GB2626197A - Shape stable phase change materials - Google Patents
Shape stable phase change materials Download PDFInfo
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- GB2626197A GB2626197A GB2300637.2A GB202300637A GB2626197A GB 2626197 A GB2626197 A GB 2626197A GB 202300637 A GB202300637 A GB 202300637A GB 2626197 A GB2626197 A GB 2626197A
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- United Kingdom
- Prior art keywords
- phase change
- polymer
- composition according
- change material
- crodatherm
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- 239000012782 phase change material Substances 0.000 title claims abstract description 74
- 239000006260 foam Substances 0.000 claims abstract description 60
- 229920000642 polymer Polymers 0.000 claims abstract description 56
- 239000000203 mixture Substances 0.000 claims abstract description 32
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 150000002148 esters Chemical class 0.000 claims abstract description 13
- -1 octyl laurate (octyl decanoate) Chemical compound 0.000 claims abstract description 13
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 12
- 239000003349 gelling agent Substances 0.000 claims abstract description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000008859 change Effects 0.000 claims abstract description 11
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 6
- 229920001577 copolymer Polymers 0.000 claims abstract description 5
- 229920001400 block copolymer Polymers 0.000 claims abstract description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229920002633 Kraton (polymer) Polymers 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 8
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 7
- HOWGUJZVBDQJKV-UHFFFAOYSA-N docosane Chemical compound CCCCCCCCCCCCCCCCCCCCCC HOWGUJZVBDQJKV-UHFFFAOYSA-N 0.000 claims description 6
- NDJKXXJCMXVBJW-UHFFFAOYSA-N heptadecane Chemical compound CCCCCCCCCCCCCCCCC NDJKXXJCMXVBJW-UHFFFAOYSA-N 0.000 claims description 6
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 6
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 claims description 6
- 239000004416 thermosoftening plastic Substances 0.000 claims description 5
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 claims description 4
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- 229920006132 styrene block copolymer Polymers 0.000 claims description 3
- 229940038384 octadecane Drugs 0.000 claims description 2
- BGHCVCJVXZWKCC-NJFSPNSNSA-N tetradecane Chemical group CCCCCCCCCCCCC[14CH3] BGHCVCJVXZWKCC-NJFSPNSNSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 150000001336 alkenes Chemical class 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 17
- 238000002135 phase contrast microscopy Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 12
- 229920005832 Basotect® Polymers 0.000 description 10
- 210000003811 finger Anatomy 0.000 description 8
- 239000012071 phase Substances 0.000 description 6
- 229920002959 polymer blend Polymers 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229960005486 vaccine Drugs 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 229920005830 Polyurethane Foam Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000011496 polyurethane foam Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 101150025785 pcn1 gene Proteins 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229940127557 pharmaceutical product Drugs 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 210000003813 thumb Anatomy 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
- C08J9/42—Impregnation with macromolecular compounds
-
- 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
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
- F25D3/00—Devices using other cold materials; Devices using cold-storage bodies
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
- F28D20/00—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00
- F28D20/02—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00 using latent heat
- F28D20/023—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00 using latent heat the latent heat storage material being enclosed in granular particles or dispersed in a porous, fibrous or cellular structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
- C08J2201/036—Use of an organic, non-polymeric compound to impregnate, bind or coat a foam, e.g. fatty acid ester
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/05—Open cells, i.e. more than 50% of the pores are open
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08J2361/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08J2361/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Thermal Sciences (AREA)
- Combustion & Propulsion (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Shape-stable phase change material compositions that comprise a foam member at least partially impregnated or containing a phase change material, PCM. The PCM is a non-draining liquid or non-draining gel. The foam may be an open cell melamine foam comprising melamine formaldehyde. The PCM may be an alkene such as tetradecane or an ester such as octyl laurate (octyl decanoate). The composition may comprise a PCM and at least one gelling agent or viscosifying polymer. The viscosifying polymer may be a block copolymer such as styrene-ethylene-ethylene-propylene-styrene copolymer (SEEPS) or a thermoplastic polymer such as ethylene-butylene/styrene copolymer. A method of making a phase change composition is also described.
Description
Intellectual Property Office Application No GI323006372 RTM Date:24 July 2023 The following terms are registered trade marks and should be read as such wherever they occur in this document: CrodaTherm Septon Kraton Calprene Basotect Oasis Intellectual Property Office is an operating name of the Patent Office www.gov.uk/ipo Phase Change Materials The present invention relates to an improved phase change material and shape or form stable materials in particular.
The following description refers to phase change materials for use as a thermal store to maintain a reduced or elevated temperature, relative to the ambient temperature, within containers, for example in transport of chilled medical goods such as vaccines. The skilled person will recognise that the present invention can be used to maintain the temperature of a variety of containers and the goods contained therein and is not limited to medicines, vaccines etc. It is essential that when temperature sensitive items, including, but not limited to, vaccines and other pharmaceutical products, foods and beverages, human organs and other biological materials, are stored and/or transported they are kept at a suitable temperature. Overheating or overcooling can damage these temperature sensitive materials. To reduce/prevent the spoilage/loss of efficacy of these materials, insulated storage/transport technology has been developed. In many instances this comprises the temperature sensitive materials, or payload (i.e. that part of the package from which revenue is derived), adjacent and/or abutting one or more packs of phase change material. The payload and one or more phase change material packs are then protected by insulation and finally exterior packaging.
The phase change temperature of the phase change material is selected to match the required storage temperature of the payload. Depending on the size of the payload, the final package could be a cardboard box, a pallet cover or larger. The packages are designed to protect their contents during transport and delivery to their final destination. Water is a common phase change material and it is often thickened to form a gel, in rigid plastic bottles or pouches.
It is also common to use organic phase change materials such as alkanes (n-tetradecane, n-hexadecane and n-octadecane), acids, alcohols or esters. Typical esters are described in U.S. Patent application No. 2018/0244971, inventors Auerbach and Van Aken, which is incorporated herein by reference. These esters are reaction products of linear carboxylic acids, which have at least 4 carbon atoms and linear alcohols containing at least 4 carbon atoms, wherein the total number of carbon atoms in the ester is between 13 and 31. The use of other esters (e.g. methyl, ethyl and n-propyl) is also possible.
A problem can occur if one or more of the phase change material containers is damaged and the contents leak onto the temperature sensitive payload. This loss of integrity can lead to contamination of the payload and, potentially, a reduction in the ability of the phase change material to maintain constant temperature of the payload. Some phase change materials, such as n-tetradecane, can migrate through polyethylene bottles Or affect the seals of multi-layered pouches. This can be alleviated by treating the HDPE bottles using fluorination to increase their resistance to the migration of phase change materials or by using pouches with more resistant seals.
The cost and weight of FIDPN bottles provide a considerable contribution to the final costs of producing and distributing the temperature controlled packages. The use of plastic pouches, filled with phase change material, can significantly reduce both the weight and the cost. I lowever, should a pouch become damaged then the danger of the loss of some, or all of the phase change material into the payload space, would be of major concern. This has been resolved, to an extent, by converting the phase change material into a shape stable form. This involves adding a gelling agent, such as a viscosifying polymer to the phase change material and heating it to either dissolve or partially dissolve the polymer. The resulting system is one which remains as a solid, even above the melting point of the phase change material, which reduces/eliminates the danger of leakage should a pouch be damaged. A number of such systems currently exist on the market and some examples are covered in the following documents: US Patent application No. 2021292630 inventors Formato, Bakklas and Biswal; Patent No. W02014052409 inventors Formato and Bakklas, Patent No. DE102021005863 inventor Busch, Patent No. DE102020002843 inventor Busch, Patent No. 1)1110201 6013415 inventors Busch and Biggin. Shape stable, organic phase change materials may be prepared by various methods but linear styrene triblock polymers are often employed. These polymers comprise polystyrene end groups joined by a central hydrocarbon rubber section. This central section could comprise hydrocarbon monomers including but not limited to ethylene, propylene, butadiene, isoprene etc. The shape stable, or gelled, phase change material is prepared by mixing the phase change material and the polymer and heating the mixture until the polymer dissolves completely, or partially. It is then cooled to room temperature. Care must be taken to ensure that the heating temperature remains substantially below the flash point of the phase change material. The heated material can be poured into moulds and then cut to size, placed in a pouch and vacuum sealed, or it can be poured, whilst hot, directly into a pouch and vacuum sealed.
An alternative to the shape stable phase change materials for cold chain transport is the use of pouches containing a foam, impregnated with water or other phase change materials which are then sealed. These other phase change materials could be organic (alkanes, acids, alcohols or esters) or salt hydrates. Products based on this technology are sold by Temprecision International but tend to be based on phenol formaldehyde resins. These have a high absorptive capacity for water and phase change materials but are frangible, having low resistance to abrasion and pressure.
In US Patent No. 20020147242, inventors Salyer, Wynne and Swank, the authors claim a system based on a micropore, open cell foam, having an open cell content of >800/b and an average pore size of 200 microns or less Also claimed is the use of a polymeric thickening agent to viscosify the phase change 15 material.
In EP1498680, inventors Vath, Mocck and Wocrthwcin, the authors claim a thermal storage unit which contains an open cell foam based on a melamine formaldehyde condensation product, the cell pores of which are completely or partially filled with a free flowing heat transfer medium, and its production.
It is therefore an aim of the present invention to provide an improved shape Or form stable phase change material that 25 addresses the abovementioned problems.
It is a further aim of the present invention to provide a method of manufacturing a phase change material that addresses the abovementioned problems.
It is a yet further aim of the present invention to provide a device containing a phase change material that addresses the abovementioned problems.
In a first aspect of the invention there is provided a shape stable phase change composition comprising a foam member at least partially impregnated or containing phase change material, wherein said phase change material is a non-draining liquid or non-draining gel.
In a preferred embodiment the foam is an open cell foam. Typically the foam is melamine foam. Further typically the foam is melamine formaldehyde foam.
In a preferred embodiment the phase change material is a non-draining gel. Typically the gel is a viscosificd phase change material. Further typically the phase change material gcl includes a phase change material and at least one gelling agent or yiscosifying polymer.
In one embodiment the gelling agent or polymer is preferably substantially <15% by weight of the phase change material, more preferably at <10% by weight and most preferably at 5% or less.
In one embodiment the phase change material is an alkane. Preferably the alkane is tetradecane (C14).
In one embodiment the phase change material is an ester. Typically the ester is octyl laurate (octyl dodecanoate).
In one embodiment the phase change material is any one or any combination o f; tetradecane, hexadecane, heptadecane, octadccanc, cicosanc, docosane (from Sasol Germany GmbH), esters including CrodaTherm 5, CrodaTherm 6.5, CrodaTherm 9.5, CrodaTherm 15, CrodaTherm 19, CrodaTherm 21, CrodaTherm 24W, CrodaTherm 29, CrodaTherm 32, CrodaTherm 37, CrodaTherm 53, CrodaTherm 60 and CrodaThcrm 74 (from Croda Europe), stearyl alcohol and/or stearic acid.
In one embodiment the polymer or viscosifying polymer is a 5 block copolymer. Typically the polymer is a styrene ethylene ethylene propylene styrene copolymer (SEEPS).
in one embodiment the polymer is a thermoplastic copolymer. Typically the polymer is ethylene-butylene/styrene thermoplastic 10 copolymer.
in one embodiment the polymer is styrenejethylene-(ethylenepropylene)-styrene block copolymer.
Typically polymer selection depends on the polarity of the phase change material. Non-polar phase change materials require a relatively low molecular weight polymer such as Septon 4033 a SNI PS block copolymer or ethylene-butylene/styrene thermoplastic copolymer.
Further typically more polar phase change materials require t-a higher molecular weight polymer such as Septon 4077 a styrene[ethylene-(ethylene-propylene)j-styrene block copolymer.
In one embodiment the polymer or viscosifying polymer is any one or any combination of; Septon FIG-252, Septon 1020, Septon 4033, Septon 4055, Septon 4077, Septon 4099 (from Kuraray), Kraton 1654, Kraton 1651, Kraton 1633 (from Kraton Polymers), Calprene 1-16120, Calprene 1-16144, Calprene 1-16174 and Calprene 116410X (from Dynasol Group).
Preferably the composition is effective (absorbs energy at the phase transition) substantially at or between 2 °C -8 'C.
Typically the composition is effective to maintain a frozen temperature inside a container or the like at, or substantially around -20 °C.
Typically controlled room temperature or room temperature is defined as 15-25 "C.
Tn one embodiment the open cell foam is a phenolic foam.
In one embodiment the open cell foam is polyether polyurethane foam and/or polyester polyurethane foam.
Tn a second aspect of the invention there is provided a method of producing a phase change composition comprising an open cell foam impregnated with a phase change material gel or viscosified liquid wherein said gel or liquid is produced by heating a phase change material and a gelling agent or polymer to dissolve the gelling agent or polymer producing a substantially homogenous, low viscosity liquid.
Typically the heating temperature should be above room temperature, which is typically 15 ()C to 30 ()C, but below the flash point of the phase change material.
Further typically the hot liquid is then impregnated into the melamine formaldehyde foam and allowed to cool to room temperature.
In one embodiment the air within the foam is substantially 30 replaced by the phase change material/polymer mixture. Typically the impregnation can be achieved by vacuum and/or pressure impregnation.
In a third aspect of the invention there is provided a phase change material device, said device comprising a pouch or housing containing a phase change composition comprising a foam member at least partially impregnated or containing phase change material, wherein said phase change material is a non-draining liquid or non-draining gel.
Specific embodiments of the invention are now described.
The present invention is an open cell, melamine formaldehyde foam which is impregnated with a viscosified phase change material at an elevated temperature and then allowed to cool to form a non-draining gel within the structure of the foam.
According to one aspect of the invention, a phase change material gel is produced by heating a phase change material and a gelling agent to dissolve the gelling agent and produce a homogenous, low viscosity liquid. The heating temperature should be above room temperature, which is typically 15°C to 30°C, but below the flash point of the phase change material. The hot liquid is then impregnated into the melamine formaldehyde foam and allowed to cool to room temperature. Ideally, the air within the foam should be replaced by the hot phase change material/polymer mixture. This can be achieved by either vacuum or pressure impregnation.
Traditional packs of phase change material, for cold chain packaging and transport are made from strong, rigid high density polyethylene, are self-supporting and can be used multiple times without fear of damage or leaks. However, they are heavy and expensive, particularly if they require fluorination to minimise/eliminate the migration of the phase change material through the container.
The present invention uses melamine formaldehyde foams which possess extremely high porosity/absorptive capacity, very low density (9 kg/m3) and are both rigid and strong, to the extent that some of these are used as scouring pads to clean work surfaces etc. One disadvantage of these foams is that, due their open cell structure and inhomogeneous pore size (10 -1000 microns) absorbed phase change materials, in their liquid phase, will not be retained and will drain out due to gravity or applied pressure. This invention overcomes this problem by increasing the viscosity of the phase change material by the use of viscosifying polymers.
The phase change material/polymer blend must be selected carefully to provide a suitable balance of performance, cost and ease of manufacture. The polymer should be selected such that it can be added preferably at <15% by weight of the phase change material, more preferably at <10% by weight and most preferably at 5% or less.
The polymer type and addition level should enable a low viscosity, homogenous phase change material/polymer solution to be produced at an elevated temperature, which is nevertheless below the flash point of the phase change material. This solution is then adsorbed into the foam using either vacuum or 25 pressure and the temperature allowed to fall to room temperature.
Compatibility tests, were performed on a wide range of polymer and PCN1 blends. These involved mixing 5% by weight of viscosifying polymer with 95% by weight of PCM. The PCMs tested included alkanes such as tetradecanc, hexadecane, heptadecane, octadecane, eicosane and docosane, from Sasol Germany Gmbl I and esters including CrodaTherm 5, CrodaTherm 6.5, CrodaTherm 9.5 CrodaTherm 15, CrodaTherm 19, CrodaTherm 21, CrodaTherm 24W, CrodaTherm 29, CrodaTherm 32, CrodaTherm 37, CrodaTherm 53, CrodaTherm 60 and CrodaTherm 74 from Croda Europe. Also tested were stearyl alcohol and stearic acid.
The polymers tested included Septon HG-252, Septon 1020, Septon 4033, Septon 4055, Septon 4077, Septon 4099 from Kuraray; Kraton 1654, Kraton 1651, Kraton 1633 from Kraton Polymers, and Calprene H6120, Calprene H6144, Calprene H6174 and Calprene H6410X from Dynasol Group.
The tests involved heating the PCM/polymer mixture in a small, screw capped aluminium container until the mixture became a low viscosity liquid.
temperature above its It was then allowed crystallisation point to cool to and tested to determine whether it had formed a stable gel. The surface of the gel was contacted either with a finger, or a microscope slide to determine whether there was any free liquid on the surface of the gel or whether the gel was completely homogenous. This became known as the wet finger test. The examples below were based on PCM/polymer blends that passed the wet finger test and gave completely homogenous gels i.e. without free surface liquid.
The above tests had shown that both Septon 4033 and Calprene 1-16102 polymers gave satisfactory viscosity performance with tetradecane, i.e. they gave low viscosity liquids at 75 -80°C but formed solid gels at lower temperatures (e.g. 40°C) which passed the wet finger test. Two samples of Basotect G+ were cut to size, 75 x 75 x 12.5mm, and their volumes calculated (-70,300 mm3 or 70.3m1). Due to the possibility of losses during processing, 80m1 C14 was used for each sample, which weighed -61g (80m1 x 0.763g/m1). Opting for 59/6 polymer addition level gave a polymer addition level of -3.2g polymer/61g PCM. The two samples of tetradccanc/polymcr were placed in stainless steel beakers in an -80°C oven for 1.25 hours and then poured into pouches containing the Basotect G+ foam, vacuum impregnated/sealed and cooled to room temperature. The two 5 impregnated foams were then removed from the pouches, any excess gel removed and the foam samples weighed. Both passed the wet finger test at room temperature. The tctradccane/polymer loading in the foam was calculated and shown below as a percentage of the maximum theoretical 10 PCM/polymer loading: 1. Tetradecanc/4033 -98.8% 2. Tetradecanc/II6120 -98.7% The samples were then placed in pouches and vacuum sealed and subjected to two hours in a 40°C water bath. The pouches were opened at 40°C and both passed the wet finger test i.e. there was no free liquid PCM present. Both samples withstood squeezing, between finger and thumb, at 40°C without any exudation from the foam.
A piece of Basotect G+ foam (75 x 75 x 12.5rnm) was placed in a pouch and -60g tetradecane added (no polymer). After vacuum sealing, the PCM was not held tightly within the foam and gentle finger pressure, or gravity, was sufficient to cause the PCM to leak from the foam at room temperature.
Tests were also performed on a number of different open cell foams, with a sample of Basotect G+ (ex-BASF) used as a comparison. Apart from the Basotect G+ (melamine-formaldehyde; density 0.009 g/ml), the other foams were Oasis Floral Foam (phenol-formaldehyde -density 0.025 g/m1), TES 103 (polyether-polyurethane; density 0.025 g/m1), TES 108 (polyether-polyurethane; density 0.065 g/m1), 'ITS 200 (polyester-polyurethane; density 0.032 g/ml) and ITS 407 (reticulated polyether-polyurethane; density 0.028 g/ml). The Oasis foam was supplied by Smithers-Oasis UK. Ltd., whilst the other foams were supplied by Technical Foam Services Ltd. Apart from the Oasis foam, all the other samples would not retain all the PCI\4 without the use of a viscosifying polymer. All samples measured 100mm x 100rrim x supplied thickness. The thickness was as received from the supplier. The PCM/polymer solution comprised 5% by weight Septon 4077 and 95% by weight CrodaTherm 6.5. The solution was mixed and heated as above in Example 2. The required weight of solution was calculated and it was then weighed into a pouch, containing the foam under test, vacuum impregnated and heat sealed. All samples had been weighed and measured prior to impregnation and, once cool, the samples were removed from the pouches, any excess gel removed and the samples rewe ghed. The table below shows the estimated enthalpy of each foam sample based on the weight of impregnated PCM/polymer and an enthalpy of CrodaTherm 6.5 of 183 1 /g (CrodaTherm 6.5 Technical Data Sheet). The weights of the foams and polymer were subtracted prior to the enthalpy calculation i.e. the values are based solely on the CrodaTherm 6.5 content.
Sample Theoretical enthalpy (kJ) Basotect G+ 35.5 Oasis 28.1 TFS 103 35.3 TFS 108 25.5 TFS 200 35.2 TFS 407 33.4 Three samples (TFS 103, IFS 200 and IFS 407) showed similar performance to Basotect G-1. However, Basotect C1+ provided a stiffer, more resilient product which was extremely resistant to applied pressure The Oasis foam was structurally weaker than the other samples and partially collapsed under vacuum.
T-History type tests -small, screw topped alum mum vials were weighed and fitted with K-type thermocouples in the centre of 10 the vials. Two vials (1 and 2) had 15g tetradecane added.
A 95:5 by weight blend of tetradecane:Calprene H6120 was added to a stainless steel beaker and heated for one hour at 80oC until all the polymer had dissolved. Two "plugs" of Basotect G+ foam, cut to be a tight fit within the vials, were placed in the beaker and reheated for 10 minutes. The beaker was then placed in a vacuum chamber and evacuated to impregnate the foam. The impregnated foam pieces were placed in vials 3 and 4 and reweighed. Sample 3 contained 15g PCM/polymer and sample 4 15.87g. After allowing for the weight of the foam and polymer, the PCM contents were as follows: Sample 3 -14g tetradecane Sample 4 -14.7g tetradecane The vials were all heated for a further 30 minutes, to ensure good contact with the internal vial surface and then the thermocouples were fitted and the vials cooled to room temperature. All vials were placed in insulated foam jackets, to prevent too rapid temperature changes. The thermocouple data loggers were activated and the vials placed in a -18oC freezer. Once the samples had cooled to --18oC they were removed from the freezer and allowed to warm to room temperature.
This was repeated for a total of three freeze/melt cycles. The results are shown in figure 1 (for the 1st cycle).
There were no major differences found between the four vials in any of the tests. This was unexpected due to the slightly lower tetradecane weights in samples 3 and 4. Hence, the shape stable PCM/foam samples performed as well as the slightly increased quantities of liquid tetradecane in samples 1 and 2.
Claims (20)
- Claims 1. A shape stable phase change composition comprising a foam member at least partially impregnated or containing phase 5 change material, wherein said phase change material is a non-draining liquid or non-draining gel.
- 2. A composition according to claim 1 wherein the foam is an open cell foam.
- 3. A composition according to claim 2 wherein the foam is melamine foam.
- 4. A composition according to claim 3 wherein the foam is 15 melamine formaldehyde foam.
- 5. A composition according to any preceding claim wherein the gel is a viscosified phase change material.
- 6. A composition according to claim 5 wherein the phase change material gel includes a phase change material and at least one gelling agent or yiscosifying polymer.
- 7. A composition according to claim 6 wherein the gelling agent 25 or polymer is preferably substantially <15% by weight of the phase change material, more preferably at <10% by weight and most preferably at 5% or less.
- 8. A composition according to claim 7 wherein the phase change material is an alkane.
- 9. A composition according to claim 8 wherein the alkane is tetradecane (C14).
- 10. A composition according to claim 7 wherein the phase change material is an ester.
- 11. A composition according to claim 10 wherein the ester is octyl laurate (octyl dodecanoate).
- 12. A composition according to claim 8 wherein the phase change material is any one or any combination of; tetradecane, hexadecane, heptadecane, octadecane, eicosane, docosane (from 10 Sasol Germany GmbH).
- 13. A composition according to claim 1 wherein the phase change material is any one or any combination of CrodaTherm 5, CrodaTherm 6.5, CrodaTherm 9.5, CrodaTherm 15, CrodaTherm 19, CrodaTherm 21, CrodaTherm 24W, CrodaTherm 29, CrodaTherm 32, CrodaTherm 37, CrodaTherm 53, CrodaTherm 60 and CrodaTherm 74 (from Croda Europe), stearyl alcohol and/or stearic acid.
- 14. A composition according to claim 6 wherein the polymer or viscosifying polymer is a block copolymer.
- 15. A composition according to claim 14 wherein the polymer is a styrene ethylene ethylene propylene styrene copolymer 25 (SEEPS).
- 16. A composition according to claim 6 wherein the polymer is a thermoplastic copolymer.
- 17. A composition according to claim 16 wherein the polymer is ethylene-butylene/styrene thermoplastic copolymer.
- 18. A composition according to claim 17 wherein the polymer is styrenedethylene-(ethylene-propylene)-styrene block copolymer.
- 19. A composition according to any preceding claim wherein the polymer or viscosifying polymer is any one or any combination of; Septon HG-252, Septon 1020, Septon 4033, Septon 4055, Septon 4077, Septon 4099 (from Kuraray), Kraton 1654, Kraton 1651, Kraton 1633 (from Kraton Polymers), Calprene 1-16120, Calprene H6144, Calprene H6174 and Calprene IT641 OX (from Dynasol Group).
- 20. A method of producing a phase change composition comprising an open cell foam impregnated with a phase change material gel or viscosificd liquid wherein said gel or liquid is produced by heating a phase change material and a gelling agent or polymer to dissolve the gelling agent or polymer producing a substantially homogenous, low viscosity liquid.
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Citations (5)
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US20020147242A1 (en) * | 2001-02-20 | 2002-10-10 | Salyer Ival O. | Micropore open cell foam composite and method for manufacturing same |
EP1498680A1 (en) * | 2003-07-16 | 2005-01-19 | Basf Aktiengesellschaft | Accumulator of melamine-formaldehyde foam for keeping warm and cold |
US20180244971A1 (en) * | 2015-09-08 | 2018-08-30 | Croda International Plc | Phase Change Materials and Methods of Regulating Temperature |
CN113403039A (en) * | 2021-07-01 | 2021-09-17 | 四川大学 | Multifunctional phase change energy storage composite material and preparation method thereof |
WO2022245226A1 (en) * | 2021-05-18 | 2022-11-24 | Auckland Uniservices Limited | Polyurethane foams comprising phase change materials |
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US9598622B2 (en) | 2012-09-25 | 2017-03-21 | Cold Chain Technologies, Inc. | Gel comprising a phase-change material, method of preparing the gel, thermal exchange implement comprising the gel, and method of preparing the thermal exchange implement |
WO2014052409A2 (en) | 2012-09-25 | 2014-04-03 | Cold Chain Technologies, Inc. | Gel comprising a phase-change material, method of preparing the gel, and thermal exchange implement comprising the gel |
DE102016013415A1 (en) | 2016-11-10 | 2018-05-17 | Rainer Busch | Method for producing a dimensionally stable, leak-proof phase Change Material System (PCM-S) |
DE102020002843A1 (en) | 2020-05-12 | 2021-11-18 | Rainer Busch | Process for the production of a dimensionally stable and leak-proof energy storage medium |
DE102021005863A1 (en) | 2020-12-29 | 2022-06-30 | Rainer Busch | Process for the production of an energy storage medium by the so-called cold mixing process and reduced melt flow index (MFR) |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20020147242A1 (en) * | 2001-02-20 | 2002-10-10 | Salyer Ival O. | Micropore open cell foam composite and method for manufacturing same |
EP1498680A1 (en) * | 2003-07-16 | 2005-01-19 | Basf Aktiengesellschaft | Accumulator of melamine-formaldehyde foam for keeping warm and cold |
US20180244971A1 (en) * | 2015-09-08 | 2018-08-30 | Croda International Plc | Phase Change Materials and Methods of Regulating Temperature |
WO2022245226A1 (en) * | 2021-05-18 | 2022-11-24 | Auckland Uniservices Limited | Polyurethane foams comprising phase change materials |
CN113403039A (en) * | 2021-07-01 | 2021-09-17 | 四川大学 | Multifunctional phase change energy storage composite material and preparation method thereof |
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