A kind of fire-proof high-temperature resistant organic silicon rubber material and preparation method thereof
Technical field
Silicon rubber is a kind of macromolecular elastomer with organic trait and inorganic characteristic, and main chain is duplicate-Si-O-
Unit, the side group being connected with silicon atom have the organic groups such as methyl, vinyl, phenyl, and silicon rubber is made to become a kind of typical half
Organic half inorganic polymer has many excellent performances, such as has excellent high temperature resistant low temperature properties, electric insulating quality, weather-proof
Property, chemical corrosion resistance etc..
Background technique
Ceramic organosilicon material is a kind of novel fire-proof high-temperature resistant material, it is led to using organosilicon material as matrix
Addition is crossed at obtained by porcelain filling, auxiliary agent and other function filler.It is General Purpose Rubber state flexible under room temperature state, tool
There is good tensile property, under hot conditions, will be changed by rubbery state with fine and close and hard ceramic body.Pottery
The factors of porcelain organosilicon material mainly include two processes: inorganic evenly dispersed at porcelain filling a) in lower temperature
Inside silicone rubber matrix;B) when being in hot environment, SiO is resolved into along with organosilicon2, opened at the fluxing agent in porcelain filling
Begin to melt, forms liquid phase eutectic at filler edge, make SiO2Eutectic reaction occurs at porcelain filling, it is upper with calcination temperature
Rise the extension with calcination time, SiO2" bridge joint " is formed between particle and filler, to form inorganic ceramic body.
In order to obtain excellent in mechanical performance at room temperature and high temperature resistant, ceramic fire-retardant, fast at porcelain, porcelain body intensity is high
Organosilicon material has carried out a large amount of research both at home and abroad.Such as Li Han heavily fortified point etc. has studied white carbon black type and its dosage to silicon rubber
The three-point bending strength of ceramic body that glue porcelainization is formed, compressive strength, ablation mass loss rate and ablation linear shrinkage shadow
It rings, the results showed that compared to the silicon rubber that precipitated silica is added, the ceramic body that the silicon rubber of fume colloidal silica is formed is added
Three-point bending strength and compressive strength it is higher, ceramic body section is finer and close, and the porcelain effect of silicon rubber is preferable, works as vapor phase method
When white carbon black dosage is 40 parts, the maximum deflection intensity and greatest compressive strength of ceramic body are respectively 14.1 MPa and 6.0 Mpa;
Once great equal using silicon rubber as matrix, it is prepared for having both fire-retardant and fire resistance ceramic SiClx by addition glass powder and fire retardant
Rubber material has studied the influence of fire retardant magnesium hydroxide, aluminium hydroxide and zinc borate to silicon rubber porcelain performance, and 3 kinds fire-retardant
The addition of zinc borate makes silicon rubber have optimal anti-flammability in agent, and the limit oxygen index of sample reaches 48%, vertical combustion etc.
Grade reaches FV-0, and the addition of magnesium hydroxide keeps the ceramic effect of silicon rubber more obvious, the density of porcelain compound, water absorption rate and curved
Qu Qiangdu can respectively reach 1.63344 g/cm3, 9.86% and 6.43 MPa;Lou etc. using silicon rubber as matrix, with ammonium polyphosphate,
Calcium carbonate, mica, glass powder are additive, are prepared for ceramic flame-proof silicon rubber composite material, the results showed that, Ceramic silicon rubber
LOI value be 31.2%, the bending strength for the ceramic residue that 1000 DEG C of whens are formed is 19.7 MPa, with the liter of sintering temperature
Height, hole count are reduced, and form fine and close structure, making forming ceramic at high temperature has excellent mechanical property;The research such as Hamdani
It was found that filling the silicon rubber of the wollastonite surface of ceramic body obtained by ablation at 940 DEG C only has a small amount of crackle, cubical contraction is only
It is 7%, can be observed from stereoscan photograph, there are some biggish wollastonites for the ablation residue surface containing wollastonite
Particle, and there is bridge joint phenomenon between wollastonite particles and the silica of remnants, wollastonite promotes silicon rubber in ablation process
It is middle to form hard layer of charcoal, improve the intensity of ablation residue;M. Imiela etc. explores addition different content carbon fiber
Can the organic silicon composite of ceramics, have studied the characterization and its hot property of ceramic structure in composite material heat treatment process.As a result
The compression strength of the thermal stability and ceramic body that show fiber filled composite materials is improved, when filling 5 parts of carbon fibers,
The compressing force of ceramic body is promoted from 46.7 N to 187.9 N at 1000 DEG C;109401634 A of Chinese patent CN discloses one
Kind can have ceramic organosilicon material of flame-retardant smoke inhibition and preparation method thereof, 4.0 Mpa of tensile strength, elongation at break
313%, flame retardant property meets UL94V-0, and obtained organosilicon material 1 h of ablation in 900 DEG C of Muffle furnaces obtains flame-retardant smoke inhibition
Ceramic body three-point bending strength can reach 9.9 MPa;It is anti-that 107760039 A of Chinese patent CN discloses a kind of ceramic flame-proof
Fiery silicon rubber and preparation method thereof, silicon rubber contain the component of following parts by weight: 100 parts of raw silicon rubber, 10~50 parts of white carbon blacks,
10~100 parts of aluminium hydroxides, 10~50 parts of glass powder with low melting point, 10~100 parts of mica powders, 1~20 part of hydroxy silicon oil, 1~
20 parts of hexamethyldisilazane, 0.1~3 part of platinum compounds and 0.1~5 part of vulcanizing agent, obtained ceramic flame-proof fire resisting silicon rubber
Glue has excellent anti-flammability, can achieve UL94V-0 grades, 4.2 MPa of tensile strength, elongation at break 231%, at high temperature
(600~1200 DEG C) burnings will not generate fusant, dropping, and the ceramic body of hard and compact is formed after burning, and bending strength is
5.3 MPa;106009695 A of Chinese patent CN discloses a kind of preparation method of high-strength ceramic silicon rubber, with sericite in powder
End and glass powder are as filler, raising inorganic filler dispersibility in silicone rubber matrix, with rubber matrix modified by surface
Compression molding is hot-forming after blending, so that the preparation method of high-strength ceramic SiClx rubber is obtained, the addition of modified glass powder
Porcelain compound surface is set to form fine and close glass phase, porcelain compound is fine and close and hard, and ceramic layer intensity is lower after compensating for ablation
Defect.
Since preparation process is simple, simple equipments, ceramic organic silicon rubber can be widely applied to fire-proof high-temperature resistant at present
Material can be used for thermal insulation layer, fireproof and heat-insulating material, cable protection route, while can design different structure according to demand
The ceramic organic silicon rubber of size.Such as United States Patent (USP) US 4269757 is disclosed a kind of can form ceramic body at high temperature
Silicone compositions, it includes siloxane polymer, at porcelain filling and peroxide vulcanizing agent, very when temperature is heated to 500 DEG C
To higher temperature, ceramic material can be changed into, which is with excellent in dimension stability, intensity, electrical isolation capabilities
Light ceramic material, can be used as the insulating coating of conductive materials;Chinese patent CN109467936 A discloses one kind can porcelain
Fire-proof and thermal-insulation foam silicone rubber and preparation method thereof is catalyzed including base rubber, at porcelain filling (1000 mesh glass powder), platinum
Agent, foaming agent, silicone oil and vulcanizing agent, base rubber are the rubber compound of methyl vinyl silicone rubber preparation, are had after foamed silastic ablation
There is good ceramic effect, without face crack, quality is hard, keeps complete foaming structure, guarantees that volume conservation rate is
85% or higher, and there is excellent fire protecting performance;It is organic that 109423202 A of Chinese patent CN discloses a kind of chemical method
Silicon heat-resisting paint and preparation method thereof, using organic siliconresin as filmogen, and with earth silicon material, special ceramics material
Material, trbasic zinc phosphate, fibrous material are filler, and insulation anti-corrosion heat-resisting paint is made, has heat-resisting, oil resistant after Berlin black solidification,
It is moisture-proof, insulation, the features such as adhesive force is strong, better mechanical property, and there is preferable heat insulation, and at high temperature being capable of shape
At fine and close ceramic layer;United States Patent (USP) US 20060155039 discloses a kind of organic silicon composite of fire resisting, including silicon
Oxygen alkane polymer, mica, fluxing agent, the material are suitable for firewall lining, fire barrier, screen, ceiling or lining, structure
Fire prevention, fire resistant doorsets plug-in unit, door-window sealing member, expansion sealing element, the product formed in electric distribution cabinet or cable;Chinese patent CN
The preparation method and its application in wire and cable that 102850805 A disclose a kind of refractory silicon rubber, the rubber bag
100 parts of methyl vinyl silicone rubber are included, 30 80 parts of white carbon black, 9 40 parts of aluminium oxide, 1.5 8 parts of constitution controller, is sintered
35 parts of additive, 0.25 1.5 parts of surface treating agent, 0.5 2 parts of crosslinking agent, such fire-resistant silicon rubber material has ceramics
The features such as body is fine and close, stable structure, and fire resistance is stablized, good insulation preformance;World Intellectual Property Organization patent WO
2017070893 disclose a kind of Ceramic silicon rubber and preparation method thereof, which adds in silicon rubber system
Highly effective flame-retardant catalyst, inorganic mineral powder, nano-metal-oxide and/or metal hydroxides, lamella nano-powder etc.
Filler, gained Ceramic silicon rubber is fire-retardant to meet UL94V-0 requirement, can be at 400 DEG C at porcelain, after stranding when 950 DEG C of fire resistings
Between 180 min do not power off.
Although at present there are many document report can ceramic fire-proof high-temperature resistant organic silicon rubber material, including research
Different matrix, difference are at the use of porcelain filling and applied to different field, but the prepared material come out is in hot environment
Under it is still relatively low at porcelain intensity, when encountering some pendant objects or influenced that the complete of ceramic protective layer can be destroyed by own wt
Property, thus can ceramic fire-proof high-temperature resistant organic silicon rubber material still need to further study.
This patent provides a kind of preparation method of fire-proof high-temperature resistant organic silicon rubber material, by adding in organic silicon rubber
Add metallic tin powder (Sn), at porcelain filling and vulcanizing agent, the organic silicon rubber material of preparation not only has good flame retardant property, simultaneously
The ceramic body formed under the high temperature conditions is finer and close, and preparation process is simple, equipment requirement is low, can be widely applied for preventing fires
Heat-resisting material and field.
Summary of the invention
It is an object of the invention to will be dispersed in organic silicon rubber at porcelain filling including metallic tin powder herein
In matrix, it is cross-linked to form three-dimensional net structure with peroxide vulcanizing agent, prepares the organic silicon rubber material with fire resistant.
It has excellent flame retardant property at room temperature, while the ceramic body changed under the high temperature conditions is finer and close.
The principle of the present invention is: using vinyl organosilicon rubber as matrix, add including metal Sn powder at porcelain filling,
Pass through peroxide vulcanizing agent sulfidization molding.Metal Sn powder therein is a kind of low-melting-point metal, and fusing point only has 231.89 DEG C,
Action principle in its fire resistant organic silicon rubber material of the present invention is: firstly, when encountering high temperature, metallic tin powder first melts
Change, forms liquid phase at other filler edges, organic silicon rubber is made to decompose the SiO generated2With acicular wollastonite etc. is other fills out at porcelain
Material is infiltrated and is bonded, to form dense ceramic body;Secondly, Sn is under high temperature environment, it can be with fire resistant organosilicon
Remaining oxygen reaction in rubber mass, reduces the porosity of the ceramic body changed under hot conditions, improves the density of ceramic body;Most
Afterwards, the SnO that Sn is generated under the high temperature conditions2On the one hand there is fire retardation, on the other hand can be used as solid phase filler, ceramic body
Internal finer and close, intensity is higher.
The contents of the present invention are: a kind of fire-proof high-temperature resistant organic silicon rubber material, it is characterised in that it is by organic silicon rubber, gold
Belong to glass putty, wollastonite, white carbon black and vulcanizing agent to be prepared;Mass percent shared by each raw material are as follows: organic silicon rubber 100
Part, 10~50 parts of metallic tin powder, 150~190 parts of wollastonite, 40 parts of white carbon black, 5 parts of hydroxy silicon oil, 1 part of vulcanizing agent, each raw material
The sum of shared mass percent is 100%.The organic silicon rubber is vinyl organosilicon rubber, and the wollastonite is needle-shaped
Wollastonite, the white carbon black are precipitated silica, and the vulcanizing agent is 2,5- dimethyl -2,5- di-tert-butyl peroxide
Hexane (DBPMH).
Another content of the invention is: a kind of fire-proof high-temperature resistant organic silicon rubber preparation method for material.It is characterized in that comprising
Following steps:
(1) organic silicon rubber, metallic tin powder, white carbon black, hydroxy silicon oil, wollastonite are weighed in proportion, are sequentially added in mixer,
After 105 DEG C of 15 min of mixing, is uniformly mixed after mixing glue is taken out, add 15 min of mixing in mixer, mixing 30 altogether
Min makes to be uniformly mixed between filler and colloid;
(2) mixing glue obtained by step (1) is placed on open mill, a certain amount of vulcanizing agent is added and is uniformly mixed, is prevented
Fiery high-temperature-resisting organic silicon rubber material.
The invention has the advantages that: by organic silicon rubber add including metallic tin powder at porcelain filling and vulcanization
The organic silicon rubber material of agent, preparation not only has good flame retardant property, while the ceramic body formed under the high temperature conditions is more
Densification, and preparation process is simple, equipment requirement is low, can be widely applied for fire-proof high-temperature resistant material and field.
Specific embodiment
Below by specific embodiment, invention is further explained, but the following example is only used for helping to skill of the present invention
The understanding purpose of art, must not be in this, as the further limitation to the scope of the present invention.
For the implementation result for illustrating embodiment, fire-proof high-temperature resistant organic silicon rubber material prepared by embodiment, with 175 DEG C,
10MPa 10 min of hot-forming vulcanization, are put into 180 DEG C of baking ovens, 2 h of post vulcanization for the rubber after vulcanization.The anti-flammability of rubber
The vertical burn test of film can be carried out according to standard ANSI/UL94-2009, sample is having a size of mm × 0.2 200 mm × 50
Mm prolongs longitudinally wound on stick, vertically accommodates;The density of ceramic body is according to GB/T25992-2010 high technology ceramics under hot conditions
Density testing method is tested, and sample is having a size of the mm × 10 of 5 mm × 10 mm.
Specific embodiment 1
(1) 100 parts of vinylsiloxane rubbers are put into mixers, then sequentially add 40 parts of precipitated silicas, 5 parts of hydroxy silicon oils,
50 parts of Sn, 150 parts of acicular wollastonites carry out 15 min of mixing after 105 DEG C of 15 min of mixing again after taking-up, mixing 30 altogether
Min makes to be uniformly mixed between filler and colloid, obtains mixing glue;
(2) obtained mixing glue is placed on open mill, 1 part of 10 min of vulcanizing agent DBPMH room temperature mill is added, is prevented fires
High-temperature-resisting organic silicon rubber material.Specific performance is as shown in table 1.
Specific embodiment 2
(1) 100 parts of vinylsiloxane rubbers are put into mixers, then sequentially add 40 parts of precipitated silicas, 5 parts of hydroxy silicon oils,
40 parts of Sn, 160 parts of acicular wollastonites carry out 15 min of mixing after 105 DEG C of 15 min of mixing again after taking-up, mixing 30 altogether
Min makes to be uniformly mixed between filler and colloid, obtains mixing glue;
(2) will be obtained, mixing glue is placed on open mill, and 1 part of 10 min of vulcanizing agent DBPMH room temperature mill is added, is prevented
Fiery high-temperature-resisting organic silicon rubber material.Specific performance is as shown in table 1.
Specific embodiment 3
(1) 100 parts of vinylsiloxane rubbers are put into mixers, then sequentially add 40 parts of precipitated silicas, 5 parts of hydroxy silicon oils,
30 parts of Sn, 170 parts of acicular wollastonites carry out 15 min of mixing after 105 DEG C of 15 min of mixing again after taking-up, mixing 30 altogether
Min makes to be uniformly mixed between filler and colloid, obtains mixing glue;
(2) obtained rubber compound is placed on open mill, 1 part of 10 min of vulcanizing agent DBPMH room temperature mill is added, prevented
Fiery high-temperature-resisting organic silicon rubber material.Specific performance is as shown in table 1.
Specific embodiment 4
(1) 100 parts of vinylsiloxane rubbers are put into mixers, then sequentially add 40 parts of precipitated silicas, 5 parts of hydroxy silicon oils,
20 parts of Sn, 180 parts of acicular wollastonites carry out 15 min of mixing after 105 DEG C of 15 min of mixing again after taking-up, mixing 30 altogether
Min makes to be uniformly mixed between filler and colloid, obtains mixing glue;
(2) obtained mixing glue is placed on open mill, 1 part of 10 min of vulcanizing agent DBPMH room temperature mill is added, prevented
Fiery high-temperature-resisting organic silicon rubber material.Specific performance is as shown in table 1.
Specific embodiment 5
(1) 100 parts of vinylsiloxane rubbers are put into mixers, then sequentially add 40 parts of precipitated silicas, 5 parts of hydroxy silicon oils,
10 parts of Sn, 190 parts of acicular wollastonites carry out 15 min of mixing after 105 DEG C of 15 min of mixing again after taking-up, mixing 30 altogether
Min makes to be uniformly mixed between filler and colloid, obtains mixing glue;
(2) obtained mixing glue is placed on open mill, 1 part of 10 min of vulcanizing agent DBPMH room temperature mill is added, prevented
Fiery high-temperature-resisting organic silicon rubber material.Specific performance is as shown in table 1.
In order to illustrate advantage of the invention, the present invention will be illustrated with comparative example herein.
Comparative example 1
(1) 100 parts of vinylsiloxane rubbers are put into mixers, then sequentially add 40 parts of precipitated silicas, 5 parts of hydroxy silicon oils,
190 parts of acicular wollastonites carry out 15 min of mixing after 105 DEG C of 15 min of mixing again after taking-up, 30 min of mixing, makes to fill out altogether
Expect and be uniformly mixed between colloid, obtains mixing glue;
(2) obtained mixing glue is placed on open mill, 1 part of 10 min of vulcanizing agent DBPMH room temperature mill is added, prevented
Fiery high-temperature-resisting organic silicon rubber material.Specific performance is as shown in table 1.
Comparative example 2
(1) 100 parts of vinylsiloxane rubbers are put into mixers, then sequentially add 40 parts of precipitated silicas, 5 parts of hydroxy silicon oils,
170 parts of acicular wollastonites carry out 15 min of mixing after 105 DEG C of 15 min of mixing again after taking-up, 30 min of mixing, makes to fill out altogether
Expect and be uniformly mixed between colloid, obtains mixing glue;
(2) obtained mixing glue is placed on open mill, 1 part of 10 min of vulcanizing agent DBPMH room temperature mill is added, prevented
Fiery high-temperature-resisting organic silicon rubber material.Specific performance is as shown in table 1.
Comparative example 3
(1) 100 parts of vinylsiloxane rubbers are put into mixers, then sequentially add 40 parts of precipitated silicas, 5 parts of hydroxy silicon oils,
150 parts of acicular wollastonites carry out 15 min of mixing after 105 DEG C of 15 min of mixing again after taking-up, 30 min of mixing, makes to fill out altogether
Expect and be uniformly mixed between colloid, obtains mixing glue;
(2) obtained mixing glue is placed on open mill, 1 part of 10 min of vulcanizing agent DBPMH room temperature mill is added, prevented
Fiery high-temperature-resisting organic silicon rubber material.Specific performance is as shown in table 1.
Comparative example 4
(1) 100 parts of vinylsiloxane rubbers are put into mixer, then sequentially add 40 parts of precipitated silicas, 5 parts of hydroxy silicon oils,
After 105 DEG C of 15 min of mixing, 15 min of mixing is carried out after taking-up again, 30 min of mixing, makes to mix between filler and colloid altogether
Uniformly, mixing glue is obtained;
(2) obtained mixing glue is placed on open mill, 1 part of 10 min of vulcanizing agent DBPMH room temperature mill is added, is prevented fires
High-temperature-resisting organic silicon rubber material.Specific performance is as shown in table 1.
1 specific embodiment of table and comparative example rubber mass performance comparison
Specific embodiment 1~9 and comparative example 1, which reflect metallic tin powder and wollastonite etc., has fire-proof high-temperature resistant at porcelain filling
The influence of machine silicon rubber, including rubber flame-retarded performance, 1000 DEG C of high temperature at the ceramic volume density after porcelain.From performance parameter table
In as can be seen that when being added without acicular wollastonite and Sn, under high temperature under the conditions of directly resolve into SiO2Powder can not form pottery
Porcelain body, also can not high temperature resistant, do not have flame retardant property;After only adding wollastonite, ceramic body can be formed at high temperature, and
With increasing at porcelain filling, density has rising;When Sn and acicular wollastonite is added simultaneously in proportion, rubber can not only be improved
Flame retardant property, reach VTM-0 level, and be capable of forming fine and close ceramic body, ceramic volume density increased.
Invention is prepared for fire-proof high-temperature resistant rubber mass at porcelain filling including metallic tin powder by adding.For
It prepares fire-proof high-temperature resistant material and provides new method, the organic silicon rubber material of preparation not only has good flame retardant property, simultaneously
The ceramic body formed under the high temperature conditions is finer and close.Fire-proof high-temperature resistant rubber mass prepared by the present invention also has production cost
Low, the environmentally friendly, advantages such as preparation process is simple, equipment requirement is low.
Bound, the bound of section value and technological parameter, the section value of each raw material of the present invention can realize this
Invention, is not listed one by one example here.