WO2017070893A1

WO2017070893A1 - Ceramic silicone rubber, preparation method and use thereof

Info

Publication number: WO2017070893A1
Application number: PCT/CN2015/093202
Authority: WO
Inventors: 张良培; 张晖; 张忠
Original assignee: 国家纳米科学中心
Priority date: 2015-10-29
Filing date: 2015-10-29
Publication date: 2017-05-04

Abstract

Disclosed in the invention are a ceramic silicone rubber, a preparation method and use thereof. As to the ceramic silicone rubber, the silicone rubber system is added with fillers such as a highly effective flame retardant catalyst, inorganic mineral powders, a nanosized metal oxide and/or metal hydroxide, and lamellar nanosized powders, and when being heated, a silicone rubber forms, in a wide range of temperature, a rigid ceramic body with the fillers therein in the presence of a catalyst. The ceramic silicone rubber has halogen-free, smoke-free characteristics upon burning and has excellent fire prevention, flame retardant, mechanical, electrical insulating and processing performances. This can be used in the fields of cable materials, sealing rings, silicone rubber coatings, ablation resistant materials, and fire clay and the like.

Description

Ceramicized silicone rubber, preparation method and use thereof

Technical field

The invention relates to a flame retardant fireproof ceramizable silicone rubber, a preparation method and a use thereof, and belongs to the technical field of rubber preparation.

Background technique

Fire is one of the major disasters in the fields of construction, nuclear power, chemicals, and transportation. Aging of the circuit and fire of wires and cables are important causes of fire. When burning, the fire will spread rapidly along the wires and cables, causing power and communication interruptions, which is not conducive to rapid escape and fire. In addition, the traditional halogen-containing flame retardant polymer material will release a large amount of corrosive and toxic gas, causing secondary damage to personnel, and the application is subject to many restrictions.

Porcelain-based silicone rubber composites are a new type of fireproofing material, the concept of which was first proposed in 2004 by Hanu et al. [J Mater Process Technol, 2004, 153-154, 401]. Under the condition of high temperature ablation, the porcelain ceramic rubber sample can be transformed into a hard ceramic body with almost no change in shape and size, thereby blocking the external heat from diffusing into the material, suppressing the evaporation loss of the material inside the material, and blocking the spread of the flame. The ceramicized silicone rubber composite can withstand ablation at 650-1000 °C in a short time (30-120 min). In addition, this material has the advantages of low smoke generation, non-toxicity, and no melt dripping. Porcelain-based silicone rubber composites are widely used in aerospace, aviation, nuclear power, ships, vehicles, large buildings, industrial and mining enterprises and other key fire departments. The most important application form of the material is to manufacture the protective layer and insulation layer of the fireproof wire/cable, but it can also be used for other fireproof products, including fireproof sealant for doors and windows, fireproof putty, fireproof coating, fireproof foaming material and the like.

At present, there are certain researches and applications on ceramizable silicone rubber composite materials at home and abroad. Such as Chinese patent applications: CN102964836A, CN103554918A, CN103554919A, CN104672916A and so on. From the perspective of patent analysis and the actual use of materials, the ceramized silicone rubber composites currently used on the market tend to be filled with a certain amount of low-softening point glass powder into the silicone rubber. At high temperatures, the glass powder is melted and other The fillers are combined and sintered to form a ceramic body. However, the interface between the glass frit and the silica is poor. The formed ceramic body is easy to crack, and the mechanical properties are not good, and the expected effect is often not achieved in actual use. In addition, in terms of flame retardancy, the glass frit often contains elements such as potassium and sodium which promote thermal decomposition of the silicone rubber, which is disadvantageous for flame retardancy. In order to achieve the purpose of flame retardant, in the above patents, a certain amount of phosphorus-based flame retardant (such as red phosphorus, ammonium polyphosphate, etc.) is often added to the silicone rubber, and although the flame retarding effect is achieved, the silicone rubber material is also deteriorated. Mechanical properties and even processing properties.

Summary of the invention

In order to solve the defects that the ordinary ceramicized silicone rubber has poor flame retardant performance, the ceramic layer is easy to crack, and the ceramic layer has low strength, the present invention provides a ceramicized silicone rubber, a preparation method and a use thereof; the ceramicized silicone rubber has a resistance The function of integration of combustion and fire prevention; it is characterized by not using low-softening point glass powder or other porcelain powder, but in the high temperature or combustion, when the silicone rubber is heated under the catalysis of the flame retardant catalyst, it is formed by the action of the filler. Hard ceramic body. Since the low soft point glass powder and the porcelain powder are not used, the flame retardant performance is effectively improved; the nanosheet filler is introduced to effectively improve the interfacial properties between the particles after the porcelain formation, and the strength after the porcelain is greatly improved. The ceramized silicone rubber of the invention has excellent mechanical, electrical insulation and processing properties.

The invention adopts the following technical solutions:

A ceramized silicone rubber, the raw materials thereof include: silicone rubber, silicon dioxide, nanosheet filler, but no glass powder or porcelain powder with low softening point.

Preferably, the ceramized silicone rubber further comprises: a silicone oil, a high-efficiency flame retardant catalyst, a metal oxide, a metal hydroxide, a mineral powder, a coupling agent, a mold release agent, a vulcanizing agent, an MQ resin, and the like. One or several.

The glass powder or porcelain powder of the low softening point generally refers to a glass powder or a porcelain powder having a softening temperature of 300-600 ° C, such as phosphate glass powder, borate glass powder, and bismuth silicate glass powder. Wait.

Preferably, the ceramized silicone rubber, by weight, the raw materials thereof include:

100 parts of silicone rubber;

20-80 parts of silica;

Nanosheet filler 0.1-50 parts;

0-15 parts of silicone oil;

0-1 parts of high efficiency flame retardant catalyst;

0-30 parts of metal oxide;

0-30 parts of metal hydroxide;

Mineral powder 0-150 parts;

Coupling agent 0-10 parts;

0-5 parts of release agent;

Vulcanizing agent 0-5 parts

MQ resin 0-10 parts;

Further preferably, the ceramized silicone rubber, by weight, the raw materials thereof include:

100 parts of silicone rubber;

30-60 parts of silica;

Nanosheet filler 0.5-40 parts;

Silicone oil 0-12 parts;

High-efficiency flame retardant catalyst 0.000001-1 parts;

0-20 parts of metal oxide;

0-20 parts of metal hydroxide;

Mineral powder filler 50-100 parts;

Coupling agent 0-10 parts;

0-5 parts of release agent;

0-5 parts of vulcanizing agent;

MQ resin 0-6 parts;

Still more preferably, the ceramized silicone rubber, by weight, the raw materials thereof include:

100 parts of silicone rubber;

30-60 parts of silica;

Nanosheet filler 1-10 parts;

1-8 parts of silicone oil;

High-efficiency flame retardant catalyst 0.000001-1 parts;

1-10 parts of metal oxide;

0-10 parts of metal hydroxide;

Mineral powder filler 50-100 parts;

Coupling agent 0-5 parts;

Release agent 0.1-2 parts;

2-5 parts of vulcanizing agent;

MQ resin 0-6 parts

The parts by weight of the present invention may be a unit of weight known in the art such as μg, mg, g, kg, or the like, or may be a multiple thereof such as 1/10, 1/100, 10 times, 100 times or the like.

The above ceramized silicone rubber, wherein:

Preferably, the silicone rubber is one or more of methyl vinyl silicone rubber (VMQ), methyl phenyl vinyl silicone rubber (PVMQ), fluorosilicone rubber, dimethyl silicone rubber (MQ), and the like. Species

Preferably, the vinyl rubber has a vinyl content of 0.01% to 5%; more preferably, the silicone rubber or silicone rubber mixture has a gel viscosity of usually 10 to 1,000,000 cps.

The silica, commonly known as white carbon black, is a reinforcing filler commonly used for silicone rubber, and is generally classified into two types: a precipitation method and a gas phase method; preferably, the silica is a fumed silica.

In order to improve the mechanical properties of silicone rubber, surface modified (hydrophobicized) silica is usually used, such as dimethyldichlorosilane, octamethyltetrasiloxane, polysiloxane, octyltrimethoxysilane. A surface-modified white carbon black such as silane or hexamethyldisilazane may be used alone or in combination.

Preferably, the silica has a particle size between 1 nanometer and 1 micrometer; further preferably, the particle diameter is between 5 and 500 nanometers; more preferably, the particle diameter is between 10 nanometers and 100 nanometers.

Preferably, the silicone oil is one or more of a hydroxy silicone oil, a vinyl silicone oil, and the like.

Preferably, the hydroxy silicone oil contains one or more hydroxyl groups per molecular chain and has a viscosity of from 50,000 to 10,000 centipoise.

Preferably, the vinyl silicone oil has a vinyl chain molar mass fraction of 0.01% to 15%, and more preferably, the vinyl chain molar mass fraction is 1% to 12%.

Preferably, the high efficiency flame retardant catalyst may be an antioxidant or a transition metal compound.

Preferably, the antioxidant is one or more of citric acid, terephthalic acid, antioxidant 1010, and the like;

Preferably, the transition metal compound is one or a mixture of metal oxides such as cuprous oxide and ferrous oxide.

Preferably, the high-efficiency flame retardant catalyst is one or a mixture of a metal or a metal compound or a metal complex such as platinum, palladium, rhodium, molybdenum, ruthenium, nickel, cobalt or the like; preferably, the high-efficiency flame retardant The catalyst may be one or a mixture of a platinum compound or a platinum complex: such as 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum, chloroplatinic acid, Platinum siloxane, chloroplatinic acid-tetrahydrofuran complex, methylvinylsiloxane coordination platinum complex, methylvinyl coordination platinum catalyst, platinum vinyl complex, vinyl siloxane One or a mixture of a compound, a chloroplatinic acid-octanol complex catalyst.

The high-efficiency flame-retardant catalyst may be in the form of a liquid, a viscous, a powder or the like; preferably, the high-efficiency flame-retardant catalyst in a liquid state or a viscous state is used as a masterbatch with a part of the silicone rubber, or the The high efficiency flame retardant catalyst is supported on a nanoparticle carrier; further preferably, the nanoparticle carrier used is silica, ferric oxide, aluminum oxide, magnesium oxide, zinc oxide, titanium oxide or the like.

Preferably, the high efficiency flame retardant catalyst is a nanoparticle; further preferably, the nanoparticle size is from 15 to 500 nm.

The metal oxide or metal hydroxide as a synergistic flame retardant for high-efficiency flame retardant can greatly improve the flame retarding effect and reduce the dosage of the high-efficiency flame retardant.

The metal oxide is one of ferric oxide, aluminum oxide, magnesium oxide, copper oxide, zinc oxide, titanium oxide, calcium oxide, zirconium oxide, antimony trioxide, boron oxide, vanadium oxide, or the like. Several mixtures.

Preferably, the metal oxide size is on the order of micrometers or nanometers; further preferably, the microscale metal oxide has a size of from 1 to 50 micrometers and the nanoscale metal oxide has a size of from 20 to 800 nanometers.

The metal oxide has a certain role in promoting the formation of a porcelain interface or has a certain catalytic effect. Or it has the effect of promoting nucleation during the porcelain formation process.

Preferably, the metal hydroxide is one or a mixture of magnesium hydroxide, aluminum hydroxide, and the like.

Preferably, the metal hydroxide has a size of micron or nanometer; further preferably, the micron-sized metal hydroxide has a size of 1 to 50 microns, and the nano-sized metal hydroxide has a size of 20 to 800 nm.

Preferably, the nanosheet filler may be one or a mixture of nanometer mica flakes, montmorillonite, talc or hydrotalcite, graphene, kaolin, bentonite, pyrophyllite and the like.

Preferably, the mineral powder has a certain aspect ratio.

The mineral powder may be in the form of a sheet, a block or a fiber.

Preferably, the mineral powder comprises feldspar powder, bentonite, clay, wollastonite, quartz, diatomaceous earth, diopside, graphite flake, calcium carbonate, tremolite, sillimanite, attapulgite, sea blisters One or several compounds in stone or the like. Preferably, the mineral powder selected is fibrous.

The mineral powder has a porcelain-forming effect.

The coupling agent is γ-aminopropyltriethoxysilane (KH-550), γ-glycidoxypropyltrimethoxysilane (KH-560), γ-methacryloxypropyl Trimethoxysilane (KH-570), propyltriethoxysilane (KH-330), propylpropyltrimethyl(ethoxy)silane (KH580, KH590), ethylenediaminepropyltriethoxysilane ( KH792), vinyl triacetoxysilane (KH-188), ethylenediamine propylmethyldimethoxysilane (KBM602), vinyltriethoxysilane (A151), vinyltriethoxysilane (A171), hexamethyldisiloxane, hexamethyldisilazane (HDMI), isopropyl trioleate acylate, vinyl triisopropoxy silane, γ-methyl propylene One or more of acyloxypropyltriisopropoxysilane, titanate, aluminate, zirconate, borate, and the like.

The coupling agent improves the adhesion of the mineral powder to the resin.

Preferably, the release agent is one or a mixture of stearic acid, zinc stearate, paraffin wax, and the like.

Preferably, the vulcanizing agent is benzoyl peroxide (BPO), 2,4-dichloroperoxybenzene Formyl (bis 2,4), dicumyl peroxide (DCP), 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane (double 2,5), etc. One or several mixtures.

The invention also provides a preparation method of the above ceramicized silicone rubber, comprising the following steps:

1) adding the silicone rubber, silica, silicone oil (hydroxy silicone oil and/or vinyl silicone oil), MQ resin, and/or partial coupling agent, and/or release agent to the kneader according to the ratio, in Mix well at 50 to 200 ° C to obtain a rubber compound; after the glue is discharged, use an open mill to remove the sheet, and use it after parking for a period of time;

2) adding the high-efficiency flame-retardant catalyst, the nanosheet filler, the mineral powder, the metal oxide or the metal hydroxide, and/or the partial coupling agent to the kneader according to the ratio to mix uniformly with the rubber compound ;

3) Remove the material obtained in step 2) from the kneader, cool it, place it on the open mill, add the vulcanizing agent, mix well and then remove the sheet.

Preferably, the high-efficiency flame retardant catalyst is formulated into a master batch with a portion of the silicone rubber and then added to the kneader; or the high-efficiency flame retardant catalyst is supported on the nanoparticles and then added to the kneader.

The invention also includes the use of the above-described ceramicized silicone rubber for flame retardant materials.

The invention also provides a product comprising the above ceramicized silicone rubber; the product includes but is not limited to cable material, cable sheath, sealing ring, fireproof mud, ablation resistant material, silicone rubber coating, electric wire, fire door, fire prevention Plate, foam.

The ceramized silicone rubber of the invention is added with a high-efficiency flame-retardant catalyst, an inorganic mineral powder, a nano metal oxide and/or a metal hydroxide in a silicone rubber system, and the silicone rubber is under the action of a catalyst and a filler therein when heated. Produces a hard ceramic body. The present invention does not use low soft point glass powder to reduce the adverse effect on the flame retardancy of the silicone rubber; the present invention uses at least one nanosheet filler to improve the interfacial bonding performance between the fillers after the porcelain is formed. The flame-retardant, fire-proof and ceramizable silicone rubber material obtained by the invention has the characteristics of no halogen and smokeless when burned, and can form a hard ceramic body in a wide temperature range, and has excellent mechanical, electrical insulation and processing. performance.

The ceramized silicone rubber of the invention has simple processing technology and low cost. Meet British fire resistance Cable standard BS6387 and national standard GB/T 19666-2005 requirements. Flame-retardant performance meets the UL90 test standard V0 level, no halogen, smokeless, no toxic gas in the combustion process, the open flame time is very short, the porcelain does not crack, does not expand, low shrinkage, has a wide fire temperature range A ceramic layer can be formed from 400 ° C to 2000 ° C. The ceramized silicone rubber of the invention has good elasticity, tensile strength and tear strength at room temperature; and can be used in the fields of cable materials, cable sheathing, sealing rings, fireproof mud, ablation resistant materials, silicone rubber coatings and the like.

detailed description

The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.

The nanosheet fillers (mica tablets, nano-montmorillonite sheets, talc or hydrotalcite, graphene, nano kaolin sheets, nano-bentonite sheets, etc.) used in the following Examples 1-9 are nanoscale, and the particle size range thereof It is 5-80 nm.

Example 1

A ceramized silicone rubber comprising: 100 parts of methyl vinyl silicone rubber, 50 parts of white carbon black, 60 parts of wollastonite, 5 parts of feldspar powder, 5 parts of hydrotalcite, 8 parts of aluminum oxide, 1 Montmorillonite, 5 parts of hydroxy silicone oil, 1 part of chloroplatinic acid, 5 parts of hexamethyldisilazane, 1 part of stearic acid, 2 parts of 2,4-dichlorobenzoyl peroxide (double 2, 4 ); 1kg per serving.

The embodiment further provides a preparation method of the ceramized silicone rubber, comprising the following steps:

According to the ratio, methyl vinyl silicone rubber, white carbon black, hexamethyldisilazane, hydroxy silicone oil, stearic acid are added to the kneader, and uniformly mixed in a kneading machine at 80 ° C to obtain a rubber compound; Adding chloroplatinic acid, aluminum oxide, wollastonite, feldspar powder, hydrotalcite, montmorillonite to the kneader; uniformly kneading with the rubber mixture; removing the obtained material from the kneader, cooling and placing Add double 2, 4 on the open mill and mix evenly.

After testing, the ceramized silicone rubber obtained in this embodiment has a tensile strength of up to 7.5 MPa, a tear strength of 23 kN/m, an elongation at break of 750%, and a flame retardant meeting the UL94V-0 requirement after the vulcanization of the tablet. °C refractory time 180min continuous power.

Example 2

A ceramized silicone rubber comprising: 50 parts of methyl vinyl silicone rubber, 50 parts of methyl phenyl vinyl silicone rubber, 30 parts of white carbon black, 1 part of hydroxy silicone oil, 5 parts of vinyl silicon Oil, 0.5 parts zinc stearate, 3 parts MQ resin, 0.01 parts nano nickel, 60 parts mica, 50 parts magnesium hydroxide, 5 parts montmorillonite, 8 parts titanium dioxide, 2 parts diopside, 3 parts gamma-ammonia Propyltriethoxysilane KH-550, 2 parts of 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane (i.e., double 25); 1 kg per serving.

Add methyl vinyl silicone rubber, methyl phenyl vinyl silicone rubber, white carbon black, hydroxy silicone oil, vinyl silicone oil, MQ resin, zinc stearate to the kneader according to the ratio, and mix evenly at 50 ° C. Mixing rubber; adding nano nickel, mica, magnesium hydroxide, montmorillonite, titanium dioxide, diopside, KH-550 to the kneader according to the ratio; uniformly mixing with the rubber compound; removing from the kneader The obtained material was cooled, placed on an open mill, and mixed with double 25 to form a lower sheet.

After testing, the ceramized silicone rubber obtained in this embodiment has a tensile strength of 6.8 MPa, a tear strength of 21 kN/m, an elongation at break of 550%, and a flame retardant meeting the UL94V-0 requirement after the vulcanization of the tablet. °C refractory time 180min continuous power.

Example 3

A ceramized silicone rubber, the raw material comprises: 100 parts of methyl vinyl silicone rubber, 40 parts of white carbon black, 3 parts of methyl silicone oil, 5 parts of MQ resin, 1 part of paraffin, 60 parts of diopside, 5 parts of water Talc, 0.2 parts of platinum oxide, 5 parts of titanium oxide, 5 parts of magnesium oxide, 3 parts of zinc oxide, 3 parts of aluminum hydroxide, 3 parts of γ-methacryloxypropyltrimethoxysilane KH-570, 2 parts 2,5-Dimethyl-2,5-bis(tert-butylperoxy)hexane (i.e., double 25); 1 kg per serving.

According to the ratio, methyl vinyl silicone rubber, white carbon black, silicone oil, MQ resin, paraffin wax is added to the kneader, and uniformly mixed at 50 ° C to obtain a rubber compound; platinum oxide and dialysis are added to the kneader according to the ratio. Stone, hydrotalcite, titanium oxide, magnesium oxide, zinc oxide, aluminum hydroxide, KH-570; uniformly kneaded with the rubber compound; remove the material from the kneader, cool and place on the open mill to add cross-linking The agent double 25 is mixed evenly and then the lower piece.

After testing, the ceramized silicone rubber obtained in this embodiment has a tensile strength of 7.3 MPa, a tear strength of 24 kN/m, an elongation at break of 650%, and a flame retardant meeting UL94V-0. It can be made into porcelain at 400 °C, and it can be continuously powered at 950 °C after 850 °C.

Example 4

A ceramized silicone rubber, the raw material comprises: 100 parts of methyl vinyl silicone rubber, 40 parts of white carbon black, 2 parts of hydroxy silicone oil, 1 part of vinyl silicone oil, 1 part of zinc stearate, 5 parts of KH-560, 0.05 parts of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum, 5 parts of mica, 70 parts of wollastonite, 10 parts of titanium dioxide, 30 aluminum oxide, 5 parts of hydrogen Magnesium oxide, 3 parts of dicumyl peroxide; 1 kg per serving.

According to the ratio, methyl vinyl silicone rubber, white carbon black, hydroxy silicone oil, vinyl silicone oil, partial KH-560, zinc stearate is added to the kneader, and uniformly mixed at 50 ° C to obtain a rubber compound; Adding 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum, mica, wollastonite, titanium dioxide, aluminum oxide, magnesium hydroxide to the kneader; The mixture is kneaded uniformly; the obtained material is removed from the kneader, cooled, placed on an open mill, and a cross-linking agent, dicumyl peroxide, is uniformly mixed and then placed.

After testing, the ceramized silicone rubber obtained in the present embodiment has a tensile strength of up to 6.5 MPa, a tear strength of 21 kN/m, an elongation at break of 350%, and a flame retardant meeting the UL94V-0 requirement, which can be at 400 ° C. Into the porcelain, after the cable is 950 ° C refractory time 180min continuous power.

Example 5

A ceramized silicone rubber comprising: 80 parts of methyl vinyl silicone rubber, 20 parts of methyl vinyl phenyl silicone rubber, 40 parts of white carbon black, 2 parts of hydroxy silicone oil, 3 parts of MQ resin, 0.5 parts of hard Zinc citrate, 0.003 parts of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum, 60 parts of diopside, 10 parts of titanium dioxide, 30 ferric oxide, 5 parts of hydrogen Magnesium oxide, 8 parts of hexamethyldisilazane, 3 parts of kaolin, 4 parts of 2,4-dichlorobenzoyl peroxide; 1 kg per part.

According to the ratio, methyl vinyl silicone rubber, methyl vinyl phenyl silicone rubber, white carbon black, hydroxy silicone oil, MQ resin, partial hexamethyldisilazane, zinc stearate is added to the kneading machine at 70 Mixing uniformly in °C to obtain a rubber compound; adding 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum, diopside, titanium dioxide, and trioxide to the kneader according to the ratio Two iron, Magnesium hydroxide, kaolin, residual hexamethyldisilazane; uniformly kneaded with the rubber compound; remove the material from the kneader, cool and then place on the open mill to add cross-linking agent 2,4-dichloro The benzoyl peroxide is uniformly mixed and then placed under the sheet.

After testing, the ceramized silicone rubber obtained in the present embodiment has a tensile strength of up to 6.7 MPa, a tear strength of 21.5 kN/m, an elongation at break of 350%, and a flame retardant meeting the UL94V-0 requirement, which can be 400. °C into porcelain, 850 ° C after the cable is refractory time 180 min continuous power.

Example 6

A ceramized silicone rubber, the raw material comprises: 100 parts of methyl vinyl silicone rubber, 50 parts of white carbon black, 2 parts of hydroxy silicone oil, 1 part of zinc stearate, 10 parts of MQ resin, 3 parts of KH-560, 0.006 Part of chloroplatinic acid, 8 parts of mica, 70 parts of wollastonite, 10 parts of zinc oxide, 10 diopside, 2 parts of aluminum hydroxide, 4 parts of 2,4-dichlorobenzoyl peroxide; 1 kg per part.

The preparation method of the ceramized silicone rubber of this embodiment is the same as that of the first embodiment.

After testing, the tensile strength of the ceramized silicone rubber obtained in this embodiment can reach 6.8MPa, the tear strength is 21.6kN/m, the elongation at break is 350%, the flame retardant meets the requirements of UL94V-0, and can be made into porcelain at 400 °C. After the cable is 950 ° C, the fire resistance time is 180 min.

Example 7

A ceramized silicone rubber, the raw material thereof comprises: 100 parts of methyl vinyl silicone rubber, 42 parts of white carbon black, 0.3 parts of zinc stearate, 3 parts of hexamethyldisilazane, 0.5 parts of 1,3-two Vinyl-1,1,3,3-tetramethyldisiloxane platinum, 8 parts feldspar powder, 70 parts diopside, 10 parts zinc oxide, 30 hydrotalcite, 10 parts kaolin, 1 part γ-methyl Acryloyloxypropyltrimethoxysilane, 5 parts of 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane; 1 kg per part.

After testing, the ceramized silicone rubber obtained in this embodiment has been tested. The tensile strength of the ceramized silicone rubber obtained in this embodiment can reach 7.3 MPa, the tear strength is 24 kN/m, the elongation at break is 450%, and the flame retardant meets UL94V-0. Requirement, it can be made into porcelain at 400 °C, and after 850 °C, the refractory time is 180 min.

Example 8

A ceramized silicone rubber, the raw materials thereof include: 100 parts of methyl vinyl silicone rubber, 20 Parts of silica, 2 parts of hydroxy silicone oil, 5 parts of vinyl silicone oil, 0.5 part of paraffin oil, 0.5 parts of copper oxide, 10 parts of feldspar powder, 20 parts of wollastonite, 10 parts of titanium dioxide, 20 parts of magnesium oxide, 20 parts of hydroxide Aluminum, 10 parts bentonite, 6 parts γ-methacryloxypropyltrimethoxysilane, 5 parts 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane; The serving is 1kg.

After testing, the ceramized silicone rubber obtained in the present embodiment has been tested. The tensile strength of the ceramized silicone rubber obtained in this embodiment can reach 7.1 MPa, the tear strength is 23 kN/m, the elongation at break is 430%, and the flame retardant meets UL94V-0. Requirement, it can be made into porcelain at 400 °C, and after 850 °C, the refractory time is 180 min.

Example 9

A ceramized silicone rubber comprising: 100 parts of methyl vinyl silicone rubber, 80 parts of white carbon black, 10 parts of hydroxy silicone oil, 0.5 parts of zinc stearate, 0.5 parts of 1,3-divinyl-1, 1,3,3-tetramethyldisiloxane platinum, 5 parts mica, 70 parts wollastonite, 10 parts titanium dioxide, 2 hydrotalcite, 8 parts talc, 9 parts diopside, 1 part vinyl silicone oil, 3 parts of dicumyl peroxide; 1 kg per serving.

After testing, the ceramized silicone rubber obtained in the present embodiment has been tested. The tensile strength of the ceramized silicone rubber obtained in this embodiment can reach 6.9 MPa, the tear strength is 22.3 kN/m, the elongation at break is 380%, and the flame retardant meets UL94V- 0 requirements, can be made at 400 ° C porcelain, after the cable is 950 ° C fire resistance time 180min continuous power.

Comparative example 1

A ceramized silicone rubber comprising: 100 parts of methyl vinyl silicone rubber, 40 parts of white carbon black, 6 parts of hydroxy silicone oil, 0.5 parts of zinc stearate, 0.1 part of 1 chloroplatinic acid, 70 parts of wollastonite 10 parts of aluminum hydroxide, 5 parts of vinyl silicone oil, 3 parts of 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane; 1 kg per part.

After testing, the ceramized silicone rubber obtained in the present embodiment has been tested. The tensile strength of the ceramized silicone rubber obtained in this embodiment can reach 6.5 MPa, the tear strength is 20 kN/m, and the elongation at break is 280%. The flame retardant meets the requirements of UL94V-0, but cracks after combustion, the strength after burning is weak, and the power is cut off after 13 minutes of refractory time after 850 °C.

Comparative example 2

A ceramized silicone rubber comprising: 100 parts of methyl vinyl silicone rubber, 40 parts of white carbon black, 6 parts of hydroxy silicone oil, 0.5 parts of zinc stearate, 0.1 part of 1,3-divinyl-1, 1,3,3-tetramethyldisiloxane platinum, 50 parts wollastonite, 30 low soft point glass powder, 5 parts vinyl silicone oil, 3 parts dicumyl peroxide; 1 kg per serving.

After testing, the ceramized silicone rubber obtained in the present embodiment has been tested. The tensile strength of the ceramized silicone rubber obtained in this embodiment can reach 6.6 MPa, the tear strength is 21.1 kN/m, the elongation at break is 380%, and the flame retardant does not satisfy UL94V. -0 requirements, but will promote combustion, can be made at 600 ° C porcelain, after the cable 950 ° C refractory time 34 minutes after power off.

Although the present invention has been described in detail with reference to the preferred embodiments of the present invention, it will be apparent to those skilled in the art Therefore, such modifications or improvements made without departing from the spirit of the invention are intended to be within the scope of the invention.

Industrial applicability

The invention provides a ceramized silicone rubber which is added with a high-efficiency flame retardant catalyst, an inorganic mineral powder, a nano metal oxide and/or a metal hydroxide in a silicone rubber system, and a sheet nano powder. The filler, when heated, the silicone rubber forms a hard ceramic body under the action of the catalyst in a wide temperature range; it has the characteristics of no halogen and smokeless when burned, and has excellent fireproof, flame retardant, mechanical, electrical insulation and Processing performance. Therefore, the ceramized silicone rubber provided by the invention is suitable for the fields of cable materials, sealing rings, silicone rubber coatings, ablation resistant materials, fireproof mud, etc., and has broad application prospects and good industrial applicability.

Claims

A ceramized silicone rubber, characterized in that the raw material comprises: silicon rubber, silicon dioxide, nanosheet filler, but no glass powder or porcelain powder with low softening point;

Preferably, the ceramized silicone rubber further comprises: a silicone oil, a high-efficiency flame retardant catalyst, a metal oxide, a metal hydroxide, a mineral powder, a coupling agent, a mold release agent, a vulcanizing agent, and an MQ resin. One or several.
The ceramized silicone rubber according to claim 1, wherein the raw materials are: by weight:

100 parts of silicone rubber;

20-80 parts of silica;

Nanosheet filler 0.1-50 parts;

0-15 parts of silicone oil;

0-1 parts of high efficiency flame retardant catalyst;

0-30 parts of metal oxide;

0-30 parts of metal hydroxide;

Mineral powder 0-150 parts;

Coupling agent 0-10 parts;

0-5 parts of release agent;

Vulcanizing agent 0-5 parts

MQ resin 0-10 parts;

Preferably, the ceramized silicone rubber, by weight, the raw materials thereof include:

100 parts of silicone rubber;

30-60 parts of silica;

Nanosheet filler 0.5-40 parts;

Silicone oil 0-12 parts;

High-efficiency flame retardant catalyst 0.000001-1 parts;

0-20 parts of metal oxide;

0-20 parts of metal hydroxide;

Mineral powder filler 50-100 parts;

Coupling agent 0-10 parts;

0-5 parts of release agent;

0-5 parts of vulcanizing agent;

MQ resin 0-6 parts;

Further preferably, the ceramized silicone rubber, by weight, the raw materials thereof include:

100 parts of silicone rubber;

30-60 parts of silica;

Nanosheet filler 1-10 parts;

1-8 parts of silicone oil;

High-efficiency flame retardant catalyst 0.000001-1 parts;

1-10 parts of metal oxide;

0-10 parts of metal hydroxide;

Mineral powder filler 50-100 parts;

Coupling agent 0-5 parts;

Release agent 0.1-2 parts;

2-5 parts of vulcanizing agent;

MQ resin 0-6 parts.
The ceramifying silicone rubber according to claim 1 or 2, wherein the silicone rubber is methyl vinyl silicone rubber, methyl phenyl vinyl silicone rubber, fluorosilicone rubber or dimethyl silicone rubber. One or several;

Preferably, the vinyl rubber has a vinyl content of 0.01% to 5%;

Further preferably, the silicone rubber or silicone rubber mixture has a gel viscosity of 10 to 1,000,000 cps;

Preferably, the silica is fumed silica;

Further preferably, the white carbon black is a surface-modified white carbon black; including dimethyldichlorosilane, octamethyltetrasiloxane, polysiloxane, octyltrimethoxysilane or hexamethyl One or more of the surface-modified silicas of disilazane;

Preferably, the silica has a particle size of between 1 nanometer and 1 micrometer; further preferably, the particle diameter is between 5 and 500 nanometers; more preferably, the particle diameter is between 10 nanometers and 100 nanometers;

Preferably, the silicone oil is one or more of a hydroxy silicone oil and a vinyl silicone oil;

Further preferably, the hydroxy silicone oil has one or more hydroxyl groups per molecular chain and has a viscosity of 50,000 to 10,000 centipoise;

Further preferably, the vinyl silicone oil has a vinyl chain molar mass fraction of 0.01% to 15%, and more preferably, the vinyl chain molar mass fraction is 1% to 12%.
The ceramized silicone rubber according to any one of claims 1 to 3, wherein

The high efficiency flame retardant catalyst is an antioxidant or a transition metal compound;

Preferably, the antioxidant is one or more of citric acid, terephthalic acid, and antioxidant 1010;

Preferably, the transition metal compound is one or a mixture of cuprous oxide and ferrous oxide;

Preferably, the high efficiency flame retardant catalyst is one or a mixture of platinum, palladium, rhodium, molybdenum, rhenium, nickel, cobalt metal or a metal compound or a metal complex;

Preferably, the high efficiency flame retardant catalyst is a nanoparticle; further preferably, the nanoparticle size is from 15 to 500 nm.
The ceramized silicone rubber according to claim 4, wherein

The high-efficiency flame-retardant catalyst is selected from one or a mixture of a platinum compound and a platinum complex; preferably 1,3-divinyl-1,1,3,3-tetramethyldisiloxane Platinum, chloroplatinic acid, platinum siloxane, chloroplatinic acid-tetrahydrofuran complex, methylvinylsiloxane coordination platinum complex, methylvinyl coordination platinum catalyst, platinum vinyl complex, One or a mixture of a vinyl siloxane complex, a chloroplatinic acid-octanol complex catalyst;

Preferably, the high-efficiency flame-retardant catalyst in a liquid state or a viscous state is used as a masterbatch with a part of the silicone rubber, or the high-efficiency flame-retardant catalyst is supported on a nanoparticle carrier; further preferably, the nanometer used is used. The particulate carrier is silica, ferric oxide, aluminum oxide, magnesium oxide, zinc oxide, titanium oxide.
The ceramized silicone rubber according to any one of claims 1 to 5, wherein

The nanosheet filler is one or a mixture of nanometer mica flakes, montmorillonite, talc or hydrotalcite, graphene, kaolin, bentonite, pyrophyllite;

Preferably, the mineral powder has a certain aspect ratio;

Preferably, the mineral powder is in the form of a sheet, a block or a fiber;

Preferably, the mineral powder comprises feldspar powder, bentonite, clay, wollastonite, quartz, diatomaceous earth, diopside, graphite flakes, mica, calcium carbonate, tremolite, sillimanite, attapulgite, One or several compounds in sepiolite.
The ceramized silicone rubber according to any one of claims 1 to 6, wherein

The metal oxide is one or more of ferric oxide, aluminum oxide, magnesium oxide, copper oxide, zinc oxide, titanium oxide, calcium oxide, zirconium oxide, antimony trioxide, boron oxide and vanadium oxide. Mixture

Preferably, the metal oxide size is on the order of micrometers or nanometers; further preferably, the microscale metal oxide has a size of 1 to 50 micrometers, and the nanoscale metal oxide has a size of 20 to 800 nanometers;

Preferably, the metal hydroxide is one or a mixture of magnesium hydroxide and aluminum hydroxide;

Preferably, the metal hydroxide has a size of micron or nanometer; further preferably, the micron metal hydroxide has a size of 1 to 50 microns, and the nanoscale metal hydroxide has a size of 20 to 800 nm;

Preferably, the coupling agent is γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, propyl Triethoxysilane, propylpropyltrimethyl (ethoxy) silane, ethylenediamine propyltriethoxysilane, vinyltriacetoxysilane, ethylenediaminepropylmethyldimethoxysilane, ethylene Triethoxysilane, vinyltriethoxysilane, hexamethyldisiloxane, hexamethyldisilazane, isopropyl trioleate acyl titanate, vinyl triisopropoxy One or more of a silane, γ-methacryloxypropyl triisopropoxysilane, a titanate, an aluminate, a zirconate, or a borate;

Preferably, the release agent is one or a combination of stearic acid, zinc stearate, and paraffin wax. Mixture

Preferably, the vulcanizing agent is benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-bis(tert-butyl) One or a mixture of peroxy)hexanes.
A method of preparing a ceramicized silicone rubber according to any one of claims 1 to 7, comprising the steps of:

1) adding the silicone rubber, silica, silicone oil, MQ resin, and/or a part of a coupling agent, and/or a release agent to a kneader according to a ratio, mixing uniformly at 50 to 200 ° C, and mixing Refining the rubber; after the glue is discharged, the film is taken from the open mill and used after being parked for a period of time;

2) adding the high-efficiency flame-retardant catalyst, the nanosheet filler, the mineral powder, the metal oxide or the metal hydroxide, and/or the partial coupling agent to the kneader according to the ratio to mix uniformly with the rubber compound ;

3) removing the material obtained in step 2) from the kneader, cooling and placing it on the open mill to add a vulcanizing agent, mixing uniformly and then lowering the sheet;

Preferably, the high-efficiency flame retardant catalyst is formulated into a master batch with a portion of the silicone rubber and then added to the kneader; or the high-efficiency flame retardant catalyst is supported on the nanoparticles and then added to the kneader.
Use of the ceramized silicone rubber according to any one of claims 1 to 7 or the ceramized silicone rubber prepared by the method of claim 8 for flame retardant materials.
a product comprising the ceramicized silicone rubber of any of claims 1-7 or the ceramicized silicone rubber prepared by the method of claim 8; preferably, the product includes, but is not limited to, cable material, cable jacket, seal Ring, fireproof mud, ablation resistant material, silicone rubber coating, wire, fire door, fireproof board, foam.