CN1735946A - Heat-vulcanizable polyorganosiloxane compositions useful in particular for making electric wires or cables - Google Patents
Heat-vulcanizable polyorganosiloxane compositions useful in particular for making electric wires or cables Download PDFInfo
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- CN1735946A CN1735946A CNA2003801085416A CN200380108541A CN1735946A CN 1735946 A CN1735946 A CN 1735946A CN A2003801085416 A CNA2003801085416 A CN A2003801085416A CN 200380108541 A CN200380108541 A CN 200380108541A CN 1735946 A CN1735946 A CN 1735946A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/46—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes silicones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
Abstract
The invention concerns polyorganosiloxane compositions heat-vulcanizable into silicone elastomers, useful in particular for making electric wires or cables with high fire resistance satisfying current standards, containing: a) at least one polyorganosiloxane polymer; b) at least one reinforcing filler; c) an organic peroxide; d) mica; e) zinc oxide; f) optionally at least one additive normally used in the preparation of heat-vulcanizable polyorganosiloxane compositions; g) platinum, a platinum compound and/or a platinum complex; h) titanium oxide; i) at least one packing filler; and j) optionally at least one mineral species belonging to the wollastonite group. Said compositions are characterized in that the packing fillers i) consist in aluminium hydroxide powders AI(OH)3 surface treated with an organoalkoxysiloxane and/or an organosilazane and/or an organosiloxane oligomer bearing OH and/or alkoxy radicals.
Description
The present invention relates to constituent polyorganosiloxane composition, but its heat cure becomes silicone elastomer, promptly at normally 100-200 ℃ and can reach when needing under 250 ℃ the material temperature and can cure.The invention still further relates to these compositions and be used in particular for producing the foreskin that constitutes a flame-proof wire or a cable part or the first purposes of class F insulating material F.At last, the invention still further relates to flame-proof wire or the cable that uses this based composition to produce.
Term " flame-proof wire or cable " is used for defining and guarantees at least at the electric wire or the cable that have the high-quality fire protecting performance aspect grey shape material caking property and the smog opacity.These characteristics that flame-proof wire or cable must have all are related subject content in the rules of many countries, and have realized strict standardization.
For example in France, a major criterion that relates to the cable fire resistance test that must satisfy is standard NF C 32-070 CR1, and this standard relates to the operating time at the cable of determining to burn under the condition.This fire resistance is attributable to the generation of grey shape material, and this ash shape material should have certain caking property, to keep enough insulating properties can use cable.In this test, each cable sample is fixed in the metal tube, and this pipe itself is put in the stove again, and furnace temperature reached 920 ℃ in 50 minutes, keeps 15 minutes under this temperature subsequently; In this process of the test, the cable sample is subjected to clocklike impacting (impact twice speed according to per minute, use the impact rod to impact this metal tube); If when the test period finishes (after 65 minutes), the control lamp that is connected with the cable that has applied nominal voltage does not extinguish, then should success of the test.
Another major criterion that relates to fire resistance test that also must satisfy is international standard IEC61 034, the 1st and 2 parts (IEC is the abbreviation of International ElectrotechnicalCommission), this standard relate to and are determined at the obscuration that cable produces that burns under definite condition.In this test, measure a 27m
3Light transmittance in the cell, this cell is covered by the smog that the multistage cable that burns under the effect of the Alcohol Flame of determining to equip under the condition produces.If light transmittance reaches at least 60%, then satisfy this standard.
Have only to its at least just the propagation of flame inhibition of the class F insulating material F electric wire or the cable that carried out special research could satisfy above-mentioned standard.In fact, according to known systems, observe, the silicone elastomer that obtains through hot vulcanization with suitable constituent polyorganosiloxane composition is that the first class F insulating material F of main component can satisfy the test of propagation of flame inhibition.This silicone elastomer the time changes in burning has certain close-burning grey shape megohmite insulant, and it discharges white smoke, and this smog is caused by the spontaneous combustion of the volatility residue that this elastomer degraded produces.Yet, the such composition that has proposed so far can not be entirely satisfactory, still need improve, especially obtaining to have more aspect the close-burning grey shape material, under the situation of catching fire, can make the longer time of cable work like this, the white smoke of emitting still less reducing obscuration, and then reduces the scheduling time of fire fighting disaster relief organization department.
According to known systems, cable is made of one or more single conductors (usually based on Cu or Al); Each conductor is all protected with foreskin or first class F insulating material F in these single conductors, and described foreskin or first class F insulating material F are made of one or more layers concentric layer based on silicone elastomer.One or more packing components and/or one or more especially based on the enhancing element of glass fibre and/or inorfil can be arranged around these one or more foreskins (having under the situation of cable of a plurality of single conductors).Carry out outer envelope then, it can comprise one or more big envelopes.Under the situation of cable, can place one or more packing components and/or one or more enhancing element of (each single conductor all is furnished with its class F insulating material F just) around these single conductors to constitute the total foreskin of all single conductors with a plurality of single conductors.Although constitute the silicone elastomer of a cable part is one or more composition materials of class F insulating material F just basically, and it also can be present in different ratios in one or more optional packing components and/or the one or more optional enhancing element (constituting total foreskin under the situation of the cable with a plurality of single conductors); And/or in one or more outer envelope.
Constitute each single conductor foreskin or first class F insulating material F, will depend primarily on according to above-mentioned standard code based on the wall thickness of the number of the concentric layer of silicone elastomer and every layer and keep the mandatory requirement of operation institute.Generally speaking, people wish by use one deck or two-layer and every layer suitably have and equal at least 0.5mm thickness and preferably equal at least that 0.8mm thickness reaches such operational effect.
Therefore, but an object of the present invention is to develop the constituent polyorganosiloxane composition that heat cure becomes silicone elastomer, also can give electric wire or cable very high-quality fire protecting performance even it only is used to produce first class F insulating material F, this very high-quality fire protecting performance is at least by realizing that the following shows:
* improve the caking property of grey shape material, so that all compositions of the present invention are under 500 volts, by the operating time of electric wire or cable is satisfied this standard with respect to standard NF C 32-070 CR1 threshold value prolongation in desired 65 minutes greater than 25%;
* improve the ability that reduces the smog opacity, this opacity is to measure according to standard IEC 61034, the 1 and 2 parts, and it can reach the target greater than 80% light transmittance usually.
But another object of the present invention also relates to the heat-vulcanized constituent polyorganosiloxane composition, its when having improved flame resistance, also have solidify and its uncured state under the favorable mechanical performance, especially under 200 ℃ according to cable standard insulating material class EI2 operation (especially aspect following: Xiao A hardness, hot strength, extension at break and modulus of elasticity) all the more so after aging 10 days.
But the constituent polyorganosiloxane composition that heat cure becomes silicone elastomer has been described in the prior art, for it, except adopt the peroxide catalyzed effect make organo-siloxanes polymer crosslinked, also use the filler of flux class and/or sheet class, this filler can use separately or use in conjunction with platinum and metal oxide, so that form the grey shape material of insulation under situation on fire, this ash shape material has certain caking property, thereby the operating time of the cable of burning is prolonged.
Can mention file EP-A-0 467 800, this document proposes to use ZnO (as flux) and mica (as laminal filter) simultaneously, and they randomly are used in combination with platinum compounds and/or metal oxide, and metal oxide for example is titanium dioxide and oxide Fe
3O
4Also can mention file WO-A-01/34705, this document has improved above-mentioned prior art, but and the proposition heat cure become the composition of silicone elastomer, it comprises, based on one or more organo-siloxanes polymers of 100 weight portions:
One or more reinforcers of-15-100 part b), siliceous filler for example,
-0.2-8 part organic peroxide c),
-0.5-30 part mica d),
-0.2-10 part zinc oxide e),
One or more auxiliary additives of-0-15 part f),
The component g that-0.0010-0.02 part is represented with (element) platinum weight) (being 10ppm to 200ppm),
-0.5-10 part titanium dioxide h),
One or more loose fillers of-20-100 part i), for example crystalline silica and
-0.5-10 part belongs to one or more materials j of wollastonite class).
In order to be suitable for all cable extruding technologies, wish to enlarge very much can meeting standard NF C 32 070 CR1 under 500 volts and satisfying the scope of the composition of relevant smog opacity requirement of in above-mentioned EP and WO file, proposing always.
Have now found that but heat cure becomes the novel polyorganosiloxane composition of silicone elastomer, said composition has constituted first purpose of the present invention just, said composition is particularly useful for replenishing the scope of the composition of the excellent performance that (compl é ter) use in producing electric wire or field of cables, in other words be exactly the scope of replenishing following this composition, fire resistance (capable referring to the 3rd page of 5-9) and formed on the other hand silicone elastomer that said composition has the close-burning requirement of relevant grey shape material that meets the front fully and proposed on the one hand have the favorable mechanical performance.
More properly, first purpose of the present invention relates to the composition (all umbers all are weight portions) that comprises following substances:
One or more organo-siloxanes polymers of-100 weight portions are a):
One or more reinforcers of-15-100 part b),
-0.2-8 part organic peroxide c),
-0.5-30 part mica d),
-0.2-10 part zinc oxide e),
One or more auxiliary additives of-0-15 part f),
The component g that-0.0005-0.02 part is represented with (element) platinum weight) (being 5ppm to 200ppm),
-0.5-10 part titanium dioxide h),
One or more loose fillers of-20-100 part i), and
-0-10 part belongs to one or more materials j of wollastonite class).
Described composition is characterised in that loose filler i) now by aluminium hydroxide Al (OH)
3Powder constitutes, and this powder surface is handled with the organoalkoxysilane of being with OH and/or alkoxyl and/or organosilazanes and/or organosiloxane oligomer, wherein:
* this organic group is represented one or more following alkyl that are selected from: the straight or branched alkyl that 1-10 carbon atom arranged; 2-6 carbon atom arranged and have the straight or branched thiazolinyl of one or two olefinic double bond; And/or phenyl;
* this alkoxyl is represented one or more alkoxyls that are selected from the straight or branched alkoxyl with 1-6 carbon atom.
Therefore, the applicant finds, following substances:
-by the aluminium-hydroxide powder Al (OH) that handled
3At least a loose filler i that constitutes), with
-the inorganic component that constitutes by siliceous filler, mica, zinc oxide, platinum (or containing platinum compounds or complex), titanium dioxide and optional wollastonite according to the WO-A-01/34705 instruction, combination the finished product elastomer is had significant humidification, it especially can obtain the ability of improved grey shape material caking property and improved reduction smog opacity in electric wire or cable application.
Therefore, composition of the present invention contains at least a organo-siloxanes polymer a), and it contains 0-4% by weight, preferably the vinyl of 0.01-3%.When these organo-siloxanes polymers a) when 25 ℃ viscosity is 50 000-1,000 000mPa.s, they are called as oil, but their viscosity can be higher than 1 000 000mPa.s, at this moment they are called as natural gum.In composition of the present invention, these organo-siloxanes polymers can be oil or natural gum or mixture.These organo-siloxanes polymers are straight chain polymers, and its diorganopolysiloxanecompositions chain is mainly by formula R
2The SiO unit constitutes.This chain is at each terminal formula R that uses
3Si
0.5Unit and/or the basic end-blocking of formula OR '.In these formulas:
-symbol R, identical or different, represent the monovalence alkyl, alkyl for example is as methyl, ethyl, propyl group, octyl group, octadecyl; Aryl is as phenyl, tolyl, xylyl; Aralkyl, for example benzyl, phenethyl; Cycloalkyl and cycloalkenyl group, for example cyclohexyl, suberyl, cyclohexenyl group; Thiazolinyl, for example vinyl, pi-allyl; Alkaryl, cyano group alkyl, for example cyano ethyl; Haloalkyl, haloalkenyl group and halogenated aryl, chloromethyl, 3,3 for example, 3-trifluoro propyl, chlorphenyl, dibromo phenyl, trifluoromethyl;
-symbol R ' represents hydrogen atom, has the alkyl or the 'beta '-methoxy ethyl of 1-4 carbon atom.
Preferably, 60%R group represent methylidene at least.But, do not get rid of a small amount of R of removing of existence along the diorganopolysiloxanecompositions chain
2Unit outside the SiO, for example formula RSiO
1.5And/or SiO
2Unit, its ratio be 2% (wherein, the T of per 100 silicon atoms of these % numeric representations and/or the number of Q unit) at the most.
As formula R
2SiO and R
3SiO
0.5The instantiation of unit and formula OR ' base, can enumerate these of following formula:
(CH
3)
2SiO，CH
3(CH
2＝CH)SiO，CH
3(C
6H
5)SiO，(C
6H
5)
2SiO，
CH
3(C
2H
5)SiO，(CH
3CH
2CH
2)CH
3SiO，CH
3(n.C
3H
7)SiO，
(CH
3)
3SiO
0.5，(CH
3)
2(CH
2＝CH)SiO
0.5，CH
3(C
6H
5)
2SiO
0.5，
CH
3(C
6H
5)(CH
2＝CH)SiO
0.5，
OH，-OCH
3，-OC
2H
5，-O-n.C
3H
7，-O-iso.C
3H
7，-O-n.C
4H
9，
-OCH
2CH
2OCH
3.
These oil and natural gum are sold by siloxanes manufacturer, or can produce these oil and gummy according to known technology.
Reinforcer b) comprises the mixture of silicon dioxide, aluminium oxide or these two kinds of materials.As spendable silicon dioxide, the filler that can mention is characterised in that its particle size often is less than or equal to 0.1 μ m, has high specific area and weight ratio, normally about 50-300m
2/ g.This class silicon dioxide is obtainable from the market product, and knows in the technical field of producing silicone rubber.Adopt method for pyrolysis (so-called pyrogenic silica) or adopt wet method (precipitated silica) can prepare these silicon dioxide, and these silicon dioxide can adopt the organo-silicon compound that are usually used in this purpose to handle or do not handle.For purpose of the present invention, its chemical property and preparation method are unimportant, as long as this silicon dioxide can apply humidification to final elastomer.Certainly, can also use the blend of different silicon dioxide.As spendable enhancing aluminium oxide, mix in a known way or the aluminium oxide of unadulterated high degree of dispersion but advantageously use.Certainly, can also use the blend of different aluminium oxide.As the limiting examples of these aluminium oxide, can enumerate
The aluminium oxide A 125 of company, CR 125 and D65CR.Preferably, the reinforcer of use is a pyrogenic silica single or that mix with aluminium oxide.
Constitute amount of component b) organic peroxide can be for the composition that forms silicone elastomer, to play any in those organic peroxides of vulcanizing agent effect.Thereby it can be any in known peroxide that uses with silicone elastomer or the perester; for example di-tert-butyl peroxide, benzoyl peroxide, monochloro-benzene formoxyl peroxide, 2; 4-dichloro-benzoyl base peroxide, t-butyl peroxy-acetate, dicumyl peroxide, 2; 5-dimethylhexane 2; 5-two perbenzoates and 2; two (t-butyl peroxy)-2 of 5-, the 5-dimethylhexane.When producing electric wire or cable, in fact the selection of peroxide is depended on makes elastomer solidify the method (vulcanization process) that is adopted.When under not having pressure, implementing vulcanization process (for example, hot-air furnace and/or (infrared) radiation, employed peroxide is monochloro-benzene formoxyl peroxide and/or 2 preferably, 4-dichloro-benzoyl base peroxide.When under pressure, implementing vulcanization process (for example, steam pipe), employed peroxide preferably 2, two (t-butyl peroxy)-2 of 5-, 5-dimethylhexane.
Formation present composition component d) mica can be muscovite class or phlogopite class, and the size of mica particle is not special The key factor, as long as it is small enough to make in its component that is dispersed in said composition.Mica preferably provides with Powdered mica or the particle size form less than the mica powder of 100 μ m.
Formation present composition component e) zinc oxide is white or micro-yellow powder.
Component g) platinum can be to be (element) metal platinum form or to be chloroplatinic acid form (chloroplatinic acid H for example especially
2PtCl
6); Or be the complex form of platinum and organic products, especially as the complex (for example Karstedt complex) of platinum and vinylic organosiloxane, suc as formula (PtCl
2, alkene)
2And H (PtCl
3, alkene) those complexs, wherein alkene is represented ethene, propylene, butylene, cyclohexene or styrene, and the complex of platinum chloride and cyclopropane.
Titanium dioxide h) be white powder.
As noted earlier, loose filler i) comprise the aluminium-hydroxide powder that has handled on the surface.The particle size of this filler is often greater than 0.1 μ m.
As the instantiation of organoalkoxysilane, can enumerate: methyltrimethoxy silane, methyl triethoxysilane, phenyltrimethoxysila,e, ethyl trimethoxy silane, the n-pro-pyl trimethoxy silane, vinyltrimethoxy silane, vinyl three (2-methoxy ethoxy) silane, vinyltriacetoxy silane, allyltrimethoxysilanis, the cyclobutenyl trimethoxy silane, the hexenyl trimethoxy silane, γ-methacryloxypropyl trimethoxy silane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethoxydiphenylsilane, the trimethyl methoxy silane, trimethylethoxysilane.
As the instantiation of organosilazanes, can enumerate: hexamethyldisiloxane or divinyl tetramethyl-disilazane.
As the instantiation of siloxane oligomer, can enumerate straight chain and/or crosslinked oligomers, it contains unit R "
3SiO
0.5And/or R "
2SiO, these unit and unit R " SiO under the situation of crosslinked oligomers
1.5And/or SiO
2In conjunction with, R wherein " mainly be 1-10 carbon atom straight chain or branched alkyl to be arranged, 2-6 carbon atom arranged and the straight or branched thiazolinyl of one or two olefinic double bond is arranged; and/or phenyl, R " at least one straight or branched alkoxyl of representing the OH base or having 1-6 carbon atom in the group.
Preferably, loose filler i) be three aluminium hydroxides of handling with organoalkoxysilane.
Composition of the present invention also contains at least a inorganic substances j that belongs to the wollastonite class as optional components).The wollastonite class comprises following inorganic substances: calcium silicates (CaSiO
3) or wollastonite; Mix calcium silicates sodium (NaCa
2HSi
3O
9) or osmelite; And mixing calcium silicates manganese [CaMn (SiO
3)
2] or bustamite.Certainly use the mixture of these inhomogeneity materials.Preferably, when using a kind of component j, component j) be wollastonite.Wollastonite exists with two kinds of forms: wollastonite itself, chemists are expressed as α-CaSiO with it
3, it exists with nature usually; And pseudowollastonite or β-CaSiO
3More preferably, use wollastonite α-CaSiO
3The inorganic substances j that belongs to the wollastonite class) can not carry out surface treatment, the organo-silicon compound of those types of mentioning in the time of maybe can using in front about aluminium-hydroxide powder are handled.
Except that the component that offers some clarification on previously a), b), c), d), e), g), h), i) and j), composition of the present invention can randomly also contain one or more auxiliary additives f), for example at least a especially so-called " anti-structuring " product f1); And/or at least a polyorganosiloxane resin f2); And/or at least a stabilizer f3); And/or at least a pigment f4), described pigment is used to produce painted electric wire and cable; And/or at least a boryl compound f5).
According to a preferred embodiment of the present invention, but being heat cure, target becomes the composition of silicone elastomer, it contains in one or more organo-siloxanes polymers of 100 weight portions a):
One or more reinforcers of-20-50 part b),
-0.5-6 part organic peroxide c),
-1-12 part mica d),
-2-6 part zinc oxide e),
One or more auxiliary additives of-0-12 part f),
The component g that-0.0010-0.015 part is represented with (element) metal platinum weight) (being 10ppm-150ppm),
-1-5 part titanium dioxide h),
One or more loose fillers of-30-80 part i), this filler belong to processing three aluminium hydroxides and
-2-8 part belongs to one or more materials j of wollastonite class).
According to the execution mode of " more preferably " of the present invention, but being heat cure, target becomes the composition of silicone elastomer, it contains in one or more organo-siloxanes polymers of 100 weight portions a):
One or more reinforcers of-30-40 part b),
-1-5 part organic peroxide c),
-7-12 part mica d),
-4-6 part zinc oxide e),
One or more auxiliary additives of-5-10 part f),
The component g that-0.002-0.01 part is represented with (element) metal platinum weight) (being 20ppm-100ppm),
-3-5 part titanium dioxide h),
One or more loose fillers of-50-80 part i), this filler belong to processing three aluminium hydroxides and
-4-8 part belongs to one or more materials j of wollastonite class).
According to another kind of expression way (amount of various components is to represent with the weight % based on composition total weight at this in this mode), the present invention's's " more preferably " composition contains (each component sum is equal to 100 weight % in each case):
-one or more polysiloxane are a): 40-50%,
-one or more reinforcers b): 12-20%,
-organic peroxide c): 0.4-2.5%,
-mica d): 2.8-6%,
-zinc oxide e): 1.6-3%,
-one or more auxiliary additives f): 2-5%,
-metal platinum g): 0.0008-0.005%,
-titanium dioxide h): 1.2-2.5%
-one or more loose fillers i) 20-40%
The material j of-one or more wollastonite classes) 1.6-4%.
With regard to one or more auxiliary additives f) with regard to, when using this one or more auxiliary additive f) time, these one or more auxiliary additives more properly are expressed as follows [based on per one or more organo-siloxanes polymers of 100 weight portions a)]:
So-called " anti-structuring " product f1 of-0.1-15 weight portion), it based on one or more its viscosity 25 ℃ be 10-3000mPa.s and at each end of the chain with hydroxy-end capped polydimethyl siloxane oil, and/or based on one or more its viscosity 25 ℃ be 10-1000mPa.s and at each end of the chain with hydroxy-end capped poly-(methyl ethylene) silicone oil; And/or
One or more polyorganosiloxane resins f2 of-0.1-5 part), it is expressed as: be known as the resin of MQ, it mainly contains R
3SiO
0.5And SiO
2The unit, wherein R representative has the monovalence alkyl of the optional halogenation that is less than 7 carbon atoms, R "
3SiO
0.5With SiO
2Weight ratio be 0.5/1 to 1/2/1; M ' Q resin, it mainly contains HR "
2SiO
0.5And SiO
2The unit, wherein R has the meaning that provides previously, HR "
2SiO
0.5With SiO
2Weight ratio be 0.5/1 to 10/1; And/or
One or more stabilizers of-0.01-4 part f3), concrete as: the organic acid slaine, for example molysite or cerium salt are as iron octoate or cerium octoate (its ratio is 0.01-1 part more specifically); Cerium oxide, cerium hydroxide or iron oxide (its ratio is 0.1-4 part more specifically); Oxide CaO, oxide M gO (its ratio is 0.01-4 part more specifically); And/or
One or more coloring pigments of-0.01-5 part f4); And/or
One or more boryl compounds of-0.01-3 part f5), as boric acid and derivative thereof, the alkyl esters derivative of 1-3 carbon atom is for example arranged;
-when using one or more additives, the total amount of these one or more additives should equal: under the situation of the general composition that adopts is 15 weight portions; In " preferably " is 12 weight portions under the situation of composition; And be 10 parts under the situation of " more preferably " composition.
In order to prepare composition of the present invention, these different components use the equipment of knowing in silicone elastomer industry fully to mix, and the interpolation order of these components can be arbitrarily.But, advantageously, for example at first according to order given below, with these components be dispersed in one or more polysiloxane a) in: add one or more reinforcers b one or more times), be possible one or more additives f1 then) and f2), be mica d afterwards), be zinc oxide e then), be titanium dioxide h then), be the material j of one or more wollastonite classes then), be Pt base component g then), be possible one or more additives f3 afterwards), be one or more loose fillers i then), they belong to three aluminium hydroxides of processing; The then catalyst c of interpolation aequum in this mixture) and possible one or more additives f4) and f5).
In addition, second purpose of the present invention relates to the constituent polyorganosiloxane composition of having described be particularly useful for producing the foreskin of the single conductor that uses or the first purposes of class F insulating material F in making flame-proof wire or cable.
The 3rd purpose of the present invention relates to the electric wire or the cable of the constituent polyorganosiloxane composition production of using first purpose of the present invention.
In the scope of this purposes, the present composition adopt standard method (especially extrusion method) be deposited on each single conductor around.Then, make the material of deposition like this crosslinked, form the first class F insulating material F of making by silicone elastomer by heating.Obviously, change with material temperature and possible operating pressure heating time.Normally 100-200 ℃ of material temperature.Can use the series connection of having disposed crosshead to extrude or use the co-extrusion two-layer or multilayer of common deposited of coming out.
To illustrate in greater detail the present invention by following embodiment.
Embodiment:
The present composition (all umbers all are weight portions):
1.-preparation:
In having the kneader of Z-shaped blade, following component was mixed 2 hours down in room temperature (23 ℃):
-66.61 parts of polysiloxane a), it is that two every ends of end are all used the unit terminated dimethyl silicone polymer of dimethylvinylsiloxy, contains the Vi group of 120ppm, its viscosity is 2,000 ten thousand mPa.s at 25 ℃;
-33.39 parts of polysiloxane a), it is that two every ends of end are all used unit terminated poly-(dimethyl) (methyl ethylene) siloxanes of trimethylsiloxy, contains the Vi group of 720ppm in its chain, its viscosity is 2,000 ten thousand mPa.s at 25 ℃;
The pyrogenic silica b that-19.07 parts of D4 (octamethylcy-clotetrasiloxane) handle), its specific area is 200m
2/ g;
-12.4 parts of pyrogenic silica b), its specific area is 150m
2/ g;
All use the unit terminated polydimethyl siloxane oil f1 of present as dimethylhydroxysilox(at the every end in its two ends for-2.86 parts), it comprises 9 weight %OH, and viscosity is 50mPa.s at 25 ℃;
-1.91 parts of poly-(methyl ethylene) silicone oil f1 that all use methyl ethylene hydroxyl siloxy units end-blocking at the every end in its two ends), it comprises 9 weight %OH, contains the Vi group of 3 weight % in its chain, and viscosity is 25mPa.s at 25 ℃;
-9.61 parts of muscovite class mica d);
-4.89 parts of zinc oxide e);
-3.46 parts of pyrolysismethod TiO
2H);
-6.62 parts of α-CaSiO
3Wollastonite j), used the methyl alkoxy silane treatment, sold with trade name wollastonite Tremin 283-800 TST by QUARTZ WERKE company;
-0.003 part of metal platinum g), provide (Karstedt complex) to comprise 10 weight % with the form of the divinyl tetramethyl disiloxane solution of the platinum complex of the platinum of divinyl tetramethyl disiloxane coordination;
-0.28 part of calcium oxide f3);
-0.39 part of iron octoate f3);
-2.76 parts of Ce (OH)
4F3) and
-66.17 parts of filler i), it is three aluminium hydroxides with 1 weight % vinyl three (2-methoxy ethoxy) silane treatment, is sold with trade name aluminium hydroxide AP 40 VS1 by NABALTEC company.
At this moment the mixture that obtains is above processed on the blender with 2 rollers, again to wherein add constituting catalyst c) organic peroxide.
2.-the sign of said composition:
(i) part in the homogeneous material that obtains in this blender is used to measure the mechanical performance of silicone elastomer, and this elastomer is obtained through hot vulcanization by described constituent polyorganosiloxane composition.For this reason, this part homogeneous material that is used for this purpose uses 0.6 part 2 according to per 100 parts of homogeneous materials subsequently, two (t-butyl peroxy)-2 of 5-, the 5-dimethylhexane carries out catalysis, 170 ℃ of sulfurations 10 minutes, in suitable mold, operate simultaneously, to obtain the plate of thickness 2mm.Obtain being in the plate of uncured (UC) state thus.A part of plate is solidified down or aging 10 days at 200 ℃.Then, obtain the standardization sample of all these plates, and measure following performance:
-Xiao A hardness (the H that measures according to standard DIN 53505
SA);
-according to the hot strength (TS) that standard A FNOR NF T 46002 measures, represent with MPa;
-according to the extension at break (E/B) of above-mentioned canonical measure, represent with %;
-according to above-mentioned canonical measure at 100% o'clock modulus of elasticity (EM), represent with MPa.
(ii) the another part in the homogeneous material that obtains in this blender uses 1.25 part 2 according to per 100 parts of homogeneous materials, and 4-dichloro-benzoyl base peroxide carries out catalysis.Be cut into bar then, and these are added to the extruder that is used for producing cable.The production of cable is a kind of standard fabrication methods, comprise the cable of making the diameter 3mm that comprises the single conductor of 1.38mm diameter copper, around it, be furnished with foreskin or first class F insulating material F that silicone elastomer is made, its thickness is 0.81mm, it obtains by following operation: in hot-air furnace, under about 250 ℃ of temperature (making material temperature reach about 130-140 ℃), will use the single conductor of above-mentioned uniform constituent polyorganosiloxane composition coating to vulcanize 46 seconds.Obtain the standardization sample from this cable then, measure following performance:
-according to standard NF C 32-070 CR1, use the grey shape material caking property under 500 volts that the stainless steel metal pipe measures and
-according to the smog opacity that standard IEC 61 034 part 1s are measured, % represents with light transmittance.
Gained the results are summarized in the following table.
Table
| Embodiment | ||
| Mechanical performance UA H SA TS(MPa) E/B(％) EM100(MPa) | 71 6.6 230 3.3 | |
| Mechanical performance A H SA TS(MPa) E/B(％) EM100(MPa) | 76 6 170 4.1 | |
| The caking property of the grey shape material under 500 volts (with a minute express time) | Test 1 | 69 |
| Test 2 | 79 | |
| Test 3 | 73 | |
| Test 4 | 82 | |
| Test 5 | ＞95 | |
| Test 6 | 57 | |
| Test 7 | ＞95 | |
| Test 8 | ＞95 | |
| Test 9 | ＞95 | |
| Test 10 | ＞95 | |
| On average (branch) | 84 | |
| Balance (bilan) | 9/10 | |
| Success rate | 90％ | |
| Smog opacity (light transmittance %) | 86％ | |
Be noted that the present invention can: (i) under 500 volts, satisfy standard NF C 32-070 CR1, compare with 65 minutes threshold values of this standard-required, operating time of electric wire or cable prolongs 29%; (ii) satisfy standard IEC 61 034 part 1s, compare with 60% threshold value of this standard-required, light transmittance % improves 43%.
Claims (10)
1. but heat cure becomes the constituent polyorganosiloxane composition of silicone elastomer, and it comprises (all umbers all are weight portions):
One or more organo-siloxanes polymers of-100 weight portions a),
One or more reinforcers of-15-100 part b),
-0.2-8 part organic peroxide c),
-0.5-30 part mica d),
-0.2-10 part zinc oxide e),
One or more auxiliary additives of-0-15 part f),
The component g that-0.0005-0.02 part is represented with (element) platinum weight) (being 5ppm to 200ppm),
-0.5-10 part titanium dioxide h),
One or more loose fillers of-20-100 part i), and
One or more belong to the material j of wollastonite class-0-10 part),
Described composition is characterised in that loose filler i) now by aluminium hydroxide Al (OH)
3Powder constitutes, and this powder surface is with the organoalkoxysilane that has OH and/or alkoxyl and/or organosilazanes and/or the processing of organosiloxane oligomer, wherein:
* this organic group is represented one or more following alkyl that are selected from: the straight or branched alkyl that 1-10 carbon atom arranged; 2-6 carbon atom arranged and have the straight or branched thiazolinyl of one or two olefinic double bond; And/or phenyl;
* this alkoxyl is represented one or more alkoxyls that are selected from the straight or branched alkoxyl with 1-6 carbon atom.
2, the composition of claim 1 is characterized in that it comprises in one or more organo-siloxanes polymers of 100 weight portions a):
One or more reinforcers of-20-50 part b),
-0.5-6 part organic peroxide c),
-1-12 part mica d),
-2-6 part zinc oxide e),
One or more auxiliary additives of-0-12 part f),
The component g that-0.0010-0.015 part is represented with (element) platinum weight) (being 10ppm-150ppm),
-1-5 part titanium dioxide h),
One or more loose fillers of-30-80 part i), this filler belong to processing three aluminium hydroxides and
One or more belong to the material j of wollastonite class-2-8 part).
3. each composition in the claim 1 and 2 is characterized in that component a) comprises at least a organo-siloxanes polymer, it contain 0-4 weight % vinyl and its viscosity at 25 ℃ for being higher than 100 ten thousand mPa.s.
4. each composition among the claim 1-3 is characterized in that components b) comprise the mixture of silicon dioxide, aluminium oxide or these two kinds of materials.
5. each composition among the claim 1-4 is characterized in that component i) comprise at least a three aluminium hydroxides of handling with organoalkoxysilane.
6. each composition among the claim 1-5 is characterized in that component j) comprise at least a following material that is selected from when a kind of using: calcium silicates (CaSiO
3) or wollastonite; Mix calcium silicates sodium (NaCa
2HSi
3O
9) or osmelite; And mixing calcium silicates manganese [CaMn (SiO
3)
2] or bustamite.
7. each composition among the claim 1-6 is characterized in that the component f that chooses wantonly) when use is a kind of, comprise: at least a " anti-structuring " product f1); And/or at least a polyorganosiloxane resin f2); And/or at least a stabilizer f3); And/or at least a coloring pigment f4); And/or at least a boryl compound f5).
8. each composition is used to produce the foreskin of the one or more single conductors that use or the first purposes of class F insulating material F among the claim 1-7 when making flame-proof wire or cable, it deposits described composition around being included in each single conductor, make material temperature reach 100-200 ℃ by heating then, make said composition be cross-linked into silicone elastomer.
9. flame-proof wire or the cable of producing by the purposes of the claim 8 of each composition among the claim 1-7.
10. the electric wire of claim 9 or cable, it is characterized in that: (1) according to standard IEC 61034 part 1s, the smog opacity that they provide can reach the light transmittance greater than 80%;
(2) under 500 volts, they satisfy standard NFC 32-070 CR1, compare with 65 minutes threshold values of this standard-required, and the operating time of electric wire or cable prolongs greater than 25%.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR02/15525 | 2002-12-09 | ||
| FR0215525 | 2002-12-09 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1735946A true CN1735946A (en) | 2006-02-15 |
| CN100351954C CN100351954C (en) | 2007-11-28 |
Family
ID=32696202
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003801085416A Expired - Fee Related CN100351954C (en) | 2002-12-09 | 2003-11-25 | Heat-vulcanizable polyorganosiloxane compositions useful in particular for making electric wires or cables |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP1570494A1 (en) |
| KR (1) | KR100694556B1 (en) |
| CN (1) | CN100351954C (en) |
| AU (1) | AU2003294073A1 (en) |
| WO (1) | WO2004064081A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100400570C (en) * | 2006-06-01 | 2008-07-09 | 浙江新安化工集团股份有限公司 | Pugging type silicon rubber structured control agent |
| CN100457829C (en) * | 2006-07-11 | 2009-02-04 | 上海统帅有机硅材料有限公司 | Liquid flame-proof silicon rubber and its preparation process |
| CN103834170A (en) * | 2006-12-14 | 2014-06-04 | 蓝星有机硅法国公司 | Hot-vulcanisable polyorganosiloxane compositions essentially used in the production of electric wires or cables |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2899905B1 (en) * | 2006-04-12 | 2008-07-18 | Rhodia Recherches & Tech | HOT VULCANIZABLE POLYORGANOSILOXANE COMPOSITIONS USEFULLY USEFUL FOR THE MANUFACTURE OF ELECTRIC WIRES OR CABLES |
| KR102033211B1 (en) | 2013-06-27 | 2019-10-16 | 엘켐 실리콘즈 프랑스 에스에이에스 | Hot-vulcanisable polyorganosiloxane compositions for use in particular for the production of electrical wires or cables |
| CN107674423A (en) * | 2017-10-30 | 2018-02-09 | 安徽嘉中金属材料有限公司 | A kind of high-performance building engineering cable sheath material and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2689281B2 (en) * | 1990-07-26 | 1997-12-10 | 日本碍子株式会社 | Silicone rubber composition for insulators used outdoors |
| US5668205A (en) * | 1994-05-27 | 1997-09-16 | Shin-Etsu Chemical Co., Ltd. | Silicone rubber compositions for high-voltage electrical insulators |
| JP3406776B2 (en) * | 1996-05-24 | 2003-05-12 | 東レ・ダウコーニング・シリコーン株式会社 | Silicone rubber composition for electrical insulation materials |
| DE60044226D1 (en) * | 1999-08-18 | 2010-06-02 | Shinetsu Chemical Co | Silicone rubber compositions, their preparation and use as high voltage insulating material |
| FR2800742B1 (en) * | 1999-11-09 | 2001-12-21 | Rhodia Chimie Sa | HOT VULCANIZABLE POLYORGANOSILOXANE COMPOSITIONS FOR USE IN PARTICULAR FOR THE MANUFACTURE OF ELECTRIC WIRES OR CABLES |
| FR2800743B1 (en) * | 1999-11-09 | 2002-12-06 | Rhodia Chimie Sa | HOT-VULCANIZABLE POLYORGANOSILOXANE COMPOSITIONS FOR USE IN PARTICULAR FOR THE MANUFACTURE OF ELECTRIC WIRES OR CABLES |
-
2003
- 2003-11-25 KR KR1020057010438A patent/KR100694556B1/en not_active IP Right Cessation
- 2003-11-25 WO PCT/FR2003/003474 patent/WO2004064081A1/en not_active Application Discontinuation
- 2003-11-25 AU AU2003294073A patent/AU2003294073A1/en not_active Abandoned
- 2003-11-25 CN CNB2003801085416A patent/CN100351954C/en not_active Expired - Fee Related
- 2003-11-25 EP EP03789489A patent/EP1570494A1/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100400570C (en) * | 2006-06-01 | 2008-07-09 | 浙江新安化工集团股份有限公司 | Pugging type silicon rubber structured control agent |
| CN100457829C (en) * | 2006-07-11 | 2009-02-04 | 上海统帅有机硅材料有限公司 | Liquid flame-proof silicon rubber and its preparation process |
| CN103834170A (en) * | 2006-12-14 | 2014-06-04 | 蓝星有机硅法国公司 | Hot-vulcanisable polyorganosiloxane compositions essentially used in the production of electric wires or cables |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100351954C (en) | 2007-11-28 |
| KR20050084216A (en) | 2005-08-26 |
| AU2003294073A1 (en) | 2004-08-10 |
| WO2004064081A1 (en) | 2004-07-29 |
| KR100694556B1 (en) | 2007-03-13 |
| EP1570494A1 (en) | 2005-09-07 |
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