Flame-retardant smoke inhibition can ceramic room temperature vulcanized organosilicon sealant and preparation method thereof
Technical field
The present invention relates to the fire protection flame retarding technical fields of organosilicon sealant, more particularly to a kind of making pottery for flame-retardant smoke inhibition
Porcelain room temperature vulcanized organosilicon sealant and preparation method thereof.
Background technique
With the fast development of China's building trade, skyscraper is increasing, and building fire protection class requirement also constantly mentions
It is high.As glass curtain wall or the silicone sealant of aluminium alloy extrusions bonding, higher flame-retardancy requirements are equally also proposed to it.
Currently, general largely using nothings such as aluminium hydroxide, magnesium hydroxide, zinc borates for existing commercial flame-proof silicone sealant
Machine fire retardant can be only achieved flame retardant effect, and on the one hand this method will cause the mechanical properties decrease of sealant, on the other hand
Sealant can be reduced to the adhesive strength of glass curtain wall or aluminium alloy.In addition, flame retardant sealant is acted in the sustained combustion of flame
Under, finally can powdered, follow the string and intensity, cause the adhesive failure of curtain wall, result even in curtain wall from high-altitude large area
It peels off, be easy to cause the secondary injury of ground rescue personnel.
Ceramic silicon rubber is a kind of novel applied fireproofing, have at normal temperature usual silicone rubber elasticity and
Electrical insulating property can be transformed into hard ceramic body under open fire or hot conditions.
In addition to country's report can other than the solid heat vulcanized silicone rubber of ceramic, it is domestic to can ceramic liquid silastic
Also there is relevant report.For example, Chinese invention patent 201310401446.0 discloses a kind of porcelain fire-retardant fireproof silicone seal
Glue and preparation method thereof, by 100 parts of base polymer, 3-40 parts of plasticizer, 5-200 parts of filler, 30-150 parts of Vitrified powder, crosslinking
1-15 parts of agent, 0.1-3 parts of stabilizer, 0.5-3 parts of catalyst, 0.5-3 parts of coupling agent compositions, when preparation, above-mentioned raw materials are added
It is stirred 60-180 minutes and is made in vacuum degree 0.06-0.095MPa, revolving speed 20-600rpm in high velocity dispersators,
The sealant continues to form hard ceramic material under ablation in 500 DEG C or more of high temperature, will not lose fixed and sealing and make
With, play the role of completely cut off flame, smog, fireproof, ensure that the safety of personnel escape in case of fire;In addition, of the invention
The preparation method of the sealant is provided, the preparation method is easy to operate.
Chinese invention patent application 201610884326.4 discloses a kind of organosilicon sealant of ceramic at high temperature,
Including 70-100 parts of matrix resins, 20-80 portions of reinforcing agents, 10-30 parts of silane coupling agents, 1-10 parts of catalyst, 10-50 parts of fillings
Powder, wherein filling powder by glass powder, fire retardant and helps porcelain agent to form, and help porcelain agent be selected from di-iron trioxide, titanium dioxide,
One of antimony oxide, silicon carbide, mica powder, magnesium phosphate and diatomite are a variety of.
Chinese invention patent application 201510359220.8 discloses a kind of Flame-retardant ceramic silicone rubber, by following parts by weight
Several raw materials are made: 100 parts of methyl vinyl silicone rubber, 30~50 parts of reinforcing agent, 5~15 parts of constitution controller, silane coupled
0.1~5 part of agent, 1~50 part of ceramic filler, 1~50 part of zinc borate, 1~50 part of zinc oxide, 1~50 part of talcum powder, platinum complexing
Object is 10 in terms of platinum quality-6~1 part and 0.1~0.5 part of inner pattern releasing agent applicable;The flame retardant rating of the silastic material reaches UL94V-0 grades,
The characteristic that rubber is kept under room temperature, when high temperature can ceramic form hard ceramic layer, and ceramic layer has certain intensity, energy
Certain impact force is born, can guarantee that product continues to work normally in a fire.
Chinese invention patent application 201610996576.7 discloses a kind of ceramic fire resisting silicon that can be used for medium temperature vulcanization
Rubber and preparation method thereof.The rubber include 100 parts of methyl vinyl silicone rubber, 10-40 parts of white carbon black, 9-20 parts of aluminium oxide,
5-10 parts of boric acid, 30-50 parts of Vitrified powder, 0.25-1.5 parts of surface treating agent, 0.5-2 parts of crosslinking agent, chloroplatinic acid are with the quality of platinum
It counts (20-60) × 10-6Part, 1-9 parts of delayer, this silicon rubber do not use peroxide vulcanizing agent, can be at medium temperature (80 DEG C of <)
Vulcanization.Such rubber product does not use peroxide vulcanizing agent, can vulcanize at medium temperature (80 DEG C of <), greatly economize on resources,
Hard, fine and close ceramic product can be formed after combustion test, have flame retardant property good, the features such as excellent insulating property.
But a variety of Ceramic silicon rubbers of the above-mentioned prior art do not fully consider Ceramic silicon rubber in formula design aspect
Adhesive property, do not account for especially after its ceramic gained ablation resultant with by the viscous of viscous substrate (such as glass or aluminium alloy)
Connecing property, only itself can ceramic, be usually used in the fields such as fireproof cable.And as a kind of fire proof construction bonding agent, silicon rubber
Glue not only need itself can ceramic, but also silicon rubber ablation products therefrom is especially needed and is closed by viscous substrate such as glass or aluminium
Gold has relatively good adhesive strength, will be clearly separated phenomenon between glued glass after otherwise burning, and then lead to glass
Glass falls off.Therefore, the Ceramic silicon rubber of the prior art still has many skills as fire prevention organosilicon sealant for building
Deficiency in art.
Summary of the invention
The present invention can only be realized for existing organosilicon sealant itself can occur ceramic, and ablation obtained produces
Object cannot be chemically reacted with glued substrate (such as glass or aluminium alloy), can not be formed firm bonding interface, be not achieved
The problem of purpose for preventing glass curtain wall from falling off, provide a kind of flame-retardant smoke inhibition can ceramic room temperature vulcanized organosilicon sealant and
Preparation method, the organosilicon sealant at high temperature ablation can get compact structure, the high ceramic product of porcelain intensity, with
Substrate is completely embedded, and has the function of flame-retardant smoke inhibition.
To flame-proof fluid sealant for construction in the prior art during high temperature or flame combustion, with the glass of sealing glue sticking
For curtain wall after high-temp combustion the problem of occurrence of large-area peeling, the present invention prepares the ceramic presoma of siliceous-boron covalent bond, makes
The ablation resultant for obtaining Ceramic silicon rubber can be chemically reacted with glued substrate (such as glass, aluminium alloy), in turn
Siliceous-boron-aluminium key reaction product is generated at bonding interface, so that can obtain between glass and glass after high temperature ablation
Than interfacial adhesion strength higher before sealant ablation, fabulous adhesive effect is kept, is effectively prevented the big face of glass curtain wall
Product is peeled off.
Purpose to realize the present invention, the technical scheme adopted by the invention is as follows:
Flame-retardant smoke inhibition can ceramic room temperature vulcanized organosilicon sealant, be made of the raw material of following mass percentage:
Silicon rubber 40~70%, reinforcing agent 5~30%, porcelain filler 10~40%, fluxing agent 3~10%, anti-flaming smoke-inhibiting agent 1~5%,
Coupling agent 1~10%, catalyst 1~5%, crosslinking agent 1~10%;
The silicon rubber is α, and alpha, omega-dihydroxy polydimethyl siloxane, trimethoxy block dimethyl silicone polymer, methyl
Dimethoxy blocks one of dimethyl silicone polymer or a variety of;
The fluxing agent is the one or more of antifungin, line borate and barium metaborate;
The reinforcing agent is one of nanometer calcium carbonate, precipitated silica and gas-phase silica or a variety of;
The porcelain filler is hectorite (lithium magnesium silicate), pyrophillite (hydrous alumino silicates), serpentine (aqueous magnesium silicic acid
Salt) and one of aluminium-magnesium silicate or a variety of;
The anti-flaming smoke-inhibiting agent is one or more in nano molybdenum disulfide and ammonium dihydrogen phosphate;
The catalyst is tin dilaurate dioctyl tin, dibutyltin diacetate, stannous octoate and two neodecanoic acid dimethyl
One of tin is a variety of;
The silane coupling agent is gamma-aminopropyl-triethoxy-silane, γ-glycidyl ether oxygen propyl trimethoxy silicon
Alkane, 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane, mercaptopropyltriethoxysilane and 3- isocyanate group propyl three
It is one or more in methoxy silane;
The crosslinking agent is one kind of ethyl orthosilicate, methyl tributanoximo silane and vinyl tributyl ketoximyl silane
Or it is a variety of.
To further realize the object of the invention, it is preferable that the viscosity of the silicon rubber is 200~300000mPas.
Preferably, the partial size of the fluxing agent is 5~200 μm.
Preferably, the specific surface area of the precipitated silica is 50~100m2·g-1。
Preferably, the specific surface area of the gas-phase silica is 200~400m2·g-1。
The flame-retardant smoke inhibition can ceramic room temperature vulcanized organosilicon sealant preparation method, include the following steps:
1) fluxing agent and porcelain filler are stirred to fluxing agent surface layer at a temperature of 500~900 DEG C and are melted, and adhered to
Part porcelain filler forms between fluxing agent and porcelain filler and contains silicon-boron covalent bond ceramic presoma;
2) kneading is added to by silicon rubber, reinforcing agent, containing silicon-boron covalent bond ceramic presoma, anti-flaming smoke-inhibiting agent
In machine, controlled at 110~160 DEG C, vacuum degree is 0.05~0.10MPa, 300~600rmin of revolving speed-1, it is mixed,
It is dehydrated mixture, 30~40 DEG C is cooled to, obtains base-material;
3) base-material is mixed with crosslinking agent, catalyst and silane coupling agent, control vacuum degree be 0.05~
0.10MPa, 200~500rmin of revolving speed-1, stir evenly, obtain unvulcanized sealant;
4) the unvulcanized sealant is vulcanized in air, vulcanization time is 1~5 day, obtains room temperature vulcanization
Organosilicon sealant.
Preferably, fluxing agent described in step 1) and porcelain filler are stirred at a temperature of 500~900 DEG C to fluxing agent
The time of surface layer melting is 1~3h, 30~80rmin of mixing speed-1。
Preferably, the time of mixing described in step 2) is 90~240min;It is stirred evenly described in step 3)
Time is 30~60min;Mixing described in step 3) is carried out in planetary mixer.
Preferably, the temperature of vulcanization described in step 4) is 20~40 DEG C, relative humidity 50~80%.
Preferably, the resulting room temperature vulcanized organosilicon sealant of step 4) in 800~900 DEG C of Muffle furnace porcelainization 1~
Ceramic body is made in 3h, furnace cooling.
Compared with the existing technology, the invention has the advantages that and the utility model has the advantages that
Flame-retardant smoke inhibition can ceramic room temperature vulcanization sealant mechanical property and adhesive property it is excellent, combustion process smoke density
Low, flame-retardant smoke inhibition effect is good.The preparation process of sealant is simple, and sealant can be achieved between glass after high temperature ablation
High strength bonding.Sealant will form hard ceramic body, and the SiO in ceramic body and glass after refractory ceramics2Or
The Al of aluminum alloy surface2O3It is chemically reacted in interface, siliceous-boron-aluminium key reaction product is formed, so that glass after porcelain
Adhesive strength between glass is substantially more than the adhesive strength between porcelain front glass, effectively prevents glass curtain wall after fire
Adhesive failure prevents glass from peeling off from high-altitude, reduces the generation of secondary injury.
Specific embodiment
Below in conjunction with specific embodiment, the features of the present invention and advantage are further illustrated, but the embodiment is only used for
Advantage of the invention is embodied, the range being not intended to restrict the invention.
Embodiment 1
By mass percentage, flame-retardant smoke inhibition can ceramic room temperature curing sealant raw material components proportion are as follows:
When preparation, line borate and hectorite are added in crucible, are stirred 1h, mixing speed at a temperature of 600 DEG C
50r·min-1, so that line borate surface layer melts, and adhesion section hectorite, formation contains silicon-boron covalent bond ceramic forerunner
Body.It is respectively the α of 1500 and 200000mPas, alpha, omega-dihydroxy polydimethyl siloxane 6:1 in mass ratio by viscosity at 25 DEG C
Mixing, is added in kneader, and gas-phase silica is then added, contains silicon-ceramic presoma of boron covalent bond, curing
Molybdenum, 110 DEG C of set temperature, vacuum degree 0.05MPa, revolving speed 300rmin-1, 240min is blended, is dehydrated raw material sufficiently, it is cold
But to 30~40 DEG C, base-material is obtained;Base-material is added in planetary mixer, ethyl orthosilicate, tin dilaurate dioctyl are added
Tin and gamma-aminopropyl-triethoxy-silane, vacuum degree 0.05MPa, in 400rmin-130min is stirred under revolving speed, is obtained not
The organosilicon sealant of vulcanization vulcanizes sealant 5 days at 25 DEG C, relative humidity 55%, the ablation 1h in 900 DEG C of Muffle furnaces,
Obtain flame-retardant smoke inhibition can ceramic room temperature vulcanized organosilicon sealant;Can ceramic room temperature vulcanized organosilicon sealant in height
Physical property difference before and after warm ablation is as shown in Tables 1 and 2.
Embodiment 2
By mass percentage, flame-retardant smoke inhibition can ceramic room temperature curing sealant raw material components proportion are as follows:
When preparation, antifungin and pyrophillite are added in crucible, are stirred 3h, mixing speed at a temperature of 900 DEG C
80r·min-1, so that antifungin surface layer melts, and adhesion section pyrophillite, formation contains silicon-boron covalent bond ceramic forerunner
Body.It is respectively the α of 200 and 20000mPas by the viscosity at 25 DEG C, alpha, omega-dihydroxy polydimethyl siloxane is according to mass ratio
4:1 mixing, is added in kneader, then adds precipitated silica, containing silicon-boron covalent bond ceramic presoma, two sulphur
Change molybdenum, 160 DEG C of set temperature, vacuum degree 0.05MPa, revolving speed 400rmin-1, 180min is blended, is dehydrated raw material sufficiently,
30~40 DEG C are cooled to, base-material is obtained;Base-material is added in planetary mixer, methyl tributanoximo silane, two vinegar are added
Sour dibutyl tin and γ-glycidyl ether oxygen propyl trimethoxy silicane, control vacuum degree is 0.05MPa, in 300rmin-1
60min is stirred under revolving speed, obtains unvulcanized organosilicon sealant, sealant is vulcanized 5 days at 35 DEG C, relative humidity
55%, the then ablation 1h in 900 DEG C of Muffle furnaces, obtain flame-retardant smoke inhibition can ceramic room temperature vulcanized organosilicon sealant, can
Physical property difference of the room temperature vulcanized organosilicon sealant of ceramic before and after high temperature ablation is as shown in Tables 1 and 2.
Embodiment 3
By mass percentage, flame-retardant smoke inhibition can ceramic room temperature curing sealant raw material components proportion are as follows:
When preparation, barium metaborate and hectorite are added in crucible, are stirred 3h, mixing speed at a temperature of 700 DEG C
80r·min-1, so that barium metaborate surface layer melts, and adhesion section hectorite, before being formed containing silicon-boron covalent bond ceramic
Drive body.It is respectively the α of 2000 and 100000mPas by the viscosity at 25 DEG C, alpha, omega-dihydroxy polydimethyl siloxane presses quality
It is mixed than 5:1, is added in kneader, then adds nanometer calcium carbonate, containing silicon-boron covalent bond ceramic presoma, two
Molybdenum sulfide, 160 DEG C of set temperature, vacuum degree 0.10MPa, revolving speed 400rmin-1, 90min is blended, is dehydrated raw material sufficiently,
30~40 DEG C are cooled to, base-material is obtained;Base-material is added in planetary mixer, methyl tributanoximo silane, octanoic acid are added
Stannous and 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane, control vacuum degree is 0.10MPa, in 300rmin-1Revolving speed
Lower stirring 30min, obtains organosilicon sealant, sealant is vulcanized 4 days at 30 DEG C, relative humidity 80%, then at 900 DEG C
Ablation 1h in Muffle furnace, obtain flame-retardant smoke inhibition can ceramic room temperature vulcanized organosilicon sealant, can ceramic room temperature vulcanization
Physical property difference of the organosilicon sealant before and after high temperature ablation is as shown in Tables 1 and 2.
Embodiment 4
By mass percentage, flame-retardant smoke inhibition can ceramic room temperature curing sealant raw material components proportion are as follows:
When preparation, antifungin and serpentine are added in crucible, are stirred 2h, mixing speed at a temperature of 900 DEG C
80r·min-1, so that antifungin surface layer melts, and adhesion section serpentine, formation contains silicon-boron covalent bond ceramic forerunner
Body.It is respectively the α of 200 and 300000mPas by the viscosity at 25 DEG C, alpha, omega-dihydroxy polydimethyl siloxane is according to mass ratio
5:1 mixing, is added in kneader, then adds precipitated silica, containing silicon-boron covalent bond ceramic presoma, two sulphur
Change molybdenum, 160 DEG C of set temperature, vacuum degree 0.05MPa, revolving speed 400rmin-1, 180min is mixed, is dehydrated raw material sufficiently,
30~40 DEG C are cooled to, base-material is obtained;Base-material is added in planetary mixer, vinyl tributyl ketoximyl silane, two are added
Dioctyltin laurate and mercaptopropyltriethoxysilane, control vacuum degree is 0.05MPa, in 300rmin-1It is stirred under revolving speed
60min obtains unvulcanized organosilicon sealant, sealant is vulcanized 5 days at 25 DEG C, relative humidity 55%, in 800 DEG C of horses
Not ablation 3h in furnace, obtain flame-retardant smoke inhibition can ceramic room temperature vulcanized organosilicon sealant, can the room temperature vulcanization of ceramic have
Physical property of the machine silicone sealant before and after high temperature ablation is as shown in Tables 1 and 2.
Embodiment 5
By mass percentage, flame-retardant smoke inhibition can ceramic room temperature curing sealant raw material components proportion are as follows:
When preparation, barium metaborate and serpentine are added in crucible, are stirred 2h, mixing speed at a temperature of 700 DEG C
80r·min-1, so that barium metaborate surface layer melts, and adhesion section serpentine, before being formed containing silicon-boron covalent bond ceramic
Drive body.It is respectively the α of 500 and 100000mPas by the viscosity at 25 DEG C, alpha, omega-dihydroxy polydimethyl siloxane is in mass ratio
5:1 mixing, is added in kneader, adds gas-phase silica, containing silicon-boron covalent bond ceramic presoma, biphosphate
Ammonium, molybdenum disulfide, 160 DEG C of set temperature, vacuum degree 0.05MPa, revolving speed 400rmin-1, 240min is mixed, raw material is filled
Divide dehydration, is cooled to 30~40 DEG C, obtains base-material;Base-material is added in planetary mixer, methyl tributanoximo silicon is added
Alkane, tin dilaurate dioctyl tin and 3- isocyanate group propyl trimethoxy silicane, control vacuum degree are 0.05MPa,
300r·min-160min is stirred under revolving speed, obtains unvulcanized organosilicon sealant, sealant is vulcanized 1 day at 25 DEG C, phase
To humidity 80%, the ablation 1h in 900 DEG C of Muffle furnaces, obtain flame-retardant smoke inhibition can ceramic room temperature vulcanized organosilicon sealant,
Can ceramic physical property of the room temperature vulcanized organosilicon sealant before and after high temperature ablation it is as shown in Tables 1 and 2.
Embodiment 6
By mass percentage, flame-retardant smoke inhibition can ceramic room temperature curing sealant raw material components proportion are as follows:
When preparation, line borate and aluminium-magnesium silicate are added in crucible, are stirred 2h, mixing speed at a temperature of 600 DEG C
60r·min-1, so that line borate surface layer melts, and adhesion section aluminium-magnesium silicate, before being formed containing silicon-boron covalent bond ceramic
Drive body.The methyl dimethoxy oxygroup sealing end dimethyl silicone polymer that viscosity at 25 DEG C is respectively 3000 and 50000mPas is pressed
Mass ratio 4:1 mixing, is added in kneader, then adds precipitated silica, containing silicon-boron covalent bond ceramic forerunner
Body, molybdenum disulfide, 160 DEG C of set temperature, vacuum degree 0.05MPa, revolving speed 400rmin-1, 180min is blended, fills raw material
Divide dehydration, is cooled to 30~40 DEG C, obtains base-material;Base-material is added in planetary mixer, vinyl tributanoximo is added
Silane, two neodecanoic acid stannous methides and gamma-aminopropyl-triethoxy-silane, control vacuum degree is 0.05MPa, in 500rmin-1
30min is stirred under revolving speed, obtains unvulcanized organosilicon sealant, sealant is vulcanized 5 days at 25 DEG C, relative humidity
55%, the ablation 1h in 900 DEG C of Muffle furnaces, obtain flame-retardant smoke inhibition can ceramic room temperature vulcanized organosilicon sealant, can ceramics
Physical property difference of the room temperature vulcanized organosilicon sealant of change before and after high temperature ablation is as shown in Tables 1 and 2.
In each embodiment of table 1 flame-retardant smoke inhibition can ceramic room temperature vulcanized organosilicon sealant physical property
In each embodiment flame-retardant smoke inhibition can ceramic body obtained by ceramic room temperature vulcanized organosilicon sealant ablation performance
As shown in table 2.
The physical property of ceramic body obtained by ablation in each embodiment of table 2
Compared with prior art Chinese invention patent 201310401446.0 (domestic comparative sample in table), the embodiment of the present invention
In 1~6 can ceramic room temperature vulcanized organosilicon sealant tensile strength and adhesive property it is more excellent, the smoke density of burning
Lower, smoke suppressing effect is fabulous.Importantly, the organosilicon sealant in the present invention after high temperature ablation gained ceramic body due to
It is chemically reacted between the substrate (glass) glued, siliceous-boron-aluminium key reaction product is generated, therefore, even if organosilicon
After sealant is ablated, ablation resultant still can form high-intensitive bonding between glass curtain wall.And in the prior art, have
Machine silicone sealant is after high temperature ablation, although ceramic itself can occur, ablation resultant and glued substrate (such as glass
Glass) it is difficult to form firm adhesive interface layer, it can be fallen off at high temperature so as to cause glass curtain wall, cause personnel and property
Loss.
The present invention is not constrained by above-described embodiment, and others are any to be made without departing from the spirit and principles of the present invention
Changes, modifications, substitutions, combinations, simplifications, should be equivalent alternative, be included within the scope of the present invention.