WO2020132020A1 - Compositions de caoutchouc silicone et matériaux élastomères - Google Patents

Compositions de caoutchouc silicone et matériaux élastomères Download PDF

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Publication number
WO2020132020A1
WO2020132020A1 PCT/US2019/067097 US2019067097W WO2020132020A1 WO 2020132020 A1 WO2020132020 A1 WO 2020132020A1 US 2019067097 W US2019067097 W US 2019067097W WO 2020132020 A1 WO2020132020 A1 WO 2020132020A1
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Prior art keywords
composition
subsea
groups
accordance
silicone rubber
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Inventor
Timothy S. DE VRIES
Kevin P. LAWRY
Zhanjie Li
Robert L. Sammler
Sanil SREEKUMAR
Brian J. Swanton
Lauren Tonge
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Dow Global Technologies LLC
Dow Silicones Corp
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Dow Global Technologies LLC
Dow Silicones Corp
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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
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L59/00—Thermal insulation in general
    • F16L59/14—Arrangements for the insulation of pipes or pipe systems

Definitions

  • the present invention relates to an elastomeric silicone rubber insulation material for use on subsea oil and gas production equipment, a composition used in the making of the elastomeric material and articles made from the elastomeric material.
  • Subsea wells and pipelines are used globally in connection with the production of hydrocarbons, in the form of oil and/or gas.
  • a well extends from the seabed to the required depth at which the hydrocarbon reservoir is located and recovery of the hydrocarbons from the well to the surface is typically carried out using pipes, often referred to as“subsea risers”.
  • Subsea risers extend from a well head or manifold on the seabed to a platform or vessel tethered on the surface above the well. It is not unusual for the risers to extend over hundreds or indeed thousands of meters between the wellhead and the surface.
  • Suitable insulation materials also need to be unaffected by the extreme temperatures of the hydrocarbon fluids exiting the well. In some cases the temperature of the exiting fluids may reach 150°C or higher, and the fluids will consequently heat both the surrounding equipment and the insulation. Therefore, any insulation material which is used on such wells must be able to withstand these extreme temperatures without detriment to its thermal or mechanical properties.
  • any damage to the outer surface of the riser can allow seawater to permeate into the layers of the riser and from there into the hydrocarbon stream, or alternatively, can allow the hydrocarbons flowing in the riser to leak into the surrounding seawater.
  • the corrosive effects of the seawater are particularly evident in the area immediately below the surface of the sea, up to a depth of about 50m because it can be subjected to the effects of weather and turbulence under the surface due to prevailing weather conditions.
  • a thermal insulation material must have a low thermal conductivity, exhibit acceptable mechanical properties such as flexibility and impact resistance, and be economical to install and preferably should be resistant to the corrosive nature of the seawater.
  • a variety of insulation materials for this application are known, for example syntactic phenolic foams and high temperature epoxy resins have been used because they can withstand these relatively high temperatures but unfortunately they are inherently brittle and as such are unable to meet the flexibility and impact resistance requirements. Furthermore, because of their brittle nature and exothermic curing properties, these materials are difficult and expensive to install and repair.
  • Liquid silicone rubber based materials made using organopolysiloxane polymers having viscosities of up to about 500,000 mPa.s at 25°C have been utilised for subsea insulation but whilst having advantages over the above because of the ability to withstand wide temperature variations without an appreciable effect on their physical properties and being virtually unaffected by ultraviolet radiation, even over long periods of time, ozone, oil, salt, water and the like. They have had adhesion problems after exposure to the high temperatures of the hydrocarbons transported through the riser pipes.
  • subsea insulation silicone rubber composition comprising (i) one or more polydiorganosiloxane polymer(s) having a viscosity of from 1000 to 500,000mPa.s at 25°C containing at least two alkenyl groups or alkynyl groups per molecule;
  • an organosilicate resin comprising R '
  • one or more Si-H scavengers selected from the group of (a) an unsaturated hydrocarbon having 2 to 20 carbons which may be linear branched and/or cyclic and (b) a short chain siloxane having a degree of polymerisation of from 2 to 15 and comprising one or more unsaturated groups where the unsaturation is an alkenyl group and wherein (a) and or (b) may additionally contain one or more electron-attracting substituents;
  • the residual SiH in the composition is identified as the amount of SiH functionality subtracted by the amount of Si-alkenyl + Si-alkynyl, typically Si-vinyl functionality in the fully formulated combination of part A and part B.
  • hydrosilylation catalyst package comprising a polydiorganosiloxane polymer having at least 2, alternatively at least 3 Si-H groups per molecule;
  • a hydrosilylation catalyst and optionally (v) an organosilicate resin comprising R ' d R 2 -dS iO i /2 (M) siloxane units and S1O4/2 (Q) siloxane units having a weight average molecular weight of from 3000 to 30,000 g/mol and a molar ratio of M groups : Q groups of from 0.60: 1 to 1.50 and wherein R 2 is as described above and R 4 is an alkenyl or alkynyl group having from 2 to 10 carbons and d is 0, 1 or 2;
  • one or more Si-H scavengers selected from the group of (a) an unsaturated hydrocarbon having 2 to 20 carbons which may be linear branched and/or cyclic and (b) a short chain siloxane having a degree of polymerisation of from 2 to 15 and comprising one or more unsaturated groups where the unsaturation is an alkenyl group and wherein (a) and/or (b) may additionally contain one or more electron-attracting substituents; in an amount of at least 50 mol% of the Si-H scavengers unsaturated functionality content relative to residual SiH in the composition.
  • hydrosilylation catalyst package comprising a polydiorganosiloxane polymer having at least 2, alternatively at least 3 Si-H groups per molecule;
  • siloxane units having a weight average molecular weight of from 3000 to 30,000 g/mol and a molar ratio of M groups : Q groups of from 0.60: 1 to 1.20 and wherein R 2 is as described above and R 4 is an alkenyl or alkynyl group having from 2 to 10 carbons and d is 0, 1 or 2;
  • one or more Si-H scavengers selected from the group of (a) an unsaturated hydrocarbon having 2 to 20 carbons which may be linear branched and/or cyclic and (b) a short chain siloxane having a degree of polymerisation of from 2 to 15 and comprising one or more unsaturated groups where the unsaturation is an alkenyl group and wherein (a) and/or (b) may additionally contain one or more electron-attracting substituents; in an amount of at least 50 mol% of the Si-H scavengers unsaturated functionality content relative to residual SiH in the composition.
  • hydrosilylation catalyst package comprising a polydiorganosiloxane polymer having at least 2, alternatively at least 3 Si-H groups per molecule;
  • siloxane units having a weight average molecular weight of from 3000 to 30,000 g/mol and a molar ratio of M groups : Q groups of from 0.60: 1 to 1.20 and wherein R 2 is as described above and R 4 is an alkenyl or alkynyl group having from 2 to 10 carbons and d is 0, 1 or 2; characterised in that the composition also comprises
  • one or more Si-H scavengers selected from the group of (a) an unsaturated hydrocarbon having 2 to 20 carbons which may be linear branched and/or cyclic and (b) a short chain siloxane having a degree of polymerisation of from 2 to 15 and comprising one or more unsaturated groups where the unsaturation is an alkenyl group and wherein (a) and/or (b) may additionally contain one or more electron-attracting substituents; in an amount of at least 50 mol% of the Si-H scavengers unsaturated functionality content relative to residual SiH in the composition.
  • the composition may include one or more optional additives but the total weight % of the composition is 100 wt. % and the alkenyl and or alkynyl content of polymer (i) is determined using quantitative infra-red analysis in accordance with ASTM E168.
  • Component (i) is one or more polydiorganosiloxane polymer(s) having a viscosity of from 1000 to 500,000mPa.s at 25°C containing at least two alkenyl groups per molecule;
  • Polydiorganosiloxane polymer (i) has multiple units of the formula (I):
  • each R is independently selected from an aliphatic hydrocarbyl, aromatic hydrocarbyl, or organyl group (that is any organic substituent group, regardless of functional type, having one free valence at a carbon atom).
  • Saturated aliphatic hydrocarbyls are exemplified by, but not limited to alkyl groups such as methyl, ethyl, propyl, pentyl, octyl, undecyl, and octadecyl and cycloalkyl groups such as cyclohexyl.
  • Unsaturated aliphatic hydrocarbyls are exemplified by, but not limited to, alkenyl groups such as vinyl, allyl, butenyl, pentenyl, cyclohexenyl and hexenyl; and by alkynyl groups.
  • Aromatic hydrocarbon groups are exemplified by, but not limited to, phenyl, tolyl, xylyl, benzyl, styryl, and 2-phenylethyl.
  • Organyl groups are exemplified by, but not limited to, halogenated alkyl groups such as chloromethyl and 3-chloropropyl; nitrogen containing groups such as amino groups, amido groups, imino groups, imido groups; oxygen containing groups such as polyoxyalkylene groups, carbonyl groups, alkoxy groups and hydroxyl groups.
  • Further organyl groups may include sulfur containing groups, phosphorus containing groups and/or boron containing groups.
  • the subscript“a” may be 0, 1, 2 or 3, but is typically mainly 2 or 3.
  • Siloxy units may be described by a shorthand (abbreviated) nomenclature, namely - "M,”
  • Examples of typical groups on the polydiorganosiloxane polymer (i) include mainly alkenyl, alkyl, and or aryl groups.
  • the groups may be in pendent position (on a D or T siloxy unit), or may be terminal (on an M siloxy unit).
  • alkenyl and or alkynyl groups are essential when the composition is being cured by hydrosilylation but are optional if the sole curing agent for the cure process is a peroxide.
  • suitable alkenyl groups in polydiorganosiloxane polymer (i) typically contain from 2 to 10 carbon atoms, e.g. vinyl, isopropenyl, allyl, and 5-hexenyl.
  • the silicon-bonded organic groups attached to polydiorganosiloxane polymer (i) other than alkenyl groups are typically selected from monovalent saturated hydrocarbon groups, which typically contain from 1 to 10 carbon atoms, and monovalent aromatic hydrocarbon groups, which typically contain from 6 to 12 carbon atoms, which are unsubstituted or substituted with groups that do not interfere with curing of this inventive composition, such as halogen atoms.
  • Preferred species of the silicon-bonded organic groups are, for example, alkyl groups such as methyl, ethyl, and propyl; and aryl groups such as phenyl.
  • polydiorganosiloxane polymer (i) is typically linear, however, there can be some branching due to the presence of T units (as previously described) within the molecule.
  • the viscosity of polydiorganosiloxane polymer (i) should be at least lOOOmPa.s at 25 °C.
  • the upper limit for the viscosity of polydiorganosiloxane polymer (i) is limited to a viscosity of up to 500,000mPa.s at 25°C.
  • the or each polydiorganosiloxane containing at least two silicon-bonded alkenyl groups per molecule of ingredient (a) has a viscosity of from 1000 mPa.s to 150,000mPa.s at 25 °C, alternatively from 2000mPa.s to 125,000mPa.s, alternatively from 2000mPa.s to
  • the polydiorganosiloxane polymer (i) may be selected from polydimethylsiloxanes, alkylmethylpolysiloxanes, alkylarylpolysiloxanes or copolymers thereof containing e.g. alkenyl and/or alkynyl groups and may have any suitable terminal groups, for example, they may be trialkyl terminated, alkenyldialkyl terminated or may be terminated with any other suitable terminal group combination providing each polymer contains at least two alkenyl groups per molecule.
  • Polydiorganosiloxane polymer (i) may be, for the sake of example, dimethylvinyl terminated polydimethylsiloxane, dimethylvinylsiloxy-terminated dimethylmethylphenylsiloxane, trialkyl terminated dimethylmethylvinyl polysiloxane or dialkylvinyl terminated dimethylmethylvinyl polysiloxane copolymers.
  • a polydiorganosiloxane polymer (i) containing alkenyl groups at the two terminals may be represented by the general formula (II):
  • each R' may be an alkenyl group or an alkynyl group, which typically contains from 2 to 10 carbon atoms.
  • Alkenyl groups include but are not limited to vinyl, propenyl, butenyl, pentenyl, hexenyl an alkenylated cyclohexyl group, heptenyl, octenyl, nonenyl, decenyl or similar linear and branched alkenyl groups and alkenylated aromatic ringed structures.
  • Alkynyl groups may be selected from but are not limited to ethynyl, propynyl, butynyl, pentynyl, hexynyl an alkynylated cyclohexyl group, heptynyl, octynyl, nonynyl, decynyl or similar linear and branched alkenyl groups and alkenylated aromatic ringed structures.
  • R" does not contain ethylenic unsaturation
  • Each R" may be the same or different and is individually selected from monovalent saturated hydrocarbon group, which typically contain from 1 to 10 carbon atoms, and monovalent aromatic hydrocarbon group, which typically contain from 6 to 12 carbon atoms.
  • R" may be unsubstituted or substituted with one or more groups that do not interfere with curing of this inventive composition, such as halogen atoms.
  • R'" is R' or R".
  • Organopolysiloxane polymer (i) is typically present in an amount of from 40 to 80 wt% of the composition.
  • resin (v) is present in the composition
  • Organopolysiloxane polymer (i) is generally present in an amount of from 40 to 60% by weight of the composition, but in the absence of resin (v) organopolysiloxane polymer (i) may be present in an amount of from 50 to 75% by weight of the composition.
  • Component (ii) of the composition is a reinforcing filler such as finely divided silica.
  • Silica and other reinforcing fillers (ii) 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.
  • 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 (ii) 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; and alternatively from 15 to 30% wt. based on the weight of the composition.
  • reinforcing filler (ii) When reinforcing filler (ii) 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 (ii) do not clump, and can be homogeneously incorporated into polydiorganosiloxane polymer (i) as the surface treatment makes the fillers easily wetted by polydiorganosiloxane polymer (i). 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 (ii) is treated in situ with a treating agent in the presence of polydiorganosiloxane polymer (i), whereafter mixing a silicone rubber base material is obtained, to which other ingredients may be added.
  • reinforcing filler (ii) 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.
  • the composition may include one or more optional additives but the total weight % of the composition is 100 wt. % and the alkenyl and/or alkynyl content of polymer (i) is determined using quantitative infra-red analysis in accordance with ASTM E168.
  • composition as described herein is cured using a hydrosilylation cure package comprising an organohydrogenpolysiloxane having 3 or more silicon-bonded hydrogen atoms per molecule and a hydrosilylation catalyst.
  • organohydrogenpolysiloxane(s) (iii), which operate(s) as cross-linker(s) for polydiorganosiloxane polymer (i) and the resin (v) when present will undergo a hydrosilylation (addition) reaction by way of its silicon-bonded hydrogen atoms with the alkenyl groups in polydiorganosiloxane polymer (i) catalysed by one or more hydrosilylation catalysts discussed below.
  • the organohydrogenpolysiloxane (iii) 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 polydiorganosiloxane polymer (i) to form a network structure therewith and thereby cure the composition.
  • the molecular configuration of the organohydrogenpolysiloxane (iii) 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 measured in accordance with ASTM D 1084-16 using a Brookfield rotational viscometer with the most appropriate spindle for the viscosity being measured at 1 rpm, unless otherwise indicated.
  • the organohydrogenpolysiloxane (iii) is typically added in an amount such that the molar ratio of silicon bonded hydrogen atoms to unsaturated groups, e.g. alkenyl and/or alkynyl groups, (typically, vinyl, (Vi) groups in the composition is from 0.75 : 1 to 2 : 1.
  • unsaturated groups e.g. alkenyl and/or alkynyl groups, (typically, vinyl, (Vi) groups in the composition is from 0.75 : 1 to 2 : 1.
  • organohydrogenpolysiloxane (iii) examples include but are not limited to:
  • copolymers composed of (CtBbSiOic units, (CtB ⁇ HSiOic units, and S1O4/2 units.
  • the amount used is within the range described above, i.e. dependent on the molar ratio of silicon bonded hydrogen atoms to Vi groups discussed above but in terms of weight % they will typically be present in the composition in an amount somewhere within the approximate range of 2 to 10% by weight of the composition but this may vary depending on the cross-linker chosen.
  • the composition is cured via a hydrosilylation reaction catalysed by a hydrosilylation (addition cure) catalyst (iv) 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 iv
  • 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 (iv) 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 (iv) 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
  • the hydrosilylation catalyst (iv) 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 (iv) can be used to tailor reaction rate and cure kinetics.
  • the catalytic amount of the hydrosilylation catalyst (iv) is generally between 1.00 ppm, and 1000 parts by weight of platinum-group metal, per million parts (ppm), based on the combined weight of the components (i) and (ii) and (v) when present; alternatively between 1.0 and 500ppm; alternatively between 0.01 and 300 ppm, and alternatively between 1.0 and 100 ppm.
  • the catalytic amount of the catalyst may range from 1.0 to 100 ppm, alternatively 1.0 to 75 ppm, alternatively 1.0 to 50 ppm and alternatively 1.0 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 also contain an organosilicate resin (v) comprising R '
  • organosilicate resin v
  • organosilicate resins (v) when present is a source of unsaturation in the form of alkenyl or alkynyl groups having from 2 to 10 carbons which are reactive with reactive with organohydrogenpolysiloxane (iii).
  • R 2 is as described above.
  • suitable alkyl groups include methyl, ethyl, propyl, pentyl, octyl and decyl groups.
  • R 4 is an alkenyl and/or alkynyl group having from 2 to 10 carbons, alternatively having from 2 to 6 carbons for example vinyl, propenyl, hexenyl, ethynyl, propynyl and hexynyl groups, alternatively vinyl groups. Whilst d may be 0, 1 or 2, typically d is 1 or 2, alternatively d is 1.
  • the resinous portion of organosilicate resin (v) has a weight average molecular weight (Mw) of 3,000 to 30,000g/mol when measured by gel permeation chromatography (GPC).
  • Organosilicate resin (v) can be prepared by any suitable well-known method.
  • the composition also includes one or more Si-H scavengers (vi) selected from the group of (a) an unsaturated hydrocarbon having 2 to 20 carbons which may be linear branched and/or cyclic and (b) a short chain siloxane having a degree of polymerisation of from 2 to 15 and comprising one or more unsaturated groups where the unsaturation is an alkenyl group and wherein (a) and/or (b) may additionally contain one or more electron-attracting substituents;
  • Si-H scavengers selected from the group of (a) an unsaturated hydrocarbon having 2 to 20 carbons which may be linear branched and/or cyclic and (b) a short chain siloxane having a degree of polymerisation of from 2 to 15 and comprising one or more unsaturated groups where the unsaturation is an alkenyl group and wherein (a) and/or (b) may additionally contain one or more electron-attracting substituents;
  • Scavengers are able to scavenge residual Si-H functionality by post-cure hydro silylation, which it has been surprisingly found improves the thermal stability without excessive loss of the liquid silicone rubbers (LSR’s) initial mechanical properties.
  • any suitable small unsaturated molecule may be utilised as the scavenger (vi).
  • suitable small unsaturated molecule include, norbornene, bis-norbornene, alkenyl or alkynyl containing polyhedral oligomeric silsequoxanes(POSS), e.g.
  • PHS-vinyl dihexenyltetramethyldisiloxane, methyl acrylate, methyl methacrylate, olefins such as 1 -hexene, 1-octene, 1-dodecene; dienes such as 1,9-decadiene, norbornene derivatives such as Ethylidene norbornene, Stilbene, Cycloalkenes and indene; and short chain dimethylvinyl terminated polydimethylsiloxanes having molecular weights of under 1000 such as:
  • Additives may be present in the composition depending on the intended use of the curable silicone elastomer composition. For example, given the composition is cured via hydrosilylation, inhibitors designed to inhibit the reactivity of the hydrosilylation catalysts may be utilised.
  • Other examples of 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 3,989,667 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-l-cyclohexanol (ETCH), 2-methyl-3-butyn-2-ol, 3-butyn-l-ol, 3-butyn-2-ol, propargylalcohol, 2-phenyl-2-propyn- l-ol, 3,5-dimethyl-l-hexyn-3-ol, 1-ethynylcyclopentanol, l-phenyl-2-propynol, 3 -methyl- 1-penten- 4-yn-3-ol, and mixtures thereof.
  • ECH 1-ethynyl-l-cyclohexanol
  • 2-methyl-3-butyn-2-ol 3-butyn-l-ol
  • 3-butyn-2-ol propargylalcohol
  • 2-phenyl-2-propyn- l-ol 3,5-dimethyl-l-hexyn-3-ol
  • inhibitor concentrations as low as 1 mole of inhibitor per mole of the metal of catalyst (iv) 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 (iv) 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.
  • additives may be present in the composition as and when required depending on the intended use of the curable silicone elastomer composition.
  • additives include non-reinforcing fillers, 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.
  • Non-reinforcing filler may comprise crushed quartz, diatomaceous earths
  • barium sulphate iron oxide, titanium dioxide and carbon black
  • wollastonite and platelet type fillers such as, graphite, graphene, talc, mica, clay, sheet silicates, kaolin,
  • aluminite used alone or in addition to the above include aluminite, calcium sulphate (anhydrite),
  • hydroxide brucite
  • graphite copper carbonate
  • nickel carbonate e.g.
  • zarachite barium carbonate, e.g. witherite and/or strontium carbonate e.g. strontianite.
  • Non-reinforcing fillers may alternatively or additionally be selected from aluminium oxide, silicates from the group consisting of olivine group; garnet group; aluminosilicates; ring silicates; chain silicates; and sheet silicates.
  • the olivine group comprises silicate minerals, such as but not limited to, forsterite and MgaSiCE.
  • the garnet group comprises ground silicate minerals, such as but not limited to, pyrope; MgsAESEO ⁇ ; grossular; and CaaAESEOia.
  • Aluminosilicates comprise ground silicate minerals, such as but not limited to, sillimanite; AI2S1O5 ; mullite;
  • 3AI2O3.2S1O2; kyanite; and AhSiOs Thc ring silicates group comprises silicate minerals, such as but not limited to, cordierite and Al 3 (Mg,Fe) 2 [Si 4 A10i 8 ].
  • the chain silicates group comprises ground silicate minerals, such as but not limited to, wollastonite and Ca[Si03].
  • Suitable sheet silicates e.g. silicate minerals which may be utilised include but are not limited to mica; K ⁇ AT ⁇ SieAECEoKOHE; pyrophyllite; AL ⁇ SisCEoKOH ⁇ ; talc; MgeCSisCEoKOtfU; serpentine for example, asbestos; Kaolinite; AUfSUOioKOHh; and vermiculite.
  • the non-reinforcing filler(s) is/are present up to a cumulative total of from 1 to 50% wt. of the composition,
  • the non-reinforcing filler may include glass or the like micro beads or microspheres to enhance the thermal insulation of the material.
  • the micro beads or microspheres may be glass e.g. for example borosilicate glass micro-beads and/or microspheres.
  • the non-reinforcing filler may also be treated as described above with respect to the reinforcing fillers (ii) 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 makes them easily wetted by polydiorganosiloxane polymer (i) and resin (v) when present which may result in improved properties of the compositions, such as better processability (e.g. lower viscosity, better mold releasing ability and/or less adhesive to processing equipment, such as two roll mill), heat resistance, and mechanical properties.
  • Examples of electrical conductive fillers 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, silicon carbide, metal oxides (such as zinc oxide, magnesium oxide, and aluminium oxide, graphite, diamond, and mixtures or derivatives thereof.
  • non-conductive fillers examples include quartz powder, diatomaceous earth, talc, clay, 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 include aluminium trihydrate, magnesium hydroxide, calcium carbonate, zinc borate, wollastonite, mica and chlorinated paraffins, hexabromocyclododecane, triphenyl phosphate, dimethyl methylphosphonate, tris(2,3-dibromopropyl) phosphate (brominated tris), and mixtures or derivatives thereof.
  • lubricants include tetrafluoroethylene, resin powder, graphite, fluorinated graphite, talc, boron nitride, fluorine oil, silicone oil, phenyl functional silicone oil, molybdenum disulfide, 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.
  • Examples of colouring agents 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 al
  • 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 polydiorganosiloxane polymer (i), thereby linking two or more molecules of polydiorganosiloxane polymer (i) 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 0.
  • the chain extender is a polyorganosiloxane, it has terminal units of the general formula HR a 2SiOi/2 and non terminal units of the formula R b 2SiO.
  • 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
  • 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 will be stored prior to use in two parts Part A and part B.
  • part A will contain some of polydiorganosiloxane polymer (i) and reinforcing filler (ii) and hydrosilylation catalyst (iv) and part B will contain the remainder of polydiorganosiloxane polymer (i) and reinforcing filler (ii) together with components
  • organohydrogenpolysiloxane (iii) and, if present, the inhibitor may be designed to be mixed together in any suitable ratio, dependent on the amounts of polydiorganosiloxane polymer (i) and reinforcing filler (ii) in part B and as such can be mixed in a Part A : Part B weight ratio of from 15 : 1 to 1 : 1.
  • Component (v), when present, and component (vi) may be individually introduced into either or both Part A and/or Part B.
  • composition of the present invention may be prepared by combining all of ingredients at ambient or elevated temperature as desired. Any mixing techniques and devices described in the prior art can be used for this purpose. The particular device to be used will be determined dependent on the viscosities of ingredients and the final curable composition. Suitable mixers include but are not limited to paddle type mixers and kneader type mixers. Cooling of ingredients during mixing may be desirable to avoid premature curing of the composition.
  • composition as hereinbefore described may be prepared by combining all of ingredients at ambient or elevated temperature as desired. Any mixing techniques and devices described in the prior art can be used for this purpose. The particular device to be used will be determined dependent on the viscosities of ingredients and the final curable composition. Suitable mixers include but are not limited to paddle type mixers and kneader type mixers. Cooling of ingredients during mixing may be desirable to avoid premature curing of the composition.
  • a method for the manufacture of a self-lubricating silicone elastomer comprising the steps of providing a composition as described herein; mixing the composition together and curing.
  • the mixing step may involve mixing all the individual ingredients together or in the presence of component (v) when the composition is in two parts mixing the two parts together.
  • component (v) when the composition is in two or more parts, the parts may be mixed together in a multi-part mixing system prior to cure.
  • the viscosity of the composition ranges of from 10 to 1,000 Pa.s, alternatively of from 10 to 500 Pa.s, alternatively of from 100 to 500 Pa.s in each case at 25°C measured in accordance with ASTM D 1084-16 using a Brookfield rotational viscometer with the most appropriate spindle for the viscosity being measured at 1 rpm.
  • the silicone rubber composition may dependent on viscosity and application etc., be further processed by injection moulding, encapsulation moulding, press moulding, dispenser moulding, extrusion moulding, transfer moulding, press vulcanization, centrifugal casting, calendering, bead application or blow moulding.
  • Curing of the silicone rubber composition may be carried at as required by the type of cure package utilized. Whilst it is usually preferred to use raised temperatures for curing hydrosilylation cure systems e.g. from about 80°C to 150°C, subsea silicone rubber compositions are generally designed to be cured at lower temperatures, e.g. between room temperature and 80°C, alternatively between room temperature, i.e. about 23-25°C to about 50°C.
  • the composition herein will produce an elastomeric thermal insulation material which is resistant to cracking and or splitting under thermal and/or mechanical stress.
  • Curing can for example take place in a mold to form a moulded silicone article.
  • the composition may for example be injection moulded to form an article, or the composition can be overmoulded by injection moulding around an article or over a substrate.
  • composition as disclosed herein and resulting elastomer provided upon cure of the composition may be utilised for any suitable application requiring an elastomeric subsea insulation silicone rubber material made by curing the composition as hereinbefore described.
  • the elastomeric subsea insulation silicone rubber material as hereinbefore described may be utilised in the thermal insulation of, for example, piping including riser pipes, wellheads, Xmas bees, spool pieces, manifolds, risers and pipe field joints.
  • any insulation material or system must be capable of being easily formed into complex shapes to accommodate the components of a pipe line assembly.
  • the relatively low viscosity of the pre-cured composition allows the composition to be pumped into prepositioned molds in order to enable the composition to cure into the shapes required to insulate the part concerned.
  • compositions and components of the compositions, elastomers, and methods are intended to illustrate and not to limit the invention.
  • the vinyl and Si-H content of polymers was determined using quantitative infra-red analysis in accordance with ASTM E168. All viscosities were measured using a measured in accordance with ASTM 1084 using a Brookfield rotational viscometer with the most appropriate spindle for the viscosity being measured at 1 rpm, unless otherwise indicated.
  • Part A composition was described in Table 1 below and was used as standard for all examples.
  • a base was first prepared by mixing the polymer, resin and filler ingredients and the remaining ingredients were added subsequent to the preparation of the base.
  • a standard part B composition was also utilised in order to show the differences measured in the examples were caused by the effects of the scavengers (vi).
  • the cross-linker (iii) in Table 2 is a short chain polymer mixture having an average formula of MD l ;i ;iiD 2 s ;i2M where (M is Mc sSi-, D is -OSiMe2- and, D’ is -OSiMe’H-), where the molar ratio of D 1 : D 2 is 0.6 : 1; i.e. Me3Si-[OSiMe2]3 . 34-[OSiMeH]5 . 32-Si Mc ⁇ .
  • the scavengers (vi) used in the examples are listed in Table 3 below. The amounts shown therein indicate the amount (g) added into test samples of lOOg of the above part A composition.
  • a two-step protocol was used to assess the thermal stability of the cured materials at 180 °C in a nitrogen environment.
  • Samples were cured at 40 °C for a period of two hours between two parallel-plate sample fixtures (disposable, aluminum, 25-mm-diameter, 1-mm gap between plates) using an ARES-G2 rheometer from TA Instruments). This step is designed to mimic the curing of the silicone rubber material under end-use conditions.
  • the cured silicone rubber materials were then heated rapidly at a rate of 28 °C/min for approximately 5 minutes to reach a target thermal stability temperature T (e.g. 170, 180, 190, 200, ...260 °C).
  • T target thermal stability temperature
  • the modulus G* was subsequently measured at temperature T every 20 seconds for a total of 20 to 24 hours (h).
  • the modulus falls (or grows) at an even slower rate when held at 180 °C for more than ten hours.
  • the slope of this data, dlG*l/df, is called the modulus loss rate, and is used henceforth as a key metric of the thermal stability at 180 °C.
  • Tables 3a and 3b below show the results of an initial screening test of stability, with a small sample (ca 10 g, cured on a rheometer at 40 °C for 2 hours then heated to 180 °C and held overnight.
  • the modulus IG*(10 h)l ⁇ (G”) + (G”) ⁇ 1/2 refers to the magnitude of the complex modulus G* after 10 hours at 180 °C. This modulus is a key metric of the rubber crosslink level. Rubbers with IG*(10 h)l exceeding that (529000 Pa) of the reference sample (no additives) are thought to be more crosslinked.
  • This viscous fluid was then poured into a molding chase.
  • a Teflon-coated sheet of aluminum was positioned between the chase and the metal support plate to create a defect free surface to cast on.
  • the freshly poured material and substrate was then placed back into a vacuum oven at room temperature and full vacuum was applied for about 10 min (depending on the viscosity of the corresponding mixture).
  • the plaque was then removed from the oven and any bubbles that were created during the vacuum step were popped using a syringe. Finally, the plaque was placed on a level surface in a fume hood and allowed to sit undisturbed at room temperature until curing was complete.
  • Example 1 retained 37% of its tensile strength and 30% of its elongation, while the Control retained only 26% of its tensile strength and 20% of its elongation, an improvement of 43% and 47% in retention of these properties respectively.

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  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition et un procédé de fabrication d'un matériau de caoutchouc silicone d'isolation sous-marine. La composition comprend un piégeur pour conférer une stabilité thermique au caoutchouc silicone.
PCT/US2019/067097 2018-12-19 2019-12-18 Compositions de caoutchouc silicone et matériaux élastomères Ceased WO2020132020A1 (fr)

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CN115926464A (zh) * 2022-11-15 2023-04-07 清远高能结加改性材料科技有限公司 一种硅橡胶增强粒子及增强型橡胶粉的制备方法
CN116438243A (zh) * 2020-11-27 2023-07-14 信越化学工业株式会社 混炼型硅橡胶组合物及硅橡胶固化物
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CN117532973A (zh) * 2023-11-24 2024-02-09 长春中科应化特种材料股份有限公司 一种单组份室温快速自固化绝缘包材及其制备方法
RU2819625C1 (ru) * 2023-07-20 2024-05-22 Акционерное Общество "Фэйт" Состав силиконовой смеси для изготовления изделий с улучшенной теплопроводностью
CN121471881A (zh) * 2026-01-08 2026-02-06 辽宁汽众润滑油生产有限公司 一种含石墨烯导热剂的高效冷却液

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CN117532973A (zh) * 2023-11-24 2024-02-09 长春中科应化特种材料股份有限公司 一种单组份室温快速自固化绝缘包材及其制备方法
CN121471881A (zh) * 2026-01-08 2026-02-06 辽宁汽众润滑油生产有限公司 一种含石墨烯导热剂的高效冷却液

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