U.S. patent application number 10/570374 was filed with the patent office on 2006-12-14 for moulded bodies, in particular fibres and the structures thereof exhibiting thermoregulation properties.
Invention is credited to Detlef Gersching, Frank Meister.
Application Number | 20060279017 10/570374 |
Document ID | / |
Family ID | 34202272 |
Filed Date | 2006-12-14 |
United States Patent
Application |
20060279017 |
Kind Code |
A1 |
Gersching; Detlef ; et
al. |
December 14, 2006 |
Moulded bodies, in particular fibres and the structures thereof
exhibiting thermoregulation properties
Abstract
The invention related to a method for producing molded bodies
made of cross-linked native polymers in such a way that a network
is formed by chemically coupled functional groups, hydrogen bridges
or polymer or oligomer structures helically connected to each other
and up to 200 mass % of micro-encapsulated phase change material is
included into a polymer matrix with respect to the cross-linked
polymer. Said cross-linked polymers can, for example be embodied in
the form of polysaccharides and/or globular proteins. In the form
of fibers the molded bodies can be processed to textile fabrics
having enhanced thermoregulation properties and an improved
wearability to the textiles produced therefrom, as well as a high
functionality with respect to heat storage and heat removal when
used in other applications.
Inventors: |
Gersching; Detlef;
(Rudolstadt, DE) ; Meister; Frank; (Rudolstadt,
DE) |
Correspondence
Address: |
HORST M. KASPER
13 FOREST DRIVE
WARREN
NJ
07059
US
|
Family ID: |
34202272 |
Appl. No.: |
10/570374 |
Filed: |
August 25, 2004 |
PCT Filed: |
August 25, 2004 |
PCT NO: |
PCT/DE04/01893 |
371 Date: |
February 28, 2006 |
Current U.S.
Class: |
264/203 ;
264/178F |
Current CPC
Class: |
D01F 1/10 20130101; D01F
4/00 20130101; D01F 2/00 20130101; D01F 4/04 20130101 |
Class at
Publication: |
264/203 ;
264/178.00F |
International
Class: |
D01D 5/08 20060101
D01D005/08 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 30, 2003 |
DE |
103 40 110.5 |
Claims
1. Method for producing molded bodies, in particular fibers and
textile fabrics thereof, with thermo-regulation properties on the
basis of network forming polymeric matrix materials dissolved in
aqueous amino oxides, preferably in n-methylmorpholin-n-oxides,
characterized in that up to 200 weightpercent of a
micro-encapsulated phase change material, related to the network
forming polymer, are inserted into a matrix network setup of
polysaccharides and/or globular proteins in such a way that either
a) the micro-encapsulated phase change material is given as a
component directly into the suspension consisting of the polymer,
the aqueous n-methylmorpholin-n-oxide solution and propylgallate as
a stabilizer into a dissolving vessel with stirrer, or b) in the
case of the globular protein, used as polymer, after the
pre-interlinking of the former the micro-encapsulated phase change
material is given together with the aqueous n-methylmorpholin-n
oxide solution and the propylgallate as a stabilizer, and, if
necessary, with a further network forming polymer such as, for
example, cellulose, into a jacket heated kneading machine, then the
dissolving vessel and the kneading machine, respectively are
evacuated, the suspension is heated, stirred, the water is
evaporated and fibers are molded from the respectively achieved
highly viscous spinning solution after a dry/wet-extrusion process
or c) the micro-encapsulated phase change material is mixed
together with an aqueous n-methylmorpholin-n-oxide solution to a
stock solution, and the latter is given to an already completed
spinning solution consisting of an aqueous n-methylmorpholin-n
oxide solution, polymer and propylgallate as stabilizer and, by
intimately mixing both, the solutions are given into a mixer, and
from the high viscous spinning solution achieved in this manner
also fibers are molded after passing a dry/wet extrusion
process.
2. Method as claimed in claim 1, characterized in that
polysaccharides and/or polysaccharide derivatives are employed as
network forming polymers, which are formed from hexoses with
glycosidic 1,4-bonds and 1,6-bonds or at least partially from
uronic acids.
3. Method as claimed in claim 1, characterized in that as the
network forming polysaccharides are cellulose and/or cellulose
compounds.
4. Method as claimed in claim 1, characterized in that a
water-soluble homopolysaccharide or a heteropolysaccharide or the
derivates thereof are inserted as polysaccharides.
5. Method as claimed in claim 1, characterized in that the network
forming polysaccharides are native globular proteins.
6. Method as claimed in claim 1, characterized in that natural
globular proteins are, by aid of aldehydes such as, for example,
glutaraldehyde, pre-interlinked via amino-groups and/or amide
groups and/or imino-groups of the peptide bonds and/or oxy-groups
of the serine and/or cysteine components.
7. Method as claimed in claim 1, characterized in that up to 99.5
weightpercent of polysaccharides and 0.5 to 100 weightpercent,
preferably 60 to 90 weightpercent of globular proteins are
inserted, related to the entire mass of the solved compounds.
8. Method as claimed in claim 1, characterized in that
micro-encapsulated phase change materials such as Thermasorb.RTM.
TY 83 of Outlast Technologies Inc., which have been screened before
to a maximal grain size of 50 .mu.m, or Lurapret.RTM. PMC 28 of
BASF AG are employed.
Description
[0001] Object of the invention is a method of producing molded
bodies consisting of native polymers forming networks and phase
change materials included therein, which in the form of fibers can
be processed to textile fabrics having enhanced thermoregulation
properties and which convey an improved wearability to the textiles
produced therefrom, as well as a high functionality with respect to
heat storage and heat removal when used in other applications.
PRIOR ART
[0002] Thermoregulation properties of polymer fibers are generated
in that phase change materials are applied on to or inserted into a
polymer matrix. When changing their phasing or their conformation,
phase change materials can absorb and emit, respectively, large
amounts of heat at constant temperatures. At the moment of a phase
change or a change of conformation an increased heat capacity can
be noticed which finds its physical measurable expression in the
occurring melting enthalpy and permits the storage or delivery of
greater amounts of heat than would correspond to the normal heat
capacity of the material outside of the temperature range of the
phase change or the conformation change. The absorption of heat at
a change of the phasing or of the conformation is, on the one hand,
due to the absorption of thermal energy at a heat supply from
outside, which subjectively is felt as a cooling effect, and on the
other hand, when there is a cooling, reversibly supplies in the
reverse direction the same amount of heat, which is felt as
warming. Paraffin or salts and solutions of suitable salts,
respectively, can be used as phase change materials. When paraffin
are used, the temperature range of the phase transition from the
solid state into the molten state can be, due to varying the chain
length, controllably matched to each desired temperature at which
the heat is to be delivered or stored. Salts or the solutions
thereof can be selected at will to the desired temperature range of
the conformation change. Particularly the micro-encapsulated form
is suited for use in the textile technology. In this case the phase
change material is encased in ceramic spheres and polymer spheres,
respectively, having diameters within the .mu.m-range and in this
manner are brought into a form that can be manipulated and that
permits the inclusion in matrix materials of cross-linked polymers,
whereby the degree of the thermo regulation potential depends on
the kind and the amount of the enclosed PCM material. Synthetic
polymers as well as native network forming polymers can be used as
matrix materials.
[0003] Fibers having thermo-regulating properties and textile
fabrics made therefrom are already known per se. So the teaching of
EP 0306202 and U.S. Pat. No. 4,756,958 is that synthetic fibers
from melt-spinnable polymers can be provided with temperature
stabilizing behaviour by including therein temperature regulating
materials. A disadvantage thereby is the low amount of temperature
regulating materials that can be inserted into the fibers.
Furthermore, clothing is described in U.S. Pat. No. 5,885,475 which
is composed of fibers made of a mixture of polymers which
additionally includes phase change material. Also here the
fiber-forming substances are selected from the group of synthetic
thermoplastic polymers which can be spun when molten.
[0004] Multi-component fibers with enhanced and reversible thermal
properties and textile fabrics manufactured therefrom are described
in WO 03027365, US 200212079, and US 200129648. The fiber bodies
which consist of a plurality of elongated components contain at
least in one of said elongated components one temperature
regulating material distributed therein. This material may be a
phase change material and may optionally be selected from the class
of the hydrocarbons, the hydrated salts, paraffin, oil, water,
fatty acids, fatty acid ester, dibasic acids and ester, halide,
clusters and semi-clusters, gas-cluster, stearin anhydride,
carbonate ethylene, higher alcohols, polymers, and metals and
mixtures thereof.
[0005] The arrangement of the different components of the fiber can
be optionally arranged in a core-sheath-structure, polysectionally,
in bundles or in stripes with variously formed cross-sections. The
matrix material of the multi-component fiber described may consist
of different linear chain molecules.
[0006] Its is disadvantageous with these fibers and the textile
fabrics manufactured from said fibers that, due to the described
arrangement of the individual components, only a part of the fibers
formed from said components contains phase change material, and the
part of the temperature regulation material in the entire fiber is,
naturally, limited. Due to the presence of
multi-component-structures made of a plurality of elongated
components the portion of phase change material which can be
inserted into the polymer structure is limited to a portion of
maximally 50 weight percent related to the respective matrix
material.
[0007] In WO 02095314 and CH 0200245 there are also methods
described in which the temperature regulation properties are to be
obtained by textile printing of a textile fabrics structure with
micro-encapsulated phase change material. In other words, the
temperature regulation effect is obtained by applying a coating
which contains a phase change material. Such a method, however,
involves the disadvantage that only a comparatively low amount of
phase change material can be fixed to the surface of the
structures, in particular when only a part of the surface is
printed with a suspension of micro-encapsulated phase change
material and, hence, the temperature regulation effect, related to
the amount of material, is comparatively locally limited.
Additionally, the printing of the textile surface with a suspension
of micro-encapsulated phase change material applied in a
comparatively thick layer has a disadvantageous effect on the
flexibility of the textile products manufactured therefrom and,
hence, on the wearability. Furthermore, the suspensions of
micro-encapsulated phase change materials applied to textile
surfaces are only restrictedly mechanically stable and fast to
washing.
[0008] In US 2003124278 and US 2003124318 an arrangement of textile
materials in layers is described which are provided with
temperature regulation properties in such a manner that the
micro-encapsulated phase change materials are enclosed between
them. Such a layer setup has the disadvantage that the exchange of
heat through the external layers is obstructed and so the heat
capacity of the enclosed micro-encapsulated phase change material
can only be utilized to a limited degree. Due to the lack of
bonding the micro-encapsulated phase change material to the
material of the base structure, both, the amount of introducible
phase change material and the capability of an effective heat
transfer to the phase change material are limited.
[0009] A similar arrangement is disclosed in U.S. Pat. No.
6,217,993 and U.S. Pat. No. 6,077,597.
[0010] Nearly all the PCM-fibers described herein before are
manufactured on the basis of synthetic melt-spinnable polymer
fibers. The use of network forming matrix material which occurs in
nature and can be obtained in a simple way such as cellulose and/or
globular proteins has neither been mentioned before, nor have
exemplary PCM-fibers been produced therefrom.
[0011] It is known that cross-linked structures can be, for
example, manufactured from cellulose form matter and spinning
matter in that cellulose is dissolved in tertiary amino oxides,
preferably in n-methylmorpholin-n-oxide and a non-solvent agent,
preferably water. In this case a spinning solution consisting of
cellulose in n-methylmorpholin-n-oxide and water is molded after a
dry/wet-spinning process, coagulated for example in an aqueous
spinning bath, the solvent is completely removed by repeated
washing and the solidified molded bodies are dried. The molded
bodies obtained in this manner exhibit a network structure
characterized by a hydrogen bridge linkage. (Refer to Berger, W.:
Moglichkeiten und Grenzen alternativer Cellulosauflosung; Lenziger
Berichte 74 [1994] 9, pg. 11-18).
[0012] DE 10059111 teaches the cross-linking of proteins via the
existing functional groups which results in mechanically stable
molded bodies. The globular proteins exhibit, as the name already
tells, a spherical tertiary structure and can be found in nature in
a comparatively great number. Examples for these are casein (a
lactic protein), zein (corn protein) and ardenine (arachis
protein).
OBJECT OF THE INVENTION
[0013] The object of the invention is to provide a method for
producing thermo regulating molded bodies, in particular fibers and
nonwoven textile fabrics thereof from native network forming
polymers having phase change material included in the network which
in contrast to PCM-fibers produced on a synthetic basis have an
increased portion of incorporated phase change materials and thus,
in avoiding the mentioned disadvantages of the prior art, exhibit
an enhanced thermo regulation potential.
[0014] Furthermore, an aspect will be the application of parent
materials occurring in nature and the environmental-friendly
production of fibers having the described properties by the fewest
possible process steps under exploitation of natural resources.
[0015] According to the invention the object is realized in that
phase change materials up to an amount of 200 weight percent are
included into network forming polymers, wherein the network is
formed by chemically coupling functional groups, hydrogen bridges
or polymer and oligomer, respectively, structures helically
connected to one another.
[0016] A suitable network forming polymer matrix material is native
cellulose. The latter forms bonds which, on the one hand, effect a
cross-linkage of the polymer structure and, on the other hand,
result in the formation of a super lattice structure due to the
developing of hydrogen bridge linkages. This structure formation
permits the embedment of even larger amounts of micro-encapsulated
phase change materials. The micro-encapsulation results in a
separation of the phase change material from the polymer matrix.
For example, paraffins of different chain lengths will be used as
phase change materials, whereby the temperature of the phase
transition depends on the chain length of the molecules and can be
adapted to the required temperature range of the phase transition
by varying the chain lengths. But inorganic hydrated salts can also
be utilized which can be selected in dependence on the desired
temperature range of the phase change. Due to their higher density
compared to paraffins it is possible in particular, to insert far
more than 50 weightpercent of phase change material into the
polymer matrix.
[0017] Globular proteins which are present in nature in a great
number and which can be extracted in a simple manner are further
network forming polymer materials, which are suitable for realizing
the object of the invention. Starting from a primary structure
based on peptide bonds, a three-dimensionally interlinked tertiary
structure results in these proteins via a secondary structure in
the form of the folded-up amino acid chain, based on a hydrogen
bridge linkage. Said tertiary structure will be stabilized, for
example, via disulphide bridges, hydrogen bridge linkages or by
ion- or hydrophobic interactions. It was surprisingly found in DE
10059111 that pre-interlinked globular proteins are also soluble in
tertiary amino-oxides and could be molded in a dry/wet-process.
Furthermore, it is possible to add a polysaccharide as, for example
cellulose, as a further component to the solution of the
pre-interlinked globular proteins. Thus the chance is given to
affect at will the properties of the molded bodies.
[0018] In a particularly preferred embodiment of the inventional
solution phase change materials up to an amount of 200
weightpercent, related to the mass of the contained cellulose, are,
for example, added to a cellulose solution in an aqueous tertiary
aminoxide, and this solution drafted via an air gap and
subsequently the cellulose with the phase change material contained
therein is precipitated in a coagulating bath consisting of, for
example, water or a water/alcohol mixture under formation of
physical networks. After the depleted extraction of the solvent the
following drying process leads to the formation of hydrogen bridge
linkages which in spite of the comparatively high amount of phase
change material permit a sufficiently high textile-physical
stability for application of the molded bodies in, for example,
apparel textiles. The cross-linkage of the polymer matrix provides
for a complete and mechanically stable inclusion of the
micro-encapsulated phase change materials in addition to an optimal
heat transfer into and from out of, respectively, the phase change
material.
[0019] In another embodiment of the inventional solution,
micro-encapsulated phase change material is added to
pre-crosslinked globular proteins in n-methylmorpholin-n-oxide, if
necessary under addition of polysaccharides such as cellulose, are
transferred into a spinning solution and spun to filaments by using
known methods.
[0020] The produced PCM-fibers according to the invention based on
native polymers find a wide range of applications such as, for
example, in material for producing textiles, fleeces, textiles for
the automobile industry, and in yarns and blended yarns.
[0021] The phase change heat, characterizing the thermo regulation
properties of the inventional native PCM-fibers exhibits, compared
to the PCM-fibers based on synthetic polymers a value which is up
to a factor of 8 higher.
[0022] The invention will be explained in more detail hereinafter
by virtue of examples of embodiment.
EXAMPLES
Example 1
[0023] 15779 g of a 60%-solution of n-methylmorpholin-n-oxide are
given into a dissolving vessel with agitator of 37 l volume
together with 1160 g cellulose of an average polymerisation degree
500 and 464 g (=40% related to the employed amount of cellulose)
micro-encapsulated phase change material of a phase change
temperature of 28.degree. C. (Thermasorb.RTM. TY 83 of Frisby
Technologies Inc.) under addition of 6.8 g propylgallate. The
micro-encapsulated phase change material has been screened before
to a grain size of maximally 50 .mu.m. The dissolving vessel will
be evacuated to 20 mbar and is heated from 20.degree. C. to
94.degree. C. in the course of 6 hours at a stirrer RPM of 18
min.sup.-1 und the evaporating water is condensed in a connected
condenser. The spinning solution obtained exhibits a viscosity of
1560 PAS and a refractive index of 1.484. At a spinning pump RPM of
25 min.sup.-1 the spinning solution is at 80.degree. C. extruded
through a spinneret having a number of nozzles of 150 and a nozzle
diameter of 200 .mu.m via an air slot into a coagulating bath
consisting of water. The drain speed is 25 m/min so that a draught
of 3.75 results at the air slot. The spun fibers exhibit a titre of
about 14 dtex and will subsequently washed in washing baths and
then are cut to staple. The phase change temperature of the
obtained fibers is 30 J/g.
[0024] Compared thereto, cellulose fibers without embedded phase
change materials exhibit a heat capacity of 6 J/g. The breaking
strength related to the count of the obtained fibers is about 15
cN/tex. The modified fibers could be processed to a needle fleece
having a flat mass of 300 g/m.sup.2 after carding in a carding
engine.
Example 2
[0025] 100 g casein are dispersed in 250 ml water and crosslinked
by addition of 2 g glutaraldehyde and 0.1 g MgCl.sub.2 at
25.degree. C. After squeezing out to a moisture content of 50%, the
casein is suspended in 430 g of 60%-NMMNO. 0.5 g propylgallate are
added as a stabilizer. 100 g of a micro-encapsulated phase change
material such as, for example, Lurapret.RTM. TX PMC 28 from BASF AG
are added to the suspension what corresponds to an amount of 100
weightpercent of phase change material related to the protein in
the solution. The suspension is transferred into a spinning
solution in a kneading machine with a jacket heating under a vacuum
of 30 mbar and at a temperature of 90.degree. C. by distilling off
of 130 g water. The homogeneity of the spinning solution is checked
with an optical microscope and turns out, as a rule, 15 minutes
after the end of the distillation. The spinning solution is
extruded at a spinning temperature of 80.degree. C. in filaments
through a spinneret having 150 nozzles each of a diameter of 90
.mu.m via an air slot into an aqueous coagulating bath and
subsequently is washed in distilled water without residue and then
cut to a staple length of 40 mm. The drying of the fibers is
carried out at 60.degree. C. in a through-circulation drier. The
strength of the spun fibers is about 15 cN/tex at an elastic
stretch of 10% and a titre of about 15 dtex. The heat absorption
capacity of the obtained fibers is about 60 J/g compared to 8 J/g
of the non-modified fibers.
Example 3
[0026] 50 g casein are dispersed in 250 ml water and crosslinked by
addition of 1 g glutaraldehyde and 0.1 g MgCl.sub.2 at 25.degree.
C. After squeezing out to a moisture content of 50%, the casein is
suspended in 430 g of 60%-NMMNO. Additionally 25 g of dry ground
sulphite cellulose (DP 760) as well as 100 g of a
micro-encapsulated phase change material such as, for example,
Lurapret.RTM. TX PMC 28 from BASF AG are added. This corresponds to
an amount of 133% PCM related to cellulose. 0.5 g propylgallate are
added as a stabilizer. This suspension is transferred into a
spinning solution in a kneading machine with a jacket heating under
a vacuum of 30 mbar and at a temperature of 90.degree. C. by
distilling off of 140 g water. The homogenisation of the spinning
solution is achieved 15 minutes after the end of the distillation
and is checked with an optical microscope. The resulting spinning
solution is extruded through a spinneret having 150 nozzles each of
a diameter of 90 .mu.m via an air slot into an aqueous coagulating
bath and the formed fiber skein is washed in distilled water
without residue and then cut to a staple length of 40 mm. The
drying of the fibers is carried out at 60.degree. C. in a
through-circulation drier. The fibers exhibit a strength of 30
cN/tex at an elastic stretch of 8%. The titre is about 20 dtex. The
heat absorption capacity of the modified fibers is about 70 J/g
compared to 7 J/g of the non-modified fibers.
Example 4
[0027] 7607 g of a 60%-solution of n-methylmorpholin-n-oxide are
given together with 784 g cellulose of an average polymerisation
degree 500 under addition of 4.6 g propylgallate into a dissolving
vessel with agitator of 37 l volume. The dissolving vessel will be
evacuated to 20 mbar and is heated from 20.degree. C. to 94.degree.
C. in the course of 6 hours at a stirrer RPM of 18 min.sup.-1 and
the evaporating water is condensed in a condenser. Thereby 2361 g
water are, in total, condensed. The spinning solution obtained
exhibits a viscosity of 8072 PAS, the refractive index of the
spinning solution is about 1.487.
[0028] Furthermore, a stock solution will be produced from 1500 g
of an 80%-solution of n-methylmorpholin-n-oxide and 750 g of a
micro-encapsulated phase change material such as, for example,
Lurapret.RTM. TX PMC 28 from BASF AG and 45 g xanthane. Both
solutions are, after intimate mixing in a dynamic mixer, extruded
at 80.degree. C. through a spinneret having a number of nozzles of
150 and a nozzle diameter of 200 .mu.m, drafted through an air gap,
regenerated in an aqueous coagulating bath and is washed in
distilled water to be entirely free of solvents. The setting of the
mixing ratio is carried out such that the extruded fibers exhibit a
concentration of micro-encapsulated phase change material of 60%
related to the cellulose. The spun fibers have a fiber count of
about 10 dtex and are cut to staple after washing. The phase change
heat of the achieved fibers is 80 J/g. In contrast thereto the
cellulose fibers without an inserted phase change material exhibit
in the corresponding temperature range a heat capacity of 6 J/g.
The tenacity related to the fineness of the obtained fibers is
about 15 cN/tex.
* * * * *