JP6944933B2 - Cable made of phase change material - Google Patents

Description

Cross-reference to related applications This application claims priority under US Provisional Patent Application Nos. 62 / 250,206 filed on November 3, 2015, pursuant to Article 119 of the US Patent Act. This application is incorporated herein by reference in its entirety.

The present specification provides phase change materials (PCM) for thermal management in various applications such as automobiles, buildings, packaging, clothing, and footwear. Specifically, the present specification describes a cable including PCM, a method of manufacturing the cable, and the use of the cable in a plurality of applications.

Several patents and publications are cited herein to better illustrate the state-of-the-art technology to which the present invention belongs. The entire disclosure of each of these patents and publications is incorporated herein by reference.

A phase change material (PCM) is a latent heat storage material capable of absorbing and releasing a large amount of latent heat during melting and crystallization. Thermal energy transfer occurs when the material is converted from solid phase to liquid phase or from liquid phase to solid phase. During such phase changes, the temperature of the PCM material remains largely constant, as is the space surrounding the PCM material, and the heat flowing through the PCM is "captured" within the PCM material. Among the many well-known PCMs, paraffin is frequently used because of its low cost and low toxicity.

PCM can be introduced into a matrix made of various materials, or these can be applied as a coating. For example, US Pat. No. 4,003,426, US Pat. No. 4,528,328, US Pat. No. 5,053,446, US Patent Application Publication No. 2006/0124892 (International). See Publication No. 2006/062610), International Publication No. 98/04644, and International Publication No. 2004/0443445.

For convenient use of PCM in thermal management applications, they have been incorporated into matrix polymers that absorb and retain PCM even at temperatures above the melting point of PCM. This allowed the resulting PCM composite to be manufactured into slabs, panels, or other shapes that could be easily attached to the wall. However, most matrix polymers have multiple drawbacks, such as limited PCM absorption capacity or a large loss of PCM due to leaching during the life of the product. Partial solutions to these problems are proposed in International Publication No. 2006/062610, International Publication No. 2011/143278, and International Publication No. 2011/014636.

Nevertheless, it provides a large heat storage capacity and large surface contact for optimal heat exchange; -20 ° C ~ with permanent exposure to chemicals (particularly lubricants or ethylene glycol) as well as air. It is resistant to temperatures of 130 ° C.; retains its effect for a long period of time; provides high thermal conductivity; PCM-containing materials are still in need.

Therefore, in the present specification, the cable includes a core and a PCM layer surrounding the core, wherein the PCM layer is made of a PCM composition.
a) The PCM composition contains 1,3-propanediol fatty acid ester;
b) The core consists of threads, strands, or wires made of natural or synthetic polymeric material or metal;
Cables are provided.

Preferably, the PCM composition is made from living organisms.

In a preferred embodiment, the PCM composition contains or consists essentially of 1,3-propanediol dibehenate or 1,3-propanediol dipalmitate.

Preferably, the thread, strand, or wire is made of polyparaphenylene terephthalamide (para-aramid) or copper.

In another embodiment, the cable further comprises one or more layers of protective polymer. Preferably, the cable comprises one protective polymer layer. Preferably, the protective polymer is made from a blend of ionomer and polyamide. More preferably, the cable comprises two protective polymer layers. Preferably, the first layer of protective polymer is made from a blend of ionomer and polyamide and the second layer is a grafted or ungrafted polypropylene homopolymer, grafted or grafted. Made from polymers selected from the group consisting of non-polypropylene copolymers, perfluoroethylene-propylene (FEP), perfluoroalkoxy alkanes (PFA), ethylene tetrafluoroethylene (ETFE), and / or ethylene acrylate rubber (AEM). NS.

Preferably, each layer of protective polymer has a thickness of 50-300 μm. More preferably, when two layers are present, the total thickness of both layers is 50-600 μm.

Preferably, the amount of PCM in the cable is at least 70% by weight based on the total weight of the cable.

The preferred cable of the present invention has a diameter of 3-6 mm.

Further provided herein are methods of manufacturing cables. The method is
a) Steps of providing a core of yarn, strands, or wire made of natural or synthetic polymeric material or metal; and b) containing or essentially from 1,3-propanediol fatty acid ester. PCM composition to be extruded onto a core;
including.

Optionally, the method further comprises c) extruding one or more layers of one or more protective polymers onto the PCM composition and core; Preferably, one protective polymer layer is extruded onto the PCM composition and core. Preferably, the protective polymer is made from a blend of ionomer and polyamide. More preferably, two protective polymer layers are extruded onto the PCM composition and core. More preferably, the first layer is made from a blend of ionomer and polyamide and the second layer is a grafted or ungrafted polypropylene homopolymer, grafted or ungrafted. It is made from a polymer selected from the group consisting of polypropylene copolymers, perfluoroethylene-propylene (FEP), perfluoroalkoxy alkanes (PFA), ethylene tetrafluoroethylene (ETFE), and / or ethylene acrylate rubber (AEM).

Cables are useful for thermal management, especially in automotive applications.

Definitions As used herein, the term "a" refers to at least one, not just one, and is not an article that necessarily limits the referent noun to the singular.

As used herein, the term "about, at or out" means that the quantity or value of interest may be a specified value or another value that is approximately the same. Is intended to mean. This phrase is intended to convey that similar values promote equal results or effects of the present invention.

As used herein, the term "acrylate" means an acrylic acid ester having an alkyl group. An acrylate having an alkyl group having 1 to 4 carbon atoms is preferable.

As used herein, the term "(meth) acrylic acid" means acrylic acid, methacrylic acid, or both acrylic acid and methacrylic acid. Similarly, the term "(meth) acrylate" means methacrylate and / or acrylate, and "poly (meth) acrylate" means a polymer derived from the polymerization of either monomer or a mixture of both monomers.

As used herein, the term "copolymer" means a polymer containing copolymerization units resulting from the copolymerization of two or more comonomer. In this regard, copolymers are described herein in relation to their constituent comonomer, or with respect to the amount of constituent comonomer, eg, "copolymers containing ethylene and 18% by weight acrylic acid", or similar. May be done. Such a statement does not refer to comonomer as a copolymerization unit; it does not include trivial nomenclature for copolymers, such as the International Union of Pure and Applied Chemistry (IUPAC) nomenclature; It does not use product-by-process terms; or may be considered informal for other reasons. However, as used herein, the description of the copolymer in relation to its constituent comonomer or the amount of its constituent comonomer refers to the copolymerization unit of the comonomer in which the copolymer is embodied (if embodied, specific). Means to include (in a converted amount). As a corollary, the copolymer will not be the product of a reaction mixture containing a given comonomer in a given amount, unless explicitly stated in limited circumstances as such. The term "copolymer" is essentially a polymer consisting of copolymerization units of two different monomers (dipolymer), or a polymer essentially consisting of more than two different monomers (terpolymer consisting essentially of three different comomers). It can mean a tetrapolymer, etc., which is essentially composed of four different comonomer).

Moreover, the amounts of all components in the polymer or composition are complementary. That is, the sum of the amounts of all the components is the total amount of the polymer composition. For example, when describing an ethylene copolymer by specifying the weight% of the copolymerized comonomer, the sum of the copolymerized ethylene, the copolymerized comonomer, and the other copolymerized comonomer (if any) is , 100% by weight.

The term "acid copolymer" refers to α-olefins, α, β-ethylenic unsaturated carboxylic acids, and optionally other suitable comonomer (s) (such as α, β-ethylene unsaturated carboxylic acid esters). It means a polymer containing a copolymerized unit.

The term "ionomer" refers to a polymer produced by partially or completely neutralizing an acid copolymer.

In the present specification, a cable including a core and a PCM layer surrounding the core is provided. The PCM layer consists of a PCM composition.

The PCM composition contains, consists of, or is essentially composed of 1,3-propanediol fatty acid ester.

More specifically, the 1,3-propanediol fatty acid ester is one of the fatty acids in which each propanediol molecule reacts to form an ester with one fatty acid (“monoester”) or with two fatty acids (“diester”). , 3-Propanediol ester. Preferably, 1,3-propanediol, fatty acids, and 1,3-propanediol diesters and monoesters of fatty acids are entirely biologically sourced, reproducible and biodegradable. For example, these PCMs are synthesized from food grade raw materials.

The PCM composition contains a 1,3-propanediol diester, a 1,3-propanediol monoester, or a mixture of a 1,3-propanediol diester and a 1,3-propanediol monoester.

The 1,3-propanediol ester can be produced by direct esterification using excess fatty acid and 1,3-propanediol. After esterification, the remaining free fatty acids and alcohols are removed by distillation. The remaining ester can be used directly or can be further produced, for example, by additional distillation of the product as described in WO 08/123845.

In a preferred embodiment, the PCM composition is made from an organism. More specifically, PCM is manufactured from biological products in an environmentally friendly manner. For example, vegetable oils serve as a source of fatty acids, and 1,3-propanediol is produced by fermentation of corn syrup (bioseparation of 1,3-propanediol). This process uses 40% less energy than traditional 1,3-propanediol production by chemical methods starting with fossil fuels and reduces greenhouse gas emissions by 20% (Source: http: // brew). .Geo.uu.nl/BREWsymposium Wiesbaden11mei2005 / WEBSITEBrewPresentations51105.PDF).

Renewable 1,3-propanediols made from living organisms can be produced, for example, as described in Pamphlet International Publication No. 1996/035796.

In a further embodiment, the 1,3-propanediol diester is a "symmetric diester". The term, as used herein, means a diester in which two identical fatty acids have reacted with one 1,3-propanediol molecule. Symmetric diesters are typically characterized by more regular crystal packing.

In a further embodiment, the diester is an "asymmetric diester". The term, as used herein, means a diester in which two different fatty acids have reacted with one 1,3-propanediol molecule. By changing the symmetry of fatty acids and diesters, the melting point of PCM can be changed and fine-tuned.

In a further embodiment, the 1,3-propanediol ester is a monoester. Usually, the melting point of a 1,3-propanediol monoester is lower than that of the corresponding 1,3-propanediol diester.

In a further embodiment, the ester comprises a reaction residue of a fatty acid having a chain length of 2 to 24 carbon atoms (C _{3 to} C ₂₅ fatty acids). The preferred chain length is 8 to 22 carbon atoms (C _{9 to} C ₂₃ fatty acids). Generally, a PCM having a high melting point also has a high latent heat. Again, typically, the longer the fatty acid chain, the higher the melting point of the 1,3-propanediol ester, and more heat can be absorbed and released by the PCM composition. Therefore, the characteristics of PCM can be changed by changing the length of the fatty acid chain.

Fatty acids include, but are not limited to, propionic acid, butyric acid, valeric acid, caproic acid, enatoic acid, capric acid, pelargonic acid, capric acid, undecyl acid, ruphosphate, tridecyl acid, myristic acid, pentadecic acid, palmitic acid. , Margaric acid, stalilic acid, nonadesyl acid, arachidic acid, henicosyl acid, bechenic acid, tricosyl acid, lignoceric acid, α-linolenic acid, stearidonic acid, eicosapentaenoic acid, docosahexaenoic acid, linoleic acid, γ-linolenic acid, dihomo- Saturated or unsaturated fatty acids such as γ-linolenic acid, arachidonic acid, docosatetraenoic acid, palmitrenic acid, baxenoic acid, pauphosphoric acid, oleic acid, ellagic acid, gondoic acid, erucic acid, nervonic acid, and meadic acid. May be good.

The PCM composition may comprise saturated, unsaturated, linear or fatty acid esters, or esters of saturated or unsaturated branched or unbranched fatty acid mixtures.

In a preferred embodiment, the fatty acids are linear and saturated.

In a more preferred embodiment, the PCM composition contains, consists of, or consists essentially of 1,3-propanediol dibehenate or 1,3-propanediol dipalmitate. Again, these diesters are preferably made from living organisms.

PCM compositions include, but are not limited to, plasticizers; stabilizers (such as viscosity stabilizers and hydrolysis stabilizers); primary and secondary antioxidants; UV absorbers; antioxidants; dyes. , Pigments, or other colorants; inorganic fillers; flame retardants; lubricants; reinforcing agents such as glass fibers and flakes, synthetic (eg aramid) fibers, or pulps; foaming agents or swelling agents; processing aids (eg ethylene vinyl) Ethylene copolymers such as acetate (EVA); lubricants; anti-adhesive agents such as silica or talc; mold release agents; seed crystal additives to suppress the occurrence of overcooling; and one or more additions such as tack-imparting resins The agent may be further contained in an amount of 0.01 to 15, 0.01 to 10 or 0.01 to 5% by weight based on the total weight of the PCM composition. These additives are described in Kirk Othmer Energy of Chemical Technology. Examples of suitable antioxidants for thermal stabilization of 1,3-propanediol ester include, for example, tert-butylhydroquinone (TBHQ), pentaerythritol tetrakis (3- (3,5-di-tert-butyl). -4-Hydroxyphenyl) propionate), butylated hydroxytoluene (BHT), tris (2,4-ditert-butylphenyl) phosphite, and propyl-3,4,5-trihydroxybenzoate.

Additives can be incorporated into the composition by any known method, such as dry mixing, extrusion of mixtures of various components, masterbatch, and the like.

The cables provided herein include a PCM layer surrounding the core, one or more optional polymer layers surrounding the PCM layer, and a core.

Cables can be manufactured by extrusion molding the PCM composition onto threads, strands, or wires. Alternatively, the cable can be manufactured by other methods, such as passing the yarn through a molten PCM composition and stretching it, or immersing it in a PCM composition.

The threads, strands, or wires are preferably made of natural or artificial polymeric material or metal. Suitable polymeric materials include, but are not limited to, cotton, polyester, polyamide, or polyphenylene terephthalamide (aramid), and / or mixtures or blends thereof. Preferably, the thread, strand, or wire is made of polyparaphenylene terephthalamide (para-aramid) or copper. Some suitable polyparaphenylene terephthalamide (para-aramid) threads, strands, or wires are commercially available from DuPont under the trademark Kevlar®.

Threads, strands, or wires can be used to pull the entire cable during the extrusion process of the PCM composition without breaking due to the weakness or brittleness of the PCM material. The PCM composition containing 1,3-propanediol fatty acid ester can be used alone to extrude the PCM composition without the need for other thermoplastic polymers. Although not bound by theory, the melting range of compositions containing 1,3-propanediol fatty acid esters is wide enough to obtain adequate and stable melt viscosities and is therefore extruded. It is hypothesized that a stable process during molding is guaranteed.

Preferably, the PCM composition is fed to a wire-coated extrusion line and extruded onto a yarn, strand, or wire at a temperature above its melting point to the desired thickness.

Optionally, one or more additional layers can be extruded onto the cable obtained by extruding the PCM composition onto threads, strands, or wires. A polymer layer is preferred as the additional layer.

The cross section of the cable does not have to be circular and may be any shape determined by the shape of the die attached to the outlet of the extruder.

Since the thermal performance of the composition is generally directly proportional to the concentration of PCM in the PCM composition, it is desirable that the amount of PCM in the cable be as large as possible. The amount of PCM in the cable is at least about 70% by weight, about 70 to about 95% by weight, or about 75 to about 85% by weight based on the total weight of the cable.

Optionally, the cable containing the core and the PCM layer additionally contains one or more layers of protective polymer. A layer of protective polymer usually surrounds the PCM layer. However, a layer of protective polymer could also be inserted between the PCM layer and the core.

The protective layer may be any polymer. However, the layer of protective polymer preferably imparts some properties to the cable, such as heat resistance, chemical resistance, sealing properties and the like. Specifically, the cables described herein can be bent 180 ° without breakage after being exposed to air, glycol, or lubricant at 95 ° C. for 1000 hours. In addition, the protective polymer is preferably impermeable to PCM compositions. More preferably, the protective layer is impermeable to the PCM composition when it is in a molten state. Preferred protective polymers include, but are not limited to, ionomers, polyamides, grafted or ungrafted polypropylene homopolymers, grafted or ungrafted polypropylene copolymers, perfluoroethylene-propylene ( FEP), perfluoroalkoxy alkane (PFA), ethylene tetrafluoroethylene (ETFE), ethylene methyl acrylate copolymers with a methyl acrylate content greater than 50% by weight; or mixtures or blends of two or more of these polymers. ..

In certain embodiments, the protective polymer layer is made from a blend of ionomer and polyamide. Specifically, the layer is made from a blend of ethylenic acid copolymer ionomer and polyamide.

Ionomers are polymers produced by partially or completely neutralizing acid copolymers. Suitable ethylenic acid copolymers and ionomers are described, for example, in US Pat. No. 7,641,965 by Bennison et al. However, briefly, the ethylenic acid copolymer is with a copolymerization unit of an α-olefin having 2 to 10 carbon atoms in an amount of about 8 to about 30% by weight, preferably about 15 to about 30% by weight, more preferably. Approximately 20 to about 30% by weight, more preferably about 20 to about 25% by weight, even more preferably about 21 to about 23% by weight, α, β-ethylene unsaturated carboxylics having 3 to 8 carbon atoms. Includes an acid copolymerization unit. % By weight is based on the total weight of the ethylenic acid copolymer. Preferably, the α-olefin comprises ethylene, and more preferably, the α-olefin consists of or essentially consists of ethylene. Also preferably, the α, β-ethylenically unsaturated carboxylic acid comprises (meth) acrylic acid. More preferably, the α, β-ethylenically unsaturated carboxylic acid consists of or is essentially composed of (meth) acrylic acid.

The ethylenic acid copolymer may further contain copolymerization units of other comonomer (s) such as derivatives of unsaturated carboxylic acids having 2 to 10 carbon atoms, preferably 3 to 8 carbon atoms or derivatives thereof. .. Suitable acid derivatives include acid anhydrides, amides, and esters. Esters are the preferred derivatives. Preferably, the ester is an α, β-ethylenically unsaturated carboxylic acid ester comonomer, and examples thereof include, but are not limited to, methyl acrylate, ethyl acrylate, isopropyl acrylate, butyl acrylate, and combinations thereof. ..

The ethylenic acid copolymer can be synthesized by any suitable polymerization method. For example, ethylenic acid copolymers are described in US Pat. No. 3,404,134; US Pat. No. 5,028,674; US Pat. No. 6,500,888; and US Pat. No. 6,518. , 365 can be polymerized as described.

Preferably, the ethylenic acid copolymer is about 60 g / 10 min or less, more preferably about 45 g / 10 min or less, even more preferably about 30 g / 10 min or less, even more preferably about 25 g / 10 min or less, even more preferably. It has a melt index (MI) measured at 190 ° C. and 2.16 kg by ASTM method D1238, about 10 g / 10 min or less.

Some suitable ethylenic acid copolymer resins are available from Wilmington, DE. I. It is commercially available under the trademark Nucl® from the duPont de Nemours and Company (“DuPont”).

To obtain an ionomer, at least a portion of the carboxylic acid moiety of the ethylenic acid copolymer is neutralized to form a carboxylate group. Preferably, it is about 5 to about 90%, more preferably about 10 to about 50%, even more preferably about 20 to about 50%, even more preferably about 20 to about 20%, based on the total carboxylic acid content of the ethylenic acid copolymer. 35% of carboxylic acid groups are neutralized. Examples of suitable procedures for neutralizing ethylenic acid copolymers are also described in US Pat. No. 3,404,134.

Ionomers contain cations as counter ions to carboxylate anions. Suitable cations include any positively charged species that is stable under the conditions under which the ionomer composition is synthesized, treated and used. Preferably, the cation is a metal cation that may be monovalent, divalent, trivalent, or multivalent. Combinations of two or more cations that can have various valences, such as ^{a mixture of Na +} and Zn ²⁺ , or a mixture of NH ⁴⁺ and K ⁺ , are also suitable. The cation is more preferably a monovalent or divalent metal ion. More preferably, the metal ion is selected from the group consisting of sodium, lithium, magnesium, zinc, and potassium ions, and combinations thereof. More preferably, the metal ion is selected from the group consisting of sodium ion, zinc ion, and a combination thereof. More preferably, the metal ion contains or will be essentially zinc ion.

The ionomer is preferably about 10 g / 10 minutes or less, more preferably about 5 g / 10 minutes or less, still more preferably about 3 g / 10 minutes or less, about 1.0 g / 10 minutes or less, about 0.5 g / 10 minutes or less, It has MI measured at 190 ° C. and 2.16 kg by ASTM method D1238, at about 0.2 g / 10 min or less, or about 0.1 g / 10 min or less. Ionomers are measured by ASTM Method D790 (Procedure A), preferably above about 40,000 psi (276 MPa), more preferably over about 50,000 psi (345 MPa), even more preferably over about 60,000 psi (414 MPa). It also has a flexural modulus.

Some suitable ionomer resins are commercially available from DuPont as Trademark Surlyn® resins.

Suitable polyamides can be selected from semi-aromatic polyamides having a melting point of 150-330 ° C., aliphatic polyamides, and blends thereof.

The polyamide may be a total aliphatic polyamide. The total aliphatic polyamide resin may be formed from an aliphatic monomer such as a diamine, a dicarboxylic acid, a lactam, an aminocarboxylic acid, and a reaction equivalent thereof, and an alicyclic monomer. Suitable aminocarboxylic acids include 11-aminododecanoic acid. As used herein, the term "total aliphatic polyamide resin" is a blend of total aliphatic polyamides having three or more different copolymerized repeating units and two or more total aliphatic polyamide resins. Things are also included. Linear, branched, and cyclic monomers are suitable.

Suitable dicarboxylic acid monomers for use in the synthesis of total aliphatic polyamide resins are, but are not limited to, for example, adipic acid (C6), pimelic acid (C7), sebacic acid (C8), azelaic acid (C9). ), Sebacic acid (C10), dodecanedioic acid (C12), and tetradecanedioic acid (C14), and aliphatic dicarboxylic acids such as mixtures of two or more of these. Suitable diamines for use in the synthesis of total aliphatic polyamide resins have four or more carbon atoms, which are, but are not limited to, tetramethylenediamine, hexamethylenediamine, octamethylenediamine, deca. Methylenediamine, 2-methylpentamethylenediamine, 2-ethyltetramethylenediamine, 2-methyloctamethylenediamine; trimethylhexamethylenediamine, and mixtures of two or more thereof can be mentioned.

Suitable examples of total aliphatic polyamide resins include PA6; PA6,6; PA4,6; PA6,10; PA6,12; PA6,14; P6,13; PA6,15; PA6,16; PA11; PA12; PA10; PA9,12; PA9,13; PA9,14; PA9,15; P6,16; PA9,36; PA10,10; PA10,12; PA10,13; PA10,14; PA12,10; PA12,12; PA12, 13; 12, 14, and copolymers and blends thereof. Preferred examples of the total aliphatic polyamide resin include PA6, PA11, PA12, PA4,6, PA6,6, PA, 10; PA6,12; PA10,10; and copolymers and blends of these polyamides.

The layer of protective polymer containing the blend of ionomer and polyamide may have a thickness of 50-500 μm, preferably 50-250 μm, more preferably 100-200 μm.

In another embodiment, the protective polymer layer is a grafted or ungrafted polypropylene homopolymer, a grafted or ungrafted polypropylene copolymer, perfluoroethylene-propylene (FEP), par. Includes one or more polymers selected from the group consisting of fluoroalkoxy alkane (PFA), ethylene tetrafluoroethylene (ETFE), and ethylene acrylate rubber (AEM).

Copolymers of grafted or ungrafted polypropylene and grafted or ungrafted propylene graft propylene polymers or monomers with organic functional groups such as acid, anhydride, or epoxide functional groups. And / or by copolymerizing. Examples of acids and anhydrides used to modify polypropylene include (meth) acrylic acid, maleic acid, maleic acid monoethyl ester, fumaric acid, fumaric acid, itaconic acid, crotonic acid, itaconic acid anhydride, malein. Acid anhydrides and substituted maleic acid anhydrides (eg, dimethylmaleic acid anhydrides), or citrotonic acid anhydrides, nad acid anhydrides, methyl nad acid anhydrides, and tetrahydrophthalic acid anhydrides, or two of these. It is a mono-, di-, or polycarboxylic acid such as the above combination, and maleic acid anhydride is preferable.

Preferred protective polymer layers include grafted polypropylene or propylene grafted copolymers. Some suitable grafted polypropylene and propylene grafted copolymers are commercially available from DuPont under the Trademark Bynel®.

Fluoropolymer FEP (fluorinated ethylene propylene copolymer) is generally a copolymer of tetrafluoroethylene and hexafluoropropylene. Generally, FEPs are all based on the total weight of FEP, 87% by weight to 94% by weight of tetrafluoroethylene and 6% to 13% by weight of hexafluoropropylene, more preferably 88% by weight to 90% by weight of tetrafluoroethylene. Contains 10% to 12% by weight hexafluoropropylene with ethylene.

Fluoropolymer PFA (perfluoroalkoxy copolymer) is generally a copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether (such as perfluoropropyl vinyl ether, perfluoroethyl vinyl ether, or perfluoromethyl vinyl ether). Generally, PFA comprises 90% to 98 or 99% by weight of tetrafluoroethylene and 1 or 2% to 10% by weight of perfluoropropyl vinyl ether, perfluoroethyl vinyl ether, or perfluoromethyl vinyl ether. More preferably, it is 92% to 97% by weight tetrafluoroethylene and 3% to 8% by weight perfluoropropyl vinyl ether, perfluoroethyl vinyl ether, or perfluoromethyl vinyl ether, all based on the total weight of PFA. be.

Fluoropolymer ETFE (ethylene tetrafluoroethylene copolymer) is generally a copolymer of ethylene and tetrafluoroethylene. Generally, ETFE is based on the total weight of ETFE, which is 15% by weight to 25% by weight of ethylene and 75% by weight to 85% by weight of tetrafluoroethylene, more preferably 15% by weight to 20% by weight of ethylene and 80% by weight. Includes ~ 85% by weight tetrafluoroethylene.

Ethylene acrylate rubber (AEM) is a cured composition of a copolymer of ethylene and alkyl (meth) acrylate. The term "curable" means a material that can be crosslinked by a chemical reaction or irradiation. The curable composition may be cured by any suitable means, or by a curing agent such as a chemical additive or irradiation. The AEM may contain at least 45% by weight, preferably 45-70% by weight, more preferably 55-65% by weight of alkyl (meth) acrylates based on the total weight of the AEM. The alkyl (meth) acrylate may be selected from methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate, and is preferably methyl (meth) acrylate.

Ethylene acrylate rubber or AEM is commercially available from DuPont under the trademark VAMAC®.

The cable of the present invention can be used in a plurality of applications where thermal control is required. Although temperature control inside buildings is one of the most relevant applications, PCM compositions are used in automotive applications (eg, for heat control of latent heat batteries or electric batteries, for vehicle ceilings and seats); air filters for air ducts; Air conditioners; Transport applications; Food packaging (to keep food cold or warm); Medical packaging (eg, transporting organs or vaccines); Woven and non-woven fabrics for clothing, clothing and sportswear; Footwear; Greening tape; Hand grips It can also be used in; bedding; carpets; wood composites; wires; and plastic tubes for hot media such as water; (eg in tools, exercise equipment, and vehicles).

A particularly preferred application is in the latent heat battery of a car, where energy is stored in the cables of the present invention while the engine is running, where the cables can be used as needed (eg, for starting in cold environments or cold seasons). It can release the stored energy. This release of energy can reduce the viscosity of the lubricating oil and cooling fluid, ultimately resulting in lower fuel consumption and lower CO ₂ emissions.

The following examples are provided to illustrate the invention in more detail. These examples show specific embodiments and preferred modes currently envisioned for practicing the present invention, are intended to illustrate the invention, and are intended to limit it. It has not been.

Example 1: Encapsulated PCM cable encapsulated in PA6-ionomer coating In the first step, a powder of 1,3-propanediol dibehenate is fed to a wire-coated extrusion line and copper having a diameter of 250 μm. A cable having a thickness of 1.675 mm and a temperature of 72 ° C. was extruded onto the wire to form a cable having a diameter of 3.6 mm.

In the second step, a melt blend of 60% by weight PA6 and 40% by weight ionomer (zinc-neutralized methacrylic acid copolymer) is extruded at a temperature of 250 ° C. using a separate wire coating line. bottom. A 200 μm thick ionomer / PA blend coating was applied to a 3.6 mm diameter cable. The final encapsulated PCM cable had a diameter of about 4 mm.

A sample (10 cm in length) was cut from a 4 mm cable. Both ends of each sample were sealed at a temperature of 250 ° C. using an impulse seal device (“Medsea 410/610 MSI” from Audio Elektro). The sealed sample was exposed to:
− 24 hours in air at a temperature of 130 ° C − A mixture of ethylene glycol (product “G12 plus plus” supplied by Volkswagen AG) and deionized water (50/50 by weight, 24 at a temperature of 130 ° C) time)
− Car lubricating oil at a temperature of 130 ° C (Michang Oil product “ATF-SP4 (M)”) for 24 hours

After the 24-hour deterioration period was over, the sealed sample was carefully checked and the following observations were made. The results are summarized in Table 1:
− Damage to the sample deteriorated in ethylene glycol − No damage or melting of the cable sample after deterioration in hot air and lubricating oil − Opening of the sealing end after deterioration in hot air and lubricating oil No-No PCM leaching or loss from cable sample after degradation in hot air and lubricating oil, as determined by weight difference

Example 2: Encapsulated PCM cable encapsulated in PA6 / 12-ionomer coating In the first step, powder of 1,3-propanediol dibehenate is fed to a wire-coated extrusion line to a diameter of 250 μm. A cable having a thickness of 1.675 mm and a temperature of 72 ° C. was extruded onto the copper wire to form a cable having a diameter of 3.6 mm.

In the second step, a melt blend of 60% by weight PA6 / 12 and 40% by weight ionomer (zinc-neutralized methacrylic acid copolymer) was applied at a temperature of 250 ° C. using a separate wire coating line. Extruded. A 200 μm thick ionomer-PA6 / 12 blend coating was applied to a 3.6 mm diameter cable. The final encapsulated PCM cable had a diameter of about 4 mm.

Samples were cut and sealed according to the procedure used in Example 1 and exposed to the same test conditions as the sample sealed in Example 1.

After the 24-hour deterioration period was over, the sealed sample was carefully checked and the following observations were made. The results are summarized in Table 2:
-No damage or melting of any cable sample under test conditions-No sealing end opening under test conditions-No PCM leaching or loss from cable sample under test conditions

Although some of the preferred embodiments of the present invention have been described and exemplified above, it is not intended to limit the invention to such embodiments. Various modifications may be made without departing from the scope and gist of the invention as set forth in the claims below.

The present invention includes the following aspects.
[1]
A cable including a core and a PCM layer surrounding the core, wherein the PCM layer is made of a PCM composition.
a) The PCM composition is made from living organisms;
b) The core consists of filaments, threads, strands, or wires containing polymeric materials or metals;
A cable in which the PCM composition is a 1,3-propanediol fatty acid ester.
[2]
The cable according to [1], wherein the PCM composition contains 1,3-propanediol dibehenate or 1,3-propanediol dipalmitate.
[3]
The cable according to [1], wherein the filament, thread, strand, or wire contains polyamide, polyparaphenylene terephthalamide, or copper.
[4]
The cable according to [1], wherein the amount of the PCM is at least 70% by weight based on the total weight of the cable.
[5]
The cable according to [1], wherein the cable has a diameter of 3 to 6 mm.
[6]
The cable according to [1], further comprising one or more layers of a protective polymer.
[7]
The cable according to [1], wherein at least one of the one or more layers of the protective polymer comprises a blend of ionomer and polyamide.
[8]
The cable according to [7], wherein one or more layers of the protective polymer have a thickness of 50 to 600 μm.
[9]
Use of the cable according to [1] in thermal management.
[10]
Use of the cable described in [1] in the automobile industry.
[11]
Use of the cable described in [1] in an electric battery or a latent heat battery.
[12]
a) A step of providing a core made of a polymer material or a metal, made of a thread, a strand, or a wire; and
b) A step of extruding a PCM composition containing 1,3-propanediol fatty acid ester onto the core;
The method for manufacturing a cable according to [1].
[13]
The method according to [12], further comprising the step of extruding one or more layers of the protective polymer onto the PCM composition and the core.
[14]
13. The method of [13], wherein the protective polymer comprises a blend of ionomer and polyamide.

Claims (14)

A cable including a core and a PCM layer surrounding the core, wherein the PCM layer is made of a PCM composition.
a) The PCM composition is made from living organisms;
b) The core consists of filaments, threads, strands, or wires containing polymeric materials or metals;
A cable in which the PCM composition is a 1,3-propanediol fatty acid ester. The cable according to claim 1, wherein the PCM composition contains 1,3-propanediol dibehenate or 1,3-propanediol dipalmitate. The cable according to claim 1, wherein the filament, thread, strand, or wire comprises polyamide, polyparaphenylene terephthalamide, or copper. The cable according to claim 1, wherein the amount of PCM is at least 70% by weight based on the total weight of the cable. The cable according to claim 1, wherein the cable has a diameter of 3 to 6 mm. The cable of claim 1, further comprising one or more layers of protective polymer. The cable of claim 6 , wherein at least one of one or more layers of the protective polymer comprises a blend of ionomer and polyamide. The cable of claim 7, wherein one or more layers of the protective polymer have a thickness of 50-600 μm. Use of the cable according to claim 1 in thermal management. Use of the cable according to claim 1 in the automobile industry. Use of the cable according to claim 1 in an electric battery or a latent heat battery. a) A step of providing a core made of a polymer material or a metal made of a thread, a strand, or a wire; and b) Extruding a PCM composition containing a 1,3-propanediol fatty acid ester onto the core. Molding process;
The method for manufacturing a cable according to claim 1. 12. The method of claim 12, further comprising the step of extruding one or more layers of the protective polymer onto the PCM composition and the core. 13. The method of claim 13, wherein the protective polymer comprises a blend of ionomer and polyamide.