CN103937155B - A kind of dual anti-High-strength solid buoyancy material - Google Patents
A kind of dual anti-High-strength solid buoyancy material Download PDFInfo
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- CN103937155B CN103937155B CN201410051148.8A CN201410051148A CN103937155B CN 103937155 B CN103937155 B CN 103937155B CN 201410051148 A CN201410051148 A CN 201410051148A CN 103937155 B CN103937155 B CN 103937155B
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Abstract
The invention discloses a kind of dual anti-High-strength solid buoyancy material, it is characterized in that: the recipe ingredient of this material is counted with mass parts: epoxy resin 100 parts, Graphite Powder 99 1 ~ 15 part, epoxide diluent 5 ~ 20 parts, toughner 2 ~ 20 parts, cenosphere 10 ~ 80 parts, spherical nano-silver powder 0.5 ~ 10 part, 50 ~ 80 parts, solidifying agent, catalyzer 0.1 ~ 3 part.Wherein, described cenosphere is the modification cenosphere after adopting silane coupling agent KH560 to carry out surface treatment; Described spherical nano-silver powder is particle diameter is that 5 ~ l00nm also carries out surface-treated modified spherical or class spherical nano-silver powder by adopting containing sulfydryl and imidazoles functional compounds; Described Graphite Powder 99 is particle diameter is natural flake graphite and the synthetic graphite powder of 5 ~ 324 orders also by adopting hexadecyl brometo de amonio (CTAB) to carry out surface modification treatment.Solid buoyancy material of the present invention has that production technique is simple, cost is low, intensity is high, the advantage of antibacterial, antistatic and long service life.
Description
Technical field
The present invention relates to a kind of solid buoyancy material of antibacterial, antistatic and high strength, belong to functional nonmetallic composite technical field, specifically a kind of dual anti-High-strength solid buoyancy material.
Background technology
Along with the development of Ocean Development Technology and the propelling of deep-sea exploration, deep-sea solid buoyancy material became studies in China focus in recent years.The application of solid buoyancy material achieves the function that hardware is difficult to realize, the application that all obtained of the aspect such as bathyscaph, underwater robot, subbottom tunnel, submarine optical fiber cable, petroleum transportation pipeline under water, and can use safely under the deep-sea of thousands of meters under water.Solid buoyancy material forms mainly through polymkeric substance or resene matrix and hollow glass micropearl or hollow ceramic microspheres composite.Wherein main with epoxy group(ing) solid buoyancy material for representative, the ultra-high-strength buoyancy material that patent CN1018242206A will obtain after hollow glass micropearl and epoxy resin composite curing, is applicable to 6000 ~ 9000 meters of deepwater environments; Patent CN103013050A equally by hollow glass micropearl and epoxy resin compound, and is spliced to form the solid buoyancy material of epoxy group(ing) by module.
But when solid buoyancy material is used to deep ocean work, subbottom tunnel, submarine optical fiber cable, petroleum transportation pipeline, outer field solid buoyancy material is not only subject to the impact of deep-sea pressure, and the surface attachment of microorganism in the seawater that can not be ignored, simultaneously in deep ocean work process, the function influence of electrostatic is very important, especially, in deep-sea oil pipeline uses, the process of outer solid buoyancy material anti-electrostatic seems more important.Current solid buoyancy material expands a lot of work in enhancing resistance to compression etc., but mainly concentrates on solidifying agent selection, glass microballon surface treatment, linking agent use etc.Therefore process and the improvement of solid buoyancy material being carried out to antibacterial, antistatic aspect is necessary very much.Have good anti-microbial property based on nanometer silver itself, therefore we introduce the nano-silver powder of modification in solid buoyancy material; Graphite itself has excellent conductivity, usually used as composite material conductive filler, make matrix material have good conductivity, Graphite Powder 99 is incorporated in solid buoyancy material, make solid buoyancy material possess certain conductivity, thus possess antistatic property.Based on this, nano-silver powder and Graphite Powder 99 modification are incorporated in the solid composite material of epoxy group(ing) by we, can prepare high strength antibacterial antistatic solid buoyancy material, there is not yet report and the application of antibacterial antistatic epoxy group(ing) solid buoyancy material.
Summary of the invention
The object of the invention is to: a kind of dual anti-High-strength solid buoyancy material is provided, merge the conductivity of nano-silver powder good antimicrobial property and graphite excellence, spherical nano-silver powder is prepared by adopting liquid phase reduction, and utilize and containing sulfydryl and imidazoles functional compounds, the modifying surface of spherical nano-silver powder is applied in epoxy base material and prepares solid buoyancy material, reach and make prepared solid buoyancy material possess object that is antistatic, antibacterial and high strength.
To achieve these goals, the present invention adopts following technical scheme:
A kind of dual anti-High-strength solid buoyancy material, it is characterized in that: in mass parts, the recipe ingredient of this material comprises following raw material: epoxy resin 100 parts, Graphite Powder 99 1 ~ 15 part, epoxide diluent 5 ~ 20 parts, toughner 2 ~ 20 parts, cenosphere 10 ~ 80 parts, spherical nano-silver powder 0.5 ~ 10 part, 50 ~ 80 parts, solidifying agent, catalyzer 0.1 ~ 3 part.
Described epoxy resin is the one in bisphenol A type epoxy resin, novolac epoxy, aliphatic epoxy resin or hydridization type epoxy resin.
Described toughner is the common toughner of epoxy, can be one or more in rubber-like toughner, thermoplastic elastomer class toughner, Versamid and low molecular nonactive toughner.
Described solidifying agent is the matching used solidifying agent of epoxy, comprises one or more in alkaline amine curing agent, acid acid anhydride type curing agent, fatty amines, low molecular polyamides class add-on type solidifying agent or imidazole curing agent.
Described catalyzer is one or more in methyl tetrahydro phthalic anhydride, methyl hexahydrophthalic anhydride, diethylenetriamine, triethylene tetramine etc.
Described cenosphere is ultimate compression strength is 30 ~ 125MPa, and real density is 0.125 ~ 0.6g/cm
3, particle diameter is 10 ~ 120 μm, and inner chamber is filled with gas or is the hollow glass micropearl of vacuum and hollow ceramic microspheres, it is characterized in that: described cenosphere is the modification cenosphere after adopting silane coupling agent KH560 to carry out surface treatment.
Further, the concrete implementation step of the surface modification treatment of described cenosphere is: by the cenosphere aqueous sodium hydroxide solution of 30 ~ 50% or the superoxol process of 30%, make cenosphere surface hydroxylation; Then after filtration, join in ethanolic soln after washing, drying, add the silane coupling agent KH560 being equivalent to cenosphere quality 1 ~ 5% again, by silane hydrolysis reaction, silane coupling agent KH560 is grafted on cenosphere on the surface, then after filtration, washing, drying obtains silane coupling agent KH560 surface-treated cenosphere.
Silane coupling agent KH560 is adopted to be the object that cenosphere carries out surface modification treatment: treated cenosphere can well be scattered in epoxy base material, and then for the filler of solid buoyancy material, the bonding force between cenosphere and epoxy resin can be significantly improved.
Described spherical nano-silver powder is spherical or class spherical nano-silver powder, it is characterized in that: this spherical nano-silver powder adopts liquid phase reduction to prepare, its particle diameter is 5 ~ l00nm, concrete preparation method is: take Silver Nitrate as raw material, liquid phase reduction is adopted to carry out reaction preparation after adding reductive agent, stablizer and dispersion agent, reaction terminates rear solid-liquid separation, and purifying washs, and obtains spherical nano-silver powder after drying.Wherein, described reductive agent is hydrazine hydrate (N
2h
4h
2o), sodium borohydride (NaBH
4), sodium hypophosphite (NaPO
2h
2) or L-AA (C
6h
8o
6) in one or more; Described stablizer and dispersion agent are sodium lauryl sulphate (SDS), Sodium dodecylbenzene sulfonate (SDBS), polyvinylpyrrolidone (one or more in PVP, polyvinyl alcohol (PVA) or polyoxyethylene glycol (PEG).
Further, described spherical nano-silver powder carries out surface-treated modified spherical nano-silver powder by adopting containing sulfydryl and imidazoles functional compounds, and described functional compound is 2-mercaptoimidazole (C
3h
4n
2s), 2-sulfydryl-1-Methylimidazole (C
4h
6n
2or 2-mercaptobenzimidazole (C S)
7h
6n
2etc. S) one in.
Utilize and be containing sulfydryl and the object of imidazoles functional compounds to the modifying surface process of spherical nano-silver powder: utilize complexing action very strong between spherical nano-silver powder and sulfydryl, the functional of this compounds is grafted to nano-silver powder surface, strengthen the dispersiveness of nano-silver powder in epoxy base material on the one hand, in addition on the one hand because the existence of imidazoles group substantially increases spherical nano-silver powder and epoxy base material bonding force.
Described Graphite Powder 99 is natural flake graphite and synthetic graphite powder, order number is 5 ~ 324 orders, it is characterized in that: described Graphite Powder 99 adopts hexadecyl brometo de amonio (CTAB) to carry out surface modification treatment, concrete modifying process is: take 5 ~ 10g Graphite Powder 99, join 20 ~ 50mL deionized water for stirring, with salt acid for adjusting pH value 7 ~ 8, ultrasonic 1 ~ 10 minute, add the cetyl trimethylammonium bromide of 1 ~ 5g, after ultrasonic 10 ~ 30 minutes, decompress filter, obtain filter cake with distilled water wash and be that 60 ~ 70 DEG C of vacuum-dryings obtain surface-treated Graphite Powder 99 in 24 ~ 48 hours.
The preparation method of described dual anti-High-strength solid buoyancy material is: by the epoxy resin of described mass fraction, Graphite Powder 99, epoxide diluent, toughner and cenosphere join in vacuum mixer, stir 20 ~ 30 minutes in the vacuum mixer of 60 ~ 80 DEG C, then spherical nano-silver powder is added, solidifying agent and catalyzer continue stirring 20 minutes, gained mixture is injected mould, adopt vulcanizing press hot-press solidifying under the pressure of 20MPa shaping, at program curing is followed successively by 110 DEG C 2 hours, at 140 DEG C 4 hours, at 160 DEG C 4 hours, the demoulding after cooling, obtain that there is high strength, antibacterial, anlistatig solid buoyancy material.
Compared with prior art, beneficial effect of the present invention is:
In conjunction with the anti-microbial property of spherical nano-silver powder and the conductivity of Graphite Powder 99, by adopting containing sulfydryl and imidazoles functional compounds the process of spherical nano-silver powder modifying surface to adopt CTAB to the process of Graphite Powder 99 modifying surface, then add in epoxy matrix as filler, the epoxy group(ing) buoyancy material of preparation is made to possess excellent antibacterial, antistatic effect, required step is few, cost is low, and technique is simpler, easily realizes large-scale commercial production; In addition, add in epoxy matrix after first silver powder and Graphite Powder 99 being carried out modification, the dispersiveness of nano-silver powder in epoxy base material can be strengthened and improve spherical nano-silver powder and epoxy base material bonding force, solid buoyancy material is made not only to have very high intensity, and reduce the effect that in use, biological adsorption and electrostatic produce, thus improve work-ing life and the security of solid buoyancy material.
Embodiment
Below in conjunction with specific examples, technical scheme of the present invention is described further.
Embodiment 1
A kind of dual anti-High-strength solid buoyancy material, it is characterized in that: in mass parts, the recipe ingredient of this material comprises following raw material: epoxy resin 100 parts, Graphite Powder 99 5 parts, epoxide diluent 15 parts, toughner 10 parts, cenosphere 50 parts, spherical nano-silver powder 2 parts, 60 parts, solidifying agent, catalyzer 0.5 part.
Described epoxy resin is bisphenol A type epoxy resin E51.
Described epoxide diluent is ethylene glycol diglycidylether type.
Described toughner is acrylonitrile-butadiene-styrene copolymer (ABS).
Described solidifying agent is 1-cyanoethyl-2-ethyl-4-methylimidazole.
Described catalyzer is methyl hexahydrophthalic anhydride.
Described cenosphere is ultimate compression strength is 30 ~ 125MPa, and real density is 0.125 ~ 0.6g/cm
3, particle diameter is 10 ~ 120 μm, and inner chamber is the hollow glass micropearl K37 of vacuum.
Described cenosphere is the modification cenosphere after adopting silane coupling agent KH560 to carry out surface treatment, the concrete implementation step of its surface modification treatment is: be the aqueous sodium hydroxide solution stirred at ambient temperature 2 hours of 50% by 20g cenosphere 500mL weight fraction, make cenosphere surface hydroxylation; Washing is carried out 5 ~ 10 times with a large amount of deionized water, then by the vacuum-drying 6 hours at 80 DEG C of the hollow glass micropearl that obtains, join in a large amount of ethanolic soln, add the silane coupling agent KH560 of 10g again, as a child took out at 60 DEG C of stirring reactions 5, after a large amount of deionized water wash, in 60 DEG C of vacuum drying ovens, drying obtains silane coupling agent KH560 surface-treated hollow glass micropearl K37 for 6 hours.
Described spherical nano-silver powder is particle diameter is the spherical of 30nm or class spherical nano-silver powder, prepare by adopting liquid phase reduction, concrete preparation method is: the aqueous solution that the deionized water that the PVP-K30 taking 20g is dissolved in 200mL obtains PVP is for subsequent use, takes solid nitric acid silver 50g in addition and is dissolved in the silver nitrate solution obtaining 100mg/mL in the deionized water of 500mL; Measure after the PVP aqueous solution of 100mL and 100mL silver nitrate solution be mixed evenly, under magnetic agitation, the hydrazine hydrate solution 10mL of 80% is dripped under room temperature, then the mixing solutions obtained is contained in sealing in sample bottle to preserve, after ultrasonic 10 ~ 20 minutes, is placed in 80 DEG C of baking ovens, react 6 hours, centrifugation, uses a large amount of deionized water wash by precipitation, and in 60 DEG C of vacuum drying ovens, dry 12 as a child obtained spherical nano-silver powder.
Further, described spherical nano-silver powder carries out surface-treated modified spherical nano-silver powder by adopting containing sulfydryl and imidazoles functional compounds, concrete method of modifying is: the spherical nano-silver powder taking 5g, join 100mL deionized water for ultrasonic and disperse 30 minutes, obtain the aqueous dispersions of spherical nano-silver powder, add the 2-mercaptoimidazole of 5g until all dissolve, react 2 hours at 80 DEG C, precipitation is used a large amount of deionized water wash by centrifugation, and in 60 DEG C of vacuum drying ovens, drying 12 as a child obtained the spherical nano-silver powder of 2-mercaptoimidazole functionalization.
Described Graphite Powder 99 is natural flake graphite and synthetic graphite powder, order number is 5 ~ 324 orders, hexadecyl brometo de amonio (CTAB) is adopted to carry out surface modification treatment, concrete modifying process is: the Graphite Powder 99 taking 5g joins in 250mL deionized water water, add the acetum of 5mL1%, after ultrasonic 10 ~ 20 minutes, add after 20g hexadecyl brometo de amonio (CTAB) continues ultrasonic 10 ~ 20 minutes, to filter and with a large amount of deionized water wash dry Graphite Powder 99 obtaining ctab surface process for 12 hours by the filter obtained and in 60 DEG C of vacuum drying ovens.
The preparation method of described dual anti-High-strength solid buoyancy material is: by the epoxy resin of described mass fraction, Graphite Powder 99, epoxide diluent, toughner and cenosphere join in vacuum mixer, stir 20 ~ 30 minutes in the vacuum mixer of 60 ~ 80 DEG C, then spherical nano-silver powder is added, solidifying agent and catalyzer continue stirring 20 minutes, gained mixture is injected mould, adopt vulcanizing press hot-press solidifying under the pressure of 20MPa shaping, at program curing is followed successively by 110 DEG C 2 hours, at 140 DEG C 4 hours, at 160 DEG C 4 hours, the demoulding after cooling, obtain that there is high strength, antibacterial, anlistatig solid buoyancy material.
Embodiment 2
A kind of dual anti-High-strength solid buoyancy material, it is characterized in that: in mass parts, the recipe ingredient of this material comprises following raw material: epoxy resin 100 parts, Graphite Powder 99 2 parts, epoxide diluent 10 parts, toughner 8 parts, cenosphere 60 parts, spherical nano-silver powder 2 parts, 60 parts, solidifying agent, catalyzer 0.2 part.
Described epoxy resin is bisphenol A type epoxy resin E44.
Described epoxide diluent is polypropylene glycol diglycidyl ether.
Described toughner is liquid polybutadiene rubber.
Described solidifying agent is MALEIC ANHYDRIDE.
Described catalyzer is mphenylenediamine.
Described cenosphere is ultimate compression strength is 30 ~ 125MPa, and real density is 0.125 ~ 0.6g/cm
3, particle diameter is 10 ~ 120 μm, and inner chamber is the hollow glass micropearl K46 of vacuum.
Described cenosphere is the modification cenosphere after adopting silane coupling agent KH560 to carry out surface treatment, the concrete implementation step of its surface modification treatment is: be the aqueous sodium hydroxide solution stirred at ambient temperature 2 hours of 50% by 20g cenosphere 200mL weight fraction, make cenosphere surface hydroxylation; Washing is carried out 5 ~ 10 times with a large amount of deionized water, then by the vacuum-drying 6 hours at 80 DEG C of the hollow glass micropearl that obtains, join in a large amount of ethanolic soln, add the silane coupling agent KH560 of 10g again, as a child took out at 60 DEG C of stirring reactions 5, after a large amount of deionized water wash, in 60 DEG C of vacuum drying ovens, drying obtains silane coupling agent KH560 surface-treated hollow glass micropearl K46 for 6 hours.
Described spherical nano-silver powder is particle diameter is the spherical of 30nm or class spherical nano-silver powder, prepare by adopting liquid phase reduction, concrete preparation method is: the aqueous solution that the deionized water that the PVP-K30 taking 20g is dissolved in 200mL obtains PVP is for subsequent use, takes solid nitric acid silver 50g in addition and is dissolved in the silver nitrate solution obtaining 100mg/mL in the deionized water of 500mL; Measure after the PVP aqueous solution of 100mL and 100mL silver nitrate solution be mixed evenly, under magnetic agitation, sodium borohydride solids 0.5g is added to dissolving completely under room temperature, then the mixing solutions obtained is contained in sealing in sample bottle to preserve, after ultrasonic 10 ~ 20 minutes, is placed in 80 DEG C of baking ovens, react 6 hours, centrifugation, uses a large amount of deionized water wash by precipitation, and in 60 DEG C of vacuum drying ovens, dry 12 as a child obtained spherical nano-silver powder.
Further, described spherical nano-silver powder carries out surface-treated modified spherical nano-silver powder by adopting containing sulfydryl and imidazoles functional compounds, concrete method of modifying is: the spherical nano-silver powder taking 5g, to join in 100mL acetone soln ultrasonic disperse 30 minutes, obtain the acetone dispersion liquor of spherical nano-silver powder, add the 2-mercaptoimidazole of 5g until all dissolve, react 2 hours at 80 DEG C, precipitation is used a large amount of washing with acetone by centrifugation, and in 60 DEG C of vacuum drying ovens, drying 12 as a child obtained the spherical nano-silver powder of 2-mercaptoimidazole functionalization.
Described Graphite Powder 99 is natural flake graphite and synthetic graphite powder, order number is 5 ~ 324 orders, hexadecyl brometo de amonio (CTAB) is adopted to carry out surface modification treatment, concrete modifying process is: the Graphite Powder 99 taking 5g joins in 250mL deionized water water, add the acetum of 5mL1%, after ultrasonic 10 ~ 20 minutes, add after 20g hexadecyl brometo de amonio (CTAB) continues ultrasonic 10 ~ 20 minutes, to filter and with a large amount of deionized water wash dry Graphite Powder 99 obtaining ctab surface process for 12 hours by the filter obtained and in 60 DEG C of vacuum drying ovens.
The preparation method of described dual anti-High-strength solid buoyancy material is: by the epoxy resin of described mass fraction, Graphite Powder 99, epoxide diluent, toughner and cenosphere join in vacuum mixer, stir 20 ~ 30 minutes in the vacuum mixer of 60 ~ 80 DEG C, then spherical nano-silver powder is added, solidifying agent and catalyzer continue stirring 20 minutes, gained mixture is injected mould, adopt vulcanizing press hot-press solidifying under the pressure of 20MPa shaping, at program curing is followed successively by 110 DEG C 2 hours, at 140 DEG C 4 hours, at 160 DEG C 4 hours, the demoulding after cooling, obtain that there is high strength, antibacterial, anlistatig solid buoyancy material.
Claims (7)
1. a dual anti-High-strength solid buoyancy material, it is characterized in that: in mass parts, the recipe ingredient of this material comprises following raw material: epoxy resin 100 parts, Graphite Powder 99 1 ~ 15 part, epoxide diluent 5 ~ 20 parts, toughner 2 ~ 20 parts, cenosphere 10 ~ 80 parts, spherical nano-silver powder 0.5 ~ 10 part, 50 ~ 80 parts, solidifying agent, catalyzer 0.1 ~ 3 part, described spherical nano-silver powder is the particle diameter adopting liquid phase reduction to prepare is the spherical of 5 ~ l00nm or class spherical nano-silver powder, and carry out surface treatment by adopting containing sulfydryl and imidazoles functional compounds, wherein, described functional compound is 2-mercaptoimidazole, one in 2-sulfydryl-1-Methylimidazole or 2-mercaptobenzimidazole.
2. a kind of dual anti-High-strength solid buoyancy material as claimed in claim 1, is characterized in that: described cenosphere is ultimate compression strength is 30 ~ 125MPa, and real density is 0.125 ~ 0.6g/cm
3, particle diameter is 10 ~ 120 μm, and inner chamber is filled with gas or is the hollow glass micropearl of vacuum and hollow ceramic microspheres.
3. a kind of dual anti-High-strength solid buoyancy material as claimed in claim 1, is characterized in that: described Graphite Powder 99 is particle diameter is 5 ~ 324 object natural flake graphites and synthetic graphite powder.
4. a kind of dual anti-High-strength solid buoyancy material as claimed in claim 2, is characterized in that: described cenosphere is the modification cenosphere after adopting silane coupling agent KH560 to carry out surface treatment.
5. a kind of dual anti-High-strength solid buoyancy material as claimed in claim 4, it is characterized in that: the method for modifying of described cenosphere is: by the cenosphere aqueous sodium hydroxide solution of 30 ~ 50% or the superoxol process of 30%, make cenosphere surface hydroxylation; Then after filtration, join in ethanolic soln after washing, drying, add the silane coupling agent KH560 being equivalent to cenosphere quality 1 ~ 5% again, by silane hydrolysis reaction, silane coupling agent KH560 is grafted on cenosphere on the surface, then after filtration, washing, drying obtains silane coupling agent KH560 surface-treated cenosphere.
6. a kind of dual anti-High-strength solid buoyancy material as claimed in claim 3, is characterized in that: described Graphite Powder 99 is the modified graphite powder adopting hexadecyl brometo de amonio to carry out surface modification treatment to cross.
7. a kind of dual anti-High-strength solid buoyancy material as claimed in claim 3, it is characterized in that: the concrete modifying process of described Graphite Powder 99 is: take 5 ~ 10g Graphite Powder 99, join 20 ~ 50mL deionized water for stirring, with salt acid for adjusting pH value 7 ~ 8, ultrasonic 1 ~ 10 minute, add the cetyl trimethylammonium bromide of 1 ~ 5g, after ultrasonic 10 ~ 30 minutes, decompress filter, filter cake is obtained with distilled water wash, again under 60 ~ 70 DEG C of conditions, vacuum-drying 24 ~ 48 hours, obtains surface-treated Graphite Powder 99.
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| EP3307978B1 (en) | 2015-06-12 | 2020-04-01 | 3M Innovative Properties Company | Buoyancy module and method of making such a module |
| CN105524424A (en) * | 2015-12-10 | 2016-04-27 | 上海复合材料科技有限公司 | Antibacterial antistatic epoxy composite material and preparation method thereof |
| CN106751484A (en) * | 2016-12-05 | 2017-05-31 | 钦州市钦南区生产力促进中心 | A kind of deep-sea High-strength solid buoyancy material and preparation method thereof |
| CN107400945B (en) * | 2017-08-29 | 2019-08-06 | 张伟夫 | A kind of antibacterial silver-plating fabric core-spun yarn, antibacterial fabric and antibacterial socks |
| CN112341206A (en) * | 2020-11-05 | 2021-02-09 | 衡阳凯新特种材料科技有限公司 | Forming method of rare earth praseodymium-holmium-stabilized silicon nitride ceramic |
| CN113603501B (en) * | 2021-08-12 | 2022-08-02 | 南京工业大学 | Selective adsorption cooling material and preparation method and application thereof |
| CN115093194B (en) * | 2022-08-24 | 2022-11-08 | 江苏夸迪安防集团有限公司 | Antibacterial floating bead fireproof heat-insulation plate and preparation method and application thereof |
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