CN108352213A - The cable made of phase-change material - Google Patents
The cable made of phase-change material Download PDFInfo
- Publication number
- CN108352213A CN108352213A CN201680063652.7A CN201680063652A CN108352213A CN 108352213 A CN108352213 A CN 108352213A CN 201680063652 A CN201680063652 A CN 201680063652A CN 108352213 A CN108352213 A CN 108352213A
- Authority
- CN
- China
- Prior art keywords
- cable
- pcm
- acid
- core
- compositions
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- D—TEXTILES; PAPER
- D07—ROPES; CABLES OTHER THAN ELECTRIC
- D07B—ROPES OR CABLES IN GENERAL
- D07B1/00—Constructional features of ropes or cables
- D07B1/16—Ropes or cables with an enveloping sheathing or inlays of rubber or plastics
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/34—Waxes
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
- D06M13/2243—Mono-, di-, or triglycerides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/29—Protection against damage caused by extremes of temperature or by flame
- H01B7/292—Protection against damage caused by extremes of temperature or by flame using material resistant to heat
Abstract
A kind of phase-change material (PCM) can be used for the heat management of a variety of applications and device, application such as automobile, building, packaging, clothes and the footwear, described device such as metal wire and cable.Cable described herein includes core and wraps the PCM layer of the core.The PCM layer includes PCM compositions, and the composition includes 1,3 methyl glycol fatty acid esters in turn.Core yarn made of natural or synthetic polymer material or metal, strand or metal wire form.
Description
Cross reference to related applications
The U.S. Provisional Application No. 62/250,206 that the application requires to submit on November 3rd, 2015 according to 35U.S.C. § 119
Priority, which is combined here with the full text by reference.
Technical field
There is provided herein a kind of phase-change material (PCM) of the heat management for a variety of applications, it is described application such as automobile,
Building, packaging, clothes and footwear.Specifically, there is described herein the cable comprising PCM, for manufacturing these cables
The purposes of method and these cables in several applications.
Background technology
Several patent and publications are referred in this specification so that technology according to the present invention is described more fully with
Development level.Whole disclosure contents of each of these patent and publications are incorporated herein by reference.
Phase-change material (PCM) is the latent heat storage material that can absorb and discharge a large amount of latent heat during fusing and crystallization.
When material from solid phase be changed into liquid phase or from liquid phase be solid phase when, occur heat energy transfer.During this class phase transformation, the PCM
The temperature of material keeps nearly constant, and the space around the PCM material is also in this way, the heat for flowing through the PCM is existed by " retention "
In the PCM itself.In other well known PCM, paraffin is commonly used, because of its low cost and hypotoxicity.
PCM can be introduced into the matrix being made from a different material or they can be used as coating to apply.See, for example,
U.S.4,003,426、U.S.4,528,328、U.S.5,053,446、U.S.2006/0124892(WO 2006/062610)、WO
98/04644 and WO 2004/044345.
In order to easily use PCM in thermal management applications, PCM is attached in matrix polymer, these matrix
Polymer even absorbs at a temperature of higher than PCM fusing points and keeps the PCM, and thus makes it possible to by gained PCM composite woods
Material is manufactured into the sheet, panelling or other shapes being easily mounted on wall.However, most of matrix polymers are limited by a variety of lack
It falls into, for example, limited PCM absorptive capacities or any substantial loss for passing through PCM caused by extrusion in the lifetime of product.To this
The partial solution of a little problems carries in WO 2006/062610, WO 2011/143278 and WO 2011/014636
Go out.
Nevertheless, still in need for the material containing PCM, these materials for containing PCM provide high fever storage volume
And the high surface for most suitable heat exchange contacts；When being exposed permanently under air to the temperature from -20 DEG C to 130 DEG C and
Also there is tolerance to chemicals, especially to lubricating oil or ethylene glycol；Their efficiency is kept over time；And
High thermoconductivity is provided.
Invention content
Therefore, there is provided herein the cables for including core and the PCM layer for wrapping the core, wherein the PCM layer is combined by PCM
Object forms, and wherein
A) the PCM compositions include 1,3-PD aliphatic ester；And
B) core yarn made of natural or synthetic polymer material or metal, strand or metal wire form.
Preferably, which is biology base.
In a preferred embodiment, which includes two palm fibre of two behenate of 1,3-PD or 1,3-PD
Glycerin monostearate is consisting essentially of.
Preferably, the yarn, strand or metal wire are by poly(p-phenylene terephthalamide) (p- aromatic polyamides) or copper
It is made.
In another embodiment, these cables further include one or more protection polymeric layers.Preferably these
Cable includes a protection polymeric layer.Preferably, which is made of the blend of ionomer and polyamide.Even
It is highly preferred that these cables include two protection polymeric layers.Preferably, the first protection polymeric layer is by ionomer and polyamides
The blend of amine is made and the second layer is made of polymer selected from the group below, which is made of the following terms：Grafting or not
Polypropylene homopolymer, grafting or the non-grafted polypropylene copolymer of grafting, perfluoroethylene-propylene (FEP), perfluoro alkoxyalkane
Hydrocarbon (PFA), ethylene-tetrafluoroethylene (ETFE) and/or ethylene-acrylate rubber (AEM).
Preferably, each protection polymeric layer has the thickness between 50 and 300 μm.It is highly preferred that when there are two layers
When, this two layers overall thickness is between 50 and 600 μm.
Preferably, the amount of PCM based on the cable total weight is at least 70 weight percent in cable.
The preferred cable of the present invention has 3 to 6mm diameter.
A kind of method for manufacturing these cables further provided herein.This approach includes the following steps：
A) core is provided, core yarn made of natural or synthetic polymer material or metal, strand or metal wire form；
And
B) it will be expressed on the core comprising 1,3-PD aliphatic ester or consisting essentially of PCM compositions.
Optionally, this method further comprises step c), wherein by the one or more of one or more protection polymer
Layer is expressed on the PCM compositions and the core.Preferably, by one protection polymeric layer be expressed into the PCM compositions and
On the core.Preferably, which is made of the blend of ionomer and polyamide.Even further preferably, two are protected
Shield polymeric layer is expressed on the PCM compositions and the core.It is highly preferred that blending of the first layer by ionomer and polyamide
Object is made and the second layer is made of polymer selected from the group below, which is made of the following terms：Grafting is non-grafted poly-
Noblen, grafting or non-grafted polypropylene copolymer, perfluoroethylene-propylene (FEP), perfluoroalkoxyalkanes (PFA),
Ethylene-tetrafluoroethylene (ETFE) and/or ethylene-acrylate rubber (AEM).
Cable can be used in heat management, especially in automotive vehicles applications.
Specific implementation mode
Definition
As used herein, term " one/one kind (a) " refers to one/a kind of and at least one/one kind and not must
The article that its signified noun is odd number must be limited.
As used herein, term " about " and " for or about " be intended to mean that discussed amount or value can be designated value or substantially one
Some other values of sample.The phrase is intended to convey, and according to the present invention, similar value produces result or effect of equal value.
As used herein, term " acrylate " means the acrylate with alkyl.It is preferred that the alkyl carried have 1 to
The acrylate of 4 carbon atoms.
As used herein, term " (methyl) acrylic acid " refers to acrylic acid, methacrylic acid or acrylic acid and metering system
It is both sour.Equally, term " (methyl) acrylate " means methacrylate and/or acrylate, and " poly- (methyl) third
Olefin(e) acid ester " means the polymer obtained from the polymerization of the mixture of monomer or two kinds of monomers.
As used herein, term " copolymer " refers to comprising the copolymerization obtained by the copolymerization of two or more comonomers
The polymer of unit.At this point, copolymer can constitute comonomer or it constitutes comonomer herein with reference to it
Amount description, such as " copolymer of the acrylic acid comprising ethylene and 18 weight percent " or similar description.Such description can be with
It is considered informal, because it is not related to comonomer as copolymerization units；Because it does not include the conventional life of copolymer
Name method, such as International Union of Pure and Applied Chemistry (IUPAC) nomenclature；Because it does not use the art for limiting product in method
Language；Or for Another reason.As used herein, however, constituting the amount of comonomer or its composition comonomer with reference to it
The description of copolymer refer to copolymerization units that the copolymer contains specified comonomer (with specified amount when specified).As pushing away
By it follows that copolymer is not the product of the reaction mixture of the given comonomer containing specified rate, unless in restriction
In the case of to clearly state be such.Term " copolymer " can refer to the copolymerization units group substantially by two different monomers
At (dimer) or substantially by the polymer more than two different monomer compositions (substantially by three kinds of different copolymerization lists
The trimer of body composition, the tetramer being substantially made of four kinds of different comonomers, etc.).
In addition, the amount of all components in polymer or composition is complementary, that is, the summation of the amount of all components is whole
The amount of a polymer composition.For example, describing ethylene copolymer when the weight percent of the comonomer by specified copolymerization
When, the weight percent of the comonomer (if present) of the ethylene of copolymerization, the comonomer of copolymerization and other copolymerization
Summation be 100wt.%.
Term " acid copolymer " refers to comprising alpha-olefin, α, β-ethylenic unsaturated carboxylic acid and optionally one kind or more
The polymer of the copolymerization units of other suitable comonomers (for example, α, β-ethylenically-unsaturated carboxylic acid ester) of kind.
Term " ionomer " refers to the polymer by partially or even wholly neutralizing acid copolymer generation.
Provided herein is the cables for including core and the PCM layer for wrapping the core.The PCM layer is made of PCM compositions.
The PCM compositions include 1,3-PD aliphatic ester, are made from it or consisting essentially of.
More specifically, 1,3-PD aliphatic ester is the 1,3-PD ester of aliphatic acid, wherein each propylene glycol molecules
It is reacted that form tool, there are one aliphatic acid (" monoesters ") or the esters of two aliphatic acid (" diester ").Preferably, 1, the 3- third
The 1,3-PD diester and monoester of glycol, these aliphatic acid and these aliphatic acid be complete biology base, reproducible
With it is biodegradable.For example, these PCM are synthesized by food grade materials.
The PCM compositions include 1,3-PD diester, 1,3-PD monoesters or 1,3-PD diester and 1,3- third
The mixture of diol monoester.
Direct esterification can be carried out by using excessive aliphatic acid and 1,3-PD to produce these 1,3-PDs
Ester.After esterification, remaining free fatty and alcohol are removed by distilling.It can pass through the directly application of remaining ester or for example
The additional distillation of product is further purified, as described in WO 08/123845.
In a preferred embodiment, which is biology base.More specifically, the PCM is with environmental-friendly place
Method is produced by biological products.For illustrating, vegetable oil serves as the source of aliphatic acid, and by the fermentation of corn syrup (1,
The bio-separation of 3-propanediol) produce 1,3-PD.This method is started by chemical method with fossil fuel than conventional
Produce the little energy 40% that 1,3-PD uses, and the discharge capacity of greenhouse gases reduces 20% (reference：http：// brew.geo.uu.nl/BREWsymposiumWiesbadenllmei2005/ WEBSITEBrewPresentations51105.PDF)。
Biology base and reproducible 1,3-PD can be for example such as the production described in WO1996/035796.
In another embodiment, which is " symmetrical diester ".This term is as used herein
Refer to diester, the identical aliphatic acid of two of which is reacted with a single 1,3-PD molecule.Symmetrical diester allusion quotation
It is characterized as more regular crystal accumulation to type.
In another embodiment, which is " asymmetrical diester ".This term refers to as used herein diester,
In two different aliphatic acid reacted with a single 1,3-PD molecule.By changing aliphatic acid and diester
Symmetry, the fusion temperature of PCM can change and intense adjustment.
In another embodiment, which is monoesters.Generally, molten with corresponding 1,3-PD diester
Change temperature to compare, the fusion temperature of 1,3-PD monoesters reduces.
In another embodiment, these esters include the aliphatic acid (C of the chain length with 2 to 24 carbon atoms3To C25Fat
Acid) reactive residue.Preferred chain length is 8 to 22 carbon atom (C9To C23Aliphatic acid).Generally, there is higher fusing temperature
The PCM of degree will also have higher latent heat.Equally typically, the chain length of aliphatic acid is longer, the fusing temperature of 1,3-PD ester
Degree is higher and more by the heat that the PCM compositions can be absorbed and be discharged.Therefore, by changing the chain length of aliphatic acid,
It is possible that changing the feature of PCM.
These aliphatic acid can be saturated or unsaturated aliphatic acid, such as, but not limited to propionic acid, butyric acid, valeric acid, oneself
Acid, enanthic acid, octanoic acid, n-nonanoic acid, capric acid, hendecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, 17
Alkanoic acid, stearic acid, nonadecylic acid, arachidic acid, heneicosanoic acid (heneicosylic acid), behenic acids, tricosanic acid
(tricosylic acid), lignoceric acid, alpha-linolenic acid, linolenic acid, eicosapentaenoic acid, docosahexaenoic acid, Asia
Oleic acid, gamma-Linolenic acid, dihomo-gamma-linolenic acid, arachidonic acid, docosatetraenoic acid, palmitoleic acid, octadecenoic acid,
Eicosenoic acid (paullinic acid), oleic acid, elaidic acid, gondoic acid, erucic acid, nervonic acid and eicosatrienoic acid.
The PCM compositions can include saturation, undersaturated, straight chain fatty acid or saturated or unsaturated, branch or
The ester of the mixture of non-branched aliphatic acid.
In a preferred embodiment, these aliphatic acid are straight chain and saturation.
In a more preferred embodiment, which includes the following terms, is made from it or consisting essentially of：
Two behenate of 1,3-PD or 1,3-PD dipalmitate.Again, these diester are preferably biology bases.
The PCM compositions can be based further on the PCM compositions total weight include from 0.01 to 15 weight percent,
One or more additives of 0.01 to 10 weight percent or 0.01 to 5 weight percent, one or more additive packets
It includes but is not limited to：Plasticizer；Stabilizer, including viscosity stabiliser and hydrolysis stabilizer；Primary anti-oxidant and secondary are anti-
Oxidant；Ultra-violet absorber；Antistatic agent；Dyestuff, pigment or other colorants；Inorganic filler；Fire retardant；Lubricant；
Reinforcing agent such as glass fibre and thin slice, synthesis (for example, aromatic polyamides) fiber or slurry；Foaming agent or foaming agent；
Processing aid (such as ethylene copolymer, such as ethylene vinyl acetate (EVA))；Help sliding additive；Anticaking agent such as titanium dioxide
Silicon or talcum；Releasing agent；Crystal seed additive, for reducing the generation of sub-cooled；And tackifying resin.These additives exist
In Kirk-Othmer Encyclopedia of Chemical Technology [Ke Keaosimo chemical encyclopedias] into
Description is gone.The example of the suitable antioxidant of thermostabilization for 1,3-PD ester includes such as tert-butyl hydroquinone
(TBHQ), pentaerythrite four (3- (3,5- di-t-butyl -4- hydroxy phenyls) propionic ester), Butylated Hydroxytoluene (BHT), three (2,4- bis-
Tert-butyl-phenyl) phosphite ester and propyl-Gallic Acid ester.
These additives can be attached to by any of method in the composition, such as pass through dry blending, extrusion
Multicomponent mixture, masterbatch technique etc..
Cable provided herein includes the PCM layer for wrapping core and one or more that optionally wraps the PCM layer and the core
A polymeric layer.
These cables can be manufactured by the way that the PCM compositions to be expressed on yarn, strand or metal wire.Alternatively,
Cable can be manufactured by other methods, and the yarn is for example such as pulled through the PCM compositions of melting or is immersed the yarn molten
The PCM compositions melted.
The yarn, strand or metal wire are preferably made of natural or synthetic polymer material or metal.Suitable polymerization
Object material includes but not limited to cotton, polyester, polyamide or poly-paraphenylene terephthalamide's phenylenediamine (aromatic polyamides) and/or its mixing
Object or blend.Preferably, the yarn, strand or metal wire are by poly(p-phenylene terephthalamide) (p- aromatic polyamides)
Or copper at.Some suitable poly(p-phenylene terephthalamide) (p- aromatic polyamides) yarn, strand or metal wires can quotient
Purchased from DuPont (Du Pont), trade mark is
During the extrusion of PCM compositions, the use of the yarn, strand or metal wire allow to draw entire cable without
It can be broken due to the weak property or brittleness of the PCM material.Including the use of the PCM compositions of 1,3-PD aliphatic ester allows
The PCM compositions are squeezed out by oneself without other thermoplastic polymers.It is not wishing to be bound by theory, it is assumed that include 1,3- third
The fusion range of the composition of diol fatty acid ester is with being enough to provide melt viscosity that is suitable and stablizing wide, therefore is protected
The process of the stabilization during extrusion is demonstrate,proved.
Preferably, which is fed to metal wire coating extruding production line and in the temperature of the fusing point higher than it
It is expressed into a desired thickness on yarn, strand or metal wire under degree.
It is optionally possible to which one or more extra plays are expressed on cable, which is by squeezing the PCM compositions
Go out to obtaining on the yarn, strand or metal wire.Polymeric layer is particularly preferred as extra play.
The section of the cable needs not be round and can be any shape, as by mounted on the exit of extruder
The shape of die orifice is determined.
Wish that the amount of PCM in cable is high as far as possible because the hot property of composition generally directly in PCM compositions
The concentration of PCM is proportional.Total weight of the amount of PCM based on the cable is at least about 70 weight percent, about 70 weight in cable
Percentage is to about 95 weight percent or about 75 weight percent to about 85 weight percent.
Optionally, including the cable of core and PCM layer further includes one or more protection polymeric layers.The protection polymerize
Nitride layer is usually to wrap the PCM layer；However, the protection polymeric layer can be inserted between the PCM layer and the core.
The protection polymer can be any polymer；However, the one or more of one or more protection polymer
Layer is preferably that cable provides some characteristics, such as example, heat resistance, chemical resistance, sealability.Specifically, it is described herein
Cable be exposed to air, ethylene glycol or lubricating oil at 95 DEG C and can be bent 180 ° after 1000 hours and not broken.In addition, protecting
It is impermeable that shield polymer is preferably the PCM compositions.It is highly preferred that the protective layer is when PCM compositions are in molten
The PCM compositions are impermeable when state.Preferably protection polymer includes but not limited to：Ionomer, polyamide, grafting or not
Polypropylene homopolymer, grafting or the non-grafted polypropylene copolymer of grafting, perfluoroethylene-propylene (FEP), perfluoro alkoxyalkane
Hydrocarbon (PFA), ethylene-tetrafluoroethylene (ETFE), the ethylene methyl third with the methyl acrylate content more than 50 weight percent
Olefin(e) acid ester copolymer；Or the mixture or blend of two or more in these polymer.
In one embodiment, protection polymeric layer is made of the blend of ionomer and polyamide.Specifically, should
Layer is made of the ionomer of ethylene acid copolymer and the blend of polyamide.
The ionomer is the polymer by partially or even wholly neutralizing acid copolymer production.Suitable hexenoic acid copolymerization
Object is described with ionomer in the U.S. Patent number 7,641,965 for for example authorizing Bennison et al..Briefly, however say,
The ethylene acid copolymer includes the copolymerization units with the alpha-olefin from 2 to 10 carbon atoms；And about 8 weight percent to about
30 weight percent, preferably about 15 weight percent are to about 30 weight percent, more preferably about 20 weight percent to about
30 weight percent and more preferably about 20 weight percent are to about 25 weight percent or still more preferably about 21 weight hundred
Divide than the α with 3 to 8 carbon atoms to about 23 weight percent, the copolymerization units of β-ethylenic unsaturated carboxylic acid.The weight
Percentage is the total weight based on the ethylene acid copolymer.Preferably, which includes ethylene；It is highly preferred that the alpha-olefin
It is made of ethylene or consisting essentially of.It is further preferred that the α, β-ethylenic unsaturated carboxylic acid includes (methyl) acrylic acid.More
Preferably, the α, β-ethylenic unsaturated carboxylic acid are made of or consisting essentially of (methyl) acrylic acid.
Ethylene acid copolymer can further include the copolymerization units of other one or more comonomers, such as with 2
To 10 carbon atoms or the olefinically unsaturated carboxylic acid derivatives or derivatives thereof of preferably 3 to 8 carbon atoms.Suitable acid derivative
Including acid anhydrides, amide and ester.Ester is preferred derivative.Preferably, ester is α, and β-ethylenically-unsaturated carboxylic acid ester is copolymerized single
Body and include but not limited to, methyl acrylate, ETHYL CYANOACRYLATE, isopropyl acrylate, butyl acrylate with and combinations thereof.
Ethylene acid copolymer can be synthesized by any suitable polymerization.For example, ethylene acid copolymer can be as
It polymerize described in U.S. Patent number 3,404,134,5,028,674,6,500,888 and 6,518,365.
Preferably, it is such as measured with 190 DEG C and 2.16kg by ASTM methods D1238, the melting which has
Index (MI) is about 60g/10min or smaller, more preferably about 45g/10min or smaller and more preferably about 30g/10min or
Smaller or again more preferably about 25g/10min or smaller, or still more preferably about 10g/10min or smaller.
Some suitable ethylene acid copolymer resins are available commercially from Wilmington, DE E.I.Du Pont Company (E.I.du
Pont de Nemours and Company of Wilmington, DE) (" Du Pont (DuPont) "), trade mark is
In order to obtain these ionomers, at least part of the carboxylic moiety of ethylene acid copolymer is neutralized to be formed
Carboxylate group.Total carboxylic acid's content based on ethylene acid copolymer, will preferably from about 5% to about 90%, more preferably about 10% to
About 50% and more preferably about 20% is neutralized to the carboxylic acid group of about 50% or still more preferably about 20% to about 35%.
The example of suitable program for neutralization of ethylene acid copolymer is also described in U.S. Patent number 3,404,134.
These ionomers include counter ion of the cation as carboxylate anion.Suitable cation be included in synthesis,
Processing and to use be stable any positively charged species under conditions of the ionomer compositions.Preferably, cation is gold
Belong to cation, these metal cations can be unit price, divalent, trivalent or multivalence.Two or more cations (can have
There are different valence states, such as Na+With Zn2+Mixture or NH4 +With K+Mixture) combination be also suitable.Cation is more
Preferably unit price or bivalent metal ion.It is more preferred still that these metal ions are selected from the group, the group is by the following terms group
At：Sodium ion, lithium ion, magnesium ion, zinc ion and potassium ion and its combination of two or more.It is more preferred still that
These metal ions are selected from the group, which is made of the following terms：Sodium ion, zinc ion, with and combinations thereof.It is more preferred still that
Metal ion includes or is substantially made of zinc ion.
It is such as measured with 190 DEG C and 2.16kg by ASTM methods D1238, the MI which preferably has is about 10g/
10min or smaller, more preferably about 5g/10min or smaller or still more preferably about 3g/10min or smaller, about 1.0g/
10min or smaller, about 0.5g/10min or smaller, about 0.2g/10min or smaller or about 0.1g/10min or smaller.Such as pass through
ASTM method D790 (program A) are measured, and the bending modulus which preferably has is greater than about 40,000psi
(276MPa), more preferably more than about 50,000psi (345MPa) are still more preferably greater than about 60,000psi (414MPa).
For some suitable ionomer resins available commercially from E.I.Du Pont Company, trade mark is entitledResin.
Suitable polyamide can be selected from semiaromatic polyamide composition, fatty polyamide and its blend (have from
150 DEG C to 330 DEG C of fusion temperature).
The polyamide can be full fatty polyamide.Full aliphatic polyamide resin can be by aliphatic and alicyclic list
Body such as diamines, dicarboxylic acids, lactams, amino carboxylic acid and their reactive equivalent are formed.Suitable amino carboxylic acid includes
11- aminododecanoic acids.As it is used herein, term " full aliphatic polyamide resin " also includes having three or more
The blending of the full fatty polyamide and two or more full aliphatic polyamide resins of different copolymerization repetitive units
Object.Straight chain, branch and cricoid monomer are suitable.
Suitable dicarboxylic acid monomer for synthesizing full aliphatic polyamide resin includes, but are not limited to aliphatic dicarboxyl
Acid, such as adipic acid (C6), pimelic acid (C7), suberic acid (C8), azelaic acid (C9), decanedioic acid (C10), dodecanedioic acid
(C12) and tetracosandioic acid (C14) and its mixture of two or more.For synthesizing full fatty polyamide tree
The suitable diamines of fat has four or more carbon atoms, and includes but not limited to, tetra-methylenedimine, hexamethylene diamine, pungent
Diamines, decamethylene diamine, 2 methyl pentamethylenediamine, 2- ethyls tetra-methylenedimine, 2- methyl octamethylenediamines；Trimethylhexane diamine, Yi Jiqi
The mixture of two or more.
The suitable example of full aliphatic polyamide resin includes PA6；PA6,6；PA4,6；PA6,10；PA6,12；PA6,14；
P 6,13；PA 6,15；PA6,16；PA11；PA 12；PA10；PA 9,12；PA9,13；PA9,14；PA9,15；P 6,16；
PA9,36；PA10,10；PA10,12；PA10,13；PA10,14；PA12,10；PA12,12；PA12,13；12,14；And it is total
Polymers and blend.The preferred embodiment of full aliphatic polyamide resin includes PA6, PA11, PA12, PA4,6, PA6,6, PA, 10,
PA6,12, PA10,10；And the copolymer and blend of these polyamide.
Including the protection polymeric layer of the blend of ionomer and polyamide can have from 50 to 500 μm, preferably from 50
To 250 μm and more preferably from 100 to 200 μm of thickness.
In another embodiment, protection polymeric layer include one or more polymer selected from the group below, the group by with
Lower every composition：Grafting or non-grafted polypropylene homopolymer, grafting or non-grafted polypropylene copolymer, perfluoroethylene-the third
Alkene (FEP), perfluoroalkoxyalkanes (PFA), ethylene-tetrafluoroethylene (ETFE) and ethylene-acrylate rubber (AEM).
The grafting or non-grafted polypropylene and grafting or non-grafted propylene copolymer can be by with organic functionals
Group's (including acid, acid anhydrides or epoxy-functional) grafting and/or co-polypropylene polymer or monomer obtain.For modified polypropene
Acid and the example of acid anhydrides be：Mono-, two- or polybasic carboxylic acid, such as：(methyl) acrylic acid, maleic acid, ethyl maleate, richness
Horse acid, fumaric acid, itaconic acid, crotonic acid, itaconic anhydride, maleic anhydride and substituted maleic anhydride, for example, dimethyl Malaysia
Acid anhydrides or crotonic anhydride (citrotonic anhydride), carbic anhydride, Na Dike methyl anhydride and tetrahydrochysene neighbour benzene two
Formic anhydride or its combination of two or more, wherein it is preferred that maleic anhydride.
Preferred protection polymeric layer includes the propylene of grafting or the propylene copolymer of grafting.Some are suitably grafted poly-
Available commercially from E.I.Du Pont Company, trade mark is entitled for propylene and the propylene copolymer of grafting
Fluoropolymer FEP (fluorinated ethylene propylene copolymer) is usually the copolymer of tetrafluoroethene and hexafluoropropene.It is logical
Often, FEP includes from 87 weight percent to the tetrafluoroethene of 94 weight percent and from 6 weight percent to 13 weight percent
Hexafluoropropene, more preferably from 88 weight percent to the tetrafluoroethene of 90 weight percent and from 10 weight percent to 12
The hexafluoropropene of weight percent, all these weight percent are the total weights based on FEP.
Fluoropolymer PFA (perfluoroalkyl alkoxy copolymer) is usually tetrafluoroethene and perfluoroalkyl vinyl ether (for example, complete
Fluoropropyl vinyl ethers, perfluoroethylvinyl ether or perfluoro methyl vinyl ether) copolymer.In general, PFA includes from 90 weights
Measure tetrafluoroethene of the percentage to 98 or 99 weight percent and the perfluor third from 1 or 2 weight percent to 10 weight percent
Base vinyl ethers, perfluoroethylvinyl ether or perfluoro methyl vinyl ether.More preferably from 92 weight percent to 97 weight
The tetrafluoroethene of percentage and from 3 weight percent to the perfluoro propyl vinyl ether of 8 weight percent, perfluoroethyl vinyl base
Ether or perfluoro methyl vinyl ether, all these is the total weight based on PFA.
Fluoropolymer ETFE (ethylene-tetrafluoroethylene copolymer) is usually the copolymer of ethylene and tetrafluoroethene.In general,
ETFE includes from 15 weight percent to the ethylene of 25 weight percent and from 75 weight percent to the four of 85 weight percent
Fluoropropene, more preferably from 15 weight percent to the ethylene of 20 weight percent and from 80 weight percent to 85 weight percents
The tetrafluoropropene of ratio, all these weight percent are the total weights based on ETFE.
Ethylene-acrylate rubber (AEM) is the curable combination of ethylene and the copolymer of (methyl) alkyl acrylate
Object.Term is " curable " to indicate that crosslinked material can be carried out by chemically reacting or radiating.The curable composition can
To be cured by any suitable means or by curing agent, for example, as chemical addition agent or radiation.Based on the total of AEM
Weight, AEM may contain (methyl) alkyl acrylate of at least 45 weight percent, preferably from 45 weight percent to 70
Weight percent, more preferably from 55 weight percent to 65 weight percent.Being somebody's turn to do (methyl) alkyl acrylate can be selected from
In following item：(methyl) methyl acrylate, (methyl) ethyl acrylate and (methyl) butyl acrylate, and preferably (methyl)
Methyl acrylate.
Available commercially from E.I.Du Pont Company, trade mark is by ethylene-acrylate rubber or AEM
The cable of the present invention can be used in several applications, and wherein heat management is needed.Although the temperature of interior of building
Management is one of maximally related application, which can also be used for automobile application (such as latent heat battery or vehicle
The heat management of battery, roof and seat)；Air filter in ventilation shaft；Air-conditioning；Transport applications；Food packaging (keeps food
Object refrigeration or warm)；Medical package (such as organ or vaccine transport)；The weaving of clothes, clothes and sportswear with it is non-woven
Fabric；Footwear；Set wrappage；Handle (for example, on tool, sporting goods and vehicle)；Bed course；Carpet；Wood composite material；Electricity
Cable；And the plastic tube for thermal medium (including water).
Particularly preferred application is the latent heat battery of automobile, wherein engine at runtime energy storage the present invention cable
In line, and wherein these cables can discharge the energy of storage (such as opening in cold environment or in dead season if necessary
It is dynamic).The release of this energy allow to reduce the viscosity of lubricating oil and cooling fluid and eventually lead to lower fuel consumption and
The CO of reduction2Discharge capacity.
Following instance is provided to describe the present invention in further detail.It illustrates specific embodiment and is presently contemplated for implementing
These examples of the preferred embodiment of the present invention are intended to the illustrative and not limiting present invention.
Example
Example 1：It is encapsulated in the PCM cables of the encapsulating in PA6- ionomer coatings
In the first step, by the powder feed of two behenate of 1,3-PD to metal wire coating extruding production line simultaneously
And it is expressed on the copper wire with 250 μ diameters to be formed at a temperature of 72 DEG C and with the thickness of 1.675mm straight with 3.6mm
The cable of diameter.
In the second step, by the ionomer (methacrylic acid copolymer of the PA6 of 60 weight percent and 40 weight percent
Object is neutralized with zinc) melt blended material squeezed out using another metal line coating production line at a temperature of 250 DEG C.It will tool
There is the coating of ionomer/PA blends of 200 μ m thicks to be administered on the cable of the 3.6mm diameters.The PCM cables finally encapsulated
Line has the diameter of about 4mm.
From cutting sample (10cm long) on the 4mm cables.The both ends of each sample use pulse sealing at a temperature of 250 DEG C
Equipment is sealed (" Medseal 410/610MSI " comes from Audion Elektro companies).The sample of sealing is set to be exposed to：
24 hours in air at a temperature of 130 DEG C
Ethylene glycol (product " G12plus plus " is distributed by Volkswagen AG companies) is mixed with softened water
Close object (by weight 50/50,24 hours at a temperature of 130 DEG C)
For the lubricating oil (product " ATF-SP4 (M) " comes from Michang Oil companies) of automobile, at a temperature of 130 DEG C
24 hours
Once 24 hours aging periods terminate, goes through the sample of sealing and carried out following sight and look into and be summarised in table
In 1：
The damage of the sample of aging in ethylene glycol
In hot-air and lubricating oil after aging, cable sample nondestructive is bad or melts
In hot-air and lubricating oil after aging, edge sealing imperforation
In hot-air and lubricating oil after aging, the PCM of cable sample is such as determined by weight difference without exudation or loss
's
Example 2：It is encapsulated in the PCM cables of the encapsulating in PA6/12- ionomer coatings
In the first step, by the powder feed of two behenate of 1,3-PD to metal wire coating extruding production line simultaneously
And it is expressed on the copper wire with 250 μ diameters to be formed at a temperature of 72 DEG C and with the thickness of 1.675mm straight with 3.6mm
The cable of diameter.
In the second step, by the ionomer (methacrylic acid of the PA6/12 of 60 weight percent and 40 weight percent
Copolymer is neutralized with zinc) melt blended material squeezed out using another metal line coating production line at a temperature of 250 DEG C.
The coating of ionomer-PA6/12 blends with 200 μ m thicks is administered on the cable of the 3.6mm diameters.This is finally wrapped
The PCM cables of envelope have the diameter of about 4mm.
Sample is cut and sealed according to program used in example 1, and these samples are exposed to and example 1
The same test condition of middle sealed sample.
Once 24 hours aging periods terminate, goes through the sample of sealing and carry out following see and look into and be summarised in table 2
In：
Any cable sample nondestructive is bad under test conditions or melts
Edge sealing imperforation under test conditions
The PCM of cable sample is without exudation or loss under test conditions
Table 1
Ageing results at 130 DEG C after aging 24 hours
Table 2
Ageing results at 130 DEG C after aging 24 hours
Although certain preferred embodiments of the present invention have been described and particular instantiation above, be not intended to by
The present invention is limited to such embodiment.Various modifications can be carried out without departing from the scope and spirit of the present invention, such as
Described in following following claims.
Claims (according to the 19th article of modification of treaty)
1. a kind of cable comprising core and the PCM layer for wrapping the core, wherein the PCM layer is made of PCM compositions, and
A) the PCM compositions are biology bases；And
B) core is made of the long filament comprising polymer material or metal, yarn, strand or metal wire,
Wherein, which is 1,3-PD aliphatic ester.
2. cable as described in claim 1, wherein the PCM compositions include two behenate of 1,3-PD or 1,3- third
Glycol dipalmitate.
3. cable as described in claim 1, wherein the long filament, yarn, strand or metal wire include polyamide, gather to benzene two
Formyl p-phenylenediamine or copper.
4. cable as described in claim 1, wherein the amount of PCM is at least 70 weight percent based on the cable total weight.
5. cable as described in claim 1, wherein the cable has 3 to 6mm diameter.
6. cable as described in claim 1 further includes one or more protection polymeric layers.
7. cable as described in claim 1, wherein the one or more protects at least one of polymeric layer comprising from poly-
The blend of object and polyamide.
8. cable as claimed in claim 7, wherein the one or more protects polymeric layer with 50 to 600 μm of thickness.
9. the purposes of cable as described in claim 1 in thermal management.
10. the purposes of cable as described in claim 1 in the automotive industry.
11. purposes of the cable as described in claim 1 in battery or latent heat battery.
12. a kind of method for manufacturing cable as described in claim 1 the described method comprises the following steps：
A) yarn made of polymer material or metal is provided, the core that strand or metal wire form；And
B) the PCM compositions comprising 1,3-PD aliphatic ester are expressed on the core.
13. method as claimed in claim 12, further comprises the steps：One or more protection polymeric layer is squeezed out
Onto the PCM compositions and the core.
14. method as claimed in claim 13, wherein the protection polymer includes the blend of ionomer and polyamide.
Claims (15)
1. a kind of cable comprising core and the PCM layer for wrapping the core, wherein the PCM layer is made of PCM compositions, and
A) the PCM compositions are biology bases；And
B) core is made of the long filament comprising polymer material or metal, yarn, strand or metal wire.
2. cable as described in claim 1, wherein the PCM compositions are 1,3-PD aliphatic esters.
3. the cable as described in claim 1 or claim 2, wherein the PCM compositions include two behenic acid of 1,3-PD
Ester or 1,3-PD dipalmitate.
4. cable as claimed in any preceding claim, wherein the long filament, yarn, strand or metal wire include polyamide, gather
Poly P phenylene diamine terephthalamide or copper.
5. cable as claimed in any preceding claim, wherein the amount of PCM is at least 70 weight hundred based on the cable total weight
Divide ratio.
6. cable as claimed in any preceding claim, wherein the cable has 3 to 6mm diameter.
7. cable as claimed in any preceding claim further includes one or more protection polymeric layers.
8. cable as claimed in claim 7, wherein the one or more protects at least one of polymeric layer comprising from poly-
The blend of object and polyamide.
9. such as claim 7 or cable according to any one of claims 8, wherein one or more protect polymeric layer with 50 to
600 μm of thickness.
10. the purposes of cable as claimed in any preceding claim in thermal management.
11. the purposes of cable as claimed in any preceding claim in the automotive industry.
12. purposes of the cable as claimed in any preceding claim in battery or latent heat battery.
13. a kind of method for manufacturing cable as claimed in any one of claims 1-9 wherein, the method includes following steps
Suddenly：
A) yarn made of polymer material or metal is provided, the core that strand or metal wire form；And
B) the PCM compositions comprising 1,3-PD aliphatic ester are expressed on the core.
14. method as claimed in claim 13, further comprises the steps：One or more protection polymeric layer is squeezed out
Onto the PCM compositions and the core.
15. method as claimed in claim 14, wherein the protection polymer includes the blend of ionomer and polyamide.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201562250206P | 2015-11-03 | 2015-11-03 | |
| US62/250206 | 2015-11-03 | ||
| PCT/US2016/059022 WO2017079018A1 (en) | 2015-11-03 | 2016-10-27 | Cables made of phase change material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108352213A true CN108352213A (en) | 2018-07-31 |
| CN108352213B CN108352213B (en) | 2020-10-09 |
Family
ID=57354430
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680063652.7A Expired - Fee Related CN108352213B (en) | 2015-11-03 | 2016-10-27 | Cable made of phase change material |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20180334775A1 (en) |
| EP (1) | EP3371815A1 (en) |
| JP (1) | JP6944933B2 (en) |
| CN (1) | CN108352213B (en) |
| WO (1) | WO2017079018A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112048909A (en) * | 2020-09-08 | 2020-12-08 | 惠州华盛家庭用品有限公司 | Constant-temperature cotton and preparation process thereof |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3732421B1 (en) * | 2017-12-29 | 2023-08-23 | Dupont Polymers, Inc. | Composition and methods for a heat storage capacity device for thermal management of fluids |
| DE102018108181A1 (en) * | 2018-04-06 | 2019-10-10 | Volkswagen Aktiengesellschaft | Charging coupler with cooling device, charging cable with charging coupler and a motor vehicle with charging coupler |
| DE102018126854A1 (en) * | 2018-10-26 | 2020-04-30 | Bayerische Motoren Werke Aktiengesellschaft | Charging device for connecting an electrical energy storage device of a motor vehicle to a charging station |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110281485A1 (en) * | 2010-05-13 | 2011-11-17 | E.I. Du Pont De Nemours And Company | Phase change material compositions |
| US20140166338A1 (en) * | 2012-12-13 | 2014-06-19 | General CableTechnologies Corporation | Fire and water resistant cable cover |
| CN104464911A (en) * | 2014-12-31 | 2015-03-25 | 湖南华菱线缆股份有限公司 | Low smoke halogen-free flame-retardant fireproof medium-voltage flexible cable |
| CN104710622A (en) * | 2010-12-02 | 2015-06-17 | 陶氏环球技术有限责任公司 | Intumescent halogen-free Si-P-N-based polymer fire retardants |
| CN107667157A (en) * | 2015-05-28 | 2018-02-06 | 杜邦营养生物科学有限公司 | phase-change material |
Family Cites Families (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL128027C (en) | 1961-08-31 | 1900-01-01 | ||
| US4003426A (en) | 1975-05-08 | 1977-01-18 | The Dow Chemical Company | Heat or thermal energy storage structure |
| US4528328A (en) | 1983-10-12 | 1985-07-09 | Occidental Chemical Corporation | Blends of vinyl halide-polyolefin graft polymers and ASA polymers |
| US5053446A (en) | 1985-11-22 | 1991-10-01 | University Of Dayton | Polyolefin composites containing a phase change material |
| US5028674A (en) | 1990-06-06 | 1991-07-02 | E. I. Du Pont De Nemours And Company | Methanol copolymerization of ethylene |
| JPH0517760A (en) * | 1991-07-10 | 1993-01-26 | Mitsubishi Cable Ind Ltd | Thermal energy storing type heater |
| US5686276A (en) | 1995-05-12 | 1997-11-11 | E. I. Du Pont De Nemours And Company | Bioconversion of a fermentable carbon source to 1,3-propanediol by a single microorganism |
| US5565132A (en) * | 1995-06-06 | 1996-10-15 | The University Of Dayton | Thermoplastic, moldable, non-exuding phase change materials |
| JPH09287884A (en) * | 1996-04-23 | 1997-11-04 | Matsushita Electric Works Ltd | Heat exchanger |
| DE19630073B4 (en) | 1996-07-25 | 2004-04-01 | Sgl Carbon Ag | Device for storing heat or cold in a storage system made of pressed graphite expandate and a solid-liquid phase change material and method for its production |
| JP5027368B2 (en) | 1999-07-28 | 2012-09-19 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | High melt swell polymer |
| JP2002133952A (en) * | 2000-10-27 | 2002-05-10 | Sumitomo Wiring Syst Ltd | Insulated wire |
| US6500888B2 (en) | 2000-12-27 | 2002-12-31 | E. I. Du Pont De Nemours And Company | Surface treatment of ethylene based polymer pellets to improve blocking resistance |
| US7241509B2 (en) | 2002-11-05 | 2007-07-10 | Barbara Pause | Wall covering assembly with thermo-regulating properties |
| ES2319412T3 (en) * | 2002-12-20 | 2009-05-07 | Ewald Dorken Ag | PROCEDURE FOR THE MANUFACTURE OF ELEMENTS OF A MATERIAL THAT ACCUMULATES LATENT HEAT. |
| JP5204491B2 (en) | 2004-12-09 | 2013-06-05 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Phase change material (PCM) composition for temperature control |
| US20070241306A1 (en) * | 2006-02-10 | 2007-10-18 | Ann Wehner | Biodegradable compositions comprising renewably-based, biodegradable 1,3-propanediol |
| US7641965B1 (en) | 2008-06-30 | 2010-01-05 | E.I. Du Pont De Nemours And Company | Transparent light-weight safety glazings |
| US20110024433A1 (en) | 2009-07-30 | 2011-02-03 | E.I. Du Pont De Nemours And Company | Thermal insulation unit |
| ES2562188T3 (en) * | 2012-03-07 | 2016-03-02 | Siemens Aktiengesellschaft | Transformer encapsulated in resin |
| US20140206249A1 (en) * | 2013-01-24 | 2014-07-24 | Edizone, Llc | Elastomer-enhanced fabrics, articles of manufacture including such fabrics, and methods of making same |
| CN106233395B (en) * | 2014-05-01 | 2019-09-03 | 纳幕尔杜邦公司 | The cable made of phase-change material |
-
2015
- 2015-11-03 US US15/757,701 patent/US20180334775A1/en not_active Abandoned
-
2016
- 2016-10-27 EP EP16798588.6A patent/EP3371815A1/en not_active Withdrawn
- 2016-10-27 CN CN201680063652.7A patent/CN108352213B/en not_active Expired - Fee Related
- 2016-10-27 WO PCT/US2016/059022 patent/WO2017079018A1/en active Application Filing
- 2016-10-27 JP JP2018522728A patent/JP6944933B2/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110281485A1 (en) * | 2010-05-13 | 2011-11-17 | E.I. Du Pont De Nemours And Company | Phase change material compositions |
| CN104710622A (en) * | 2010-12-02 | 2015-06-17 | 陶氏环球技术有限责任公司 | Intumescent halogen-free Si-P-N-based polymer fire retardants |
| US20140166338A1 (en) * | 2012-12-13 | 2014-06-19 | General CableTechnologies Corporation | Fire and water resistant cable cover |
| CN104464911A (en) * | 2014-12-31 | 2015-03-25 | 湖南华菱线缆股份有限公司 | Low smoke halogen-free flame-retardant fireproof medium-voltage flexible cable |
| CN107667157A (en) * | 2015-05-28 | 2018-02-06 | 杜邦营养生物科学有限公司 | phase-change material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112048909A (en) * | 2020-09-08 | 2020-12-08 | 惠州华盛家庭用品有限公司 | Constant-temperature cotton and preparation process thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| US20180334775A1 (en) | 2018-11-22 |
| CN108352213B (en) | 2020-10-09 |
| JP6944933B2 (en) | 2021-10-06 |
| JP2019500441A (en) | 2019-01-10 |
| EP3371815A1 (en) | 2018-09-12 |
| WO2017079018A1 (en) | 2017-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106233395B (en) | The cable made of phase-change material | |
| CN108352213A (en) | The cable made of phase-change material | |
| CN1332805C (en) | Multi-layer hose | |
| ES2670876T3 (en) | Flexible composition based on semi-aromatic polyamide, its preparation process and its uses | |
| TW200906907A (en) | Copolyamide, composition comprising said copolyamide and their use | |
| US11142628B2 (en) | Plasticizers polyamide compositions | |
| WO2013101891A1 (en) | Polyamide composition containing ionomer | |
| JP6676426B2 (en) | Multilayer composite material having a layer composed of partially aromatic polyamide | |
| US20150291794A1 (en) | Composition containing a semi-aromatic copolyamide, a polyolefin and a copper heat stabilizer, preparation thereof and uses thereof | |
| KR20150127666A (en) | Inner liner for a pneumatic tire assembly | |
| CN109563400A (en) | Heat accumulation cable comprising closed system | |
| US20150051329A1 (en) | Plasticized polyamide compositions | |
| CN105722893A (en) | Thermoplastic composition, in particular for photovoltaic modules | |
| CN108473745A (en) | The manufacturing method of ethylene-ethenol system copolymer composition pellet and the ethylene-ethenol system copolymer composition pellet | |
| CN103890076A (en) | Curable elastomeric compositions | |
| JP6403560B2 (en) | Method for producing saponified ethylene-vinyl ester copolymer composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20200429 Address after: Michigan, USA Applicant after: Performance Materials North America, Inc. Address before: Delaware, USA Applicant before: E. I. du Pont de Nemours and Co. |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20201009 Termination date: 20211027 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |