Classifications

• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B7/00—Mixing; Kneading
  • B29B7/02—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type
  • B29B7/06—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices
  • B29B7/10—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary
  • B29B7/18—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary with more than one shaft
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/04—Carbon
  • C08K3/041—Carbon nanotubes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/06—Polyethene
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/01—Hydrocarbons

Definitions

• the invention relates to a method for producing a Ausschwitzarmen, preferably ausschwitzRON polymer-bonded and phase change material having phase change material composition.
• phase change materials have already become known in various embodiments. For example, reference is made to EP 0747 431 Bl, WO 98/12366, US 2006/0124892 A1, US 4,908,166 A1, US 2002/0105108 A1, US 2006/0124892 A1 and US 2005/0208286 A1.
• Suitable phase change materials are, in particular, salt-based phase change materials.
• the invention has the object to provide a method for producing a sweat-poor, preferably sweat-free phase change material with increased mechanical strength and improved as possible heat resistance and / or improved thermal conductivity, which provides the desired success with favorable manufacturability.
• phase change material at a temperature between 50 ° and 130 ° C, but in any case 20 ° to 70 ° C above the Melting temperature of the phase change material is introduced into an extruder, in which the polymer or polymers are introduced, wherein the extruder kneading, conveying and baffle elements, and that the introduction of the phase change material in the extruder in the extrusion direction immediately after the introduction of the Polymer is carried out in an area in which a first intense kneading action has already taken place on the polymer.
• the phase change material is thus introduced into the extruder not only at a relatively high temperature, but also in a range in which the polymer material is already kneaded to some extent. And preferably in a first calming section, which is essentially only about the promotion of the material. Due to the high temperature of the phase change material are good fluid properties of the phase change material ensured during insertion.
• the polymers introduced preferably polyethylene, in particular low-density polyethylenes, for example also diblock and triblock copolymers
• Preferably additionally introduced polymer PMMA can act in particular as a viscosity promoter and synergistic component with an improved formation of a three-dimensional network of diblock and triblock copolymers in the PCM polymer composites and in particular both the Auswitz the PCM component of the PCM polymer composites at elevated temperature and Improve compressive stress, as well as improve the mechanical stability of the obtained molded body of the PCM polymer composite.
• Carbon nanotubes also called CNTs (English carbon nanotubes) are microscopic tubular structures (molecular nanotubes) made of carbon.
• the diameter of the tubes is usually in the range of 1 to 50 ⁇ m, but it was which also produces tubes with a diameter of up to 0.4 ⁇ m. Lengths of several millimeters for single tubes and up to 20cm for tube bundles have already been achieved. It is important that at least one of the dimensions (diameter) of the nanotubes is in the nano range and that the properties of these nanoparticles differ significantly from those of the same composition, but not with diameters in the nanometer range.
• the multi-wall carbon nanotubes also significantly improve the strand formation behavior (increase of the strand strength) of the polymer melt during discharge from the extruder and thus provide increased process reliability in the granulation stage of the melt-compounding route according to the invention.
• the PCM can exude Component at levels up to 80 wt% of PCM are completely or at least almost completely suppressed.
• the multi-walled carbon nanotubes used also have the role of inhibiting the PCM component from blooming out of the polymer composite, especially when liquid or liquefying PCM materials are already present in the polymer composites at room temperature or at human body temperature.
• the multiwall carbon nanotubes already form a higher-viscosity network structure with liquid paraffin alone, which, in conjunction with the PMMA / block copolymer network, form an even denser network structure for encapsulated PCMs.
• phase change material used is preferably unencapsulated paraffin.
• the extruder is a screw extruder, in particular a twin-screw extruder.
• Fig. 1 shows a preferred arrangement of the configuration of the screw elements, the peripheral dosing technique and the addition sites for the polymer components and the PCM again.
• the liquid or liquefied paraffin (5) is preheated in a melting and preheating vessel to the respective required addition temperature and metered with a feed pump (6) via a metering lance in an extruder, preferably twin-screw extruder.
• Solid, flaky paraffin can be added via a metering balance (2) together with the respective polymer component (3) into the feed zone of the extruder.
• the PMMA component can be added via the polymer dosing scales (2) as well as the dosing trolley (3).
• Solid additives, such as, for example, claimed multiwall carbon nanotubes, are likewise metered into the feed zone of the extruder via a special powder dosing scale.
• the extruder can be operated at a speed of between 100 and 1200 revolutions per minute. Preferably between 300 and 1200 U / min, more preferably between 800 and 1200 U / min.
• these stated numerical bandwidths also include all intermediate values, in particular in steps of one revolution per minute. In this case, such a step can be made from the lower and / or upper limit to the respective other limit.
• the residence time begins with a feed of the polymer (s) and of the additives which are initially and preferably fed simultaneously. In any case, the residence time but begins with entry of the later-fed component regarding polymer or additive. These are intimately mixed already in the first conveying zone, before the phase change material such as paraffin is added.
• a residence time of the melt in the extruder is between one and four minutes. All intermediate values, in particular in one-second increments, are also included in the stated numerical bandwidth of the residence time. In this case, the intermediate values from the lower and / or upper limit to the respective other limit can provide a restriction.
• LDPE Low Density Polyethylene
• HDPE High Density Polyethylene
• LLDPE Linear Low-Density Polyethylene
• phase change material composition 10 to 40 percent by weight is then the polymer matrix.
• additives are added.
• the introduction of the phase change material is carried out so far preferably after the introduction of the matrix polymer and the additive, in a region in which already a first kneading action has taken place on the mixture of polymer and additive.
• An additive may be given in particular by a block co-polymer.
• styrene copolymers such as SEBS, SEEPS and SBS come into question.
• Kraton-G and Septon copolymers the known under the trade names Kraton-G and Septon copolymers.
• propylene block copolymers such as EPR.
• MWCNT Multi Wall Carbon Nanotubes
• SWCT Single Wall Carbon Nanotubes
• These are nanostructures with a length to diameter ratio of 1: 100 to 1: 1000 and more, possibly up to 1: 1,000,000 or more. They are formed by cylindrical carbon lenstoff molecules.
• all intermediate values are also included in increments of increments, be it as a restriction of the area from above and / or from below.
• the residence time of the materials in the extruder is more preferably provided in such a way that a residence time of 2 minutes is at any rate not undershot.
• a residence time in the range of 2 to 5 minutes is preferred, whereby all intermediate values, in particular in one-second increments, are also included in this bandwidth. This means in steps from the lower and / or upper limit to the other limit.
• the temperature in the extruder is adjusted so that it is at least 20 ° C -180 ° C, preferably 50 ° C -150 ° C above the feed temperature of the phase change material.
• These intermediate temperature ranges also include all intermediate values, in particular in 1 ° C increments. This is also such that such a step can be made from the lower or upper limit to the respective other limit.
• the obtained phase change material composition has a content of the phase change material of 60% or more, particularly 70% or more, more preferably 75% or more, up to 80%, with more preferably a range of 65-75 % is.
• all intermediate values, in particular in 1/10 percentage steps, are included in the disclosure, so that the phase change material can also be provided of 60.1% or more, etc.
• the intermediate values also refer to limitations of the respectively specified areas, be it from above and / or from below.
• phase change material composition achieved was:
• PCM 75 percent by weight
• phase change material (paraffin).
• a sample of these granules was further an extraction test subject water mixture with 50 weight percent (parts by mass of water to mass of ethylene glycol) at 30 nachorif olgenden temperature cycles between 30 0 C and 105 0 C in an E thylenglykol /, whereby in each case a heating and cooling cycle 8 h lasted ,
• the extract solution was transparent.
• the content of paraffin in the ethylene glycol / water extract solution was determined to be ⁇ 50 ppm.
• the granules did not stick together when hot or when cooled.
• phase change material composition achieved was as follows:
• PCM Raster RT 58, Rubitherm Technologies GmbH
• SEEPS Septon TM 4055, KURARAY Co. Ltd
• a sample of this granulate was further subjected to an extraction test in an ethylene glycol / water mixture with 50% by weight (parts by weight of water to parts by weight of ethylene glycol) at 30 successive Tempe- cycles between 30 0 C and 105 0 C, each with a heating and cooling 8 h took.
• the extract solution was transparent.
• the content of paraffin in the ethylene glycol / water extract solution was determined to be ⁇ 50 ppm.
• the granules did not stick together in both the hot and the cooled state.
• the phase change material composition was as follows:
• PCM 60 percent by weight
• PCM Percent by weight
• PCM Rubitherm Technologies GmbH
• the invention also provides a polymer-bound phase change material composition with a proportion of phase change material and carbon nanotubes as additive.
• polymer materials one or more of the aforementioned materials may be included, also with regard to the proportions already mentioned above.
• additives which may be provided in any case supplementary, is also referred to above Revelation directed.
• carbon nanotubes reference is made to the details explained further above.
• Figure 1 shows schematically the arrangement suitable for carrying out the method.
• Fig. 2 is a schematic representation, enlarged, of leakproof recorded paraffin domains in the network of styrene / ethylene / butadiene block copolymers and PMMA;
• FIG. 3 shows a microscope image of a paraffin-PMMA / SEBS copolymer blend, in an enlargement in which 6 mm in the illustration corresponds to 100 ⁇ m;
• FIG. 4 shows a reproduction according to FIG. 3, in which 7 mm in the reproduction correspond to 10 ⁇ m;
• FIG. 5 shows a reproduction according to FIG. 3 or FIG. 4, in which 3 mm corresponds to 1 ⁇ m in the reproduction; 6 shows a reproduction according to FIGS. 3 to 5, in which 4 mm in the reproduction correspond to 20 ⁇ m;
• FIGS. 3 to 6 shows a reproduction according to FIGS. 3 to 6, in which 3 mm in the reproduction correspond to 20 ⁇ m;
• FIGS. 3 to 7 shows a reproduction according to FIGS. 3 to 7, in which 4 mm in the reproduction correspond to 20 ⁇ m.
• a twin-screw extruder 1 is shown, which is shown in side view.
• the polymer is introduced from a supply container 2, in the exemplary embodiment PMMA.
• an additive 3 is introduced, in the embodiment SEBS.
• liquid phase change material 5 namely in this case paraffin
• nozzle 4 denotes a heatable liquid metering pump.
• the introduction takes place in the second conveying zone with storage zone c, downstream of the first kneading zone b.
• the resulting phase change material composition After leaving the extruder 1, the resulting phase change material composition passes through a water bath 9 and then a granulation 10. The granules obtained are taken up in a granule collecting container 11.
• a desired dense polymeric network structure is mainly characterized, obtains that in the first kneading zone (b), the second conveying zone (c) and the second kneading zone (d) a very high melt temperature of preferably from 50 0 C - 150 ° C above the feed temperature PCM is sought, the phase change material is preferably added in liquid form at a temperature of 50 0 C to 130 ° C above the melting temperature of the PCM itself, a high shear rate by screw speeds of 500 - 1200 U / min is applied and residence times of Melt in the extruder from 1 to 4 minutes. Longer residence times above 4 minutes are possible but not advantageous because the low throughputs of PCM polymer composites are not a cost effective manufacturing process.
• the stowage elements arranged according to FIG. 1, or more generally a stowage effect provide the desired effect of an extended residence time of the PCM polymer composite melt in the extruder of preferably 2 minutes or more, in particular up to 5 minutes, whereby also in this case all intermediate values, especially in one-second increments, be it restrictive from above and / or from below with respect to an area.
• FIG. 2 schematically illustrates how the PCM domains 12 (here paraffin) are formed into the network structure of the rigid styrene-13 and elastic butadiene block constituents 14 of the SEBS block copolymer (Kraton 1651) and the rigid PMMA segments 15 embedded present.
• the PMMA segments 15 form annular structures within which, but also overlying, the network structures of the coupled rigid styrene components 13 and elastic butadiene block components 14 are embedded.
• Within a network mesh are a subsidiary of PCM domains 12.
• FIGS. 3 to 8 are various SEM images of a paraffin-PMMA / SEBS copolymer blend obtained after Kryobruch on the granules obtained in Example 1.
• the sample was deep-frozen and exposed to such high mechanical loads that a break occurred due to the cold-related high rigidity (Kryobruch).
• the PMMA / block copolymer polymer network structure formed encloses the paraffin domains on all sides in such a way that they can no longer emerge from the network network, since even some apparently isolated paraffin domains already exist in their interior own the PMMA / Block networks.
• FIGS. 7 and 8 the manifestation of the paraffin / PMMA / block copolymer network structure can be seen in FIGS. 7 and 8.

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• Chemical & Material Sciences (AREA)
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• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Materials Engineering (AREA)
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• Combustion & Propulsion (AREA)
• Thermal Sciences (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Mechanical Engineering (AREA)
• Nanotechnology (AREA)
• Processes Of Treating Macromolecular Substances (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

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• 2008
  • 2008-03-26 DE DE102008015782A patent/DE102008015782A1/de not_active Withdrawn
• 2009
  • 2009-03-25 JP JP2011501222A patent/JP2011515551A/ja active Pending
  • 2009-03-25 CA CA2719724A patent/CA2719724A1/en not_active Abandoned
  • 2009-03-25 WO PCT/EP2009/053526 patent/WO2009118344A1/de active Application Filing
  • 2009-03-25 AU AU2009228817A patent/AU2009228817B2/en not_active Ceased
  • 2009-03-25 US US12/736,258 patent/US8262925B2/en not_active Expired - Fee Related
  • 2009-03-25 KR KR1020107023967A patent/KR20100139088A/ko not_active Application Discontinuation
  • 2009-03-25 CN CN2009801193738A patent/CN102046715B/zh not_active Expired - Fee Related
  • 2009-03-25 EP EP09725735A patent/EP2265668A1/de not_active Withdrawn

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