GB2460512A - A Silicone Rubber including a Mineral filler - Google Patents

Abstract

A silicone rubber composition comprising an organopolysiloxane having a viscosity of at least 100 mPa.s at 25°C, a filler comprising one or more acicular minerals selected from the group of halloysite, sepiolite and/or attapulgite, and a curing agent. The mineral may be treated with an alkoxysilane which renders the minerals more hydrophobic. The curing agent may be a peroxide selected from benzoly peroxide, 2,4-dichlorobenzoyl peroxide and di-t-butyl peroxide. Alternatively the curing agent can be an organohydrosiloxane used with a platinum group metal hydrosilylation catalyst. The method of forming the silicone rubber composition includes steps of mixing an organopolysiloxane and mineral filler at room temperature, then adding a curing agent and curing the mixture by the application of heat. The silicon rubber composition may be used for silicone profile extrusions, wire and cable coatings, glazing gaskets and for construction gaskets.

Description

SILICONE RUBBER COMPOSITIONS

[0001] This invention is related to filled silicone rubber compositions containing acicular fillers.

[0002] Silicone rubbers, often referred to as silicone elastomers, are composed of three essential ingredients. These ingredients are (i) a substantially linear high molecular weight silicone polymer, (ii) one or more filler(s), and (iii) a curing agent, sometimes referred to as a crosslinking agent or a vulcanising agent. Generally, there exist two main types of silicone rubber compositions heat vulcanised, (HTV) silicone rubber and room temperature vulcanising (RTV) silicone rubber. Heat vulcanised or high temperature vulcanising (HTV) silicone rubber compositions are often further differentiated as high consistency rubber (HCR) or liquid silicone rubber (LSR) depending on uncured viscosity of the composition.

The name room temperature vulcanising (RTV) silicone rubber compositions, however may be misleading as many RTV compositions require a modicum of heat to progress the reaction at a reasonable rate.

[0003] HTV silicone rubber compositions are typically prepared by mixing the substantially linear high molecular weight silicone polymer with the filler and other desired additives to form a base or raw stock. Prior to use, the base is compounded to incorporate the curing agent, other fillers, and additives such as pigments, anti-adhesive agents, plasticizers, and adhesion promoters; and it can be vulcanised by press vulcanisation, injection or transfer moulding or continuously by extrusion, to form the final silicone rubber product. For example silicone rubber compositions used for cable insulation applications are extruded by special techniques in which the silicone rubber is applied to cable cores by means of angular extruder heads.

[0004] For high consistency rubber (HCR) the substantially linear high molecular weight silicone polymer most widely employed is a very high viscosity polysiloxane. Such linear high molecular weight silicone polymers have a viscosity of 1,000,000 mPa.s or more at 25°C. Typically these linear high molecular weight silicone polymers have such high viscosities at 25°C that they are in the form of gum like materials which have such high viscosities that the measurement of viscosity is extremely difficult and therefore they are often referred by reference to their Williams plasticity number (ASTM 0926). The Williams plasticity number of high viscosity polysiloxane gum-like polymers are generally at least 30, typically they are in the range of from about 30 to 250. The plasticity number, as used herein, is defined as the thickness in millimeters x 100 of a cylindrical test specimen 2 cubic cm in volume and approximately 10 mm in height after the specimen has been subjected to a compressive load of 49 Newtons for three minutes at 25°C. These polysiloxane gum-like polymers generally contain a substantially siloxane backbone (-Si-O-) to which are linked alkyl groups such as for example methyl, ethyl, propyl, isopropyl and t-butyl groups, and unsaturated groups for example alkenyl groups such as allyl, 1-propenyl, isopropenyl, or hexenyl groups but vinyl groups are particularly preferred and/or combinations of vinyl groups and hydroxyl groups to assist in their crosslinking. Such polysiloxane gum-like polymers typically have a degree of polymerisation (DP) of 500-20,000, which represents the number of repeating units in the polymer.

[0005] Historically HTV silicone rubber compositions contain one or more fillers. The fillers used are usually referred to as reinforcing fillers and non-reinforcing fillers. Reinforcing fillers impart high strength to vulcanised rubber and may comprise finely divided amorphous silica such as fumed silica and precipitated silica. Extending or non-reinforcing fillers are generally used to reduce the cost of the silicone rubber composition, and generally comprise inexpensive filler materials such as ground quartz, calcium carbonate, and diatomaceous earth. Reinforcing fillers are typically used alone or together with extending or non-reinforcing fillers. The reinforcing fillers are usually treated with organosilanes, organosiloxanes, or organosilazanes, in order to improve the physical and/or mechanical properties of the silicone rubber composition, i.e., tensile strength and compression set.

[0006] Wollastonite which is in some forms an acicular shaped mineral has previously been proposed as a filler for silicone rubber as described in U56051642, GB2360780, Wool /34696, W001/34705, W000/4681 7 and JPO9-551 25.

[0007] The present invention has identified that a number of acicularly shaped minerals make acceptable fillers for silicone rubber compositions.

[0008] In accordance with a first embodiment of the present invention there is provided a silicone rubber composition comprising: (i) an organopolysiloxane having a viscosity of at least 100 mPa.s at 25°C (ii) filler, comprising one or more acicular minerals selected from the group of halloysite, sepiolite and/or attapulgite, and (iii) a curing agent.

[0009] Unless otherwise indicated all viscosity measurements are at 25°C. The composition in accordance with the invention can be utilised as a liquid silicone rubber (LSR) composition. When the composition in accordance with the present invention is an LSR the viscosity of the organopolysiloxane polymer used is from 100 to 150 000 mPa.s at 25°C.

The composition in accordance with the invention can be utilised as a high consistency rubber (HCR) composition. When the composition in accordance with the present invention is an HCR, the viscosity of the organopolysiloxane polymer used is preferably at least 250 000 mPa.s at 25°C but is typically greater than 1 000 000 mPa.s at 25°C, and has a Williams Plasticity number of at least 30. There is nothing preventing the man skilled in the art using an organopolysiloxane polymer with a viscosity of between 150 000 mPa.s and 250 000 mPa.s at 25°C but the above ranges are preferred for LSR and HCR type compositions respectively.

[0010] The organopolysiloxane polymer comprises one or more polymers which preferably have the formula: RR12SiO[(R2Si-R5-(R2)SiO)(R2SiO)(RZSiO)] SiRR12 wherein each R is the same or different and is an alkyl group containing 1-6 carbon atoms, a phenyl group or a 3,3,3-trifluoroalkyl group; each Z is the same or different and is hydrogen or an unsaturated hydrocarbon group such as an alkenyl group or an alkynyl group; each R1 may be the same or different and needs to be compatible with the curing agent used such that the curing agent will cause the polymer to cure. R1 may be selected from Z, R; a hydroxyl group and/or an alkoxy group. Each R5 may be the same or different and is a difunctional saturated hydrocarbon group having from I to 6 carbon atoms x is an integer and y is zero or an integer; s is zero or an integer between 1 and 50; and the sum of x + y +5 is a number which results in a suitable polymer viscosity for the end product required. In the case of HCR compositions preferably the viscosity of the polymer is at least 500,000 mPa.s at 25°C. Alternatively In the case of HCR compositions the viscosity of the polymer is at least 1 000,000 mPa.s at 25°C. When y and/or s are integers the (R2SIO) groups,(RZSiO) groups and/or (R2Si-R5-(R2)SiO) groups in the polymer chain are either randomly distributed or the organopolysiloxane polymer may be in the form of a block copolymer.

[0011] Preferably each R group is an alkyl group, most preferably each R is a methyl or ethyl group. Preferably when Z is an alkenyl group it has between 2 and 10 carbon atoms, more preferably between 2 and 7 carbon atoms, preferred examples being vinyl or hexenyl groups. R5 may be, for example, -CH2-, -CH2CH2-and -CH2CH2CH2-but most preferably each R5 is -CH2CH2-.

[0012] In one preferred embodiment of the present invention in which the composition is an HCR composition the organopolysiloxane constituent of the composition may be a mixture of two or more organopolysiloxanes such as a two component mixture having the following formulae: RR12SiO[(R2Si-R5-(R2)SiO) (R2SiO)(RZSiO)]Si RR12 (1) and RR12SiO[(R2Si-R5-(R2)SiO)1(R2SiO)1 (RZSiO)1]SiRR12 (2) wherein each R is the same or different and is as described above and each R1 is the same or different and is as described above; x, y and s are as previously defined and the value of x1 y1 and s1 are in the same ranges as x, y and s respectively but at least one of x, y and s has a different value from the value of x1 y1 and s1 respectively. Preferably at least 25% of R1 groups are Z groups, most preferably alkenyl groups and a viscosity of the polymer mixture of at least 500,000 mPa.s at 25°C, alternatively at least 1 000,000 mPa.s at 25°C with polymer (1) having a degree of polymerisation (DP) i.e. the value of x or the sum of x and y and/or s (when present) of at least 1,000 and polymer (2) having a DP i.e. the value of x1 or the sum of x1 and y1 and/or s1 (when present) of at least 100.

[0013] Hence, the composition may comprise a mixture of two high viscosity organopolysiloxane polymers with the formulae: Me2ViSiO[(Me2SiO)(MeViSiO)]Si Me2Vi and Me2ViSiO[(Me2SiO)1]Si Me2Vi wherein Me represents the methyl group (-CH3) , Vi represents the vinyl group (CH2=CH-), the value of the sum of x and y is at least 1,000 and the value of x1 is at least 1000.

[0014] Alternatively in another preferred embodiment the organopolysiloxane comprises a mixture of a two components having the following formulae: RR12SiO[(R2SiO)(RZSiO)(R2Si-R5-(R2)SiO)] SiRR12 and RR12SiO[(R2SiO)1 (RZSiO)1]SiRR12 wherein, in each formula, R Z and R1 are as described above and x, y, s, x1 and y1 are as previously described and the viscosity of the mixture has a value of at least 500,000 mPa.s at 25°C, alternatively at least 1 000,000 mPa.s at 25°C with the value of x or the sum of x and y and/or s (when either or both are present) being at least 1,000 and the value of x1 and y1 being between 100 and 1000. Preferably at least 25% of R1s are Z groups, most preferably alkenyl groups and the value of x or the sum of x and y and/or s (when present) provides a viscosity of the polymer mixture of at least 500,000 mPa.s at 25°C, alternatively at least 1 000,000 mPa.s at 25°C. Typically the value of x or the sum of x and y and/or s (when present) is at least 1,000.

[0015] The filler used in the present invention must comprise halloysite, sepiolite and/or attapulgite. Preferably the filler in the present invention is substantially free of reinforcing silica fillers For the sake of this invention a reinforcing silica filler is intended to mean precipitated silica and fumed silica and any other reinforcing silica (and therefore excludes ground silica which is does not provide silicone rubber compositions with a reinforcing effect). It is to be understood that the term "substantially free" is intended to mean that the composition is essentially free of reinforcing silica fillers, such that silica fillers can only be present up to a maximum amount of 5 parts by weight per 100 parts by weight of the cumulative total weight of the polymer + optionally treated halloysite, sepiolite and/or attapulgite filler. Alternatively, reinforcing silica fillers are present up to a maximum amount of 3 parts by weight per 100 parts by weight of the cumulative total weight of the polymer + optionally treated halloysite, sepiolite and/or attapulgite filler. Alternatively, reinforcing silica fillers are present up to a maximum amount of 1 part by weight per 100 parts by weight of the cumulative total weight of the polymer + optionally treated halloysite, sepiolite and/or attapulgite filler. In a further alternative the composition consists of halloysite, sepiolite and/or attapulgite as the only reinforcing filler and contains zero reinforcing silica fillers.

Alternatively halloysite, sepiolite and/or attapulgite is! the only filler(s) present in the composition. It is to be noted that a reinforcing effect is not generally noticed in the physical properties of a silicone rubber unless present in an amount of at least 25 parts by weight of reinforcing filler per 100 parts by weight of polymer. Hence at the levels permitted the reinforcing silica fillers present will have minimal or no reinforcing effect on the physical properties of the silicone rubber. As will be discussed in more detail below when present precipitated silica and/or fumed silica are used for their properties of rheology modifiers.

Essentially the reinforcing effect which can be seen in compositions as described herein is provided by the reinforcing properties of halloysite, sepiolite and/or attapulgite.

However, additional other fillers may be included in the composition of the present invention.

[0016] Preferably the acicular mineral used in the present invention as a filler for the silicone rubber composition is treated to render the filler(s) hydrophobic and therefore easier to handle and obtain a homogeneous mixture with the other components in the composition in accordance with the present invention. Hydrophobing the acicular mineral results in the resulting hydrophobically modified acicular mineral is easily wetted by the silicone polymer.

Hydrophobically modified acicular mineral does not clump, and therefore is easily homogeneously incorporated into the silicone polymer. This results in improved room temperature mechanical properties of the uncured compositions. Furthermore, the surface treated fillers give a lower conductivity than untreated or raw material.

[0017] Treated acicular mineral filler comprises the majority of filler present in the composition and is present in an amount of from about 5 to 200 parts by weight per 100 parts by weight of polymer, more preferably 30 -150 parts by weight per 100 parts by weight of the polymer.

[0018] Any suitable treating agent which renders the surface of the halloysite, sepiolite and/or attapulgite hydrophobic may be used. Examples include organic treating agents such as fatty acids and/or fatty acid esters e.g. a stearate, or organosilanes, organosilazanes such as hexaalkyl disilazane or short chain organopolysiloxane polymers e.g. short chain siloxane diols.

[0019] Silanes found to be most suitable for the treatment of halloysite, sepiolite and/or attapulgite are alkoxysilanes of the general formula R3(4n)Si(0R3)n, wherein n has a value of 1-3; and each R3 is the same or different and represents a monovalent organic radical such as an alkyl group, an aryl group, or a functional group such as an alkenyl group, e.g. vinyl or allyl, an amino group or an amido group. Some suitable silanes therefore include alkyltrialkoxysilanes such as methyltriethoxysilane, methyltrimethoxysilane, phenyl tialkoxysilanes such as phenyltrimethoxysilane, or alkenyltrialkoxysilanes such as vinyltriethoxysilane, and vinyltrimethoxysilane. If desired, silazanes can also be used as treating agents for the halloysite, sepiolite and/or attapulgite filler. These include (but are not restricted to) hexamethyldisilazane; 1,1,3,3-tetramethyldisilazane; and 1,3-divinyltetramethyldisilazane. Other suitable treating agents which may be utilised in the present invention include those described in the applicant's co-pending patent application [0020] Short chain organopolysiloxanes might for example include hydroxy terminated polydimethylsiloxanes having a degree of polymerisation of from 2 to 20, hydroxy terminated polydialkyl alkylalkenylsiloxanes having a degree of polymerisation of from 2 to 20 and organopolysiloxanes comprising at least one Si-H group, which may or may not be a terminal group, e.g. those having the formula: R4hH3h wherein in each formula, R4 represents an alkyl group containing 1-6 carbon atoms; H is hydrogen, h is zero or an integer from 1 to 3, f and g are independently zero or an integer with the proviso that the treating agent has at least one Si-H group and a viscosity of from 5 to 5000 mPa.s at 25°C.

[0021] Preferably when treated approximately 1 to 10% by weight of the optionally treated halloysite, sepiolite and/or attapulgite filler will be treating agent. Alternatively the treating agent will be from 2.5 to 10% weight of the treated halloysite, sepiolite and/or attapulgite filler. The filler may be pre-treated before addition into the composition or may be treated in situ during mixing with the polymer.

[0022] A curing agent, as noted above, is required and compounds which can be used herein include organic peroxides such as dialkyl peroxides, diphenyl peroxides, benzoyl peroxide, 1,4-dichlorobenzoyl peroxide, paramethyl benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, tertiary butyl-perbenzoate, monochlorobenzoyl peroxide, d itertiary-butyl peroxide, 2,5-bis-(tertiarybutyl-peroxy)-2, 5-d imethylhexane, 1,1 -bis(t-butylperoxy)-3,3,5-trimethylcyclohexane tertiary-butyl-trimethyl peroxide, tertiary-butyl-tertiary-butyl-tertiary-triphenyl peroxide, and t-butyl perbenzoate. The most suitable peroxide based curing agents are benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, di-t-butyl peroxide, and dicumyl peroxide. Organic peroxides such as the above are particularly utilised when R1 in the polymer as defined above is an alkyl group but the presence of some unsaturated hydrocarbon groups per molecule is preferred. It may also be used as the curing agent when R1is Z as hereinbefore described.

[0023] These organic peroxides may be formed into a paste by dispersing in a silicone oil for ease of introduction into the composition. It is recommended that they are be used in an amount of 0.1 to 10 parts by weight, preferably 0.5 to 2.0 parts by weight, per 100 parts by weight of polymer.

[0024] In the case when R1 is a hydroxy group or an alkoxy group the curing agent may comprise a suitable condensation reaction catalyst alone or in combination with a cross-linking material which undergoes a condensation reaction with the hydrolysable polymer end groups. Typically this means of cure is not preferred for the present invention.

[0025] The present compositions can also be cured and/or crosslinked by a hydrosilylation reaction catalyst in combination with an organohydrogensiloxane as the curing agent instead of an organic peroxide, providing each polymer molecule contains at least two unsaturated groups suitable for cross-linking with the organohydrogensiloxane. These groups are typically alkenyl groups, most preferably vinyl groups. To effect curing of the present composition, the organohydrogensiloxane must contain more than two silicon bonded hydrogen atoms per molecule. The organohydrogensiloxane can contain, for example, from about 4-200 silicon atoms per molecule, and preferably from about 4 to 50 silicon atoms per molecule and have a viscosity of up to about 10 Pa*s at 25 °C. The silicon-bonded organic groups present in the organohydrogensiloxane can include substituted and unsubstituted alkyl groups of 1-4 carbon atoms that are otherwise free of ethylenic or acetylenic unsaturation. Preferably each organohydrogensiloxane molecule comprises at least 3 silicon-bonded hydrogen atoms in an amount which is sufficient to give a molar ratio of Si-H groups in the organohydrogensiloxane to the total amount of alkenyl groups in polymer of from 1/1 to 10/1.

[0026] Preferably the hydrosilylation catalyst is a platinum group metal based catalyst selected from a platinum, rhodium, iridium, palladium or ruthenium catalyst. Platinum group metal containing catalysts useful to catalyse curing of the present compositions can be any of those known to catalyse reactions of silicon bonded hydrogen atoms with silicon bonded alkenyl groups. The preferred platinum group metal for use as a catalyst to effect cure of the present compositions by hydrosilylation is platinum. Some preferred platinum based hydrosilylation catalysts for curing the present composition are platinum metal, platinum compounds and platinum complexes. Representative platinum compounds include chloroplatinic acid, chioroplatinic acid hexahydrate, platinum dichloride, and complexes of such compounds containing low molecular weight vinyl containing organosiloxanes. Other hydrosilylation catalysts suitable for use in the present invention include for example rhodium catalysts such as [Rh(O200H3)2]2, Rh(O200H3)3, Rh2(C8H1502)4, Rh(C5H702)3, Rh(C5H702)(CO)2, Rh(C0)[Ph3P](C5H702), RhX3[(R3)25]3, (R23P)2Rh(CO)X, (R23P)2Rh(CO)H, Rh2X2Y4, HaRhbolefincCld, Rh (O(CO)R3)3(OH) where X is hydrogen, chlorine, bromine or iodine, Y is an alkyl group, such as methyl or ethyl, 00, C8H14 or 0.5 C8H12, R3 is an alkyl radical, cycloalkyl radical or aryl radical and R2 is an alkyl radical an aryl radical or an oxygen substituted radical, a is 0 or 1, b is 1 or 2, c is a whole number from 1 to 4 inclusive and d is 2,3 or 4, n is 0 or 1. Any suitable iridium catalysts such as lr(OOCCH3)3, lr(C5H702)3, [lr(Z1)(En)2]2, or (Ir(Z1)(Dien)]2, where Z1 is chlorine, bromine, iodine, or alkoxy, En is an olefin and Dien is cyclooctadiene may also be used.

[0027] The platinum group metal containing catalyst may be added to the present composition in an amount equivalent to as little as 0.001 part by weight of elemental platinum group metal, per one million parts (ppm) of the composition. Preferably, the concentration of platinum group metal in the composition is that capable of providing the equivalent of at least 1 part per million of elemental platinum group metal. A catalyst concentration providing the equivalent of about 3-50 parts per million of elemental platinum group metal is generally the amount preferred.

[0028] To obtain a longer working time or "pot life", the activity of hydrosilylation catalysts under ambient conditions can be retarded or suppressed by addition of a suitable inhibitor.

Known platinum group metal catalyst inhibitors include the acetylenic compounds disclosed in U.S. Pat. No. 3,445,420. Acetylenic alcohols such as 2-methyl-3-butyn-2-oI and 1-ethynyl-2-cyclohexanol constitute a preferred class of inhibitors that suppress the activity of a platinum-based catalyst at 25°C. Compositions containing these catalysts typically require heating at temperatures of 70°C or above to cure at a practical rate. Room temperature cure is typically accomplished with such systems by use of a two-part system in which the crosslinker and inhibitor are in one of the two parts and the platinum is in the other part. The amount of platinum is increased to allow for curing at room temperature.

[0029] Inhibitor concentrations as low as one mole of inhibitor per mole of platinum group metal will in some instances impart satisfactory storage stability and cure rate. In other instances inhibitor concentrations of up to 500 or more moles of inhibitor per mole of platinum group metal are required. The optimum concentration for a given inhibitor in a given composition can readily be determined by routine experimentation.

[0030] As hereinbefore described the composition of the present invention is preferably substantially free of reinforcing silica fillers. However the composition may comprise up to 5 parts per weight per 100 parts by weight of polymer + optionally treated halloysite, sepiolite and/or attapulgite of a rheology modifier. Preferably when present the rheology modifier is present in an amount of from 1 to 3 parts by weight per 100 parts by weight of polymer + optionally treated halloysite, sepiolite and/or attapulgite. The rheology modifier may comprise polytetrafluoroethylene (PTFE), boric acid, amorphous precipitated or fumed silica.

It is to be understood that the amount of silica present within the ranges permitted are such that it is present in such low amounts so as to have a negligible effect on the physical properties of the resulting composition.

[0031] Whilst the composition may also be free of all other fillers, the composition may comprise additional fillers (other than silica reinforcing fillers) such as finely divided, calcium carbonate or additional non-reinforcing fillers such as crushed quartz, diatomaceous earths, barium sulphate, iron oxide, titanium dioxide and carbon black, talc, wollastonite. Other fillers which might be used alone or in addition to halloysite, sepiolite and/or attapulgite 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.

[0032] 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 Mg2SiO4. The garnet group comprises ground silicate minerals, such as but not limited to, pyrope; Mg3Al2Si3O12; grossular; and Ca2A12Si3O12. Aluninosilicates comprise ground silicate minerals, such as but not limited to, sillimanite; AI2SiO5; mullite; 3A1203.2SiO2; kyanite; and AI2SiO5. The ring silicates group comprises silicate minerals, such as but not limited to, cordierite and A13(Mg,Fe)2[Si4A1O18]. The chain silicates group comprises ground silicate minerals, such as but not limited to, wollastonite and Ca[Si03].

[0033] The sheet silicates group comprises silicate minerals, such as but not limited to, mica; K2A114[Si6Al2O20](OH)4; pyrophyllite; A14[Si8020](OH)4; talc; Mg6[Si8020](OH)4; serpentine for example, asbestos; Kaolinite; A14[Si4010](OH)8; and vermiculite.

[0034] The above fillers may be used untreated but are preferably treated with one of the hydrophobing treating agents described above in any suitable manner.

[0035] Other ingredients which may be included in the compositions include but are not restricted to; rheological modifiers; Adhesion promoters, pigments, colouring agents, desiccants, heat stabilizers, Flame retardants, UV stabilizers, cure modifiers, electrically and/or heat conductive fillers, blowing agents, anti-adhesive agents, handling agents, peroxide cure co-agents such as metal salts of carboxylic acids and amines, acid acceptors, water scavengers typically only when the composition is condensation cured, (typically the same compounds as those used as cross-linkers or silazanes). It will be appreciated that some of the additives are included in more than one list of additives. Such additives would then have the ability to function in all the different ways referred to.

[0036] Any suitable adhesion promoter(s) may be incorporated in a rubber composition in accordance with the present invention. These may include for example alkoxy silanes such as aminoalkylalkoxy silanes, epoxyalkylalkoxy silanes, for example, 3-glycidoxypropyltrimethoxysilane and, mercapto-alkylalkoxy silanes and y-aminopropyl triethoxysilane, reaction products of ethylenediamine with silylacrylates. Isocyanurates containing silicon groups such as 1,3,5-tris(trialkoxysilylalkyl) isocyanurates may additionally be used. Further suitable adhesion promoters are reaction products of epoxyalkylalkoxy silanes such as 3-glycidoxypropyltrimethoxysilane with amino-substituted alkoxysilanes such as 3-aminopropyltrimethoxysilane and optionally alkylalkoxy silanes such as methyl-trimethoxysilane. epoxyalkylalkoxy silane, mercaptoalkylalkoxy silane, and derivatives thereof.

[0037] Heat stabilizers may include Iron oxides and carbon blacks, Iron carboxylate salts, cerium hydrate, barium zirconate, magnesium oxide, cerium and zirconium octoates, and porphyri ns.

[0038] Flame retardants may include for example, carbon black, hydrated aluminium hydroxide, and silicates such as wollastonite, platinum and platinum compounds.

[0039] Electrically conductive fillers may include carbon black, metal particles such as silver particles any suitable, electrically conductive metal oxide fillers such as titanium oxide powder whose surface has been treated with tin and/or antimony, potassium titanate powder whose surface has been treated with tin and/or antimony, tin oxide whose surface has been treated with antimony, and zinc oxide whose surface has been treated with aluminium.

[0040] Thermally conductive fillers may include metal particles such as powders, flakes and colloidal silver, copper, nickel, platinum, gold aluminium and titanium, metal oxides, particularly aluminium oxide (A1203) and beryllium oxide (BeO);magnesium oxide, zinc oxide, zirconium oxide; Ceramic fillers such as tungsten monocarbide, silicon carbide and aluminium nitride, boron nitride and diamond.

[0041] Handling agents are used to modify the uncured properties of the silicone rubber such as green strength or processability sold under a variety of trade names such as SILASTIC� HA-i, HA-2 and HA-3 sold by Dow Corning corporation).

[0042] Peroxide cure co-agents are used to modify the properties, such as tensile strength, elongation, hardness, compression set, rebound, adhesion and dynamic flex, of the cured rubber. These may include di-or tn-functional acrylates such as Trimethylolpropane Triacrylate and Ethylene Glycol Dimethacrylate; Triallyl Isocyanurate, Triallyl Cyanurate, Polybutadiene oligomers and the like. Silyl-hydride functional siloxanes may also be used as co-agents to modify the peroxide catalysed cure of siloxane rubbers.

[0043] The acid acceptors may include Magnesium oxide, calcium carbonate, Zinc oxide and the like.

[0044] The ceramifying agents can also be called ash stabilisers and include silicates such as wollastonite.

[0045] Silicone rubber compositions having acceptable mechanical properties when compared to conventional silicone rubber compositions can be produced according to the present invention in a process which involves no heat, and which avoids the necessity to use expensive fumed silica as a reinforcing filler.

[0046] Silicone rubber compositions having acceptable mechanical properties when compared to conventional silicone rubber compositions can be produced according to the present invention in a process which involves no heat, and which avoids the necessity to use expensive fumed silica as a reinforcing filler.

[0047] Compositions in accordance with the present invention may be prepared in accordance with any suitable method. For example by first making a treated calcined mineral filler containing silicone rubber composition consisting essentially of the steps of (i) mixing an organopolysiloxane polymer and treated calcined mineral filler under room temperature conditions, the mixture prepared in (i) being free of reinforcing silica fillers; (ii) adding a curing agent to the mixture in (i); and curing the mixture in (ii) at a temperature above room temperature by the application of heat.

[0048] However, in a preferred embodiment of the present invention there is provided a method of making a treated hydroxyapatite containing silicone rubber composition consisting essentially of the steps of (i) mixing an organopolysiloxane polymer and treated hydroxyapatite under room temperature conditions, the mixture prepared in (i) being free of reinforcing silica fillers; (ii) adding a curing agent to the mixture in (i); and curing the mixture in (ii) at a temperature above room temperature by the application of heat.

[0049] It is to be understood that room temperature conditions means atmospheric pressure and a room temperature at normal ambient temperature of 20-25 °C. It is a major advantage in the case of the present invention that heat is not required to be added during step (i) as is required when undertaking the in-situ treatment of reinforcing fillers. As in all mixing processes the effect of mixing will generate heat but mixing in the case of the present invention will not require any additional heat input.

[0050] Compositions in accordance with the present invention may be prepared in accordance with any suitable method. The conventional route of preparing highly filled silicone rubber compositions is to first make a silicone rubber base by heating a mixture of reinforcing filler (typically e.g. fumed silica), a treating agent for the reinforcing filler (fumed silica), and an organopolysiloxane e.g. a polysiloxane gum in a mixer. The silicone rubber base is removed from the first mixer and transferred to a second mixer where generally about 150 parts by weight of a non-reinforcing or extending filler such as ground quartz is added per 100 parts by weight of the silicone rubber base. Other additives are typically fed to the second mixer such as curing agents, pigments and colouring agents, heat stabilizers, anti-adhesive agents, plasticisers, and adhesion promoters. This route may also be utilised for compositions of the present invention with the reinforcing filler being halloysite, sepiolite and/or attapulgite.

[0051] Because the halloysite, sepiolite and/or attapulgite filler(s) disperses much more easily than fumed silica in polysiloxane gums, the total mixing cycle is considerably reduced, giving much greater mixer utilization. In addition, since the halloysite, sepiolite and/or attapulgite filler(s) are semi-reinforcing fillers, they are capable of providing a finished composition having adequate mechanical properties. However, because the halloysite, sepiolite and/or attapulgite filler(s) are only semi-reinforcing, a higher loading level needs to be used than would be the case for fumed silica. On the other hand, because of the lower cost of these fillers compared to silica, it is not necessary to use a large amount of them to obtain the right level of economic attractiveness for the finished composition. Preferably the ratio of optionally treated halloysite, sepiolite and/or attapulgite filler(s) to organopolysiloxane is from 1:2 to 2:1. Thus, one is enabled to use, for example, about 100 parts by weight of acicular filler in 100 parts by weight of the organopolysiloxane e.g. polysiloxane gum, without using fumed silica.

[0052] The same level of mechanical properties can thereby be obtained as with finished compositions containing fumed silica. Furthermore, the elimination of fumed silica means that no heating is required, and the whole compounding process can be carried out in a single mixer. In addition, the incorporation time for acicular filler is much higher than for fumed silica, with the result that mixer capacity is increased by utilizing the faster throughput.

Finally acicular filler has a much higher bulk density than fumed silica, which allows much improved ease of handling and storage.

[0053] These finished halloysite, sepiolite and/or attapulgite filler containing silicone rubber compositions are useful in applications such as silicone profile extrusions, wire and cable coatings, glazing, and for construction gaskets. Specific examples include the use of this product in window glazing gaskets, wire and cable such as plenum or safety cable sheathing applications, double glazing spacer gaskets. The only requirement relative to its use is that the finished composition have a property profile roughly equivalent to that acceptable for the particular application. The composition of the present invention may also be used in the production of silicone rubber sponges with the addition of a suitable foaming agent. Any suitable foaming agent may be used. The resulting product is particularly useful for manufacturing insulating glazing spacer gaskets.

Claims (17)

1. CLAIMS1. A silicone rubber composition comprising: (i) an organopolysiloxane having a viscosity of at least 100 mPa.s at 25°C (ii) filler, comprising one or more acicular minerals selected from the group of halloysite, sepiolite and/or attapulgite, and (iii) a curing agent.
2. 2. A composition according to Claim 1 in which the organopolysiloxane polymer comprises one or more polymers which preferably have the formula: RR12SiO[(R2Si-R5-(R2)SiO)(R2SiO)(RZSiO)] SiRR12 wherein each R is the same or different and is an alkyl group containing 1-6 carbon atoms, a phenyl group or a 3,3,3-trifluoroalkyl group; each Z is the same or different and is hydrogen or an unsaturated hydrocarbon group such as an alkenyl group or an alkynyl group; each R1 may be the same or different and needs to be compatible with the curing agent used such that the curing agent will cause the polymer to cure. R1 may be selected from Z, R; a hydroxyl group and/or an alkoxy group; each R5 may be the same or different and is a difunctional saturated hydrocarbon group having from 1 to 6 carbon atoms; x is an integer, y is zero or an integer; s is zero or an integer between 1 and 50.
3. 3. A composition according to Claim 1 or 2 in which the organopolysiloxane polymer is a two component mixture comprise a mixture of two high viscosity organopolysiloxane polymers with the formulae: Me2ViSiO[(Me2SiO)(MeViSiO)]Si Me2Vi and Me2ViSiO[(Me2SiO)1]Si Me2Vi wherein Me represents the methyl group (-OH3) , Vi represents the vinyl group (CH2=CH-), the value of the sum of x and y is at least 1,000 and the value of x1 is at least 1000.
4. 4. A composition according to Claim 1 or 2 in which the organopolysiloxane polymer is a two component mixture having the following formulae: RR12SiO[(R2SiO)(RZSiO)(R2Si-R5-(R2)SiO)] SiRR12 and RR12SiO[(R2SiO)1(RZSiO)1]SiRR12 wherein, in each formula, R Z and R1 are as described above and x, y, s, x1 and y1 are as previously described and the viscosity of the mixture has a value of at least 500,000 mPa.s at 25°C with the value of x or the sum of x and y and/or s (when either or both are present) being at least 1,000 and the value of x1 and y1 being between 100 and 1000.
5. 5. A composition according to any preceding claim characterised in that the halloysite, sepiolite and/or attapulgite is treated with an organopolysiloxane selected from the group of hydroxy terminated polydimethylsiloxanes having a degree of polymerisation of from 2 to 20, hydroxy terminated polydialkyl alkylalkenylsiloxanes having a degree of polymerisation of from 2 to 20 and a treating agent having the formula: R4ciH3ciSO[(R42SO)f(R4HSO)g1S R4dH3d wherein in each formula, R4 represents an alkyl group containing 1-6 carbon atoms; H is hydrogen, d is zero or an integer from 1 to 3, represents the vinyl group; and f and g are independently is zero or an integer which treating agent has at least one Si-H groups and a viscosity of from 5 to 500 mPa.s at 25°C.
6. 6. A composition according to any preceding claim wherein the halloysite, sepiolite and/or attapulgite comprises a halloysite, sepiolite and/or attapulgite treated with an alkoxysilane of the formula: R3(4n)Si(0R3)n wherein n has a value of 1-3; and R3 is an alkyl group, an aryl group, or an alkenyl group.
7. 7. A composition according to Claim 6 in which the alkoxysilane is a compound selected from the group consisting of methyltriethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, vinyltriethoxysilane, and vinyltrimethoxysilane.
8. 8. A composition according to any preceding Claim comprising about equal amounts of polysiloxane gum and halloysite, sepiolite and/or attapulgite.
9. 9. A composition according to any preceding claim in which the curing agent is a peroxide selected from the group consisting of benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, di-t-butyl peroxide, and dicumyl peroxide.
10. 10. A composition in accordance with any one of claims 1 to 8 in which the curing agent is an organohydrogensiloxane curing agent, and a platinum group metal hydrosilylation catalyst is added in an amount sufficient to cure the composition.
11. 11. A method of making an optionally treated halloysite, sepiolite and/or attapulgite containing silicone rubber composition in accordance with any one of claims 1 to 10 which method consists essentially of the steps: (i) mixing an organopolysiloxane and optionally treated halloysite, sepiolite and/or attapulgite under room temperature conditions, (ii) adding a curing agent to the mixture in (i); and curing the mixture in (ii) at a temperature above room temperature by the application of heat.
12. 12. A method according to Claim 11 in which room temperature is normal ambient temperature of 20-25 °C.
13. 13. Use of an optionally treated halloysite, sepiolite and/or attapulgite as a reinforcing filler in silicone rubber composition.
14. 14. Use in accordance with claim 13 characterised in that the silicone rubber composition is free of silica.
15. 15. Use in accordance with claim 13 wherein the optionally treated halloysite, sepiolite and/or attapulgite is the sole reinforcing filler in the silicone rubber composition.
16. 16. Use of a silicone rubber composition in accordance with any one of claims 1 to 7 in silicone profile extrusions, wire and cable coatings, glazing gaskets, and for construction gaskets.
17. 17. A composition as hereinbefore described with reference to the description.