EP3914438A1 - Method for dyeing a textile article made of modified polyester - Google Patents
Method for dyeing a textile article made of modified polyesterInfo
- Publication number
- EP3914438A1 EP3914438A1 EP20700933.3A EP20700933A EP3914438A1 EP 3914438 A1 EP3914438 A1 EP 3914438A1 EP 20700933 A EP20700933 A EP 20700933A EP 3914438 A1 EP3914438 A1 EP 3914438A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- dyeing
- polyester
- polyether
- polyethylene terephthalate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004043 dyeing Methods 0.000 title claims abstract description 90
- 229920000728 polyester Polymers 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 49
- 239000004753 textile Substances 0.000 title claims abstract description 41
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 160
- 229920000570 polyether Polymers 0.000 claims abstract description 160
- 150000001412 amines Chemical class 0.000 claims abstract description 122
- 229920001897 terpolymer Polymers 0.000 claims abstract description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 149
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 149
- -1 polyethylene terephthalate Polymers 0.000 claims description 83
- 229920000642 polymer Polymers 0.000 claims description 30
- 150000004985 diamines Chemical class 0.000 claims description 27
- 238000001816 cooling Methods 0.000 claims description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 229920005594 polymer fiber Polymers 0.000 claims description 2
- 229920000136 polysorbate Polymers 0.000 claims 1
- 230000002311 subsequent effect Effects 0.000 claims 1
- 239000000835 fiber Substances 0.000 description 28
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 23
- 239000000975 dye Substances 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 18
- 125000002091 cationic group Chemical group 0.000 description 16
- 235000004879 dioscorea Nutrition 0.000 description 16
- 239000000047 product Substances 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 13
- 238000001125 extrusion Methods 0.000 description 11
- 239000004970 Chain extender Substances 0.000 description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 229920001451 polypropylene glycol Polymers 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- 239000004952 Polyamide Substances 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229920002647 polyamide Polymers 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 238000007306 functionalization reaction Methods 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000004745 nonwoven fabric Substances 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 239000011265 semifinished product Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920006309 Invista Polymers 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000003827 glycol group Chemical group 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000009958 sewing Methods 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 238000010420 art technique Methods 0.000 description 1
- 239000000981 basic dye Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013037 co-molding Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229960005215 dichloroacetic acid Drugs 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical compound CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 238000009972 garment dyeing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 238000009970 yarn dyeing Methods 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
- 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
- D01F6/92—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 polyesters
-
- 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
- D06P3/02—Material containing basic nitrogen
- D06P3/024—Material containing basic nitrogen using dispersed dyes
-
- 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
- D06P3/54—Polyesters using dispersed dyestuffs
-
- 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
- D01D5/38—Formation of filaments, threads, or the like during polymerisation
Definitions
- the present invention relates to the field of polymers.
- aspects disclosed herein relate to improvements to methods for producing or processing polymers for producing synthetic threads, fibers and yams, for example for producing woven, nonwoven or other textile articles.
- some aspects of the present invention relate to improvements to methods for dyeing polymer textile threads or yarns, or other textile articles, in particular based on polyesters and specifically on polyethylene terephthalate (hereinafter also PET).
- the dye bath has high temperatures, higher than the boiling temperature at ambient pressure. Therefore, to reach the temperature required for dyeing, pressurized machines are necessary. Typically, dyeing of PET -based yarns takes place at temperatures that, in some steps of the cycle, are around 130°.
- cationic PET has costs around 25-35% higher than a standard PET. This nullifies or at least reduces the economic benefit of energy saving in the dyeing step.
- the textile product obtained from dyeing cationic PET has poor dyeing quality. The dye is not well fixed to the fiber.
- a PET with a polyethylene terephthalate chain that has been modified with the introduction of at least a polyether amine can be dyed at low temperatures, which can be reached at ambient pressure, in times comparable with those required for pressurized dyeing of standard (unmodified) PET.
- the cost of a PET modified with polyether amine can in some cases be comprised between the cost of the standard PET and the cost of more expensive cationic PETs, with consequent reduction of the cost of the finished product.
- the terpolymer comprising the monomers forming the PET in combination with polyether amine can be obtained with a polymerization process starting from the three components of which it is formed.
- the polyether amine-functionalized PET can be made available in granules or chips.
- the terpolymer is melted and extruded to produce thread.
- the terpolymer, i.e., the polyether amine- functionalized PET is obtained from PET previously produced through a polymerization process, proceeding by melting the PET in the presence of polyether amine.
- the procedure can be a reactive extrusion procedure, where a standard PET is brought into contact with polyether amine at high temperature and pressure and the molten mass comprising both the constituents is extruded to obtain the thread or yam.
- the present invention relates to a use of a polymer comprising polyester containing polyethylene terephthalate and at least a polyether amine, for the production of a thread having improved dyeability properties.
- the invention provides for the use of a polyether amine as functional group in a polyethylene terephthalate to improve the dyeability of a textile article containing said polyethylene terephthalate and said functional group.
- textile article is intended genetically as a semi-finished or finished article, in thread or in garment form.
- the textile article can be a thread or yam, a wick, a garment, a piece of woven or nonwoven fabric, intended for subsequent converting operations, such as cutting and sewing.
- the invention relates to a method for dyeing a textile article made at least partly of polymer fiber or polymer yam, comprising the steps of:
- a textile article comprising a polyethylene terephthalate and a polyether amine, for example in the form of fibers and/or threads or yams, into a dye bath;
- dyeing the textile article at a dyeing bath temperature no greater than 100°C and preferably greater than 70°C, preferably greater than 80°C, more preferably comprised, for example, between around 90 and around 99°C, so as to be able to carry out said dyeing step at ambient pressure.
- the textile article can be a package of thread or yam, for example a reel or a bobbin.
- the textile article or product can be a knitted or woven textile article, or a nonwoven textile article, or any other textile article utilizing fibers, threads or yams made of the aforesaid polymer comprising PET functionalized with polyether amine.
- the article can be a finished garment and therefore not intended to undergo further operations of cutting, sewing or the like.
- the textile article can be a semi-finished article intended to undergo further conversions of form, such as cutting and/or assembly with other components to obtain the finished product.
- the textile article can therefore also be a piece of woven or nonwoven fabric.
- thread or yam as used herein can indicate in particular a substantially one-dimensional article, which can be formed by spun fibers or by single or multiple continuous filaments.
- a thread or a yarn can thus consist of discontinuous fibers (for example staple fibers) spun to form a substantially continuous article, or of one or more continuous filaments, obtained by extrusion of a polymer mass, for example by means of an extruder or a drawing machine.
- WO2014/057364 and W02015/001515 disclose methods for producing modified polyamides, comprising nylon and a polyether diamine, to increase moisture regain, i.e. the capacity to absorb and retain moisture.
- these modified polyamides are suggested to improve the hand of fabrics and garments obtained therewith.
- WO2018154403 discloses PET functionalized with polyether amines to obtain biocidal properties. In this publication, however, no particular properties concerning the dyeability of yarns obtained with this modified PET are disclosed.
- the polyether amine is mainly positioned as chain terminal in the polyethylene terephthalate, with a free amino terminal (ME).
- the polyether amine can be a polyether monoamine.
- the polyether amine comprises more than one amino group and can therefore for example be a polyether diamine or a polyether tri amine.
- the polyether amine can be present in a percentage by weight equal to at least about 1%, preferably equal to at least about 2%, more preferably equal to at least about 5%, with respect to the total weight of the polyester.
- the polyether amine can be present in an amount by weight no greater than about 50%, preferably no greater than about 30%, more preferably no greater than about 25%, even more preferably no greater than about 20%, with respect to the total weight of the polyester.
- the percentage by weight of poly ether amine in the polyester can be comprised between about 1% and about 50%, preferably between about 1% and about 25%.
- the polyester comprises a percentage of polyether amine comprised between about 1% and about 20%, for example between about 2% and about 20%, or between about 2.5% and about 15%.
- the polyester can comprise a percentage of polyethylene terephthalate of at least about 50% by weight, preferably at least about 60% by weight, more preferably at least about 70% by weight, even more preferably at least about 80% by weight, with respect to the total weight of the polyester.
- the percentage by weight of polyethylene terephthalate is no greater than about 99%, preferably no greater than about 98% by weight, even more preferably no greater than about 95% by weight, with respect to the total weight of the polyester.
- the polyester can comprise from about 50% to about 99% by weight, preferably between about 75% and about 99% by weight, for example between about 80% and about 99% by weight, or between about 80% and about 98%, or between about 85% and about 97.5% by weight of polyethylene terephthalate.
- the polyether amine has a weighted average molecular weight (Mw) equal to at least about 500, preferably equal to at least about 800, more preferably equal to at least about 1000, even more preferably equal to at least about 1500, and preferably no greater than about 5000, more preferably no greater than about 3000, for example comprised between 1500 and 2800.
- Mw weighted average molecular weight
- the thread or yam made of PET modified and dyed according to the methods described herein can comprise only polyester containing polyethylene terephthalate and at least a polyether amine, as described above, but in some embodiments, the thread or yarn can contain one or more further components in addition to the modified polyester containing PET and polyether amine.
- different polymers can be combined with the polyester containing PET and polyether amine.
- embodiments can have bi-component threads or fibers, where one of the components consists of polyester containing PET and poly ether amine, and the other component can consist of a different polymer, for example a polyamide, or polyethylene terephthalate without polyether amine.
- the bi-component fibers or filaments can, for example, comprise a percentage by weight of polyester, containing polyethylene terephthalate and polyether amine, in a percentage equal to at least about 40% by weight, preferably equal to at least about 50% by weight, even more preferably equal to at least about 60% by weight with respect to the total weight of the textile product.
- Threads, filaments, fibers or yams produced with modified polyester, containing polyethylene terephthalate and polyether amine as described herein, can be used as is or in a blend with other natural, artificial or synthetic threads, filaments, fibers or yams, for example produced with other polymers such as polyester without polyether amine, or polyamide or other suitable components.
- the polyester containing polyethylene terephthalate and polyether amine can be present in a percentage by weight equal to at least about 10%, preferably equal to at least about 50%, more preferably equal to at least 60% or 70%. Preferably, this percentage is no greater than about 95%, more preferably no greater than about 80% of the total weight of the textile product.
- a polyester containing polyethylene terephthalate and at least a polyether amine for producing a product or article with easy dyeability properties at ambient pressure.
- a method for conferring improved dyeability properties on a polyester containing polyethylene terephthalate comprising the step of introducing a poly ether amine into the chain of the polyethylene terephthalate, for example in a polymerization process, or subsequently to a polymerization process, causing previously polymerized polyester and polyether amine to react.
- a method for producing a polyester comprising reacting terephthalic acid, ethylene glycol and a polyether amine at temperatures and pressures sufficient to cause polymerization and formation of polyester containing polyethylene terephthalate and polyether amine.
- the method comprises the steps of:
- the method provides for modifying a previously polymerized polyester, in order to introduce at least a polyether amine into the polyethylene terephthalate chain.
- the method can comprise the step of reacting polyethylene terephthalate with a polyether amine and obtaining a polyester having improved dyeability properties and containing polyethylene terephthalate and polyether amine.
- the method can, for example, be implemented in an extruder for producing a continuous monofilament or multifilament thread, made of polyethylene terephthalate modified with polyether amine, having improved dyeability properties, starting from polyester containing polyethylene terephthalate for example in the form of chips, granules or the like, to which there is added, directly in the extruder or in a container separated from the extruder and for example in fluid connection therewith, a suitable amount of at least a polyether amine.
- the polyester reacts with the polyether amine and the polyester thus modified is extruded to form a semi-finished article, for example a thread, for textile applications or the like.
- the method can comprise the step of adding a grafter or a chain extender.
- the method can comprise the steps of reacting the grafter or the chain extender with the polyethylene terephthalate for obtaining a functionalized polyethylene terephthalate; and of reacting the polyethylene terephthalate functionalized with polyether amine.
- the invention relates to the use of a polyester fiber or thread, containing polyethylene terephthalate and at least a polyether amine, for producing a yarn or thread subjected to dyeing at ambient pressure.
- the polyether amine has at least two amino groups
- Fig. 1 shows a dyeing cycle with a standard PET in a first embodiment
- Fig.2 shows a dyeing cycle with a cationic PET in a first embodiment
- Fig.3 shows a dyeing cycle with a PET functionalized with polyether amine according to the present description in a first embodiment
- Fig. 4 shows a dyeing cycle with a standard PET in a second embodiment
- Fig.5 shows a dyeing cycle with a cationic PET in a second embodiment
- Fig.6 shows a dyeing cycle with a PET functionalized with polyether amine according to the present description in a second embodiment.
- a range comprises only the numerical data explicitly indicated as limits of the range. Instead, a range of values must be understood as extensive and flexible, in the sense of comprising all the numerical values individually contained in the range, and all the sub-ranges, delimited by any two numerical values contained in the range. Therefore, in general, the expression“a range from about A to about B” discloses not only the range defined by the ends A and B, but also any sub-range from“about X to about Y”, where X and Y are values contained between A and B.
- a content of a substance A in a set B of substances is defined with a series of percentages of maximum values and a series of percentages of minimum values, it must be understood that the substance A can be contained in the set B with amount within a plurality of ranges each defined by a pair of any one of the minimum values and any one of the maximum values.
- the definition“containing at least x%, preferably at least (x-n)%, and no more than y%, preferably no more than (y-m)%”, comprises the ranges [x; y], [x; (y-m)], [(x-n); y], [(x-n); (y-m)].
- Each of these ranges also comprises each sub-range defined between its maximum and minimum limits.
- polyester based polymer containing polyethylene terephthalate (PET) having an improved dyeability
- PET polyethylene terephthalate
- a polyether amine bonded to one or more monomers of polyethylene terephthalate in the polyester chain are used.
- the polyester containing polyethylene terephthalate and polyether amine can be obtained starting from monomers (terephthalic acid and ethylene glycol) for producing polyethylene terephthalate, with batch or continuous polymerization reaction, during which at least a polyether amine is added.
- Examples of polyether amines, and in particular of polyether diamines and polyether triamines that can be used in the methods and in the products described herein will be indicated below.
- the method provides for reacting terephthalic acid and ethylene glycol with an excess of ethylene glycol to obtain polyethylene terephthalate with terminal carboxyl groups, according to the reaction:
- the reaction is conducted at pressures comprised between about 150°C and about 200°C and at pressure of about 4 bar with acid catalyst.
- the PET thus obtained is reacted with a polyether diamine obtaining modified polyethylene terephthalate with terminal groups NEE, according to the reaction where H2N-R-NH2 is a generic polyether diamine, examples of which are given later on in the present description.
- the reaction can take place at temperatures comprised between about 120°C and about 140°C for 24 hours at atmospheric pressure.
- the modified polyethylene terephthalate thus obtained can be in granules, chips or other suitable form and can be used in subsequent production processes, for example for molding, injection, co-molding, extrusion, blowing, etc.
- the polyester containing polyethylene terephthalate and polyether amine thus obtained can be melted and extruded to obtain monofilament or multifilament threads, as semi-finished products for the subsequent production of textile articles.
- the continuous filaments can be cut into fibers, which can then be used for producing nonwoven fabrics, or can be spun to obtain continuous filaments.
- the modified polyester can be produced starting from previously polymerized polyethylene terephthalate, for example in the form of chips, granules or the like, causing a functionalization reaction, through which molecules of polyether amine react with terminal groups of the molecules of polyethylene terephthalate, or with two consecutive monomers of the molecules of PET.
- the following reaction can take place between a chain terminal group of the polyethylene terephthalate and a generic polyether diamine H2N-R-NH2 obtaining the modified polyester with formation of ethanol:
- chain extenders or grafters can be used to facilitate the formation of bonds between the molecule of poly ether amine and the monomers of the polyethylene terephthalate.
- a sequence of formaldehyde and bromoacetic acid can be used as chain extender.
- a first step the previously polymerized polyethylene terephthalate reacts with the chain extender to form a polyethylene terephthalate functionalized with carboxyl group, according to the following reactions [0054]
- the first reaction can be conducted at about 30°C for about 4 hours in acetic acid 1M, while the second at about 30°C in sodium hydroxide 2M for 18 h.
- the molecules thus obtained can react with the respective terminal groups
- H2N-R-NH2 once again represents a generic polyether diamine, examples of which will be given below and were m represents the number of monomers of PET, of a molecule containing n monomers of PET that reacted with the poly ether amine.
- the reaction can be conducted at about 120-140°C for 24 hours at atmospheric pressure.
- the parameter n can be comprised between about 10 and about 1000.
- the parameter m can be comprised between 1 and 100.
- the reaction above can take place in a batch process.
- the polyethylene terephthalate can be functionalized with polyether amine in a continuous process, in which the polyethylene terephthalate is reacted with poly ether amine, with or without grafters or chain extenders, according to the reaction described above, in temperatures and pressure conditions such as to obtain the functionalization reaction in short times, compatible with the residence time of the reagents in a continuously fed volume.
- polyester and poly ether amine can be fed into an extruder, both in the same position or in different positions along the longitudinal extension of the extruder, i.e. along the extension of the auger or other feeding system of the material along the extruder.
- polyethylene terephthalate can be fed in a position upstream into a container with longitudinal extension containing a single or double feed auger.
- the polyether amine can be introduced downstream of the polyethylene terephthalate feed-in point, with respect to the direction of feed of the auger, in this way coming into contact with previously melted polyethylene terephthalate in a section upstream of the path defined by the feed auger. Downstream of the polyether amine feed-in point, this latter reacts with the polyethylene terephthalate in this way obtaining the polyester functionalized with polyether amine, which is then extruded in line.
- reaction facilitators for example grafters or chain extenders as described above
- these can be introduced together with the polyethylene terephthalate, or subsequently, for example between the polyethylene terephthalate feed-in point and the polyether amine feed-in point, or together with the poly ether amine or downstream of the poly ether amine feed-in point.
- the molten mass of polyethylene terephthalate that has reacted or is reacting with the polyether amine can be extruded to produce threads or filaments, or other semi-finished products of indefinite length.
- the polyethylene and the polyether amine can be made to react in the extruder with a residence time of 200-800 seconds, for example comprised between about 300 and about 700 seconds, preferably between about 450 and about 600 seconds, typically about 550 seconds.
- the residence temperatures can be comprised between about 250°C and about 350°C, preferably between about 270°C and about 310°C, for example, in particular about 290°C).
- the pressure in the extruder can, for example, be comprised between about 100 bar and about 300 bar, preferably between about 100 bar and about 250 bar.
- the polymeric mass of polyethylene terephthalate functionalized with polyether amine can be extruded with a total flow rate comprised between 10 and 20 kg/h, preferably between 12 and 18 kg/h, for example about 15 kg/h. Exemplary embodiments defined by specific parameters of the monofilament or multifilament thread are described below.
- the starting polyethylene terephthalate can have a weighted average molecular weight (Mw) comprised between about 10,000 and about 40,000 and in some embodiments a relative viscosity (method: dichloroacetic acid in 1% solution) that can be comprised between about 0.4 and about 1.0 dl/g.
- the PET can contain percentages by weight of TiCh up to 2%, preferably up to 1.5%.
- polyethylene terephthalate useful for producing modified polyester as described herein, particularly for textile use, are: the polyester RT20 produced and marketed by INVISTA Resins & Fibers GmbH & Co KG, Germany; SM-01/D535, marketed by Novapet, Spain.
- polyether monoamines, or polyether triamines can be used instead of polyether diamines as indicated by way of example in the previous reactions.
- the modified polymer obtained by reacting PET and polyether amine can be converted once again into chips, granules or into other forms, different than thread, to be used subsequently in any converting process, for example molding, or extrusion.
- polyether amine can be a polyether monoamine with general formula
- Polyether monoamines of formula (1) are available, for example, from Huntsman Corporation, USA, with the trade name Jeffamine® M series.
- the polyether amine has more than one free NH2 group, so that in the reaction with the polyethylene terephthalate one of the NH2 groups forms a covalent bond with the chain of the polyethylene terephthalate while the remaining NH2 groups remain available.
- the poly ether amine is a poly ether diamine, of formula
- Polyether diamines of general formula (2) are available, for example, from Huntsman Corporation, USA, under the trade name Jeffamine® ED series and Elastamine® RE series.
- the polyether diamine has a weighted average molecular weight (Mw) equal to at least about 500, preferably equal to at least about 800, more preferably equal to at least about 1000, even more preferably equal to at least about 1500, and preferably no greater than about 5000, more preferably no greater than about 3000, for example comprised between about 1500 and about 2500.
- Mw weighted average molecular weight
- An embodiment provides for the use of Elastamine® RE-2000 (Huntsman) or Jeffamine® ED2003, both of formula (1) wherein:
- y is equal to about 39 and
- polyether diamine of formula (2) with the following characteristics can be used:
- the polyether diamine has an AHEW (Amine Hydrogen Equivalent Weight) no greater than 10% with respect to the idealized AHEW.
- AHEW is defined as the weighted average molecular weight of the polyether amine divided by the number of active amine hydrogens per molecule.
- an idealized polyether amine having a weighted average molecular weight of 2000 and in which all the ends of the polyether are amine ends, hence contributing with 4 active amine hydrogens per molecule, would have an AHEW of 500 g per equivalent. If 10% of the ends are hydroxyl rather than amine, there will be only 3.6 active amine hydrogens per molecule and the poly ether amine will have an AHEW of 556 g per equivalent.
- the number of active amine hydrogens per molecule, and hence the AHEW of a given polyether amine, can be calculated according to prior art and conventional techniques, for example by calculating the nitrogen content of the amine groups using the procedure defined by the standard ISO 9702.
- the polyether amine is a polyether diamine, preferably having a weighted average molecular weight equal to or greater than 1500 and an AHEW that does not exceed by more than 10% the idealized AHEW for this polyether amine.
- the polyether diamine has a general formula (2) and a composition of the chain with prevalence of PEG (polyethylene glycol) groups with respect to the PPG (polypropylene glycol) groups, i.e. with y >(x+z).
- the polyether diamine can have a chain containing polyethylene glycol (PEG) and polypropylene glycol (PPG) groups with predominance of PPG groups.
- PEG polyethylene glycol
- PPG polypropylene glycol
- Polyether diamines of this type are available from Huntsman Corporation, with the trade name Elastamine® RP series.
- the polyether diamine can have a base structure of polypropylene glycol and poly(tetramethylene ether glycol) (PTMEG).
- PTMEG poly(tetramethylene ether glycol)
- Examples of poly ether diamines of this type are the poly ether diamines marketed by Huntsman
- the RE series polyether diamines with weighted average molecular weight equal to or greater than about 1500 and equal to or less than about 2500 are currently preferred, in particular for applications to polyesters intended for the production of fibers and threads, it would also be possible to use polyether diamines with a higher weighted average molecular weight, for example up to about 5000, such as Elastamine® RP3-5000 (Huntsman).
- the polyether diamine can have weighted average molecular weights (Mw) of less than 1500, for example no greater than 1000, or no greater than 800.
- polyether diamine has a chain composed of polypropylene glycol PPG groups, of general formula [0084]
- polyether diamines of this type are polyether diamines of the Jeffamine® D series produced and marketed by Huntsman Corporation, with weighted average molecular weight (Mw) variable from about 230 to about 4000 and in which x can vary from about 2.5 to about 68.
- polyether amines with a number of amino groups (ME) greater than two can be used.
- the poly ether amine can be a polyether triamine of general formula
- polyether triamine in which (x+y+z) can be comprised between 5 and 6 and the weighted average molecular weight Mw can be equal to about 440.
- polyether triamine can have the general formula
- Polyether triamines of this type are, for example, the Jeffamine® T series produced and marketed by Huntsman Corporation, USA.
- the amount of polyether amine in the polyester can be comprised between about 1% and about 50% by weight, for example between about 2% and about 30%, preferably between about 2% and about 25% by weight, for example between about 2.5% and about 20% by weight, or between about 5% and about 20% by weight, with respect to the total weight of the polyester.
- the polyester comprises an amount of polyethylene terephthalate of at least about 50%, preferably at least about 60%, more preferably at least about 70%, even more preferably at least about 80%, for example at least about 85% by weight with respect to the total weight of the polyester.
- the percentage of polyethylene terephthalate is no greater than about 99%, preferably no greater than about 98%, for example no greater than about 95%, or no greater than about 90%, or no greater than about 85 % by weight with respect to the total weight of the polyester.
- the modified polyester containing poly ether amine is used in a blend or in combination with other polymers, for example in the case of bi-component fibers, or in the case of blends with fibers, threads or filaments made with other polymers, the percentages of polyethylene terephthalate and of polyether amine indicated above are referred to the total weight of the polyester containing polyethylene terephthalate and polyether amine, excluding the weight of any second or further blended polymer.
- the polyester usable can have a molar mass for example comprised between about 1,000 and about 1,000,0000 g/mol. In some embodiments, the polyester has a molar mass between about 2,000 and about 1,000,000 g/mol.
- the polyester described herein can be advantageously used for producing semi-finished products intended for the textile industry, in the form of continuous thread or of staple fiber.
- the thread can be monofilament or multifilament.
- the thread can be obtained by extrusion and the staple fiber can be obtained by cutting the extruded continuous thread.
- the thread obtained from extrusion of the polymer according to the method described herein can be a multifilament textile thread of the LOY (low orientation yarn), POY (Partially Oriented Yam), or FDY (Fully Drawn Yarn) type.
- the fibers can, for example, have a length comprised between about 2 and about 200 mm, preferably between about 10 and about 100 mm.
- the staple fibers can be converted into continuous filaments using known spinning processes.
- the staple fibers can be used for producing nonwoven fabrics, forming plies of fibers subsequently subjected to mechanical, hydraulic, chemical or thermal bonding processes, or combinations thereof.
- the threads or yarns can be used in weaving processes, knitting processes or for other uses.
- Threads produced with the process described herein can subsequently be processed to modify their physical and mechanical characteristics.
- the threads can be combined with other threads to obtain composite articles.
- the threads obtained from the spinneret can be texturized, or taslanized, stretched, combined with elastomeric threads for example through an interlacing or covering jet, or other suitable device.
- the thread or the fiber can be mono-component. In this case the filament or filaments of which it is formed consist of a single material.
- the thread can be multi-component, for example bi component.
- One, some or each filament forming the thread comprises, in this case, two parts formed by two different polymers.
- the filament comprises an inner core and an outer coating (“core-skin” bi-component fiber) produced in different polymers.
- the outer part, or skin, that surrounds the inner core can be produced with polyester containing polyethylene terephthalate and polyether amine, while the core can be produced with a different polymer.
- the bi-component fiber can have a second component consisting of or comprising polyamide, polypropylene or thermoplastic polyurethane, or polyester, for example polyethylene terephthalate or polybutylene terephthalate, without polyether amine.
- each filament can be side by side with one another (“side-by-side” bi-component fiber), rather than inserted one inside the other.
- Extrusion heads for producing multi-component, in particular bi-component, threads are known and can be used advantageously in the context of the methods described herein.
- bi-component threads can be produced in which from 10% to 95% by weight, preferably from 50% to 80% by weight, of the polymer of which they are composed is a polyester containing polyethylene terephthalate and polyether amine, while the remaining part consists of polyamide, non-modified polyester, i.e. without polyether amine, or a polymer of another kind, for example polypropylene.
- the thread can have a number of filaments comprised between 1 (monofilament) and 10,000. In some embodiments the thread can have a count comprised between about 5 and about 6000 dtex, preferably between about 5 and about 5000 dtex, for example between about 5 and about 3000 dtex.
- the thread is extruded with a number of filaments comprised between 1 and 300, for example between 5 and 200.
- the thread can have a DPF (dtex per filament) value comprised between 0.3 and 20, for example between 0.4 and 20.
- the thread in particular for example for use in the production of garments, can have a number of filaments comprised between 1 (monofilament) and about 100, preferably between about 30 and about 80, in some embodiments between about 40 and about 75, and a count comprised between about 7 and about 140 dtex, preferably between about 40 and about 120 dtex, for example between about 50 and about 100 dtex, in some embodiments about 90 dtex.
- the polymer is extruded at an extrusion speed between 20 and 80 cm/s.
- the filaments exiting from the spinneret can advantageously be cooled in a known manner, for example in a current of air.
- the single filaments are cooled with a lateral flow of air and made to converge toward and through an oiler to be thus combined to form a multi-filament thread.
- Downstream the thread can be fed around one or more stretching and/or relaxing and/or stabilizing rollers, motorized and controlled at peripheral speeds that can differ from one another to give the thread the required and desired degree of stretch and/or orientation.
- the thread can be subjected to a stretching and/or texturizing, with elongation percentages comprised between about 15% and about 200%. In some embodiments the thread is subjected to elongation comprised between 20% and 150%.
- the winding speed can be comprised between about 1000 and about 5500 m/min, preferably between about 2000 and about 3500 m/min, for example between about 2500 and about 3000 m/min, in some embodiments about 2800 m/min.
- a thread or yam made with a polymer based on functionalized polyester terephthalate, as described above, by means of a poly ether amine has a dyeability, i.e. a capacity to absorb and retain a dye, much greater than a standard PET, commonly used for producing threads or yams and which also has considerable advantages with respect to cationic PETs. Therefore, the polyester terephthalate described here makes it possible to carry out dyeing cycles that are simpler, less onerous from the point of view of energy consumption and environmental impact and with lower consumptions of materials or with the use of less costly materials.
- FIG.1 shows a time-temperature diagram, in which the dyeing cycle performed with a standard PET is summarized.
- a polyester RT20 manufactured by INVISTA was used to produce a textured thread DTY 50dtex/68filaments.
- Garment dyeing was carried out, i.e. dyeing of the finished garment, but similar results are also obtained if the textile product is yarn-dyed, i.e., introducing reels of wound thread, destined for the subsequent production of garments, into the dyeing machine.
- the dyeing cycle of Fig.1 is carried out with a water-based bath, containing a dispersant and a dye for polyester.
- the article to be dyed is placed in the bath at about 40°C for a duration of about 15 min. This temperature is defined here as a pre-dyeing temperature.
- a heating step up to 130°C is carried out.
- the process is carried out in an autoclave or in any case in a pressurized container, where the operating pressures can typically reach 0.7 bar.
- the overall dwell time of the product in the bath can typically be about 120- 125 minutes. In general, the dwell time at 130°C is about 30 minutes.
- the dyeing step is followed by a cooling step at 40°C and stripping at about 80°C, to eliminate the excess dye from the thread.
- the stripping step takes about 50 minutes and is followed by a finishing step in which additives are added to soften the fabric or yarn and obtain the desired consistency to the touch, with soft and pleasant hand.
- the cycle can be carried out at ambient pressure without requiring pressurized tanks. This is followed by stripping and finishing steps, just as for conventional PET.
- Dyeing cationic PET has the advantage of not requiring pressurized vessels, but in order for it not to require execution times incompatible with the requirements of a sufficiently high productivity of the system, it is necessary to use carriers to accelerate the dyeing process. In any case, as mentioned above, the dwell times of the product to be dyed at the highest temperature of the cycle are about four times higher than the times required to dye standard PET. Dyeing cationic PET also requires double the amount of dye with respect to standard PET (Fig. l).
- Fig.3 shows, similarly to Figs. 1 and 2, the steps of a dyeing cycle of a modified PET, i.e. functionalized with polyether amine, according to the description above.
- the dyeing cycle is substantially equivalent to that of standard PET with regard to the succession of the steps and the time of each step.
- the duration of the initial bath step (at the pre-dyeing temperature) and high temperature bath (dyeing temperatures), up to lowering of the temperature to 40°C for the start of the stripping step can be lower with respect to the cycle for dyeing standard PET.
- Fig.3 shows, similarly to Figs. 1 and 2, the steps of a dyeing cycle of a modified PET, i.e. functionalized with polyether amine, according to the description above.
- the dyeing cycle is substantially equivalent to that of standard PET with regard to the succession of the steps and the time of each step.
- the duration of the initial bath step (at the pre-dyeing temperature) and high temperature bath (dyeing temperatures) up to
- l indicates a time of about 125 minutes, while in Fig.3 it can be observed that the dyeing cycle of a PET modified as described herein requires an actual dyeing step of 110 minutes, followed by cooling at 40°C and subsequent stripping.
- the lower dwell time is justified by the fact that dyeing takes place at temperatures lower than 100°C, typically between 90°C and 99°C. In the example illustrated dyeing takes place at 98°C. This temperature can be reached in shorter times with respect to those required to reach the 130° C required for dyeing standard PET.
- the temperature of the dyeing cycle of the PET functionalized with polyether amine is below boiling temperature and therefore does not require equipment with pressurized tanks.
- the lower operating temperature also implies an energy saving.
- the dyeing cycle of the cationic polyethylene terephthalate implies an energy saving of about 10-15%
- the dyeing cycle of the PET functionalized or modified with polyether amine as described here implies an energy saving of about 32%.
- Added to this, with respect to standard PET, is a saving of 10% on the cost of the machinery, equivalent to the saving obtainable with cationic PET.
- the reduced cycle times obtainable with the PET functionalized with polyether amine increases the total productivity of the system due to a reduction of 75% of the time required for the actual dyeing step.
- Figs. 4, 5 and 6 show the same dyeing cycles as Figs. 1, 2 and 3, respectively, but in which a cooling step from the dyeing temperatures to an intermediate temperature of 80°C is added, before discharging the dye bath and replacing it with the stripping bath at 40°C.
- This cooling step has a duration of about 40 min in the case of dyeing cycle with standard PET, with initial temperature (dyeing temperatures) of 130°C.
- the cooling step has a shorter duration, of about 20 minutes, as the starting temperature is lower (98°C in the example illustrated).
- the reduced operating temperature of the dyeing machines also allows a saving on the processing costs of the thread, as a thread with lower features of resistance to temperature can be used.
- the cost of the raw material for production in the case of cationic PET is about 30% higher than standard PET, while the PET modified with polyether amine has a cost equal to or slightly higher (about 10% higher) than the cost of standard PET.
- Dyeing of the PET modified with poly ether amine is carried out with normal dyes dispersed for dyeing standard PET, carrying out a thermodynamic control in the case of two colors and three colors, to verify dye affinity as they are used at a temperature below 100°C. The use of the dispersant is variable based on the intensity of the shade to be obtained.
- the tables below provide four dyeing recipes that can be used to dye PET modified with polyether amine according to the present description.
- the products indicated as“Prochimica” are available from Prochimica Novarese S.p.A., Novara, Italy.
- the production indicated as Archroma are available from Archroma Management GmbH, Basel, Switzerland.
- the amounts of dispersant and chemical agent for controlling the pH are indicated in grams per liter of dye.
- the amount of dyes is indicated in percentage by weight referred to the weight of the material (e.g. thread) to be dyed.
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Abstract
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PCT/EP2020/051526 WO2020152225A1 (en) | 2019-01-23 | 2020-01-22 | Method for dyeing a textile article made of modified polyester |
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US6576340B1 (en) * | 1999-11-12 | 2003-06-10 | E. I. Du Pont De Nemours And Company | Acid dyeable polyester compositions |
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US7585550B2 (en) * | 2004-02-02 | 2009-09-08 | College Of William And Mary | Process for modifying polymeric surfaces using deep UV irradiation |
US20070112110A1 (en) * | 2005-09-06 | 2007-05-17 | Mcsheehy Brendan F Jr | Composition for producing polyester and polyamide yarns with improved moisture management properties |
CN104822732B (en) | 2012-10-10 | 2018-06-22 | 金莱迪公司 | Polyamide apparel textile yarn and the fabric and dress ornament being made from it |
ITFI20130162A1 (en) | 2013-07-04 | 2015-01-05 | Golden Lady Co Spa | "METHOD FOR THE PRODUCTION OF A SYNTHETIC WIRE RETURNED WITH HUMIDITY AND THREAD OBTAINED" |
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