CN105419141B - A kind of manufacture method of the excellent insulation material of fire protecting performance - Google Patents
A kind of manufacture method of the excellent insulation material of fire protecting performance Download PDFInfo
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- CN105419141B CN105419141B CN201610049224.0A CN201610049224A CN105419141B CN 105419141 B CN105419141 B CN 105419141B CN 201610049224 A CN201610049224 A CN 201610049224A CN 105419141 B CN105419141 B CN 105419141B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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Abstract
The invention discloses a kind of manufacture method of the excellent insulation material of fire protecting performance, the insulation material includes the compound of graphene, zirconium oxide, aluminum oxide and polystyrene, and its manufacture method comprises the following steps：Prepare graphene；Prepare graphene zirconia alumina composite；Prepare fire-retardant heat insulation compound；Prepare insulation material.The material has better flame resistance and low smoke density compared with prior art, and nontoxic pollution-free, with higher fire-protection rating, meets environmental requirement.
Description
Technical field
The present invention relates to a kind of construction material, more particularly to a kind of insulation material for building.
Background technology
In the art, widely used insulation material is expandable polystyrene.Polystyrene, molecular formula is C8H8, it is main
It is used for foaming, as insulation, heat-insulated, shockproof and packaging material.Foamed polystyrene is shaped to spherical granules, for bubble
Foam, the foam wt is light, and heat-proof quality is good, is added in cement material and is mixed with cement, building light-weight material can be prepared by drying,
With insulation, prevent fires, the performance such as waterproof.But have that inflammable, smoke amount is big, dropping is more due to polystyrene, after burning be in nothing
The features such as setting viscous liquid, burning grade is not high, does not meet the higher requirement of present materials for wall fire-protection rating.In addition,
In the heat-preserving wall that the polystyrene of early stage is prepared with cement mixing, also exist and mix uneven, or moisture in long-time wall
Peeling etc., limits popularization and application of the polystyrene in warming plate caused by being lost in.
In order to preferably manufacture warming plate using polystyrene, play the advantage of its good heat insulating, people have developed by
The compound insulating material that various inorganic or organic material is made after being mixed with polystyrene.At initial stage, protected to improve polystyrene
The fire resistance of warm plate, people add organic fire-retardant into expandable polystyrene and play flame retardant effect.Organic fire-retardant bag
Halogen containing flame-retardant is included, such as HBCD, TDE, deca-BDE, but due to halogen containing flame-retardant burning
When can produce a large amount of smog, do not reach environmental requirement, be unsuitable for its large area and use.
Later, foaminess polyphenyl second was made using expanded graphite as fire retardant in people after it is mixed with polystyrene
Alkene particle, improves anti-flammability, heat insulating ability and intensity after compression molding.Wherein expansible graphite is coated on polyphenyl second as fire retardant
The surface of alkene expanded beads, without organic fire-retardant, this method has preferable effect, but its to the anti-flammability for improving polystyrene
Have the disadvantage, because the fire-retardant principle of expansible graphite is to produce expansion when meeting fire, so that it is fire-retardant to be carbonized, but expanded graphite exists
The skeleton of coating layer can be destroyed in expansion carbonisation, powder phenomenon-tion can be produced；Secondly, micronic dust can be produced during expansion, micro-
Grain and slag-off phenomenon, or even Mars is also produced, national associated safety regulation is not met, there is potential safety hazard.
In addition to the component included in the composite mixed to research with polystyrene, people are also studied in composite
Surface coat one layer of special coating, so as to further enhance its fire resistance.In a kind of polystyrene foam compound heat-insulation
In insulation material, using phenolic resin and expansible graphite, capsule red phosphorus, nano-aluminum hydroxide as coating, by this coating
It is coated in compression molding behind expandable polystyrene particle surface.But, because red phosphorus can generate phosphorus pentoxide in burning,
And the moisture content in the further absorption air of phosphorus pentoxide can be changed into phosphoric acid, corrosion is produced to matrix building materials；In addition, being needed when preparing
After phenolic resin and other mixing materials are stirred in high-speed mixer foamed polystyrene is coated on as coating
Grain, due to the curing characteristics of phenolic resin, in actual production, after the time of preparing slightly is grown, coating easily solidifies blocking, it is impossible to after
It is continuous to use, cause loss too big, improve production cost.
As technology develops, people have developed in another polystyrene foam composite heat insulatant thermal insulation material, using phenolic aldehyde
Or the method that furane resins are combined expandable polystyrene as continuous phase, combine phenolic aldehyde or the good anti-flammability of furane resins
Can and the good heat-insulating property of polystyrene, be a kind of preferable solution, but in actual applications there is also defect, by
It is inadequate in the conjugation of polystyrene, cause its intensity decreases；Due to fire-retardant, the free monomer such as phenol, in production toxicity it is big,
Organic volatile is more, and pollution is brought to environment, influences the health of staff.In a kind of organic expanded polystyrene (EPS) of same type
In insulation material, wherein with vinyl acetate resin as functional skin layer, then flame retardant type polyphenyl second is made in compound addition fire retardant
Alkene.The shortcoming of the material is that polyvinyl acetate must be dissolved into solution using methanol, and because granules of polystyrene is easy to stick
Even, it is necessary to which in stirring, sprinkling ethylene glycol remover can just make polystyrene turn into independent particle；Simultaneously as poly- acetic acid second
It is curable performance that alkene ester, which does not have when heating or adding curing agent, thus the addition of fire retardant is limited, and product exists
Deterioration can be produced when molded, it is impossible to reference to or curing molding；In addition, using poisonous, inflammable methanol, second two during production
Alcohol is volatile, and the health and environment to staff are also adversely affected.
In view of the shortcomings of the prior art, those skilled in the art wish to research and development fire resistance be good, Environmental Safety, cost it is low
Polystyrene compound insulating material and preparation method thereof.
The content of the invention
The invention discloses a kind of manufacture method of the excellent insulation material of fire protecting performance, the material has compared with prior art
There are better flame resistance and low smoke density, nontoxic pollution-free, with higher fire-protection rating, meets environmental requirement.
The manufacture method of the insulation material of the present invention, comprises the following steps：
First, graphene is prepared, is comprised the following steps：
(1) expanded graphite is prepared.Wherein, graphite oxide is placed in crucible first, be then heated to Muffle furnace necessarily
Temperature, crucible is put into after Muffle furnace after held for some time, crucible is taken out, and expanded graphite is made.Wherein, heating muffle stove
The rate of heat addition be preferably 10~15 DEG C/min, Muffle furnace is preferably heated to 1000~1100 DEG C, crucible is in Muffle furnace
Soaking time is preferably 3~5min.
(2) expanded graphite is dispersed in water, ultrasound after addition polystyrene sphere aqueous dispersions, obtained expanded graphite-
Polystyrene composite dispersion liquid；Wherein, the mass ratio of expanded graphite and water is 1:1~1:2, expanded graphite and polystyrene sphere
The mass ratio of aqueous dispersions is 80:1~60:1, the preferred 2h~3h of ultrasonic time；
(3) it on expanded graphite-polystyrene composite dispersion liquid suction filtration to nickel foam, will will be loaded with expanding stone after drying
The nickel foam of ink-polystyrene is placed in the mixed solution of hydrazine hydrate and ammoniacal liquor, and graphene-polystyrene-based ground is taken after reaction
Material；Wherein, the speed of suction filtration is preferably 3~4L/s, preferably 50~60 DEG C of drying temperature, drying time preferably 10~13h, hydration
Hydrazine is 1 with ammoniacal liquor volume ratio:5~1:10, reaction temperature is preferably at 80~85 DEG C；
(4) graphene-polystyrene base material is warming up to 600~650 DEG C in vacuum tube furnace, is incubated 2~3h
After take out, wherein, heating rate is preferably 3~4 DEG C/min, obtains graphene.
2nd, graphene-Zirconia-alumina composite is prepared；
(1) graphene obtained in step one is mixed with aluminic acid ammonia, ball milling is graphene-aluminic acid ammonia composite；Its
In, the mass ratio of graphene and aluminic acid ammonia is preferably 1:1-3:1；Using ball mill to composite ball milling, the rotating speed of ball milling is excellent
Elect 200-280rpm as；
(2) above-mentioned graphene-aluminic acid ammonia composite is heated to 800-950 DEG C, is incubated, cools under nitrogen protection,
Obtain graphene-alumina compound；Wherein it is possible to heated, be incubated and cooled in tube furnace, the heating rate of heating
For 5-10 DEG C/min, soaking time is 2-4h, room temperature is then down to, by the way of Temperature fall.
(3) graphene-alumina compound is mixed with nano zircite, ball milling obtains graphene-zirconium oxide-oxidation
Aluminium composite material；Wherein, the mass ratio of graphene-alumina compound and nano zircite is preferably 3:1-4:1；Ball mill
Rotational speed of ball-mill is preferably 300-350rpm.
3rd, fire-retardant heat insulation compound is prepared；
(1) graphene-Zirconia-alumina composite is made after solution and mixed with polystyrene；Wherein, in stone
In black alkene-Zirconia-alumina aqueous solution, the mass ratio of graphene-Zirconia-alumina and water is 1:20~1:25；Graphite
The mass ratio of alkene-Zirconia-alumina and polystyrene is preferably 1:6~1:8；
(2) phenolic resin and curing agent are added in above-mentioned mixed solution, curing agent is the mixing of water, sulfuric acid and phosphoric acid
Thing；The mass ratio of compound and phenolic resin is 25 in mixed solution:1~28:1；The mass ratio of phenolic resin and curing agent is
3:1~4:1.The mechanical strength of the sheet material of obtained fire-retardant heat insulation plate is not good outside the ratio ranges.The wherein quality hundred of sulfuric acid
It is 97% to divide content, and the weight/mass percentage composition of phosphoric acid is 38%；The mass ratio of water and sulfuric acid is 2:1~3:1；The matter of water and phosphoric acid
Amount is than being 1.5:1~2:1；Obtain fire-retardant heat insulation compound.
4th, fire-retardant heat insulation plate is prepared；
(1) melt-mixed material is obtained in the first double screw extruder；Add mixture into the first double screw extruder
In, the compound melted.Wherein, the working region in the first double screw extruder is divided into seven sections：First to the 3rd
Section is heating melt zone, and the 4th to the 5th section is high pressure-temperature mixing for melting pressurization mixing area, the 6th to SECTOR-SEVEN section
Area.Wherein, 120 DEG C of the first zone temperatures；Second 150 DEG C of section；3rd 170 DEG C of section, pressure 3Mpa；4th zone temperatures
190 DEG C, pressure 8MPa；5th 210 DEG C of zone temperatures, pressure 11Mpa；6th 220 DEG C of zone temperatures, pressure 18MPa, SECTOR-SEVEN
200 DEG C of Duan Wendu, pressure 22Mpa.
(2) in the SECTOR-SEVEN section end of the first screw extruder, supercritical carbon dioxide is added in the compound of melting
Fluid；The mass ratio of supercritical carbon dioxide fluid and compound is about 80:1~90:1, filling pressure 24MPa.
(3) compound of melting is subjected to part mixing；First double screw extruder is exported and the second screw extruder the
Homogenizing barrier is provided between nine sections and release is managed.The Section Eight Duan Yu nine that partial blend passes through the second screw extruder
Squeezing passage between section enters the front end of Section Eight section, after the 9th section is entered by the screw extruding of Section Eight section；Portion
Divide compound to enter the 9th section of the second screw extruder by being homogenized barrier and release pipe, advance through screw extruding；So as to
Realize that part is kneaded.Wherein, the mass ratio into Section Eight section and the melt-mixed material of the 9th section is 1:1.
(4) mixture particle is obtained by the second screw machine extruder；Second screw extruder is divided into five sections, point
It is not Section Eight Duan Zhi Twelve-sections.The sections of Section Eight Duan Zhi ten are cooling decompression area；11st section is dynamic mixing
Area, Twelve-section is static mixing area.Wherein, 150 DEG C of temperature of Section Eight section, pressure 16MPa, the 9th 70 DEG C of zone temperatures,
Pressure 20MPa, the tenth 50 DEG C of zone temperatures, pressure 15MPa；11st 40 DEG C of zone temperatures, pressure 13MPa；Twelve-section
80 DEG C of temperature, pressure 10Mpa.Extrusion die, 90 DEG C of the temperature in die head region, pressure 8Mpa are installed in Twelve-section end.
(5) fire-retardant heat insulation plate is made of compound particles.
According to another implementation of the invention, the present invention with compound particles before fire-retardant heat insulation plate is made, first
Compound particles are mixed with a coating, stirring makes coating be evenly applied to particle surface, then the mixture that will be coated with coating
Fire-retardant heat insulation plate is made in particle, because the coating has good fire-retardant, low cigarette effect, therefore, further increases fire-retardant guarantor
The fire-protection rating of warm plate, and meet environmental requirement.
The Flame-retardant low-smoke coating of the present invention, including following components in parts by weight：Aluminium hydroxide 15~25, zirconium oxide 35~
45th, graphite powder 3~7, laterite 15~25, miberal powder 4~6, ceramic powder 8~12.
Preparing the method for the Flame-retardant low-smoke coating is, by the aluminium hydroxide of said components, zirconium oxide, graphite powder, laterite, ore deposit
Powder, ceramic powder, polystyrene, epoxy resin, dimethylaminopropylamine mixing, obtain melting mixing by double screw extruder and apply
Material, extrusion, tabletting is air-cooled, is milled, and sieving obtains Flame-retardant low-smoke coating.Then, compound particles and the coating, surface are lived
Property agent mixing, stirring, coating is evenly applied to particle surface, fire-retardant guarantor finally be made with the compound particles for being coated with coating
Warm plate.
Embodiment
The manufacture method of fire-retardant heat insulation plate disclosed by the invention, comprises the following steps：
First, graphene is prepared, is comprised the following steps：
(1) expanded graphite is prepared.Wherein, graphite oxide is placed in crucible first, be then heated to Muffle furnace necessarily
Temperature, crucible is put into after Muffle furnace after held for some time, crucible is taken out, and expanded graphite is made.Wherein, heating muffle stove
The rate of heat addition be preferably 10~15 DEG C/min, Muffle furnace is preferably heated to 1000~1100 DEG C, crucible is in Muffle furnace
Soaking time is preferably 3~5min.
(2) expanded graphite is dispersed in water, ultrasound after addition polystyrene sphere aqueous dispersions, obtained expanded graphite-
Polystyrene composite dispersion liquid；Wherein, the mass ratio of expanded graphite and water is 1:1~1:2, expanded graphite and polystyrene sphere
The mass ratio of aqueous dispersions is 80:1~60:1, the preferred 2h~3h of ultrasonic time；
(3) it on expanded graphite-polystyrene composite dispersion liquid suction filtration to nickel foam, will will be loaded with expanding stone after drying
The nickel foam of ink-polystyrene is placed in the mixed solution of hydrazine hydrate and ammoniacal liquor, and graphene-polystyrene-based ground is taken after reaction
Material；Wherein, the speed of suction filtration is preferably 3~4L/s, preferably 50~60 DEG C of drying temperature, drying time preferably 10~13h, hydration
Hydrazine is 1 with ammoniacal liquor volume ratio:5~1:10, reaction temperature is preferably at 80~85 DEG C；
(4) graphene-polystyrene base material is warming up to 600~650 DEG C in vacuum tube furnace, is incubated 2~3h
After take out, wherein, heating rate is preferably 3~4 DEG C/min, obtains graphene.
Grapheme material is that a kind of single layer of carbon atom passes through sp2Hydridization it is tightly packed have bi-dimensional cellular shape structure
New material, thickness only 0.335nm.Since single-layer graphene being prepared from the scientist of Univ Manchester UK in 2004,
Graphene has received the extensive concern of scientific circles and industrial quarters.Graphene has excellent chemical stability and thermodynamics steady
Qualitative and outstanding physical property and mechanical performance.
The present invention adds graphene in fire-retardant heat insulation plate, and because graphite is natural inert substance, fusing point is up to 3600
Degree Celsius, powdered graphite can be covered on combustion boundary, play a part of completely cutting off air, and graphene has bigger ratio table
Area, a small amount of addition can achieve the goal.Graphene is combined with polystyrene foaming granule, once it is ignited, polystyrene
Combustion gas volatilizees, and graphene can then form one layer of fine and close film, be covered on combustion boundary and completely cut off air, play
Extraordinary flame retardant effect.Reach A grades of requirements of fire prevention.And the fire-retardant heat insulation plate intensity being made also is significantly improved.
2nd, graphene-Zirconia-alumina composite is prepared；
(1) graphene obtained in step one is mixed with aluminic acid ammonia, ball milling is graphene-aluminic acid ammonia composite；Its
In, the mass ratio of graphene and aluminic acid ammonia is preferably 1:1-3:1；Using ball mill to composite ball milling, the rotating speed of ball milling is excellent
Elect 200-280rpm as；
(2) above-mentioned graphene-aluminic acid ammonia composite is heated to 800-950 DEG C, is incubated, cools under nitrogen protection,
Obtain graphene-alumina compound；Wherein it is possible to heated, be incubated and cooled in tube furnace, the heating rate of heating
For 5-10 DEG C/min, soaking time is 2-4h, room temperature is then down to, by the way of Temperature fall.
(3) graphene-alumina compound is mixed with nano zircite, ball milling obtains graphene-zirconium oxide-oxidation
Aluminium composite material；Wherein, the mass ratio of graphene-alumina compound and nano zircite is preferably 3:1-4:1；Ball mill
Rotational speed of ball-mill is preferably 300-350rpm.
Zirconium oxide chemical property torpescence, and the property with high-melting-point and low thermal coefficient of expansion, make it important
Exotic material.Its relative density 5.6~6.9, because the high temeperature chemistry property of zirconium oxide in itself is stable, corrosion-resistant, anti-oxidant,
It is anti-thermal shock, non-volatile, pollution-free, it is a kind of good refractory material.
Aluminum oxide possesses fire resistance, while the characteristics of having porous, high degree of dispersion, there is very big surface area, its is micro-
Pore size distribution is uniform, and proper pore size, bulk density is small, good mechanical property, steady with good absorption property and excellent heat
It is qualitative.
The present invention in order that graphene and zirconium oxide preferably play its flame-retarding characteristic, using aluminum oxide possess it is many
Permeability and adsorptivity, give full play to the advantage of three with reference to after so that the Flame-retardant low-smoke warming plate being finally made has good
Fire protecting performance, meets fire protection requirement；And flue gas is very low, environmental pollution reduces significantly, meets environmental requirement.
In the present invention, it is preferred to which the mass ratio of graphene and aluminic acid ammonia is 1:1-3:1；Graphene-alumina compound with
The mass ratio of nano zircite is 3:1-4:1；It is possible thereby to each in graphene, zirconium oxide, alumina composite material is matched,
So that the flame retardant effect for the fire-retardant heat insulation plate being eventually fabricated reaches most preferably.
3rd, fire-retardant heat insulation compound is prepared；
(1) graphene-Zirconia-alumina composite is made after solution and mixed with polystyrene；Wherein, in stone
In black alkene-Zirconia-alumina aqueous solution, the mass ratio of graphene-Zirconia-alumina and water is 1:20~1:25；Graphite
The mass ratio of alkene-Zirconia-alumina and polystyrene is preferably 1:6~1:8；Less than the ratio, anti-flammability can not increased
Heat insulation effect can decline to a great extent in the case of energy；More than the ratio, fire protecting performance will be a greater impact, it is impossible to reach that fire prevention will
Ask.
(2) phenolic resin and curing agent are added in above-mentioned mixed solution, curing agent is the mixing of water, sulfuric acid and phosphoric acid
Thing；The mass ratio of mixed solution and phenolic resin is 25:1~28:1；The mass ratio of phenolic resin and curing agent is 3:1~4:1.
The mechanical strength of the sheet material of obtained fire-retardant heat insulation plate is not good outside the ratio ranges.The weight/mass percentage composition of wherein sulfuric acid is
97%, the weight/mass percentage composition of phosphoric acid is 38%；The mass ratio of water and sulfuric acid is 2:1~3:1；The mass ratio of water and phosphoric acid is
1.5:1~2:1；Obtain fire-retardant heat insulation compound.
4th, fire-retardant heat insulation plate is prepared；
(1) melt-mixed material is obtained in the first double screw extruder；Add mixture into the first double screw extruder
In, the compound melted.Wherein, the working region in the first double screw extruder is divided into seven sections：First to the 3rd
Section is heating melt zone, and the 4th to the 5th section is high pressure-temperature mixing for melting pressurization mixing area, the 6th to SECTOR-SEVEN section
Area.Wherein, 120~130 DEG C of the first zone temperatures；Second 150~160 DEG C of section；3rd 170~180 DEG C of section, pressure 3~
4Mpa；4th 190~200 DEG C of zone temperatures, 8~9MPa of pressure；5th 210~220 DEG C of zone temperatures, 11~12Mpa of pressure；
6th 220~230 DEG C of zone temperatures, 18~19MPa of pressure, SECTOR-SEVEN 200~210 DEG C of temperature of section, 22~23Mpa of pressure.By
Include the component differed with conventional flame retardant warming plate, therefore each section in an extruder in the composite of the present invention
Temperature, pressure must also have the innovation of adaptability, also obtain the optimal warming plate material of performance.
(2) in the SECTOR-SEVEN section end of the first screw extruder, supercritical carbon dioxide is added in the compound of melting
Fluid；The mass ratio of supercritical carbon dioxide fluid and compound is about 80:1~90:1, filling pressure 24MPa.
(3) compound of melting is subjected to part mixing；First double screw extruder is exported and the second screw extruder the
Homogenizing barrier is provided between nine sections and release is managed.The Section Eight Duan Yu nine that partial blend passes through the second screw extruder
Squeezing passage between section enters the front end of Section Eight section, after the 9th section is entered by the screw extruding of Section Eight section；Portion
Divide compound to enter the 9th section of the second screw extruder by being homogenized barrier and release pipe, advance through screw extruding；So as to
Realize that part is kneaded.Wherein, the mass ratio into Section Eight section and the melt-mixed material of the 9th section is 1:1.
(4) mixture particle is obtained by the second screw machine extruder；Second screw extruder is divided into five sections, point
It is not Section Eight Duan Zhi Twelve-sections.The sections of Section Eight Duan Zhi ten are cooling decompression area；11st section is dynamic mixing
Area, Twelve-section is static mixing area.Wherein, 150~160 DEG C of temperature of Section Eight section, 16~17MPa of pressure, the 9th section
70~80 DEG C of temperature, 20~21MPa of pressure, the tenth 50~60 DEG C of zone temperatures, 15~16MPa of pressure；11st zone temperatures
40~50 DEG C, 13~14MPa of pressure；80~90 DEG C of Twelve-section temperature, 10~11Mpa of pressure.In Twelve-section end
Extrusion die, 90~100 DEG C of the temperature in die head region, 8~9Mpa of pressure are installed.Temperature disclosed above, pressure limit with it is existing
There is technology different, its special above-mentioned composite for being adapted to the present invention obtains the optimal warming plate material of performance suitable for manufacture.
For some special buildings with requirements at the higher level, the present invention fire-retardant heat insulation plate can be made of compound particles
Before, first compound particles are mixed with a coating, coating is coated on particle surface.The Flame-retardant low-smoke coating of the present invention, bag
Include following components in parts by weight：Aluminium hydroxide 15~25, zirconium oxide 35~45, graphite powder 3~7, laterite 15~25, miberal powder 4~
6th, ceramic powder 8~12.It is preferred that, including following components in parts by weight：Aluminium hydroxide 20, zirconium oxide 40, graphite powder 5, laterite 20,
Miberal powder 5, ceramic powder 10.
Preparing the method for the Flame-retardant low-smoke coating is, by the aluminium hydroxide of said components, zirconium oxide, graphite powder, laterite, ore deposit
Powder, ceramic powder, polystyrene, epoxy resin, dimethylaminopropylamine mixing, obtain melting mixing by double screw extruder and apply
Material, extrusion, tabletting is air-cooled, is milled, and sieving obtains coating.
Warming plate material is mixed with coating, surfactant, stirring is uniform to coating, the matter of warming plate material and coating
Amount is than being 1:1.2~1:1.4, obtain wrapping up warming plate granular materials, then compression molding.Surfactant is preferably silicone.
The present invention is directed to above-mentioned polystyrene flame-retardant thermal insulation material, for the building demand of special dimension, develops above-mentioned
Composite coating, the coating material as polystyrene foam particles surface, further to solve the easy of Polystyrene heat insulation material
Fire, melt the problems such as drop, high smoke.The coating can further improve the resistance to temp effect of insulation material, using simple, can be direct
Base material is sprayed at, favorable anti-corrosion effect, cost is low.
(5) fire-retardant heat insulation plate is made of compound particles.
Embodiment 1：
The manufacture method of the fire-retardant heat insulation plate of the embodiment is as follows：
First, graphene is prepared, is comprised the following steps：
(1) expanded graphite is prepared.Wherein, graphite oxide is placed in crucible first, be then heated to Muffle furnace necessarily
Temperature, crucible is put into after Muffle furnace after held for some time, crucible is taken out, and expanded graphite is made.Wherein, heating muffle stove
The rate of heat addition be 10 DEG C/min, Muffle furnace is heated to 1000 DEG C, soaking time of the crucible in Muffle furnace is 3min.
(2) expanded graphite is dispersed in water, ultrasound after addition polystyrene sphere aqueous dispersions, obtained expanded graphite-
Polystyrene composite dispersion liquid；Wherein, the mass ratio of expanded graphite and water is 1:2, expanded graphite and polystyrene sphere moisture
The mass ratio of dispersion liquid is 60:1, ultrasonic time 2.2h；
(3) it on expanded graphite-polystyrene composite dispersion liquid suction filtration to nickel foam, will will be loaded with expanding stone after drying
The nickel foam of ink-polystyrene is placed in the mixed solution of hydrazine hydrate and ammoniacal liquor, and graphene-polystyrene-based ground is taken after reaction
Material；Wherein, the speed of suction filtration is 3L/s, 60 DEG C of drying temperature, and drying time 11h, hydrazine hydrate and ammoniacal liquor volume ratio are 1:6, instead
Temperature is answered at 80 DEG C；
(4) taken out after graphene-polystyrene base material being warming up into 650 DEG C, insulation 2h in vacuum tube furnace,
Obtain graphene.
2nd, graphene-Zirconia-alumina composite is prepared；
(1) graphene obtained in step one is mixed with aluminic acid ammonia, ball milling is graphene-aluminic acid ammonia composite；Its
In, the mass ratio of graphene and aluminic acid ammonia is 1:1；
(2) above-mentioned graphene-aluminic acid ammonia composite is heated to 900 DEG C, is incubated, cools under nitrogen protection, obtain
Graphene-alumina compound；Heated, be incubated and cooled in tube furnace, the heating rate of heating is 8 DEG C/min, is protected
The warm time is 2h, and then Temperature fall is down to room temperature.
(3) graphene-alumina compound is mixed with nano zircite, ball milling obtains graphene-zirconium oxide-oxidation
Aluminium composite material；Wherein, the mass ratio of graphene-alumina compound and nano zircite is 3:1；The rotational speed of ball-mill of ball mill
For 350rpm.
3rd, fire-retardant heat insulation compound is prepared；
(1) graphene-Zirconia-alumina composite is made after solution and mixed with polystyrene；Wherein, in stone
In black alkene-Zirconia-alumina aqueous solution, the mass ratio of graphene-Zirconia-alumina and water is 1:20；Graphene-oxidation
The mass ratio of zirconium-aluminum oxide and polystyrene is 1:6；
(2) phenolic resin and curing agent are added in above-mentioned mixed solution, the mass ratio of mixed solution and phenolic resin is
25:1；The mass ratio of phenolic resin and curing agent is 4:1.
4th, fire-retardant heat insulation plate is prepared；
(1) melt-mixed material is obtained in the first double screw extruder；Add mixture into the first double screw extruder
In, the compound melted.Wherein, the working region in the first double screw extruder is divided into seven sections：First section temperature
120 DEG C of degree；Second 150 DEG C of section；3rd 170 DEG C of section, pressure 3Mpa；4th 190 DEG C of zone temperatures, pressure 8MPa；5th
210 DEG C of zone temperatures, pressure 11Mpa；6th 220 DEG C of zone temperatures, pressure 18MPa, SECTOR-SEVEN 200 DEG C of temperature of section, pressure
22Mpa。
(2) in the SECTOR-SEVEN section end of the first screw extruder, supercritical carbon dioxide is added in the compound of melting
Fluid；The mass ratio of supercritical carbon dioxide fluid and compound is about 90:1, filling pressure 24MPa.
(3) compound of melting is subjected to part mixing by the Section Eight section of the second screw machine and the 9th section respectively；
Mass ratio into Section Eight section and the melt-mixed material of the 9th section is 1:1.
(4) mixture particle is obtained by the second screw machine extruder；Second screw extruder is divided into five sections, the
Eight 150 DEG C of zone temperatures, pressure 16MPa, the 9th 70 DEG C of zone temperatures, pressure 20MPa, the tenth 50 DEG C of zone temperatures, pressure
15MPa；11st 40 DEG C of zone temperatures, pressure 13MPa；80 DEG C of Twelve-section temperature, pressure 10Mpa.Twelve-section end
90 DEG C of the temperature in the extrusion die region at end, pressure 9Mpa.
(5) fire-retardant heat insulation plate is made of compound particles.
Embodiment 2：
The manufacture method of the fire-retardant heat insulation plate of the present embodiment is as follows：
First, graphene is prepared, is comprised the following steps：
(1) graphite oxide is placed in crucible, Muffle furnace is heated to 1100,15 DEG C/min of the rate of heat addition, crucible is put
Enter and be incubated after Muffle furnace after 5min, crucible is taken out, expanded graphite is made.
(2) expanded graphite is dispersed in water, the mass ratio of expanded graphite and water is 1:2, add polystyrene sphere water
The mass ratio of dispersion liquid, expanded graphite and polystyrene sphere aqueous dispersions is 70:1, ultrasonic 2h, are made expanded graphite-polyphenyl
Ethene composite dispersion liquid；
(3) by expanded graphite-polystyrene composite dispersion liquid suction filtration to nickel foam, dry temperature 60 C is dried, when drying
Between 12h, in the mixed solution that the nickel foam for being loaded with expanded graphite-polystyrene is placed in hydrazine hydrate and ammoniacal liquor, hydrazine hydrate with
Ammoniacal liquor volume ratio is 1:8, graphene-polystyrene base material is taken after reaction；
(4) taken out after graphene-polystyrene base material being warming up into 600 DEG C, insulation 2h in vacuum tube furnace,
Obtain graphene.
2nd, graphene-Zirconia-alumina composite is prepared；
(1) graphene obtained in step one is mixed with aluminic acid ammonia, the mass ratio of graphene and aluminic acid ammonia is preferably 2:
1, ball milling is graphene-aluminic acid ammonia composite, and the rotating speed of ball milling is preferably 250rpm；
(2) above-mentioned graphene-aluminic acid ammonia composite is heated to 800-950 DEG C, the heating rate of heating is 5-10
DEG C/min is incubated 2h under nitrogen protection, Temperature fall obtains graphene-alumina compound；
(3) graphene-alumina compound is mixed with nano zircite, graphene-alumina compound and nano oxygen
The mass ratio for changing zirconium is 3:1-；Ball milling, the rotational speed of ball-mill of ball mill is 350rpm, obtains graphene-Zirconia-alumina and is combined
Material.
3rd, fire-retardant heat insulation compound is prepared；
(1) graphene-Zirconia-alumina composite is made after solution and mixed with polystyrene；Wherein, in stone
In black alkene-Zirconia-alumina aqueous solution, the mass ratio of graphene-Zirconia-alumina and water is 1:20；Graphene-oxidation
The mass ratio of zirconium-aluminum oxide and polystyrene is preferably 1:6；
(2) phenolic resin and curing agent are added in above-mentioned mixed solution, curing agent is the mixing of water, sulfuric acid and phosphoric acid
Thing；The mass ratio of mixed solution and phenolic resin is 25:1~28:1；The mass ratio of phenolic resin and curing agent is 3:1~4:1.
4th, fire-retardant heat insulation plate is prepared；
(1) melt-mixed material is obtained in the first double screw extruder；Add mixture into the first double screw extruder
In, the compound melted.Wherein, in the working region in the first double screw extruder, the first 130 DEG C of zone temperatures；The
Two 160 DEG C of sections；3rd 180 DEG C of section, pressure 4Mpa；4th 200 DEG C of zone temperatures, pressure 9MPa；5th zone temperatures 220
DEG C, pressure 12Mpa；6th 230 DEG C of zone temperatures, 19MPa, SECTOR-SEVEN 210 DEG C of temperature of section, pressure 23Mpa.
(2) in the SECTOR-SEVEN section end of the first screw extruder, supercritical carbon dioxide is added in the compound of melting
Fluid；The mass ratio of supercritical carbon dioxide fluid and compound is about 90:1, filling pressure 24MPa.
(3) the 8th and the 9th section by the compound of melting in the second screw extruder carries out part mixing；Into
The mass ratio of the melt-mixed material of eight sections and the 9th section is 1:1.
(4) mixture particle is obtained by the second screw machine extruder；In second screw extruder, Section Eight section temperature
160 DEG C, pressure 17MPa, the 9th 80 DEG C of zone temperatures, pressure 21MPa, the tenth 60 DEG C of zone temperatures, pressure 16MPa；11st
50 DEG C of zone temperatures, pressure 14MPa；90 DEG C of Twelve-section temperature, pressure 11Mpa.Install and extrude in Twelve-section end
Die head, 100 DEG C of the temperature in die head region, pressure 9Mpa.
(5) fire-retardant heat insulation plate is made of compound particles.
Embodiment 3：
The manufacture method of the fire-retardant heat insulation plate of the embodiment is as follows：
First, graphene is prepared, is comprised the following steps：
(1) graphite oxide is placed in crucible, Muffle furnace is then heated to 1100 DEG C, the rate of heat addition is 12 DEG C/min,
Crucible is put into after Muffle furnace and is incubated after 4min, crucible is taken out, expanded graphite is made.
(2) expanded graphite is dispersed in water, the mass ratio of expanded graphite and water is 1:2, add polystyrene sphere water
The mass ratio of dispersion liquid, expanded graphite and polystyrene sphere aqueous dispersions is 70:1, ultrasonic 2h, are made expanded graphite-polyphenyl
Ethene composite dispersion liquid；
(3) by expanded graphite-polystyrene composite dispersion liquid suction filtration to nickel foam, the speed of suction filtration is 4L/s, is done
Dry, the nickel foam for being loaded with expanded graphite-polystyrene is placed in hydrazine hydrate and ammoniacal liquor by 60 DEG C of drying temperature, drying time 11h
Mixed solution in react, hydrazine hydrate and ammoniacal liquor volume ratio are 1:5~1:10, reaction temperature is preferably at 80~85 DEG C；Take graphite
Alkene-polystyrene base material；
(4) graphene-polystyrene base material being warming up to 650 DEG C in vacuum tube furnace, heating rate is 4 DEG C/
Taken out after min, insulation 3h, obtain graphene.
2nd, graphene-Zirconia-alumina composite is prepared；
(1) graphene is mixed with aluminic acid ammonia, mass ratio is 1:1-3:1；Ball milling is graphene-aluminic acid ammonia composite；
The rotating speed of ball milling is 260rpm；
(2) above-mentioned graphene-aluminic acid ammonia composite is heated to 900 DEG C, heating rate is 10 DEG C/min, in nitrogen
The lower insulation 3h of protection, Temperature fall, obtain graphene-alumina compound；
(3) graphene-alumina compound is mixed with nano zircite, graphene-alumina compound and nano oxygen
The mass ratio for changing zirconium is 4:1；Ball milling obtains graphene-Zirconia-alumina composite；The rotational speed of ball-mill of ball mill is preferably
330rpm。
3rd, fire-retardant heat insulation compound is prepared；
(1) graphene-Zirconia-alumina composite is made after solution and mixed with polystyrene；Graphene-oxygen
The mass ratio for changing zirconium-aluminum oxide and water is 1:20；The mass ratio of graphene-Zirconia-alumina and polystyrene is 1:8；
(2) phenolic resin and curing agent are added in above-mentioned mixed solution, curing agent is the mixing of water, sulfuric acid and phosphoric acid
Thing；The mass ratio of mixed solution and phenolic resin is 25:1；The mass ratio of phenolic resin and curing agent is 3:1.Wherein sulfuric acid
Weight/mass percentage composition is 97%, and the weight/mass percentage composition of phosphoric acid is 38%；The mass ratio of water and sulfuric acid is 3:1；Water and phosphoric acid
Mass ratio is 2:1；Obtain fire-retardant heat insulation compound.
4th, fire-retardant heat insulation plate is prepared；
(1) melt-mixed material is obtained in the first double screw extruder；Add mixture into the first double screw extruder
In, the compound melted.Wherein, the working region in the first double screw extruder is divided into seven sections：First section temperature
120 DEG C of degree；Second 150 DEG C of section；3rd 170 DEG C of section, pressure 3Mpa；4th 190 DEG C of zone temperatures, pressure 8MPa；5th
210 DEG C of zone temperatures, pressure 11Mpa；6th 220 DEG C of zone temperatures, pressure 18MPa, SECTOR-SEVEN 200 DEG C of temperature of section, pressure
22Mpa。
(2) in the SECTOR-SEVEN section end of the first screw extruder, supercritical carbon dioxide is added in the compound of melting
Fluid；The mass ratio of supercritical carbon dioxide fluid and compound is about 90:1, filling pressure 24MPa.
(3) compound of melting is subjected to part mixing by the Section Eight section of the second screw machine and the 9th section respectively；
Mass ratio into Section Eight section and the melt-mixed material of the 9th section is 1:1.
(4) mixture particle is obtained by the second screw machine extruder；Second screw extruder is divided into five sections, the
Eight 150 DEG C of zone temperatures, pressure 16MPa, the 9th 70 DEG C of zone temperatures, pressure 20MPa, the tenth 50 DEG C of zone temperatures, pressure
15MPa；11st 40 DEG C of zone temperatures, pressure 13MPa；80 DEG C of Twelve-section temperature, pressure 10Mpa.Twelve-section end
90 DEG C of the temperature in the extrusion die region at end, pressure 9Mpa.
(5) fire-retardant heat insulation plate is made of compound particles.
Embodiment 4：
The manufacture method of the fire-retardant heat insulation plate of the present embodiment is as follows：
First, graphene is prepared, is comprised the following steps：
(1) graphite oxide is placed in crucible, Muffle furnace is heated to 1100,15 DEG C/min of the rate of heat addition, crucible is put
Enter and be incubated after Muffle furnace after 5min, crucible is taken out, expanded graphite is made.
(2) expanded graphite is dispersed in water, the mass ratio of expanded graphite and water is 1:2, add polystyrene sphere water
The mass ratio of dispersion liquid, expanded graphite and polystyrene sphere aqueous dispersions is 70:1, ultrasonic 2h, are made expanded graphite-polyphenyl
Ethene composite dispersion liquid；
(3) by expanded graphite-polystyrene composite dispersion liquid suction filtration to nickel foam, dry temperature 60 C is dried, when drying
Between 12h, in the mixed solution that the nickel foam for being loaded with expanded graphite-polystyrene is placed in hydrazine hydrate and ammoniacal liquor, hydrazine hydrate with
Ammoniacal liquor volume ratio is 1:8, graphene-polystyrene base material is taken after reaction；
(4) taken out after graphene-polystyrene base material being warming up into 600 DEG C, insulation 2h in vacuum tube furnace,
Obtain graphene.
2nd, graphene-Zirconia-alumina composite is prepared；
(1) graphene obtained in step one is mixed with aluminic acid ammonia, the mass ratio of graphene and aluminic acid ammonia is preferably 2:
1, ball milling is graphene-aluminic acid ammonia composite, and the rotating speed of ball milling is preferably 250rpm；
(2) above-mentioned graphene-aluminic acid ammonia composite is heated to 800-950 DEG C, the heating rate of heating is 5-10
DEG C/min is incubated 2h under nitrogen protection, Temperature fall obtains graphene-alumina compound；
(3) graphene-alumina compound is mixed with nano zircite, graphene-alumina compound and nano oxygen
The mass ratio for changing zirconium is 3:1-；Ball milling, the rotational speed of ball-mill of ball mill is 350rpm, obtains graphene-Zirconia-alumina and is combined
Material.
3rd, fire-retardant heat insulation compound is prepared；
(1) graphene-Zirconia-alumina composite is made after solution and mixed with polystyrene；Wherein, in stone
In black alkene-Zirconia-alumina aqueous solution, the mass ratio of graphene-Zirconia-alumina and water is 1:20；Graphene-oxidation
The mass ratio of zirconium-aluminum oxide and polystyrene is preferably 1:6；
(2) phenolic resin and curing agent are added in above-mentioned mixed solution, curing agent is the mixing of water, sulfuric acid and phosphoric acid
Thing；The mass ratio of mixed solution and phenolic resin is 25:1~28:1；The mass ratio of phenolic resin and curing agent is 3:1~4:1.
4th, fire-retardant heat insulation particle is prepared；
(1) melt-mixed material is obtained in the first double screw extruder；Add mixture into the first double screw extruder
In, the compound melted.Wherein, in the working region in the first double screw extruder, the first 130 DEG C of zone temperatures；The
Two 160 DEG C of sections；3rd 180 DEG C of section, pressure 4Mpa；4th 200 DEG C of zone temperatures, pressure 9MPa；5th zone temperatures 220
DEG C, pressure 12Mpa；6th 230 DEG C of zone temperatures, 19MPa, SECTOR-SEVEN 210 DEG C of temperature of section, pressure 23Mpa.
(2) in the SECTOR-SEVEN section end of the first screw extruder, supercritical carbon dioxide is added in the compound of melting
Fluid；The mass ratio of supercritical carbon dioxide fluid and compound is about 90:1, filling pressure 24MPa.
(3) the 8th and the 9th section by the compound of melting in the second screw extruder carries out part mixing；Into
The mass ratio of the melt-mixed material of eight sections and the 9th section is 1:1.
(4) mixture particle is obtained by the second screw machine extruder；In second screw extruder, Section Eight section temperature
160 DEG C, pressure 17MPa, the 9th 80 DEG C of zone temperatures, pressure 21MPa, the tenth 60 DEG C of zone temperatures, pressure 16MPa；11st
50 DEG C of zone temperatures, pressure 14MPa；90 DEG C of Twelve-section temperature, pressure 11Mpa.Install and extrude in Twelve-section end
Die head, 100 DEG C of the temperature in die head region, pressure 9Mpa.
5th, prepare coating and coat
By following weight parts than component：Aluminium hydroxide 20, zirconium oxide 40, graphite powder 5, laterite 20, miberal powder 5, ceramic powder
10 mixing, melting mixing coating is obtained by double screw extruder, is extruded, and tabletting is air-cooled, is milled, and sieving obtains coating.
Fire-retardant heat insulation particle is mixed with coating, silicone, stirring is uniform to coating, the mass ratio of warming plate material and coating
For 1:1.2, obtain wrapping up warming plate granular materials, building thermal insulation material is made in then compression molding.
Embodiment 5：
The manufacture method of the fire-retardant heat insulation plate of the present embodiment is as follows：
First, graphene is prepared, is comprised the following steps：
(1) graphite oxide is placed in crucible, Muffle furnace is heated to 1100,15 DEG C/min of the rate of heat addition, crucible is put
Enter and be incubated after Muffle furnace after 5min, crucible is taken out, expanded graphite is made.
(2) expanded graphite is dispersed in water, the mass ratio of expanded graphite and water is 1:2, add polystyrene sphere water
The mass ratio of dispersion liquid, expanded graphite and polystyrene sphere aqueous dispersions is 70:1, ultrasonic 2h, are made expanded graphite-polyphenyl
Ethene composite dispersion liquid；
(3) by expanded graphite-polystyrene composite dispersion liquid suction filtration to nickel foam, dry temperature 60 C is dried, when drying
Between 12h, in the mixed solution that the nickel foam for being loaded with expanded graphite-polystyrene is placed in hydrazine hydrate and ammoniacal liquor, hydrazine hydrate with
Ammoniacal liquor volume ratio is 1:8, graphene-polystyrene base material is taken after reaction；
(4) taken out after graphene-polystyrene base material being warming up into 600 DEG C, insulation 2h in vacuum tube furnace,
Obtain graphene.
2nd, graphene-Zirconia-alumina composite is prepared；
(1) graphene obtained in step one is mixed with aluminic acid ammonia, the mass ratio of graphene and aluminic acid ammonia is preferably 2:
1, ball milling is graphene-aluminic acid ammonia composite, and the rotating speed of ball milling is preferably 250rpm；
(2) above-mentioned graphene-aluminic acid ammonia composite is heated to 800-950 DEG C, the heating rate of heating is 5-10
DEG C/min is incubated 2h under nitrogen protection, Temperature fall obtains graphene-alumina compound；
(3) graphene-alumina compound is mixed with nano zircite, graphene-alumina compound and nano oxygen
The mass ratio for changing zirconium is 3:1-；Ball milling, the rotational speed of ball-mill of ball mill is 350rpm, obtains graphene-Zirconia-alumina and is combined
Material.
3rd, fire-retardant heat insulation compound is prepared；
(1) graphene-Zirconia-alumina composite is made after solution and mixed with polystyrene；Wherein, in stone
In black alkene-Zirconia-alumina aqueous solution, the mass ratio of graphene-Zirconia-alumina and water is 1:20；Graphene-oxidation
The mass ratio of zirconium-aluminum oxide and polystyrene is preferably 1:6；
(2) phenolic resin and curing agent are added in above-mentioned mixed solution, curing agent is the mixing of water, sulfuric acid and phosphoric acid
Thing；The mass ratio of mixed solution and phenolic resin is 25:1~28:1；The mass ratio of phenolic resin and curing agent is 3:1~4:1.
4th, fire-retardant heat insulation particle is prepared；
(1) melt-mixed material is obtained in the first double screw extruder；Add mixture into the first double screw extruder
In, the compound melted.Wherein, in the working region in the first double screw extruder, the first 130 DEG C of zone temperatures；The
Two 160 DEG C of sections；3rd 180 DEG C of section, pressure 4Mpa；4th 200 DEG C of zone temperatures, pressure 9MPa；5th zone temperatures 220
DEG C, pressure 12Mpa；6th 230 DEG C of zone temperatures, 19MPa, SECTOR-SEVEN 210 DEG C of temperature of section, pressure 23Mpa.
(2) in the SECTOR-SEVEN section end of the first screw extruder, supercritical carbon dioxide is added in the compound of melting
Fluid；The mass ratio of supercritical carbon dioxide fluid and compound is about 90:1, filling pressure 24MPa.
(3) the 8th and the 9th section by the compound of melting in the second screw extruder carries out part mixing；Into
The mass ratio of the melt-mixed material of eight sections and the 9th section is 1:1.
(4) mixture particle is obtained by the second screw machine extruder；In second screw extruder, Section Eight section temperature
160 DEG C, pressure 17MPa, the 9th 80 DEG C of zone temperatures, pressure 21MPa, the tenth 60 DEG C of zone temperatures, pressure 16MPa；11st
50 DEG C of zone temperatures, pressure 14MPa；90 DEG C of Twelve-section temperature, pressure 11Mpa.Install and extrude in Twelve-section end
Die head, 100 DEG C of the temperature in die head region, pressure 9Mpa.
5th, prepare coating and coat
By following weight parts than component：Aluminium hydroxide 20, zirconium oxide 43, graphite powder 7, laterite 18, miberal powder 4, ceramic powder 8
Mixing, melting mixing coating is obtained by double screw extruder, is extruded, and tabletting is air-cooled, is milled, and sieving obtains coating.
Fire-retardant heat insulation particle is mixed with coating, silicone, stirring is uniform to coating, the mass ratio of warming plate material and coating
For 1:1.2, obtain wrapping up warming plate granular materials, building thermal insulation material is made in then compression molding.
With reference to some fire-retardant heat insulation plates commonly used in the prior art as comparative example, these warming plates are by as follows
What shown method was made, as shown in table 1, while the technical parameter of the above embodiment of the present invention is shown, list comparative example
Technical parameter, for reference.
Comparative example 1：
Comparative example manufacture includes the warming plate of graphite and polystyrene, is made up of following steps：
Expandable polystyrene is added in prefoaming machine, is heated by steam, is by expandable polystyrene foaming
Graininess；Expandable polystyrene particle after foaming is cured；
Expandable polystyrene particle is added in stirring container, carbon black or graphite is added, will the two uniform stirring into
Compound, makes carbon black or graphite uniformly wrap up expandable polystyrene particle；Wherein the ratio of carbon black is after foaming
The 0.2% of expandable polystyrene particle weight；The ratio of graphite is the expandable polystyrene particle weight after foaming
2%；
The compound of the expandable polystyrene particle being stirred and carbon black or graphite is transported in forming machine and is fixed into
Type.
Comparative example 2：
The comparative example is a kind of polystyrene foam composite heat insulatant thermal insulation material, is comprised the following steps：
Using 100 parts of phenolic resin as base-material, 10 parts of expansible graphites and capsule red phosphorus are separately added under stirring, 10 parts are added
Curing agent and 10 parts of foaming agents and 5 parts of surfactants, stir to being uniformly dispersed, obtain being dispersed with the polymerization of anti-flaming function component
Thing base coating, the wherein mass ratio of expansible graphite and capsule red phosphorus are 1:1；
Take the polystyrene foam particles of prefoam as base-material, then add above-mentioned polymer matrix coating, wherein, polyphenyl
The base-material of vinyl foam particle and the mass ratio of polymer matrix coating are 1:2, stirring is uniform to coating, and obtains coated compound poly-
Styrenic foams particulate material, then will obtain coated composite polystyrene foam beads material and be added in steam hot pressing die,
Feng Mo, is passed through high-pressure water vapor to after 0.05MPa, and pressurize 45s, release after cooling, is molded, and discharging obtains high flame resistance, low smoke
Density polystyrene foam composite heat insulatant thermal insulation material.
Comparative example 3：
The comparative example manufactures a kind of Polystyrene heat insulation material, and preparation method comprises the following steps：
Modifying agent is prepared first, and it is included by the component of following parts by weight：40 parts of silicate, 3 parts of methacrylic acid, stone
Black 1 part of alkene, 1 part of NPE, 1 part of sulfonation polyethylene glycol, 10 parts of water.
By the material mixing of said components it is uniform after, take 1 part according to parts by weight, take 10 parts of foamed material, together enter
Batch mixer batch mixing, under being stirred continuously of the stirrer paddle of batch mixer, is stirred 2 hours, modifying agent is uniformly applied to foam material
On material, dry stand-by.
The above-mentioned foamed material handled well is taken, according to volume ratio 1.5:1 ratio, with cement mixing, dries after being well mixed
It is dry, insulation material is made.
Table 1
A kind of excellent building thermal insulation material of fire protecting performance disclosed by the invention and its manufacture method, the material is compared to existing
Technology has better flame resistance and low smoke density, and nontoxic pollution-free, with higher fire-protection rating, meets environmental requirement.
The present invention adds graphene in insulation material, and because graphite is natural inert substance, fusing point is up to 3600 and taken the photograph
Family name's degree, powdered graphite can be covered on combustion boundary, play a part of completely cutting off air, and graphene has bigger ratio surface
Product, a small amount of addition can achieve the goal, and play extraordinary flame retardant effect.Reach A grades of requirements of fire prevention.
The present invention adds zirconium oxide in insulation material, because the high temeperature chemistry property of zirconium oxide in itself is stable, corrosion-resistant, anti-
It is oxidation, anti-thermal shock, non-volatile, pollution-free, it is a kind of good refractory material.
The present invention adds aluminum oxide in insulation material, because aluminum oxide possesses fire resistance, while having porous, high score
The characteristics of divergence, there is very big surface area, its micropore is evenly distributed, and proper pore size, bulk density is small, good mechanical property,
With good absorption property and excellent heat endurance.
The present invention combines graphene, zirconium oxide, aluminum oxide with special ratios, and the advantage of three is given full play to reference to after,
So that the Flame-retardant low-smoke warming plate being finally made has good fire protecting performance, meet fire protection requirement；And flue gas is very low, to environment
Pollution is greatly reduced, and meets environmental requirement.
The ratio of graphene-Zirconia-alumina and polystyrene causes its fire resistance and heat-insulating property in the present invention
Balance is reached, is not in obvious short slab, outside the proportioning, it will makes that its heat insulation effect can decline or fire protecting performance will be by
Considerable influence.
Because the composite of the present invention includes the component differed with conventional flame retardant warming plate, in an extruder respectively
The temperature of individual section, pressure carry out the innovation of adaptability, the advantage of component are given full play to, while not limited by manufacturing condition
System, finally obtains the optimal warming plate material of performance.
It is important that invention also discloses in addition, resistance is being made insulation material of the invention of compound particles
Fire before warming plate, first mix compound particles with a coating, stirring makes coating be evenly applied to particle surface, then will coating
Fire-retardant heat insulation plate is made in the compound particles of coating, is that one kind meets because the coating has good fire-retardant, low cigarette effect
The A level fire-retardant heat-insulation materials of environmentally friendly A grades of standard.
The present invention can also have other various embodiments, in the case of without departing substantially from spirit of the invention and its essence, be familiar with this
The technical staff in field works as can make various corresponding changes and deformation according to the present invention, but these corresponding changes and deformation are all
The protection domain of appended claims of the invention should be belonged to.
Claims (7)
1. a kind of manufacture method of insulation material, it is characterised in that comprise the following steps：
Prepare graphene：
(11) expanded graphite is prepared；Wherein, graphite oxide is placed in crucible first, Muffle furnace is then heated to a constant temperature
Degree, crucible is put into after Muffle furnace after held for some time, crucible is taken out, and expanded graphite is made；
(12) expanded graphite is dispersed in water, adds ultrasound after polystyrene sphere aqueous dispersions, expanded graphite-polyphenyl is made
Ethene composite dispersion liquid；Wherein, the mass ratio of expanded graphite and water is 1: 1~1: 2, expanded graphite and polystyrene sphere moisture
The mass ratio of dispersion liquid is 80: 1~60: 1；
(13) expanded graphite-poly- will will be loaded with after drying on expanded graphite-polystyrene composite dispersion liquid suction filtration to nickel foam
The nickel foam of styrene is placed in the mixed solution of hydrazine hydrate and ammoniacal liquor, and graphene-polystyrene base material is taken after reaction；
(14) taken after graphene-polystyrene base material being warming up into 600~650 DEG C, 2~3h of insulation in vacuum tube furnace
Go out, obtain graphene；Prepare graphene-Zirconia-alumina composite；
(21) graphene obtained in step one is mixed with aluminic acid ammonia, ball milling is graphene-aluminic acid ammonia composite；Wherein,
The mass ratio of the graphene and aluminic acid ammonia is 1: 1-3: 1；
(22) above-mentioned graphene-aluminic acid ammonia composite is heated to 800-950 DEG C, is incubated, cools under nitrogen protection, obtain
Graphene-alumina compound；Wherein, heated, be incubated and cooled in tube furnace, the heating rate of heating is 5-10
DEG C/min, soaking time is 2-4h, then Temperature fall；
(23) graphene-alumina compound is mixed with nano zircite, it is multiple that ball milling obtains graphene-Zirconia-alumina
Condensation material；Wherein, the mass ratio of the graphene-alumina compound and nano zircite is 3: 1-4: 1；
Prepare fire-retardant heat insulation compound；
(31) graphene-Zirconia-alumina composite is made after solution and mixed with polystyrene；Wherein, graphene-
In the Zirconia-alumina aqueous solution, the mass ratio of graphene-Zirconia-alumina and water is 1: 20~1: 25；Wherein, it is described
The mass ratio of graphene-Zirconia-alumina and polystyrene is 1: 6~1: 8；
(32) phenolic resin and curing agent are added in above-mentioned mixed solution, curing agent is the mixture of water, sulfuric acid and phosphoric acid, is obtained
To fire-retardant heat insulation compound；
Prepare fire-retardant heat insulation plate；
(41) melt-mixed material is obtained in the first double screw extruder：Fire-retardant heat insulation compound is added into the first twin-screw extrusion
In machine, the compound melted；
(42) in the SECTOR-SEVEN section end of the first screw extruder, stream of supercritical carbon dioxide is added in the compound of melting
Body；The mass ratio of supercritical carbon dioxide fluid and compound is 80: 1~90: 1, filling pressure 24MPa；
(43) compound of melting is subjected to part mixing in the Section Eight section of the second screw machine and the 9th section；Wherein, enter
The mass ratio of Section Eight section and the melt-mixed material of the 9th section is 1: 1；
(44) mixture particle is obtained by the second screw machine extruder；
(45) insulation material is made with compound particles.
2. the manufacture method of insulation material as claimed in claim 1, it is characterised in that in step (11), heating muffle stove
The rate of heat addition be 10~15 DEG C/min, Muffle furnace is heated to 1000~1100 DEG C, soaking time of the crucible in Muffle furnace
For 3~5min.
3. the manufacture method of insulation material as claimed in claim 1, it is characterised in that in step (13), the speed of suction filtration
For 3~4L/s, drying temperature is 50~60 DEG C, and drying time is 10~13h, and hydrazine hydrate is 1: 5~1: 10 with ammoniacal liquor volume ratio,
Reaction temperature is at 80~85 DEG C.
4. the manufacture method of insulation material as claimed in claim 1, it is characterised in that in step (32), in mixed solution
The mass ratio of compound and phenolic resin is 25: 1~28: 1；The mass ratio of phenolic resin and curing agent is 3: 1~4: 1.
5. the manufacture method of insulation material as claimed in claim 1, it is characterised in that in step (32), the quality of sulfuric acid
Percentage composition is 97%, and the weight/mass percentage composition of phosphoric acid is 38%；The mass ratio of water and sulfuric acid is 2: 1~3: 1；Water and phosphoric acid
Mass ratio is 1.5: 1~2: 1.
6. the manufacture method of insulation material as claimed in claim 1, it is characterised in that in step (41), the first twin-screw
Working region in extruder is divided into seven sections：First 120 DEG C of zone temperatures；Second 150 DEG C of section；3rd 170 DEG C of section,
Pressure 3MPa；4th 190 DEG C of zone temperatures, pressure 8MPa；5th 210 DEG C of zone temperatures, pressure 11MPa；6th zone temperatures
220 DEG C, pressure 18MPa, SECTOR-SEVEN 200 DEG C of temperature of section, pressure 22MPa.
7. the manufacture method of insulation material as claimed in claim 1, it is characterised in that in step (44), the second screw rod is squeezed
Go out machine and be divided into five sections, be Section Eight Duan Zhi Twelve-sections respectively, Section Eight 150 DEG C of temperature of section, pressure 16MPa, the 9th
70 DEG C of zone temperatures, pressure 20MPa, the tenth 50 DEG C of zone temperatures, pressure 15MPa；11st 40 DEG C of zone temperatures, pressure
13MPa；80 DEG C of Twelve-section temperature, pressure 10MPa.
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