WO1999015602A1 - Milieu de transfert de chaleur, procede de production de celui-ci et systeme d'air climatise - Google Patents

Milieu de transfert de chaleur, procede de production de celui-ci et systeme d'air climatise Download PDF

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Publication number
WO1999015602A1
WO1999015602A1 PCT/JP1998/003907 JP9803907W WO9915602A1 WO 1999015602 A1 WO1999015602 A1 WO 1999015602A1 JP 9803907 W JP9803907 W JP 9803907W WO 9915602 A1 WO9915602 A1 WO 9915602A1
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Prior art keywords
heat transfer
oily substance
monomer
transfer medium
heat storage
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PCT/JP1998/003907
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English (en)
Japanese (ja)
Inventor
Tomoki Gomi
Yoshio Irie
Tadao Shimomura
Masaaki Yoshikawa
Akira Kishimoto
Original Assignee
Nippon Shokubai Co., Ltd.
Osaka Gas Company Limited
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Application filed by Nippon Shokubai Co., Ltd., Osaka Gas Company Limited filed Critical Nippon Shokubai Co., Ltd.
Publication of WO1999015602A1 publication Critical patent/WO1999015602A1/fr

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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
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa

Definitions

  • the present invention relates to a heat transfer medium for storing or cooling heat using latent heat when an oily substance undergoes a phase change, a method for manufacturing the same, and an air conditioning system.
  • No. 0 discloses a heat transfer medium obtained by simply dispersing a lipophilic organic compound, which is an oily substance, into an oil-absorbing resin and dispersing the lipophilic organic compound in a hydrophilic liquid such as water.
  • the lipophilic organic compound is simply absorbed by the oil-absorbing resin. For this reason, an (excess) lipophilic organic compound that cannot be completely absorbed by the oil-absorbing resin adheres to the surface of the oil-absorbing resin. When an external force acts on the oil-absorbing resin, the oil-absorbing resin The lipophilic organic compound exudes from the fat.
  • the lipophilic organic compound oozing out of the oil-absorbing resin is dispersed in the hydrophilic liquid in the form of fine particles, and the hydrophilic liquid, That is, since the heat transfer medium is thickened, there is a problem that the heat transfer efficiency of the heat transfer medium is significantly reduced. Further, when the lipophilic organic compound dispersed in the lipophilic liquid solidifies, the fluidity of the heat transfer medium is reduced, and the fluid becomes difficult to flow. For this reason, there arises a problem that the transport power required to transport the heat transport medium increases or that the heat transport medium cannot be transported.
  • the inventors of the present application have intensively studied to provide a heat transfer medium, a method for manufacturing the same, and an air conditioning system.
  • a monomer component comprising a monomer (A) having a solubility parameter of a certain value or less and a monomer (B) having a hydrophilic group in the molecule, and a heat storage property are obtained. Liquefies due to phase change It has been found that a heat transfer medium can be obtained by suspension polymerization of an oily substance in an aqueous solvent.
  • a heat storage agent in which the oily substance is maintained in a state where the fluidity has substantially lost fluidity is dispersed in an aqueous solvent to be an aqueous medium.
  • the heat transfer medium power can be obtained by a simple manufacturing process. Then, they have found that the above-mentioned conventional problems can be solved by the heat transfer medium, and have completed the present invention.
  • an oily substance that has a heat storage property and that reversibly changes phase from solid to liquid or from liquid to solid in response to a change in temperature has a temperature stability and a volume change accompanying the phase change of the oily substance.
  • the composite particles, which are held inside the lipophilic polymer particles having absorbable elasticity and in which the hydrophilic groups are oriented and irregularities are formed on the surface of the particles, are dispersed in an aqueous medium. It has been found that the above-mentioned conventional problems can be solved by using a heat transfer medium.
  • the composite particles for a heat transfer medium according to the present invention have a heat storage property and a reversible phase change from a solid to a liquid or from a liquid to a solid according to a temperature change in order to solve the above-mentioned problems.
  • Oleophilic polymer particles are held inside lipophilic polymer particles having temperature stability and elasticity capable of absorbing a volume change accompanying a phase change of the oleaginous material, and have a hydrophilic surface on the particles. It is characterized in that the groups are oriented.
  • the composite particles for a heat transfer medium according to the present invention are characterized in that the lipophilic polymer particles further include an elastomer.
  • the heat transfer medium according to the present invention has a heat storage property to solve the above problems.
  • An oily substance that reversibly changes phase from a solid to a liquid or from a liquid to a solid in response to a temperature change has temperature stability and elasticity capable of absorbing a volume change accompanying the phase change of the oily substance.
  • the composite particles, which are held inside the provided lipophilic polymer particles and have a hydrophilic group oriented on the surface of the particles and have irregularities, are dispersed in an aqueous medium. .
  • the heat transfer medium according to the present invention has a heat storage property.
  • lipophilic polymer particles having elasticity and elasticity capable of absorbing a volume change caused by a phase change of an oily substance, and a hydrophilic group is oriented on the surface of the particles while the particle size is increased.
  • the composite particles are formed by dispersing the composite particles having a particle size of 1 ⁇ m to 300 m in an aqueous medium.
  • the heat transfer medium according to the present invention has a viscosity of 5 mPa at a temperature of 5 ° C. when the concentration of the composite particles is 20% by weight. ⁇ S or less.
  • An air conditioning system is characterized by performing heat transfer between a refrigerator and an air conditioner by using the above heat transfer medium in order to solve the above-mentioned problems.
  • the lipophilic polymer particles constituting the composite particles have temperature stability and elasticity capable of absorbing a volume change accompanying a phase change of the oily substance. This sufficiently prevents the lipophilic polymer particles from oozing out of the lipophilic polymer particles during use, and the lipophilic weight during the phase change of the oleaginous substance from solid to liquid or from liquid to solid. The oozing of the oily substance from the coalesced particles is sufficiently prevented.
  • the surface of the lipophilic polymer particles Since the hydrophilic group is oriented in the polymer, the aggregation of the composite particles and the thickening effect of the composite particles are sufficiently prevented.
  • the composite particles in which the lipophilic polymer particles further include an elastomer are more excellent in mechanical strength and flexibility, so that the mechanical stability during transportation is improved (the shape is maintained). ). Therefore, the flow resistance of the heat transfer medium can be reduced.
  • the heat transfer medium according to the present invention is obtained by polymerizing a monomer component in the presence of an oily substance having heat storage properties and liquefied by phase change, It is characterized in that, in a polymer obtained by polymerizing a body component, a heat storage agent holding the above-mentioned oily substance so as to decrease the fluidity is dispersed in an aqueous medium.
  • the heat transfer medium according to the present invention has a monomer (A) having a solubility parameter of 9 (ca 1 Z cm 3 ) 1/2 or less and a hydrophilic group in the molecule.
  • a polymer obtained by polymerizing a monomer component containing the monomer (B) in the presence of an oily substance having heat storage properties and liquefied by phase change, and polymerizing the monomer component It is characterized in that a heat storage agent in which the oily substance is maintained in a state of substantially losing fluidity is dispersed in an aqueous medium.
  • the heat storage agent contained in the heat transfer medium is used to reduce the fluidity of the oily substance in a polymer obtained by polymerizing a monomer component having a specific composition, It is kept in a state in which sex has been substantially lost. This sufficiently prevents oozing of oily substances from the polymer during use At the same time, the oozing of the oleaginous substance from the polymer when the oleaginous substance undergoes a phase change, that is, when it is melted and solidified, is sufficiently prevented. It is possible to provide a heat transfer medium that can maintain good heat transfer efficiency.
  • the heat transport medium according to the present invention may be configured such that the monomer component has a crosslinkable monomer (C) having at least two polymerizable unsaturated groups in a molecule. ) In the range of 20% by weight or less.
  • the heat transfer medium according to the present invention is characterized in that in the heat transfer medium, the weight ratio of the heat storage agent to the aqueous medium (heat storage agent / aqueous medium) is 50/50 to 5 / 95. According to the above configuration, it is possible to provide a heat transfer medium that does not cause a decrease in fluidity and that is more excellent in heat transfer efficiency.
  • the method for producing a heat transfer medium comprises: a monomer (A) having a solubility parameter of 9 (ca 1 / cm 3 ) 1/2 or less; A monomer component comprising a monomer having a hydrophilic group (B) and an oily substance having a heat storage property and liquefied by phase change in an aqueous solvent by suspension polymerization.
  • a monomer component comprising a monomer having a hydrophilic group (B) and an oily substance having a heat storage property and liquefied by phase change in an aqueous solvent by suspension polymerization.
  • the heat transfer medium can be manufactured in substantially one step of the polymerization step, that is, in a simple manufacturing step. That is, it is possible to provide a method for manufacturing a heat transfer medium that can exhibit the above various effects.
  • the method for producing a heat transfer medium according to the present invention is characterized in that an elastomer is mixed with the monomer component and / or the oily substance.
  • the monomer component When the monomer component is suspended in an aqueous solvent together with an oily substance, the monomer component is compatible with the oily substance and the monomer (B) is oriented to the aqueous solvent side (outside). Oil droplets.
  • the orientation of the monomer (B) during suspension polymerization can be arbitrarily controlled, so that the flowability at low temperature is not reduced, and It is possible to provide a heat transfer medium that can sufficiently prevent oozing of oily substances during use.
  • the heat storage agent contained in the heat transfer medium according to the present invention is obtained by polymerizing a monomer component in the presence of an oily substance that has heat storage properties and liquefies by phase change, and polymerizes the monomer component. The oily substance is retained in the resulting polymer such that the fluidity is reduced.
  • the heat storage agent contained in the heat transfer medium according to the present invention includes a monomer (A) having a solubility parameter of 9 (ca ca / cm 3 ) 1/2 or less, and a carboxyl group or the like in the molecule.
  • the body component is polymerized in the presence of the oily substance, and the oily substance is held in a state where the fluidity has been substantially lost in a polymer obtained by polymerizing the monomer component.
  • the above-mentioned heat transport medium can be produced, for example, by subjecting a monomer component and an oily substance to suspension polymerization in, for example, an aqueous solvent to be an aqueous medium.
  • the above-mentioned oily substance has a heat storage property due to latent heat at the time of a phase change between a liquid phase and a solid phase in a specific temperature range, and is a substance substantially insoluble or hardly soluble in water.
  • oily substance examples include n-paraffins such as tetradecane, pendudecane, and hexadecane; paraffins such as noraffin wax, isoparaffin, and polyethylene wax; stearic acid, palmitic acid And the like; fatty acids such as butyl stearate; alcohols such as decyl alcohol and dodecyl alcohol; These oily substances may be used only one type, also good c and be used in combination of two or more, the oily material, and more preferably has excellent compatibility with the monomer component.
  • paraffins are particularly preferable because they have a high latent heat of fusion and have a clear freezing point; their freezing points can be freely set; they are easily available;
  • an inclusion compound may be added to the above oily substance, if necessary, in order to adjust the heat storage property of the oily substance due to latent heat.
  • Is a ⁇ contact compound specifically, for example, C 4 Eta 8 ⁇ ⁇ 17H 2 0, (CH 3 ) 3 N ⁇ 10.25H 2 0, (C 4 H 9) 4 NCH 0 2 - 32H 2 0, (C 4 H 9 ) 4 NC H 3 C 0 2 - include 32H 2 0 and the like.
  • the amount of the clathrate compound added to the oily substance is not particularly limited.
  • the above-mentioned monomer component contains, for example, a monomer having one polymerizable unsaturated group in the molecule as a main component, and optionally contains a polymerizable unsaturated group in the molecule. It contains at least two crosslinkable monomers. More preferably, the above monomer component has a solubility parameter 9 (ca 1 / cm 3 ) 1/2 or less of the monomer (A), the monomer having a hydrophilic group in the molecule (B) and, if necessary, a polymerizable unsaturated group And at least two crosslinkable monomers (C) in the molecule.
  • the solubility parameter (SP value) is a parameter generally used as a scale indicating the polarity of a compound.
  • the solubility parameter is, for example, a value obtained by substituting the aggregation energy constant of Hoy into the calculation formula of Small, and this value is employed in the present invention.
  • the monomer (A) has an solubility parameter of 9 (ca 1 cm 3 ) 1/2 or less, and is, for example, an unsaturated monomer having one polymerizable unsaturated group in the molecule.
  • Specific examples of the monomer (A) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and n-butyl.
  • (Meth) acrylate isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate (Meth) acrylate, dodecisole (meta) acrylate, stearyl (meta) acrylate, phenyl (meta) acrylate, octylphenyl (meta) acrylate, noni Ruphenyl (meth) acrylate, dinonylphenyl (meth) acrylate, cyclohexyl (meth) acrylate, menthyl (meth) acrylate, isobornyl (meth) acrylate Relay Unsaturated carboxylic acid esters such as dibutyl (meth) acrylate, dibutyl maleate, didodecyl maleate, dodecyl crotonate, dododecyl
  • An alicyclic vinyl compound such as a vinylcyclohexane
  • Allyl ethers having a hydrocarbon group such as dodecyl aryl ether; vinyl esters having a hydrocarbon group such as vinyl caproate, vinyl laurate, vinyl palmitate and vinyl stearate [fatty acid vinyl ester];
  • Vinyl ethers having a hydrocarbon group such as butyl vinyl ether and dodecyl vinyl ether;
  • Aromatic vinyl compounds such as styrene, t-butylstyrene, octylstyrene [alkylstyrene];
  • 1 ⁇ -olefin such as 1-hexene, 1-octene, isooctene, 1-nonene, 1-decene;
  • hydroxyl-containing unsaturated carbonates such as hydroxypropyl (meth) acrylate [so-called interface-oriented monomers]; and the like, but are not particularly limited thereto.
  • hydroxypropyl (meth) acrylate such as hydroxypropyl (meth) acrylate [so-called interface-oriented monomers]; and the like, but are not particularly limited thereto.
  • One of these monomers (II) may be used alone, or two or more thereof may be used in combination.
  • the monomer ( ⁇ ) is composed mainly of a relatively long-chain unsaturated monomer, that is,
  • the content is 50% by weight or more.
  • alkyl (meth) acrylate, alkylaryl (meth) acrylate, alkyl (meth) acrylyl amide, alkylaryl (meth) acrylyl Mid, fatty acid vinyl ester, alkyl styrene At least one kind of unsaturated monomer selected from the group consisting of ren and one-year-old olefin as a main component, that is, 50% by weight or more, and the unsaturated monomer has a carbon number of at least 50% by weight.
  • Monomers (A) having 3 to 30 aliphatic hydrocarbon groups are more preferred.
  • the aliphatic hydrocarbon group preferably has 4 to 24 carbon atoms, and more preferably has 8 to 18 carbon atoms.
  • the monomer (A) is more excellent in compatibility with the oily substance. Therefore, a polymer obtained by polymerizing a monomer component containing the monomer (A) is particularly excellent in the ability to retain an oily substance. Therefore, it is possible to further suppress the liquefaction of the oily substance, and to obtain a heat transfer medium containing a heat storage agent in which the oozing of the oily substance from the polymer is more sufficiently prevented.
  • the monomer (A) may have a solubility parameter of 9 (ca 1 Z cm 3 ) 1/2 or less. Therefore, the unsaturated monomer having one polymerizable unsaturated group in the molecule as exemplified above can be used.
  • a monomer having one polymerizable group in a molecule which is polymerized by a polymerization reaction such as radical polymerization, radiation polymerization, addition polymerization, polycondensation, or ring-opening polymerization may be used.
  • a polymerization reaction such as radical polymerization or ring-opening polymerization include a norbornene-based monomer.
  • the monomer component containing the monomer is used.
  • a polymer obtained by polymerizing the compound cannot retain the oily substance in a state of substantially losing fluidity or cannot retain the oily substance in a large amount. Therefore, it is not possible to obtain a heat transfer medium containing a heat storage agent having excellent heat storage properties.
  • the monomer (B) is an unsaturated monomer having a hydrophilic group such as a carboxyl group in the molecule. It is a sum monomer.
  • Specific examples of the monomer (B) include, for example, acrylic acid, methacrylic acid, methyl acrylic acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, maleic acid, Fumaric acid, monoacrylic acid, monocyanoacrylic acid, crotonic acid, isocrotonic acid, hypophenylacrylic acid, S-acryloyloxypropionic acid, sorbic acid, monochloric acid Sorbic acid, angelic acid, gay cinnamate, p-chloro-3 gay cinnamate, 3—styrylacrylic acid, 2—methacryloyloxetyl succinic acid, 2—methacryloyloxicetyl phthalic acid, etc.
  • Amino group-containing monomers such as aminoethyl (meth) acrylate and vinylethylamine;
  • Epoxy group-containing monomers such as glycidyl (meth) acrylate
  • Acid anhydrides such as maleic anhydride
  • Sulfonate group-containing monomers such as styrene sulfonic acid; and the like. There is no particular limitation. These monomers (B) may be used alone or in combination of two or more.
  • the monomers (B) exemplified above at least one unsaturated monomer selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid
  • the body is particularly preferred.
  • the pH of the heat transfer medium can be appropriately adjusted using a hydroxide such as sodium hydroxide or calcium hydroxide, ammonia, or an alkylamine.
  • a hydroxide such as sodium hydroxide or calcium hydroxide, ammonia, or an alkylamine.
  • the weight ratio of the monomer (A) to the monomer (B) (monomer (A) Z monomer (B)) in the monomer component is not particularly limited. / 1 to 40/60 is particularly preferable. As a result, the liquefaction of the oily substance can be further suppressed, so that it is possible to obtain a heat transfer medium containing a heat storage agent in which the oozing of the oily substance from the polymer is more sufficiently prevented. If the proportion of the monomer (A) is larger than the above range, it may be difficult to sufficiently harden the surface layer of the heat storage agent. If the proportion of the monomer (A) is less than the above range, the production of the heat storage agent may cause oozing of the oily substance from the polymer. If an external force acts on the heat storage agent while the oily substance is being melted, the oily substance may have fluidity (liquefy).
  • the crosslinkable monomer (C) optionally contained in the monomer component is an unsaturated monomer having at least two polymerizable unsaturated groups in the molecule.
  • Specific examples of the crosslinkable monomer (C) include, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and polyethylene glycol di (meth) acrylate. Crylate, polyethylene glycol / polypropylene glycol (meta) acrylate, propylene glycol (meta) acrylate, polypropylene glycol
  • the proportion of the crosslinkable monomer (C) in the monomer component is preferably within the range of 20% by weight or less. This makes it possible to obtain a heat transfer medium containing a heat storage agent having a higher mechanical strength against shear stress. If the proportion of the crosslinkable monomer (C) exceeds 20% by weight, there is a possibility that oily substances may ooze out of the polymer when producing the heat storage agent. When an external force acts on the heat storage agent while the oily substance is molten, the oily substance has fluidity (liquefaction). ) May be.
  • the weight ratio between the oily substance and the monomer component is not particularly limited, but is preferably in the range of 95 to 5/40/60. preferable. This makes it possible to obtain a heat transfer medium containing a heat storage agent that is more excellent than the heat storage amount per unit amount. If the ratio of the oily substance is larger than the above range, it may be difficult to suppress the fluidity (liquefaction) of the oily substance when the oily substance is molten. If the ratio of the oily substance is smaller than the above range, a heat transfer medium containing a heat storage agent having an excellent heat storage amount per unit amount may not be obtained.
  • the heat transport medium according to the present invention can be easily produced, for example, by subjecting the above monomer component and oily substance to suspension polymerization in an aqueous solvent such as water.
  • an aqueous solvent also functions as an aqueous medium.
  • the monomer component and the oily substance can be suspended in an aqueous solvent in the presence of a protective colloid agent and a surfactant, if necessary.
  • the suspension polymerization also includes -suspension polycondensation.
  • the amount of the monomer component and the oily substance added to the aqueous solvent that is, the concentration of the monomer component and the oily substance is not particularly limited, but the weight ratio of the obtained heat storage agent to the aqueous medium (heat storage Aqueous medium), but 50 Z 50 ⁇
  • the above-mentioned protective colloid agent examples include polyvinyl alcohol, hydroxyethyl cellulose, gelatin and the like.
  • the above-mentioned surfactant specifically, for example, examples thereof include sodium, sodium alkylbenzenesulfonate, polyoxyethylene alkyl ether, and fatty acid stone.
  • the amount of the protective colloid agent and surfactant used is not particularly limited.
  • polymerization initiator suitably used in the suspension polymerization
  • examples of the polymerization initiator suitably used in the suspension polymerization include, for example, organic peroxides such as benzoyl peroxide, lauroyl peroxide, cumene peroxide, and the like; Oil-soluble radical polymerization initiators such as azo compounds such as 2′-azobisisobutyronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile); are not particularly limited.
  • One of these polymerization initiators may be used alone, or two or more thereof may be used in combination.
  • the amount of the polymerization initiator to be used based on the monomer component depends on the composition of the monomer component and the like, but is preferably in the range of 0.1% by weight to 5% by weight.
  • the reaction temperature may be set according to the composition of the monomer component, the composition and melting point of the oily substance, the type of the polymerization initiator, the type of the aqueous solvent, etc., and is not particularly limited. It is desirable that the temperature be higher than the temperature at which the liquid can be maintained. Specifically, the reaction temperature is preferably in the range of 0 ° C. to 150 ° C., and most preferably in the range of 0 ° C. to 80 ° C.
  • the reaction time is not particularly limited, and may be determined depending on the composition of the monomer component, the composition of the oily substance, the melting point, the type of the polymerization initiator, the type of the aqueous solvent, the reaction temperature, and the like. What is necessary is just to set suitably so that polymerization may be completed. Further, the suspension polymerization is more preferably performed in an atmosphere of an inert gas such as a nitrogen gas.
  • the aqueous solvent is stirred to remove the monomer component and the oily substance. Suspend.
  • the stirring method is to make a uniform suspension The method is not particularly limited as long as it can be obtained.
  • the monomer component is suspended in an aqueous solvent together with an oily substance, the monomer component is compatible with the oily substance and has a monomer having a hydrophilic group such as a carboxyl group.
  • (B) is an oil droplet oriented in the aqueous solvent side (outside).
  • the monomer component contains a crosslinkable monomer (C) having a hydrophilic group in the molecule
  • the crosslinkable monomer (C) is added together with the monomer (B). It will be in the state of being directed to the aqueous solvent side. Then, suspension polymerization of the monomer component proceeds in this state.
  • the solution may be suspended in an aqueous solvent.
  • the heat transfer medium can be produced in substantially only one polymerization step, that is, in a simple production step.
  • the aqueous solvent also functions as an aqueous medium.
  • the average particle size of the heat storage agent is not particularly limited, but is preferably 5 mm or less, more preferably 3 mm or less, and particularly preferably 1 mm or less.
  • the monomer (B) Since the monomer (B) is suspended and polymerized in the surface layer of the heat storage agent in a state where the monomer (B) is oriented toward the aqueous solvent, a hard material composed of a polymer containing more monomer (B) as a constituent component thereof A gel has formed.
  • the monomer component contains a crosslinkable monomer (C)
  • the hardness of the hard gel is further increased because the hard gel has a crosslinked structure, and thus the mechanical strength against shear stress is increased. It will be even higher.
  • a soft gel composed of a polymer containing a large amount of the monomer (A) as a constituent component and an oily substance is formed. Therefore, the oily substance is in a state where it has substantially lost fluidity. In a soft gel, that is, in a polymer.
  • the hard gel and the soft gel are distinguished for convenience, but the interface between the two gels is not clearly present.
  • the composition does not change discontinuously from the hard gel to the soft gel, but the composition changes continuously with a certain thickness. I have.
  • the heat storage agent and the aqueous solvent are separated, and then the heat storage agent is dispersed in the aqueous medium, so that heat transfer is performed.
  • the method of separating the c heat storage agent from which the medium can be produced and the aqueous solvent is not particularly limited, and a known method such as filtration, washing, and drying can be used in appropriate combination.
  • the method for dispersing the heat storage agent in the aqueous medium may be any method capable of obtaining a heat-carrying medium which is a uniform dispersion, as c aqueous medium is not particularly limited, specifically, Examples include water, an aqueous solution containing ethylene glycol, and an aqueous solution containing propylene glycol. Of these, water is more preferred.
  • the weight ratio between the heat storage agent and the aqueous medium is not particularly limited, but is particularly preferably set to be in the range of 50/50 to 5995. .
  • heat storage agent Z aqueous medium is not particularly limited, but is particularly preferably set to be in the range of 50/50 to 5995. .
  • the ratio of the heat storage agent is larger than the above range, the viscosity of the heat transfer medium increases. Therefore, the transport power required to transport the heat transport medium increases, or the heat transport medium cannot be transported, and the heat transfer efficiency decreases. May be affected.
  • the proportion of the heat storage agent is smaller than the above range, the heat storage density of the heat transfer medium becomes small, and the heat transfer efficiency may be reduced.
  • the heat storage agent Since the heat storage agent has a hard gel formed on its surface layer, the oozing of the oleaginous substance from the polymer during use is sufficiently prevented, and when the oleaginous substance undergoes a phase change, that is, melting. In the case of coagulation, oozing of oily substances from the polymer can be sufficiently prevented. Also, even if the oily substance is repeatedly melted and solidified, the oozing can be sufficiently prevented. Further, the heat storage agent has a hard gel formed on its surface layer, so that the heat storage agent can be made into a dry particle form, and has high mechanical strength against shear stress, so that it is excellent in handleability. Therefore, by separating the heat storage agent and the aqueous solvent and the like, and then dispersing the heat storage agent in the aqueous medium, the heat transfer medium can be manufactured.
  • the method for producing the heat storage agent is not limited to the above-described method (suspension polymerization).
  • a monomer component can be polymerized in the oily substance.
  • a lump containing a heat storage agent and an oily substance as a solvent is adjusted to have an appropriate particle size by pulverization or the like, and then the heat storage agent is dispersed in an aqueous medium to thereby provide a heat transfer medium.
  • Additives for improving heat transfer such as metal powders such as iron and copper, metal fibers, metal oxides, carbon, carbon fibers, etc., as necessary; sand, clay, Additives for adjusting specific gravity, such as stone, metal powders such as lead and iron, iron oxide, alumina, etc .; metal powders, inorganic compounds such as calcium carbonate, bromine-based, chlorine-based, and phosphorus-based flame retardants, etc. Additives for imparting flame retardancy; Additives for preventing supercooling; Phenyl-based sulfur-based, phosphorus-based, etc. Various additives, such as antioxidants for preventing oxidation and deterioration with time, can be added.
  • a coloring agent such as a pigment or a dye, an antistatic agent, a bactericide, or the like can be added to the heat storage agent, if necessary.
  • the amount and method of addition of these additives, coloring agents, antistatic agents, and antibacterial agents to the heat storage agent are not particularly limited.
  • Additives, coloring agents, antistatic agents, and antibacterial agents can be dry-mixed with the heat storage agent at room temperature. Alternatively, it can be added to the reaction system when producing a heat transfer medium, that is, during suspension polymerization.
  • the above-mentioned flame retardancy refers to various properties such as reduction of flammability, prevention of spread of fire, extinction of a flash point by steam, and reduction of combustion heat.
  • the heat transfer medium according to the present invention performs heat storage or cold storage using latent heat when an oily substance undergoes a phase change.
  • the heat transfer medium can store heat only by heating (heating), and can store cold only by cooling.
  • the composite particles for a heat transfer medium according to the present invention include, for example, the oily substance that has heat storage properties and that reversibly changes phase from solid to liquid or from liquid to solid in response to a temperature change, During the coalescence, that is, the lipophilic polymer particles having temperature stability and elasticity capable of absorbing a volume change accompanying a phase change of the oleaginous substance are held inside the polymer particles, and have a hydrophilic property on the surface of the particles. In this configuration, the groups are oriented. Further, the heat transfer medium according to the present invention is obtained by dispersing the composite particles having irregularities or the composite particles having a particle diameter of 1 zm to 300 m in the aqueous medium. Configuration.
  • the heat transfer medium according to the present invention has a viscosity of 5 mPas or less at a temperature of 5 ° C when the concentration of the composite particles is 20% by weight.
  • the air conditioning system according to the present invention is configured to carry out heat transfer between the refrigerator and the air conditioner using these heat transfer media.
  • the lipophilic polymer particles constituting the composite particles have temperature stability and elasticity capable of absorbing a volume change accompanying a phase change of the oily substance. This sufficiently prevents the lipophilic polymer particles from oozing out of the lipophilic polymer particles during use, and the lipophilic weight during the phase change of the oleaginous substance from solid to liquid or from liquid to solid.
  • the oozing of the oily substance from the coalesced particles is sufficiently prevented.
  • the hydrophilic groups are oriented on the surface of the lipophilic polymer particles, aggregation of the composite particles and a thickening effect by the composite particles are sufficiently prevented. Therefore, it is possible to provide a heat transfer medium which does not cause a decrease in fluidity and can maintain a good heat transfer efficiency, and an air conditioning system using the heat transfer medium.
  • the heat transfer medium according to the present invention may include an elastomer as necessary.
  • the method of including the elastomer in the heat transfer medium is not particularly limited, but prior to the above-mentioned suspension polymerization, the oily substance and the Z or monomer component, more specifically, the oily substance And / or a method in which the elastomer is dissolved in the monomer (B) is preferable.
  • the orientation of the monomer (B) at the time of the above suspension polymerization can be arbitrarily controlled by the oily substance and the Z or monomer components containing the elastomer.
  • the elastomer examples include a styrene-based elastomer such as a block copolymer of polystyrene and polyolefin such as polybutadiene polyisoprene or a hydrogenated product of the polyolefin; A mixture of polyolefin (homopolymer) and polyolefin (copolymer), and graft polymerization of polyolefin on polyolefin (copolymer)
  • Various compounds such as copolymer-based elastomers, urethane-based elastomers, ester-based elastomers, etc., ie, have rubber elasticity at room temperature or higher in the fields of rubber and plastics.
  • thermoplastic elastomers Compounds known as so-called thermoplastic elastomers; and natural rubber, styrene-butadiene copolymer rubber, butyl rubber, butadiene rubber, polybutylene, polyisobutylene, isoprene rubber, ethylene-propylene copolymer Hydrocarbon rubbers such as rubber, ethylene-propylene-propylene terpolymer rubber, styrene-ethylenebutylene terpolymer rubber, ethylene-vinyl acetate copolymer rubber, ethylene-ethyl acrylate copolymer rubber And the like, but are not particularly limited c
  • One type of these elastomers may be used alone, or two or more types may be used in combination.
  • the solubility parameter of the elastomer can be arbitrarily set by appropriately adjusting the molecular weight, the copolymerization ratio and the like of the elastomer. Therefore, the type of the elastomer used may be appropriately selected according to the type of the oily substance, the type of the monomer (B), the combination of the two, and the like.
  • the amount of the elastomer added to the oily substance is not particularly limited, but is preferably in the range of 0.1% by weight to 10% by weight, and more preferably in the range of 0.5% by weight to 5% by weight. Inside is more preferred. If the amount of the elastomer is more than 10% by weight, the viscosity of the oily substance increases, and it may be difficult to control the particle diameter of the composite particles. In addition, the amount of heat stored by the latent heat of the composite particles may decrease, or the temperature at which the oily substance changes phase may change. On the other hand, when the added amount of the elastomer is less than 0.1% by weight, the effect obtained by adding the elastomer becomes poor. In some cases, the orientation of the monomer (B) cannot be sufficiently controlled during suspension polymerization.
  • Oil-based substances and Z or monomer components during suspension polymerization contain an elastomer with a solubility parameter of 9 (cal Zcm 3 ) 12 or less, further promoting the orientation of monomer (B). Can be done. Therefore, even when the proportion of the monomer (B) in the monomer component is small, the dispersibility of the composite particles is excellent, the flowability at low temperatures is not reduced, and the oily substance during use is low. It is possible to provide a heat transfer medium capable of sufficiently preventing bleeding of the heat. Further, since the ratio of the monomer (B) in the monomer component can be further reduced, fine composite particles are generated, and the water-soluble polymer is formed by homopolymerization of the monomer (B). It is possible to suppress formation of coalescence and extremely deformed composite particles. Furthermore, since the viscosity increase and foaming of the heat transfer medium can be reduced, a heat transfer medium having excellent heat transfer characteristics can be provided.
  • elastomers those having a solubility parameter of 9 (ca 1 / cm 3 ) 1/2 or less, which are compatible with the oily substance and not compatible with the monomer (B).
  • solubility parameter 9 (ca 1 / cm 3 ) 1/2 or less, which are compatible with the oily substance and not compatible with the monomer (B).
  • examples of the elastomer include polybutylene, polyisobutylene, and styrene-ethylene-butylene terpolymer rubber.
  • the oily substance and the Z or monomer component during suspension polymerization contain an elastomer whose solubility parameter exceeds 9 (cal / cm 3 ) 1/2 , so that the degree of distribution to water is large.
  • the transfer of the monomer (B) to the aqueous solvent can be prevented, resulting in the generation of fine composite particles and the formation of a water-soluble polymer by homopolymerization of the monomer (B). You , Can be suppressed.
  • FIG. 1 is a diagram (one copy) showing the structure of the heat storage agent (composite particles) obtained in Example 1.
  • FIG. 2 is a diagram (color copy) showing the structure of the heat storage agent (composite particles) obtained in Example 4.
  • a 3 L flask equipped with a thermometer, a nitrogen gas inlet tube, a reflux condenser, and a stirrer was used as a reactor.
  • 15 g of polyoxyethylene alkyl ether surfactant, manufactured by Nippon Shokubai Co., Ltd .; trade name: Softanol 150
  • the aqueous solution was heated to 80 ° C. while stirring under a nitrogen gas atmosphere.
  • the above mixed solution was added to the aqueous solution at a time, and the suspension polymerization was carried out at 80 ° C. for 2 hours under a nitrogen gas atmosphere while mixing and stirring under the condition of a rotation speed of 400 rpm. Was.
  • the temperature of the suspension was raised to 90 ° C., and stirring was continued at the same temperature for 2 hours to complete the suspension polymerization.
  • a heat transfer medium according to the present invention was obtained.
  • the average particle size of the heat storage agent as a polymer was 40 m. As is clear from FIG. 1, it was found that no irregularities were formed on the surface of the heat storage agent (composite particles).
  • the obtained heat transfer medium was subjected to differential scanning calorimetry (DSC) under predetermined conditions to obtain a solidification temperature and a melting temperature.
  • DSC differential scanning calorimetry
  • the fluidity of the heat transfer medium at 3 ° C was evaluated. That is, 150 m 1 of the heat transfer medium was placed in a flask having a capacity of 200 m 1 and immersed in a water bath at 3 for 1 hour while stirring with a magnetic stirrer. The evaluation was made by visually checking the rotation state of the stirrer.
  • the solidification temperature was 8.0 ° C and the melting was The temperature was 7.8 ° C and the fluidity at 3 ° C was “good”.
  • the viscosity of the heat transfer medium when the concentration of the heat storage agent was set to 20% by weight was measured at a temperature of 5 ° C by a predetermined method. As a result, the viscosity was 4.8 mPa ⁇ s. C The results are summarized in Table 1.
  • Example 1 95 g of 2-ethylhexyl acrylate as the monomer (A) was used in place of 95 g of dodecyl acrylate, and 5 g of ethylene glycol dimethacrylate was used in place of crosslinkability. Use 1,6-hexanediol diacrylate 5 g as the monomer (C), and adjust the number of revolutions for mixing and stirring the suspension from 400 rpm to 300 rpm. The suspension polymerization was carried out in the same manner as in Example 1 except that the polymerization was changed to.
  • a heat transfer medium according to the present invention was obtained.
  • the average particle size of the heat storage agent as a polymer was 70 m.
  • the solidification temperature and the melting temperature were determined in the same manner as in Example 1, and the fluidity at 3 was evaluated.
  • the solidification temperature was 8.0 ° C
  • the melting temperature was 7.9
  • the fluidity at 3 ° C was “good”.
  • the viscosity of the heat transfer medium was 4.6 mPa ⁇ s at a temperature of 5 ° C.
  • Example 1 instead of 95 g of dodecyl acrylate, 83 g of 2-ethylhexyl acrylate and 7 g of hydroxypropyl methacrylate as the monomer (A) were used, and ethylene glycol dimethacrylate was used.
  • the amount of the solution used was changed from 5 g to 10 g, and the number of revolutions for mixing and stirring the suspension was changed from 400 rpm to 350 rpm.
  • the suspension polymerization was performed in the same manner as in 1.
  • the average particle size of the heat storage agent as a polymer was 50 / m.
  • the solidification temperature and the melting temperature were determined in the same manner as in Example 1, and the fluidity at 3 ° C was evaluated.
  • the solidification temperature was 8.2 ° C and the melting temperature was 8.0, and the fluidity at 3 ° C was “very good”.
  • the viscosity of the heat transfer medium was 3.5 mPa-s at a temperature of 5.
  • Example 1 instead of 95 g of dodecyl acrylate, 83 g of 2-ethylhexyl acrylate as monomer (A) and ⁇ g of methacrylic acid as monomer (B) were used instead of 95 g of dodecyl acrylate. And the amount of ethylene glycol dimethacrylate used was changed from 5 to 10 g, and the number of revolutions for mixing and stirring the suspension was changed from 400 rpm to 350 rpm. The suspension polymerization was carried out in the same manner as in Example 1.
  • a heat transfer medium according to the present invention was obtained.
  • the average particle size of the polymer heat storage agent is 50 am.
  • the solidification temperature and the melting temperature were determined in the same manner as in Example 1, and the fluidity at 3 ° C was evaluated.
  • the solidification temperature was 8.3 ° C and the melting temperature was 8.0, and the fluidity at 3 ° C was “very good”.
  • the viscosity of the heat transfer medium was 3.4 mPa ⁇ s at a temperature of 5 ° C. Table 1 summarizes these results. Further, as is apparent from FIG. 2, it was found that irregularities were formed on the surface of the heat storage agent (composite particles) in this example.
  • Example 1 95 g of dodecyl acrylate was replaced with a monomer ( Using 85 g of 2-ethylhexyl acrylate as A) and 5 g of methacrylic acid as the monomer (B), the amount of ethylene glycol dimethacrylate used was reduced from 5 g to 10 g. Then, 8 g of styrene-ethylene-butylene terpolymer rubber (manufactured by Seal Japan Co., Ltd .; trade name: Clayton 16550) as an elastomer is added and mixed. The suspension polymerization was carried out in the same manner as in Example 1 except that the number of revolutions for mixing and stirring was changed from 400 rpm to 350 rpm.
  • a heat transfer medium according to the present invention was obtained.
  • the average particle size of the polymer heat storage agent was 45 m.
  • the solidification temperature and the melting temperature were determined in the same manner as in Example 1, and the fluidity at 3 ° C was evaluated.
  • the solidification temperature was 8.2 ° C
  • the melting temperature was 8.0 ° C
  • the fluidity at 3 ° C was “very good”.
  • the viscosity of the heat transfer medium at a temperature of 5 was 3.3 mPa ⁇ s.
  • the average particle size of the oil-absorbent resin that absorbed Pencil Decane was 50 zm.
  • the solidification temperature and the melting temperature were determined in the same manner as in Example 1, and the fluidity at ⁇ 3 ° C. was evaluated.
  • the solidification temperature was 8.2 ° C and the melting temperature was 8.0, but at 3 ° C, the comparative heat transfer medium gradually began to solidify, and after several tens of minutes, completely solidified and flowed Lost sex. In other words, the liquidity in 3 was “poor”.
  • the viscosity of the heat transfer medium for comparison was 30 mPa ⁇ s or more at a temperature of 5. Table 1 summarizes the results.
  • the solidification temperature and melting temperature of the heat transfer media of Examples 1 to 5 and the solidification temperature and melting temperature of the comparative heat transfer medium of Comparative Example 1 are the melting points of pentadecane. (10 ° C). Therefore, these heat transfer media can repeatedly perform melting and solidification of pen pen decane in a temperature range of 5 ° C. to 13 ° C. suitable for use as a heat transfer medium for cooling. When evaluating the fluidity, these heat transfer media were immersed in a 3 ° C water bath for 1 hour, so that they were absorbed by pentadecane held in the heat storage agent and by the oil-absorbing resin. Penyu Decane is solidified.
  • the comparative heat transfer medium of Comparative Example 1 was completely solidified and lost its fluidity. This indicates that there is a large amount of penjudecane dispersed in water as an aqueous medium, that is, free pengudecane. In other words, pen-decane is not completely absorbed by the oil-absorbing resin, and therefore, the heat transfer medium for comparison changes its fluidity with the melting and solidification of pentadecane, and shows a good condition. Indicates that it cannot be maintained. This indicates that the comparative heat transfer medium of Comparative Example 1 cannot maintain good heat transfer efficiency.
  • the heat transfer medium according to the present invention has a reduced fluidity. It can be seen that the heat transfer efficiency can be maintained in a good state without inducing.
  • the heat transfer medium according to the present invention stores or cools heat using the latent heat when the oily substance undergoes a phase change
  • it is suitably used, for example, as a heat transfer medium for a district cooling / heating system or an absorption air conditioning system. be able to.

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Abstract

Cette invention concerne un procédé qui fait appel à un mélange contenant les éléments suivants: un composant monomère qui comprend (A) un monomère ayant un paramètre de solubilité de 9 (cal/cm3)1/2 ou moins ainsi que (B) un monomère dont la molécule contient un groupe hydrophile; et une substance huileuse qui possède des propriétés d'accumulation de chaleur et qui peut être liquéfiée par transition de phase. Ce mélange est soumis à une polymérisation en suspension dans un solvant aqueux jouant le rôle de milieu aqueux. Cette opération permet à la substance huileuse de rester à l'état globalement non fluide dans le polymère ainsi formé, et d'obtenir ainsi un agent accumulant la chaleur. Cet agent est satisfaisant en ce qu'il ne présente pas de risques d'écoulement de la substance huileuse hors du polymère, ceci non seulement lors de l'utilisation mais aussi au cours d'une transition de phase, telle que la fusion ou la solidification, de ladite substance huileuse. Il est ainsi possible d'obtenir un milieu de transfert de chaleur qui ne souffre pas d'une baisse de fluidité et qui va conserver un taux élevé de transfert de chaleur.
PCT/JP1998/003907 1997-09-19 1998-08-31 Milieu de transfert de chaleur, procede de production de celui-ci et systeme d'air climatise WO1999015602A1 (fr)

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JP27351897 1997-09-19
JP9/273518 1997-09-19

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013077379A1 (fr) * 2011-11-22 2013-05-30 Jsr株式会社 Matière de stockage de chaleur, dispositif de stockage de chaleur, microcapsule de stockage de chaleur

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0617043A (ja) * 1991-09-03 1994-01-25 Mitsubishi Paper Mills Ltd 水性保冷材
JPH09221665A (ja) * 1996-02-14 1997-08-26 Osaka Gas Co Ltd 蓄熱材用マイクロカプセル分散液
JP4072871B2 (ja) * 1996-07-26 2008-04-09 タイヨーエレック株式会社 弾球遊技機

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0617043A (ja) * 1991-09-03 1994-01-25 Mitsubishi Paper Mills Ltd 水性保冷材
JPH09221665A (ja) * 1996-02-14 1997-08-26 Osaka Gas Co Ltd 蓄熱材用マイクロカプセル分散液
JP4072871B2 (ja) * 1996-07-26 2008-04-09 タイヨーエレック株式会社 弾球遊技機

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013077379A1 (fr) * 2011-11-22 2013-05-30 Jsr株式会社 Matière de stockage de chaleur, dispositif de stockage de chaleur, microcapsule de stockage de chaleur

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