CN113388068A - Cooling and heat insulating material composition based on temperature-sensitive gel, cooling and heat insulating material based on temperature-sensitive gel and application thereof - Google Patents

Cooling and heat insulating material composition based on temperature-sensitive gel, cooling and heat insulating material based on temperature-sensitive gel and application thereof Download PDF

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CN113388068A
CN113388068A CN202010167278.3A CN202010167278A CN113388068A CN 113388068 A CN113388068 A CN 113388068A CN 202010167278 A CN202010167278 A CN 202010167278A CN 113388068 A CN113388068 A CN 113388068A
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temperature
insulating material
sensitive gel
cooling
heat insulating
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CN113388068B (en
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张日鹏
姜春明
牟善军
方煜
李智临
矫恒超
王春
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China Petroleum and Chemical Corp
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
    • 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
    • C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
    • 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
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/02—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to polysaccharides
    • 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
    • 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
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/004—Additives being defined by their length

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Abstract

The invention relates to the field of high-temperature resistance and heat insulation, and discloses a cooling and heat insulating material composition based on temperature-sensitive gel, a cooling and heat insulating material based on temperature-sensitive gel and application thereof. The cooling and heat insulating material composition based on the temperature-sensitive gel comprises chitosan-based temperature-sensitive gel, heat insulating filler and an adhesion promoter, wherein the chitosan-based temperature-sensitive gel is 100 parts by weight, the content of the heat insulating filler is 5-30 parts by weight, and the content of the adhesion promoter is 0.1-3 parts by weight. The cooling and heat insulating material provided by the invention can be quickly used under the condition of B-type fire, and has strong adhesive force and good thixotropic property.

Description

Cooling and heat insulating material composition based on temperature-sensitive gel, cooling and heat insulating material based on temperature-sensitive gel 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 based on temperature-sensitive gel, a cooling and heat insulating material based on temperature-sensitive gel 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. In the event of a fire in one tank, the hydrocarbon fire will emit intense heat radiation and the adjacent tanks will be exposed to intense heat radiation, and the following may occur: 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 method for protecting adjacent tanks in case of fire is to apply water spray, i.e. to spray water to the surfaces of adjacent storage tanks by fixing a water spray system or moving a water gun, and to take away heat through the flow and volatilization of water, thereby protecting the adjacent storage tanks. 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 bank in the tank area, water accumulation in the tank area is serious, the fire rescue is seriously hindered, and when oil leaks, the method can also help to form 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, Chinese patent CN102030540A discloses a high-temperature resistant heat-insulating coating consisting of inorganic high-temperature refractory mortar, silicon dioxide aerogel, potassium hexatitanate whisker, mica sheet and acetone/anhydrous ethanol; 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 a storage tank in fire, the coating can be used after construction and spraying after the storage tank is completely 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 defects of too high viscosity, difficult construction, small adhesive force, difficult adhesion and the like, is lack of a temperature indicator and cannot guide the field fire extinguishing work; CN103483752A discloses a super absorbent resin for a polymer gel fire extinguishing agent, the main component of the resin is sodium polyacrylate, and a part of adhesion promoters are added, but the sodium polyacrylate is not easy to degrade, and the formed super absorbent resin is difficult to meet the requirements of fluidity and wall-hanging property at the same time; CN102477136A and CN101353398A both disclose a preparation method of temperature sensitive gel, but the gel is applied to the field of biomedical engineering, the low critical solution temperature is 35-36 ℃, the temperature is too low, and in hot summer, the outdoor temperature can reach the temperature to cause the phase change of the gel, so that the gel cannot be used for protecting an adjacent storage tank.
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 and heat-insulating material composition based on temperature-sensitive gel, a cooling and heat-insulating material based on temperature-sensitive gel and application thereof. The cooling and heat insulating material provided by the invention can be quickly used under the condition of B-type fire, and has strong adhesive force and good thixotropic property.
In order to achieve the above object, a first aspect of the present invention provides a cooling and heat insulating material composition based on a temperature sensitive gel, which contains a chitosan-based temperature sensitive gel, a heat insulating filler and an adhesion promoter, wherein the content of the heat insulating filler is 5 to 30 parts by weight and the content of the adhesion promoter is 0.1 to 3 parts by weight, based on 100 parts by weight of the chitosan-based temperature sensitive gel.
Preferably, the chitosan-based temperature-sensitive gel is 100 parts by weight, the content of the heat insulation filler is 8-20 parts by weight, and the content of the adhesion promoter is 0.5-2.5 parts by weight.
Preferably, the chitosan-based temperature-sensitive gel is obtained by polymerizing a mixture containing chitosan, a temperature-sensitive monomer, acrylic acid and/or an alkali metal salt thereof, a crosslinking agent and an initiator.
Preferably, the amount of the temperature-sensitive monomer is 300-650 parts by weight, the amount of the acrylic acid and/or the alkali metal salt thereof is 50-250 parts by weight, the amount of the cross-linking agent is 10-80 parts by weight, and the amount of the initiator is 0.1-8 parts by weight, relative to 100 parts by weight of the chitosan.
Preferably, the temperature sensitive monomer is an N-alkyl acrylamide.
Preferably, the temperature-sensitive monomer is selected from one or more of N-isopropylacrylamide, N-hydroxyethylacrylamide, N-hydroxypropylacrylamide and N-isobutylacrylamide.
Preferably, the cross-linking agent is selected from one or more of N, N '-methylenebisacrylamide or N, N' -ethylenebisacrylamide and maleylated chitosan.
Preferably, the initiator is a composite redox initiator consisting of hydrogen peroxide, potassium persulfate, sodium persulfate, ammonium persulfate and sodium bisulfite.
Preferably, the conditions of the reaction include: the reaction temperature is 20-70 ℃, and the reaction time is 4-10 h.
Preferably, the chitosan-based temperature-sensitive gel is powder, the particle size of the powder is 50-200 μm, and the temperature-sensitive phase change temperature is 30-80 ℃.
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 sodium silicate cenospheres.
Preferably, the aerogel has a particle size of 1-10 μm.
Preferably, the length of the heat insulation whisker is 20-100 μm, and the diameter is 2-10 μm.
Preferably, the ceramic fibers have a length of 50 to 200 μm and a diameter of 2 to 10 μm.
Preferably, the particle size of the cenospheres is 1-20 μm.
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.
The second aspect of the invention provides a cooling and heat insulating material based on temperature-sensitive gel, which is prepared by mixing the cooling and heat insulating material composition based on temperature-sensitive gel of the invention with water.
Preferably, the mass ratio of the temperature-sensitive gel-based cooling and heat-insulating material composition to water is 1 to (60-200).
The third aspect of the invention provides an application of the cooling and heat-insulating material based on the temperature-sensitive gel in the safety protection of a storage tank area under B-type fire hazards.
According to the temperature-sensitive cooling and heat-insulating material composition and the heat-insulating material, the chitosan-based temperature-sensitive gel is used as the matrix, so that the heat-insulating material has good degradation and thixotropic properties, and the heat-insulating material containing the chitosan-based temperature-sensitive gel is in a liquid state before being in contact with the wall of the tank, so that the heat-insulating material has good fluidity; the material is roasted by fire after contacting the wall of the tank, and the material is quickly solidified by phase change under high temperature, so that the material has good protection effect; by adding the heat insulation filler and the adhesion promoter, the heat insulation material is ensured to have good adhesion capability and heat insulation effect, so that the protection effect and the construction performance are further improved.
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 based on temperature-sensitive gel, which contains chitosan-based temperature-sensitive gel, heat insulating filler and an adhesion promoter, wherein the content of the heat insulating filler is 5-30 parts by weight and the content of the adhesion promoter is 0.1-3 parts by weight based on 100 parts by weight of the chitosan-based temperature-sensitive gel.
In the invention, the chitosan-based temperature-sensitive gel is used as the matrix, so that the heat-insulating material composition has good degradation and thixotropic properties, and the heat-insulating material composition containing the chitosan-based temperature-sensitive gel is in a liquid state before contacting with the wall of the tank, so that the heat-insulating material composition has good fluidity, is roasted after contacting with the wall of the tank, and is rapidly solidified by causing phase change at high temperature, so that the heat-insulating material composition has good protection effect, and the heat-insulating material composition has good adhesive capacity and heat-insulating effect through the adhesion promoter and the heat-insulating filler, so that the protection effect and the construction performance are further improved.
In order to further improve the protection effect and the construction performance, in the invention, preferably, the chitosan-based temperature-sensitive gel is 100 parts by weight, the content of the heat insulation filler is 8-20 parts by weight, and the content of the adhesion promoter is 0.5-2.5 parts by weight.
The chitosan-based temperature-sensitive gel is not particularly limited, and any chitosan-based temperature-sensitive gel can be used as long as the temperature-sensitive phase transition temperature of the chitosan-based temperature-sensitive gel is more than 35 ℃, preferably, the temperature-sensitive phase transition temperature of the chitosan-based temperature-sensitive gel is more than 40 ℃, and further preferably, the temperature-sensitive phase transition temperature of the chitosan-based temperature-sensitive gel is more than 45 ℃. In the present invention, it is preferable that the temperature-sensitive phase transition temperature of the chitosan-based temperature-sensitive gel is below 80 ℃; more preferably, the temperature-sensitive phase transition temperature of the chitosan-based temperature-sensitive gel is below 70 ℃.
According to the present invention, the chitosan-based temperature-sensitive gel may be obtained commercially or may be prepared by using the following method. That is, the chitosan-based temperature-sensitive gel is obtained by polymerizing a mixture containing chitosan, a temperature-sensitive monomer, acrylic acid and/or an alkali metal salt thereof, a crosslinking agent, and an initiator. In the present invention, it is preferable that the chitosan-based temperature-sensitive gel is obtained by polymerizing a mixture containing chitosan, a temperature-sensitive monomer, acrylic acid and/or an alkali metal salt thereof, a crosslinking agent, and an initiator.
The amount of the chitosan, the temperature-sensitive monomer, the acrylic acid and/or the alkali metal salt thereof, the cross-linking agent and the initiator in the polymerization reaction can be changed in a wide range, in the present invention, preferably, the amount of the temperature-sensitive monomer is 300-650 parts by weight, the amount of the acrylic acid is 50-250 parts by weight, the amount of the cross-linking agent is 10-80 parts by weight and the amount of the initiator is 0.1-8 parts by weight relative to 100 parts by weight of the chitosan; more preferably, the amount of the temperature-sensitive monomer is 250-550 parts by weight, the amount of the acrylic acid is 110-220 parts by weight, the amount of the cross-linking agent is 30-60 parts by weight, and the amount of the initiator is 2-6 parts by weight, relative to 100 parts by weight of the chitosan.
In the present invention, preferably, the temperature-sensitive monomer is N-alkyl acrylamide; more preferably, the temperature sensitive monomer is selected from one or more of N-isopropylacrylamide, N-hydroxyethylacrylamide, N-hydroxypropylacrylamide and N-isobutylacrylamide.
Preferably, the cross-linking agent is selected from one or more of N, N '-methylenebisacrylamide, N' -ethylbisacrylamide, and maleylated chitosan.
Preferably, the initiator is a composite redox initiator consisting of hydrogen peroxide, potassium persulfate, sodium persulfate, ammonium persulfate and sodium bisulfite.
In a preferred embodiment of the present invention, the chitosan-based temperature-sensitive gel is prepared by the following method:
1) preparing a chitosan acetic acid solution: preparing 1-2 wt% of acetic acid solution, and adding chitosan to prepare 5-10 wt% of chitosan acetic acid solution;
2) preparing a sodium acrylate solution: sodium hydroxide is used for leading the neutralization degree of the acrylic acid to reach 60-80 percent;
3) synthesizing temperature-sensitive chitosan gel: mixing the solution obtained in the step 2) and the solution obtained in the step 1), and adding a temperature-sensitive monomer, a cross-linking agent and an initiator to carry out polymerization reaction.
The molecular weight of the chitosan is not particularly limited and can vary within a wide range, but in view of compatibility suitable for the heat insulating material composition, the number average molecular weight of the chitosan is preferably 20000-.
The degree of deacetylation of the above chitosan is not particularly limited, and preferably, the degree of deacetylation of the chitosan is 85 to 95%.
The conditions of the polymerization reaction are not particularly limited, and a mixture of the chitosan, the temperature-sensitive monomer, acrylic acid and/or an alkali metal salt thereof, the crosslinking agent, and the initiator may be polymerized, and preferably, the conditions of the polymerization reaction include: the reaction temperature is 20-70 ℃, and the reaction time is 4-10 h; more preferably, the polymerization conditions include: the reaction temperature is 30-60 ℃, and the reaction time is 5-8 h.
In the present invention, the particle size of the chitosan-based temperature-sensitive gel is not particularly limited, and in order to further enhance the protective performance of the heat insulating material composition, it is preferable that the chitosan-based temperature-sensitive gel is in the form of powder having a particle size of 50 to 200 μm, and more preferably, 80 to 150 μm.
According to the present invention, the heat insulating filler is not particularly limited, and may be any of various heat insulating fillers available to those skilled in the art. 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 sodium silicate cenospheres.
The particle size of the cenospheres is not particularly limited, and preferably, the particle size of the cenospheres is 1 to 20 μm.
According to the present invention, the adhesion promoter is not particularly limited and may be various adhesion promoters available to those skilled in the art, and in the present invention, it is preferable that 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 based on temperature-sensitive gel, which is prepared by mixing the cooling and heat insulating material composition based on temperature-sensitive gel with water.
According to the present invention, the amount of water used may be selected depending on the amount of the temperature-sensitive cooling and heat-insulating material composition, and may be selected within the range of 1: (50-1000). When the amount of the temperature-sensitive cooling and heat-insulating material composition contained is less than the range, the adhesion and heat-insulating properties of the heat-insulating material may not be at the corresponding levels and the protective effect may not be sufficiently achieved because the amount of the heat-insulating material composition is too small compared with the amount of water used; when the heat insulating material composition is contained beyond this range of values, the viscosity is relatively high, and therefore, the composition may not be normally sprayed. In the present invention, it is preferable that the mass ratio of the temperature-sensitive gel-based cooling and heat insulating material composition to water is 1: (60-200); more preferably, the mass ratio of the temperature-sensitive gel-based cooling and heat-insulating material composition to water is 1: (65-150).
The mixing condition of the temperature-sensitive cooling and heat-insulating material composition and water is not particularly limited, and the mixing temperature is lower than the temperature-sensitive phase transition temperature of the chitosan-based temperature-sensitive gel, and preferably, the mixing is carried out at room temperature (for example, 10-30 ℃); the time for mixing the heat insulating material composition with water is not particularly limited, and the purpose of sufficiently mixing the heat insulating material composition with water may be achieved, and the mixing time is preferably 5 to 15 min.
According to the present invention, the mixing method of the temperature-sensitive cooling and heat insulating material composition and water is not particularly limited, and one or more components of the temperature-sensitive cooling and heat insulating material composition may be mixed in advance and then mixed with water, or one or more components of the heat insulating material composition may be mixed in advance with water and then mixed with other components.
In a preferred embodiment of the present invention, the temperature-sensitive cooling and heat insulating material is prepared by: mixing, dispersing, stirring and grinding the chitosan-based temperature-sensitive gel, the heat-insulating filler and the adhesion promoter in predetermined weight parts until the particle size is less than 50 mu m, and then mixing the mixture with water.
The grinding treatment can adopt a high-speed dispersion machine, a horizontal sand mill, a vertical sand mill or a pin-pin type sand mill, the ball-material ratio selected during the grinding treatment can be 1 to (0.5-1), and the grinding treatment time can be 2-3 h.
The conditions for the dispersion stirring may be: the rotating speed is 2000-.
In a third aspect, the invention also provides application of the cooling and heat-insulating material based on the temperature-sensitive gel in safety protection of a storage tank area under B-type fire hazards.
According to the cooling and heat insulating material composition based on the temperature-sensitive gel and the cooling and heat insulating material based on the temperature-sensitive gel, the chitosan-based temperature-sensitive gel is adopted as the matrix, so that the temperature-sensitive cooling and heat insulating material has good degradation and thixotropic properties, and simultaneously has the characteristic of being capable of being rapidly solidified at high temperature, so that the temperature-sensitive cooling and heat insulating material has a good protection effect, and the addition of the adhesion promoter and the heat insulating filler ensures that the heat insulating material composition has good adhesion and heat insulating effects, so that the protection effect and the construction performance of the heat insulating material are further improved; 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 tank wall by emergently spraying the thermal insulation material on an adjacent storage tank by using large-scale spraying equipment when the storage tank is in fire, so that the thermal insulation material plays a role in thermal insulation protection. And after fire extinguishing, removing the heat insulation material composition by using a high-pressure water gun.
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 heat insulating material was tested for temperature sensitivity, water absorption property, adhesion property, thixotropic property and heat insulating property by the following methods.
1. Measuring the temperature-sensitive performance of the chitosan-based temperature-sensitive gel:
the chitosan-based temperature-sensitive gel obtained in preparation examples 1 to 3 was prepared into a solution having a concentration of 10 wt%, the relationship between the transmittance value T and the temperature of each solution was measured with a spectrophotometer, and the temperature corresponding to the transmittance value T of 50% was taken as the temperature-sensitive phase transition temperature.
2. The water absorption performance of the cooling and heat insulating material was measured by a gravity method.
3. 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.
4. The density of the cooling and heat insulating material was measured by the pycnometer method.
5. And (3) adopting a thermal balance instrument with programmed temperature rise to research the pyrolysis weight loss of the composite material.
6. 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 of Chitosan-based temperature-sensitive gel
Preparation example 1
Preparing 1 wt% acetic acid solution, adding chitosan, and stirring uniformly (the content of chitosan in the solution is 10 wt%). Neutralizing the acrylic acid solution by using a sodium hydroxide solution with the mass fraction of 20 wt% to ensure that the neutralization degree of the acrylic acid reaches 70%. And after the temperature of the acrylic acid solution is restored to the room temperature, transferring the solution into a chitosan solution, adding N-isopropylacrylamide, uniformly stirring, then sequentially adding N, N' -methylenebisacrylamide and ammonium persulfate, heating in a heat collection type constant-temperature heating magnetic stirrer water bath, controlling the reaction temperature at 50 ℃, introducing nitrogen for protection, and reacting for 8 hours to obtain the chitosan-based temperature-sensitive hydrogel.
The product was rinsed repeatedly 3 times by swelling shrinkage, dried under vacuum at 80 ℃ for 15h, and ground to a powder (particle size of 100 μm). Wherein, the dosage of the chitosan is 10kg, the dosage of the N-isopropylacrylamide is 50kg, the dosage of the acrylic acid is 20kg, the dosage of the ammonium persulfate is 0.5kg, the dosage of the N, N' -methylene-bisacrylamide is 5kg, and the temperature-sensitive phase-change temperature is 65 ℃.
Preparation example 2
Preparing 1 wt% acetic acid solution, adding chitosan, and stirring uniformly (the content of chitosan in the solution is 10 wt%). Neutralizing the acrylic acid solution by using a sodium hydroxide solution with the mass fraction of 20 wt% to ensure that the neutralization degree of the acrylic acid reaches 70%. And after the temperature of the acrylic acid solution is restored to the room temperature, transferring the solution into a chitosan solution, adding N-isopropylacrylamide, uniformly stirring, then sequentially adding N, N' -methylenebisacrylamide and ammonium persulfate, heating in a heat collection type constant-temperature heating magnetic stirrer water bath, controlling the reaction temperature at 50 ℃, introducing nitrogen for protection, and reacting for 8 hours to obtain the chitosan-based temperature-sensitive hydrogel.
The product was rinsed repeatedly 3 times by swelling shrinkage, dried under vacuum at 80 ℃ for 15h, and ground to a powder (particle size of 100 μm). Wherein, the dosage of the chitosan is 15kg, the dosage of the N-isopropylacrylamide is 50kg, the dosage of the acrylic acid is 20kg, the dosage of the ammonium persulfate is 0.5kg, the dosage of the N, N' -methylene-bisacrylamide is 5kg, and the temperature-sensitive phase-change temperature is 55 ℃.
Preparation example 3
Preparing 1 wt% acetic acid solution, adding chitosan, and stirring uniformly (the content of chitosan in the solution is 10 wt%). Neutralizing the acrylic acid solution by using a sodium hydroxide solution with the mass fraction of 20 wt% to ensure that the neutralization degree of the acrylic acid reaches 70%. And after the temperature of the acrylic acid solution is restored to the room temperature, transferring the solution into a chitosan solution, adding N-isopropylacrylamide, uniformly stirring, then sequentially adding N, N' -methylenebisacrylamide and ammonium persulfate, heating in a heat collection type constant-temperature heating magnetic stirrer water bath, controlling the reaction temperature at 50 ℃, introducing nitrogen for protection, and reacting for 8 hours to obtain the chitosan-based temperature-sensitive hydrogel.
The product was rinsed repeatedly 3 times by swelling shrinkage, dried under vacuum at 80 ℃ for 15h, and ground to a powder (particle size of 100 μm). Wherein, the dosage of the chitosan is 10kg, the dosage of the N-isopropylacrylamide is 50kg, the dosage of the acrylic acid is 10kg, the dosage of the ammonium persulfate is 0.5kg, the dosage of the N, N' -methylene-bisacrylamide is 5kg, and the temperature-sensitive phase-change temperature is 45 ℃.
Example 1
50kg of the chitosan-based temperature-sensitive gel prepared in preparation example 1, 5kg of hollow glass beads (silica hollow beads, average particle size of 10 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 of the chitosan-based temperature-sensitive gel prepared in preparation example 2, 5kg of heat-insulating whiskers (silicon carbide whiskers with an average length of 50 μm and an average diameter of 5 μm), 0.5kg of adhesion promoter (glycerol) and 5000kg of water were added into a high-speed stirrer, and were subjected to dispersion stirring at a rotation speed of 3000r/min for 10min to obtain a cooling and heat-insulating material A2.
Example 3
50kg of the chitosan-based temperature-sensitive gel prepared in preparation example 3, 5kg of ceramic fiber (silicon carbide fiber, average length of 50 μm and average diameter of 5 μm), 0.5kg of adhesion promoter (pentaerythritol) and 5000kg of water were 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 A3.
Example 4
50kg of the chitosan-based temperature-sensitive gel prepared in preparation example 1, 5kg of hollow glass beads (silica hollow beads, average particle size of 10 μm), 1.0kg of adhesion promoter (diethylene glycol) 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 A4.
Example 5
50kg of the chitosan-based temperature-sensitive gel prepared in preparation example 1, 3kg of hollow glass beads (silica hollow beads, average particle size of 10 μm), 1.0kg of adhesion promoter (ethylene glycol diglycidyl ether) 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 A5.
Example 6
50kg of the chitosan-based temperature-sensitive gel prepared in preparation example 1, 5kg of hollow glass beads (silica hollow beads, average particle size of 10 μm), 0.5kg of adhesion promoter (glycerol diglycidyl ether) 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 A6.
Comparative example 1
50kg of the chitosan-based temperature-sensitive gel prepared in preparation example 1, 5kg of hollow glass beads (silica hollow beads, average particle size of 10 μm) and 5000kg of water were respectively added to 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 D1.
Comparative example 2
50kg of chitosan-based temperature-sensitive gel prepared in preparation example 1, 0.5kg of adhesion promoter (pentaerythritol) and 5000kg of water are respectively added into a high-speed stirrer and are dispersedly stirred for 10min at the rotating speed of 3000r/min, so that a cooling and heat-insulating material D2 is obtained.
Comparative example 3
30kg of chitosan-based temperature-sensitive gel (25 kg of hollow silica microspheres with the average particle size of 10 μm) prepared in preparation example 1, 0.5kg of adhesion promoter (pentaerythritol) and 5000kg of water were added into a high-speed stirrer, and dispersed and stirred at a rotating speed of 3000r/min for 10min, so as to obtain a cooling and heat insulating material D3.
The cooling and heat insulating materials A1-A6 and D1-D3 were subjected to performance tests, and the results are shown in Table 1.
TABLE 1
Figure BDA0002407897010000151
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 heat-insulating materials of embodiments 1-6 of the invention can be rapidly solidified at high temperature, have strong adhesion and good thixotropic property, and have good cooling and heat-insulating effects.
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 based on the temperature-sensitive gel is characterized by comprising 100 parts by weight of chitosan-based temperature-sensitive gel, 5-30 parts by weight of heat insulating filler and 0.1-3 parts by weight of adhesion promoter.
2. The cooling and heat insulating material composition based on temperature sensitive gel according to claim 1, wherein the content of the heat insulating filler is 8-20 parts by weight and the content of the adhesion promoter is 0.5-2.5 parts by weight based on 100 parts by weight of the chitosan-based temperature sensitive gel.
3. The cooling and heat insulating material composition based on temperature-sensitive gel according to claim 1, wherein the chitosan-based temperature-sensitive gel is obtained by polymerizing chitosan, a temperature-sensitive monomer, acrylic acid and/or an alkali metal salt thereof, a cross-linking agent and an initiator.
4. The temperature-sensitive gel-based cooling and heat insulating material composition according to claim 3, wherein the temperature-sensitive monomer is used in an amount of 300-650 parts by weight, the acrylic acid and/or its alkali metal salt is used in an amount of 50-250 parts by weight, the crosslinking agent is used in an amount of 10-80 parts by weight, and the initiator is used in an amount of 0.1-8 parts by weight, relative to 100 parts by weight of the chitosan.
5. The temperature-sensitive gel-based cooling and insulating material composition according to claim 4, wherein the temperature-sensitive monomer is N-alkylacrylamide;
preferably, the temperature-sensitive monomer is selected from one or more of N-isopropylacrylamide, N-hydroxyethylacrylamide, N-hydroxypropylacrylamide and N-isobutylacrylamide.
6. The temperature-sensitive gel-based cooling and insulating material composition according to claim 4, wherein the cross-linking agent is selected from one or more of N, N '-methylenebisacrylamide, N' -ethylenebisacrylamide, and maleylated chitosan;
preferably, the initiator is a composite redox initiator consisting of hydrogen peroxide, potassium persulfate, sodium persulfate, ammonium persulfate and sodium bisulfite.
7. The temperature-sensitive gel-based cooling and insulating material composition according to claim 4, wherein the reaction conditions include: the reaction temperature is 20-70 ℃, and the reaction time is 4-10 h.
8. The cooling and heat insulating material composition based on temperature-sensitive gel according to any one of claims 1 to 7, wherein the chitosan-based temperature-sensitive gel is in a powder form, the particle size of the powder is 50 to 200 μm, and the temperature-sensitive phase transition temperature is 30 to 80 ℃.
9. The temperature-sensitive gel-based cooling and insulating material composition according to any one of claims 1 to 7, wherein the insulating filler is selected from one or more of aerogel, insulating whisker, ceramic fiber and cenosphere.
10. The temperature-sensitive gel-based cooling and insulating material composition according to claim 9, wherein the aerogel is selected from one or more of silica aerogel, alumina aerogel, zirconia aerogel and 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 sodium silicate cenospheres.
11. The temperature-sensitive gel-based cooling and insulating material composition according to claim 9, wherein the aerogel has a particle size of 1 to 10 μm;
preferably, the length of the heat insulation whisker is 20-100 μm, and the diameter is 2-10 μm;
preferably, the ceramic fibers have a length of 50 to 200 μm and a diameter of 2 to 10 μm;
preferably, the particle size of the cenospheres is 1-20 μm.
12. The temperature-sensitive gel-based cooling and heat insulating material composition according to any one of claims 1 to 7, 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 temperature-sensitive gel-based cooling and heat insulating material characterized by being obtained by mixing the temperature-sensitive gel-based cooling and heat insulating material composition according to any one of claims 1 to 12 with water.
14. The temperature-sensitive gel-based cooling and heat-insulating material according to claim 13, wherein the mass ratio of the temperature-sensitive gel-based cooling and heat-insulating material composition to water is 1: 60-200.
15. Use of the temperature sensitive gel based cooling and insulating material according to claim 13 or 14 for tank farm safety protection in class B fire.
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