DE102017003215A1 - Process for producing a phase change material composite molding (PCM - V) with improved dimensional stability - Google Patents

Abstract

The present invention relates to a PCM composite molding (PCM - V) which consists of a component A and B and has therein shape memory polymer (SMP) which, with a suitable thermal stimulation, a shape transition from a temporary shape, in a form of their corresponding prior fabric structuring. SMP are often multiblock copolymers as well as di- or triblock copolymers. In addition, the different block copolymers contain a further property due to their lipophilic property also a PCM by adhesion energy to three - dimensional polymer chains and housings also above the predetermined melting temperature of the PCM dimensionally stable and leakproof adherent. The shape memory property is reversible and thermally stimulated. A volume change of component B (PCM), which mainly results from temperature and phase changes, is influenced by component A in the solid state as well as in the liquid state.

Description

In the RAL - GZ 896: 2013-11, PCM Phase Change Materials - Quality Assurance and PCM - Energy Storage Systems in Building Services, VDI 2164, Dec. 2016, (VDI - Guidelines) are comprehensively phase change materials (PCM) and PCM-V, PCM-O and PCM - S are described in their classifications, requirements, applications and test conditions.

• > TPE - A oder TPA (Thermoplastische Copolyamide, z.B. PEBAX, Fa. Arkema)
• > TPE - E oder TPC (Thermoplastischer Polyesterelastomere/Thermoplastische Copolyester, z.B. Keyflex, Fa. LG Chemie)
• > TPE - O oder TPO (Thermoplastische Elastomere auf Olefinbasis wie PP/EPDM
• > TPE - S oder TPS {Styrol - Blockcopolymere (SBS, SEBS, SEPS, SEEPS, MBS wie z.B. Kraton, Fa.Kraton Polymers, Septon Fa.Kuraray, Styroflex Fa. BASF, Thermoplast Fa. Kraiburg, Saxomer Fa. PCW)}
• >TPE - U oder TPU (Thermoplastischer Elastomer auf Urethanbasis wie Elastollan, Fa. BASF, Desmopan, Texin, Utechllan Fa. Bayer)
• > TPE - V oder TPV (Thermoplastische Vulkanisate oder vernetzte thermoplastische Elastomere auf Olefinbasis wie PP/EPDM wie z.B. Sarlink, Fa. DSM.

The known from the prior art thermoplastic elastomers and copolymers and block copolymers are widely described, they are commercially available, and can be divided into the following groups:

• > TPE - A or TPA (thermoplastic copolyamides, eg PEBAX, Arkema)
• > TPE - E or TPC (thermoplastic polyester elastomers / thermoplastic copolyesters, eg Keyflex, LG Chemie)
• > TPE - O or TPO (thermoplastic elastomers based on olefins such as PP / EPDM
• > TPE-S or TPS {styrene block copolymers (SBS, SEBS, SEPS, SEEPS, MBS such as Kraton, Kraton Polymers, Septon Fa.Kuraray, Styroflex Fa. BASF, Thermoplast Fa. Kraiburg, Saxomer Fa PCW)}
• > TPE-U or TPU (urethane-based thermoplastic elastomer such as Elastollan, BASF, Desmopan, Texin, Utechllan Fa. Bayer)
• > TPE-V or TPV (Thermoplastic vulcanizates or crosslinked thermoplastic elastomers based on olefins such as PP / EPDM such as, for example, Sarlink, DSM.

Because of their good mechanical properties, ease of processing, hydrophobic property, high lipophilic substance receptivity, and good adhesion to a wide range of substrates, di- or triblock copolymers can be used as structural-coating and adhesion materials in real applications.

Within the scope of this further development, the object of the invention is to provide a dimensionally stable and leak-proof phase change material composite system (PCM-V) with shape memory polymers. These are usually polymer networks where chemical (covalent) or physical (non-covalent) crosslinks determine the permanent shape.

The temporary shape of the PCM-V material according to the invention is in particular the shape which is below the switching temperature, i. is the melting temperature of the soft phase, and can be converted from the temporary shape to a permanent shape by heating the PCM -V to a temperature in a range greater than or equal to the melting point of the soft phase and the lower melting temperature of the hard phase.

Transition from a temporary form to the permanent form by heating the polymer as well as its description is by A. Landlein and S. Kelch comprehensively in: shape memory polymer, Angewandte Chemie, 2002, 114, 2138-2162 , Wiley-VCH, Weinheim, explains.

There, the terms "temporary shape", "permanent shape", "switching temperature", T _trans and T _perm , glass transition temperature "T _g ", melting temperature "T _m ", expansion fixation ratio "R _f " stretch recovery ratio "R _t " explained.

The SMPs present in component A are polymer networks in which chemical (covalent) or physical (noncovalent) crosslinks determine the permanent shape. It is novel from an innovative point of view, by means of an agglomeration process, to add the dry components of component A, which are also dry, to them and to mix them dry. In this case, an open-pored structure must continue to be ensured. To these are further attached by stirring shape memory polymers (SMP). In this dry agglomeration, the adhesion of the SMP to the open - pored particles is effected by van der Waals and Coulomb forces.

Component B, a commercial phase change material (PCM) is stirred into component A after its liquefaction and heated. A shape fixation of component A and B takes place in the above the transition temperature of a phase formed by the switching segments (switching phase). The component B adhered by adhesion to the component A is liquefied and cooled while maintaining the deformation forces below the switching temperature, crystallized, to then fix the temporary form in combination with the block copolymer.

Reheating above a switching temperature results in phase transitions and restoration of the original shape.

Since the switching temperature, in contrast to the transition temperature, depends on the mechanical movement, which defines the macroscopic shape change, both temperatures can differ.

• SEP : Polystyrene - b - Polyethylene/Propylene
• SEPS : Polystyrene - b - Poly(Ethylene/Propylene) - b - Polystyrene
• SEBS : Polystyrene - b - Poly(Ethylene/Butylene) - b - Polysterene
• SEEPS : Polystyrene - b - Poly(Ethylene/Ethylene/Propylene) - b - Polystyrene

In the following, some preferred tri - block copolymers are described which are suitable for the preparation the mixture of component A according to the invention are particularly suitable:

• SEP: Polystyrene - b - Polyethylene / Propylene
• SEPS: polystyrene - b - poly (ethylene / propylene) - b - polystyrene
• SEBS: polystyrene - b - poly (ethylene / butylene) - b - polysterene
• SEEPS: Polystyrene - b - Poly (Ethylene / Ethylene / Propylene) - b - Polystyrene

• >aliphatische Kohlenwasserstoffverbindungen
• >cyclische Kohlenwasserstoffverbindungen
• >aromatische Kohlenwasserstoffverbindungen
• >gesättigte oder ungesättigte C₆ - C₃₀ Fettsäuren
• >Fettalkohole
• >C₆ - C₃₀ Fettamine
• >Ester wie C₁ - C₁₀ Alkylester von Fettsäuren
• >natürliche und synthetische Wachse
• >halogenierte Kohlenwasserstoffe

Known to those skilled in the art and suitable lipophilic substances for incorporation into component A are those which hereinafter referred to as component B, such as:

• > aliphatic hydrocarbon compounds
• > cyclic hydrocarbon compounds
• > aromatic hydrocarbon compounds
• > saturated or unsaturated C ₆ - C ₃₀ fatty acids
• > Fatty alcohols
• > C ₆ - C ₃₀ fatty amines
• > Esters such as C ₁ - C ₁₀ alkyl esters of fatty acids
• > natural and synthetic waxes
• > halogenated hydrocarbons

In a calcined, porous material, in its composition consisting of: > silica (SiO ₂ ) > Iron (III) oxide (Fe ₂ O ₃ ) > alumina (Al ₂ O ₃ ) > titanium dioxide (TiO ₂ ) > calcium (CaO) > Potassium oxide + sodium oxide (K ₂ O + Na ₂ O) > magnesium (MgO) For example, the capillaries of these calcined, open-pore and finely-milled particles are later filled with a high lipophilic substance receptivity at room temperature or preferably at 70 ° C. The transport of the lipophilic substance into the capillary takes place from capillary and surface tensions known in the art in the capillaries.

By adding the preferred SEEPS tri - block copolymer, the adhesion forces for cohesion of the particles with SEEPS tri - block copolymer attached thereto are formed by van der Waals forces.

Further, additionally stirred in natural graphite particles improve the agglomeration process by reducing the frictional forces between the particles on the one hand, and significantly improving the adhesion of the natural graphite particles to the formed agglomerate of the component A, with respect to its thermal conductivity. An extremely high adhesion of the lipophilic substances to natural graphite particles is additionally achieved.

By stirring the component B in component A form at the interfaces of electrical double formations. These are firmly present both at the interfaces liquid / liquid and liquid. The component A, originally electrically conductive loses its existing electrical conductivity.

Unlike charging processes with solids. is necessary for the charging process of liquids, in addition the presence of ions as charge carriers. At phase boundaries liquid / solid at a phase change at an existing enclosure this situation changes. There, the different electron emission energies are correspondingly absorbed, the ions of the one polarity and form, e.g. negative charge layer on the housing wall. If the liquid was initially electrically neutral, it now has a correspondingly high positive charge due to the loss of negative ions.

As a result of Brownian motion, the ions are randomized over the entire liquid range. The diffuse charge layer is determined by the conductivity of the liquid. For the hydrocarbons as well as for the di - or triblock copolymers combined with their low conductivity, values of this charge layer are found in the millimeter range.

The stirring of the component B in component A leads to the desired transport of the ions in the diffuse positive charge layer, so that charging to the outside takes effect. In this case, it comes to a charge separation provided that the electrical resistance of component A and B is high enough to prevent a backflow of charge. Decisive for the charge is the correlation between resistance and the decisive for the separation process stirring or flow movement at the charge layer.

At the liquid / liquid phase boundary it was found that the formation of a double layer also takes place there. This preferably relates to the internal surfaces of dispersions or emulsions. When stirring the component A in component B correspondingly large amounts of charge can be released.

It was found that as long as the PCM - V is at rest, i. below or above the melting temperature of the lipophilic substance, no additional charge appears. As soon as the lipophilic substance flows, the charges diffused into it are carried along, and the charge transport is similar to solid substances. For liquids, as for solids, high resistances and / or high separation speeds lead to high charges.

Surprisingly, it has now been found that component A according to the invention, by stirring into component B, leads to the desired charge separation in the charge layer and to the formation of adhesive forces on the housing wall.

• > van der Waals Kräfte (Wirken der Anziehungskräfte zwischen Atomen/Molekülen, Ursache elektrische Dipolmomente wobei die Haftkraft abhängig ist von Abstand Adhäsionspartner, Partikelform, Oberflächenrauigkeit und der Absorptionsschichtdicke)
• > Oberflächen - und Feldkräfte durch direkten Partikelkontakt elektrostatische Kräfte (Partikel unterschiedlicher Ladung ziehen sich an, Ursache Coulomb Kräfte wobei das Entstehen der Haftkräfte und Bildung ihrer unterschiedlichen Ladung beim Partikelkontakt und Übertreten von Ladungen, Kontakt und Reibung der Partikel, Polarisierung von leitender Partikel und Kontaktpotential der Partikel bei diesem Leiter bzw. Nichtleiter entstehen).
• > Haftkräfte aus Flüssigkeitsbrückenbildung, Bindung durch Flüssigkeiten niedriger und hoher Viskosität.
• > Kapillarkraftmodell, hierbei ist der Flüssigkeitsgehalt ausschlaggebend für die Ursache der Haftkraft, Haftkraft sinkt mit steigendem Kontaktabstand, diese Haftkräfte sind durch Flüssigkeitsbrücken am intensivsten und unempfindlicher gegen Oberflächenrauhigkeit.

These adhesive forces, resulting from surface and field forces with direct particle contact, are applied to the housing wall by:

• > van der Waals forces (effects of the attraction between atoms / molecules, cause electrical dipole moments whereby the adhesion force depends on the distance between adhesion partner, particle shape, surface roughness and the absorption layer thickness)
• > Surface and field forces through direct particle contact electrostatic forces (particles of different charge attract, cause coulomb forces whereby the adhesion forces and formation of their different charge during particle contact and transgressing of charges, contact and friction of the particles, polarization of conductive particles and contact potential the particles are formed at this conductor or non-conductor).
• > Bonding forces from liquid bridge formation, bonding by liquids of low and high viscosity.
• > Capillary force model, where the liquid content determines the cause of the adhesive force, adhesive force decreases with increasing contact distance, these adhesive forces are most intense due to liquid bridges and less susceptible to surface roughness.

Steps for the formation of the component A are in the DE 102016013415.1 in a so-called wet agglomeration, described by way of example.

It has surprisingly been found in this further development that the preferred tri-block copolymers, ie thermoplastic elastomers which, although they themselves have no shape memory properties, surprisingly exhibit shape memory properties in mixtures with one another.

The shape memory effect is thus not a specific material property of individual polymers, but rather results from the combination of polymer structure and morphology combined with its processing technology. Shape memory effects occur in many polymers, but they can differ in their chemical composition. Particularly suitable are di- or tri-block copolymers for the preparation of the mixture according to the invention which has shape memory effects.

These mixtures according to the invention comprise block copolymers which have hard segments and soft segments as well as the lipophilic substances described. (Image 1)

In a preferred SEEPS polymer, the compounds (S-E-EP-S) with their various segments are stable upon exposure to water (humidity) with respect to their combination of "soft" segment with "hard" segment. Dissolution of the compound is not expected since its compounds are covalent bond.

The block copolymer present in component A is admixed with a lipophilic substance, preferably a PCM from the series of commercially available so-called "Bio PCM", for example the fatty acid ester from Croda, England, Crodatherm 21, the so-called component B, which was previously liquefied, mixed by stirring.

Component A and B can be brought into its permanent form by conventional processing techniques such as casting, injection molding, extrusion and dipping. Subsequently, the component A and B can be fixed in the desired temporary shape.

This is generated by a heating of the PCM-V, a deformation and a cooling process, or a deformation at low temperature, a so-called cold drawing. The permanent form is stored while the temporary shape is currently available.

Shape memory polymers must have two separate phases with different temperature transitions. The phase with the highest temperature transition T _{Perm determines} the permanent shape and the phase with the lower temperature transition the so-called switching temperature the shape memory effect, T _Trans .

The preferred tri-block copolymers, which are usually elastic, thus have a high transition temperature phase T _Perm , the hard segment-forming phase, which acts as a physical crosslinker, and determines the permanent shape.

The physical crosslinking is usually carried out by crystallization of individual polymer segments or by solidification of amorphous regions. This physical crosslinking is thermally reversible, they are thermoplastically processable above T _Perm . It is thus a thermoplastic elastomer.

The switching segment is a second phase which has a lower transition temperature. This transition can be both a glass transition temperature T _g or a melt transition T _m . In the case of block copolymers, both different phase-forming segments are chemically covalently linked together.

task

It is the object of the present invention to provide a PCM-V of a mixture of lipophilic and block polymer materials with shape memory effect. In this case, the lipophilic portion itself does not have a shape memory effect.

Block copolymers are preferably to be selected so that good miscibility is achieved in the presence of different soft segments. This is of particular interest so that the miscibility of the block copolymers present in the mixture, which may also be different from one another, can achieve additional mechanical properties.

According to the invention, a preferred crystalline hard segment and the soft segment are selected from amorphous segments, as is ensured in a SEEPS.

In addition to the block copolymers essential to the invention, the mixtures according to the invention should contain further constituents which, however, do not adversely affect the properties of the mixture which are desirable for use as PCM-V. The other components of the mixture are the already mentioned porous materials, and natural graphite, these form the so-called component A.

The so-called component B, a lipophilic substance, contributes to the entropy elasticity of the mixture. The elongation of the mixture material formed from component A and B is additionally increased above T _trans by the incorporation of this substance. The soft segments are amorphous and are mobile. When stretched, they are oriented and upon cooling under Ttrans these segments crystallize with the attached lipophilic substances, their temporary shape is fixed. (Picture 2)

When the temperature is raised again, the crystallites of the lipophilic substance are remelted, the molecular chains are curled up, components A and B return to their original shape. (Picture 3)

Surprisingly, it has further been found that by increasing the entropy elasticity, the existing adhesion force of components A and B remains on an enclosure. The strain recovery ratio Rt resulting from the entropy elasticity of the components A and B is smaller than the strain fixing ratio Rf.

The volume change of the lipophilic materials from liquid / crystalline or crystalline / liquid is reduced by the entropy elasticity of the SEEPS. This depends on the strain recovery ratio R _T and the adhesion of the PCM - V to the wall of the casing and the percentage proportionate mixing ratio of the constituent components of component A. These adhesive forces result from the van der Waals and Coulomb forces formed as well as liquid and solid bridges at the walls.

embodiment

The PCM-V adjusted according to the invention with entropy elasticity and shape memory is described by way of example with the following production steps for the preparation of 1,000 g (1.0 kg) of component A:

• 400 g kalziniertem offenporigen Material (Primärpartikel) mit seiner Zusammensetzung:

> Siliziumdioxid 75 Gew.-% > Eisen(III) - Oxid 7 Gew.-% > Aluminiumoxid 10 Gew.-% > Titandioxid 1 Gew.-% > Calciumoxid 1 Gew.-% > Kaliumoxid + Natriumoxid 2 Gew.-% Magnesiumoxid 1 Gew.-%

• 400 g Polystyrene - b - Poly(Ethylene/Ethylene/Propylene) - b - Polystyrene (SEEPS) Tri - Blockcopolymer (A - B - A) Type. Fa. Kuraray, Deutschland.
• 200 g Natur Graphit. Fa. Imerys, Deutschland

wird in einem Mix-Prozess mit folgendem Schritt auf ein Trockengewicht von 1.000 g (1.0 Kg) gebracht. Component A consisting of the following individual components:

• 400 g of calcined porous material (primary particles) with its composition:

> Silicon dioxide 75% by weight > Iron (III) oxide 7% by weight > Alumina 10% by weight > Titanium dioxide 1% by weight > Calcium oxide 1% by weight > Potassium oxide + sodium oxide 2% by weight magnesia 1% by weight

• 400 g of polystyrene-b-poly (ethylene / ethylene / propylene) -b-polystyrene (SEEPS) tri-block copolymer (A-B-A) type. Fa. Kuraray, Germany.
• 200 g of natural graphite. Fa. Imerys, Germany

is brought in a mix process with the following step to a dry weight of 1,000 g (1.0 kg).

I) 400 g of ground primary particles with the following particle size distribution: > 800 μm 02.0% 700 - 800 μm 10.8% 500 - 700 μm 37.5% 300 - 500 μm 40.1% 200-300 μm 09.0% 63-200 μm 02.3% <63 μm 00.1% finely ground again and brought to a preferred particle size: <005 μm 01.88% 005-065 μm 15.24% 065-100 μm 02.50% 100-150 μm 03.65% 150-300 μm 17.28% 300 - 500 μm 19.29% 500 - 700 μm 14.24% 700 - 800 μm 07.75% 800-1000 μm 12.42% > 1000 μm 05.75%

II) Add 400 g of SEEPS and stir at RT for 15 min

III) 200 g of natural graphite in II) and stir for about 15 min at RT

IV) finely ground again the mixture prepared according to III) to the preferred particle size ratios described under I) in order to effect a separation of material agglomerations of component A, and secondly to improve the distribution of the finely ground component A particles in a subsequent mixing process to reach. Component A is storable separately from component B.

Component A and B are prepared by introducing and mixing the liquid PCM, referred to herein as component B, into component A. The mixing may be accomplished by stirrers, magnetic stirrers, Taylor Couette mixers, ultra sonic mixers or extrusion.

• V) 100 g der Komponente A entnehmen und auf 70°C erwärmen
• VI) 1000 g der Komponente B entnehmen und auf 70°C erwärmen
• (VII) Komponente A und B zusammen in einem auf 70°C erwärmten Behältnis zwischen 5 bis 30 min. Rühren, bevorzugt 10 min. Rührzeit.
• VIII) Die flüssige Komponente A und B in eine Einhausung durch Gießen, Tauchen, Extrusion oder Spritzgießen einbringen und anschließend bei 70°C für 30 min, oder wahlweise bei 50°C für >> 24 h halten.
• IX) Anschließend die Komponente A und B in ihrer Einhausung oberhalb der Kristallisationstemperatur der Komponente B abkühlen, und ggf. entformen. Die Entformung der Komponente A und B innerhalb der Entropieelastizität durch Schälkraft zwischen PCM - V und Einhausungswand ist gegeben. Hierbei muss die Schälkraft oberhalb der Haftkräfte liegen. Das Einlegen und Entformen in eine Einhausung ist reversibel solange das PCM - V weiterhin seine Entropieelastizität innerhalb des vorgegebenen Temperaturschaltbereich besitzt.

Mixing process for producing a phase change material composite (PCM - V) consisting of components A and B with entropy elasticity and shape memory behavior:

• V) 100 g of component A and heat to 70 ° C.
• VI) take 1000 g of component B and heat to 70 ° C.
• (VII) components A and B together in a heated to 70 ° C container for 5 to 30 min. Stir, preferably 10 min. Stirring time.
• VIII) Introduce the liquid component A and B into a housing by casting, dipping, extrusion or injection molding and then keep at 70 ° C for 30 min, or optionally at 50 ° C for >> 24 h.
• IX) Then cool the component A and B in their housing above the crystallization temperature of the component B, and if necessary demold. The demoulding of component A and B within the entropy elasticity by peeling force between PCM-V and housing wall is given. Here, the peel force must be above the adhesive forces. The insertion and removal in an enclosure is reversible as long as the PCM - V still has its entropy elasticity within the given temperature switching range.

As suitable particles of component A, the finely ground primary particles described can be used but are not necessarily limited to their size and proportions. Likewise, thermoplastic elastomer can be selected from the named groups of copolymers and block copolymers.

Component A can be mixed with the component B in the following percentages by weight of from 5 to 80% by weight, preferably 10 to 25% by weight, of component B, with component B mixed with 95 to 20% by weight of components in component A. , Blend proportions of the weight percent of component A in component B exhibit preferred entropy, shape memory, and adhesion energies in the range of 10 to 20 weight percent of component A in component B to form the PCM-V material.

The sensible and latent enthalpy of fusion value of the exemplified PCM-V material with a 10% by weight proportion of component A and 90% by weight proportion of component B has a melting enthalpy value of 200 KJ / kg (+/- 5 %) on.

Small volume changes in the switching temperature range between 15 ° C and 28 ° C were determined for a PCM - V by way of example: Temperature range (T ° C) 15 ° C to 28 ° C Component A (wt.%) 15% Component B (wt.%) 85% Volume change (%) 0.5% Temperature range (T ° C) 15 ° C to 28 ° C Component A (wt.%) ------ Component B (wt.%) 100% Volume change (%) > 5%

As is apparent to those skilled in the art, from the different mixing proportions of components A and B, corresponding enthalpy of fusion and volume changes can be generated. The range of variation is not only subject to the mixtures described by way of example, but can be extended to mentioned lipophilic substances of component B with their specific melting temperatures and enthalpy of fusion, further by the choice of a higher molecular weight of the SEEPS.

Measurements of the electrical conductivity (surface resistance) of components A and B at a filling level of exemplarily 20% by weight (Imerys PP 44 Natural Graphite) are in the range of >> 10 ¹² ohms. They are therefore classified as non-electrically conductive (insulator).

It is known from the prior art that the heat conduction in an electrical insulator is predominantly by phonons.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• DE 102016013415 [0025]

Cited non-patent literature

• A. Landlein and S. Kelch encompassing: shape memory polymer, Angewandte Chemie, 2002, 114, 2138-2162 [0006]

Claims (15)

Material consisting of phase change material composite (PCM - V), phase change material objects (PCM - O), phase change material systems (PCM - S) which consist in their inventive composition of a component A and B, wherein the Component A has a shape memory polymer (SMP) therein, moreover, reduces a volume change of component B due to temperature and phase change, and, upon suitable thermal stimulation, has a shape transition from a temporary shape to a shape of its corresponding prior fabric structure; the thermoplastic elastomer from the group of multiblock copolymers, and there preferably a di- or Triblockcoplymer is selected with a high capacity for lipophilic substances. A PCM - V after Claim 1 ) characterized in that the component A finely ground calcined primary particles having an open-pore structure of the composition of silica, ferric oxide, alumina, titania, calcium oxide, potassium oxide + sodium oxide and magnesium oxide, and having different weight and particle diameter distribution. A PCM - V after Claim 1 ) and 2) characterized in that the capillaries and pores of the open-celled materials absorb a lipophilic substance. A PCM-V after Claim 1 ) to 3), characterized in that a copolymer, block copolymer or tri - block copolymer is selected from one of the following groups of TPE - A, TPE - E, TPE - O, TPE - S, TPE - U or TPE - V. Here, the tri - block copolymers such as SEP, SEPS, SEBS and preferably SEEPS with their own high absorption capacity for lipophilic substances can be used. A PCM - V according to previous claims, characterized in that lipophilic substances such as aliphatic hydrocarbon compounds, cyclic hydrocarbon compounds, aromatic hydrocarbon compounds, saturated or unsaturated C ₆ - C ₃₀ fatty acids, fatty alcohols, C ₆ - C ₃₀ fatty amines, esters such as C ₁ - C ₁₀ alkyl esters of fatty acids, natural and synthetic waxes, halogenated hydrocarbons as one of component B, or their mixture with each other, is selectable. A PCM - V according to previous claims, characterized in that in addition natural graphite particles are stirred in which the desired heat conduction in the PCM composite predominantly by phonons (intrinsic heat conduction), moreover, has a high adhesion to lipophilic substances. A PCM-V according to previous claims, characterized in that the partially filled with lipophilic substance capillary and wetted particle surface of the primary particles in conjunction with the said further proportions to form the component A, a dry buildup agglomeration - process is subjected. A PCM - V according to previous claims, characterized in that the particles of the component A are again finely ground to break up agglomerations, and is with their particle diameter in the described range, to subsequently the free capillary and Porenzugänge, as well as the particles located on the preferred SEEPS to bind liquid lipophilic substances, and also to fill open capillaries and pores. Air bubbles after stirring the two components can be eliminated by shaking, raising the temperature or vacuum. A PCM - V according to previous claims, characterized in that by stirring the components B in A or A in B, there is a desired charge separation in the charge layer and it comes to the formation of adhesive forces on a Einhausungswand. A PCM - V after a previous one Claim 9 ) characterized in that these adhesion forces are formed as a result of surface and field forces with direct contact of the particles with each other but also of components A and B on the enclosure walls by van der Waals forces, surface and field forces, adhesion forces from liquid bridges and fixed bridges and capillary force model , A PCM - V according to previous claims, characterized in that in this development preferred tri - block copolymer SEEPS, ie thermoplastic elastomer, itself has no shape memory property, in the mixture for forming the component A with B, surprisingly shows shape memory properties. A PCM - V according to previous claims, characterized in that within the switching temperature range of 12 ° C to 70 ° C, the volume change of the lipophilic material of liquid / crystalline or crystalline / liquid is compensated by the present in this temperature range entropy elasticity of the preferred SEEPS, and of its stretch recovery ratio R _T , as well as PCM - V adhesion to the housing enveloping walls. A PCM - V according to previous claims formed from component A and B and characterized in that the PCM - V material with its enclosure so airtight concludes with each other that destabilizing ions or water molecules from the environment does not lead to a separation. PCM-V, PCM-O and PCM-S after at least one of Claim 1 13), this composite molding possesses reversible, thermally stimulated shape memory property, and moreover influences a thermally induced volume change of the component B. The constituents (particles) of component A (primary particles, tri-block copolymer and natural graphite) each have their own high absorption capacity for a lipophilic substance.

Images