WO2014204313A1 - Process for the preparation of a fiber, a fiber and a yarn made from such a fiber - Google Patents
Process for the preparation of a fiber, a fiber and a yarn made from such a fiber Download PDFInfo
- Publication number
- WO2014204313A1 WO2014204313A1 PCT/NL2014/050407 NL2014050407W WO2014204313A1 WO 2014204313 A1 WO2014204313 A1 WO 2014204313A1 NL 2014050407 W NL2014050407 W NL 2014050407W WO 2014204313 A1 WO2014204313 A1 WO 2014204313A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- fiber
- polyethylene
- furan
- dicarboxylate
- fibers
- Prior art date
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 185
- 238000000034 method Methods 0.000 title claims abstract description 65
- 230000008569 process Effects 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims description 12
- 239000000203 mixture Substances 0.000 claims abstract description 55
- 238000002844 melting Methods 0.000 claims abstract description 28
- 230000008018 melting Effects 0.000 claims abstract description 28
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000009987 spinning Methods 0.000 claims abstract description 17
- 229960005215 dichloroacetic acid Drugs 0.000 claims abstract description 11
- 238000002074 melt spinning Methods 0.000 claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims description 59
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 26
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 26
- 229920000728 polyester Polymers 0.000 claims description 25
- 238000004043 dyeing Methods 0.000 claims description 21
- -1 polyethylene terephthalate Polymers 0.000 claims description 16
- 239000011112 polyethylene naphthalate Substances 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 8
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims description 7
- 238000000113 differential scanning calorimetry Methods 0.000 claims description 6
- 239000004753 textile Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 230000009477 glass transition Effects 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920000098 polyolefin Polymers 0.000 claims description 3
- 230000008961 swelling Effects 0.000 claims description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 2
- 230000000875 corresponding effect Effects 0.000 description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 229920006240 drawn fiber Polymers 0.000 description 5
- 229920000747 poly(lactic acid) Polymers 0.000 description 5
- 239000004626 polylactic acid Substances 0.000 description 5
- 230000001133 acceleration Effects 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 238000002788 crimping Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000012815 thermoplastic material Substances 0.000 description 4
- 239000000975 dye Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000002596 correlated effect Effects 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229920002959 polymer blend Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 210000002268 wool Anatomy 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000006629 Prosopis spicigera Nutrition 0.000 description 1
- 240000000037 Prosopis spicigera Species 0.000 description 1
- 230000002730 additional effect Effects 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229920013724 bio-based polymer Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 208000018999 crinkle Diseases 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
- D01D5/088—Cooling filaments, threads or the like, leaving the spinnerettes
-
- 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
-
- 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
-
- 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/34—Material containing ester groups
- D06P3/52—Polyesters
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D10B2321/02—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins
- D10B2321/021—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins polyethylene
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/04—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/06—Load-responsive characteristics
Definitions
- the present invention relates to a process for the preparation of a fiber, a fiber and a yarn made from such a fiber.
- a process for preparing a fiber comprising polyethylene-2,5-furan-dicarboxylate (“PEF") by melt spinning.
- PET polyethylene-2,5-furan-dicarboxylate
- FDCA 2,5-Furan-dicarboxylic acid
- the diacid is stated to be a suitable monomer for the preparation of polyesters, such as polyalkylene-2,5-furandicarboxylate.
- polyesters such as polyalkylene-2,5-furandicarboxylate.
- Such polyesters have the drawback that they tend to be unintentionally colored. That is in line with color of the polyesters that were described in other prior art documents.
- the preparation of colorless polyesters with a high molecular weight has been described in WO2010/077133. The colorless nature is allegedly due to the catalyst used.
- the high molecular weight is achieved by including a solid state polymerisation step in the polymerisation process.
- the latter document also mentions that the polyester may be used in a fiber.
- polyesters and polyester-amides can be prepared by reacting glycols with dicarboxylic acids of which at least one contains a heterocyclic ring.
- dicarboxylic acids of which at least one contains a heterocyclic ring.
- a glycol ethylene glycol is mentioned and as an example of such a
- GB 621971 describes the preparation of polyethylene-2,5-furandicarboxylate from the polymerisation of ethylene glycol and 2,5-dfurandicarboxylic acid and the methyl ester thereof. The product had a reported melting point of 205-210 °C and readily yielded filaments from the melt. No additional properties were reported.
- polyesters were colored is confirmed by Heertjes et al. in Delft Progr. Rep., Series A: Chemistry and physics, chemical and physical engineering, 1 (1974) 59-63. This article not only teaches that such polyesters are yellow to brown in color, but that they are also thermally not so stable. Moreover, the molecular weight of the polyesters obtained is rather low, and does not exceed an intrinsic viscosity of 0.6 for the polyethylene- 2,5-furan-dicarboxylate.
- US2012/0238981 discloses polyesters for a fibrous web.
- polyester terephthalate fibers that have been obtained using high speed fiber spinning and that have a fiber denier of at least 2.9 and a peak fiber load of at least 10.0.
- Denier is a ment unit and expresses the linear mass density, the mass of a filament of 9000 meters length.
- Another parameter often used is tex, the mass of a filament of 1000 meters length. So, 1 tex is 9 denier.
- the molecular weight of the polyesters may range within wide ranges and may be as low as 5,000 (Mn). For different polyesters different molecular weights are suitable.
- PEF is a suggested alternative, but no actual examples of PEF fibers are disclosed.
- WO2013/149222 and WO2013/149157 describe a single filament made from a PEF resin with a number average molecular weight of 20, 100 and a PDI of 1.93, resulting in a weight average molecular weight of about 38,800.
- the resulting fiber had a denier of 10 (-1.1 tex).
- no fiber related parameters were provided for the resulting material.
- the filament described in WO2013/149222 and WO2013/149157 appears not to have a measurable tenacity.
- the present invention provides a process for the preparation of a fiber containing polyethylene-2,5-furan-dicarboxylate by melt spinning, which fiber has excellent mechanical properties when the polyester is colorless when no dye or colorant was deliberately added, and when the polyester has a relatively high molecular weight.
- the polyester can then be drawn after spinning to a low linear density in the range of 0.05 to 2.0 tex per filament and then shows a remarkably high tenacity. It was found that when other diols, such as 1 ,3- propane diol, were used in the preparation of a polyester, the polyester did not show the same level of tenacity after having been drawn to a similar linear density.
- the present invention provides for a process for the preparation of a fiber comprising polyethylene-2,5-furan-dicarboxylate, by melt spinning wherein a molten composition comprising polyethylene-2,5-furan-dicarboxylate having an intrinsic viscosity of at least 0.55 dl/g, determined in dichloroacetic acid at 25°C, is passed through one or more spinning openings to yield molten threads;
- spun fibers are drawn to a linear density in the range of 0.05 to 2.0 tex per fiber.
- Melt spinning is a well-known process. Sometimes the process is divided in a number of types of melt spinning.
- melt spinning fibers are formed by extruding a molten thermoplastic material through a plurality of fine, usually circular, die capillaries (a spinneret) as molten threads. These move downward through an area of controlled temperature where the molten threads are cooled to below the melting temperature of the thermoplastic material, and are eventually brought into contact with a spinning roller.
- This spinning roller also known as the filament take-up roll
- This filament take up roll can provide an acceleration of the molten filaments as they leave the die capillaries.
- This filament take up roll may then be followed by one or more additional rollers and winders to further condition, draw, and wind the fiber. Depending on the speed of the filament take-up roll the process can be used to produce yarns with different orientation levels.
- This process is typically used to produce fibers of very long, essentially continuous, length. If the yarn is also subsequently chopped into discrete lengths it can be used to produce a so-called staple fiber. These staple fibers can then be used either alone or in combination with other types of staple fibers and put through a "yarn spinning" process to produce yarn, such as is used to produce yarn from natural fibers such as those of cotton, wool or silk.
- the staple fibers can also be laid down in the form of a web or mat and entangled by a variety of means and chemically or thermally bonded to form a non-woven material.
- Meltblowing refers to a process for making continuous fibers, generally as described above, wherein the fibers are formed by extruding a molten thermoplastic material through a spinneret into converging high velocity, usually heated, gas (for example air) streams which attenuate the threads of molten thermoplastic material to reduce their diameter.
- heated, gas for example air
- spunbonding Another type of melt spinning is known as spunbonding.
- the extrusion process is similar to the production of continuous filaments and uses similar extruder conditions for a given polymer. Fibers are formed as the molten polymer exits the spinneret and is quenched by cool gas, e.g. air.
- cool gas e.g. air
- the output of a spinneret i.e. individual filaments
- a spinneret i.e. individual filaments
- This is accomplished by rapidly stretching (drawing) the fibers after exiting the spinneret.
- the fibers are usually
- an acceleration is provided by the speed of the roller which may be higher than the speed with which the fibers leave the spinneret.
- the ratio of the roller speed to the extrusion velocity of the spinneret is known as the spin draft.
- spin draft When the spin draft is greater than one, a certain drawing already takes place. Suitable values of spin draft are 60 - 600 to produce yarns with sufficient orientation and initial drawing that are suitable for further drawing.
- the acceleration is provided by the gases at the pneumatical acceleration. It is evident that in all cases the spun fibers are drawn.
- the holes in a spinneret typically have a diameter of 0.1 to 0.8 mm. In view of the small size of the holes, the molten composition must be free from impurities and is typically filtered before being passed through the holes.
- the holes have a certain length.
- the length of the channel (L) in the spinneret is usually selected in relation to the diameter (D) of the hole.
- the L/D ratio is suitably in the range of 1 to 4.
- the holes are typically circular. Other shapes, however, such as trigonal, multilobal, square or cross-like, are possible.
- the molten threads are cooled. Such is typically done in a quench zone where the threads are contacted with gas, such as air.
- gas such as air.
- the air may be cooled, but also air at room temperature, i.e. around 20 to 25°C, and even heated air may be used.
- the process of the present invention enables the skilled person to prepare fibers containing polyethylene-2,5-furan-dicarboxylate from a wide range of polymer mixtures. It is possible to draw fibers according to the present invention from a polymer consisting completely of polyethylene-2,5-furan-dicarboxylate.
- the molten composition suitably comprises at least 75%wt, preferably up to 100%wt of polyethylene- 2,5-furan-dicarboxylate, based on the weight of the molten composition.
- Such other polymers different from polyethylene-2,5-furan-dicarboxylate, include polyolefins, such as polyethylene and polypropylene, polyamides, such as nylon-6,6 and nylon-6, and polyesters, such as polylactic acid, (PLA), polyethylene terephthalate (PET) and polyethylene-naphthalate (PEN). Especially mixtures with PET or PEN are preferred for technical reasons, such as retention and even improvement of tenacity.
- Such other polymers may form the basis of the molten composition to which polyethylene-2,5-furan-dicarboxylate is added as a minority component. In such case the properties of the other polymer may be retained or even improved.
- the molten composition then comprises 99 to 75 %wt of the other polymer and 1 to 25 %wt of polyethylene-2,5-furan-dicarboxylate, based on the weight of the polymers in the molten composition.
- another polymer may be added to the polyethylene-2,5-furan-dicarboxylate. Therefore, the molten composition suitably comprises from 0 to 25 %wt, preferably from 1 to 25 %wt, of such other polymer and from 75 to 100 %wt polyethylene-2,5-furan-dicarboxylate, based on the weight of the polymers in the molten composition.
- the at least one polymer different from polyethylene-2,5- furan-dicarboxylate is preferably present in an amount of 99 to 75 %wt or 1 to 25 %wt, based on the weight of the at least one polymer different from polyethylene-2,5-furan- dicarboxylate and polyethylene-2,5-furan-dicarboxylate.
- the molten composition comprises another polymer, it may enable the skilled person to adjust the properties of the resulting fibers in accordance with the properties of the other polymer. In this way it may become possible to combine the best properties of the other polymer or polymers with those of polyethylene-2,5-furan-dicarboxylate.
- the molten composition preferably further comprises at least one polymer different from polyethylene-2,5-furan-dicarboxylate.
- the preferred other polymer is PET or PEN.
- the molten composition advantageously further comprises polyethylene terephthalate or polyethylene naphthalate, preferably in an amount of 99 to 85 %wt, more preferably from 99 to 90%wt, based on the total composition. It has been found that the present invention makes it possible to recycle PET and combine the recycled PET with amounts of suitably up to 15 %wt of polyethylene-2,5-furan-dicarboxylate, without deteriorating the PET properties, and at the same time providing the mixture obtained with the properties of polyethylene-2,5- furan-dicarboxylate. In this way an excellent fiber is obtained that partly may consist of biobased material, which reduces the carbon footprint of such fibers.
- the fiber is called a bicomponent.
- examples include side-by-side, sheath-core, matrix fibril, island in the sea and pie slice configurations.
- a side-by-side fiber comprised of a PET segment and a segment of polyethylene-2,5-furan-dicarboxylate may have preferential bulking tendency due to curling caused by differential shrinkage of the two components.
- such a fiber may be used to create subtle changes in visual appearance of a yarn, due to the likely small changes in dyeability. Since both components of the fiber have a similar melting point of above 200 °C, the fiber may be processed at a high speed and the ironability of any textiles produced from such fiber will not be adversely affected.
- a sheath core construction could be used, with a core of polyethylene-2,5-furan-dicarboxylate and a sheath of PET.
- Such a construction could be up to 70%, 80% or even up to 90% or more of the polyethylene-2,5-furan-dicarboxylate biobased material, while retain the surface and processing characteristics of the conventional PET based fiber. It may further be desirable to have a textured fully biobased fiber with side by side construction.
- a bicomponent fiber with polyethylene-2,5-furan-dicarboxylate and a second biobased polymer, such as PLA, polytri- or polytetramethylene-2,5-furan-dicarboxylate or other furanic polyesters can be arranged in a side-by-side type structure to create such an effect. It may also be desirable to have a microdenier biobased fiber with excellent thermal and hydrolytic stability. Such a microdenier fiber might be made through a bicomponent structure, wherein a material which is hydrolytically unstable, such as PLA, is used as a matrix for islands of polyethylene-2,5- furan-dicarboxylate fiber in an island in the sea construction.
- a material which is hydrolytically unstable such as PLA
- the PLA material would then be hydrolysed or reacted away, leaving a microdenier fiber of PEF.
- a "peelable" pie slice structure might also be used, where small pie slices of polyethylene-2,5-furan-dicarboxylate are subsequently freed to form a microdenier fiber.
- the spun fibers obtained after cooling the molten threads, are drawn to the desired linear density. As described above, this can be done immediately after the exit from the openings of the spinneret as part of the continuous extrusion process, but also in a post-draw step in a secondary drawing step.
- the spun fibers before drawing tend to be comprised of polymer chains with relatively low orientation. By drawing (also known as stretching) the spun fibers the polymer chains get into a higher degree of orientation and crystallization.
- draw ratio is understood a measure of the degree of stretching (or drawing) during the orientation of a fiber, expressed as the ratio of the cross-sectional area of the undrawn material to that of the drawn material.
- fiber by fiber is meant a monofilament. It is evident that in the majority of applications fibers are used in the form of multifilaments. In the context of this specification a multifilament combination of fibers will be referred to as yarn.
- the spun fibers are suitably combined to a multifilament yarn before or after being drawn. In the more preferred case, the drawing is conducted on a multifilament yarn.
- the melting temperature of polyethylene-2,5-furan-dicarboxylate is typically in the range of 190 to 230°C. Therefore, the composition according to the present process is suitably brought to and maintained at a temperature ranging from 250 to 300°C, in particular from 260 to 290 °C, to keep the composition in a molten state and bring it to a viscosity that is suitable for extrusion through the holes of the spinneret.
- the temperature is suitably at least 20°C, more preferably at least 30°C, above the melting point of the polymer composition. Suitably this is done at 20 to 70°C, above the melting point of the polymer composition.
- the melting point of the polymer composition in the case of a blend of polymers, the melting point of the polymer with the highest melting temperature is meant.
- the molten threads, extruded at a temperature above the melting point of the molten composition, are cooled to a temperature below this melting point.
- the thus obtained fibers are preferably drawn at a temperature below the melting point of the composition in a secondary drawing step.
- these fibers are drawn at an ambient temperature of 50 to 180 °C. It was found that at relatively low draw temperatures the tenacity of the resulting fiber was improved compared to higher draw temperatures. Accordingly, it is preferred that the temperature at which the spun fibers are drawn is at least 25 °C below the melting temperature of the composition, more preferably, between 40 and 150°C below the melting temperature of the composition. Typically, this will be between the glass transition temperature and the melting temperature of the polymer composition. This may suitably result in a preferred temperature at which the fibers are drawn in the range of 80 to 150 °C.
- the composition that is used in the process of the present invention contains polyethylene-2,5-furan-dicarboxylate.
- the molecular weight of this polymer is relatively high but may vary between wide ranges.
- the weight average molecular weight of the polyethylene-2,5-furan-dicarboxylate in the molten composition is in the range of 55,000 to 200,000, preferably from 62,000 to 180,000, more preferably from 65,000 to 150,000.
- the weight average molecular weight can be determined by GPC using polystyrene standards
- the weight average molecular weight can be correlated to the intrinsic viscosity (IV), measured in dichloroacetic acid in a concentration of 1 gram per 200 ml dichloroacetic acid at 25 °C.
- the time for the sample to elute is measured and a correlated with the time for the dichloroacetic acid solvent alone to elute, yielding a relative viscosity. Therefrom the intrinsic viscosity can be determined.
- An IV for polyethylene-2,5-furan-dicarboxylate of 0.58 corresponds with a weight average molecular weight of 55,000, and an IV of 1.55 corresponds with a weight average molecular weight of 200,000. Therefore, the IV is suitably in the range of 0.55 to 1.55 dl/g.
- the intermediate molecular weights may be determined via a relationship
- the molecular weight of the polyethylene-2,5-furandicarboxylate in the molten composition is preferably at least 100,000, e.g. in the range of 100,000 to 150,000.
- the molecular weight may slightly change during the spinning process. Such a change may result in fibers that after drawing contain polymers with a lower molecular weight than the molecular weight of the polymers in the molten composition. Such an amendment may be caused by a thermal reaction. The result is not only apparent from a lower molecular weight, but also from a narrower polydispersity index (PDI) which is the ratio between the weight average molecular weight and the number average molecular weight.
- Fibers and yarns may be used as prepared by the process according to the invention after drawing. Yarns may also be textured, either in part of a continuous spinning process as described above, or in a subsequent process.
- Texturing is the formation of crimp, loops, coils, or crinkles in filaments. Such changes in the physical form of a fiber affect the hand of fabrics made from them. Hand, or handle, is a general term for the characteristics perceived by the sense of touch when a fabric is held in the hand, such as drapability, softness, elasticity, coolness or warmth, stiffness, roughness, and resilience. Most apparel texturizing techniques are high- speed processes. The spun fibers obtained by the current process are preferably textured. Such texturing can be done via techniques that are known in the art.
- Such techniques include the introduction of crimping, knit-de-knitting technique, or by air jet texturing, the bulk continuous filament (BCF) gas jet process, twist processes such as the false twist process, stuffer box crimping, and bicomponent structures.
- BCF bulk continuous filament
- twist processes such as the false twist process, stuffer box crimping, and bicomponent structures.
- the skilled person will be able to select the optimal texturing process for the desired purpose. For example, for apparel textiles it may be use of the false twist texturing machine, for staple fiber it might be stuffer box crimping, and for carpet yarns it might be the BCF gas jet process.
- the drawn fiber may be subjected to a so-called spin finishing step. Thereto, the drawn fiber is treated with a suitable liquid.
- a suitable liquid The skilled person has at his disposal a wide variety of liquids depending on the property that is to be added to the fiber.
- the spin finishing liquid may provide for example lubrication or static charge reduction.
- the liquid may therefore be a lubricant, an anti-static agent and/or an emulsifier. Additionally, it may include adhesion promoters, corrosion inhibitors, antibacterial components and/or antioxidants.
- PEF fibers can be dyed using dyeing techniques such as for example but not limited to carrier or carrier free dyeing, high temperature and high pressure (HTHP) dyeing, thermosol dyeing, plasma techniques, solvent free, supercritical C0 2 -based dyeing or dyeing using swelling agents. Also modifications can be made to the PEF polymer to improve the dyeability of PEF fibers.
- Polymerizing a third monomer can produce a functionalized dyeable polyester chain. This third monomer has introduced functional groups as the sites to which for example cationic dyes can be attached. The third monomer can contribute to disturbing the regularity of PEF polymer chains, so as to make the structure of dyeable polyester less compact than that of normal PEF fibers.
- the polyethylene-2,5-furan-dicarboxylate has preferably been modified by the introduction of a third monomer to facilitate dyeing, which third monomer contains functionalized groups or disturbs the regularity of the chain of the polyethylene-2,5- furan-dicarboxylate.
- a disperse dye in a microemulsion can be used for dyeing PEF.
- the process according to the present invention provides for the first time a fiber that not only contains polyethylene-2,5-furandicarboxylate, but that has also a fineness as measured by the linear density that has not been provided in the prior art.
- the present invention also provides a fiber comprising polyethylene-2,5-furan-dicarboxylate having a linear density of 0.05 to 2.0 tex.
- a fiber is surprising since the fibers comprising polytrimethylene-2,5-furandicarboxylate do not allow the easy manufacture of fibers with similar linear density having similar tenacity.
- the fibers have a linear density in the range of 0.05 to 0.5 tex.
- Such fibers are excellently suitable for textile purposes, and show excellent mechanical properties.
- the fibers not only have a desirable linear density, but that they also have desirable mechanical properties.
- the fibers show a desirable tenacity.
- the fiber has a tenacity ranging from 200 to 1 ,000 mN/tex.
- the tenacity of the fiber is improved if the molecular weight of the polyethylene-2,5-furandicarboxylate is increased. It has also already been described that the molecular weight of the polymer in the yarn may differ from the molecular weight of the polymer in the molten composition. Therefore, the polyethylene-2,5-furandicarboxylate has preferably a weight average molecular weight in the range of 40,000 to 100,000, more preferably from 50,000 to 95,000, more preferably from 55,000 to 90,000. Most preferably, the weight average molecular weight of the fiber ranges from 65,000 to 90,000. Fibers with the latter molecular weights have shown to have very good tenacity.
- the intrinsic viscosity is preferably in the range from 0.45 to 0.85 dl/g as determined above, in dichloroacetic acid at 25 °C.
- the tenacity is also improved if the orientation and/or crystallization of the polymers in the fiber has been enhanced. Such enhanced orientation can be achieved by drawing a spun fiber. The drawing may be done in one step, but it is also possible to conduct the drawing of a fiber in several steps, e.g. two to four. Such multistep procedure has the advantage that each step of drawing of the fiber may be conducted at different temperatures, dependent on the desired draw ratio and/or mechanical property. As indicated above, the draw temperatures are preferably in the range of 50 to 180°C.
- the fiber has therefore preferably been obtained by drawing an undrawn spun fiber at a draw ratio of 1 : 1.4 to 1 :6.0. It is to be understood that if the drawing is done in several steps then the resulting overall draw ratio is the multiplicative product of the draw ratio of each of the individual steps.
- the drawing may be conducted either in-line with the spinning process, as part of a continuous operation, or it may be conducted in a separate step where the as-spun yarn has first been wound and collected onto a bobbin or roller, and then is subsequently unwound and drawn to its final form.
- polyethylene-2,5-furan-dicarboxylate polymers are very slow to crystallize. In the absence of significant orientation caused through drawing, the polymer will crystallize only very slowly. For example, when a polyethylene-2,5-furan- dicarboxylate polymer is cooled from above its melting point at a rate of 30 °C/min, 20 °C/min, 10 °C/min, or even only 5 °C/min, no crystallinity is developed on the cool-down. It was further found that polyethylene-2,5-furan-dicarboxylate does crystallize readily when it is drawn and oriented.
- Drawn fibers of a polyethylene- 2,5-furan-dicarboxylate composition typically exhibit crystallinity of more than 5 J/g, and often more than 10 J/g, as determined by DSC (Differential Scanning Calorimetry).
- the reported crystallinity is determined by the net crystallinity from an upheat of the fiber by DSC, being the total melting endotherm less any crystallization exotherm exhibited on the upheat. This represents the crystallinity of the fiber.
- the crystallinity as expressed in J/g and determined by DSC, is preferably more than 30 J/g since fibers with such a level of crystallinity show low shrinkage, e.g. less than 10% shrinkage in length when placed in boiling water.
- the crystallinity may be as high as 50 J/g.
- the spinning and drawing processes for polyethylene-2,5-furan-dicarboxylate polymer give rise to an amount of crystallinity in the fiber.
- the fiber properties can be further controlled and optimized by applying a step of heat-setting to the drawn (and, if desired, textured) fiber yarn. This step can be accomplished through the use of dry hot air, saturated or superheated steam, hot rolls, hot plates, and so forth.
- the orientation already developed in the fiber or yarn through the spinning and drawing process leads to a rapid development of a crystalline network.
- the process can be carried out either under tension or without tension, as known in the art, to modify final fiber or yarn properties, such as hot air shrinkage, elongation to break, tenacity, and crimp retention.
- Birefringence is an optical property, given by the difference of the value of the refractive index in two directions. For fibers it is measured perpendicular and parallel to the fiber axis. It is a useful measure of the degree of orientation in a fiber. A fiber which experiences no draw during either spinning or in a post-drawing operation will have no orientation and it will have a birefringence of virtually zero. A polyethylene-2,5-furan- dicarboxylate fiber according to the present invention that has been drawn, has a level of birefringence which is greater than zero, due to the preferential orientation of the polymer chains in the direction of the drawing. Fibers according to the invention preferably have a birefringence value of greater than 0.01 and more preferably greater than 0.03. The upper limit may be as high as 0.4.
- the fiber may consist essentially of polyethylene-2,5-furandicarboxylate.
- the fiber may also comprise mixtures of other polymers with polyethylene-2,5-furan-dicarboxylate.
- Such other polymers include polyolefins, such as polyethylene and polypropylene, polyamides, such as nylon-6,6 and nylon-6, and polyesters, such as polyethylene terephthalate (PET) and polyethylene-naphthalate (PEN).
- PET polyethylene terephthalate
- PEN polyethylene-naphthalate
- the fiber suitably comprises from 75 to 100 %wt polyethylene-2,5-furan-dicarboxylate, based on the weight of the fiber.
- the fiber according to the present invention suitably further comprises polyethylene terephthalate or polyethylene naphthalate, preferably in an amount of 99 to 85 %wt, based on the total fiber.
- the fibers according to the present invention are suitably combined into a yarn, yielding a yarn comprising a plurality of such fibers.
- the fibers and yarns may be used for all different fiber applications. Such includes the application in textiles, which may be knit, woven or non-woven. Hence, it may be admixed with wool or cotton for the manufacture of clothes or carpets. It can also be used in furniture upholstery or curtains. Alternatively it may be used as technical fiber, e.g. in safety belts, in transportation belts, or as reinforcement in tires, so-called tire cords. It may also be reinforced by combination with glass fibers etc.
- PEF polyethylene-2,5-furandicarboxylate
- the yarn as spun was subjected to stretching (drawing) to different draw ratios and at different draw temperatures.
- the yarn had an IV of 0.67 dl/g, corresponding with a weight average molecular weight of 66,400.
- the resulting linear densities per filament, breaking tenacities and elongations at break are shown in the Table 1 below. Table 1
- Example 2 The same polymer that was used in Example 1 was subjected to a two-step stretching (drawing) process. First the polymer composition was melt spun in the same way as was done in Example 1. A resulting yarn was subsequently preliminarily drawn at 85 °C to a draw ratio of 2.5. In a second stage the preliminarily drawn fiber was further drawn to different final draw ratios in an oven heated to 125 or 130 °C. The tenacity and elongation was again determine for each of the resulting yarns. The results are shown in Table 2. Table 2
- Example 2 The same polymer that was used in Example 2 and melt spun in the same way. In a first step the spun fibers were drawn at 90°C to a first draw ratio of 2.4. Then the
- the results show that when the draw temperature also in the second step is at most 100°C, the tenacity of the resulting fibers is increased.
- the yarn showed a melting point of 204 - 210°C.
- the crystallinity of the yarn of Experiment No. 26 amounted to 30 J/g.
- sample A Two samples of PEF, one having a Mw of 85,200
- sample B Two samples of PEF, one having a Mw of 111 ,000
- sample B Two samples of PEF, one having a Mw of 85,200
- sample B Two samples of PEF, one having a Mw of 111 ,000
- sample B Two samples of PEF, one having a Mw of 85,200
- sample B Two samples of PEF, one having a Mw of 85,200
- sample B the second having a Mw of 111 ,000
- the yarn from Sample A as spun had an IV of 0.71 dl/g, corresponding with a Mw of 71 ,600, and the yarn as spun from Sample B had an IV of 0.82, corresponding with a Mw of 86,600.
- the yarns as spun were subjected to stretching (drawing) to different draw ratio in one or two steps.
- the draw temperature in the first step was 90 °C; the temperature at the second step was 100 or 150°C.
- the resulting linear densities per filament, breaking tenacities and elongations at break are shown in the Table 4 below.
- the yarn was processed on a Barmag AFK 2 false twist texturing machine to produce textured drawn yarns.
- the spun yarn is heated in the texturing machine in an oven, heated to 160 or 170°C so that it becomes malleable. In this state, it is drawn with a draw ratio of 1.6 or 1.7, and is twisted.
- the thread is cooled by means of a jet of air jand the twist reversed, which creates crimping.
- the thus textured yarn is wound.
- the yarns with a draw ratio of 1.6 had an average linear density of 0.17 tex
- the yarns with a draw ratio of 1.7 had an average linear density of 0.16 tex.
- Samples of the textured yarns were measured as to tenacity and elongation at break. The results, showing the average of 30 samples for each parameter, are shown in Table 5.
- This example shows that textured yarns can be made with satisfactory tenacity.
- PEF polyethylene terephthalate
- the PET used had an intrinsic viscosity of 0.64 dl/g.
- the polymer, or polymer mixture was melted to a temperature of 270 °C and melt spun via a 72-hole spinneret at a temperature of 270 °C.
- the molten threads were cooled.
- the 72 filaments were combined to a yarn.
- the yarns were drawn in three steps at 60, 100 and 100 °C to a final draw ratio of 2.5.
- the linear densities per filament of the yarns were determined and found to be 0.56 ⁇ 0.01 tex.
- the maximum draw ratio was determined by drawing the yarns in the third step till they broke. The results are shown in Table 6.
- polytrimethylene-2,5-furandicarboxylate also known as polypropylene- 2,5-furandicarboxylate, hereinafter "PPF"
- PPF polypropylene- 2,5-furandicarboxylate
- the yarns were drawn at different temperatures. Since the glass transition temperature of PPF is about 50-51 °C, the draw temperature can be lower than for PEF. Temperatures below 60°C resulted in yarn breaks. Drawing at a temperature above 80 °C resulted in an undesirably low level of orientation and crystallization in the fiber. Therefore, the draw temperatures were kept between 60 and 80 °C.
- the yarns obtained were drawn at different draw ratios ("DR") in two steps at different temperatures.
- the draw conditions and the resulting tenacity of the yarns are shown in Table 7.
- the yarn was drawn at 110 °C, followed by a heat set at 155 °C.
- the resulting yarns ahd an crystallinity of more than 40 J/g, a Tg of about 80 °C and a melting temperature of 212 °C.
- the shrinkage in boiling water was less than 5%.
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Abstract
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EP14737041.5A EP3011086B8 (en) | 2013-06-20 | 2014-06-20 | Process for the preparation of a fiber, a fiber and a yarn made from such a fiber |
CN201480035343.XA CN105452548B (en) | 2013-06-20 | 2014-06-20 | Prepare method, fiber and the yarn made of such fiber of fiber |
BR112015031668A BR112015031668A2 (en) | 2013-06-20 | 2014-06-20 | process for the preparation of a fiber, a fiber, a yarn made from such a fiber and knitted or crocheted article |
ES14737041.5T ES2693373T3 (en) | 2013-06-20 | 2014-06-20 | Procedure for the preparation of a fiber, a fiber and a yarn made with said fiber |
CA2915810A CA2915810C (en) | 2013-06-20 | 2014-06-20 | Process for the preparation of a fiber, a fiber and a yarn made from such a fiber |
MX2015017378A MX2015017378A (en) | 2013-06-20 | 2014-06-20 | Process for the preparation of a fiber, a fiber and a yarn made from such a fiber. |
KR1020167001614A KR102213562B1 (en) | 2013-06-20 | 2014-06-20 | Process for the preparation of a fiber, a fiber and a yarn made from such a fiber |
US14/899,832 US10351973B2 (en) | 2013-06-20 | 2014-06-20 | Process for the preparation of a fiber, a fiber and a yarn made from such a fiber |
SG11201510340UA SG11201510340UA (en) | 2013-06-20 | 2014-06-20 | Process for the preparation of a fiber, a fiber and a yarn made from such a fiber |
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2014
- 2014-06-20 JP JP2016521243A patent/JP6507156B2/en active Active
- 2014-06-20 EP EP14737041.5A patent/EP3011086B8/en active Active
- 2014-06-20 ES ES14737041.5T patent/ES2693373T3/en active Active
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Also Published As
Publication number | Publication date |
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US10351973B2 (en) | 2019-07-16 |
CN105452548B (en) | 2018-02-06 |
JP2016522334A (en) | 2016-07-28 |
SG11201510340UA (en) | 2016-01-28 |
CA2915810C (en) | 2021-10-19 |
EP3011086B8 (en) | 2018-11-14 |
KR20160021878A (en) | 2016-02-26 |
CN105452548A (en) | 2016-03-30 |
BR112015031668A2 (en) | 2017-07-25 |
MX2015017378A (en) | 2016-04-06 |
ES2693373T3 (en) | 2018-12-11 |
US20160138193A1 (en) | 2016-05-19 |
EP3011086A1 (en) | 2016-04-27 |
EP3011086B1 (en) | 2018-08-08 |
JP6507156B2 (en) | 2019-04-24 |
KR102213562B1 (en) | 2021-02-08 |
CA2915810A1 (en) | 2014-12-24 |
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