CN113388299A - Cooling and heat insulating material composition, cooling and heat insulating material and application thereof - Google Patents

Cooling and heat insulating material composition, cooling and heat insulating material and application thereof Download PDF

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Publication number
CN113388299A
CN113388299A CN202010167288.7A CN202010167288A CN113388299A CN 113388299 A CN113388299 A CN 113388299A CN 202010167288 A CN202010167288 A CN 202010167288A CN 113388299 A CN113388299 A CN 113388299A
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cooling
weight
insulating material
parts
heat insulating
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CN113388299B (en
Inventor
张日鹏
赵祥迪
李磊
杨帅
陈国鑫
马浩然
朱先俊
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Sinopec Safety Engineering Research Institute Co Ltd
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China Petroleum and Chemical Corp
Sinopec Qingdao Safety Engineering Institute
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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
    • C09D133/00—Coating compositions based on 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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    • 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
    • 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
    • C09D5/20—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for coatings strippable as coherent films, e.g. temporary coatings strippable as coherent films
    • 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
    • C09D5/26—Thermosensitive paints
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
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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
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres

Abstract

The invention relates to the field of high-temperature resistance and heat insulation, and discloses a cooling and heat insulating material composition, a cooling and heat insulating material and application thereof. The cooling and heat insulating material composition comprises high water-absorbent resin, heat insulating filler, temperature indicating material, thixotropy regulating material and adhesion promoter, wherein the high water-absorbent resin is 100 parts by weight, the content of the heat insulating filler is 5-30 parts by weight, the content of the temperature indicating material is 5-15 parts by weight, the content of the thixotropy regulating material is 1-15 parts by weight, and the content of the adhesion promoter is 0.1-3 parts by weight. The thermal insulation material provided by the invention has good viscosity, high water absorption performance, thermal insulation performance and thixotropic performance, can be quickly solidified, has good adhesiveness to a tank wall, can display the temperature of the tank wall in real time, and further improves the safety of a storage tank.

Description

Cooling and heat insulating material composition, cooling and heat insulating material and application thereof
Technical Field
The invention relates to the field of high-temperature resistance and heat insulation, in particular to a cooling and heat insulating material composition, a cooling and heat insulating material and application thereof.
Background
In recent years, with the development of petrochemical industry, the number of storage tank areas is more and more, the scale is larger and larger, and the fire accidents in the tank areas are frequent. When a fire breaks out in one tank, the hydrocarbon fire will release intense heat radiation, and the adjacent tanks will be exposed to intense heat radiation, and the following may happen: 1. the strength of the adjacent storage tanks is reduced, the tank walls are torn, liquid in the tanks leaks, and then fire disasters occur; 2. the medium in the tank volatilizes, the pressure in the tank increases, and physical explosion occurs; 3. the medium in the tank volatilizes, the pressure in the tank increases, and the gas in the tank is discharged from a breather valve and the like and is combusted when meeting a fire source. Therefore, when a tank is on fire, it is necessary to protect the adjacent tank to prevent the tank fire accident from spreading. The existing protection method of adjacent tanks under the condition of fire disaster is to apply water spray, namely, the water spray system is fixed or a movable water gun is used for spraying water to the surfaces of the adjacent storage tanks, and heat is taken away through the flowing volatilization of water, so that the adjacent storage tanks are protected. However, the method needs to continuously spray water to the surface of the storage tank, so that a large amount of water is consumed; meanwhile, due to the existence of the fire dike of the tank field, the accumulated water in the tank field is serious, and the fire rescue is seriously hindered; when oil leaks, it can also help to form a flowing fire.
At present, no relevant research report on emergency materials for protecting adjacent tanks under the condition of B-type fire exists in China, and more researches on high-temperature resistant coatings are carried out, for example, CN102030540A discloses a high-temperature resistant heat-insulating coating consisting of inorganic high-temperature refractory mortar, silica aerogel, potassium hexatitanate whiskers, mica sheets and acetone/absolute ethyl alcohol; CN105860790A discloses a high-temperature resistant heat-insulating coating consisting of a solvent, organic silicon resin and high-temperature resistant filler; CN103725074A discloses a high temperature resistant thermal insulation coating composed of high reflection pigment, thermal insulation powder, toughening agent, high temperature binder, water and auxiliary agent, but the high temperature resistant thermal insulation coating disclosed in the above 3 patent applications only has simple thermal insulation and high temperature resistance, and when applied to thermal insulation of storage tank fire, it is required to be applied after construction and spraying after the storage tank is constructed. Therefore, each storage tank needs to be sprayed with the high-temperature-resistant heat-insulating coating in advance, and the engineering amount and the cost are huge.
With respect to the application of superabsorbent polymers, the most relevant application today is the fire suppression, mainly for class a fires. CN106039625A discloses a water-based fire extinguishing agent based on super absorbent resin, but the fire extinguishing agent has the disadvantages of too high viscosity, difficult construction, small adhesion force, difficult adhesion and the like, and is lack of temperature indicator and unable to guide the field fire extinguishing work.
Therefore, a new material which can be used rapidly under the condition of B-type fire, has strong adhesive force and good thixotropic property and can replace water to play a role in heat insulation and protection needs to be developed.
Disclosure of Invention
The invention aims to solve the problems that the existing high-temperature-resistant heat-insulating coating needs to be sprayed on a storage tank in advance to form a heat-insulating layer, the engineering quantity and the cost consumption are huge, and the emergency treatment application cannot be carried out in case of fire, and provides a cooling heat-insulating material composition, a cooling heat-insulating material and application thereof. The cooling and heat insulating material composition and the cooling and heat insulating material provided by the invention have good viscosity, high water absorption performance, heat insulating performance and thixotropic performance, can be rapidly solidified, have good adhesion to a tank wall, have good protection effect, can display the temperature of the tank wall in real time, and adopt a spray supplementing measure to an overhigh temperature, thereby further improving the safety of a storage tank.
In order to achieve the above object, in one aspect, the present invention provides a cooling and heat insulating material composition, which contains a super absorbent resin, a heat insulating filler, a temperature indicating material, a thixotropy regulating material, and an adhesion promoter, wherein the super absorbent resin is 100 parts by weight, the heat insulating filler is 5 to 30 parts by weight, the temperature indicating material is 5 to 15 parts by weight, the thixotropy regulating material is 1 to 15 parts by weight, and the adhesion promoter is 0.1 to 3 parts by weight.
Preferably, the super absorbent resin is 100 parts by weight, the content of the heat insulation filler is 10-20 parts by weight, the content of the temperature indicating material is 8-13 parts by weight, the content of the thixotropy regulating material is 5-10 parts by weight, and the content of the adhesion promoter is 0.5-2.5 parts by weight.
Preferably, the super absorbent resin is obtained by polymerizing acrylic acid, acrylamide, a cross-linking agent, an initiator and a clay material.
Preferably, the clay material is used in an amount of 10-40 parts by weight, the cross-linking agent is used in an amount of 1-5 parts by weight, and the initiator is used in an amount of 0.01-1 part by weight, relative to 100 parts by weight of the acrylic acid and acrylamide monomer material.
Preferably, the monomer material for preparing the high water-absorbent resin is acrylic acid, acrylamide; the cross-linking agent is selected from one or more of N, N '-methylene bisacrylamide, N' -ethylene bisacrylamide, maleylated chitosan and maleylated gelatin; the initiator is a composite redox initiator consisting of hydrogen peroxide, potassium persulfate, sodium persulfate, ammonium persulfate and sodium bisulfite.
Preferably, the thermal insulation filler is selected from one or more of aerogel, thermal insulation whisker, ceramic fiber and cenosphere.
Preferably, the aerogel is selected from one or more of silica aerogel, alumina aerogel, zirconia aerogel and silicon carbide aerogel.
Preferably, the thermal insulation whiskers are selected from one or more of potassium hexatitanate whiskers, calcium sulfate whiskers, silicon carbide whiskers and alumina whiskers.
Preferably, the ceramic fibers are selected from one or more of aluminum silicate fibers, aluminum oxide fibers, and silicon carbide fibers.
Preferably, the cenospheres are selected from one or more of silica cenospheres, zirconia cenospheres, alumina cenospheres and hollow glass cenospheres.
Preferably, the temperature indicating material is a reversible thermochromic material.
Preferably, the thixotropy control material refers to a clay material and/or a natural renewable polymer material.
Preferably, the natural renewable polymer material is selected from one or more of hydroxyethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose, carboxymethyl starch, xanthan gum, maleylation chitosan and modified sodium alginate.
Preferably, the clay material is selected from one or more of sodium bentonite, attapulgite clay, kaolin and organobentonite.
Preferably, the adhesion promoter is selected from one or more of diethylene glycol, propylene glycol, glycerol, pentaerythritol, polyethylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerol diglycidyl ether, and polyglycerol diglycidyl ether.
In a second aspect, the invention provides a cooling and heat insulating material, which is prepared by mixing the cooling and heat insulating material composition of the invention and water.
Preferably, the mass ratio of the cooling and heat insulation material composition to the water is 1 to (60-200).
In a third aspect, the invention provides the use of the cooling and heat insulating material composition or the cooling and heat insulating material of the invention in the safety protection of a storage tank area in a B-type fire.
The cooling and heat insulating material composition has good viscosity, high water absorption performance, heat insulating performance and thixotropic performance, can be quickly solidified, and has good adhesion to the tank wall, so that the heat insulating material can play a good protection effect at high temperature of fire; the thermal insulation material does not need to be sprayed in advance, can be stored in a tank area, and can be quickly attached to the wall of a tank by utilizing large-scale spraying equipment to be sprayed to an adjacent storage tank in an emergency when the storage tank is in a fire disaster, so that the thermal insulation material plays a role in thermal insulation protection; meanwhile, the temperature indicating material can display the temperature of the tank wall in real time, and a spray supplementing measure is taken for the position with overhigh temperature, so that the safety of the storage tank is further improved. And after fire extinguishing, removing the heat insulation material composition by using a high-pressure water gun.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The term "thermal insulation" as used in this specification is to be understood in a broad sense to include both heat and temperature resistant meanings.
Class B fires refer to liquid fires and meltable solid matter fires, such as petroleum products and the like. Petroleum products refer to natural gas; natural and synthetic liquid hydrocarbon products (including but not limited to biodegradable oils, crude oils, refinery products including gasoline, other fuels, and solvents); and semi-solid/solid hydrocarbon products (including but not limited to tar sands, bitumen, etc.).
According to a first aspect, the invention provides a cooling and heat insulating material composition, which comprises 100 parts by weight of super absorbent resin, 5-30 parts by weight of heat insulating filler, 5-15 parts by weight of temperature indicating material, 1-15 parts by weight of thixotropy regulating material and 0.1-3 parts by weight of adhesion promoter.
By using the synergistic effect of the specific components, the cooling and heat insulating material obtained from the cooling and heat insulating material composition has good viscosity, high water absorption performance, heat insulating performance and thixotropic performance, can be quickly solidified, and has good adhesion to the tank wall, so that the heat insulating material can play a good protection effect at high temperature of fire; the temperature indicating material can display the temperature of the tank wall in real time, and a supplementary spraying measure is taken for the position with overhigh temperature, so that the safety of the storage tank is further improved.
In order to further improve the protective performance of the heat insulating material composition, in the invention, preferably, the super absorbent resin is 100 parts by weight, the content of the heat insulating filler is 10-20 parts by weight, the content of the temperature indicating material is 8-13 parts by weight, the content of the thixotropy regulating material is 5-10 parts by weight, and the content of the adhesion promoter is 0.5-2.5 parts by weight.
In the present invention, the super absorbent resin is not particularly limited, and any resin having a high water absorption may be used as long as the water absorption capacity is 100 times or more of the self weight. In order to further improve the water absorption performance of the heat insulation material composition, thereby improving the protective performance of the heat insulation material, in the invention, the water absorption capacity of the super absorbent resin is preferably 1200 times of the self weight; more preferably, the water absorption capacity of the super absorbent resin is 200-1000 times of the self weight.
In the present invention, the super absorbent resin can be obtained commercially or can be prepared by using the following method. That is, the super absorbent resin is obtained by polymerizing a mixture containing acrylic acid, acrylamide, a cross-linking agent and an initiator in an aqueous suspension system in the presence of a clay material. In the present invention, it is preferable that the super absorbent resin is polymerized from acrylic acid, acrylamide, a cross-linking agent, an initiator and a clay material.
In order to further improve the water absorption performance of the heat insulation material composition and thus improve the protective performance of the heat insulation material, in the present invention, preferably, the amount of the clay material is 10 to 40 parts by weight, the amount of the cross-linking agent is 1 to 5 parts by weight, and the amount of the initiator is 0.01 to 1 part by weight, relative to 100 parts by weight of the acrylic acid and acrylamide monomer materials; more preferably, the clay material is used in an amount of 20 to 30 parts by weight, the crosslinking agent is used in an amount of 1.5 to 4.5 parts by weight, and the initiator is used in an amount of 0.05 to 0.5 part by weight, with respect to 100 parts by weight of the acrylic acid and acrylamide monomer material, wherein the acrylic acid content may be 60 to 90 wt%, preferably 65 to 85 wt%, in 100 parts by weight of the acrylic acid and acrylamide monomer material.
In the present invention, preferably, the crosslinking agent is selected from one or more of N, N '-methylenebisacrylamide, N' -ethylenebisacrylamide, maleylated chitosan, and maleylated gelatin; more preferably, the crosslinker is N, N' -methylenebisacrylamide.
In the present invention, preferably, the initiator is selected from a complex redox initiator consisting of hydrogen peroxide, potassium persulfate, sodium persulfate, ammonium persulfate and sodium bisulfite; more preferably, the initiator is a composite redox initiator consisting of ammonium persulfate and sodium bisulfite.
The conditions of the above polymerization reaction are not particularly limited, and for example, the reaction conditions may include: the reaction temperature is 20-70 ℃, and the reaction time is 2-10 h; preferably, the reaction temperature is 30-60 ℃ and the reaction time is 5-8 h.
The particle size of the super absorbent resin is not particularly limited, and in order to further enhance the protective performance of the heat insulating material composition, the super absorbent resin is preferably in the form of powder, and the particle size of the powder is preferably 50 to 500 μm; more preferably, the particle size of the powder is 50-200 μm.
In a specific embodiment of the present invention, the super absorbent resin is prepared by the following steps:
1) preparing sodium acrylate and acrylamide solution, adjusting the neutralization degree of acrylic acid to 60-80% by using sodium hydroxide, adding clay material, and stirring to form suspension;
2) adding a cross-linking agent and an initiator into the solution obtained in the step 1) to carry out polymerization reaction at the reaction temperature of 30-60 ℃ for 5-8 h;
3) cutting the gel obtained in the step 2), drying at the temperature of 120-200 ℃, grinding and screening to obtain the super absorbent resin with the particle size of 50-200 mu m.
In the present invention, the thermal insulation filler is not particularly limited, and may be various thermal insulation fillers available to those skilled in the art, and preferably, the thermal insulation filler is selected from one or more of aerogel, thermal insulation whisker, ceramic fiber and cenosphere.
The aerogel is not particularly limited and may be various aerogels available to those skilled in the art, and preferably, the aerogel is selected from one or more of silica aerogel, alumina aerogel, zirconia aerogel and silicon carbide aerogel.
The particle size of the above aerogel is not particularly limited, and preferably, the particle size of the aerogel is 1 to 10 μm.
The above-mentioned thermal insulation whisker is not particularly limited, and may be any of various thermal insulation whiskers available to those skilled in the art, and preferably, the thermal insulation whisker is selected from one or more of potassium hexatitanate whisker, calcium sulfate whisker, silicon carbide whisker and alumina whisker.
The length of the thermal insulation whisker is not particularly limited, and preferably the length of the thermal insulation whisker is 20 to 100 μm, and the diameter of the thermal insulation whisker is also not particularly limited, and preferably 2 to 10 μm.
The ceramic fiber is not particularly limited and may be various ceramic fibers available to those skilled in the art, and preferably, the ceramic fiber is selected from one or more of aluminum silicate fiber, alumina fiber and silicon carbide fiber.
The length of the ceramic fiber is not particularly limited, preferably, the length of the ceramic fiber is 50 to 200 μm, and the diameter of the ceramic fiber is also not particularly limited, preferably, 2 to 10 μm.
The cenospheres are not particularly limited and may be various cenospheres available to those skilled in the art, and preferably, the cenospheres are one or more selected from the group consisting of silica cenospheres, zirconia cenospheres, alumina cenospheres, and hollow glass cenospheres.
The particle size of the cenospheres is not particularly limited, and preferably, the particle size of the cenospheres is 1 to 20 μm.
The kind of the above-mentioned temperature indicating material is not particularly limited, and may be any of various materials capable of showing a change in temperature, and in the present invention, it is preferable that the temperature indicating material is a reversible thermochromic material, and in a specific embodiment of the present invention, solid cobalt chloride hexahydrate and solid hexamethylenetetramine are mixed in an equimolar ratio to prepare the temperature indicating material by a solid phase synthesis method, and the wet color of the material is pink, and the dry color changes to bluish violet after heating, and the change in color is remarkable.
The thixotropic material is not particularly limited, and may be various thixotropy regulating materials available to those skilled in the art, and in order to further enhance the protective performance of the thermal insulation material composition, in the present invention, preferably, the thixotropy regulating material refers to a clay material and/or a natural renewable polymer material.
In the present invention, preferably, the clay material is selected from one or more of sodium bentonite, attapulgite clay, kaolin and organobentonite; more preferably, the clay material is sodium bentonite or organobentonite.
The particle size of the clay material is not particularly limited, and may be, for example, 20 to 200 μm.
Preferably, the natural renewable polymer material is selected from one or more of hydroxyethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose, carboxymethyl starch, xanthan gum, maleylation chitosan and modified sodium alginate; more preferably, the natural renewable polymer material is hydroxypropyl cellulose, carboxymethyl starch, xanthan gum, maleylation chitosan or modified sodium alginate.
In the present invention, preferably, the adhesion promoter is selected from one or more of diethylene glycol, propylene glycol, glycerol, pentaerythritol, polyethylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerol diglycidyl ether, and polyglycerol diglycidyl ether; more preferably, the adhesion promoter is glycerol, pentaerythritol, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, or glycerol diglycidyl ether. Because the existing common organic silicon adhesion promoters have unobvious adhesion effect by forming chemical bonds or Van der Waals force with inorganic base materials, the polyol adhesion promoters are adopted to replace the conventionally used organic silicon adhesion additives, so that the adhesion of the heat-insulating material composition is increased, the protective performance of the heat-insulating material is further improved, and the safety of the storage tank is further improved.
In a second aspect, the present invention provides a cooling and heat insulating material prepared by mixing the above cooling and heat insulating material composition with water.
According to the invention, the amount of the water can be selected according to the amount of the cooling and heat insulating material composition, can be selected within the range of 1: 50-1000, and in order to further ensure that the heat insulating material has good high temperature resistance, heat insulation, thixotropic property, quick condensation property and adhesion property and good construction performance, in the invention, the mass ratio of the cooling and heat insulating material composition to the water is preferably 1: 60-200; more preferably, the mass ratio of the cooling and heat insulating material composition to the water is 1: (65-150).
The conditions for mixing the cooling and heat insulating material composition with water are not particularly limited, and the mixing may be performed at 15 to 45 ℃, for example; the time for mixing the heat insulating material composition with water is not particularly limited, and the purpose of uniformly mixing the components can be sufficiently achieved, and for example, the mixing time may be 5 to 15 min.
In a third aspect, the invention also provides the application of the cooling and heat insulating material composition or the cooling and heat insulating material in the safety protection of the storage tank area in the B-type fire.
The present invention will be described in detail below by way of examples, but the present invention is not limited to the following examples.
In the following examples and preparation examples, the water absorption property, adhesion property, thixotropic property and heat insulating property of the heat insulating material were measured by the following methods.
1. The water absorption performance of the cooling and heat insulating material was measured by a gravity method.
2. The rheological properties of the cooled insulation material were measured using a Bohler rheometer (Bohler Corp., USA)), the viscosity of the cooled insulation material during the change of the viscometer rotor from 6RPM to 60RPM was tested, and the thixotropic properties of the cooled insulation material were examined.
3. The density of the cooling and heat insulating material was measured by the pycnometer method.
4. And (3) adopting a thermal balance instrument with programmed temperature rise to research the pyrolysis weight loss of the composite material.
5. And (3) heating the simulated tank body to 170 ℃ by adopting a high-temperature heating device (the heating temperature is set to be 600 ℃), then spraying a cooling and heat-insulating material, testing and recording the cooling effect of the composite resin by a dynamic signal continuous monitoring system, and inspecting the cooling and heat-insulating effect.
Preparation example 1
A room temperature solid phase synthesis method is used for synthesizing a temperature indicating material, solid cobalt chloride hexahydrate and solid hexamethylene tetramine are mixed according to an equimolar ratio, a sample gradually becomes sticky and caked along with the grinding, the continuously ground caked gradually disappears, the dried sample becomes powder, and meanwhile, the red color of the reactant cobalt chloride hexahydrate completely disappears to become a blue product.
Preparation example 2
2 parts by weight of a crosslinking agent (N, N' -methylenebisacrylamide), 20 parts by weight of sodium bentonite, and 500 parts by weight of water were added to a vessel, and stirred to be sufficiently dissolved. After the dissolution was completed, acrylic acid (70 parts by weight) and acrylamide (30 parts by weight) were added to dissolve them sufficiently, and a sodium hydroxide solution (20 wt%) was added dropwise to neutralize them so that the neutralization degree of acrylic acid became 70%. Then 0.1 weight part of ammonium persulfate and 0.1 weight part of sodium bisulfite are added, the mixture is continuously stirred for 5min, and the mixture is statically polymerized for 3h at the temperature of 60 ℃ to obtain gel. The obtained gel was cut into small pieces and dried in a dryer at 200 ℃ and then pulverized and sieved to obtain a super absorbent resin having a particle size of 80 to 200 μm and a water absorption capacity of 1029.1 g/g.
Preparation example 3
1 part by weight of a crosslinking agent (N, N' -methylenebisacrylamide), 20 parts by weight of sodium bentonite, and 500 parts by weight of water were added to a vessel, and stirred to be sufficiently dissolved. After the dissolution was completed, acrylic acid (80 parts by weight) and acrylamide (20 parts by weight) were added to dissolve them sufficiently, and a sodium hydroxide solution (20 wt%) was added dropwise to neutralize them so that the neutralization degree of acrylic acid became 80%. Then 0.1 weight part of ammonium persulfate and 0.1 weight part of sodium bisulfite are added, the mixture is continuously stirred for 5min, and the mixture is statically polymerized for 3h at the temperature of 60 ℃ to obtain gel. The obtained gel was cut into small pieces and dried in a dryer at 200 ℃ and then pulverized and sieved to obtain a super absorbent resin having a particle size of 80 to 200 μm and a water absorption capacity of 882.5 g/g.
Preparation example 4
2 parts by weight of a crosslinking agent (N, N' -methylenebisacrylamide), 30 parts by weight of sodium bentonite, and 500 parts by weight of water were added to a vessel, and stirred to be sufficiently dissolved. After the dissolution was completed, acrylic acid (80 parts by weight) and acrylamide (20 parts by weight) were added to dissolve them sufficiently, and a sodium hydroxide solution (20 wt%) was added dropwise to neutralize them so that the neutralization degree of acrylic acid became 80%. Then adding 0.1 weight part of initiator ammonium persulfate and 0.1 weight part of sodium bisulfite, continuing stirring for 5min, and carrying out static polymerization reaction at 60 ℃ for 3h to obtain gel. Cutting the obtained gel into pieces, drying in a dryer at 200 deg.C, taking out the pieces, and sieving to obtain super absorbent resin with particle diameter of 80-200 μm and water absorption capacity of 969.1 g/g.
Example 1
50kg (average particle size 100 μm) of the super absorbent resin prepared in preparation example 2, 2kg of the temperature indicating material prepared in preparation example 1, 2kg of xanthan gum, 0.5kg of maleylated chitosan, 10kg of hollow glass beads (silica hollow beads, average particle size 5 μm), 0.5kg of adhesion promoter (pentaerythritol) and 5000kg of water were respectively added to a high-speed stirrer and dispersed and stirred at a rotation speed of 3000r/min for 10min to obtain a cooling and heat insulating material A1.
Example 2
50kg (average particle size of 100 μm) of the super absorbent resin obtained in production example 2, 2kg of the temperature indicating material obtained in production example 1, 1kg of xanthan gum, 1kg of sodium bentonite, 5kg of calcium sulfide whisker (average length of 25 μm and average diameter of 2 μm), 0.5kg of adhesion promoter (glycerol) and 5000kg of water were separately added to a high-speed mixer, and dispersed and stirred at 3000r/min for 10min to obtain a cooling and heat insulating material A2.
Example 3
50kg (average particle size 100 μm) of the super absorbent resin obtained in production example 2, 2kg of the temperature indicating material obtained in production example 1, 1kg of xanthan gum, 1kg of hydroxymethyl cellulose, 5kg of hollow glass beads (silica hollow beads, average particle size 5 μm), 0.5kg of adhesion promoter (glycerol), and 5000kg of water were separately added to a high-speed mixer, and dispersed and stirred at 3000r/min for 10min to obtain a cooling and heat insulating material A3.
Example 4
50kg (average particle size 100 μm) of the super absorbent resin prepared in preparation example 3, 2kg of the temperature indicating material prepared in preparation example 1, 2kg of xanthan gum, 0.5kg of carboxymethyl starch, 5kg of hollow glass beads (silica hollow beads, average particle size 5 μm), 0.5kg of adhesion promoter (glycerol), and 5000kg of water were respectively added to a high-speed stirrer, and dispersed and stirred at 3000r/min for 10min to obtain a cooling and heat insulating material A4.
Example 5
50kg (average particle size 100 μm) of the super absorbent resin obtained in production example 4, 2kg of the temperature indicating material obtained in production example 1, 2kg of sodium bentonite, 0.5kg of maleylated chitosan, 5kg of hollow glass beads (silica hollow beads, average particle size 5 μm), 0.5kg of adhesion promoter (glycerol), and 5000kg of water were separately added to a high-speed mixer, and dispersed and stirred at 3000r/min for 10min to obtain a cooling and heat insulating material A5.
Example 6
50kg (average particle size 100 μm) of the super absorbent resin obtained in production example 2, 2kg of the temperature indicating material obtained in production example 1, 2kg of sodium bentonite, 0.5kg of maleylated chitosan, 0.5kg of an adhesion promoter (propylene glycol diglycidyl ether), 5kg of hollow glass beads (silica hollow beads, average particle size 5 μm), and 5000kg of water were separately charged into a high-speed mixer, and dispersed and stirred at 3000r/min for 10min to obtain a cooling and heat insulating material A6.
Example 7
30kg (average particle size of 100 μm) of the super absorbent resin prepared in preparation example 2, 2kg of the temperature indicating material prepared in preparation example 1, 1kg of xanthan gum, 1kg of sodium bentonite, 0.5kg of maleylated chitosan, 5kg of hollow glass beads (silica hollow beads, average particle size of 5 μm), 0.5kg of adhesion promoter (ethylene glycol diglycidyl ether) and 5000kg of water were respectively added into a high-speed stirrer, and dispersed and stirred at a rotating speed of 3000r/min for 10min to obtain a cooling and heat insulating material A7.
Example 8
30kg (average particle size of 100 μm) of the super absorbent resin prepared in preparation example 2, 2kg of the temperature indicating material prepared in preparation example 1, 1kg of xanthan gum, 1kg of sodium bentonite, 0.5kg of maleylated chitosan, 10kg of hollow glass beads (silica hollow beads, average particle size of 5 μm), 0.5kg of adhesion promoter (ethylene glycol diglycidyl ether) and 5000kg of water were respectively added into a high-speed stirrer, and dispersed and stirred at a rotating speed of 3000r/min for 10min to obtain a cooling and heat insulating material A8.
Comparative example 1 (comparison with example 1, without adding super absorbent resin + temperature indicating material)
2kg of xanthan gum, 0.5kg of maleylation chitosan, 10kg of hollow glass beads (silicon dioxide hollow beads with the average particle size of 5 microns), 0.5kg of adhesion promoter (pentaerythritol) and 5000kg of water are respectively added into a high-speed stirrer and are dispersed and stirred for 10min under a stirring dispersion machine with the rotating speed of 3000r/min to obtain the cooling and heat insulating material D1.
Comparative example 2 (comparison with example 1, without addition of adhesion promoter)
50kg (average particle size of 100 μm) of the super absorbent resin prepared in preparation example 2, 2kg of the temperature indicating material prepared in preparation example 1, 2kg of xanthan gum, 0.5kg of maleylated chitosan, 10kg of hollow glass beads (silica hollow beads, average particle size of 5 μm) and 5000kg of water were respectively added to a high-speed stirrer, and dispersed and stirred at 3000r/min for 10min to obtain a cooling and heat insulating material D2.
Comparative example 3 (comparison with example 1, without addition of insulating Filler + temperature indicating Material)
50kg of the super absorbent resin (average particle size 100 μm) prepared in preparation example 2, 2kg of xanthan gum, 0.5kg of maleylated chitosan, 0.5kg of adhesion promoter (pentaerythritol), and 5000kg of water were added to a high-speed mixer, and dispersed and stirred at 3000r/min for 10min to obtain a cooling and heat insulating material D3.
Comparative example 4 (comparison with example 1, without addition of insulating Filler)
50kg of the super absorbent polymer (average particle size 100 μm) obtained in production example 2, 2kg of the temperature indicating material (temperature indicating material) obtained in production example 1, 2kg of xanthan gum, 0.5kg of maleylated chitosan, 0.5kg of adhesion promoter (pentaerythritol), and 5000kg of water were separately added to a high speed mixer, and dispersed and stirred at 3000r/min for 10min to obtain a cooling and heat insulating material D4.
The cooling and heat insulating materials A1-A8 and D1-D4 were subjected to performance tests, and the results are shown in Table 1.
TABLE 1
Figure BDA0002407894970000151
Wherein the thickness of the adhesionAUniformly spraying a cooling and heat-insulating material on the surface of a simulated tank body, enabling the cooling and heat-insulating material to naturally flow, and measuring the average attachment thickness of the material on the surface of the tank body;
thixotropic PropertiesBThe viscometer rotor cools the viscosity change of the insulation material during the change from 6RPM to 60 RPM;
heat insulation performanceCAnd heating the cooling heat-insulating material to 170 ℃.
As can be seen from table 1: the thermal insulation materials of the embodiments 1-8 of the invention can be rapidly solidified at high temperature, have strong adhesive force and good thixotropic property and thermal insulation property, and simultaneously can display the temperature of the tank wall in real time by adding the temperature indicating material, and a spray supplementing measure is taken for the position with over-high temperature, so that the safety of the storage tank is further improved.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (15)

1. The cooling and heat insulating material composition is characterized by comprising 100 parts by weight of super absorbent resin, 5-30 parts by weight of heat insulating filler, 5-15 parts by weight of temperature indicating material, 1-15 parts by weight of thixotropy regulating material and 0.1-3 parts by weight of adhesion promoter.
2. The cooling and heat insulating material composition according to claim 1, wherein the content of the heat insulating filler is 10 to 20 parts by weight, the content of the temperature indicating material is 8 to 13 parts by weight, the content of the thixotropy regulating material is 5 to 10 parts by weight, and the content of the adhesion promoter is 0.5 to 2.5 parts by weight, based on 100 parts by weight of the super absorbent resin.
3. The cooling and heat insulating material composition according to claim 1, wherein the super absorbent resin is obtained by polymerizing acrylic acid, acrylamide, a cross-linking agent, an initiator and a clay material.
4. The cooling and heat insulating material composition as claimed in claim 3, wherein the clay material is used in an amount of 10-40 parts by weight, the cross-linking agent is used in an amount of 1-5 parts by weight, and the initiator is used in an amount of 0.01-1 part by weight, relative to 100 parts by weight of the acrylic acid and acrylamide monomer material.
5. The cooling and heat insulating material composition according to claim 4, wherein the monomer material for the production of the super absorbent resin is acrylic acid, acrylamide; the cross-linking agent is selected from one or more of N, N '-methylene bisacrylamide, N' -ethylene bisacrylamide, maleylated chitosan and maleylated gelatin; the initiator is a composite redox initiator consisting of hydrogen peroxide, potassium persulfate, sodium persulfate, ammonium persulfate and sodium bisulfite.
6. The cooling insulation material composition of claim 1, wherein the insulation filler is selected from one or more of aerogels, insulation whiskers, ceramic fibers, and cenospheres.
7. The cooling insulation composition of claim 6, wherein the aerogel is selected from one or more of a silica aerogel, an alumina aerogel, a zirconia aerogel, and a silicon carbide aerogel;
preferably, the heat insulation whisker is selected from one or more of potassium hexatitanate whisker, calcium sulfate whisker, silicon carbide whisker and alumina whisker;
preferably, the ceramic fibers are selected from one or more of aluminum silicate fibers, aluminum oxide fibers and silicon carbide fibers;
preferably, the cenospheres are selected from one or more of silica cenospheres, zirconia cenospheres, alumina cenospheres and hollow glass cenospheres.
8. The cooling and insulating material composition of claim 1, wherein the temperature indicating material is a reversible thermochromic material.
9. The cooling and insulating material composition according to claim 1, wherein the thixotropy regulating material is clay material and/or natural renewable polymer material.
10. The cooling and insulating material composition according to claim 9, wherein the natural renewable polymer material is selected from one or more of hydroxyethylcellulose, hydroxymethylcellulose, hydroxypropylcellulose, carboxymethyl starch, xanthan gum, maleylated chitosan and modified sodium alginate.
11. The cooling and insulating material composition of claim 3 or 9, wherein the clay material is selected from one or more of sodium bentonite, attapulgite clay, kaolin and organobentonite.
12. The cooling and insulating material composition according to claim 1, wherein the adhesion promoter is selected from one or more of diethylene glycol, propylene glycol, glycerol, pentaerythritol, polyethylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerol diglycidyl ether, and polyglycerol diglycidyl ether.
13. A cooling and heat insulating material, characterized in that it is obtained by mixing the cooling and heat insulating material composition according to any one of claims 1 to 12 with water.
14. The cooling and insulating material according to claim 13, wherein the mass ratio of the cooling and insulating material composition to water is 1: (60-200).
15. Use of the cooling and insulating material composition according to any one of claims 1 to 12, the cooling and insulating material according to claim 13 or claim 14 for tank farm safety protection in group B fires.
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