EP1658395B1 - Methode pour la preparation de corps moules a proprietes thermoregulatives - Google Patents
Methode pour la preparation de corps moules a proprietes thermoregulatives Download PDFInfo
- Publication number
- EP1658395B1 EP1658395B1 EP04786178A EP04786178A EP1658395B1 EP 1658395 B1 EP1658395 B1 EP 1658395B1 EP 04786178 A EP04786178 A EP 04786178A EP 04786178 A EP04786178 A EP 04786178A EP 1658395 B1 EP1658395 B1 EP 1658395B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- phase change
- fibers
- change material
- polysaccharides
- polymer
- 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.)
- Expired - Lifetime
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 5
- 230000028016 temperature homeostasis Effects 0.000 title claims 2
- 230000001747 exhibiting effect Effects 0.000 title 1
- 239000012782 phase change material Substances 0.000 claims abstract description 46
- 229920000642 polymer Polymers 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000011159 matrix material Substances 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 8
- 239000000835 fiber Substances 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000009987 spinning Methods 0.000 claims description 17
- 229920002678 cellulose Polymers 0.000 claims description 15
- 239000001913 cellulose Substances 0.000 claims description 15
- ZTHYODDOHIVTJV-UHFFFAOYSA-N Propyl gallate Chemical compound CCCOC(=O)C1=CC(O)=C(O)C(O)=C1 ZTHYODDOHIVTJV-UHFFFAOYSA-N 0.000 claims description 14
- 239000004753 textile Substances 0.000 claims description 13
- 102000034238 globular proteins Human genes 0.000 claims description 11
- 108091005896 globular proteins Proteins 0.000 claims description 11
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 claims description 10
- 150000004676 glycans Chemical class 0.000 claims description 9
- 229920001282 polysaccharide Polymers 0.000 claims description 9
- 239000005017 polysaccharide Substances 0.000 claims description 9
- 239000004744 fabric Substances 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- 229940075579 propyl gallate Drugs 0.000 claims description 7
- 235000010388 propyl gallate Nutrition 0.000 claims description 7
- 239000000473 propyl gallate Substances 0.000 claims description 7
- -1 for example Polymers 0.000 claims description 4
- 238000004898 kneading Methods 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 239000011550 stock solution Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 2
- 238000001125 extrusion Methods 0.000 claims 2
- 229920000869 Homopolysaccharide Polymers 0.000 claims 1
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 claims 1
- 150000001299 aldehydes Chemical class 0.000 claims 1
- 125000003368 amide group Chemical group 0.000 claims 1
- 125000003277 amino group Chemical group 0.000 claims 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims 1
- 235000018417 cysteine Nutrition 0.000 claims 1
- 150000002402 hexoses Chemical class 0.000 claims 1
- 125000001841 imino group Chemical group [H]N=* 0.000 claims 1
- SBOJXQVPLKSXOG-UHFFFAOYSA-N o-amino-hydroxylamine Chemical class NON SBOJXQVPLKSXOG-UHFFFAOYSA-N 0.000 claims 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims 1
- 239000012188 paraffin wax Substances 0.000 claims 1
- 235000019809 paraffin wax Nutrition 0.000 claims 1
- 235000019271 petrolatum Nutrition 0.000 claims 1
- 239000001257 hydrogen Chemical group 0.000 abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 238000012412 chemical coupling Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 11
- 230000008859 change Effects 0.000 description 7
- 230000001331 thermoregulatory effect Effects 0.000 description 7
- 239000005018 casein Substances 0.000 description 5
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 5
- 235000021240 caseins Nutrition 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 235000018102 proteins Nutrition 0.000 description 4
- 108090000623 proteins and genes Proteins 0.000 description 4
- 102000004169 proteins and genes Human genes 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- 229920003043 Cellulose fiber Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 238000000386 microscopy Methods 0.000 description 2
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- 238000006116 polymerization reaction Methods 0.000 description 2
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- 230000001105 regulatory effect Effects 0.000 description 2
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- 229920001059 synthetic polymer Polymers 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- IVNPXOUPZCTJAK-UHFFFAOYSA-N 4-methylmorpholin-4-ium;hydroxide Chemical compound O.CN1CCOCC1 IVNPXOUPZCTJAK-UHFFFAOYSA-N 0.000 description 1
- 235000017060 Arachis glabrata Nutrition 0.000 description 1
- 244000105624 Arachis hypogaea Species 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 235000018262 Arachis monticola Nutrition 0.000 description 1
- 229920000875 Dissolving pulp Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- DCXXMTOCNZCJGO-UHFFFAOYSA-N Glycerol trioctadecanoate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 1
- 102000014171 Milk Proteins Human genes 0.000 description 1
- 108010011756 Milk Proteins Proteins 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 229920002494 Zein Polymers 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003275 alpha amino acid group Chemical group 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 238000009960 carding Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001891 gel spinning Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 235000021239 milk protein Nutrition 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 239000005019 zein Substances 0.000 description 1
- 229940093612 zein Drugs 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F4/00—Monocomponent artificial filaments or the like of proteins; Manufacture thereof
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F4/00—Monocomponent artificial filaments or the like of proteins; Manufacture thereof
- D01F4/04—Monocomponent artificial filaments or the like of proteins; Manufacture thereof from casein
Definitions
- the invention relates to a process for the production of moldings, consisting of native network-forming polymers and phase change materials incorporated therein, which as. Fibers can be processed into fabrics with improved thermoregulatory properties and give textiles made from them a better comfort and have in other applications a high degree of functionality in terms of heat storage and delivery.
- phase change materials can absorb or release relatively large amounts of heat when their phase state or conformation changes at a constant temperature.
- an increased heat capacity is found, which finds its physically measurable expression in the enthalpy of fusion and allows the storage or release of larger amounts of heat than correspond to the normal heat capacity of the material outside the temperature range of the phase transition or the conformational change would.
- phase change material paraffins or salts or solutions of suitable salts can be used.
- the temperature range of the phase transition from the solid to the molten state can be adjusted in a targeted manner to the respective required temperature at which the heat is to be released or stored by varying the chain length.
- Salts or their solutions can be selected specifically according to the desired temperature range of the conformational change.
- the microencapsulated form is particularly suitable.
- phase change material is enclosed in ceramic or polymer spheres with diameters in the micron range and thus brought into a manageable form that allows inclusion in crosslinked polymeric matrix materials, the amount of the thermoregulatory potential on the type and amount of enclosed PCM material is dependent.
- Suitable matrix materials include both synthetic polymers and native network-forming polymers.
- US 5,885,475 describes apparel composed of fibers consisting of a polymer blend additionally containing phase change material.
- the fiber-forming substances are made selected from the group of synthetic melt-spinnable thermoplastic polymers.
- Multicomponent fibers with increased, reversible thermal properties and textile fabrics produced therefrom are described in WO 03027365, US 200212079 and US 200129648.
- the fiber bodies consisting of a multiplicity of elongated components, contain at least in one of these stretched components a temperature-regulating material distributed therein.
- This may be a phase change material and optionally the classes of hydrocarbons, hydrated salts, waxes, oils, water, fatty acids, fatty acid esters, 2-basic acids and esters, halides, clusters and semiclusters, gas clusters, stearin anhydrite, ethylene carbonate, higher alcohols, polymers and metals and their mixtures belong.
- the arrangement of the various components of the fiber can optionally take place in a core-sheath structure, polysetational, bundled or strip-shaped at different shaped cross-section.
- the matrix material of the multicomponent fiber described can consist of different, linear chain molecules.
- a disadvantage of these fibers and textile fabrics made therefrom is that only a portion of the fibers formed therefrom contain phase change material as a result of the described arrangement of the individual components and the proportion of temperature-regulating material in the overall fiber is naturally limited. Due to the presence of multicomponent structures of a plurality of elongated constituents, the proportion of phase change material that can be introduced into the polymer structure is limited to a proportion of at most 50 percent by mass, based on the respective matrix material.
- WO 02095314 and CH 0200245 likewise describe processes in which the temperature-regulating properties are to be achieved by printing on a textile fabric with microencapsulated phase change material.
- the temperature-regulating effect is thus achieved by applying a coating containing phase change material.
- such a method has the disadvantage that only comparatively small amounts of phase change material can be fixed on the surface of the structures, in particular if only a part of the surface is printed with a suspension of microencapsulated phase change materials and thus the temperature regulating effect, based on the Amount of material, comparatively localized.
- the printing of a textile surface with a suspension of microencapsulated phase materials applied in a comparatively large layer thickness has an adverse effect on the flexibility of textile products made therefrom and thus also on the wearing properties.
- suspensions of microencapsulated phase change materials applied to textile surfaces have only limited mechanical resistance and are washable.
- PCM fibers described so far are made on the basis of synthetic melt-spun polymer fibers.
- network-forming structures can be prepared, for example, from cellulosic forming and spinning compositions by dissolving cellulose in tertiary amine oxides, preferably N-methylmorpholine-N-oxide, and a non-solvent, preferably water.
- a spinning solution of cellulose in N-methylmorpholine-N-oxide and water is deformed by a dry-wet spinning process, coagulated in, for example, an aqueous spinning bath, the solvent completely removed by washing several times and the solidified shaped bodies dried.
- the resulting shaped articles then have a network structure characterized by hydrogen bonds.
- the globular proteins have, as the name implies, a spherical tertiary structure and occur in nature in relatively frequent numbers. Examples are the casein (milk protein), the zein (maize protein) and the ardenin (peanut protein).
- the invention has for its object to develop a process for the preparation of thermoregulatory moldings, in particular fibers and their fabrics, from native network-forming polymers with trapped in the network Phasen prial, one, compared to generated on a synthetic basis PCM fibers, increased proportion of introduced phase change material contain and thus, while avoiding the disadvantages of the prior art, have an increased thermoregulatory potential.
- the object is achieved by introducing phase change materials up to a content of 200% by mass into network-forming polymers, wherein the network is formed by the chemical coupling of functional groups, hydrogen bonds or helically interconnected polymeric or oligomeric structures.
- a suitable network-forming polymeric matrix material is native cellulose. This forms bonds which on the one hand cause crosslinking of the polymer structure and on the other hand through the formation of hydrogen bonding the formation of a superstructure. By this structure formation, the embedding of larger amounts of microencapsulated phase change materials is possible.
- the microencapsulation causes the demarcation between the phase change material and the polymer matrix.
- a phase change material find, for example Paraffins of different chain length application, wherein the temperature of the phase transition depends on the chain length of the molecules and can be adjusted by changing the chain lengths the required temperature range of the phase transition. But also inorganic hydrated salts are applicable, which can be selected depending on the desired temperature range of the conformational change. Due to their higher density compared to paraffins, it is possible in particular to introduce far more than 50% by mass of phase change material into the polymer matrix.
- a secondary structure in the form of folds of the amino acid chain based on hydrogen bonding results in a spatially cross-linked tertiary structure that is stabilized, for example, by disulfide bridges, hydrogen bonds, or ionic or hydrophobic interactions.
- precrosslinked globular proteins are likewise soluble in tertiary amine oxides and can be shaped by a dry-wet process.
- the solution of the precrosslinked globular protein can be added as a further constituent of a polysaccharide such as cellulose. This gives the possibility of being able to influence the properties of the moldings in a targeted manner.
- a cellulose solution in a water-containing tertiary amine oxide phase change materials up to a content of 200 Percent by weight, based on the mass of the cellulose containing added and this solution over an air gap and then the cellulose precipitated with the phase change material enclosed in a precipitation bath, for example, water or a water / alcohol mixture, precipitated to form physical networks.
- a precipitation bath for example, water or a water / alcohol mixture
- phase change material associated with an optimal heat transfer to the phase change material or away from it.
- precrosslinked globular proteins in N-methylmorpholine N-oxide are admixed with microencapsulated phase change material, optionally with the addition of polysaccharides such as e.g. Cellulose, transferred into a spinning solution and spun by known methods into filaments.
- polysaccharides such as e.g. Cellulose
- the native polymer-based PCM fibers produced according to the invention have a wide range of uses, for example for fabrics for the production of textiles, for nonwovens, in textiles for the automotive industry, in yarns and blended yarns.
- phase-change heat characterizing the thermoregulatory properties of the native PCM fibers of the present invention has a value up to a factor of 8 compared to the synthetic polymer-based PCM fibers.
- microencapsulated phase change material of a phase change temperature of 28 ° C (Thermasorb ® TY 83 from Outlast Technologies Inc.) with the addition of 6.8 g of propyl gallate in a dissolving vessel with agitator of 37 1 volume introduced.
- the microencapsulated phase change material was previously screened to a grain size of 50 microns maximum.
- the dissolving vessel is evacuated to 20 mbar and heated in the course of 6 hours from 20 ° C to 94 ° C at a stirrer speed of 18 min -1 and the evaporating water condensed in a connected condenser.
- the spinning solution obtained has a viscosity of 1560 Pas and a refractive index of 1.484.
- the spinning solution is extruded at 80 ° C through a spinneret with a number of holes of 150 and a hole diameter of 200 microns via an air gap in a precipitation bath of water.
- the take-off speed is 25 m / min, which results in a distortion in the air gap of 3.75.
- the spun fibers have a denier of about 14 dtex and are washed in subsequent rinse baths and then cut into stacks.
- the phase change heat of the obtained fibers is 30 J / g.
- the cellulose fibers without introduced phase change material have a heat capacity of 6 J / g.
- the fineness-related tear strengths of the resulting fibers are about 15 cN / tex.
- the modified fibers After being carded on a carding machine, the modified fibers could be processed into a needle-punched nonwoven having a basis weight of 300 g / m 2 .
- casein 100 g of casein are dispersed in 250 ml of water and crosslinked by the addition of 2 g of glutaraldehyde and 0.1 g of MgCl 2 at 25 ° C. After pressing to a moisture content of 50%, the casein is suspended in 430 g of 60% NMMNO. As a stabilizer, 0.5 g of propyl gallate is added.
- phase change material such as Lurapret TX PMC 28 ® from BASF AG
- the suspension is transferred in a jacketed kneading apparatus under a vacuum of 30 mbar and a temperature of 90 ° C by distilling off 130 g of water in a spinning solution.
- the homogeneity of the spinning solution is checked by light microscopy and is usually reached 15 minutes after the end of the distillation.
- the solution is extruded through a spinneret with 150 holes of 90 microns in diameter as filaments through an air gap at 80 ° C spinning temperature in an aqueous precipitation bath and then washed with distilled water residue and cut to a staple length of 40 mm.
- the fibers are dried at 60 ° C in a convection oven.
- the strength of the spun fibers is 15 cN / tex at an elongation of 10% and a titer of about 15 dtex.
- the Heat-absorbing capacity of the resulting fibers is 60 J / g versus 8 J / g for unmodified fibers.
- casein 50 g of casein are dispersed in 250 ml of water and crosslinked by addition of 1 g of glutaraldehyde and 0.1 g of MgCl 2 at 25 ° C. After pressing to a moisture content of 50%, the casein is suspended in 430 g of 60% NMMNO. In addition, 25 g of dry ground sulphite be (DP 760) and 100 g microencapsulated phase change material such as Lurapret TX PMC 28 ® from BASF AG, was added. This corresponds to a content of 133% PCM based on cellulose. 0.5 g of propyl gallate are added for stabilization.
- This suspension is transferred in a jacketed kneading apparatus under a vacuum of 30 mbar at a temperature of 90 ° C by distilling off 140 g of water in a spinning solution. Homogenization of the solution was achieved 15 minutes after the end of the distillation and was checked by light microscopy.
- the spinning solution obtained was extruded through an air hole into an aqueous precipitation bath through a spinneret of 150 holes, each 90 ⁇ m in diameter, and the resulting fiber strand was washed without residue in distilled water and cut to a staple length of 40 mm.
- the fibers were dried in a convection oven at 60 ° C.
- the fibers have a strength of 30 cN / tex.
- the titer is about 20 dtex.
- the heat capacity of the modified fibers is 70 J / g versus 7 J / g for unmodified fibers.
- 7607 g of a 60% solution of N-methylmorpholine-N-oxide are introduced together with 784 g of pulp of average polymerization degree 500 with the addition of 4.6 g of propyl gallate in a 37 l stirred volume dissolving vessel.
- the dissolving vessel is evacuated to 20 mbar and heated in the course of 6 hours from 20 ° C to 94 ° C at a stirrer speed of 18 min -1 and condenses the evaporating water in a condenser. A total of 2361 g of water are evaporated.
- the spinning solution obtained has a viscosity of 8072 Pas, the refractive index of the spinning solution was 1.487.
- a stock solution of 1500 g of an 80% solution of N-methylmorpholine-N-oxide and 750 g of a microencapsulated phase change material such as Lurapret ® TX PMC 28 from BASF AG, and 45 g of xanthan gum is prepared. Both solutions are extruded after intimate mixing in a dynamic mixer at 80 ° C through a spinneret with a number of holes of 150 and a hole diameter of 200 microns, warped over an air gap, regenerated in an aqueous precipitation bath and washed solvent-free with distilled water. The adjustment of the mixing ratio is such that the extruded fibers have a concentration of microencapsulated phase change material of 60% based on cellulose.
- the spun fibers have a fineness of about 10 dtex and are cut into stacks after washing.
- the phase change heat of the obtained fibers is 80 J / g.
- the cellulose fibers without introduced phase change material have a heat capacity of 6 J / g in the corresponding temperature range.
- the fineness-related tear strengths of the resulting fibers are about 15 cN / tex.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
- Polyesters Or Polycarbonates (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
- Heating, Cooling, Or Curing Plastics Or The Like In General (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Nonwoven Fabrics (AREA)
Claims (8)
- Procédé pour la production de corps moulés, en particulier de fibres et de leurs structures en nappe, à propriétés thermorégulatives à base de matières de matrice polymères formant un réseau et dissoutes dans des oxydes d'amine tertiaires aqueux, de préférence dans du N-méthylmorpholine-N-oxyde, caractérisé par le fait que l'on incorpore jusqu'à 200 % en masse, par rapport audit polymère formant un réseau, d'une matière micro-encapsulée à changement de phase dans un réseau de matrice construit de polysaccharides et/ou de protéines globulaires, de telle façon que soita) ladite matière micro-encapsulée à changement de phase est incorporée directement, en tant que composante, dans la suspension composée du polymère, de la solution aqueuse de N-méthylmorpholine-N-oxyde et de gallate de propyle comme stabilisateur et se trouvant dans un récipient de dissolution à agitateur, ou que,b) dans le cas de la protéine globulaire mise en oeuvre comme polymère, après la pré-réticulation de celle-ci, ladite matière micro-encapsulée à changement de phase est introduite conjointement avec la solution aqueuse de N-méthylmorpholine-N-oxyde et avec le gallate de propyle comme stabilisateur ainsi que, le cas échéant, avec un autre polymère formant un réseau, telle que la cellulose, dans un appareil à pétrir à enveloppe chauffée, qu'on réalise le vide dans ledit récipient de dissolution ou bien dans l'appareil à pétrir, que la suspension est chauffée, remuée, que l'eau est évaporée et que des fibres sont formées à partir de la solution à filer fortement visqueuse respectivement obtenue, selon un procédé d'extrusion par voie sèche-humide, ou quec) la matière micro-encapsulée à changement de phase est mélangée avec la solution aqueuse de N-méthylmorpholine-N-oxyde pour obtenir une solution mère et que cette dernière est ajoutée à une solution à filer déjà finie composée de solution aqueuse de N-méthylmorpholine-N-oxyde, de polymère et de gallate de propyle comme stabilisateur, tout en mélangeant intimement les deux solutions dans un mélangeur, et que des fibres sont formées à partir de la solution à filer fortement visqueuse ainsi obtenue, également selon un procédé d'extrusion par voie sèche-humide.
- Procédé selon la revendication 1, caractérisé par le fait que l'on utilise en tant que polymères formant un réseau les polysaccharides et/ou les dérivés de polysaccharides qui sont formés à partir d'hexoses à liaison glycosidique en 1,4 et 1,6 ou, au moins en partie, d'acides uroniques.
- Procédé selon les revendications 1 et 2, caractérisé par le fait que les polysaccharides sont la cellulose et/ou des composés cellulosiques.
- Procédé selon les revendications 1 et 2, caractérisé par le fait que l'on utilise en tant que polysaccharide un homopolysaccharide soluble dans l'eau ou un hétéropolysaccharide ou les dérivés de ceux-ci.
- Procédé selon la revendication 1, caractérisé par le fait que les polymères formant un réseau sont des protéines globulaires natives.
- Procédé selon les revendications 1 et 5, caractérisé par le fait que, à l'aide d'aldéhydes, tels que l'aldéhyde glutarique, les protéines globulaires natives sont pré-réticulées par des groupes amino et/ou groupes amide et/ou groupes imino de la liaison peptidique et/ou par des groupes oxy de la sérine et/ou de l'élément constitutif de cystéine.
- Procédé selon les revendications 1 à 6, caractérisé par le fait que l'on utilise jusqu'à 99,5% en masse de polysaccharide et entre 0,5 et 100 % en masse, de préférence entre 60 et 90 % en masse, de protéines globulaires, par rapport à la masse totale de composés dissous.
- Procédé selon les revendications 1 à 7, caractérisé par le fait que l'on utilise en tant que matières à changement de phase des cires de paraffine micro-encapsulées.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL04786178T PL1658395T3 (pl) | 2003-08-30 | 2004-08-25 | Sposób wytwarzania wytworów formowanych o właściwościach termoregulacyjnych |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10340110 | 2003-08-30 | ||
PCT/DE2004/001893 WO2005024102A1 (fr) | 2003-08-30 | 2004-08-25 | Corps moules, en particulier fibres et leurs structures en surface, a proprietes thermoregulatives |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1658395A1 EP1658395A1 (fr) | 2006-05-24 |
EP1658395B1 true EP1658395B1 (fr) | 2006-11-08 |
Family
ID=34202272
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP04786178A Expired - Lifetime EP1658395B1 (fr) | 2003-08-30 | 2004-08-25 | Methode pour la preparation de corps moules a proprietes thermoregulatives |
Country Status (6)
Country | Link |
---|---|
US (1) | US20060279017A1 (fr) |
EP (1) | EP1658395B1 (fr) |
AT (1) | ATE344844T1 (fr) |
DE (3) | DE102004041684A1 (fr) |
PL (1) | PL1658395T3 (fr) |
WO (1) | WO2005024102A1 (fr) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7244497B2 (en) * | 2001-09-21 | 2007-07-17 | Outlast Technologies, Inc. | Cellulosic fibers having enhanced reversible thermal properties and methods of forming thereof |
US7579078B2 (en) | 2001-09-21 | 2009-08-25 | Outlast Technologies, Inc. | Temperature regulating cellulosic fibers and applications thereof |
US9434869B2 (en) | 2001-09-21 | 2016-09-06 | Outlast Technologies, LLC | Cellulosic fibers having enhanced reversible thermal properties and methods of forming thereof |
AT501252B1 (de) * | 2004-12-23 | 2008-02-15 | Chemiefaser Lenzing Ag | Cellulosischer formkörper und verfahren zu seiner herstellung |
TWI287996B (en) * | 2005-10-19 | 2007-10-11 | Taiwan Textile Res Inst | Temperature regulating gel and article comprising the same |
US20090051068A1 (en) * | 2006-01-12 | 2009-02-26 | Thüringisches Institute Für Textil-Und Kunststoff-Forschung E.V. | Method for Producing Molded Bodies from Proteins |
FR2911153B1 (fr) * | 2007-01-10 | 2009-04-10 | Lainiere De Picardie Bc Soc Pa | Substrat textile incorporant une composition de regulation thermique entourant des ilots de transfert. |
DE102007054702B4 (de) | 2007-11-14 | 2018-10-18 | Smartpolymer Gmbh | Verfahren zur Herstellung von cellulosischen Formkörpern, cellulosischer Formkörper und dessen Verwendung |
AT509289B1 (de) | 2009-12-28 | 2014-06-15 | Chemiefaser Lenzing Ag | Funktionalisierter cellulosischer formkörper und verfahren zu seiner herstellung |
DE102010054661A1 (de) * | 2010-12-15 | 2012-06-28 | Anke Domaske | Verfahren zur Herstellung von Milchproteinfasern und daraus gewonnene Milchproteinfaserprodukte |
MX2017004349A (es) | 2014-10-03 | 2017-10-25 | Erie Foods Int Inc | Alimento con alto contenido de proteinas. |
DE102018100140B3 (de) | 2017-12-14 | 2019-03-28 | Institut Für Luft- Und Kältetechnik Gemeinnützige Gmbh | Lüftungsanlage mit Wärmespeicher |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4908238A (en) * | 1984-07-02 | 1990-03-13 | The United States Of America As Represented By The Secretary Of Agriculture | Temperature adaptable textile fibers and method of preparing same |
US4756958A (en) * | 1987-08-31 | 1988-07-12 | Triangle Research And Development Corporation | Fiber with reversible enhanced thermal storage properties and fabrics made therefrom |
US5354524A (en) * | 1993-05-24 | 1994-10-11 | Alan Sellars | Monitoring concentration of dope in product manufacture |
US5885475A (en) * | 1995-06-06 | 1999-03-23 | The University Of Dayton | Phase change materials incorporated throughout the structure of polymer fibers |
GB9617043D0 (en) * | 1996-08-14 | 1996-09-25 | Courtaulds Plc | Manufacture ofd extruded articles |
US6077597A (en) * | 1997-11-14 | 2000-06-20 | Outlast Technologies, Inc. | Interactive thermal insulating system having a layer treated with a coating of energy absorbing phase change material adjacent a layer of fibers containing energy absorbing phase change material |
US6855422B2 (en) * | 2000-09-21 | 2005-02-15 | Monte C. Magill | Multi-component fibers having enhanced reversible thermal properties and methods of manufacturing thereof |
US20030124278A1 (en) * | 2002-01-02 | 2003-07-03 | Clark Dustin L. | Thermal barriers with solid/solid phase change materials |
US20030124318A1 (en) * | 2002-01-02 | 2003-07-03 | Magill Monte C. | Thermal barriers with reversible enhanced thermal properties |
-
2004
- 2004-08-25 PL PL04786178T patent/PL1658395T3/pl unknown
- 2004-08-25 DE DE102004041684A patent/DE102004041684A1/de not_active Withdrawn
- 2004-08-25 DE DE502004001972T patent/DE502004001972D1/de not_active Expired - Lifetime
- 2004-08-25 DE DE112004002148T patent/DE112004002148D2/de not_active Withdrawn - After Issue
- 2004-08-25 EP EP04786178A patent/EP1658395B1/fr not_active Expired - Lifetime
- 2004-08-25 WO PCT/DE2004/001893 patent/WO2005024102A1/fr active IP Right Grant
- 2004-08-25 AT AT04786178T patent/ATE344844T1/de active
- 2004-08-25 US US10/570,374 patent/US20060279017A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
DE112004002148D2 (de) | 2006-07-13 |
PL1658395T3 (pl) | 2007-04-30 |
DE102004041684A1 (de) | 2005-03-17 |
US20060279017A1 (en) | 2006-12-14 |
ATE344844T1 (de) | 2006-11-15 |
EP1658395A1 (fr) | 2006-05-24 |
DE502004001972D1 (de) | 2006-12-21 |
WO2005024102A1 (fr) | 2005-03-17 |
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