CN112724729A - Double-wall-layer intumescent fire retardant co-microcapsule and preparation method thereof - Google Patents
Double-wall-layer intumescent fire retardant co-microcapsule and preparation method thereof Download PDFInfo
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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
- C09D5/185—Intumescent paints
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34922—Melamine; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
Abstract
The invention relates to a double-wall-layer intumescent fire retardant co-microcapsule, which comprises a core material, wherein the outer layer of the core material is coated with a first-layer wall material, the outer layer of the first-layer wall material is coated with a second-layer wall material, the core material is a mixture of an acid source, a carbon source and a gas source of an intumescent fire retardant, the first-layer wall material is epoxy resin, and the second-layer wall material is melamine-formaldehyde resin.
Description
Technical Field
The invention relates to the technical field of flame retardants, in particular to a double-wall-layer intumescent fire retardant co-microcapsule and a preparation method thereof.
Background
At present, steel structures in large buildings are used more and more commonly, although steel cannot be combusted, the mechanical strength of the steel is rapidly reduced along with the temperature rise, and when the temperature rises to a critical point of the steel, the steel loses the bearing capacity; therefore, when a building is in fire, the steel loses bearing capacity along with temperature rise, so that the building collapses; the steel structure fireproof coating can prolong the process that the steel structure reaches the critical temperature as far as possible, thereby striving for the time for fire extinguishing and people saving, and being the guarantee of life rescue.
The surface of the intumescent flame retardant material can play a good role in isolating air, insulating heat and suppressing smoke, and can prevent or weaken the dripping of molten drops generated during combustion, thereby playing a good flame retardant effect. The intumescent flame retardant is called as a revolution in the flame retardant technology, and the IFR (intumescent flame retardant) is commonly used in the current fireproof coating, wherein the IFR comprises three components of an acid source, a carbon source and a gas source, and the acid source comprises ammonium polyphosphate, melamine phosphate and the like; carbon-derived starch, pentaerythritol and derivatives thereof and the like; the gas source comprises melamine, urea resin dicyandiamide and the like. However, the common acid source has strong water solubility, and the carbon source pentaerythritol is completely water soluble and is added into the coating to influence the anti-corrosion performance of the coating. The water-based flame-retardant coating prepared by using the intumescent flame retardant has poor water resistance, is easy to foam, wrinkle and peel, and greatly limits the use of the water-based flame-retardant coating. Therefore, the prepared composite flame retardant with strong hydrophobicity can ensure the fireproof performance of the coating, does not influence the corrosion resistance of the coating, and has very important significance.
The research on the hydrophobic modification of the intumescent flame retardant is more, but most of the intumescent flame retardant focuses on the hydrophobic modification of acid source ammonium polyphosphate, and Sun and the like modify the APP surface by adopting melamine and 2, 4-toluene diisocyanate; liulin and the like modify APP (ammonium polyphosphate) with a melamine-formaldehyde resin as a coating, but hydrophobic modification of water-soluble PER (pentaerythritol) and hydrophilic MEL (melamine) is less studied.
The intumescent flame retardant has strong hydrophilicity and poor compatibility with polymers, and meanwhile, the coating has generally poor water resistance and is easy to wrinkle, foam and fall off, so that the application of the water-based fireproof coating is limited.
Only APP is subjected to hydrophobic modification, so that the water resistance of the coating cannot be effectively improved, because the common PER in the intumescent fire retardant is completely water-soluble, MEL also has certain hydrophilicity, and the influence of the PER on the water resistance of the coating cannot be ignored.
Disclosure of Invention
Technical problem to be solved
In order to solve the problems in the prior art, the invention provides a double-wall-layer intumescent fire retardant co-microcapsule and a preparation method thereof, and the acid source ammonium polyphosphate with stronger hydrophilicity, the carbon source pentaerythritol with complete water solubility and the melamine with slight water solubility are subjected to double-layer microencapsulation by adopting a two-step coating method, so that the coating efficiency is improved, the hydrophobicity of the coating is enhanced, the water resistance of the coating is not influenced when the coating is added into a fire-proof coating, and a better fire-proof effect can be achieved, and the possibility is provided for preparing a water-based coating with fire-proof and anti-corrosion functions.
(II) technical scheme
In order to achieve the purpose, the invention adopts the main technical scheme that:
the double-wall-layer intumescent fire retardant co-microcapsule comprises a core material, wherein a first layer of wall material is coated on the outer layer of the core material, a second layer of wall material is coated on the outer layer of the first layer of wall material, the core material is a mixture of an acid source, a carbon source and an air source of an intumescent fire retardant, the first layer of wall material is epoxy resin, and the second layer of wall material is melamine-formaldehyde resin.
Further, the mass ratio of the acid source, the carbon source and the gas source of the intumescent fire retardant is 2-3: 0.8-1.2: 1.
further, the acid source of the intumescent fire retardant is ammonium polyphosphate or melamine phosphate; the carbon source is pentaerythritol and derivatives thereof or starch; the gas source is melamine or urea resin dicyandiamide.
A preparation method of a double-wall layer intumescent fire retardant co-microcapsule comprises the following specific steps:
step S1, coating the mixture of the acid source, the carbon source and the gas source of the intumescent fire retardant with the epoxy resin:
uniformly mixing 10-30g of epoxy resin and 300g of 120-plus solvent under the stirring condition of 300rpm of 100-plus solvent, then adding 90-110g of mixture of an acid source, a carbon source and a gas source of the intumescent fire retardant, stirring at the constant temperature of 40-50 ℃ for 30-60min at the rotation speed of 5000rpm in a constant-temperature water bath kettle, adding 1-8g of amine curing agent, reacting for 2-4h, performing suction filtration, and drying at 50 ℃ for 36-48h to obtain EP-Mix;
step S2, coating the epoxy resin with melamine-formaldehyde resin:
adding 10-20g of melamine, 10-25g of formaldehyde aqueous solution (37%) and 80-120g of water into a 500ml four-neck flask, fully stirring, adjusting the pH of the solution to 7.5-9 by using saturated sodium carbonate aqueous solution, heating to 60-80 ℃ while stirring, and reacting for 45-90min to obtain an MF resin prepolymer;
under the stirring condition of the stirring speed of 100-200rpm, adding 100g of the MF resin prepolymer, then adding 20-40g of absolute ethyl alcohol and 50-100g of deionized water, adjusting the pH to 4.5-5.5 by using an acid solution, then adding 50-80g of EP-Mix obtained in the step S1, wherein the stirring speed is 1000-3000rpm, carrying out heat preservation reaction for 1.5-3h under the water bath condition of 65-75 ℃, filtering, cleaning and drying to obtain the MF-EP-Mix double-layer co-microcapsule intumescent flame retardant.
Further, the solvent is compatible with the epoxy resin, but is not soluble or sparingly soluble in the single solvent or in a mixture of solvents of the intumescent flame retardant additive.
Further, the solvent is acetone.
(III) advantageous effects
The invention has the beneficial effects that: according to the invention, the acid source ammonium polyphosphate with strong hydrophilicity, the completely water-soluble carbon source pentaerythritol and the slightly water-soluble melamine are microencapsulated together in a double layer by adopting a two-step coating method, so that the coating efficiency is improved, the hydrophobicity of the coating is enhanced, the water resistance of the coating is not influenced when the coating is added into a fireproof coating, a good fireproof effect can be achieved, and the possibility is provided for preparing the water-based coating with fireproof and anticorrosion functions.
The common intumescent fire-retardant material is subjected to hydrophobic modification together, so that the water resistance of the coating is improved; meanwhile, the three components are prepared into the additive, so that the use is convenient and the operation is simple.
Drawings
FIG. 1 is a schematic flow chart of the present invention.
Detailed Description
For the purpose of better explaining the present invention and to facilitate understanding, the present invention will be described in detail by way of specific embodiments with reference to the accompanying drawings.
The double-wall-layer intumescent fire retardant co-microcapsule comprises a core material, wherein a first layer of wall material is coated on the outer layer of the core material, a second layer of wall material is coated on the outer layer of the first layer of wall material, the core material is a mixture of an acid source, a carbon source and an air source of an intumescent fire retardant, the first layer of wall material is epoxy resin, and the second layer of wall material is melamine-formaldehyde resin.
Further, the mass ratio of the acid source, the carbon source and the gas source of the intumescent fire retardant is 2-3: 0.8-1.2: 1.
further, the acid source of the intumescent fire retardant is ammonium polyphosphate or melamine phosphate; the carbon source is pentaerythritol and derivatives thereof or starch; the gas source is melamine or urea resin dicyandiamide.
A preparation method of a double-wall layer intumescent fire retardant co-microcapsule is shown in figure 1, and comprises the following specific steps:
step S1, coating the mixture of the acid source, the carbon source and the gas source of the intumescent fire retardant with the epoxy resin:
uniformly mixing 10-30g of epoxy resin and 300g of 120-plus solvent under the stirring condition of 300rpm of 100-plus solvent, then adding 90-110g of mixture of an acid source, a carbon source and a gas source of the intumescent fire retardant, stirring at the constant temperature of 40-50 ℃ for 30-60min at the rotation speed of 5000rpm in a constant-temperature water bath kettle, adding 1-8g of amine curing agent, reacting for 2-4h, performing suction filtration, and drying at 50 ℃ for 36-48h to obtain EP-Mix;
step S2, coating the epoxy resin with melamine-formaldehyde resin:
adding 10-20g of melamine, 10-25g of formaldehyde aqueous solution (37%) and 80-120g of water into a 500ml four-neck flask, fully stirring, adjusting the pH of the solution to 7.5-9 by using saturated sodium carbonate aqueous solution, heating to 60-80 ℃ while stirring, and reacting for 45-90min to obtain an MF resin prepolymer;
under the stirring condition of the stirring speed of 100-200rpm, adding 100g of the MF resin prepolymer, then adding 20-40g of absolute ethyl alcohol and 50-100g of deionized water, adjusting the pH to 4.5-5.5 by using an acid solution, then adding 50-80g of EP-Mix obtained in the step S1, wherein the stirring speed is 1000-3000rpm, carrying out heat preservation reaction for 1.5-3h under the water bath condition of 65-75 ℃, filtering, cleaning and drying to obtain the MF-EP-Mix double-layer co-microcapsule intumescent flame retardant.
Further, the solvent is compatible with the epoxy resin, but is not soluble or sparingly soluble in the single solvent or in a mixture of solvents of the intumescent flame retardant additive.
Further, the solvent is acetone.
The invention carries out double-layer and co-coating on the substances with stronger hydrophilicity of the common intumescent flame retardant by the microcapsule, carries out hydrophobic modification on the substances with stronger hydrophilicity, simultaneously ensures that the three are mixed according to a certain proportion, ensures better fireproof effect, solves the problems of strong hydrophilicity and poor compatibility with polymers of the intumescent flame retardant additive, expands the application range of the aqueous fireproof coating, and even provides possibility for preparing the aqueous fireproof and anticorrosive coating.
According to the invention, the acid source ammonium polyphosphate with strong hydrophilicity, the completely water-soluble carbon source pentaerythritol and the slightly water-soluble melamine are microencapsulated together in a double layer by adopting a two-step coating method, so that the coating efficiency is improved, the hydrophobicity of the coating is enhanced, the water resistance of the coating is not influenced when the coating is added into a fireproof coating, a good fireproof effect can be achieved, and the possibility is provided for preparing the water-based coating with fireproof and anticorrosion functions.
Example 1:
the epoxy resin is coated with the mixture of the acid source, the carbon source and the gas source of the intumescent fire retardant: uniformly mixing 15g of epoxy resin and 150g of acetone under the condition of stirring at 150rpm, then adding 100g of APP, PER and MEL mixture, stirring in a thermostatic water bath kettle at 50 ℃ for 30min at the stirring speed of 2000rpm, adding 2.2g of triethylene tetramine curing agent, heating to 70 ℃, reacting for 2h, performing suction filtration, and drying at 50 ℃ for 36h to obtain EP-Mix.
Coating epoxy resin with melamine-formaldehyde resin:
adding 13g of melamine, 10g of formaldehyde aqueous solution (37%) and 77g of water into a 250ml four-neck flask, fully stirring, adjusting the pH of the solution to 7.5 by using saturated sodium carbonate aqueous solution, heating to 80 ℃ while stirring, and reacting for 45min to obtain the MF resin prepolymer.
Under the condition of stirring, 20g of absolute ethyl alcohol and 50g of deionized water are added into the MF resin prepolymer solution, the pH value is adjusted to 5 by using an acetic acid water solution, then 70gEP-Mix is added, the stirring speed is 1000rpm, the heat preservation reaction is carried out for 1.5h under the water bath condition of 65 ℃, and the MF-EP-Mix double-layer co-microcapsule intumescent flame retardant can be obtained by filtering, cleaning and drying.
Example 2:
the epoxy resin is coated with the mixture of the acid source, the carbon source and the gas source of the intumescent fire retardant:
and (2) uniformly mixing 10g of epoxy resin and 120g of acetone under the stirring condition of 300rpm, then adding 100g of APP, PER and MEL mixture, stirring in a constant-temperature water bath kettle at 40 ℃ for 60min at the constant temperature of 2000rpm, adding 1.5g of triethylene tetramine curing agent, reacting for 4h, performing suction filtration, and drying at 50 ℃ for 48h to obtain EP-Mix.
Coating epoxy resin with melamine-formaldehyde resin:
adding 20g of melamine, 25g of formaldehyde aqueous solution (37%) and 120g of water into a 500ml four-neck flask, fully stirring, adjusting the pH of the solution to 8 by using saturated sodium carbonate aqueous solution, heating to 70 ℃ while stirring, and reacting for 45min to obtain the MF resin prepolymer.
Under the condition of stirring, 100g of the MF resin prepolymer solution is added, then 40g of absolute ethyl alcohol and 100g of deionized water are added, the pH value is adjusted to 5 by using an acetic acid aqueous solution, then 80gEP-Mix is added, the stirring speed is 2000rpm, the heat preservation reaction is carried out for 3h under the condition of 75 ℃ water bath, and the MF-EP-Mix double-layer co-microcapsule intumescent flame retardant can be obtained by filtering, cleaning and drying.
Example 3:
the epoxy resin is coated with the mixture of the acid source, the carbon source and the gas source of the intumescent fire retardant:
and (2) uniformly mixing 30g of epoxy resin and 150g of acetone under the stirring condition of 300rpm, then adding 110g of APP, PER and MEL mixture, stirring in a thermostatic water bath kettle at 50 ℃ for 30min at the rotation speed of 5000rpm, adding 4.5g of triethylene tetramine curing agent, reacting for 2h, performing suction filtration, and drying at 50 ℃ for 36h to obtain EP-Mix.
Coating epoxy resin with melamine-formaldehyde resin:
10g of melamine, 10g of aqueous formaldehyde solution (37%) and 80g of water are added into a 500ml four-neck flask, the mixture is fully stirred, the pH value of the solution is adjusted to 7.5 by using saturated aqueous sodium carbonate solution, then the solution is heated to 80 ℃ while being stirred, and the reaction is carried out for 90min, thus obtaining the MF resin prepolymer.
Under the condition of stirring, 100g of the MF resin prepolymer solution is added, 20g of absolute ethyl alcohol and 50g of deionized water are added, the pH value is adjusted to 4.5-5.5 by using an acetic acid aqueous solution, 70gEP-Mix is added, the stirring speed is 3000rpm, the heat preservation reaction is carried out for 3h under the condition of a water bath at the temperature of 75 ℃, and the MF-EP-Mix double-layer co-microcapsule intumescent flame retardant can be obtained by filtering, cleaning and drying.
Comparative example 1:
coating the intumescent fire-retardant material mixture with only epoxy resin: uniformly mixing 15g of epoxy resin and 150g of acetone under the condition of stirring at 150rpm, then adding 100g of APP, PER and MEL mixture, stirring in a thermostatic water bath kettle at 50 ℃ for 30min at the stirring speed of 2000rpm, adding 2.2g of triethylene tetramine curing agent, heating to 70 ℃, reacting for 2h, performing suction filtration, and drying at 50 ℃ for 36h to obtain EP-Mix.
Comparative example 2:
unmodified APP, PER and MEL mixtures.
The performance of the flame retardant additive of the invention was tested according to the following formulation:
deionized water: 20.0 parts (parts by mass, the same applies hereinafter);
bentone LT: 0.2 part;
BYK-190: 0.6 part;
tego Foamax 901 w: 0.5 part;
titanium dioxide: 8.0 parts of (B);
1250 mesh talcum powder: 2.0 parts of (B);
intumescent flame retardant additive: 45.0 parts of (B);
water-based acrylate emulsion: 25.0 parts;
BYK 345: 0.5 part;
DMEA: 0.2 part;
SN 660T polyurethane thickener: 0.3 part;
tego Foamax 810: 0.3 part;
deionized water: 1.0 part.
The performance test data for the examples and comparative examples are shown in the following table:
note: solubility test method: weighing 100g of the composite flame retardant, dispersing the composite flame retardant into 100g of deionized water, performing ultrasonic dispersion for 30min, filtering, taking 10g of clear liquid, drying, and obtaining a solubility calculation formula of the composite flame retardant additive when the weighed mass is m: solubility m/10 1000
From the above table it can be concluded that: the solubility of the intumescent fire-retardant additive prepared by the invention in water is far lower than that of the unmodified intumescent fire-retardant additive, and the water resistance of the prepared fire-retardant coating is obviously improved.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (6)
1. The double-wall-layer intumescent fire retardant co-microcapsule is characterized by comprising a core material, wherein a first layer of wall material is coated on the outer layer of the core material, a second layer of wall material is coated on the outer layer of the first layer of wall material, the core material is a mixture of an acid source, a carbon source and a gas source of an intumescent fire retardant, the first layer of wall material is epoxy resin, and the second layer of wall material is melamine-formaldehyde resin.
2. The double-wall-layer intumescent fire retardant co-microcapsule according to claim 1, wherein the mass ratio of the acid source, the carbon source and the gas source of the intumescent fire retardant is 2-3: 0.8-1.2: 1.
3. the double-walled layer intumescent fire retardant co-microcapsule of claim 2, wherein the intumescent fire retardant acid source is ammonium polyphosphate or melamine phosphate; the carbon source is pentaerythritol and derivatives thereof or starch; the gas source is melamine or urea resin dicyandiamide.
4. A method for preparing a double-walled intumescent fire retardant co-microcapsule according to any of claims 1-3, characterized in that the specific steps are as follows:
step S1, coating the mixture of the acid source, the carbon source and the gas source of the intumescent fire retardant with the epoxy resin:
uniformly mixing 10-30g of epoxy resin and 300g of 120-plus solvent under the stirring condition of 300rpm of 100-plus solvent, then adding 90-110g of mixture of an acid source, a carbon source and a gas source of the intumescent fire retardant, stirring at the constant temperature of 40-50 ℃ for 30-60min at the rotation speed of 5000rpm in a constant-temperature water bath kettle, adding 1-8g of amine curing agent, reacting for 2-4h, performing suction filtration, and drying at 50 ℃ for 36-48h to obtain EP-Mix;
step S2, coating the epoxy resin with melamine-formaldehyde resin:
adding 10-20g of melamine, 10-25g of formaldehyde aqueous solution (37%) and 80-120g of water into a 500ml four-neck flask, fully stirring, adjusting the pH of the solution to 7.5-9 by using saturated sodium carbonate aqueous solution, heating to 60-80 ℃ while stirring, and reacting for 45-90min to obtain an MF resin prepolymer;
under the stirring condition of the stirring speed of 100-200rpm, adding 100g of the MF resin prepolymer, then adding 20-40g of absolute ethyl alcohol and 50-100g of deionized water, adjusting the pH to 4.5-5.5 by using an acid solution, then adding 50-80g of EP-Mix obtained in the step S1, wherein the stirring speed is 1000-3000rpm, carrying out heat preservation reaction for 1.5-3h under the water bath condition of 65-75 ℃, filtering, cleaning and drying to obtain the MF-EP-Mix double-layer co-microcapsule intumescent flame retardant.
5. A process for the preparation of a double-walled intumescent fire retardant co-microcapsule as claimed in claim 4 wherein the solvent is a single solvent or a mixture of solvents compatible with the epoxy resin but insoluble or slightly soluble in the intumescent fire retardant additive.
6. The process for the preparation of a double-walled intumescent fire retardant co-microcapsule according to claim 4 wherein the solvent is acetone.
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| CN113493624A (en) * | 2021-07-27 | 2021-10-12 | 黑龙江省科学院石油化学研究院 | Biomass flame retardant, water-based flame retardant coating, and preparation method and application thereof |
| CN113493624B (en) * | 2021-07-27 | 2022-04-12 | 黑龙江省科学院石油化学研究院 | Biomass flame retardant, water-based flame retardant coating, and preparation method and application thereof |
| CN114748830A (en) * | 2022-06-15 | 2022-07-15 | 浙江虹达特种橡胶制品有限公司杭州分公司 | Perfluorohexanone microcapsule fire extinguishing material and preparation method thereof |
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