively between 100°C to 150°C, alternatively between 100°C to 130°C.
  • the fluorosilicone rubber damping materials as described herein may be used in any suitable systems and applications requiring vibration damping and/or noise reduction, e.g. to decrease vibrations and noise transmitted from engines and/or machinery e.g. power and suspension devices and/or other machine/engine parts. They may also be used to limit the effect of shocks transmitted from foundations in buildings.
  • fluorosilicone elastomeric materials can be used to dampen vibrations in macro situations e.g. in automotive applications, e.g. road vehicles and trains, aircraft applications, industrial machinery applications, construction applications, i.e. building and bridge structures and/or they can be used in “micro” situations e.g. electronics and music/acoustic systems.
  • automotive applications e.g. road vehicles and trains
  • industrial machinery applications e.g. building and bridge structures
  • micro e.g. electronics and music/acoustic systems.
  • Specific examples include but are not limited to shock absorbers, vehicle suspension systems, vibroisolators, engine mounts, hydraulic systems, and for decreasing noise and vibrations between floors in multi-storey buildings.
  • Our fluorosilicone elastomeric materials suitable to function as vibration dampers have the ability to support weight, e.g. of an engine/machine part, imparting heat resistance to high heat generated in an engine room during e.g. the running of a vehicle or machine and providing durability against repetitive loading.
  • weight e.g. of an engine/machine part
  • they may be used in anti-vibration systems for e.g. automotive engine mounts, because of their strength, fatigue resistance, high resilience and low level of strain sensitivity particularly at low temperatures and as will be seen in the examples herein they can function over wide temperature ranges, even better than typical standard silicone rubber vibration damping elastomeric materials. They may be utilised in high temperature environments (>100°C. ) .
  • the fluorosilicone rubber elastomeric materials as described herein made from the composition described may be utilised in a wide range of applications.
  • they may be used to dampen vibrations/noise in macro situations such as in automotive applications, e.g. in road vehicles, trams, trains and aircraft applications; in industrial machinery applications; in construction applications, i.e. building and bridge structures and/or they can be used in “micro” situations e.g. for damping electronics and music/acoustic systems.
  • shock absorbers include but are not limited to shock absorbers, vehicle suspension systems, vibroisolators, engine mounts, bushes, hydraulic systems, for decreasing shocks, noise and vibrations between floors in multi-storey buildings; noise and vibration reduction in washing machines and dryers and also in electronic devices such as in loud speakers, mobile phones, laptops, drones, wearable electronic devices, and televisions and the like.
  • compositions and components of the compositions, elastomers, and methods are intended to illustrate and not to limit the invention.
  • Values of vinyl content are the cumulative totals of the weight %of vinyl groups in the composition, i.e. typically in gums/polymers, determined using quantitative infra-red spectroscopy in accordance with ASTM E168. Values of silicon bonded hydrogen atoms in weight %of were also determined by infra-red spectroscopy in accordance with ASTM E168. The ratio of silicon bonded hydrogen atoms: vinyl groups in the composition is a molar ratio. The measurements taken using ASTM D412 used Die C, Modulus M100 means at 100%extension and modulus M300 means at 300%extension.
  • the filler (s) and filler treating agent (s) were first mixed with and evenly dispersed into the gum (s) to form a silicone rubber base.
  • peroxide cure comparatives in Table 1a comps 1, 3 and 4
  • the catalyst was added and dispersed into the base and the compositions were press cured for 10 minutes at a temperature of 170°C.
  • Tan delta E”/E’
  • E is the viscous (loss) modulus in the tensile mode
  • E is the elastic (storage) modulus in the tensile mode.
  • the storage and loss modulus in viscoelastic materials measure the stored energy, representing the elastic portion, and the energy dissipated as heat, representing the viscous portion. It varies with the state of the material being analysed, its temperature, and with the frequency.
  • compositions were prepared and cured in the same manner as the above.
  • the compositions are provided in table 2 a below.
  • Comp 8 Comp 3
  • Comp 4 Comp 5 Tan delta at -30°C 0.118 0.095 0.163 0.126 Tan delta at 0°C 0.202 0.098 0.140 0.140 Tan delta at 25°C 0.212 0.098 0.103 0.104 Tan delta at 50°C 0.197 0.089 0.089 0.087 Tan delta at 80°C 0.180 0.086 0.075 0.105
  • Tan delta of silicone rubber greatly enhanced after substituted some of the methyl groups on PDMS chain with trifluoropropyl groups (Ex. 1 and 2) .
  • the Tan delta decreases with increasing temperature and reduces to a much lower level at 80°C.
  • non-reinforcing fillers such as quartz and talc (Ex. 3 and 4) , were introduced into the formulations.
  • the Tan delta at higher temperature is evidently improved especially for the sample with platelet shape of filler, talc.
  • the Tan delta differences at -30 and +80°C, which is represented by stability factor, are bigger, which is not preferred in some of the applications.
  • Tan delta (the Loss factor) was determined in the tensile mode in the analogous way as described above over the same range of temperatures and the results are depicted in Table 3c below.
  • compositions used in a further set of examples in accordance with the disclosure herein are depicted in Table 4a below.
  • Tan delta (the Loss factor) was determined in the tensile mode in the analogous way as described above over the same range of temperatures and the results are depicted in Table 4c below.

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Abstract

Un matériau d'amortissement en caoutchouc de fluorosilicone ayant un tan delta dans le mode de traction de > 0,12 dans une plage de température allant de -30 °C à +80 °C, la composition de caoutchouc de silicone à partir de laquelle le matériau est fabriqué, un procédé de fabrication du matériau et ses utilisations.
PCT/CN2018/123335 2018-12-25 2018-12-25 Compositions de caoutchouc de fluorosilicone WO2020132846A1 (fr)

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