CN106280466A - A kind of flame-retardant silicon polymer compositions - Google Patents
A kind of flame-retardant silicon polymer compositions Download PDFInfo
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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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
- C08K3/34—Silicon-containing compounds
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- 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
- C08K3/38—Boron-containing compounds
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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
- C08K3/40—Glass
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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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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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
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- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
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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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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Abstract
The invention discloses a kind of flame-retardant silicon polymer compositions, said composition includes: siloxane polymer；The Muscovitum of based on composition total weight 5 30wt% amounts；With the glass additive of based on composition total weight 0.3 8wt% amount, wherein said glass additive includes the glass additive of low softening point and the glass additive of high softening-point.A kind of flame-retardant silicon polymer compositions of the present invention, owing to comprising low content glass additive present in the fire proofing composition of siloxane polymer and Muscovitum, significantly improves the mechanical strength of the pottery formed when heating combination；In fire wall liner, fire partition, barrier, ceiling and liner thereof, structural fire protection, fire door insert, door-window sealing member, expansion sealing element or Electricity distribution panel box.
Description
Technical field
The present invention relates to a kind of flame-retardant silicon polymer compositions.
Background technology
The fireproofing passiveness of structure and element be one by the field of growing interest.The terms " passively " refers to
Use the material giving fire resistance.Fireproofing passiveness system is widely used, throughout building and transport service, typically via following side
Formula works: hinder heat and/or the motion of cigarette, seals hole, extends the structural stability of its system of application, and/or produces anti-
Fire, solar heat protection and the heat resistant layer of anti-cigarette channel and/or physical barrier.
One relevant specific field is cable application.These cables typically by by least insulating barrier around center
Wire forms.This cable is widely used in building, constitutes nearly all electricity in indoor, office and industrial building veritably
The basis on road.In some applications, such as in emergency electric power supply circuit, even if needing to continue to work when suffering fire
And the cable of circuit integrity is provided, there is a lot of standard for such cable.In order to meet some in these standards,
Cable is heated to specify temperature within the time (such as, 15 minutes, 30 minutes, 60 minutes, 2 hours) specified in the mode of regulation
During degree (such as, 650 DEG C, 750 DEG C, 950 DEG C, 1050 DEG C), typically need at least holding circuit integrity.In certain situation
Under, cable in the heating period by regular mechanical shock.Such as, they can be in the later phases of heat cycles or adding
Water injection or spraying is experienced after the heat stage.It is true that within the persistent period, fireproofing of cable is partially due to the biggest change
Change and be likely to be exposed at more wide temperature range.In order to meet given standard, cable typically needs to protect in whole test process
Hold circuit integrity.As such it is important to insulator keeps low conductivity (after the most long-term heating), keeps shape
Shape makes it will not shrink and crush, the firmest, particularly when it in impact as by exposure to water injection or spray
In the impact process that mechanical collision causes, need to be held in position in.
A kind of method of the high-temperature behavior improving insulated cable is to use tape wound cable conductor, and described belt is by glass fibers
Dimension manufactures and coats with Muscovitum.In process of production, these tape wound, around wire, then use at least one of which insulation
Layer.After being exposed to cumulative temperature, outer layer is degraded and comes off, but glass fibre makes Muscovitum be held in position in.
Have been found that these belts are effective to holding circuit integrity in fire, but they are fairly expensive.It addition, compared to
Other cable production stage, by relatively slow for tape wound method around wire, so, is wound around these belts and slow down electricity
Overall manufacturing, and add cost.A kind of refractory coating can being applied by extrusion is needed in cable production process,
Thus avoid the use of belt.
A lot of materials have been used for giving fire resistance to structure and element.Have been found that combination based on silicone elastomer
The application of thing is the most extensive.But, these compositionss often have association shortcoming: when exposed to a fire, and they are changed into powdery
Material, because the organic component in silicone elastomer is pyrolyzed or burns.Pyrolysis or combustion product volatilization, remaining almost without
The inorganic residues of intrinsic strength or ashes.This residue is frequently not that bond or self-supporting, even often the most broken
Broken, mobile or cave in.This characteristic reduces use silicone elastomer as fireproofing passiveness composition.This means to be used as at electricity
The siloxane polymer of the insulator on cable must be protected with the most inorganic band of physical support and fabric or metallic sheath and keep
In position go up.
Summary of the invention
In order to solve above technical problem, the present invention provides a kind of flame-retardant silicon polymer compositions, the group of the present invention
Compound can form the firmest tack coat around electric lead, therefore eliminates the needs using physical support.
Herein, pottery is the inorganic non-metal solid material prepared by high-temperature process (e.g., from about more than 300 DEG C).
A kind of flame-retardant silicon polymer compositions of the present invention, said composition includes:
Siloxane polymer；
The Muscovitum of the amount of 5-30wt% based on composition total weight；With
The glass additive of the amount of 0.3-8wt% based on composition total weight, wherein said glass additive includes low softening
The glass additive of point and the glass additive of high softening-point.
In the application, limited amount glass additive, it is sufficient to higher than siloxane polymer decomposition temperature with less than combination
Self-supporting ceramic materials is formed during the temperature of thing fire-protection rating (fire rating) temperature.The polymers compositions of fire proofing composition
Substantially it is made up of siloxane polymer.
Further, described Muscovitum is the Muscovitum after silane coupler processes surface, and the amount of described silane coupler is for pressing
The amount of composition total weight meter 0.05-2wt%, the mean diameter of described Muscovitum is 15-250 μm.
Further, described Muscovitum includes one or more in phlogopite or white mica, the mean diameter of described Muscovitum
For 50-200 μm, described silane coupler include vinyltrimethoxy silane, aromatics silane, aryl-silane, epoxy silane, third
One or more in alkene acyloxy silane, polysilane or hydrosulphonyl silane.
Further, described glass additive is with one or more shapes in glass powder, glass particle or glass fibre
Formula exists；Described glass additive includes one or more in silicate, borate, phosphate or lead base glass system.
Further, described glass additive has the softening point less than 1050 DEG C；Described glass additive also includes
Alkali metal oxide less than 50% based on glass additive weight.
Further, described glass additive has the softening point less than 800 DEG C；Described glass additive also includes by
The glass additive weight meter alkali metal oxide less than 30%.
Further, described glass additive has the softening point of 300-800 DEG C.
Further, described compositions also includes fire proofing material, described fire proofing material 5-based on composition total weight
20wt% measures.
Further, one or more during described fire proofing material includes Firebrake ZB, magnesium hydroxide or aluminium hydroxide.
A kind of flame-retardant silicon polymer compositions of the present invention, for fire wall liner, fire partition, barrier, sky
In card and liner, structural fire protection, fire door insert, door-window sealing member, expansion sealing element or Electricity distribution panel box.
Glass additive is effective especially to expanding temperature range, and this results in the pottery with good mechanical properties, because of
This improves the performance of these compositionss in fireproofing passiveness is applied.Relative to there is no the equivalent compositions of glass additive, glass
Glass additive also improves the mechanical strength of gained pottery.As described herein below, the type of Muscovitum and average particle size typical case
Ground selects according to the purpose purposes of compositions.
Glass additive can take various forms such as powder, particle or fiber.Can with use in these forms a kind of or
Multiple mixture.Preferably, compositions includes powder or the glass dust of fine particle form.Not considering form, glass adds
Agent preferably has less than 1050 DEG C, such as less than 800 DEG C, the most preferably softening point between 300 and 800 DEG C.Glass softening point
Refer to temperature when glass viscosity is equal to 107.6 pool.
The applicant is own it has been observed that be subject to the temperature higher than 1000 DEG C when containing higher than the compositions of 8wt% glass additive
Time, experience lasting volume contraction.For flame retardant application, the contraction of preferably smaller than 10%, the contraction of more preferably less than 5%.Cause
This, for the application-specific under fire rating temperature, the amount adding glass is adjusted to ensure compositions or by compositions system
Obtain goods and limit consistent with required volume contraction.As previously mentioned, fireproofing of cable classification standard changes according to country, but
Be often based in a prescribed manner in given time such as 15 minutes, 30 minutes, 60 minutes and 2 hours by electric cable heating
To temperature such as 650 DEG C, 750 DEG C, 950 DEG C, 1050 DEG C.
When compositions is exposed to fire rating temperature, owing to compositions needs to form self-supporting porous ceramics (typically
There is the porosity of 40-70vol%), compositions is non-fusible is necessary.In the context of the present invention, fusing refers to combination
The liquid phase produced in thing becomes continuous phase, and/or mica particle loses its original form in large quantities, and/or due to pottery from
Heavy sensation of the body amount, the quantitative change of produced liquid phase is enough to cause ceramic deformation.The upper limit of glass ingredient addition is 8wt%, to avoid
The compositions fusing occurred when less than the ceiling temperature exposed.So, gained pottery in, due to silicon dioxide granule
" bridge joint " or with " bonding " of glass particle, mica particle is kept substantially its form, only has small change on edge.
Therefore, creating the ceramic product of bonding according to the compositions of the present invention, described ceramic product had before being exposed to high temperature
The shape essentially identical with compositions and volume.These compositionss can be described as keeping nearly end form.
The performance of the softening point of the glass pottery to being formed at high temperature has an impact.There is the glass of relatively low softening point than tool
The glass having relatively high softening point provides the mechanical strength of enhancing in lower temperature.The particle size of glass additive is the most smart
Carefully, it can get over the mechanical strength effectively strengthening gained pottery.There is the mixing of glass additive of low softening point and high softening-point
Compound can be used to provide the compositions producing pottery when heating, described pottery be exposed to show after temperature on a large scale good
Good engineering properties.
For cable application, in the case of compositions resistivity is critically important, it is necessary to select Muscovitum and/or glass to add with caution
Add the content of agent.For specific compositions, if the too high levels of Muscovitum, owing to compositions would be by group during long high temperature
Compound resistivity unacceptably reduces and/or due to dielectric breakdown, and electricity integrity is affected.When high temperature, liquid phase
Often provide conductive path from the alkali metal ion of Muscovitum or glass additive, cause needing to limit mica content and/or glass
Additive level.To this end, the most suitably select there is low alkali oxide content (e.g. preferably smaller than 30% alkali metal oxygen
U content) and/or the glass additive of fine particle size, the additive that reaching required engineering properties with reduction needs always contains
Amount.Unexpectedly, it has been found that glass additive can improve adjacent metal surface (such as cable conductor) and heat this
Bonding force between the pottery formed after inventive composition.
The compositions of the present invention includes the siloxane polymer as solvent.The character of siloxane polymer is not special
The most important, it will be appreciated by those skilled in the art that about the polymer type that can use.Useful siloxane polymer is a lot
Patent and document have a detailed description.
By more detailed description, siloxane polymer is including US 4,184,995, US 4,269,753, US 4,
The prior art of 269,757 and US 6,387,518 has a detailed description.By more detailed description, siloxane polymer is permissible
Organopolysiloxane for being made up of the unit with following formula: wherein, R can be same or different, unsubstituted or
The alkyl being replaced, r is 0,1,2 or 3, has the mean values of 1.9-2.1；
The example of alkyl R be alkyl such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, positive penta
Base, isopentyl, neopentyl, tertiary pentyl, and hexyl such as n-hexyl, heptyl such as n-heptyl, octyl group such as n-octyl and iso-octyl, such as 2,
2,4-tri-methyl-amyls, nonyl such as n-nonyl, the most positive decyl of decyl, dodecyl such as dodecyl, octadecyl the most positive ten
Eight alkyl；Cycloalkyl, such as cyclopenta, cyclohexyl and suberyl and methylcyclohexyl；Aryl such as phenyl, xenyl, naphthyl, anthracene
Base and phenanthryl；The most o-, m-or p-tolyl of alkaryl, xylyl and ethylbenzene；With aralkyl such as benzyl and α-benzene
Ethyl and β-phenethyl.
The example of substituted hydrocarbon radical R be the alkyl such as 3-chloropropyl of halogenation, 3,3,3-trifluoro propyls and perfluor base ethyl and
The most p-chlorphenyl of halogenated aryl and p-chlorophenylmethyl.
Group R preferably hydrogen atom or there is 1-8 carbon atom alkyl, preferred methyl.Other examples of group R are ethylene
Base, pi-allyl, methylallyl, 1-acrylic, 1-butylene base and 1-pentenyl, and 5-hexenyl, butadienyl, hexadiene
Base, cyclopentenyl, cyclopentadienyl group, cyclohexenyl group, acetenyl, propargyl and 1-propinyl.Group R preferably has 2-8
The alkenyl of carbon atom, especially vinyl.
The end group of polymer can be trialkylsiloxy, such as trimethylsiloxy or dimethyl second
Thiazolinyl siloxy, or the deriveding group that wherein one or more alkyl have been replaced by hydroxyl or alkoxyl.
Compositions can include a kind of or crosslinkable siloxane polymer of more than one.Crosslinkable polymer is permissible
For can any polymer of any one of by the following method crosslinking, these methods are for commercially available organic poly-silicon
Oxygen alkane polymer, including: carry out radical crosslinking, including hydrosilyl by forming alkene bridge between chain with peroxide
(silylhydride) with the additive reaction of the reaction of the pi-allyl or vinyl being connected to silicon, including producing Si-O-Si crosslinking
The condensation reaction of the silanol reaction of key, or use other reactive groups.According to the type of used siloxane polymer, combination
Thing will the most also include suitable cross-linking agent.Suitably cross-linking agent is commercially available, such as, have a wide range of useful mistake
Oxide is applicable to the application, as dibenzoyl peroxide, double (2,4-dichloro-benzoyl) peroxide, dicumyl peroxide or
2,5-bis(t-butylperoxy)-2,5-dimetylhexene or their mixture, at the appropriate time, they can be in synthesis
During be included in compositions.
Spendable siloxane polymer also include platinum catalysis, with the liquid of unsaturated (typically vinyl) side chain
State siloxane polymer, side chain cross-links by using heat in additive reaction.These polymer are usually used as just making
It is provided by the two kinds of components front mixed.The viscosity of these polymer from dumpable liquid until stiff paste.Silicone rubber
Compositions can also include the organopolysiloxane (RTV) of moisturecuring under room temperature, to this at US 5, in 023,295 in more detail
Give an example.In this case, it includes: (a) has the diorganopolysiloxanecompositions of terminal hydroxyl；(b) each point
Son has the cross-linking agent of average at least 3 hydrolyzable functional group being connected to silicone atom；(c) condensation catalyst；(d)
Platinum or compound.Also including other System Curing At Room Temperatures, they have alkyl silicate and carboxylic metallic salt as one
Point, the diorganopolysiloxanecompositions that this part terminates with silanol end mixes, and inert filler is as another part, its example
As described in US 4,184,995.
The another kind of type being especially suitable for cable insulation is that wherein siloxane polymer has high molecular, has and needs
Heating with the vinyl sidechain of crosslinking, the radical reaction cross-linking the additive reaction by platinum catalysis or peroxide initiation is entered
OK.These siloxane polymers can be buied from main siloxanes manufacturer widely.
Organopolysiloxane raw material the most also include reinforcing filler such as precipitated silica or pyrogenic silica,
And/or non-reinforcing fillers.It addition, the surface of these silica-type filleies can be by the organic poly-silicon of straight or branched
Oxygen alkane, organochlorosilane and/or hexamethyldisiloxane are modified.
The Muscovitum as solvent is included according to the compositions of the present invention.Two kinds of commercially available Muscovitum general type is white
Muscovitum and phlogopite.White mica is dioctahedral alkaline silicate aluminum.White mica is had and is faintly bonded in by potassium ion layer
The layer structure of aluminium silicate thin slice together.It has following composition: KAl3Si3O10(OH)2.Phlogopite is trioctahedral alkali
Property aluminium silicate.Phlogopite has the layer structure of the Magnesiumaluminumsilicate thin slice being faintly bonded together by potassium ion layer.Its tool
It is made up of following: KMg3AlSi3O10(OH)2.Both Muscovitum types are typically to have thin plate or the thin slice of formed sharp edge
Presented in.
When be heated to about 1000 DEG C with formed pottery time, the compositions containing phlogopite shows higher mechanical strength.But,
They also show bigger contraction than those compositionss containing white mica.White mica is preferred for needing high dimension stability
Application in.Have been found that the high temperature of the silicone polymers combination of the present invention is electrical if replacing phlogopite with white mica
Matter is the most better.
The Muscovitum of commercial grades has defined grain size distribution.Have been found that pottery is produced by the particle size of Muscovitum
Dimensional stability and the engineering properties of thing have a major impact, and described pottery is formed when the present composition is exposed to high temperature.Allusion quotation
Type ground, selects Muscovitum and makes it have from 15 μm to the average particle size of 250 μm.(average in the lower end of this scope
Particle size is less than 50 μm) Muscovitum produced by stronger but show bigger contraction on ceramic machinery, shrink and result in cracking.
The Muscovitum of between in this range and upper end is preferred for cable application or other application, and wherein shape retention is particular importance
's.If the average particle size of Muscovitum Muscovitum amount that is too big or that exist is the highest, then resulting composition be often difficult to process and
Such as it is difficult to form required structure by extruding.It addition, comprise corase particles size grades Muscovitum or the crosslinking of high-load Muscovitum
The engineering properties of siloxane polymer is poor.When compositions is extruded or molds under compression, thick mica particle often along
Their crystallization bottom surface produces prioritization, and this can cause low tearing strength.
Muscovitum can carry out surface process with silane coupler, to improve engineering properties before roasting and/or after roasting.Silicon
The example of alkane coupling agent is: ethyl trimethoxy silane, aromatics silane, aryl-silane, epoxy silane, acrylsilane, polymerization
Silane and hydrosulphonyl silane such as mercaptopropyi trimethoxy silane.Based on the weight of compositions, the content of silane coupler is preferably
0.05-2wt%.
According to the present invention, the selection of suitable Muscovitum type, average particle size and mica content will depend upon which that purpose should
By the handling properties needed for, compositions, engineering properties needed for cross-linked composition with when compositions changes into gained pottery time institute
The intensity needed and required size keep degree.When being exposed to the high temperature range the most relevant to fire, these compositions institutes
The character that need to show can be controlled by the type and particle size that suitably select Muscovitum used.In other words, these combinations
The character of thing may be adjusted to required final use.
According to the present invention, Muscovitum addition is 5-30wt% based on composition total weight.For concrete cable application, cloud
Female preferred content is 15-30wt%, more preferably 20-30wt%.For the critically important fire-resisting cable of dimensional stability and
Non-cable is applied, and the average particle size of Muscovitum is preferably in 50-200 μ m.White mica is typically the preferred of these application
Type, but use phlogopite can obtain higher mechanical strength after 1000 DEG C of roastings.
In another aspect of the present invention, it is provided that substantially by siloxane polymer, Muscovitum, glass additive and crosslinking
The fire proofing composition of agent composition.This means that compositions does not comprise any other and may inherently affect compositions and/or incite somebody to action
Compositions is heated to the component of the character of the pottery formed during high temperature.
The compositions of the present invention can comprise other components.Add Firebrake ZB, magnesium hydroxide or aluminium hydroxide to improve
The fire prevention character of compositions.It addition, some components also improve the intensity of pottery.Other components include inorfil or other fibres
Dimension reinforcing material, reduce the material (Vermiculitum such as scaled off) of heat conductivity, CBA (its be used for reduce density,
Improve thermal characteristics and further enhance sound attenuation), the non-reacted filler that extends, Silicon stone and expanding material (work as to obtain
Swellable compositions when being exposed to fire or high temperature).Suitably expanding material includes native graphite, unexpanded Vermiculitum or the most swollen
Swollen perlite.Other kinds of expansion precursor can also be used.
The compositions of the present invention can be prepared by blending and heating different components.Peroxide for siloxane polymer
Compound cross-links, and needs heating to form silicone elastomer.The synthesis device of any routine can be used.If compositions has
Relatively low viscosity, it can process with dispersing apparatus, such as the device type used in coatings industry.For cable insulation
The material of application has higher viscosity (higher molecular weight), and two-roller mill machine, internal mixture, twin screw can be used to extrude
Machines etc. are processed.According to the type adding cross-linking agent/catalyst, it is possible to use include the continuous vulcanization equipment of liquid salt bath, at band
In having the autoclave of high steam, compositions is exposed in 200 DEG C of air, and it is contemplated that ground, compositions is exposed to by
Make in any medium (including microwave, ultrasound wave etc.) that peroxide decomposes, thus solidify compositions.
The compositions of the present invention may be used for needing in fire-resistant a lot of application.Such as, compositions can be used to be formed resistance to
Fire building panel.Compositions can be used alone, or is used together with one or more layers other materials.
The compositions of the present invention can provide in many different forms, and these forms include:
1. as thin slice, section bar or complicated shape.Compositions can use standard polymers to process operation such as extrusion, molding
(including hot pressing and injection molding) is fabricated to these products.These products formed may be used in fireproofing passiveness system.Combination
Thing can independently use or as with another kind of material (such as, plywood, vermiculite board or other) laminated material or synthesis material
Material uses.In one application, compositions can be with extrusion molding to make fire resistant doorsets sealing member.If it occur that fire, compositions
Change into pottery, thus form effective mechanical sealing member, stop the diffusion of fire and cigarette.
2. as thin slice or the section bar of preexpanding.This form has additional benefit compared with above, is included in normal work
The weight reduced under the conditions of work and bigger noise attentuation and the ability of insulation.In thin slice or section bar manufacture process, Ke Yitong
Cross the thermal degradation of CBA by produce gaseous product or by before curing by gas with physics in the way of be expelled to combination
In thing, thus hole is comprised in the material.
3. as when exposed to heat or fire by the expanded product of foaming and intumescing.In this application, product is permissible
It is used in around at tubing the most between the walls or infiltration.If it occur that fire, product expands to fill space, and provides
Effective obturator is to stop the diffusion of fire.Expanding material can be with the sealing member form being extrudable paste or flexibility.
4., as adhesive material, can apply as the sealing member of window or other goods (such as conventional silica
Alkane sealant applies from pipe).
5., as paint or aerosol sill, can spray or apply with brush.
The example that the fireproofing passiveness of the present invention can be used to apply includes but not limited to: ferryboat, train and other traffic works
Fire wall liner, fire partition, barrier, ceiling and the liner of tool, the structural fire protection (structural metal of separating building thing
Framework, to allow it to keep its required bearing strength (or limiting central temperature) at a fixed time in cycle), fire resistant doorsets embedding
Enter part, window and gate seal, expansion sealing element and the compound in Electricity distribution panel box or similar application.
A kind of flame-retardant silicon polymer compositions of the present invention is owing to comprising the fire-resistant of siloxane polymer and Muscovitum
Low content glass additive present in compositions, the machinery significantly improving the pottery formed when heating combination is strong
Degree；For fire wall liner, fire partition, barrier, ceiling and liner thereof, structural fire protection, fire door insert, door
In window sealing member, expansion sealing element or Electricity distribution panel box.
Accompanying drawing explanation
Fig. 1 is the perspective view of the typical cable for the present invention.
In the design of this cable 1, the compositions 2 of the present invention can be used directly on wire 3 as extrusion insulator
Face.Compositions can add group to take the form of gap filler to as individually extrusion filler in the cable of multicore
To complete combination in component, as internal layer before electric wire or belt armour are applied, or the outer sheath layer 4 as extrusion.
Detailed description of the invention
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Describe, it is clear that described embodiment is only a part of embodiment of the present invention rather than whole embodiments wholely.Based on
Embodiment in the present invention, it is every other that those of ordinary skill in the art are obtained under not making creative work premise
Embodiment, broadly falls into the scope of protection of the invention.
It is true that compositions will be extruded on the surface of wire.This extrusion can use conventional equipment real in a usual manner
Execute.Typically, compositions will be crosslinked the most immediately.The thickness of insulating barrier will depend upon which conductor size and running voltage
The demand of specific standards.Typically, insulator has the thickness of 0.6-3mm.Such as, fixed according to Australian Standard for one
Volume is at the 35mm of 0.6/1kV2Wire, it would be desirable to the insulation thickness of approximation 1.2mm.
Compositions in all embodiments is based on commercially available silicone elastomer.The average particle size of Muscovitum passes through screen analysis
Measuring, unless otherwise noted, the Muscovitum of use is the white mica with 160 μm average particle sizes.Glass dust A has 525 DEG C
Softening point, have and analyze composition as follows: SiO2, 33.5%；Na2O, 18.2%；K2O, 10.8%；TiO2, 19.3%；P2O5,
1.8%；V2O5, 8.7%.Glass dust B has the softening point of 800 DEG C, has and analyzes composition as follows: SiO2, and 39.2%；ZnO,
36.2%；Na2O, 2.9%；K2O, 2.2%；CaO, 5.3%；MgO, 0.2%；ZrO2, 0.8%.Glass dust C has 525 DEG C
Softening point, has and analyzes composition as follows: SiO2, 37.7%；Na2O, 14.6%；K2O, 10.6%；TiO2, 16%；Fe2O3, 3%；
BaO, 2.6%；P2O5, 1.3%；Al2O3, 1.2%；CaO, 1.14%；CuO, 0.4%；MgO, 0.37%；ZrO2, 0.8%.Group
Compound comprises dicumyl peroxide to carry out heat cross-linking.The all combinations enumerated in embodiment are given with %wt/wt.By following
The method described is prepared for compositions.
Two-roller mill machine is used for preparing compositions.Silicone elastomer combines (10-20 DEG C) on grinding machine, then adds and the
One Muscovitum and glass dust, made them to disperse by separation and restructuring mixing material at mixing material before the roll gap of two rollers.
When these materials are the most dispersed, add peroxide in a similar fashion and disperse.
Then, the compositions being used for test in embodiment 1-5 and 11 is removed from grinding machine as thin slice, then 170
DEG C and 7MPa under, two 10mm billets that 250 micron polyestef diaphragms in picture frame (1.7mm or 3mm thick) mould cover
Between suppress and harden 30 minutes.
Embodiment 1
The sample of a size of 38.1mm × 13.3mm × 1.7mm is by (170 DEG C, 30 minutes, 7MPa) compositions of heat cross-linking
Preparing, described compositions comprises silicone elastomer and the peroxide of 20%wt/wt and the Muscovitum of 30%wt/wt and difference contains
The low softening point glass dust of amount, sample is heated to indicate temperature, then in 600 DEG C or 1030 DEG C of air with 10 DEG C/min
Keep 30 minutes.The change in volume percent of cooling sample is given in Table 1 below.Result shows, if the content of glass dust increases
It is added to 10%, then compositions has significantly contraction at 1030 DEG C.
Table 1
Table 1: mica content, glass dust content and the sintering temperature impact on change in volume percent.
(-represent shrinks.)
Embodiment 2
The sample of a size of 38.1mm × 13.3mm × 1.7mm is by (170 DEG C, 30 minutes, 7MPa) compositions of heat cross-linking
Preparing, described compositions comprises silicone elastomer, the peroxide of 20%wt/wt, the Muscovitum of 30%wt/wt and different content
Low softening point glass dust (A), sample is heated to 600 DEG C by 10 DEG C/min, keeps 30 the most in atmosphere
Minute.The penetration load Instron with the 90 ° of cone point pressure heads being connected to load frame top of cooled sample
Universal testing-machine (Instron Universal Testing Machine) measures.Penetration load is for thrusting and subsequently when pressure head
Make the maximum load reached during sample broke.Flat Low fire ceramic sample is placed in wooden plate, penetration load 1mm/
Min crosshead velocity determination.Result (table 2) illustrates, by using Muscovitum and the combination of low softening point glass dust, penetration load has
Collaborative raising.So, single 20% and single 7.5% glass dust provide the penetration load of 26N and 4N respectively, but this two
The combination of person provides the value of 45N.The penetration load of the compositions comprising Muscovitum and glass dust increases with the increase of glass dust content
Add.
Table 2
Table 2: the injection cooling down sample 600 DEG C of roastings after 30 minutes is carried by mica content and low softening point glass dust content
The impact of lotus.
Embodiment 3
The sample of a size of 50mm × 14mm × 3mm is prepared by (170 DEG C, 30 minutes, 7MPa) compositions of heat cross-linking, institute
State low softening point that compositions comprises silicone elastomer, peroxide, Muscovitum and different content or high softening-point glass dust (point
Wei glass dust A and B), sample is heated to 600 DEG C, 800 DEG C and 1000 DEG C, keeps 30 points the most in atmosphere
Clock.The flexural strength of cooling sample measures with Instron universal testing-machine in three-point bending model.Result (table 3) illustrates,
The combination of siloxanes/Muscovitum/glass dust creates and exceedes siloxanes/Muscovitum and the flexural strength of siloxanes/glass frit composition
Collaborative raising.
Containing compositions containing 20% Muscovitum in 2.5% glass dust A and siloxanes 1000 DEG C of roastings in siloxanes, produce respectively
Give birth to the flexural strength of 0.5 and 2.2MPa.The combination of siloxanes/Muscovitum/glass dust produces when using 2.5% glass dust A
The flexural strength of 3.2MPa, produces 5.9MPa flexural strength when using 2.5% glass dust B.Result illustrates, at this 1000 DEG C
After high-temperature roasting, high softening-point glass can more effectively strengthen flexural strength, and the content reducing glass dust B can make to scratch to 1.25%
Qu Qiangdu is reduced to 4.2MPa.
For the sample 800 DEG C of roastings, result explanation interpolation high softening-point glass dust (glass dust B) will not provide and exceed
The intensity of siloxanes/Muscovitum compositions improves.But, add low softening point glass dust (glass dust A) and lead in siloxanes/Muscovitum
Cause the flexural strength at the sample of 800 DEG C of roastings and increase to three times (0.7MPa is to 2.1MPa).
Table 3
Table 3: add Muscovitum and glass dust and roasting in the air of 600 DEG C, 800 DEG C and 1000 DEG C was cooled down sample after 30 minutes
The impact of the flexural strength of product.
(it is different that+roasting condition and flexural strength assay method are used in other embodiments from those；
* sample is the most fragile and can not test；
-do not have test sample.)
Embodiment 4
(A) particle size (average particle size=12 μm) of primary sample glass dust B is reduced to about 6 μm by ball milling
Average particle size.Sample is prepared, by it at 600 DEG C, 800 DEG C and 1000 under conditions of identical with described in preceding embodiment
DEG C air in roasting 30 minutes.The flexural strength of cooling sample is surveyed with Instron universal testing-machine in three-point bending model
Fixed, result is shown in Table 4.
Table 4
Table 4: glass dust particle size cools down sample to roasting in the air of 600 DEG C, 800 DEG C and 1000 DEG C after 30 minutes
The impact of flexural strength
The glass dust with more fine particle size makes sample strength improve about 1.3 times when maximum temperature.But, it
Significantly raising is not the most provided.
(B) sample of a size of 50mm × 14mm × 2mm is by (170 DEG C, 30 minutes, 7MPa) compositions system of heat cross-linking
, described compositions comprises: silicone elastomer, peroxide, Muscovitum and different glass fibre (～700 DEG C of softening points
The E-glass fibre of C-glass fibre and 840 DEG C of softening points)；Muscovitum and to have 12 μ .m (primary sample) and 6 μm (grinding) flat
All glass dust B of particle size；The low softening point glass dust of Muscovitum and two kinds of content and glass dust B and the mixing of glass dust C
Thing.Sample is 600 DEG C, 800 DEG C, roasting 30 minutes in the air of 1000 DEG C.The flexural strength of cooling sample is at three-point bending mould
Type measures with Instron universal testing-machine.
Table 5
Table 5: add low softening point glass dust, low softening point and the mixture of high softening-point glass dust and glass fibre to
In the air of 600 DEG C, 800 DEG C and 1000 DEG C, roasting cools down the impact of the flexural strength of sample after 30 minutes.
(* is the most fragile and cannot test.)
Result (table 5) illustrates, adds glass dust and glass fibre considerably improves the pottery obtained after high temperature cooling
Flexural strength.
For the sample 800 DEG C of roastings, result illustrates, when these additives with low content (the glass dust C of 1.25% and
The C-glass fibre of 4%) when adding, add low softening point glass dust (glass dust C) or low softening point glass fibre (C-glass fibers
Dimension) cause sample deflection intensity to increase to about 5 times.When additive (the C-glass of the glass dust C and 8% of 2.5% adding higher amount
Glass fiber) time, compared to not having the compositions of glass additive, intensity increases to up to 8 times.
When replacing high softening-point glass dust (the glass dust B ground) of half with low softening point glass dust (glass dust C),
The flexural strength of pottery is all improved (data in comparison sheet 4 and 5) under all sintering temperatures.When 1000 DEG C of roastings
Time, siloxanes/Muscovitum/glass dust be applied in combination 2.5% grind glass dust B time produce 2.52MPa flexural strength, use
The flexural strength of 4.84MPa is produced during glass dust B that 1.25% grinds and 1.25% glass dust C.Strong at 800 DEG C and 600 DEG C
Degree improves about 5 times and 3 times respectively.
(C) change in size (table 6) after baking of the cross-linked composition shown in table 4 and table 5 is determined.Result explanation adds
Add glass dust and glass fibre and improve contraction at 1000 DEG C, and it is offset or decreases the expansion at 600 DEG C.At 1000 DEG C,
Compared to adding high temp glass powder (glass dust B) and glass fibre (E-glass fibre), when adding cryogenic glass powder (glass dust C)
Or contraction during glass fibre (C-glass fibre) is bigger.
The thickness of all these samples expands at all temperatures, but interpolation glass dust and glass fibre reduce
This impact, when using glass powder with low melting point and fiber, reduces the most notable.
Table 6
Table 6: add glass dust and glass fibre to cold after roasting 30 minutes in the air of 600 DEG C, 800 DEG C and 1000 DEG C
But the impact of the change in size of sample.
Embodiment 5
Heat cross-linking (170 DEG C, 30 minutes, the 7MPa) composition sample enumerated in table 7 is heated to 10 DEG C per minute
1000℃.In heating process, applying a voltage through sample, the electric current ammeter in circuit is monitored.Then by answering
With Ohm's law, result is changed into specific insulation.It is known that in the glass comprising removable ion, resistivity is with temperature
Increase and reduce.For all different components shown in table 7 below, in the mensuration temperature of 900 DEG C, 950 DEG C and 1000 DEG C
On observe that specific insulation reduces (electric current increase) with the increase of temperature.
Add containing the reduction causing specific insulation in alkali Muscovitum to siloxanes.If taken with phlogopite (such as Muscovitum B)
For white mica, the reduction of those specific insulations is slightly larger.Add high-alkali, low softening point glass dust (glass dust A) to silicon
Oxygen alkane/Muscovitum causes the huge reduction of specific insulation, because having sodium and the potassium of high-load in glass dust.When softening with height
When point, glass with lower alkali content powder (glass dust B) replace high alkali glass powder, compared to siloxanes/Muscovitum, the reduction of specific insulation is simply
Appropriateness.Reduce in siloxanes/Muscovitum/glass frit composition by replacing Muscovitum by the silicate filler part of alkali-free
Mica content, this has the effect increasing compositions resistivity
Table 7
Table 7: Muscovitum and the impact on specific insulation of the glass dust content when high temperature.
(* has the phlogopite of 50 μm average particle sizes.)
Embodiment 6
Performance in oven test.
Experiment cable 1.5mm2 ordinary copper wire manufactures, and described wire is in one case with siloxanes/Muscovitum/peroxide
Compound (78: 20: 2) compositions insulate, in another case with siloxanes/Muscovitum/glass dust B/ peroxide (76.75: 20
: 1.25: 2) compositions insulation.Compositions is crosslinked in the fabrication process.These insulated conductors are threaded together, with commercially available Halogen
Element Flameproof thermoplastic sheathing material is as sheath.When testing cable when 240V (phase place over the ground) is energized in fire, machinery
Described in shock-testing such as British Standard test BS6387, at 950 DEG C with vigorous shock-testing once in every 30 seconds
15 minutes.It has been found that have failed in this is tested with the wire of silicone elastomer and the insulation of Muscovitum compositions, and use silica
The wire of alkane elastomer, Muscovitum and glass frit composition insulation successfully withstands experiment condition.
Embodiment 7
It is prepared for following combination thing:
Compositions 1 one siloxanes/Muscovitum/peroxide (78: 20: 2)；
Compositions 2-siloxanes/Muscovitum/glass dust A/ peroxide (70.5: 20: 7.5: 2).
These compositionss compression molding under heating (150 DEG C, 30 minutes) is plate (1200mm × 900mm × 10mm), surveys
Test plate (panel) to assess relative fire resistance, citing: if according to advanced in the world, Australian Standard AS 1530 Part 4:
Fire resistance tests of elements of building construction-Pilot furnace test
It is measured by integrity failure.These plates support against the door frame of gas-fired furnace, and this gas-fired furnace is in normal pressure
Lower operating, according to the standard cellulose heating curves test sample specified in test, rose to target temperature in 240 minutes
1150℃.For comparing the material passed through for retard flame, integrity failure is relevant, and as flame the most suddenly
The point occurred is measured, and for compositions 1, it is 24 minutes (when average measurement furnace temperature is 821 DEG C), for compositions 2,
It is 97 minutes (when average measurement furnace temperature is 1023 DEG C).Result illustrates, adds glass dust and considerably improves as fire prevention
The performance of isolated material.
Embodiment 8
Compositions 2 sample in embodiment 7 is extruded and becomes gate seal, be crosslinked (170 DEG C, 30 minutes) and
1000 DEG C are calcined.Sample shows the structural intergrity of height, keeps the shape of gate seal after baking, and illustrate only
Less contraction.
Embodiment 9
By the siloxane foams being chemically crosslinked prepare rectangle sample 1050 DEG C of roastings 30 minutes (form in table 8 to
Go out).The size of sample is 18 × 5 × 3mm, is suitable in three point bending test measuring bending with Dynamic Mechanical Analyzer (DMA)
Engineering properties.Determine five samples of every kind of compositions, and be averaged to ensure good reliability by result.Siloxanes gathers
Compound is the normal temperature crosslinked materials of two parts.Some compositions also includes silicone coupling agents, Y_ methacryloxypropyl
Trimethoxy silane.
Silicone coupling agents and add the fireproof agent mechanicalness to the ceramic residue after 1050 DEG C of roastings 30 minutes
The impact effect of matter is shown in Table 8.
Table 8
Table 8: fire-proof additive and the coupling agent impact on foamed silicone compositions engineering properties.
Adding magnesium hydroxide fireproof agent causes a small amount of of flexural modulus to reduce and a small amount of increase of flexural strength.Add more
The coupling agent of amount adds flexural modulus.
Embodiment 10
By the siloxane foams being chemically crosslinked prepare rectangle sample 1050 DEG C of roastings 30 minutes (form in table 9 to
Go out).The size of sample is 18 × 5 × 3mm, is suitable in three point bending test measuring flexure with Dynamic Mechanical Analyzer (DMA)
Engineering properties.Determine 5 samples of every kind of compositions, and be averaged to ensure good reliability by result.Have studied work
For the Firebrake ZB of fireproof agent and the glass former effect when low temperature.The low-melting glass (glass dust-B) used is 525
DEG C softening, and the softening temperature of Firebrake ZB is between 300-700 DEG C.Improving with Firebrake ZB replacement low-melting glass can ceramic
The fire resistance of system, keeps high rigidity and good shape retention simultaneously.
Employ the silicone base composition in embodiment 9.Table 9 shows and surveys with DMA in three point bending test model
Fixed flexural properties and the mass loss measured with thermogravimetry.Measure them with the assessment engineering properties of modified sample and resistance to
Fire.Less amount of mass loss illustrates preferable fire resistance.
Result illustrates, replaces low-melting glass with Firebrake ZB, does not only reach preferable engineering properties, and obtain much better
Refractory properties (lost by quality measurement and quantify).
Table 9
Table 9: replace the low-melting glass engineering properties on silicone composition and the impact of refractory properties with Firebrake ZB.
At 1050 DEG C, the change in volume of compositions I and compositions II is respectively-6% and-1%, and explanation Firebrake ZB replaces
Low-melting glass produces less change in volume.
Embodiment 11
Be suitable for the silicone rubber base composition of extrusion include silicone rubber (DC 4-7219, Dow Corning), 20 parts of Muscovitums, 3
Part glass dust A and 3 parts of glass dust B, said composition is modified with magnesium hydroxide and the Firebrake ZB of different percents, with improve by
The fire resistance of the gained pottery of 700 DEG C of roasting formation and engineering properties.Sample size is 18 × 5 × 3mm, is suitable in three-point bending
Test measures flexure engineering properties with Dynamic Mechanical Analyzer (DMA).Measure 5 samples of every individual system, and result is taken
Averagely, to ensure the good reliability of result.Result is shown in Table 10.
Compositions (II) in table 10, after 700 DEG C of roastings, shows preferable performance in terms of fire resistance and engineering properties.
Add magnesium hydroxide and Firebrake ZB can improve fire resistance, improve flexural modulus and flexural strength simultaneously.
Table 10
Table 10: fire-proof additive combines the fire prevention character to ceramic ashes and engineering properties in lower temperature range
Impact.
Embodiment 12
The sample of a size of 30mm × 13mm × 2mm by heat cross-linking (170 DEG C, 30 minutes, 7MPa) by bi-material X and
Y prepares.Material X (embodiment 4a) is the compositions according to the present invention with refractory material specification, and material Y is known 800
The compositions of DEG C temperatures above fusing.They are positioned on fire-resistant rectangular sheet, so that its major axis is perpendicular to fire-proof supporting bracer
One edge, the part of the 13mm length of each sample is stretched out from the edge of fire-proof supporting bracer.Then they are added with 12 DEG C/min
Heat, to 830 DEG C and 1000 DEG C, keeps 30 minutes in the air of these temperature.At both temperatures, the sample of compositions X does not has
There is fusing, create the bonding porous ceramics keeping sample shape before being exposed to high temperature.The sample of compositions X is at all chis
Contraction on very little is less than 2%.At both temperatures, compositions Y sample melting, the pitch portions not supported bending across
Crossing the edge of fire-proof supporting support body, to obtain the most vertical position, this illustrates that it can not keep shape or support own wt.?
1000 DEG C, the sample of compositions Y is completely melt, to be formed at above fire-proof supporting support body and along the glassy material of its side flow
Material.
Although moreover, it will be appreciated that this specification is been described by according to embodiment, but the most each embodiment only wraps
Containing an independent technical scheme, this narrating mode of description is only that for clarity sake those skilled in the art should
Description can also be formed those skilled in the art through appropriately combined as an entirety, the technical scheme in each embodiment
May be appreciated other embodiments.
Claims (9)
1. a flame-retardant silicon polymer compositions, it is characterised in that said composition includes:
Siloxane polymer；
The Muscovitum of the amount of 5-30wt% based on composition total weight；With
The glass additive of the amount of 0.3-8wt% based on composition total weight, wherein said glass additive includes low softening point
Glass additive and the glass additive of high softening-point.
A kind of flame-retardant silicon polymer compositions the most according to claim 1, it is characterised in that described Muscovitum is silane
Muscovitum behind coupling agent treatment surface, the amount of described silane coupler is the amount of 0.05-2wt% based on composition total weight, institute
The mean diameter stating Muscovitum is 15-250 μm.
A kind of flame-retardant silicon polymer compositions the most according to claim 2, it is characterised in that described Muscovitum includes gold
One or more in Muscovitum or white mica, the mean diameter of described Muscovitum is 50-200 μm, and described silane coupler includes second
In thiazolinyl trimethoxy silane, aromatics silane, aryl-silane, epoxy silane, acrylsilane, polysilane or hydrosulphonyl silane one
Plant or several.
A kind of flame-retardant silicon polymer compositions the most according to claim 1, it is characterised in that described glass additive
Exist with one or more forms in glass powder, glass particle or glass fibre；Described glass additive include silicate,
One or more in borate, phosphate or lead base glass system.
A kind of flame-retardant silicon polymer compositions the most according to claim 1, it is characterised in that described glass additive
There is the softening point less than 1050 DEG C；Described glass additive also includes the alkali gold less than 50% based on glass additive weight
Belong to oxide.
A kind of flame-retardant silicon polymer compositions the most according to claim 5, it is characterised in that described glass additive
There is the softening point less than 800 DEG C；Described glass additive also includes the alkali gold less than 30% based on glass additive weight
Belong to oxide.
A kind of flame-retardant silicon polymer compositions the most according to claim 6, it is characterised in that described glass additive
There is the softening point of 300-800 DEG C.
A kind of flame-retardant silicon polymer compositions the most according to claim 1, it is characterised in that described compositions is also wrapped
Including fire proofing material, described fire proofing material 5-20wt% based on composition total weight measures.
A kind of flame-retardant silicon polymer compositions the most according to claim 8, it is characterised in that described fire proofing material bag
Include one or more in Firebrake ZB, magnesium hydroxide or aluminium hydroxide.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107141811A (en) * | 2017-05-18 | 2017-09-08 | 东莞市天桉硅胶科技有限公司 | A kind of Ceramic silicon rubber and preparation method thereof |
| CN114759156A (en) * | 2022-03-22 | 2022-07-15 | 蜂巢能源科技股份有限公司 | Flame-retardant material for battery pole group and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1671823A (en) * | 2002-08-01 | 2005-09-21 | 陶瓷聚合体有限公司 | Fire resistant silicone polymers combination |
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2016
- 2016-07-22 CN CN201610611134.6A patent/CN106280466A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1671823A (en) * | 2002-08-01 | 2005-09-21 | 陶瓷聚合体有限公司 | Fire resistant silicone polymers combination |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107141811A (en) * | 2017-05-18 | 2017-09-08 | 东莞市天桉硅胶科技有限公司 | A kind of Ceramic silicon rubber and preparation method thereof |
| CN114759156A (en) * | 2022-03-22 | 2022-07-15 | 蜂巢能源科技股份有限公司 | Flame-retardant material for battery pole group and preparation method and application thereof |
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