Patent Application
20230383067
The present invention relates to a process for the manufacture of a non-curable silicone composition comprising carbon black, the non-curable silicone composition obtained by the process and its use for the manufacture of curable silicone compositions in particular for use in high voltage direct current applications.
Standard silicones are widely used in high voltage (HV) industry for alternating current (AC). However, the use of those materials fails in the emerging trend for direct current (DC) application. The use of carbon black (CB) as filler material provides an advantageous property to the silicone with positive tests up to 325 kV working voltage with a standard CB paste which is established for many years. This standard CB paste is produced via three roll mill technology or a twin blade kneader (US20170372815A1).
The present inventors found out, however, that there are limitations at higher voltages of up to 500 kV, by causing breakdowns of the modified silicone system.
Also, the current conductive liquid silicone rubbers (LSR) are very limited in variation of mechanical properties and have in some cases insufficient electrical conductivity.
Silicone compositions comprising carbon black as filler are for example disclosed in the following documents of the state of the art:
WO2016/110570 and US20170372815A1, respectively, disclose the use of a silicone composition comprising
Further, WO2016/110570 discloses a method for the manufacture of an insulator or a field grading assembly comprising the shaping of the above-cited silicone composition by extrusion through a nozzle or a mould, and then curing the shaped composition by heat or light.
While the present application relates to a process comprising the extrusion of a non-curable silicone composition comprising carbon black, and to a curable silicone composition comprising such specific non-curable carbon black silicone composition obtained by a process comprising an extrusion step, resulting in improved properties of the cured silicone compositions for DC applications based on such carbon black paste, WO2016/110570 and US20170372815A1 disclose extrusion as a means of shaping of a curable silicone composition as defined above.
US2004/138370A1 discloses a silicone composition for the use as a conductive liquid rubber composition in e.g. printers, comprising
Accordingly, while in the present application extrusion is a mandatory step in the provision of a non-curable carbon black silicone paste, US2004/138370A1 discloses that the mixing step of all components constituting a curable silicone composition as described therein may be effected by an extruder.
WO2020/063799A1 relates to a conductive liquid silicone rubber composition comprising carbon black, comprising
With respect to such curable silicone rubber composition, extrusion is mentioned as means for processing or forming the above-cited curable silicone rubber composition, and thus serves a different purpose than in the present application, which relates to the manufacture of a non-curable carbon black silicone masterbatch using an extrusion process.
WO2009/027133A2 relates to a process for the manufacture of shaped cured silicone articles comprising a shaping step that comprises the continuous shaping of a curable silicone mixture.
According to the disclosure of this document, a part of said mixture, i.e. the part of the uncured mixture of the components
In contrast to the invention covered by the present application, which relates to a process for the manufacture of a non-curable silicone composition comprising carbon black, the above-cited mixture of the compounds (i) to (vi) represents a curable mixture comprising all compounds required for the silicone composition to be cured: An alkenyl polysiloxane (i), an SiH-functional polysiloxane (iii) and the photoactivatable transition metal catalyst (iv).
While the presence of carbon black is mandatory in the mixture of the process of the invention of the present application, the presence of the filler component (v) of the above-cited mixture is optional.
Further, WO 2009/027133 A2 refers to a process comprising the continuous shaping of the above-cited mixture, wherein the continuous shaping step of the non-cured mixture is an extrusion step, and accordingly the shaping apparatus is an extruder. In the examples of WO 2009/027133, the extrusion of curable silicone compositions is exemplified.
In contrast to the disclosure of WO 2009/027133 A2, the present application relates to a process for the manufacture of a composition comprising the extrusion of one or more polyorganosiloxanes and one or more carbon blacks, i.e. it relates to a process comprising the extrusion of a non-curable composition.
Accordingly, the present inventors carried out extensive investigations to improve the disadvantages of the silicone compositions from the state of the art in terms of their electrical and mechanical properties.
Surprisingly they found out when a CB paste is processed by extruder technology it shows a significantly different behavior compared to a conventional CB paste. The CB nanoparticles are much more homogenously distributed through the silicone material, leading to a number of surprisingly improved electrical properties of the cured silicone rubber compositions prepared therefrom. By the extrusion process also finer particle size distributions of CB are achieved than with the conventionally prepared CB pastes.
Compared to a conventionally prepared CB paste the inventive new CB paste allows the incorporation of much higher amounts of carbon black into the cured silicone rubber compositions without reaching the so-called critical percolation threshold where the resistivity rapidly drops. This allows the incorporation of more carbon black into cured silicone compositions when used as insulators at the same high (or even higher) level of resistivity. In line with this, the cured silicone rubber compositions include a higher concentration of charge traps which allows a reduction of the electrical stress in particular under DC conditions. The resulting electrical properties of the cured silicone compositions thus give more confidence to be run in DC systems at ultra-high voltage (such as 500 kV) which is demanded by the market. Furthermore, as regards electrically conductive silicone rubber compositions, the use of the inventive new CB paste allows the incorporation of much higher amounts of carbon black into curable silicone. Accordingly, the extruded CB paste allows the use of high CB concentrations in conductive LSR whereby the mechanical properties are improved. This allows to providing silicone rubber compositions with good mechanical properties and—if required—a very high electrical conductivity in particular for use in high voltage direct current applications, in particular for one or more layers in the cable accessories.
In accordance with the present invention there is provided a process for the manufacture of a non-curable silicone composition comprising carbon black, said process comprises the extrusion of one or more polyorganosiloxanes a1) with one or more carbon blacks d).
In accordance with the present invention the term “non-curable silicone composition” intends to mean that the silicone composition does not contain the components that are required to cure the silicone composition under common polysiloxane curing conditions. Given the usual silicone rubber curing modes, including a hydrosilylation cure system, such as a platinum-catalyzed cure system, or addition cure systems, a condensation cure system, a peroxide cure system, or an oxime cure system, the non-curable silicone composition obtained according to the invention does not comprise the components required to effect such curing, in particular, of course also in the extrusion process. So, for a hydrosilylation cure systems, such as platinum-catalyzed addition cure system the non-curable silicone composition cannot comprise a hydride-, an alkenyl-functional polysiloxane and a hydrosilylation catalyst at the same time, and preferably includes only the alkenyl-functional polysiloxane. Likewise, the non-curable silicone composition cannot comprise a peroxide to cure the polyorganosiloxanes a1).
Accordingly, preferably the non-curable silicone composition of the invention does not comprise a polyorganohydrogensiloxane or a hydrosilylation curing catalyst, preferably it neither contains a polyorganohydrogensiloxane nor a hydrosilylation curing catalyst, and does also not comprise a peroxide.
In a preferred embodiment the total viscosity of the one or more polyorganosiloxanes a1) is less than 100 preferably 1 to 100 Pa·s, more preferably 5 to 100 Pa·s and still more preferably 10 or 65 Pa·s (each measured at a shear rate of D=10 s−1 at 20° C., measured e.g. according to DIN EN ISO 3219). In this respect the term “total viscosity” refers to the viscosity of the entire polyorganosiloxanes a1) if more than one polyorganosiloxane is used or to the viscosity of one polyorganosiloxane a1), if only one polyorganosiloxane a1) is used. In the former case the viscosity of the individual polyorganosiloxanes a1) may deviate from the preferred viscosity range indicated before. In a preferred embodiment the polyorganosiloxanes a1) are selected from polyorganosiloxanes having one or more unsaturated groups preferably one or more alkenyl groups as described below. Such polyorganosiloxanes a1) have organic substituents R preferably selected from the group consisting of optionally substituted alkyl, such as alkyl groups and halogenalkyl groups, optionally substituted aryl, such as phenyl and unsaturated substituents R1 preferably selected from the group consisting of alkenyl groups, such as vinyl groups, and preferably have an average degree of polymerisation Pn between 100 to 12000 siloxy units. With respect to such polyorganosiloxanes a1) it can be referred to the polyorganosiloxanes having alkenyl groups a2) which are used in the curable silicone composition as described below. The process according to the invention comprises mixing and extruding the one or more polyorganosiloxanes a1) with the one or more carbon blacks d). Basically, several kinds of extruders might be used such as the generally known single-screw extruders, twin-screw extruders, and planetary roller extruders. Among them single-screw extruders are less preferred since the homogenization and dispersion is weaker. While planetary roller extruders have an extremely good mixing effect compared to all other extruder types, their conveying effect is much lower. Therefore, from the viewpoints of the homogenization and dispersion effect on the one hand and the conveying effect on the other side in the present invention twin-screw extruders, in particular, co-rotating twin-screw extruders are preferred. In principle it is possible to prepare a premixture of components a1) and d) which is then fed into the extruder by a suitable dosing unit, but a split-feed process through at least two, preferably two dosing units, is preferred to separately feed the components a1) and d). Preferably, the extruder has two feeding sections, the first one is preferably for the polyorganosiloxanes a1), which usually forms a viscous fluid at room temperature. It may be fed for example with a twin-screw feeder, such as a twin-screw loss-in-weight feeder or a dosing system like a piston drum pump or a gear pump. The one or more carbon blacks d) are fed in one or more, preferably one or two dosing units, such as gravimetric feeders, downstream the polyorganosiloxane feeding unit. The carbon black dosing units are preferably arranged at such place of the extruder where the polyorganosiloxane is completely liquid in order to allow distributive and dispersive mixing of the carbon black and the polyorganosiloxanes.
The extrusion is usually carried out at a temperature of the extruded mass of room temperature (25° C.) to 250° C., preferably at a temperature of the extruded mass in the range of 50 to 200° C. The melting and homogenizing process in the extruder is preferably carried out without supplying heat, which is generated by the shear forces in the extruder. Optionally it is possible to supply external heat, but it is even more preferably to provide external cooling means in order not reach temperatures that may lead to decomposition of the polyorganosiloxane especially at high carbon black loads. Preferably the extrusion is carried out using one or more of the following conditions:
Preferred extruders are for example the ZSE MAXX SERIES co-rotating twin screw extruders from Leistritz Extrusionstechnik GmbH, Nuremberg Germany, with a screw diameter of 15 to 250 mm, preferably 20 to 100 mm, using high-dispersing screws.
In the extrusion process of the invention preferably the weight ratio of the weight of the one or more polyorganosiloxanes a1) to weight of the one or more carbon blacks d) is from 90:10 to 75:25, preferably from 89 to 11 to 80 to 20, even more preferably from 88 to 12 to 81 to 19.
In a preferred embodiment only the one or more polyorganosiloxanes a1) and the one or more carbon blacks d) are extruded, or with other words no other components are present in the extrusion process. Also, in a preferred embodiment only one kind of polyorganosiloxane a1) and one kind of carbon black d) are extruded to prepare a high load carbon black in polysiloxane masterbatch having an excellent homogenous particle size distribution which is also finer than the particle size distributions achieved by the conventional processes.
In a further aspect the present invention relates to a non-curable silicone composition obtained by the process of the invention. Such “non-curable composition” is also sometimes referred to as the “masterbatch”.
The non-curable silicone composition according the invention preferably comprises at least 10, preferably at least 11, more preferably at least 12 weight percent, still more preferably at least 13 weight percent and still more preferably at least 14 weight percent of the one or more carbon blacks d) based on the total weight of the entire silicone composition.
The non-curable silicone composition according to the invention preferably comprises from 10 to 25, preferably from 11 to 24, still more preferably from 12 to 23 weight percent, still more preferably from 13 to 22 weight percent and still more preferably from 14 to 21 weight percent of the one or more carbon blacks d) based on the total weight of the entire silicone composition.
While it is generally preferred that the “non-curable composition” or carbon black “masterbatch” comprises higher amounts of 10 to 25 weight percent of the one or more carbon blacks d) based on the total weight of the entire silicone composition, it is also possible to prepare non-curable compositions with lower amounts of carbon black, if required, such as from 3 to 10 weight percent of the one or more carbon blacks d) based on the total weight of the entire silicone composition. Also, those non-curable compositions with lower amounts of carbon black benefit from the more homogeneous, and finer particle size distributions achieved by the extrusion process.
Preferably the non-curable silicone composition according to the invention consists of one or more polyorganosiloxanes a1) and one or more carbon blacks d), even more preferably it consists of one kind of polyorganosiloxane a1) and one kind of carbon black d).
In the present invention the one or more carbon blacks d) preferably comprise at least one carbon black selected from conductive carbon blacks having a BET surface of >30 m2/g and an average primary particle size of D50 between 5 to 500 nm. Even more preferably the carbon black component d) in the non-curable composition according to the invention consists of conductive carbon blacks having a BET surface of >30 m2/g and/or an average primary particle size of D50 between 5 and 500 nm. In general, it has to be distinguished between primary particle size and the agglomerate particle size of the carbon black in the non-curable silicone composition of the invention. While the primary carbon black primary particles sizes or diameters are well in the range of 5 to 500 nm, the agglomerate particle sizes in the non-curable silicone composition of the invention determined in particular by the light scattering method are generally higher than about 0.5 μm, and preferably are substantially in the range of about 0.5 to about 10 μm, more preferably, substantially in the range of about 1 to about 10 μm.
The particle size distribution of the carbon black in the non-curable silicone composition may be measured, in particular, by light scattering according to DIN EN ISO/IEC 17025 in toluene solution using the scattering model according to the Mie theory measured at the lowest possible rotational speed of the dispersing unit corresponding to the lowest possible shear. Preferably the result is presented as a superposition of one or more measurements over a period of 5-15 minutes. Measurements can be carried out in particular with a Malvern Zetasizer apparatus. Such measurement method provides the number or volume percentages of the particle size distribution.
It turned out that the extrusion process in accordance with the invention surprisingly leads to a substantial increase in the number of particles having a particle size of below 10 pm compared to the conventional master batch produced via three roll mill technology or a twin blade kneader even at high carbon black loads. Without being bound to theory, it is assumed that the extrusion process according to the invention leads to a better deagglomeration or distribution of the carbon black particles in the CB-silicone masterbatch.
Preferably the percentage of the number of particles less than 10 μm is more than 70 preferably more than 80%, still more preferably more than 90%. Preferably the percentage of the number of particles of more than 10 μm is less than 30% preferably less than 20% still more preferably less than 10%, still more preferably less than 5%.
The Dn50of the particle size distribution based on the number of particles of the non-curable silicone composition is preferably less than 7 μm, more preferably less than 5 μm, and most preferably less than 3 μm.
The Dn50 of the particle size distribution based on the number of particles of the non-curable silicone composition is preferably less than 15 μm, more preferably less than 10 μm more preferably less than 8 μm and most preferably less than 5 μm.
Dn50 is the size in microns that splits the number distribution with half above and half below this diameter. The Dn50 is used is the median for number distributions. For Dn50 90% of the particles have a size below this diameter. (see https://www.horiba.com/uk/scientific/products/particle-characterization/education/general-information/data-interpretation/understanding-particle-size-distribution-calculations/).
In the non-curable silicone composition according to the invention particularly preferred the one or more carbon blacks comprise at least one carbon black selected from conductive carbon blacks having one or more of the following properties:
Preferably the one or more carbon blacks consist of at least one, preferably one carbon black selected from conductive carbon blacks having the one or more properties mentioned before.
The present invention in a further aspect relates to the use of the non-curable silicone composition as defined before for the manufacture of curable silicone compositions. Such use generally requires that the non-curable silicone composition is ultimately mixed with components that are required for manufacturing a curable silicone composition in particular as the ones described in the following. Accordingly, the present invention in a further aspect also relates to the use of the non-curable silicone composition as defined above as a masterbatch for incorporation into curable silicone composition. As is well known to the skilled person in the art, a masterbatch is usually a solid additive for plastic used for coloring plastics (color masterbatch) or imparting other properties to plastics (additive masterbatch). In the present invention the masterbatch is preferably used, but not limited to, for the incorporation of the one or more carbon blacks d) into curable silicone compositions as described in the following.
Due to its high homogeneity the non-curable silicone composition according to the invention and the beneficial electrical properties resulting therefrom the non-curable silicone composition according to the invention (masterbatch) is particular suitable in high voltage direct current applications, that is, in particular, for the manufacture of curable silicone compositions for use in high voltage direct current applications.
Accordingly, in a further aspect the present invention relates to a curable silicone composition comprising the non-curable silicone composition according to the invention as described above.
A particularly preferred curable silicone composition, comprising the non-curable silicone composition according to the invention, comprises:
Preferably the curable silicone composition of the invention comprises a crosslinker component comprising one or more polyorganohydrogensiloxanes.
Preferably the curable silicone composition of the invention comprises one or more filler components, comprising one or more reinforcing silicas or resins.
Such curable silicone compositions preferably comprise from 0.1 to 2.5 weight percent, preferably from 0.2 to 2.4 weight percent, more preferably from 0.3 to 2.3 weight percent, more preferably from 0.4 to 2.2 weight percent, more preferably from 0.5 to 2.1 weight percent, more preferably from 0.6 to 2.0, more preferably from 0.7 to 1.9 weight percent weight, more preferably from 0.8 to 1.8 weight percent of one or more carbon blacks d) based on the total 30 weight of the curable silicone composition, such carbon blacks d) resulting from the non-curable silicone composition comprising the same, i.e. from the masterbatch.
Such curable silicone compositions having a relatively low content of carbon black have a relatively low conductivity and are suitable in particular in insulator or field grading assemblies for high voltage direct current (HVDC) applications as described below in more detail.
In the following the components of the curable silicone composition according to the invention are described. As stated above the one or more polyorganosiloxanes a1) are preferably selected from the polyorganosiloxane having alkenyl groups a2) as described in the following. The polyorganosiloxanes a1) and the polyorganosiloxane having alkenyl groups a2) can be the same or different.
The curable silicone composition comprises as a base polymer one or more polyorganosiloxanes having one or more alkenyl groups a2) preferably at least two alkenyl groups.
Preferably the polyorganosiloxanes a2) are selected from the group of one or more polyorganosiloxanes having organic substituents R, i.e. having at least one carbon atom and being bond to the silicon atom by a carbon atom, preferably selected form the group which consists of optionally substituted alkyl groups, such as methyl or halogen alkyl groups such as fluorine-substituted propyl groups, optionally substituted aryl groups, such as phenyl, and one or more alkenyl groups R1, in particular vinyl groups, and an average degree of polymerisation (Pn) between 100 to 12000 siloxy units, calculated in particular from the number average molecular weight which may be determined by GPC measurement versus polystyrene standard, following in particular the procedure according to ASTM D5296-11.
The polyorganosiloxanes as component a2) having alkenyl groups, most preferably in average have at least two alkenyl groups.
Suitable components a2) may be described by the general formula (I),
(MaDbTcQdR2e)m (I)
wherein the indices in formula (I) represent the ratios of the siloxy units M, D, T and Q, which may be distributed blockwise or randomly in the polyorganosiloxane. Within a polyorganosiloxane each siloxane unit may be identical or different and
The viscosity of component a2) refers to the viscosity of a single component a2) or a mixture of components a2). The latter case of the mixture includes the presence of individual components a2) that may have a viscosity exceeding 50 kPa.s at 20° C. at a shear rate of D=10 s−1, for example resinous components or gums a2) that comprise Q and or T units.
In formula (I) the sum of indices should represent the average polymerisation degree Pn based on the average number molecular mass Mn.
In the formula (I):
divalent groups R2, which are bridging groups between siloxy groups above, which are preferably divalent optionally substituted hydrocarbyl groups, such as optionally substituted alkenyl groups having for example from 2 to 10 carbon atoms, or optionally substituted aromatic groups such as arylene groups, which are bound to silicon atom with a carbon atom thereof, and
wherein each R, which may be the same or different, and each be an organic group, which is preferably selected from optionally substituted alkyl with up to 12 carbon atoms, optionally substituted aryl with up to 12 carbon atoms, the groups R being free of aliphatic unsaturation, and
wherein
R is preferably selected from n-C1-C12-, iso-C3-C12-, or tertiary-C4-C12-alkyl, alkoxyalkyl, C5-C12-cyclic alkyl, or C6-C12-aryl, alkylaryl, which groups may be substituted in addition by one or more O-, Cl-, CN- or F-atom, or poly(C2-C4)-alkylene ethers with up to 500 alkylene oxy units the groups R being free of aliphatic unsaturation,
Examples of suitable monovalent hydrocarbon radicals include alkyl radicals, preferably such as CH3—, CH3CH2—, (CH3)2CH—, C8H17— and C10H21—, and cycloaliphatic radicals, such as cyclohexylethyl, aryl radicals, such as phenyl, tolyl, xylyl, aralkyl radicals, such as benzyl, 2-phenylethyl and 2-phenylpropyl. Preferable monovalent halohydrocarbon radicals have the formula CnF2n+1CH2CH2- wherein n has a value of from 1 to 10, such as, for example, CF3CH2CH2—, C4F9CH2CH2—, C6F13CH2CH2—, C2F5—O(CF2—CF2—O)1-10CF2—, F(CF(CF3)—CF2—O)1-5—(CF2)0-2—, C3F7—OCF(CF3)— and C3F7—OCF(CF3)—CF2—OCF(CF3)—.
The preferred groups for R in the polyorganosiloxane a2) of the inventive curable silicone composition are selected form the group which consists of methyl, phenyl, 3,3,3-trifluoropropyl groups and the most preferable group R is the methyl group.
R1 is preferably selected from unsaturated groups, comprising C=C-group-containing groups (alkenyl groups), e.g.: n-C2-C14-, iso-C3-C14-, or tertiary- C4-C14-alkenyl or C6-C14-cyclic alkenyl, C6-C14-cycloalkenyl, C8-C14 -alkenylaryl, cycloalkenylalkyl, vinyl, allyl, methallyl, 3-butenyl, 5-hexenyl, 7-octenyl, ethyliden-norbornyl, styryl, vinylphenylethyl, norbornenyl-ethyl, limonenyl, optionally substituted by one or more O- or F-atoms, or CC-group-containing groups (alkinyl groups), optionally comprising one or more O- or F-atoms.
The alkenyl radicals are preferably attached to terminal silicon atoms; the olefin function is at the end of the alkenyl group of the higher alkenyl radicals, because of the easier availability of the alpha-, omega-dienes used to prepare the alkenylsiloxanes.
Preferred groups for R1 are vinyl, allyl, 5-hexenyl, cyclohexenyl, limonyl, styryl, vinyl-phenylethyl, most preferred group R1 as vinyl.
The group R2 includes for example divalent aliphatic or aromatic n-, iso-, tertiary- or cyclo-alkylene with up to 14 carbon atoms, arylene or alkylenearyl groups. R2 forms bridging elements between two siloxy units. The content of the R2 groups does not exceed 30 mol. % preferably not exceed 20 mol. % of all siloxy units. Preferably R2 is absent. Preferred examples of suitable divalent hydrocarbon groups R2 include any alkylene residue, preferably such as —CH2—, —CH2CH2—, —CH2(CH3)CH—, —(CH2)4—, —CH2CH(CH3)CH2—, —(CH2)6—, —(CH2)8— and —(CH2)18—; cycloalkylene radical, such as cyclohexylene; arylene radicals, such as phenylene, xylene and combinations of hydrocarbon radicals, such as benzylene, i.e. —CH2CH2—C6H4—CH2CH2—, —C6H4CH2—. Preferred groups are alpha, omega-ethylene, alpha, omega-hexylene, 1,4-phenylene or 1,4-ethylenephenyl.
Further examples include divalent halohydrocarbon radicals R2 e.g. any divalent hydrocarbon group R2 wherein one or more hydrogen atoms have been replaced by halogen, such as fluorine, chlorine or bromine. Preferable divalent halohydrocarbon residues have the formula —CH2CH2(CF2)1-10CH2CH2— such as for example, —CH2CH2CF2CF2CH2CH2— or other examples of suitable divalent hydrocarbon ether radicals and halohydrocarbon ether radicals including —CH2CH2OCH2CH2—, —C6H4—O—C6H4—, —CH2CH2CF2OCF2CH2CH2—, and —CH2CH2OCH2CH2CH2—.
Such polymers as component a2) comprising R, R1 and/or R2 radicals are e.g. alkenyl-dimethylsiloxy or trimethylsiloxy terminated polydimethylsiloxanes, which may contain other siloxane units than alkenylmethylsiloxy groups dimethylsiloxy groups such as poly(dimethyl-co-diphenyl)siloxanes.
Broadly stated component a2) of the curable silicone compositions of this invention may be any polyorganosiloxane compound containing two or more silicon atoms linked by oxygen and/or divalent groups R2 wherein the silicon is bonded to 0 to 3 monovalent groups per silicon atom, with the proviso that the polyorganosiloxane compound contains at least two silicon-bonded unsaturated hydrocarbon residues including olefinic radicals and acetylenic radicals, preferably with the radicals such as alkenyl groups.
The siloxane units M, M*, D, D*, T, T* with the radicals R and/or R1 may be equal or different for each silicon atom. In a preferred embodiment the structure is
R1pR3-pSiO(R2SiO)m1(R1RSiO)nSiR1pR3-p (1)
One preferred polyorganosiloxane component a2) for the curable composition of this invention is a substantially linear polyorganosiloxane a3). The expression “substantially linear” includes polyorganosiloxanes that do not contain more than 0.2 mol. % (trace amounts) of siloxy units of the type T or Q. This means that the polymer a2) is preferably a linear, flowable fluid a3) such as of the formula:
R1pR3-pSiO(R2SiO)m1SiR3-pRp1 (1a)
wherein R1, R, p and m1 are each as defined above,
with the proviso, that there are at least two alkenyl groups per molecule.
The polyorganosiloxanes a2) or a3) are most preferably selected from those the formula (1a).
Preferred structures include
VipMe3-pSiO(Me2SiO)10-12000 SiMe3-pVip (1b),
PhMeViSiO(Me2SiO)10-12000SiPhMeVi (1c),
In the group of alkenyl comprising polysiloxanes a2) the addition of a second or third polysiloxanes as component a4) and/or a5) is preferred. The purpose of component a4) and a5), so-called vinyl rich polymers, is to modify mechanical properties and crosslinking density.
Polymers suitable for LSR (Liquid Silicone Rubber) are selected from the group of siloxane polymers with Pn of 100 to 2000 siloxy units, those for HCR (High Consistency Rubbers as explained below) are preferably selected from the group of siloxane polymers with Pn of 2000 to 12000 siloxy units.
The polymers a4) are selected either from the group consisting of polymers of the formulas (1d) to (1i), i.e. linear polyorganosiloxanes having additional alkenyl side groups wherein the concentration of T- and Q-groups are below 0.2 mol. % or polyorganosiloxanes having a higher concentration of T- and Q-groups than the previous polymer types a2) or a3).
The polymers a4) are for example represented by the formulas 1d)-1f).
R1pR3-p(R2SiO)b1(R1R SiO)b1xSiR3-pRp1 (1d)
Me3SiO(Me2SiO)b1(MeR1SiO)b1xSiMe3 (1e),
R1Me2SiO(Me2SiO)b1(Me R1SiO)b1xSiMe2R1 (1f),
where
And preferred groups for R are methyl, phenyl, 3,3,3-trifluoropropyl.
Other preferred structures of a4) are
VipMe3-pSiO(Me2SiO)10-12000(MeViSiO)1-4000SiMe3-pVip (1g),
Me3SiO(Me2SiO)10-12000(MeViSiO)1-4000SiMe3 (1h),
PhMeViSiO(Me2SiO)10-12000(MePhSiO)1-4000SiPhMeVi (1i) and
wherein in the above Me=methyl, Vi=vinyl, Ph=phenyl, and p=0 to 3, preferred p=1.
The third component of polymer a2), i.e. branched polymers a5), are preferably selected from those of the formula (Ia) wherein the polyorganosiloxane a5) comprising alkenyl groups have more than 0.2 mol. % of T=RSiO3/2 or Q=SiO4/2-units.
(M0.4-4D0-1000T0-50Q0-1)1-1000 (Ia)
where
The range of the sub-indices defines a range of the possible average polymerization degrees Pn according to the number average molecular weight Mn.
The indices relate to suitable viscosities as defined later on and describe polymers without any solvent for a viscosity adjustment.
The preferred branched polyorganosiloxanes a4) and a5) have usually a higher concentration of unsaturated groups R1. Branched polymers a5) are described e.g. in U.S. Pat. No. 5,109,095. Preferably the branched vinyl-rich polymers a5) are soluble in xylene >10 wt. % resin and have a range of D:T>10:1 preferably >33:1 and/or respectively
All these polyorganosiloxanes may be prepared by any of the conventional methods for pre-paring triorganosiloxane-terminated polydiorganosiloxanes. For example, a proper ratio of the appropriate hydrolyzable silanes, e.g., vinyldimethylchlorosilane, trimethylchlorosilane, tetrachlorosilane, methyltrichlorosilane and dimethyldichlorosilane, or its corresponding alkoxysilanes, may be co-hydrolyzed and condensed. Other reaction routes may run alternately over equilibration reactions of 1,3-divinyltetraorganodisiloxane, e.g. symmetrical divinyldimethyldiphenylsiloxane or divinyltetramethylsiloxane, which furnishes the endgroups of the polydiorganosiloxane, which may be equilibrated with an appropriate polydiorganosiloxane, e.g., octamethylcyclotetrasiloxane, in the presence of an acidic or basic catalyst.
The vinyl-rich polymers are in particular the branched polymers having MQ or MDQ structures and Si-alkenyl or SiH groups. Such branched polymers can replace the filler component c) partly or completely and provide nevertheless high mechanical reinforcement. This could be an additional option to reduce viscosity and modify electrical properties.
In a preferred embodiment the polymer component a2) in the curable silicone composition can be a mixture of polymers of the formula (1a) and/or of the formula (1d) and/or (1j) whereby the mixture has an alkenyl content in average of preferably below 2 mol. % of all siloxy units of the mixture a), whereby polymer a3) is present in a higher amount than a4) or a5).
For so-called High Consistency Rubbers the related silicone polymer (gum) viscosity is between 5-100 kPa·s at 20° C. at a shear rate of D=10 s−1 In case of polydimethylsiloxanes this relates roughly to Pn values of 3000-12000 siloxy units.
In the preferred embodiment of curable Liquid Silicone Rubber (LSR) compositions it is preferred to use viscosities of less than 1 kPa.s at 20° C. and at a shear rate of D=10 s−1; with respect to polydimethylsiloxanes this relates roughly to Pn values of <2500 siloxy units. In both embodiments polydimethylsiloxanes having vinyl groups are preferred.
The viscosity of the polyorganosiloxane a2) for this embodiment is preferably 100 to 300*103 mPa·s at 20° C. at a shear rate of D=10 s−1 and the Pn is >10 to 2500.
In a preferred embodiment for an LSR composition containing a polymer a2) or a mixture of e.g. 2-4 polymers of component a2) the blend should have a viscosity of less than 200,000 mPa·s at 20° C. and at a shear rate of D=10 s−1, in order to ensure a sufficiently low viscosity for liquid silicone rubber composition. Such a low viscosity is an assumption and is advantageous for the manufacture of compositions comprising reinforcing fillers and processing these compositions in an LSR injection molding process.
The alkenyl content of the components a2) may be determined here by way of 1H NMR—see A. L. Smith (ed.): The Analytical Chemistry of Silicones, J. Wiley & Sons 1991 Vol. 112 pp. 356 et seq. in Chemical Analysis ed. by J. D. Winefordner.
In a further preferred embodiment component a2) comprises at least one of component A1), and at least one of component A2), which are defined as follows:
A1) at least one polyorganosiloxane of the formula (Ia),
wherein each R is independently selected from saturated or aromatic organic groups, each R1 is independently selected from alkenyl groups, and x is ≥0,
A2) at least one polyorganosiloxane of the formula (Ib),
wherein x, R and R1 are as defined above; R3 is selected from R or R1, and y is 1, and wherein preferably the molar ratio of the alkenyl groups R1 in component A2) to the alkenyl groups R1 in component A1) is in the range of 0.3 to 8, preferably 0.6 to 6, more preferably 1 to 5.
Component a2) preferably used to prepare the non-curable masterbatch composition comprising the polyorganosiloxane a1) is again preferably selected from the linear component A1) as defined before.
In a preferred embodiment the curable polyorganosiloxane composition is cured by a hydrosilylation reaction and then comprises one or more polyorganohydrogensiloxanes b) as a crosslinker. In such a case the organic peroxide component e) as a crosslinking initiator is preferably omitted.
The inventive curable silicone composition comprises preferably a crosslinker component b) which is selected from the group of polyorganohydrogensiloxanes comprising preferably units selected from those of the formula RHSiO and R2HSiO0.5 and a concentration of SiH units of 1 to 100 mol. % related to all siloxane units,
whereby R an organic group as defined above, and is preferably methyl or phenyl.
The component b) is preferably at least one polyorganohydrogensiloxane having at least two Si—H-groups. Suitable polyorganohydrogensiloxanes b) comprising SiH units may be formally described by the general formula (II),
j(M1a2D1b2T1c2Qd2R2e2)m2 (II)
wherein the siloxy units
Preferably the polyorganohydrogensiloxanes b) have in average at least four, preferably at least five, still more preferably at least six silicon atoms.
The siloxy units may be distributed blockwise or randomly in the polymer chain.
The aforementioned indices should represent the average polymerization degree Pn based on the average number molecular mass Mn as described before.
The range for the M-, D-, T- and Q-units present in the molecule may cover nearly all values leading to fluids, flowable polymers, liquid and solid resins. It is preferred to use at room temperature (25° C.) liquid linear, cyclic or branched siloxanes. Optionally these siloxanes may comprise additionally traces of C1-C6-alkoxy or Si-hydroxy groups remaining from the synthesis.
Preferred structures of component b) in the curable silicone compositions of this invention are siloxanes of formula (2a) to (2e).
Ha1(R)3-a1Si(RHSiO)x(R2SiO)y(RR1SiO)zSi(R)3-a1Ha1 (2a)
more specifically:
HR2SiO(R2SiO)y(RR1SiO)z,(RHSiO)x,SiR2H (2b)
HMe2SiO(Me2SiO)y(RR1SiO)z(MeHSiO)xSiMe2H (2c)
Me3SiO(MeHSiO)xSiMe3 (2d)
{(HRSiO)v(R2SiO)w} (2e)
wherein R and R1 are as defined above, R is preferably methyl and/or phenyl, R1 is preferably vinyl, and the index ‘a1’ is 0-1, preferably 0, and
Furthermore, resinous polyorganohydrogensiloxanes of the following formula are possible:
{(T1)(R4O1/2)n2}m2 (2f)
{(SiO4/2))(R4O1/2)n2(M1)0.0-10(T1)0-50(D1)0-1000}m2 (2g)
wherein
R4 is hydrogen, C1-C25-alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-, iso- and tert.-butyl, alkanoyl, such acyl, aryl, —N═CHR, such as butanonoxime, alkenyl, such as propenyl.
One preferred embodiment of the compounds (2g) is provided by way of example by monomeric to polymeric compounds which may be described via the formula ((Me2HSiO0.5)kSiO4/2)1-1000 wherein index k is from 0.3 to 4. Such liquid or resinous molecules may contain significant concentrations of SiOH- and/or (C5-C6)-alkoxy-Si groups of up to 10 mol. % related to the silicon atoms.
Specific examples of preferred suitable compounds for component b) in the curable silicone compositions of this invention include
The component b) may be used as a single component of one polyorganosiloxane polymer or mixtures thereof.
If an increase of the cure rate is required, it is preferred to use some polyorganosiloxanes b) having HMe2SiO0.5-units or homo MeHSiO-polymers to adjust the cure rate to shorter times.
The component b) has preferably a viscosity at 20° C. from 2 to 1000 mPa·s, measured at a shear rate of D=10 s−1.
Preferably the crosslinker b) should have at least more than 3 reactive SiH-groups per molecule. So-called chain extenders having in average of >1 to 3 reactive SiH-groups per molecule may be present in addition.
The molar ratio of the total of SiH groups in component b) to the total of the unsaturated hydrocarbyl residues R1 in component a) and if present in b) in the formulation is between 0.7 and 15, preferably 0.8 to 8, more preferably 1.0 to 7, most preferably is 1.0 to 4.
It is further preferred to use polyorganohydrogensiloxanes wherein the molar ratio of R2SiO:RHSiO units is >1.
The preferred R groups in the polyorganohydrogensiloxanes are methyl, phenyl and 3,3,3-trifluoropropyl. The preferred viscosities are below 1000 mPa·s, more preferred below 400 mPa·s at 20° C. (measured at a shear rate of D=10 s−1).
The inventive curable silicone composition may comprise one or more preferably reinforcing filler components, comprising one or more reinforcing silicas or resins, preferably silicone resins. Preferably, the curable silicone composition comprises one or more preferably reinforcing filler components.
Preferably they are selected from the group of fumed silicas having a surface area according to BET of 50 to 400 m2/g.
The fumed silicas are, if appropriate, surface-modified reinforcing fillers c). Reinforcing fillers c) are characterized by a BET surface area of 50 m2/g or more and primary particle size of <50 nm. In the context of the present invention the component d) is not comprised by the reinforcing filler c).
Preferably these fillers are surface-hydrophobized. If component c) is used, its amount is preferably up to 100 parts by weight, preferably from 0 to 60 parts by weight, even more preferably from 0 to 50 parts by weight, even more preferably from 5 to 30 parts by weight based on 100 parts by weight of component a), i.e. the polyorganosiloxanes a2).
Fillers having BET surface areas of above 50 m2/g permit the production of silicone elastomers with improved mechanical properties. In view of strength, electrical resistivity and flame retardancy fumed silicas are preferred, and even more preferred silicas are, for example,
Aerosil® 200, 300, 400, HDK® N20 or T30, Cab-O-Sil® MS7 or HS5 having more than 200 m2/g BET surface area, supplied by Evonik (formerly Degussa), Wacker or Cabot and others.
The fillers c) may be subject of any suitable conventional surface-treatment with suitable surface-treatment agents belonging to reactive silanes or siloxanes as auxiliary additives f).
Preferred silanes or siloxanes for the surface treatment are preferably for example silazanes, such as hexamethyldisilazane and/or 1,3-divinyl-tetra-methyldisilazane, in the presence of water, in a preferred embodiment it may take place by an ‘in-situ’-hydrophobization of the filler surface. In other embodiments it may also take place with other familiar filler-treatment agents such as poly-organosiloxanediols whose chain lengths are from 2 to 50 and which bear unsaturated organic radicals.
The agent for filler treatment may provide reactive sites for the crosslinking reaction.
In case of the preferred embodiment of curable liquid silicone rubbers the treatment with hexaorganodisilazanes and water and its reaction products are preferred.
Examples of commercially available silicas pre-hydrophobized with various silanes are: Aerosil R 972, R 974, R 976, or R 812, or, for example, HDK 2000 or H30. Rheological properties, i.e. technical processing properties, of the non-cured silicone rubber mixtures may be influenced by the selection the amount of the type of the filler, its amount, and the nature of hydrophobization.
Other fillers named semi- or non-reinforcing fillers which include by way of example all of the fine-particle fillers whose particles size are smaller than 100 pm having a BET surface of <50 m2/g are counted under component f) as auxiliary additives.
The curable silicone compositions according to the invention contain one or more carbon blacks d), which are—preferably exclusively—incorporated into the curable silicone compositions of the invention by mixing the other components of the curable compositions with the non-curable compositions, i.e. the carbon black masterbatch.
The amount of the one or more carbon blacks d) in the curable silicone compositions of the invention is from 0.1-2 parts by weight based on 100 parts of the more polyorganosiloxanes a2) having one or more unsaturated groups.
More preferably the amount of the one or more carbon blacks d) in the curable silicone compositions of the invention can be for example from about 0.15-2 parts by weight, more preferably 0.2-1.5 parts by weight and still more preferably 0.3-1 parts by weight each based on hundred parts by weight of the polyorganosiloxanes a2) having one or more unsaturated groups.
Preferably the curable compositions of the invention contain only one kind of carbon black.
Preferably, the curable silicone compositions according to the invention comprise from about 0.1 to about 2.4 wt-% (weight percent), preferably from about 0.3 to about 2.2 weight percent, still more preferably from about 0.5 to about 2.0 weight percent of one or more carbon blacks d) based on the total weight of the curable silicone composition.
As carbon blacks d), basically, all kind of carbon blacks may be used (such as acetylene black, channel black, furnace black, lamp black or thermal black). As it is well known to a skilled person in the art carbon black is a form of paracrystalline carbon that has generally a high surface-area-to-volume ratio, albeit lower than that of activated carbon. It is dissimilar to soot in its much higher surface-area-to-volume ratio and significantly lower (negligible and non-bioavailable) polycyclic aromatic hydrocarbon (PAH) content.
In a preferred embodiment of the invention the at least one dielectric active compound d) is a conductive carbon black, preferably furnace carbon black, i.e. manufactured by the furnace black process.
In a preferred embodiment the one or more carbon blacks d) comprise at least one carbon black selected from conductive carbon blacks having a BET surface of >30 m2/g and/or an average primary particle size of D50 between 5 to 500 nm.
In a further preferred embodiment, the one or more carbon blacks comprise at least one carbon black selected from conductive carbon blacks having one or more of the following properties:
Preferably, only one kind of carbon black is contained in the curable silicone compositions according to the invention.
Commercially available carbon blacks include in particular PrintexXE2, PrintexHV (Evonik), Black Pearls 2000, VulcanoxC72, VulcanoxC72 (Cabot), Ketjen Black EC300J, Ketjen Black EC600JD (Akzo Nobel), Ensaco 360 g, Ensaco 350 g, Ensaco 350 p, Ensaco 250 g (Timcal), CL-08 (Continental Carbon), Denka Black HS100, Denka Black HS100, Denka Black HS100 (Denka Chemicals), CD 7087 (Columbian Chemicals), TokaBlack5500 (TokaiCarbon), Chezacarb A (Unipetrol) etc.
Particularly preferred carbon blacks are conductive carbon blacks marketed under the trademark Ketjenblack (from Akzo Nobel), especially Ketjenblack EC-300J, and electroconductive carbon black (CAS number 1333-86-4) in the form of pellets.
The curable silicone composition according to the invention may optionally contain apart from the one or more carbon blacks d) other (one or more) dielectric active compounds dl) as auxiliary additives f), which are selected from the group consisting of conductive or semi-conductive fillers.
Such other dielectric active compounds d1) preferably selected from the group of conductive or semi-conductive fillers which comprises e.g. graphite, graphenes, fullerenes, carbon nanotubes, oxides, carbides, ferrites or spinels of Ti, Al, Zn, Fe, Mn, Mo, Ag, Bi, Zr, Ta, B, Sr, Ba, Ca, Mg, Na, K, Si, inorganic salts, such as chlorides, sulfates thereof and are selected from the group of ionic liquids and ionic polymers.
The amount of such other dielectric active compounds can be for example from about 0-2 parts by weight, preferably 0.1 to 2 parts by weight, more preferably >0.15-2 parts by weight, more preferably >0.2 — 1.5 parts by weight and still more preferably >0.3-1 parts by weight each based on hundred parts by weight of the polyorganosiloxanes a2) having one or more unsaturated groups.
The particulate dielectric active compounds have preferably an average diameter D50 from 5 to 500 nm, preferred 5 to 200 nm.
D50 is measured by light scattering according to ISO 22412:2008. Particles with a diameter according to grit sieve analysis of more than 125 μm should be below 10 wt. % in particular in pellet materials.
Other compounds suitable as component d1) are ionic liquids and ionic polymers which are selected from the group consisting of compounds comprising ammonium, phosphonium, carboxylic, phosphate or sulfonate groups and counter ions such as cations or anions.
Other preferred dielectric active component d1) are selected from the group of titanium dioxide (TiO2), iron and zinc, oxides in particular of spinels and ferrites. In a preferred embodiment the use of ZnO is however not preferred.
The preferred titanium dioxides as dielectric active component d1) have a BET surface range of 35-300 m2/g and particles sizes below 30 nm. For example, fumed TiO2 P25 (Degussa-Evonik) has a number average primary particle size of 21 nm and a BET surface of 50 m2/g. Another TiO2-type is a precipitated anatase (Kronos 7050) has e.g. a BET surface of about 225 m2/g and a number average primary particle /crystallite size of 15 nm.
The use of TiO2 or Fe3O4 as component d1) are also helpful to enhance the effect on flame retardancy achieved by the crosslinking catalysts based on Pt compounds as component e).
In a preferred embodiment of the invention, the curable silicone composition comprises only the one or more carbon blacks d) as dielectric active compounds.
If, however, any of the dielectric active compounds d1) other than the carbon black d) is present in the curable silicone compositions according to the invention, its amount can be from 0.01 weight percent (wt %) to 1.96 weight percent, preferably 0.05 to 1.90 wt %, more preferred 0.1 to 1.8 wt. %, more preferred 0.15 to 1.7 wt. %, more preferred 0.2 to 1.5 wt. %, more preferred 0.3 to 1.0 wt. %, more preferred 0.3 to 0.7 wt. %, related to the total weight of the curable silicone composition.
In accordance with the present invention the amount and kind of the dielectric active compounds d) (one or more carbon blacks) and d1) (dielectric active compounds other than carbon black), preferably only d), is suitably adjusted such that the cured silicone compositions have in particular such electrical properties making them suitable as insulator for high voltage direct current (HVDC) applications, in particular such that the insulator has a volume resistivity in the range of 25 to 90° C. at an electric field of 10 kV/mm to 30 kV/mm of more than 1*1011 Ohm*cm, preferably more than 1*1012 Ohm*cm, more preferably more than 1*1013 Ohm*cm, still more preferably more than 1*1014 Ohm*cm, and preferably at most 1*1016 Ohm*cm.
Furthermore, in accordance with the present invention the amount and kind of the dielectric active compounds d) and d1) (preferably only d)) is suitably adjusted such that the inventive cured silicone composition has a temperature dependency of the volume resistivity in the range of 25 to 90° C. at an electric field of 10 kV/mm to 30 kV/mm, such that the ratio of the maximum volume resistivity and the minimum volume resistivity is <10, and/or the volume resistivity in the range of 25 to 90° C. at an electric field of 10 kV/mm to 30 kV/mm is preferably greater than 1*1011 Ohm*cm, more preferably greater than 1*1013 Ohm*cm, more preferably greater than 1*1016 Ohm*cm, and even more preferred greater than 1*1017 Ohm*cm, preferably up 1*1018 Ohm*cm. Furthermore, the inventive cured silicone composition preferably has a volume resistivity in the range of 25 to 90° C. at an electric field of 10 kV/mm to 30 kV/mm between 1*1011 and 1*1018 Ohm*cm, preferably between 1*1013 and 1*1018 Ohm*cm, more preferably between 1*1014 and 1*1018 Ohm*cm, and most preferably between 1*1016 and 1*1018 Ohm*cm. Most preferred is a cured silicone composition having a carbon black content of 1.0 to 2.0 wt-% of one or more carbon blacks d) based on the total weight of the curable composition and a volume resistivity in the range of 25 to 90° C. at an electric field of 10 kV/mm to 30 kV/mm between 1*1016 and 1*1018 Ohm*cm.
The volume resistivities of the cured silicone compositions are measured according to DIN EN 62631-3-1 with test sheets of 31 mm effective diameter and thickness of 1 mm.
The measurements were carried out at room temperature unless other temperatures are explicitly mentioned. The electrodes are made of brass and were polished before use. A conductive coating (e.g. silver ink) was not used, since the silicone was well contacted to the electrodes. For polarization a DC source of type PNChp-30000-2 from Heinzinger company was used with a maximum voltage of 30 kV/mm and a maximum current of 2 mA. The minimum detectable current is 1 fA (femtoampere). In the test setup the best resolution was at 10 fA.
Process for the Incorporation of the Non-Curable Silicone Composition as Defined Above (Masterbatch) into the Curable Silicone Composition According to the Invention
The carbon black component d) is suitably incorporated into the curable silicone composition of the invention in the form of the non-curable silicone composition according to the invention, i.e. as a masterbatch, for example with a dissolver mixer.
Generally, in case of a hydrosilylation/addition-curable silicone composition according to the invention, they are prepared by producing two parts, one of which comprises the polyorganosiloxanes a2) and the carbon black masterbatch (i.e. the non-curable silicone composition according to the invention), the optional filler component c), the hydrosilylation-catalyst e) and the optional auxiliary additives f), the other comprises the polyorganohydrogensiloxanes b), the optional filler component c) and the optional auxiliary additives f). For curing, these parts are mixed and subsequently heated to obtain the cured silicone composition according to the invention.
Component e) Crosslinking Catalyst In one preferred embodiment the curing catalyst is selected from the group which consists of 0-1000 ppm (related to the sum of the weight amounts of the components a) to d)) of a compound enabling curing by a hydrosilylation reaction.
The curing catalyst e) applied as hydrosilylation catalyst in the invention is selected from the group which consists of metals or metal compounds of Pt, Pd, Rh, Co, Ni, Ir or Ru.
The inventive curable silicone composition contains preferably platinum or at least one platinum compound e) which is acting as a curing catalyst if component b), the SiH-polyorganosiloxane is present and optionally necessary for the required flame retardancy.
The possible Pt component e) may be selected for example from usual platinum catalysts components e.g. selected from the group of organo platinum compounds, salts or metals of platinum, with or without a solid carrier such as activated charcoal, carbon, silica powders as taught e.g. in U.S. Pat. Nos. 3,159,601; 3,159,662; 3,419,593; 3,715,334; 3,775,452 and 3,814,730.
The curing reaction by hydrosilylation may of course be initiated by other metals or metal compounds known by people skilled in the art. Other metals may comprise metals or metal compounds of Pd, Rh, Co, Ni, Ir or Ru.
Suitable platinum compounds also include photo-activatable catalysts, including (1-diolefin)-(sigma-aryl)-platinum complexes (see e.g. U.S. Pat. No. 4,530,879 or US 2003/0199603), η5cyclopentadienyl platinum complex compounds or complexes with optionally substituted cyclopentadienyl ligands having sigma-bonded ligands, preferably sigma-bonded alkyl or aryl ligands. Other platinum compounds whose reactivity may be controlled by way for example using azodi-carboxylic esters, as disclosed in U.S. Pat. No. 4,640,939 or diketonates may be used also in principle. Platinum compounds capable of being photo-activated that may be used are moreover those selected from the group having ligands selected from diketones. Other Pt-catalysts are mentioned by way of example in U.S. Pat. No. 3,715,334 or U.S. Pat. No. 3,419,593, EP 1 672 031 A1 and Lewis, Colborn, Grade, Bryant, Sumpter, and Scott in Organometallics, 1995, 14, 2202-2213, all hereby incorporated by reference in this invention.
The component e) if used for the hydrosilylation reaction of the inventive curable silicone composition acts as a catalyst compound, which catalyzes the reaction of the silicon-bonded hydrogen atoms of component b) with the silicon-bonded olefinic hydrocarbon substituents of component a). The metal or organo metal compound may be any catalytically active metal and is generally a platinum group metal-containing a catalytic active component. Preferably, the metal of component e) is any platinum complex compound.
A typical platinum containing catalyst component in the curable polyorganosiloxane compositions of this invention is any form of platinum (0), (II) or (IV) compounds which are able to form complexes with phosphites. Preferred complexes are Pt-(0)-alkenyl complexes, such alkenyl, cycloalkenyl, alkenylsiloxane such vinylsiloxane, because of its easy dispersibility in polyorganosiloxane compositions.
A particularly useful form of the platinum complexes are the Pt(0)-complexes with aliphatically unsaturated organosilicon compound such as 1,3-divinyltetramethyldisiloxane (Vinyl-M2 or Karstedt catalyst), as disclosed by U.S. Pat. No. 3,419,593 incorporated herein by reference are especially preferred, cyclohexene-Pt, cyclooctadiene-Pt and tetravinyl-tetramethyl-tetracyclosiloxane (Vinyl-D4). Such catalysts possess best dispersibility in the inventive curable silicone composition(s).
Pt(0)-olefin complexes are prepared by way of example in the presence of 1,3-divinyl-tetramethyldisiloxane (MVi2) via reduction of hexachloroplatinic acid or of other platinum chlorides by the way of example by alcohols in the presence of basic compounds such as alkali carbonates or hydroxides (hydrazine reduction products of Pt(IV) and Pt(II) can also be used).
The amount of platinum-containing catalyst component that is used in the curable silicone compositions of this invention as flame retardant additive is limited by two constraints.
On the one side the amount should provide the desired flame resistance on the other side the amount should be as low as possible for cost reasons and balancing reactivity and pot-life under storage.
Therefore, it is preferred to provide a curable polyorganosiloxane composition wherein the platinum concentration is between 1 to 120 ppm, preferably 1 to 100 ppm, more preferably 1-70 ppm, and still more preferably 1-38 ppm (based on metal related to components a) to f)).
Generally, the reactivity of the Pt-catalyst must be controlled in terms of curing time by so-called inhibitors defined as auxiliary additives under component f).
In another embodiment of the invention the curing catalyst e) is selected from the group of 0.1 to 2 wt.-% of an organic peroxide related to a) to f), whereby such organic peroxide is selected from the group which consists of substituted or unsubstituted dialkyl-, alkylaroyl-, diaroyl- peroxides.
Suitable peroxides are peroxides commonly used in High Consistency Silicone Rubber (HCR, HV, HTV) selected from the group of dialkyl-, alkylaroyl, diaroyl peroxides. Preferred peroxides are all peroxides having a half-life period which allows storing mixtures of the inventive curable polyorganosiloxane composition comprising that peroxide at 25° C. for at least more than 10 days preferably more than 30 days without scorching. Scorching means premature curing i.e. either the increase of the Mooney viscosity of more than 20 Mooney units or gelling that is the increase of the loss modulus G″ measured in a rheometer up to the level of the elastic modulus G′.
The reactivity for the preferred peroxides is such that the curing of the polymethyl- or polymethylvinylsiloxanes occurs within less than 15 min at a temperature below 180° C.
Preferred examples of such curing agents are organic peroxides such as bis-benzoyl peroxide, bis o-methyl or p-methyl benzoylperoxide, bis-2,3-, bis-2,4- or bis-2,5-dichlorobenzoyl peroxide, di-tert.-butyl peroxide, preferably used for pressure-less hot air vulcanization and peroxides such as e.g. butyl perbenzoate, dicumyl peroxide α,α′-di-(t-butylperoxy)di-isopropylbenzenes and 2,5-bis-(tert.-butylperoxy)-2,5-dimethylhexane for transfer or injection molding under pressure.
The HCR silicone compositions can also be cured with component b) and a hydrosilylation catalyst. In view of flame retardancy it is preferred to use Pt hydrosilylation catalyst as dual additive not only as crosslinking catalyst but also to improve flame retardancy.
Optionally the curable silicone composition according to the invention can comprise auxiliary additives f) which are preferably selected from the group consisting of pigments, adhesion promotors, plasticizers, flame retardant additives, solvents, diluents, process aids for the filler treatment and other Dielectric Active Compounds d1) as explained above.
In one embodiment the curable silicone composition according to the invention comprises at least one adhesion promotor. These compounds improve the ability of the inventive composition to adhere onto several surfaces of substrates such as metals, thermoplastic or duromeric plastic surfaces, glass, natural or synthetic textile fibers other ceramic substrates.
The adhesion promotors are preferably employed in amount of 0.1 to 2 wt. % related to component a). Some of the crosslinkers b) may work as adhesion promotor if they exhibit substituents like e.g. aryl, acryl, methylacryl or epoxy groups beside the SiH units. Also some of the nitrogen compounds f) may act as adhesion promotors in particular if alkoxysilyl groups are present.
One preferred class of adhesion promotors is selected from the group which consists of silanes of the formula (3)
X—(CR92)e—Y—(CH2)eSiR9d(OR8)3-d (3)
wherein
X is selected from the group consisting of halogen, pseudohalogen, unsaturated aliphatic group with up to 14 carbon atoms, epoxy-group-containing aliphatic group with up to 14 carbon atoms, cyanurate-containing group, and an isocyanurate-containing group,
Y is selected from the group consisting of a single bond, a heteroatomic group selected from —COO—, —O—, —S—, —CONH—, —HN—CO—NH—,
R9 is selected from hydrogen and R as defined above,
R8 is a C1-C8 alkyl group is 0, 1 to 8, and may be identical or different,
d is 0, 1 to 2.
Preferred examples of the adhesion promotor of f) include:
gamma-glycidyloxypropyltrialkoxysilanes, (3,4-epoxycyclohexyl)alkyltrialkoxy silanes methacryloxyypropyltrialkoxysilanes, isocyanatopropyltrialkoxysilanes, isocyanatomethyl-trialkoxysilanes and vinyltrialkoxysilanes.
Other optional auxiliary additives are used in an amount of 0-15 pt.wt. per 100 pt.wt. of component a). The auxiliary or conventional additives include e.g.: plasticizers, release oils, hydrophobizing oils, such as polydimethylsiloxane, polydiphenyldimethylsiloxane oils having a viscosity that is preferably 0.001-10 Pa·s at 20° C.
Furthermore, it can be desired to color the layer if present in particular as outer layer with inorganic or organic pigments with lowest amount of pigments, since very often these pigments weaken or impair the mechanical or electrical properties. Additional mould-release or flow improving agents may also be used, examples being fatty acid derivatives or fatty alcohol derivatives, fluoroalkyl surfactants. Compounds advantageously used in this invention are those, which separate rapidly and migrate to the surfaces. Stability after exposure to hot air may by way of example be increased using known hot-air stabilizers, such as Fe-, Mn-, Ti-, Ce- or La-compounds, and organic salts, preferably their organic complexes such as di- or tri-ketonates.
Furthermore, the auxiliary additives f) can include hydrophobizing agents for the treatment of reinforcement filler components c), e.g. organosilanols or organosilazane and water, for example trimethylsilanol, vinyldimethylsilanol, hexamethyldisilazane, 1,3-divinyltetramethyldisilazane.
The auxiliary additives may also include so-called inhibitors for controlling the hydrosilylation crosslinking reaction. In case where the curable silicone composition contains all ingredients for a hydrosilylation reaction i.e. alkenyl groups of a1), SiH groups of b) and platinum or its compounds, the reactions speed should be preferably controlled by inhibitors in order to avoid premature curing of the reactive curable silicone composition at 25° C. before the desired curing and or shaping step for the manufacture of coatings or moulded articles. Inhibitors useful in hydrosilylation reactions are well-known. Examples of advantageous inhibitors include for example vinylsiloxanes, 1,3-divinyltetramethyldisiloxane, or tetravinyl-tetramethyltetracyclo-siloxanes. It is also possible to use other known inhibitors, for example alkynols such as ethynylcyclohexanol, 3-methylbutynol, dimethylmaleate, alkyl-, aryl or alkylaryl-phosphines, alkyl-, aryl- or alkylaryl phosphites or alkyl-, aryl-amines are used in accordance with the invention interact with those Pt-compounds, thereby influencing the hydrosilylation activity of the catalyst to provide an excellent balance between storage stability on the one hand and reactivity at elevated temperatures upon curing.
In order to increase the flame retardancy it is preferred to use nitrogen or phosphoric compounds which can enhance the effect of Pt compounds. These flame-retardant additives are selected form the group of azo, hydrazo, triazole, tetrazole, guanidine, melamine, urea or phosphite derivatives.
Solvents and/or Diluents
In a particular embodiment the curable silicone composition according to the invention is suitable for spray applications. In such case the curable silicone composition according to the invention may contain solvents and/or diluents. Such solvents and/or diluents can be selected for example from siloxanes, organic solvents, such as hydrocarbon solvents, ester-based solvent and alcohol-based solvents.
The auxiliary additives may also include other extending fillers. Such other fillers are different from the dielectric active compounds d) or d1). Their use should not impair the effect of the components d) or d1). Additional pigments or extending fillers should only be incorporated as long as they do not interact or impair or suspend the dielectric properties of component d) or d1).
Therefore, extending fillers or pigments can only merely be employed since they may have immediately similar effects as component d) or interact with d). Concentration must be therefore if used below 1 wt. % preferably smaller than 0.1 wt. %.
Typical organic pigments are selected e.g. from the group of perylenes, phthalocyanines organic pigments.
Extending fillers can be selected from the group which consists of silicates, diatomaceous earth, ground silicas, quartz, micas, amorphous carbonates, borates, hydroxides/oxides and oxides of Al, Ca, Mg, Fe, Zn having particle sizes above those of component d). These abrasive fillers and pigments are preferably semi- or non-reinforcing fillers or pigments whose particle sizes are between 1 to 100 μm having a BET surface of <30 m2/g.
Since many of these fillers are in addition very often abrasive towards metal nozzles and surfaces in an injection moulding or mixing machine or moulds most of these fillers are omitted for several other reasons. It is part of the inventive concept that the concentration of abrasive fillers should be as low possible in order to increase the life-time of the nozzles in injection molding machines and mold itself. Such abrasive fillers may be tolerated if not abrasive to metal surfaces of nozzles in the injection molding process, but in principle these fillers should be avoided or be less than 3 pt.wt. per 100 parts by weight of component a). Abrasive fillers like ground quartz or cristobalite powders or diatomaceous earth are generally less preferred.
All of the inventive curable silicone compositions are curable by any of the processes known in silicone technology and the related processes for the manufacture of formed shaped articles, including coated articles, which are obtained by spray-coating articles with the inventive curable silicone compositions. The cured material of the inventive curable silicone compositions are elastomers preferably for the use in the manufacture of an insulator for high voltage direct current application. Preferably the inventive curable silicone composition is formed and cured before the assembling of the cable joint or termination with the cable but in general the curing step can be carried out at any point of time in the process chain of assembling cable accessories, i.e. curing and shaping must not happen at the same time.
The present invention relates also to a method for the manufacture of insulators useful for the application in high voltage application, whereby the inventive curable silicone composition is shaped by extrusion through a nozzle or by a mould and curing the shaped composition by heat or light to form a shaped insulator. Such process is optionally carried out in the presence of at least one other silicone material which differs from the inventive curable silicone composition. Such different other materials may be a silicone, a rubber or thermoplastic materials which at least differ in terms of the physical properties and ratios and/or concentrations of the single components a) to f).
The inventive curable silicone composition which has been cured can be used per se as insulating material but preferably is used in combination with other materials well known in the design of HVDC cable accessories. For example, cable joints or cable terminations have very often a multi-layer design, whereby at least one of the materials providing high conductivity is part of the joint as shielding material, e.g. conductive EPDM or conductive silicone rubber or conductive thermoplastic having a volume resistivity below 1*104 Ohm*cm. Some parts of such cable accessories can have the form of a tube or tube-like trumpet and can therefore be manufactured by an extrusion process.
The final insulator needs very often a more complicated assembling of 2 to 4 different materials and therefore is manufactured by assembling of extruded and moulded parts, sometimes the final outer layer is applied as encapsulant by pouring of low viscous silicone rubbers in particular for joints with a big volume under assistance of an optionally open mold cavity.
The inventive curable silicone composition is preferably for the use as cured composition for high voltage direct current application and preferably for the manufacture of cable joints, boots, sleeves, fittings etc. cable accessories, cable terminations.
The cured inventive silicone composition is in particular for the use of the manufacture of a cable joint intended for sealing cable ends of one or more cables having a thermoplastic polyolefin or rubber cable insulation, wherein the cable joint seals cable ends of one or more cables having a thermoplastic polyolefin or rubber cable insulation.
The invention relates also to a method for the manufacture of a cable joint comprising the steps A1) providing at least one conductive shaped silicone composition which differs from the silicone composition according to the invention and which is optionally cured, B1) encapsulating the composition of step A1) with a silicone composition according to the invention in a mould to form and cure a cable joint or cable termination.
The invention relates furthermore to a method for sealing and/or insulating connected cables or closing cable ends by the use of a cable joint as defined before comprising the steps of
This assembling process i.e. the sealing step of one or more insulated cables can be carried out in a way wherein the cable joint or cable termination is stretched by widening the tube-like holes under assistance of pressed air or by stent-like plastic or a metal tool or by means which keep the joint in an extended shape and let it relax under heat like as a shrinking tube.
Another process according to the invention includes the use of an optional transparent form and start curing after encapsulation of the cable or cables with all materials in the field at temperatures between 0 to 200° C. or under assistance of light and light activatable curing catalysts e).
The cured inventive silicone composition according to the invention have unique electrical properties compared to the cured silicone compositions that are prepared using the conventional—non-extruded—carbon black masterbatch.
In a further embodiment of the invention it relates to a curable silicone composition, comprising:
Such curable silicone composition preferably comprises more than 2.4 wt-%, preferably 3 to 10 wt-% of one or more carbon blacks d) based on the total weight of said curable silicone composition.
These high carbon black-load curable compositions can be cured to generally electrically and also thermally conductive silicone compositions and can be used in applications where electrically and/or thermally conductive silicone rubbers are required, such as for the manufacture of connectors, electrically conductive films, electrode materials, heat-radiating materials.
Preferred Embodiments of the Invention
In the following the preferred embodiment of the invention are shown.
1. Process for the manufacture of a non-curable silicone composition comprising carbon black, said process comprises the extrusion of one or more polyorganosiloxanes a1) with one or more carbon blacks d).
2. A process according to the previous embodiment, wherein the total viscosity of the one or more polyorganosiloxanes a1) is less than 100 preferably 1 to 100 Pa·s (measured at a shear rate of D=10 s−1 at 20° C.).
3. A process according to any of the previous embodiments, wherein the polyorganosiloxanes a1) are selected from polyorganosiloxanes having one or more unsaturated groups, preferably one or more alkenyl groups.
4. A process according to any of the previous embodiments wherein the polyorganosiloxanes a1) have organic substituents R selected from the group consisting of optionally substituted alkyl, such as alkyl groups and halogenalkyl groups, optionally substituted aryl, such as phenyl and have one or more substituents R1 selected from the group consisting of alkenyl groups, such as vinyl groups, and have an average degree of polymerisation Pn between 100 to 12000 siloxy units.
5. A process according to any of the previous embodiments, wherein the extrusion is carried out with an extruder, such as a multi screw extruder, preferably a twin-screw extruder, more preferably a co-rotating twin-screw extruder.
6. A process according to any of the previous embodiments, wherein the extrusion is carried out at a temperature of the extruded mass of room temperature (25° C.) to 250° C., preferably at a temperature of the extruded mass in the range of 50 to 200° C., more preferably in the range of 100 to 175° C.
7. A process according to any of the previous embodiments, wherein the extrusion is carried out using one or more of the following conditions:
8. A process according to any of the previous embodiments, wherein the weight ratio of the weight of the one or more polyorganosiloxanes a1) to weight of the one or more carbon blacks d) is from 90:10 to 75:25, preferably from 89 to 11 to 80 to 20.
9. A process according to any of the previous embodiments, wherein solely the one or more polyorganosiloxanes a1) and the one or more carbon blacks d) are extruded.
10. A non-curable silicone composition obtained by the process as defined by any of the previous embodiments.
11. A non-curable silicone composition according to any of the previous embodiments comprising at least 10, preferably at least 11, still more preferably at least 12 weight percent or one or more carbon blacks d) based on the total weight of the entire silicone composition.
12. A non-curable silicone composition according to any of the previous embodiments comprising from 10 to 25, preferably from 11 to 24, still more preferably from 12 to 23 weight percent of one or more carbon blacks d) based on the total weight of the entire silicone composition.
13. A non-curable silicone composition according to any of the previous embodiments consisting of one or more polyorganosiloxanes a1) and one or more carbon blacks d).
14. A non-curable silicone composition according to any of the previous embodiments, wherein the one or more carbon blacks comprise at least one carbon black selected from conductive carbon blacks having a BET surface of >30 m2/g and/or an average primary particle size of D50 between 5 to 500 nm.
15. A non-curable silicone composition according to any of the previous embodiments, wherein the one or more carbon blacks comprise at least one carbon black selected from conductive carbon blacks having one or more of the following properties:
16. A non-curable silicone composition according to any of the previous embodiments, wherein the percentage of the number of particles less than 10 μm is more than 70% preferably more than 80%, still more preferably more than 90%, and/or the percentage of the number of particles of more than 10 μm is less than 30% preferably less than 20% still more preferably less than 10%, still more preferably less than 5% as determined by dynamic light scattering.
17. A non-curable silicone composition according to any of the previous embodiments, wherein the Dn50 of the particle size distribution based on the number of particles of the non-curable silicone composition is preferably less than 7 μm, more preferably less than 5 μm, and most preferably less than 3 μm.
18. A non-curable silicone composition according to any of the previous embodiments, wherein the Dn90 of the particle size distribution based on the number of particles of the non-curable silicone composition is preferably less than 15 μm, more preferably less than 10 μm more preferably less than 8 μm and most preferably less than 5 μm.
19. Use of the non-curable silicone composition according to any of the previous embodiments for the manufacture of curable silicone compositions.
20. Use of the non-curable silicone composition according to any of the previous embodiments as a masterbatch for incorporation into curable silicone composition.
21. Use of the non-curable silicone composition according to any of the previous embodiments in high voltage direct current applications.
22. Curable silicone composition comprising the non-curable silicone composition according to any of the previous embodiments.
23. Curable silicone composition according to the previous embodiment 22, comprising:
24. Curable silicone composition according to any of the previous embodiments 22 or 23, comprising from 0.1 to 2.4 wt-% preferably 0.2 to 2.4 wt-%, more preferably 0.5 to 2.2 wt-%, even more preferred 1.0 to 2.0 wt-%, and even more preferred 1.3 to 1.8 wt-% of one or more carbon blacks d) based on the total weight of the curable silicone composition.
25. Cured silicone compositions, obtained by curing the curable silicone compositions according to any of the previous embodiments 22 to 24.
26. Cured silicone compositions according to embodiment 25, having in a PEA charge movement diagram determined according to the method described in the examples a movement of any charge <0.2 mm, preferably <0.3 mm from one or each electrode.
27. Cured silicone compositions according to embodiment 25, having in a PEA charge movement diagram determined according to the method described in the examples a movement of the peak max/min of <0.05 mm, preferably <0.1 mm from one or each electrode.
28. Cured silicone compositions according to embodiment 25, wherein after 5 h, preferably after 2.5h in the total charge accumulation diagram (as shown exemplary in
29. Cured silicone compositions according to embodiment 25, having a maximum mean charge density in the total charge accumulation diagram (as shown exemplary in
30. Cured silicone compositions according to any of embodiments 25 to 29, having a volume resistivity in the range of 25 to 90° C. at an electric field of 10 kV/mm to 30 kV/mm of preferably greater than 1*1011 Ohm*cm, more preferably greater than 1*1013 Ohm*cm, more preferably greater than 1*1016 Ohm*cm, and even more preferred greater than 1*1017 Ohm*cm, preferably up 1*1016 Ohm*cm. volume resistivity in the range of 25 to 90° C. at an electric field of 10 kV/mm to 30 kV/mm of between 1*1011 and 1*1019 Ohm*cm, preferably between 1*1011 and 1*1016 Ohm*cm, preferably between 1*1013 and 1*1018 Ohm*cm, more preferably between 1*1014 and 1*1018 Ohm*cm, and most preferably between 1*1016 and 1*1018 Ohm*cm.
32. Cured silicone compositions according to any of embodiments 25 to 31, having a carbon black content of 1.0 to 2.3 wt-% of one or more carbon blacks d) based on the total weight of the curable silicone composition and a volume resistivity in the range of 25 to 90° C. at an electric field of 10 kV/mm to 30 kV/mm between 1*1016 and 1*1018 Ohm*cm.
33. Use of the curable silicone composition according to any of the previous embodiments for the manufacture of an insulator or field grading assembly for high voltage direct current (HVDC) applications.
34. An insulator or a field grading assembly for high voltage direct current application which is obtained by curing the curable silicone composition according to any of the previous embodiments.
35. A cable accessory for high voltage direct current application comprising the insulator, or the field grading assembly, according to the previous embodiment.
36. A cable accessory according to the previous embodiment, which is selected from the group consisting of cable joints, cable terminations and cable connectors each for high voltage direct current application.
37. A cable joint according to embodiment 36, wherein the cable joint seals the ends of cables having a thermoplastic polyolefin or rubber cable insulation.
38. Curable silicone composition according to the previous embodiment 22, comprising:
39. Curable silicone composition according to the previous embodiments 22 and 38, comprising more than 2.4 wt-%, preferably 3 to 10 wt-% of one or more carbon blacks d) based on the total weight of the curable composition.
40. Cured silicone compositions, obtained by curing the curable silicone compositions according to any of the previous embodiments 38 and 39.
41. Use of the cured silicone compositions according to embodiment 40 for the manufacture of connectors, electrically conductive films, electrode materials, heat-radiating materials, and electro active elastomers.
All parts are weight parts unless otherwise indicated. All percentages are weight percentages unless otherwise indicated.
A vinyl terminated linear polydimethylsiloxane having a viscosity of 10 Pa·s at 20° C. and a shear rate of D=10 s−1 (component a1) and carbon black Ketjenblack EC 300 J (Akzo) having BET surface 800 m2/g (350 DBP pore volume ml/100 g) with a primary particle size of 40 nm (component d) were extruded at 25° C. on a co-rotating twin-screw extruder from Leistritz, size ZSE40MAXX having an L/D ratio of 52 (L is the Length of the extruder and D its Diameter) and a screw diameter 41.4 mm. The throughput rates varied from 100 to 175 kg/h. The temperature of the extruded mass raised with increasing carbon black contents and reached above 230° C. at very high carbon black contents, despite cylinder cooling.
Carbon black contents were varied from 10 to up to 23 wt-%.
100 kg of a vinyl terminated linear polydimethylsiloxane having a viscosity of 10 Pa·s at 20° C. and a shear rate of D=10 s−1 was placed in a planetary mixer and mixed with 12.7 kg carbon black Ketjenblack EC 300 J (Akzo) having BET surface 800 m2/g (350 DBP pore volume ml/100 g) with a primary particle size of 40 nm. This mixture was stirred in a twin blade kneader till a homogeneous mixture was obtained after 45 min.
The homogeneous mixture was then further dispersed over 30 min on a three-roll mill to obtain a dispersion of the carbon black.
The particle size distribution of the carbon black in the non-curable silicone composition of the Masterbatch Example 1 and the Masterbatch Comparative Example 1 were measured by light scattering according to DIN EN ISO/IEC 17025 in toluene solution using the scattering model according to the Mie theory measured at the lowest possible rotational speed of the dispersing unit corresponding to the lowest possible shear using a Malvern Zetasizer apparatus.
Masterbatch Example 1 has almost no particles above 10 μm and particles down to about 1 μm, the Masterbatch Comparative Example 1 has significant parts of particles bigger than 10 μm up to about 100 μm and almost no particles of less than about 3 μm. It is assumed that this different particle size distribution of the inventive masterbatch (non-curable silicone composition) is surprisingly effective to improve the electronic properties of the cured silicone compositions of the invention especially in high voltage direct current applications as described below.
Examples of curable compositions
Example SR1 and Comparative Example SR1
A curable silicone rubber composition SR1 according to the invention was prepared according to the following process:
In a dissolver mixer 9.47 parts carbon black paste according to Masterbatch Example 1, 11.12 parts of a dimethylvinylsiloxy-terminated polydimethylsiloxane having a viscosity of 10 Pa·s at 20° C. and at a shear rate of 10 s−1 and 20.14 parts of a dimethylvinylsiloxyterminated polydimethylsiloxane having a viscosity of 65 Pa·s (components a2) each) were mixed with 3.08 parts of hexamethyldisilazane (surface treating agent—part of component c)), 0.026 parts of divinyltetramethyldisilazane (surface treating agen—part of component c)) and 1.29 parts of water (additive—component f)). The mixture was then mixed with 14.25 parts of fumed silica having a Brunauer-Emmett-Teller (BET) specific surface area of 300m2/g (Aerosil® 300 from Evonik) (component c)) and heated at 100° C. for 1h so that a silica filler with a mixture of trimethylsilyl- and vinyldimethylsilyl groups at its surface was formed. Water and resulting volatile compounds from the surface treatment reaction were subsequently removed from the silicone mixture at ca. 150° C. under vacuum (<80 mbar) for 1h. Resulting volatiles were removed from the silicone mixture at ca. 150° C. under vacuum (<80 mbar) for 1 h. The mixture was later cooled down and diluted with 39.13 parts of dimethylvinylsiloxy-terminated polydimethylsiloxane having a viscosity of 10 Pas. Subsequently 3.97 parts of a dimethylvinylsiloxy-terminated poly(dimethylsiloxane-comethylvinylsiloxane) having a vinyl content of 2.08 mmol/g and a viscosity of 0.2 Pas (component a)) is added. Finally, 0.2 parts of a solution of a Pt(0) complex with tetramethyltetravinylcyclotetrasiloxane that contains 1.5 wt % Pt was added (Ashby catalyst) (component e)).
In a dissolver mixer 9.47 parts carbon black paste according to Masterbatch Example 1, 11.23 parts of a dimethylvinylsiloxy-terminated polydimethylsiloxane (component a2)) having a viscosity of 10 Pa·s and 20.33 parts of a dimethylvinylsiloxyterminated polydimethylsiloxane having a viscosity of 65 Pa·s (component a2)) were mixed with 3.06 parts of hexamethyldisilazane (surface treating agent—part of component c)), 0.025 parts of divinyltetramethyldisilazane (surface treating agent—part of component c)) and 1.27 parts of water (additive—component f)). The mixture was then mixed with 14.15 parts of fumed silica having a Brunauer-Emmett-Teller (BET) specific surface area of 300 m2/g (Aerosil® 300 from Evonik) (component c)) and heated at 100° C. for 1 h so that a silica filler with a mixture of trimethylsilyl- and vinyldimethylsilyl groups at its surface was formed. Water and resulting volatile compounds from the surface treatment reaction were subsequently removed from the silicone mixture at ca. 150° C. under vacuum (<80 mbar) for 1h. Resulting volatiles were removed from the silicone mixture at ca. 150° C. under vacuum (<80 mbar) for 1 h. The mixture was later cooled down and diluted with 28.51 parts of a dimethylvinylsiloxy-terminated polydimethylsiloxane having a viscosity of 10 Pa·s. Subsequently, 8.94 parts of a first crosslinker (linear poly(dimethyl)co(methylhydrogen)siloxane with an SiH content at 4.15 mmol/g and a viscosity of 0.035 Pa s (component b)) and 5.54 parts of a second crosslinker (linear poly(dimethyl)co(methylhydrogen)siloxane with an SiH content at 2.30 mmol/g and a viscosity of 0.21 Pa s (component b)), and 0.12 parts of 1-ethynyl-1-cyclohexanol (ECH) (component f)) were added.
Cured silicone rubber compositions according to the invention were prepared as follows: Parts A and B were mixed in a 1:1 weight ratio and cured by heating to 175° C. for 10 minutes.
Example SR1 (curable silicone composition) was repeated except that the Masterbatch from Comparative Example 1 is used in the amount given in the Table 3.
Additional cured compositions were prepared as described for example SR1 and comparative example SR1 above with varying amounts of carbon black using the inventive non-curable master batch carbon black paste and the non-inventive non-curable master batch as described above and subjected to the measurements of various electrical properties as described in the following.
The volume resistivities of the cured compositions were measured according to DIN EN 62631-3-1, test sheets of 31 mm effective diameter and thickness of 1 mm for high volume resistivities (higher than about 1014 Ω·cm). For lower volume resistivities (lower than about 1014 Ω·cm) the volume resistivities were determined according to IS01853.
For highly insulating materials, the electrical conductivity or the volume resistivities of the samples of cured compositions with the measurement equipment, the principal structure of which is shown in
Further parameters of the measurement were:
The determination of the duration of the measurement is done with a double logarithmic plot of the current over time as principally shown in
The measurements were carried out at room temperature unless other temperatures are explicitly mentioned. The electrodes are made of brass and were polished before use. A conductive coating (e.g. silver ink) was not used, since the silicone was well contacted to the electrodes. For polarization a DC source of type PNChp-30000-2 from Heinzinger company was used with a maximum voltage of 30 kV/mm and a maximum current of 2 mA. The minimum detectable current is 1 fA (femtoamper). In the test setup the best resolution was at 10 fA.
Further parameters:
The test sample is a stripe with 2 cm width and 2 mm thickness, distance to between electrodes is 2 cm according to ISO norm above. Measurements were carried out at room temperature.
As shown in
The breakdown voltage of the inventive compositions and the comparative compositions of varying amounts of carbon black was measured according to IEC 60243-2.
The specific parameters were as follows:
To avoid oil uptake the so called short-time (rapid rise)-test according to IEC 60243-2 was applied.
The generator allowed a maximum output voltage of 100 kV in combination with a smoothening capacitor of Cg=10 nF a maximum output of 140 kV could be achieved. The so-called ripple factor of the DC remained below 1%. The stress voltage is applied with an ohm-capacitive voltage splitter of type VD 150 North Star company with a Standard Divider Ratio of 10000:1 (DC error<0.1%).
The results are shown in
As shown in
The PEA (Pulsed Electro Acoustic) measurement is used for the localization of charges inside a material, e.g. a silicone sheet. This allows the measurement of charge movements over time inside a material induced by polarization current at certain temperatures. This method is crucial for the development and justification of insulating materials (cable accessories) for HVDC applications. It should be mentioned that all samples had a thickness of 1 mm, and no silicone oil or grease was used at the interfaces of the samples because it was observed that the silicone oil/grease would migrate into the LSR. For each parameter combination, a fresh and depolarized LSR sample was used. In the case of PEA, the acoustic impulse is generated directly at the place of the space charge which allows to determine their position via the speed of the acoustic waves. The electric impulse is a voltage impulse which creates a short-term electrical field Ep inside the sample. It does not cause any further polarization because of the very short time range but exerts coulomb forces onto the space charge and a pressure impulse subsequently. This impulse spreads through the sample as an acoustic wave until reaching a piezo membrane which transforms the acoustic signals back to an electric signature.
After correction of the system response and other factors including calibration, the transformation to space coordinates (1D) gives basically the following pattern with a charge density as a function of place (x). The total charge density (Q) can be calculated with
A detailed description of the whole setup and the signal processing of PEA (Pulsed Electro Acoustic) measurement is given in:
1) R. Hussain, J. Moxter and V. Hinrichsen, “Development and optimization of a Pulsed Electroacoustic system suitable for silicone rubbers with carbon black nanofillers,” 10th International conference on insulated power cables, Session C4-1, Paris, 2019;
2) R. Hussain and V. Hinrichsen, “Development and Optimization of a Pulsed Electroacoustic System with Temperature Controlled Electrodes,” 26th Nordic Insulation Symposium on Materials, Components and Diagnostics, Tampere, Finland, 2019;
3) G. C. Montanan and D. Fabiani, “Evaluation of DC insulation performance based on space-charge measurements and accelerated life tests,” in IEEE Transactions on Dielectrics and Electrical Insulation, vol. 7, no. 3, June 2000, pp. 322-328;
4) Antti Penttinen DESIGN OF PULSED ELECTROACOUSTIC MEASUREMENT SYSTEM FOR SPACE CHARGE CHARACTERISATION, Master Thesis, Lappeenranta University of Technology 2012, and further
5) R. Hussain, PhD thesis “Electrical Characterization of Liquid Silicone Rubber with Carbon Black Nanofiller for HVDC Cable Accessories” TU Darmstadt (will be published in 2020).
The PEA measurement is a method to proof the concept of charge traps which cause a kind of charge barrier that prevents further injection of charges into the material and thus also prevent the cable joint from breakdowns. The higher the amount of charge traps, the stronger the built up of this charge barrier (so called homo-charges). In accordance with the present invention CB is used in particular as a charge trap material because the potential well for the charges is relatively deep and needs high energy to remove charges from that potential well. This allows to maintain charges at the place of injection which itself prevents from further migration into the material as well builds up the mentioned charge barrier.
The
The inventive examples of the cured silicone composition SR1 (
Preferably the cured silicone compositions according to the invention SR have in the PEA charge movement diagram determined according to the method described above a movement of any charge <0.2 mm, preferably <0.3 mm from one or each electrode.
Preferably the cured silicone compositions according to the invention SR have in a PEA charge movement diagram determined according to the method above a movement of the peak max/min of <0,05 mm, preferably <0,1 mm from one or each electrode.
The mean charge density is calculated according to the following equation at a certain time.
The resulting diagram is shown in
The behavior of the space charges (mobility and max. mean charge density) is finally dependent on the filler loading. However, the inventive CB masterbatch extrusion process (Ex. 1) allows a higher CB loading at volume resistivity and breakdown voltage than the comparative CB masterbatch does.
For a safe operation it is crucial that the steady state (no further increase of the charge density) is reached as quick as possible (
The cured silicone compositions according to the invention preferably after 5 h, more preferably after 2.5 h in the total charge accumulation diagram (as shown exemplary in
The cured silicone compositions according to the invention preferably have a maximum mean charge density in the total charge accumulation diagram (as shown exemplary in
| Number | Date | Country | Kind |
|---|---|---|---|
| 20203115.9 | Oct 2020 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2021/079174 | 10/21/2021 | WO |
