Background

[0001] Over the years there have been a number of approaches to incorporate polyether segments into polyamides with the objective of improving the properties of yarns made from such polyamides.

[00Θ2] Within polyamides, poly(adipamides) demonstrate advantageous properties including high temperature stability, tensile strength and abrasion resistance.

Poly(adipamides) also enjoy relatively uniform batch-to-batch dyeability. They can be spun as-produced (from the melt) or by melting and extruding chips or pellets. It would be desirable to provide polymers with the desirable temperature stability, tensile strength and abrasion resistance advantages characteristics of poly(adipamide) while at the same time improving the moisture uptake properties.

[0003] Patent 3,946,089 to Furukawa et. al. relates to a block copolymer comprising a polyamide segment and a polyether segment.

[0004] Published Japanese Application 1983/0156353 (abstract) relates to a copolymer comprising an aminoaryl group.

[0005] U.S. Patent 4,873,296 to Ciaperoni et al. relates to an A-B-A block copolymer where the B comprises a modified poly(ethylene glycol).

[0006] U.S. Patent 4,963,638 to Pazos et al. relates to a superabsorbent thermoplastic polymer comprising a poly(oxyethlene) diol soft segment.

[0007] Published Japanese Application JP 1990/0203954 relates to a polyamide mixed with a poly (ethylene glycol) complex produced in the presence of a metal halide.

[0008] European Patent 0 504 784 relates to polyetheresteramides containing 20 to 40 wt.% poly(ether) diol / dicarboxylic acid monomer.

[0009] U.S. Patent 5,306,761 to Ohwaki et al. relates to a polyamide containing a copolymerized polyalkylene oxide unit.

[0010] U.S. Patent 6,420,045 to Faulhammer et al. relates to a polyamide with hydrophilic blocks.

[0011] While inclusion of an ether backbone in a polyamide through the amine component can provide a desirable improvement in certain properties (such as moisture uptake) it has also been found to compromise certain other properties of some condensation polyamides. For example, adding the ether backbone through the amine can compromise color. [0012] While it would be desirable to improve moisture uptake in finished products, it would be desirable to provide polymer beads that can be melt spun into fiber without the need for a separate drying step after storage. For example, it would be desirable to provide polymer beads suitable for spinning into apparel fibers that can be stored for a week at 50% to 65% Relative Humidity without the need for a separate drying step before melt spinning.

[0013] Similarly, it would be desirable to provide fibers and fabrics that retain their improved moisture uptake properties after being exposed to hot water.

Summary

[0014] The applicants have undertaken an extensive study of hydrophilicity in nylon yarns for use in apparel applications, including examining hydrophilicity improvement as a function of the incorporation of oxyethylene (-OCH2CH2-) repeat units into polyamides. The desirable property of softness in nylon yarns for use in apparel applications may become manifest through incorporation of ether (-OR-) repeat units, where R, for example but not limited to, is CH2CH2 or CH ₂ CHMe or CH2CH2CH2CH2. Substantial study has been undertaken to find the right balance of oxyethylene repeat units in the polyamide polymer backbone. As a result, it has been found that such a modified polymer may require altered polymerization conditions and the yarn spinning conditions are not readily predictable or readily adapted to conventional spinning assets. Disclosed herein are synthetic polyamide compositions and methods for the production thereof that are suitable for spinning into apparel fibers using conventional melt spinning equipment.

[0015] Disclosed is a polyamide product containing poly(ether glycol) [one such class also described as poly(alkyl oxide)] components in the backbone in which the ether (i.e., the poly(ether glycol)) functionality originates from the carboxylic acid component of the polycondensation reaction rather than from the amine.

[0016] In one disclosed polyamide composition, the ether functionality may be present in at least a portion of the diamine, as well as in at least a portion of the dicarboxylic acid.

[0017] Suitable dicarboxylic acids include PEG (poly(ethylene) glycol)-derived dicarboxylic acids.

[0018] Also disclosed is a polycondensation process to give the ether-containing polyamide. Fibers and fabrics (including knit, woven and direct laydown nonwoven fabrics) are also disclosed having enhanced higher moisture retention/hydrophilicity compared to similar compositions lacking the ether in the dicarboxylic acid component.

[0019] The disclosed polyamide may comprise a nylon and a poly(ether glycol) dicarboxylic acid, where the poly(ether glycol) dicarboxylic acid has a number average molecular weight of≥250 Da, for example≥600 Da and≥1500 Da and≥2500 Da and≥5000 Da. The moisture regain for such a polyamide can range from≥5% to≤35% by weight. Unless otherwise stated, the number average molecular weight is given in the units of Daltons (Da).

[0020] The disclosed polyamides are well-suited for making hydrophilic polyamide compositions. As such, the disclosure herein also relates to improved synthetic polyamide (nylon) polymer compositions. The disclosed polyamides can comprise a nylon and a poly(ether glycol) dicarboxylic acid, and optionally a polyetheramine. Disclosed

compositions can be suitable for making a yarn or fiber and a textile or fabric or garment containing such yarns or fibers.

[0021] Disclosed polyamides comprise a nylon and a poly(ether glycol) dicarboxylic acid and can have a moisture regain ranging (measured as described herein) ranging from about 5% to about 35%, for example from about 10 to about 25%, for example from about 15 to about 20%; all moisture regain values being on the weight basis. Such regain can allow for improved processability during subsequent processing of the present polyamide

compositions. For example, the polyamide can have an elongation to break of from 20% to 90% when spun into a yarn. The polyamide composition may be either an acid (anionic) or base (cationic) dyeable polymer, as discussed herein. In one embodiment, at least 85 per cent of the polymer backbone (between amide units) can comprise aliphatic groups. The nylon discussed herein can, for instance but without limitation, be polyhexamethylene adipamide (nylon 6,6), polycaproamide (nylon 6), or copolymers of either of these. In one embodiment, the nylon can be nylon 6,6. The nylon can be present in the polyamide in an amount ranging from about 50% to 99% by weight.

[0022] The poly(ether glycol) dicarboxylic acid can be made, without limiting to such a process, by reacting a polyfether glycol) with an organic base such as potassium tert- butoxide and an alkylating agent such as ethyl bromoacetate. Greenwald, R. B. et al, J. Med. Chem., 1996, 39, 424-431. This adds an ester functionality to the hydroxyl groups of the poly(ether glycol). The ester groups are then saponified using an aqueous base such as sodium hydroxide. The dicarboxylic acid product may be isolated by acidifying the mixture with a mineral acid such as aqueous hydrochloric acid and extracting with an organic solvent such as dichloromethane. The solution is then evaporated to form a concentrated solution and the polymer is precipitated by adding the solution slowly to a stirred antisolvent such as /-butyl methyl ether.

[0023] Alternatively, low molecular weight poly(ether glycol) dicarboxylic acids such as poly(ethylene glycol) may be purchased from suppliers such as the Sigma-Aldrich company.

[0024] Non-limiting examples of suitable poly(ether glycol) dicarboxylic acids can include polypropylene glycol dicarboxylic acid, polytetramethyleneoxide dicarboxylic acid, block copolymers comprising blocks of polyethyieneglycol (PEG), polypropyleneglycol (PPG) and polytertramethyleneglycol (PTMG), such as: (PEG)-b-(PPG); or (PEG)-b-(PPG)- b-(PEG); or (PPG)-b-(PEG)-b-(PPG).

[0025] As discussed herein, a poly(ether glycol) dicarboxylic acid can be employed in the polymerization of nylon monomers to form a polyamide which may be spun into nylon yarns which exhibit good hydrophilicity properties. Such properties can impart tactile aesthetics and wear comfort highly desired in apparel goods manufactured from these yarns.

[0026] Furthermore, the poly(ether glycol) dicarboxylic acids can be present in the polyamide and can have various molecular weights depending upon the desired properties of the resulting polymer, including processability as discussed herein. In one embodiment, the poly(ether glycol) dicarboxylic acid can have a number-average molecular weight (M _n measured in Daltons, Da) of at least 250 Da. In other aspects, the poly(ether glycol) dicarboxylic acid can have a number-average molecular weight of at least 600 Da or at least 1500 Da, or at least 2500 Da, or even at least 5000 Da. Additionally, the poly(ether glycol) dicarboxylic acid can be present in an amount ranging from about 1 wt.% to about 50 wt.% of the polyamide. In one aspect, the poly(ether glycol) dicarboxylic acid can be present in an amount ranging from about 5 wt.% to about 25 wt.%, for example from about 8 wt.% to about 25 wt.%. In another embodiment, the poly(ether glycol) dicarboxylic acid is present in an amount from about 8 wt.% to about 20 wt.%.

[0027] The polyamides described herein comprise aliphatic diamines. In one example, the diamine can be an aliphatic diamine containing from 6 to 12 carbon atoms. In one aspect, the diamine can be hexamethylenediamine. A portion of the diamine can be present in the polymer in an amount to give substantially equimolar proportions of amine groups to acid groups of the poly(ether glycol) dicarboxylic acid. The polyamides described herein can have various physical properties. In one embodiment, the polyamide can have 25- 130 amine end group gram-equivalents per 1000 kilograms of polymer. Additionally, the polyamide can have a relative viscosity ranging from about 20 to about 80. In another embodiment, the relative viscosity can be calculated based on a formic acid test method according to ASTM D789-86 known at the time of filing the present disclosure in the United States Patent and Trademark Office. Disclosed polyamides can have a yellowness index [YI] from about 25 to about 45. The disclosed polyamide can be characterized by one or more of of: an L* color coordinate from about 75 to about 85; an a* color coordinate from about -5 to about 5 and a b* color coordinate from about 5 to about 25.

[0028] The disclosed polyamides can further comprise one or more po!y(ether glycol) dicarboxylic acid as described above. In one embodiment, the poly(ether glycol)

dicarboxylic acid can have a number-average molecular weight (M _n ) of≥250 Daltons (Da), for example,≥500 Da,≥600 Da, and≥1500 Da. In other aspects, the poly(ether glycol) dicarboxylic acid can have a M _n of≥2500 Da, or even≥5000 Da.

[0029] The disclosed polyamides can further comprise one or more polyetheramines, as described in published PCT Application WO 2014/057363.

[0030] Whiteness can be determined using a test method conforming to the CIE whiteness rating for each sample. Samples can be measured individually for whiteness (W) and yellowness (Y), using a GRETAG MACBETH "COLOR EYE" reflectance

spectrophotometer. First, by determining the CIELAB color coordinates L, a* and b*; and then, calculating W and Y by means known in the art (see: ASTM Method E313-1996 Standard Practice for Calculating Whiteness and Yellowness Indices from Instrumentally Measured Color Coordinates). Details of this measurement are found in Color Technology in the Textile Industry 2nd Edition, published by Committee RA 36, AATCC (1997); see in this volume: Special Scales for White Colors by Harold and Hunter, pp 140-146, and the references therein, all are incorporated herein by reference in their entirety.

[0031] Additionally, the present polyamides can further comprise a catalyst. In one embodiment, the catalyst can be present in the polyamide in an amount ranging from 10 ppm to 1,000 ppm by weight. In another aspect, the catalyst can be present in an amount ranging from 10 ppm to 100 ppm by weight. The catalyst can include, without limitation, phosphoric acid, phosphorus acid, hypophosphoric acid, arylphosphonic acids, aiylphosphinic acids, salts thereof, and mixtures thereof. In one embodiment, the catalyst can be sodium hypophosphite, manganese hypophosphite, sodium phenylphosphinate, sodium phenylphosphonate, potassium phenylphosphinate, potassium phenylphosphonate, hexamethylenediammonium bis-phenylphosphinate, potassium tolylphosphinate, or mixtures thereof. In one aspect, the catalyst can be sodium hypophosphite. [0032] The disclosed polyamides and polyamide compositions may include an

"optical brightener." Such an optical brightener can be provided according to the disclosures of United States Patent Application No. 20080090945 Al assigned to INVISTA North America S.a r.l.

[Θ033] The polyamides and polyamide compositions in accordance with embodiments disclosed herein can be improved in whiteness appearance through the addition of an optical brightener. Such polyamides can exhibit a permanent whiteness improvement and can retain this whiteness improvement through operations such as heat setting. In one embodiment, the optical brightener can be present in the polyamide in an amount ranging from 0.01 wt.% to 1 wt.%.

[0034] In another embodiment, an improvement in whiteness appearance can be achieved by addition of a delustering agent. The delustering agent can be titanium dioxide.

[0035] In addition, these polyamide compositions may contain an antioxidant stabilizer or an antimicrobial additive. Additionally, the polyamide compositions may contain an anti-foaming additive. In one embodiment, the anti-foaming additive can be present in the polyamide in an amount ranging from 1 ppm to 500 ppm by weight.

[0036] The disclosed polyamides include those that are inherently acid (anionic) dyeable, but may also be rendered into a basic (cationic) dyeing form by modifying these polymers or copolymers with a cationic dye receptive monomer copolymerized in the polymer. This modification makes compositions particularly receptive to coloration with base (cationic) dyes. 5-sodium sulfoisophthalic acid is an example of such a cationic dye receptive monomer.

[0037] In a further aspect, disclosed is a process for producing a polyamide, comprising contacting a diamine, a poly(ether glycol) dicarboxylic acid, and a nylon salt; forming a mixture; heating the mixture in a closed vessel to a temperature and autogenous pressure sufficient to cause polymerization of the mixture; and forming the polyamide.

[Θ038] In a further aspect, disclosed is a process for producing a polyamide, comprising contacting a diamine, and a nylon salt; forming a mixture; heating the mixture in a closed vessel to a temperature and autogenous pressure sufficient to cause polymerization of the mixture; then adding a poly(ether glycol) dicarboxylic acid, continue the process and forming the desired polyamide.

[0039] The processes for producing the polyamides can further comprise providing to the mixture a catalyst, including those discussed herein. The processes can further comprise providing an anti-foaming additive to the mixture. The processes can further comprise providing an optical brightener to the mixture.

[ΘΘ40] The nylon monomers of the polyamide can be added as a salt, aminoacid, or lactam. The nylon monomer can be a nylon 6,6 salt and can comprise nearly all of the polyamide (for example, 99 wt.%, 99.5 wt.%, 99.9 wt.% or greater) or can be present in the polyamide in an amount ranging from about 50 wt.% to 95, 96, 97 or 98 wt.%.

[0041] Various processing parameters can be used in the polymerization of the present polyamides including temperature and pressure. The temperature can range from about 190 °C to about 290 °C and the autogenous pressure can range from about 250 pounds per square inch absolute (psia) to about 300 pounds per square inch absolute (psia).

Additionally, the heating can be performed under partial vacuum. The partial vacuum attained is subject to autoclave design and economic considerations with the process.

[ΘΘ42] The present polymerization can involve various serial heating cycles. Such cycles can individually comprise a heating temperature profile and a pressure profile. The intent is to keep the system fluid through a combination of temperature for sufficient melt, and water content for sufficient solubility. The serial heating cycles can comprise: a first heating cycle (CI) having a temperature starting between 170 °C to 215 °C and finishing between 190 °C to 230 °C over a period of 20 to 40 minutes under a pressure of between 130 to 300 psia; a second heating cycle (C2) having a temperature starting between 190 °C to 230 °C and finishing at between 240 °C to 260 °C over a period of 20 to 45 minutes under a pressure of between 130 to 300 psia; a third heating cycle (C3) having a temperature starting between 240 °C and 260 °C and finishing between 250 °C to 320 °C over a period of between 15 to 45 minutes under a pressure of between 300 psia to atmospheric pressure; and a fourth heating cycle (C4) having a temperature starting between 250 °C to 320 °C and finishing between 250 °C to 320 °C over a period of 15 to 80 minutes under a pressure of between atmospheric pressure and about 200 mbar absolute vacuum. Finally, the polymer is extruded using methods well known in the art. Disclosed polyamide compositions can be inherently acid dyeable and may, as an option, comprise a cationic dyeable polymer.

[0043] The disclosed polyamide compositions may be made by an autoclave process.

The process may start with a concentrated slurry (the term slurry also incorporating the concept of a solution) prepared from an aqueous solution of a nylon salt, aminoacid or lactam or mixtures of e.g., a nylon 6,6 salt, that is provided to an autoclave vessel. Optionally, the slurry may be dilute and become more concentrated by means of an evaporation step. The slurry may be prepared from an aqueous solution of the monomers, such as, hexamethylene diamine and adipic acid, in the manner known in the art. The autoclave vessel may then be heated to about 230 °C (or some other functional temperature) allowing the internal (autogenous) pressure to rise. A delusterant, titanium dioxide (Ti0 ₂ ) may optionally be injected into the autoclave and monomer mixture as an aqueous dispersion.

[0044] In one embodiment, an aqueous slurry of a poly(ether glycol) dicarboxylic acid, and optionally a polyetheramine may be injected to the mixture in the autoclave vessel along with a quantity of a diamine such as hexamethylenediamine, to give substantially equimolar proportions of acid groups to amine groups. The mixture may then be heated in the autoclave to about 245 °C (or some other functional temperature). While at this temperature or other desired temperature regime, the autoclave pressure may be reduced to atmospheric pressure and further reduced in pressure by application of a vacuum in the known manner, to form the polyamide composition. The autoclave, containing the polyamide composition would be maintained at this temperature for about 30 minutes. This step may be followed by further heating of the polyamide polymer composition in the autoclave to about 285 °C, for example. The polymer composition may be released from the autoclave by opening a port in the autoclave vessel and applying 4 to about 5 bar dry nitrogen allowing the molten polyamide composition to flow from the vessel in the form of laces. These laces may be cooled and quenched the in a current of water. Next, the laces of polyamide polymer may be granulated by known means and further cooled with water.

[0045] In some embodiments, the polymer composition may be released from the autoclave vessel at the end of Cycle Stage and allowing the molten composition to flow from the vessel in the form of laces. In other embodiments, the polymer composition may be directly supplied to polymer extrusion equipment designed and operated to handle the polymer melt. For example, the disclosed polymer composition can be processed in a screw extruder, for example a twin-screw extruder.

[0046] In one embodiment, a quantity of a diamine such as hexamethylenediamine, can be added so that the total number of acid and the total number of amine groups present are approximately equal. The mixture may then be heated in the autoclave to about 245 °C (or some other functional temperature) whilst being maintained at a desired pressure. While at this temperature or other desired temperature regime, the autoclave pressure may be reduced to atmospheric pressure and further reduced in pressure by application of a vacuum in the known manner, to form the polyamide composition. During these periods of heating and/or pressure reduction poly(ether glycol) dicarboxylic acid, and optionally a -polyetheramine may be injected to the mixture. The autoclave, containing the polyamide composition, may be maintained at this temperature for about 30 minutes. This step may be followed by further heating of the polyamide polymer composition in the autoclave to about 285 °C, for example. The polymer composition may be released from the autoclave by opening a port in the autoclave vessel, and applying 4-5 bar dry nitrogen and allowing the molten polyamide composition to flow from the vessel in the form of laces. These laces may be cooled and quenched the in a current of water. Next, the laces of polyamide polymer may be granulated by known means and further cooled with water.

[0047] The autoclave process described above can provide a polyamide composition with a formic acid method RV of about 20 to about 80. In another embodiment, the autoclave process described above can provide a polyamide composition with a formic acid method RV of about 38 to about 45.

[0048] Optionally, the process may be modified to make a polyamide composition having about 25 to about 130 moles of amine ends per 1000 kilograms of polymer, provided by the addition of an excess of an aqueous hexamethylenediamine solution to the aqueous solution of nylon salt.

[0049] The polymerization reaction can be carried out in a continuous polymerizer.

Examples of continuous polymerizers are known to those of ordinary skill in the art, and one example is disclosed in WO2014179048 to Micka and Poinsatte, the contents of which are incorporated by reference as if set forth at length herein.

[0050] The composition may optionally be partially polymerized in an autoclave or continuous polymerizer and then finished in a solid-phase polymerizer. Examples of solid- phase polymerizers are known to those skilled in the art, and taught by Yao and McAuley, Simulation of continuous solid-phase polymerization of nylon 6,6 (II): processes with moving bed level and changing particle properties Chemical Engineering Science 56 (2001) 5327- 5342.

[0051] The composition may optionally be prepared in an extruder. Such a process can include feeding reactants including diacid and diamine separately or together to a feed throat of an extruder. Alternatively, such a method can include feeding reactants to one or more auxiliary feed throats at one or more points located across the length of the extruder, where the extruder includes various zones which can include melt zones, mixing zones and transport zones. PCT/US16/61604 to Langrick and Hunt (Attorney Docket PI4212) discloses polymerization in a screw extruder with multiple feed throats, and is incorporated by reference as if set forth at length herein. [0052] The nylon polymers and copolyamides described herein can be inherently acid-dyeable. In one embodiment, the number of free amine end groups (AEG) in these polymers is at least 25 moles per 1000 kilograms of nylon polymer. In order to make the polymers more deeply acid dyeing, an enhanced level of free amine end groups can be utilized. More deeply acid dyeing nylon polymers have an enhanced AEG level, e.g., AEG levels of at least 60 to 130 moles per 1000 kilograms of nylon polymer may be used.

[0053] Furthermore, it is noted that a masterbatch of poly(ether glycol) dicarboxylic acid, and optionally a polyetheramine comprising the amine end equivalent of a suitable diacid, e.g. adipic acid, can be made. This masterbatch can then be provided to the autoclave process. In an alternative embodiment, the polyamide composition herein may be made by a masterbatch process in which a flake or melt form is used comprising a poly(ether glycol) dicarboxylic acid, and optionally a polyetheramine dispersed in nylon, either nylon 6,6 or nylon 6. The flake or melt form is then subsequently added as a masterbatch comprising the nylon. In an embodiment, the masterbatch nylon flake containing the poly(ether glycol) dicarboxylic acid, and optionally a polyetheramine and the nylon, in flake form, are both melted. In an embodiment, the nylon flake containing poly(ether glycol) dicarboxylic acid, and optionally a polyetheramine is melted and added to the nylon melt. In either case, the melt is forced from an extruder to a pump, which pumps the polyamide compositions to a pack and a spinneret for making yarns, for example.

[0054] The nylon polymers and copolyamides described herein may also be rendered into a basic dyeing form, i.e., receptive to coloration with base dyes also called cationic dyes. Such base-dyeing compositions are made from polyamide polymer with a cationic dye modifier copolymerized in the polymer. United States Patent No. 5,164,261 to Windley describes the preparation of such cationic dye modified polyamides. In one embodiment, the polymer can be modified during polymerization with from 0.5 wt.% to 4 wt.% of a cationic dye modifier, e.g., 5-sulfoisophthalic acid. Typically, a weighed quantity of the sodium salt of 5-sulfoisophthalic acid can be combined with a known amount of the polyamide precursor salt in an autoclave using standard polymerization procedures known in the art. In one embodiment, the amount of cationic dye modifier present in the polymer can be from about 0.75 wt.% to about 3 wt.%, as determined by total sulfur analysis of the polymer. This amount of cationic dye modifier is reported as equivalent sulfonate groups. The sulfonate group concentration can be at least 25 moles per 1000 kilograms polymer up to about 150 moles per 1000 kilograms polymer. Polyamide Yarns

[0055] The polyamide composition of the present disclosure is particularly useful when spun into yarns. In one embodiment, the poly(ether glycol) dicarboxylic acid, and optionally a polyetheramine can be provided to the polyamide composition, and hence inherent to the yarn itself when formed into a fabric, as opposed to being applied on a fabric. In one embodiment, said yarn exhibits improved hydrophilic properties as measured by various water wicking and moisture regain tests.

[0056] A yarn made from the polyamides described herein can be a multifilament textile yarn in the form of either a low orientation yarn (LOY), a partially oriented yarn (POY) or a fully drawn yarn (FDY). The yarn may be a textured yarn made from partially oriented yarn. Moreover, the yarn may be substantially continuous, i.e. formed by one or more continuous filaments. In other embodiments, a continuous filament can be cut into staple fibers and the latter can be converted into a continuous thread by a spinning process, resulting in a continuous article of manufacture or comprised of shorter fibers. Such yarns may be used to make fabrics, which in turn may be used to make garments.

[0057] In an embodiment, the disclosed polymer can be stored in the form of bead or flake at relative humidity of 50 to 65% for one week and then melt-spun into apparel fiber without an intervening drying step between storage and melt-spinning.

[0058] In one embodiment, apparatuses and methods for spinning yarns are disclosed in United States Patent No. 6,855,425, and similar techniques can be likewise in the context of the polyamides prepared and described herein.

[0059] Yarns made from the polyamides described herein may be textile yarns that are especially useful for apparel fabric applications. For example, having a yarn weight of from 5 to 300 dtex, and a filament weight of from 0.5 to 7 dtex can be desirable. In certain embodiments, the yarn comprises from 1 to 300 filaments. According to some embodiments the yarn comprises 3 to 150 filaments. The linear mass density of a fiber is given in the units of dtex [one dtex means one decitex and equals 1 gram/10,000 meters of yarn]. And the unit of 1 "tex" equals the linear mass density of 1 gram/1000 meters of yarn.

[0060] According to some embodiments the yarn has a DPF (dtex per filament) from

0.5 to 2.5, for example from 1 to 1.5.

[0061] Yarns made from the polyamides described herein can have a filament uniformity in Uster percent (U%) of 1.5% or less, more typically 1% or less. Such uniformity can be desirable in order for the yarn to have the high appearance uniformity needed for apparel applications, and also to reduce yarn breaks in texturing, weaving and knitting operations.

[0062] Yarns made from the polyamides described herein can have an elongation to break of from 20% to 120%. According to some embodiments the yarns have an elongation to break of from 20% to 90%. Typically, the yarns have a tenacity of from 25 to 65 cN/tex, for example from 30 to 45 cN/tex. These tensile properties are all desirable for apparel textile applications. The breaking force is expressed in centi-Newton per tex [cN/tex].

[0063] In certain embodiments, the yarn of the polyamide can have a titanium dioxide content less than 0.1 wt.%, and more typically, less than 0.01 wt.%, giving the yarn a clear or bright luster. In other embodiments, the yarn of the polyamide can have a titanium dioxide content greater than 0.3 wt.% and or even greater than 2 wt.%, giving the yarn a matt or dull luster. Titanium dioxide content between these ranges can also be used, e.g., from 0.1 wt.% to 0.3 wt.%, as well.

[0064] In one specific embodiment, yarns of the polyamide may be prepared by using known melt spinning process technology. With such technology, the granulated polyamide composition made by using the autoclave process, or the melt made by the masterbatch process, can both have an optical brightener therein as described above, and can be provided to the spinning machine. The molten polymer is forwarded by a metering pump to a filter pack, and extruded through a spinneret plate containing capillary orifices of a shape chosen to yield the desired filament cross-section at the spinning temperature. These cross-sectional shapes known in the art can include circular, non-circular, trilobal, hollow and diabolo shapes. Typical hollow filaments can be produced as disclosed in US Pat. N. 6,855,425. Spinning temperatures can range from 270 °C to 300 °C, for example. The bundle of filaments emerging from the spinneret plate is cooled by conditioned quench air, treated with spin finish (an oil/water emulsion), optionally interlaced, e.g. using an interlacing air jet.

[0065] In some embodiments, the continuous yarn thus obtained is cut and transformed into staple fibers, which are subsequently used to produce threads or yarns by spinning, or for manufacturing nonwovens, by hydro-entanglement, needle-punching, ultrasonic bonding, chemical bonding, heat bonding or the like.

[0066] In the case of FDY, the in-line processing on the spinning machine typically includes making several turns around a set of Godet rolls (feed rolls), the number of turns being sufficient to prevent slippage over these rolls, then passing the yarn over another set of rolls (draw rolls) rotating at sufficient speed to stretch the yarn by a predetermined amount (the draw ratio). Finally, the process is continued by heat setting and relaxing the yarn with a steam-box before winding up at a speed of at least 3000 m/min, for example at least 4000m/min _} for example 4800 m/min or more. Optionally, an alternative heat setting (or relaxing) method can be used, such as heated rolls, and an additional set of Godet rolls may be incorporated between draw rolls and winder to control the tension while the yarn is set or relaxed. Also, optionally, a second application of spin finish and/or additional interlacing may be applied before the final winding step.

[0067] In the case of POY, the additional in-line processing typically includes only making an S-wrap over two Godet rolls rotating at the same speed, and then passing the yarn to a high-speed winder, winding at a speed of at least 3000 m/min, for example at least 4000m/min, for example 4800 m/min or more. Use of the S-wrap is beneficial to control tension, but not essential. Such a POY may be used directly as a fiat yarn for weaving or knitting, or as a feedstock for texturing.

[0068] The LOY spinning process is similar to POY except that a windup speed of

1000 m/min or below is used. These low orientation yarns, in general, are further processed via a second stage, e.g., on a conventional draw-twister or draw-wind machine.

[0069] In one embodiment, the polyamide polymer disclosed herein can be highly suited for spinning into continuous filaments which may be converged to form multifilament yarns. The process of spinning synthetic polymers as continuous filaments and forming multifilament yarns is known to the skilled person. In general, successful spinning of filaments uses a spinneret plate having at least a single capillary orifice. The capillary orifices correspond to each individual filament comprising the yarn. Circular and non- circular cross-section spinneret capillary orifices (or extrusion orifice) are employed depending upon the cross-sectional shape sought for the filament. In general, for a certain polymer throughput G (e.g., in grams per minute) per capillary, the following equation applies;

[0070] In this equation, p is the polymer melt density (e.g., for melted nylon 6,6 at

290°C equal to 1.0 gram per cm ³ ), D is the diameter (equal to twice the radius) of the capillary assuming a circular orifice, and v is the velocity of the filament.

The extrusion velocity is given by the following equation:

[0071] In one embodiment, the polymer is extruded at an extrusion velocity in the range of 20 centimeters per second to 80 centimeters per second. In another embodiment, the freshly extruded filaments can be quenched with conditioned air in the known manner. In this step, the individual filaments are cooled in a quench cabinet with a side draft of conditioned air and converged and oiled with a primary finish, as known in the art, into a yam. The yarn is forwarded by feed roll onto a draw roll pair where the yarn is stretched and oriented to form a drawn yarn which is directed by roll into a yarn stabilization apparatus. Such a stabilization apparatus is common to the art and here optionally employed as a yarn post- treatment step. Finally, the yarn is wound up as a yarn package at a yarn speed in the range of 1000 to 6500 meters per minute. The yarn RV (or relative viscosity by the formic acid method) is about 20 to about 80.

[0072] In an embodiment, the yarn is a drawn yarn with elongation of 22% to about

60%, the boiling water shrinkage is in the range of 3% to about 10%, the yarn tenacity is the range of 3 to about 7 grams per denier, and the RV of the yarn can be varied and controlled well within a range of about 20 to about 80, for example about 40 to about 60.

[0073] A derived parameter characterizing the superior properties of this yam is called the Yarn Quality and found by the product of the yarn tenacity (grams per denier) and the square root of the % elongation, as in Equation 3.

[0074] The Yarn Quality is an approximation to the measure of yarn "toughness." As is known to those skilled in the art, the area under the yarn load elongation curve is proportional to the work done to elongate the yarn. Where tenacity is expressed in terms of force per unit denier, for example, and the elongation expressed as a per cent change per unit of length, the load elongation curve is the stress-strain curve. In this case, the area under the stress-strain curve is the work to extend the yarn or the yarn toughness. The yarn quality improvement provides an apparel polyamide yarn which is more acceptable in varied applications. These applications may include, without limitation, warp knit fabrics, circular knit fabrics, seamless knit garments, hosiery products, nonwoven fabrics and light denier technical fabrics.

[0075] In certain embodiments, the polyamide yarns have different dyeing characteristics with anionic dyes or cationic dyes. These dyeing characteristics may arise from different numbers of amine end groups. The concentration of amine end groups (AEG) influences how deeply the polyamide is dyed by anionic dyes. Alternatively or additionally, the polyamides may contain anionic end groups, such as sulfonate or carboxylate end groups, that render the polyamide cationic-dyeable. [0076] In certain embodiments, the polyamide yarns are dyed with fiber reactive dyes which incorporate vinylsulfonyl and/or β-sulfatoethylsulfonyl groups. Such fiber reactive dyes are known from United States Patent No. 5,810,890.

[0077] In certain embodiments, the polyamide yarns are dyed with fiber reactive dyes which incorporate halogen derivatives of nitrogen hetrocyclic groups, such as, triazine, pyrimidine and quinoxaline. Such fiber reactive dyes are described, for example, in United States Patent No. 6,869,453.

[0078] In other embodiments, the filaments comprise an amine component of hexamethylenediamine.

[0079] In other embodiments, the filaments comprise an amine component which is a mixture of hexamethylenediamine with at least 20 wL% of methyl pentamethylenediamine based on the total weight of diamine,

[0080] In still other embodiments, the polyamides may comprise nylon 6.

[0081] The following testing discussion can be used to characterize the various parameters as discussed herein. Yarn tenacity and the yarn elongation can be determined according to ASTM method D 2256-80 (known at the time of filing the present disclosure with the United States Patent and Trademark Office) using an INSTRON tensile test apparatus (Instron Corp., Canton, Massachusetts, USA 02021) and a constant cross head speed. Tenacity is expressed as centi-Newtons per tex (cN/tex) or grams of force per denier, and the elongation percent is the increase in length of the specimen as a percentage of the original length at breaking load.

[0082] Yarn linear density evenness, also known as the yarn Uster percent (U%), can be determined using a Uster evenness tester 3, type C, which is known in the art to the skilled person.

[0083] Polymer amine ends can be measured by direct titration with standardized perchloric acid solution of weighed polymer samples taken up in solution.

[0084] The moisture regain of a polymer may be measured by the following method.

A sample (100 g) of the polymer is dried for 18 hours at 80 °C under vacuum. The initial moisture level of this dried polymer sample is, for example, measured using an Aquatrac (PET version (4 Digit); Brabender Messtechnik) at 160 °C setting, on about 1.9 g polymer. A moisture level measured using this method of less than 0.5 wt.% is taken to indicate that the polymer had been dried sufficiently.

[0085] The dried sample is then immersed in demineralized water (500 g) at ambient temperature (20 °C) without any agitation. After 48 hours, a sample is removed (approx. 10 g) and patted dry with an absorbent tissue. A portion of the sample (approx. 5 g; weight of wet sample) is weighed accurately into a foil dish and placed in an oven at 80 °C under vacuum for 18 hours. The dish is removed and placed in a desiccator to cool, and then reweighed (weight left after drying). This procedure is repeated at intervals thereafter (e.g. 72, 144, 190 and 220 hours) up to 220 hours. Moisture uptake is determined by the following calculation:

[0086] The moisture regain of the polymer is defined as the moisture uptake after 220 hours or until the sample has reached moisture uptake equilibrium (which is defined as a weight change of no more than 1% in a 24-hour period), whichever is the earlier. Thus, if moisture uptake equilibrium has not been reached by 220 hours the moisture regain is the moisture uptake at 220 hours. When the moisture uptake equilibrium is reached before 220 hours, the moisture regain is the average (mean) of the moisture uptake for the first two consecutive measurements taken at equilibrium.

[0087] Alternatively, the moisture regain may be measured by a method such as DIN

53814, which involves the saturation of textile samples with deionized water at 20 °C for 2 hours, removal of the water by centrifugation at 4000 m/min, and measuring the change in weight upon drying at 105 °C until no further weight loss is observed.

[0088] The water wicking rates of fabrics constructed from the yarn can be measured by vertically immersing the bottom 1.8 inches (4.6 cm) of a one inch (2.5 cm) wide strip of the scoured fabric in de-ionized water, visually determining the height of the water wicked up the fabric, and recording the height as a function of time. "Initial wicking rate" means the average wicking rate during the first two minutes of the wicking test.

[0089] A fabric or garment "Percent Dry Time" test can be used to characterize the hydrophilic polyamide yarns, fabric and garments. These are also known as percent dry time tests or "horizontal wicking" determinations. Percent dry time tests are done using a balance and computer; e.g., Mettler balance AE163 and computer running a Mettler BalanceLink 3.0 program. The weight of a circular sample of fabric 2 inches (5.1 cm) in diameter is obtained and recorded. Using an automated pipette, 0.10 g of tap water is placed on the balance and its weight recorded. The circular fabric sample is immediately centered over and then placed on the water. The total weight of fabric and water is recorded at that time (time = zero minutes) and every two minutes thereafter for the next 30 minutes. Percent dry results for a given time are calculated according to the following formula: %Dry = 100 - [W _total - W _fabric )

/W _H2O ] x 100.

EXAMPLES

[0090] The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how to perform the methods and use the compositions and compounds disclosed and claimed herein. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), but some errors and deviations should be accounted for. Unless indicated otherwise: parts are parts by weight, temperature is in °C, and pressure is in atmospheres. Standard temperature and pressure are defined as 25 °C and 1 atmosphere.

Materials used in the Examples

[0091] PoIy(ethylene glycol) with a number average molecular weight, M _n , of 2000

Daltons was obtained from a commercial source, Alfa Aesar (product code B22181).

[0092] Hexamethylenediamine or HMD is commercially available from INVISTA

Intermediates, with offices in Wichita, Kansas and Wilmington, Delaware, USA.

[0093] The term "poly(ether glycol) dicarboxylic acid", as used herein, refers to a class of poly(ethylene glycol)bis(carboxymethyl) ether having a general chemical structure of wherein n is a numerical value.

[0094] Poly(ether glycol) dicarboxylic acid with a number average molecular weight,

M _n , of 600 (herein referred to as Compound 2 in the examples of this disclosure) was obtained from a commercial source, VWR International.

[0095] The term "RE 2000", as used herein, refers to ELASTAMINE ^® RE-2000 amine; a commercial product available from Huntsman Corp. ELASTAMINE ^® RE-2000 amine is a water soluble aliphatic polyetherdiamine derived from a propylene oxide capped polyethylene glycol. Polyetheramines of this type are useful in a variety of polymers.

Nylon 66 Salt

[0096] As used herein, the term "Nylon 66 salt" refers to a salt formed via an acid- base neutralization reaction between the amine groups of at least one diamine and the acidic protons from the carboxylic acid groups of at least one dicarboxylic acid.

[0097] The dicarboxylic acid component of the salt is suitably at least one dicarboxylic acid of the formula (I): H0 ₂ C-R ¹ -C02H, wherein R ¹ represents a divalent aliphatic, cycloaliphatic or aromatic radical or a covalent bond. R ¹ suitably comprises from 2 to 20 carbon atoms, for example 2 to 12 carbon atoms, for example 2 to 10 carbon atoms. R ¹ may be a linear or branched, for example linear, alkylene radical comprising 2 to 12 carbon atoms, or 2 to 10 carbon atoms, for example 2, 4, 6 or 8 carbon atoms, an unsubstituted phenylene radical, or an unsubstituted cyclohexylene radical. Optionally, R ¹ may contain one or more ether groups. For example, R ¹ is an alkylene radical, for example a linear alkyiene radical, comprising 2 to 12 carbon atoms, or 2 to 10 carbon atoms, for example 2, 4, 6 or 8 carbon atoms.

[0098] Specific examples of suitable dicarboxylic acids include hexane-l,6-dioic acid

(adipic acid), octane- 1,8-dioic acid (suberic acid), decane-l,10-dioic acid (sebacic acid), dodecane-l,12-dioic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxyIic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanediacetic acid, 1,3- cyclohexanediacetic acid, benzene-l,2-dicarboxylic acid (phthalic acid), benzene-1,3- dicarboxylic acid (isophthalic acid), benzene- 1,4-dicarboxylic acid (terephthalic acid), 4,4'- oxybis(benzoic acid), and 2,6-naphthalene dicarboxylic acid. A preferred dicarboxylic acid is hexane-l,6-dioic acid (adipic acid).

[0099] The diamine component of the salt is suitably at least one diamine of the formula (II): H ₂ N-R ² -NH2, wherein R ² represents a divalent aliphatic, cycloaliphatic or aromatic radical. R ² suitably comprises from 2 to 20 carbon atoms, for example 4 to 12 carbon atoms, for example 4 to 10 carbon atoms. R ² may be a linear or branched, for example linear, alkylene radical comprising 4 to 12 carbon atoms, for example 4 to 10 carbon atoms, for example 4, 6 or 8 carbon atoms, an unsubstituted phenylene radical, or an unsubstituted cyclohexylene radical. Optionally, R ² may contain one or more ether groups. For example, R ² is an alkylene radical, for example a linear alkylene radical, comprising 4 to 12 carbon atoms, or 4 to 10 carbon atoms, for example 2, 4, 6 or 8 carbon atoms.

[00100] Specific examples of suitable diamines include tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, octamethylene diamine, decarnethylene diamine, dodecamethylene diamine, 2-methylpentamethylene diamine, 3- methylpentamethylene diamine, 2-methylhexamethylene diamine, 3-methylhexamethylene diamine, 2,5-dimethylhexamethylene diamine, 2,2,4-trimethylhexamethylene diamine, 2,4,4- uimethylhexamethylene diamine, 2,7-dimethyloctamethylene diamine, 2,2,7,7- tetramethyloctamethylene diamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediarnine, 1,4- cyclohexanediamine, 4,4 ^, -diaminodicyclohexyImethane, benzene- 1,2-diamine, benzene- 1,3- diamine and benzene- 1,4-diamine. A preferred diamine is hexamethylene diamine. [00101] For example, the dicarboxylic acid component of the salt may be at least one dicarboxylic acid of the formula (I), wherein R ¹ is an alkylene radical comprising 2 to 12 carbon atoms, or 2 to 10 carbon atoms, for example 2, 4, 6 or 8 carbon atoms, and the diamine component of the salt may be at least one diamine of the formula (Π) wherein R ² is an alkylene radical comprising 4 to 12 carbon atoms, or 4 to 10 carbon atoms, for example 2, 4, 6 or 8 carbon atoms.

[00102] For instance, at least one dicarboxylic acid may be selected from hexane-1,6- dioic acid (adipic acid), octane-l,8-dioic acid (suberic acid), decane-lJO-dioic acid (sebacic acid), and dodecane-l,12-dioic acid, and at least one diamine may be selected from tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, octamethylene diamine, decamethylene diamine, dodecamethylene diamine, 2-methylpentamethylene diamine, 3-methylpentamethylene diamine, 2-methylhexamethylene diamine, 3- methylhexamethylene diamine, 2,5-dimethylhexamethylene diamine, 2,2,4- trimethylhexamethylene diamine, 2,4,4-trimethylhexamethyIene diamine, 2,7- dimethyioctamethylene diamine, and 2,2,7,7-tetramethyIoctamethylene diamine.

[00103] Preferred salts include those in which the dicarboxylic acid component comprises one or more of hexane-l,6-dioic acid (adipic acid), octane-l,8-dioic acid (suberic acid), decane-l,10-dioic acid (sebacic acid), and dodecane-l,12-dioic acid and the diamine component comprises one or more of tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, octamethylene diamine, decamethylene diamine, dodecamethylene diamine. A particularly preferred salt is the neutralization salt formed from hexane-l,6-dioic acid (adipic acid) and hexamethylene diamine ("Nylon 66 salt").

Example 1 - Synthesis ofPoly(ethylene glycol)his(carboxymethyl) ether (Compound 1)

[00104] All glassware was oven-dried prior to use.

[00105] Polyethylene glycol) (PEG, M„ of 2000 Daltons, 50 g, 25 mmol) was mixed with anhydrous toluene (250 ml), warmed to 30 °C and stirred until the solids dissolved completely (in about 30 min). The reaction mixture was held at 30 °C throughout the following process. A solution of potassium i-butoxide (75 ml, 1M in t-butanol, 75 mmol) was added over 30 min. Throughout the addition, minimal temperature rise was seen and the colorless solution became yellow. When the addition was complete the solution was stirred for 1 hour. Ethyl bromoacetate (8.3 ml, 75 mmol) was added over 30 min at a rate that kept the internal temperature below 45°C (to control exothermic process). The resulting mixture was stirred overnight. [00106] At this point an in-process check was carried out by evaporating a sample and obtaining a 1H NMR spectrum using deuterated DMSO as solvent. Completion of the reaction was defined as the absence of a triplet at δ 4.6 ppm that corresponded to the hydroxyl protons of the PEG starting material.

[00107] The mixture was evaporated under reduced pressure until a viscous oil remained. This viscous oil tended to solidify if left to cool.

[00108] The above viscous oil was mixed with aqueous sodium hydroxide solution (250 ml, 1M, 250 mmol) and stirred at room temperature for four hours. The residue dissolved steadily to form an orange-colored solution. The solution was acidified slowly (to control the exotherm) with aqueous hydrochloric acid solution (130 ml, 2M, 260 mmol) until the pH was less than 4 (a color change to near-colorless was seen at this point). The solution was allowed to cool to room temperature, and then extracted twice with dichloromethane. The extracts were combined, washed with water, dried over anhydrous sodium sulfate and filtered. The organic solution was evaporated under reduced pressure until less than 50 ml volume remained. The residue was added drop-wise to a beaker of stirred f-butyl methyl ether (300 ml) to form an off-white precipitate. The solids were filtered and dried to give about 46.3 g of product diacid Compound 1.

[00109] For another method of making a poly(ether glycol) dicarboxylic acid, see the journal article Greenwald, R. B. etal, J. Med Chem., 1996, 39, 424-431, at 430.

[00110] Note that if the product yield obtained was low, the aqueous phase may not have been acidified sufficiently. If this was the case, additional product could be obtained by adding further dilute hydrochloric acid to the aqueous phase until the pH was less than 4, and extracting with dichloromethane as described above.

Characterization

[00111] The product may be characterized by NMR, FTIR and/or acid value.

[00112] In subsequent examples of this disclosure, Compound 1 (derived from M _n 2000 Dalton PEG and according to Example 1) was used in Example 2, while Compound 2 (derived from M _n 600 Dalton PEG) was used in Examples 3 through 5 and in Example 7. Such Poly(ether glycol) dicarboxylic acids may be either synthesized from the corresponding PEG or obtained from commercial sources. Example 2 - Polyamide with 8 wt.% Poly (ether glycol) dicarboxylic acid (Compound 1) Salt Preparation

[00113] To a 20-Liter stirred and jacketed temperature controlled glass vessel filled with nitrogen and purged with nitrogen was added 4000 g water and the vessel was warmed to 35 °C. Nylon 66 salt (3661 g, 13.96 mol), Compound 1 (280.8 g, 0.14 mol) according to Example 1, and 80 % (by weight) aqueous hexamethylenediamine (16.3 g, 0.14 mol) were added (calculated to balance the carboxylic acid ends of Compound 1) and the mix was stirred until dissolved to produce a roughly 50 wt.% strength salt solution. On polymerization this produced approximately 3500 g of polymer.

Polymerization

[00114] The above salt preparation solution was added to a 15-Liter autoclave. The polymer was targeted to contain about 8 wt.% Compound 1 with respect to the final polymer weight,

[00115] For the polymerization, no evaporator was used, but rather a serial heating cycle 0 (CO) was developed to provide a position of salt concentration similar to an evaporator batch. Essentially in "CO," the mixture was heated up to around 185 °C and vented at 137 psia for a period of 87 minutes while the temperature was raised to about 202 °C before going into serial heating cycle (CI).

[00116] The process for the serial heating cycles was as follows: CI - T started at about 202 °C finished at about 220 °C, pressure reaching 265 psia defined the end of CI, and took about 18 min; C2 - 265 psia for 22 min, T was raised to 242 °C temperature defined the end of C2; serial heating cycle 3 (C3) - pressure was let down to 14.5 psia (atm) over 35 min, temperature was raised to a final temperature of 275 °C; serial heating cycle 4 (C4) - 6 min at atmospheric pressure, applied vacuum of 400 mbar for 30 min, then released with nitrogen back to atmospheric and held for 5 min. The polymer was then cast in the water bath. The polymer was characterized with the results provided in Table 1.

TABLE 1 Example 3—Polyamide with 12 wt.% ofPofy (ether glycol) dicarboxylic acid Salt Preparation

[00117] To a 20-Liter stirred and jacketed temperature controlled glass vessel filled with nitrogen and purged with nitrogen was added 4000 g water and the vessel was warmed to 35 °C. Nylon 66 salt (3423 g, 13.05 mol), PEG (M _n 600) dicarboxylic acid (Compound 2; 439 g, 0.73 mol), and 80% (by weight) aqueous hexamethylenediamine (85.0 g, 0.73 mol) were added (calculated to balance the carboxylic acid ends of PEG diacid) and the mix was stirred until dissolved to produce a roughly 50 wt.% strength salt solution. On

polymerization this produced approximately 3500 g of polymer.

Polymerization

[00118] The above Salt Preparation solution was added to a 15-Liter autoclave. The polymer was targeted to contain about 12 wt.% Compound 2 with respect to the final polymer weight.

[00119] For the polymerization, no evaporator was used, but rather a serial heating cycle 0 (CO) was developed to provide a position of salt concentration similar to an evaporator batch. Essentially in "CO" the mixture was heated up to around 185 °C and vented at 137 psia for a period of 90 minutes while the temperature was raised to about 202 °C, before going into serial heating cycle 1 (CI).

[00120] The process for the serial heating cycles was as follows: C 1 - T started at about 202°C and finished at about 220 °C, pressure reaching 265 psia defined the end of CI ; C2 - 265 psia held for 24 min, T was raised to 243 °C temperature defined the end of C2; serial heating cycle 3 (C3) - pressure let down to 14.5 psia (1 atm) over 25 min, temperature was raised to a final temperature of 274 °C; and serial heating cycle 4 (C4) - 11 min at atmospheric pressure, applied vacuum of 350 mbar for 24 min, then released with nitrogen back to atmospheric and held for 6 min. The polymer was then cast in the water bath. The polymer was characterized with the results provided in Table 2.

TABLE 2 Example 4 - Polyamide with 20 wt. % of Poly (ether glycol) dicarboxylic acid

Salt Preparation

[00121] To a 20-Liter stirred and jacketed temperature controlled glass vessel filled with nitrogen and purged with nitrogen was added 4000 g water and the vessel was warmed to 35 °C. Nylon 66 salt (3038 g, 11.58 mol), PEG (M _n 600) dicarboxylic acid (Compound 2; 731.6 g, 1.22 mol), and 80% (by weight) aqueous hexamethylenediamine (141.7g, 1.22 mol) were added (calculated to balance the carboxylic acid ends of PEG diacid) and the mix was stirred until dissolved to produce a roughly 50 wt.% strength salt solution. On

polymerization this produced approximately 3500 g of polymer.

Polymerization

[0Θ122] The above Salt Preparation solution was added to a 15 -Liter autoclave. The polymer was targeted to contain about 20 wt.% Compound 2 with respect to the final polymer weight.

[00123] For polymerization, no evaporator was used. Rather, a serial heating cycle 0 (CO) was developed to provide a position of salt concentration similar to an evaporator batch. Essentially in "CO" the mixture was heated up to around 185 °C and vented at 137 psia for a period of 87 minutes while the temperature was raised to about 202 °C, before going into serial heating cycle 1 (CI).

[00124] The process for the serial heating cycles was as follows: CI - T started at about 202 °C and finished at about 220°C, pressure reaching 265 psia defined the end of CI, took about 17 min; C2 - 265 psia was held for 25 min, T was raised to 243 °C temperature defined the end of C2; serial heating cycle 3 (C3) - pressure was let down to 14.5 psia (1 atm) over 36 min, temperature was raised to a final temperature of 275 °C; and serial heating cycle 4 (C4) - 5 min at atmospheric pressure, vacuum of 350 mbar for 30 min, then was released with nitrogen back to atmospheric and was held for 10 min. The polymer was then cast in the water bath. The polymer was characterized with the results provided in Table 3.

TABLE 3 Example 5 - Polyamide with 8 wt. % of Poly (ether glycol) dicarboxylic acid made with late addition of the Poly (ether glycol) dicarboxylic acid

Salt Preparation

[00125] To a 20-Liter stirred and jacketed temperature controlled glass vessel filled with nitrogen and purged with nitrogen was added 4000 g water and the vessel was warmed to 35 °C. Nylon 66 salt (3615 g, 13.78 mol) _} and the mix was stirred until dissolved to produce a roughly 50 wt.% strength salt solution.

Polymerization

[00126] The above Salt Preparation solution was added to a 15-Liter autoclave.

[00127] For the polymerization, no evaporator was used, but rather a serial heating cycle 0 (CO) was developed to provide a position of salt concentration similar to an evaporator batch. Essentially in "CO" the mixture was heated up to around 185 °C and vented at 137 psia for a period of 90 minutes while the temperature was raised to about 202 °C, before going into serial heating cycle 1 (CI).

[00128] The process for the serial heating cycles was as follows: CI - T was started about 202°C and finished at about 220 °C, pressure reaching 265 psia defines end of CI; C2 - 265 psia was held for 24 min, T was raised to 244 °C temperature defined the end of C2; serial heating cycle 3 (C3) - pressure was let down to 14.5 psia (1 atm) over 25 min, then a mixture of PEG (M _n 600) dicarboxylic acid (Compound 2; 292.6 g, 0.49 mol) and 80% (by weight) aqueous hexamethylenediamine (71 g, 0.49 mol) was injected in and the temperature was raised to a final temperature of 285 °C; and serial heating cycle 4 (C4) - 11 min at atmospheric pressure, applied vacuum of 350 mbar for 24 min, then released with nitrogen back to atmospheric and held for 6 min. The late addition of Compound 2 was targeted to give about 8 wt.% Compound 2 with respect to the final polymer weight. The polymer was then cast in the water bath. The polymer was characterized with the results provided in Table 4.

TABLE 4 Examples 6fa-g) - Melt Spinning and Fiber Testing

[00129] Using similar procedures and methods to those described in Examples 2 through 5, seven polyamide test samples were prepared, melt-spun into fibers and tested to determine their melt spinning behavior and drawing properties. Table 5 below represents these seven test polyamide samples in terms of the composition and measured water content before spinning. In Table 5, Compound 1 refers to poIy(ether glycol) dicarboxylic acid prepared using a 2000 Daltons Mn polyfethylene glycol) and according to Example 1, while Compound 2 refers to poIy(ether glycol) dicarboxylic acid with a number average molecular weight of 600 Daltons. In Example 6(f) no additives were present in the N66 polyamide, and this was used as a control sample. In Example 6(g), only the RE 2000 component was present in the N66 polyamide at about 10 wt.%. RE 2000 refers to ELAST AMINE ^® RE- 2000 amine; a commercial product available from Huntsman Corp.

TABLE 5

[00130] Partially oriented yarn (POY) spinning was performed using a single-screw extruder (e.g.: Haake extruder or equivalent) and a winder (e.g.: Barmag SW 46 or equivalent). The POY yarn was drawn to a fully drawn yarn (FDY) using a two-stage Zinser draw-twisting setup. Mechanical properties of the yarn were determined using a Textechno Statimat M tensile tester. Water uptake was determined according to the water retention capacity method No. DIN 53814.

[00131] To improve the spinning stability the single filament fineness was achieved by using thirteen 300-um diameter holes in the spinneret. The single filament titre was increased from 2.75 to 5.07 dtex. The Example 6(c) through 6(g) samples were successfully spun using the conditions shown in Table 6 below. The successfully spun POY yarns were drawn to an elongation of 25%. For each sample four yarns were combined and knitted.

TABLE 6

[00132] In all test cases, the pump rotational speed was maintained at 24 RPM and the pump output was 1.2 cm ³ . The winder conditions were maintained at 4000 m/min winding speed, 3980-3990 m/min Godet speed and 1007 Traverse DH.

[00133] The mechanical properties of the above POY and FDY were determined and are represented in Table 7 below. The 6(a) and 6(b) yam samples were not available for testing as the winding for these samples encountered some technical difficulty.

TABLE 7

[00134] The term "tex" is a unit of measure for the linear mass density of fibers, yarns and thread and is defined as the mass in grams per 1000 meters. The decitex, abbreviated as "dtex", is a unit of measure for the linear mass density of fibers, yarns and thread and is defined as the mass in grams per 10,000 meters. The unit "cN/tex" for tenacity

measurements means centi-Newton per tex.

[00135] Water uptake was determined by filling the yarn samples into dried weighed vessels, the vessels were filled with deionized water at 20 °C. After 2 hours, the water was removed by centrifugation at 4000 RPM. The samples were dried at 105 °C until no further weight reduction could be observed. The water uptake data are represented in Table 8 below.

TABLE 8

Example 7— 24-Liter Autoclave Batch Preparation ofPolyamide with 8 wt.% Poly (ether glycol) dicarboxylic acid

Salt Preparation

[00136] Following the procedures according to Example 2, multiple batch preparations were performed using a 24-Liter stirred and jacketed temperature-controlled glass vessel filled with nitrogen and purged with nitrogen. The initial charge for each batch was about 15,000 g, which included about 6,800 g of Nylon 66 salt, about 7,500 g of water, about 549 g of Compound 2 [i.e., dicarboxylic acid prepared from M _n 600 Dalton PEG] and about 133 g of 80% (by weight) aqueous hexamethylene diamine. The mix was stirred until dissolved to produce roughly 50 wt.% strength salt solution. On polymerization, each batch produced approximately 6,500 g of polymer.

Polymerization

[00137] The polymer was targeted to contain about 8 wt.% Compound 2 with respect to the final polymer weight. For the polymerization, the temperature-pressure cycles as described in Example 2 through 5 were employed and no evaporator was used. Upon completing the polymerization, the polymer from each batch was cast in the water bath.

[00138] Using the Example 7 procedures, a total of sixteen 24-Liter autoclave batches was sequentially run to produce sufficient quantities of the disclosed polymer containing about 8 wt.% of Compound 2 with respect to the final polymer weight. This multiple batch production also demonstrated that the disclosed method resulted in consistent quality product from batch-to-batch production. The measured RV values ranged between 37 - 43 with an average of about 39 RV and the AEG values ranged between 37 - 50 with an average of about 44 AEG.

[00139] Table 9 below gives a summary of polymer products that were prepared and characterized according to the present disclosure.

TABLE 9

[00140] A representative polymer sample was constituted using the multiple batch- made product of Example 7 and its color parameters [as listed in the last row of Table 9] were measured to be L* = 78.83, a* =-0.69, b* = 10.42, and Yellowness Index [YI] of 26.07.

[00141] The combined polymer material, as produced in multiple batches of Example 7, can be useful for fiber spinning and/or other downstream applications as conventionally known in the field.

[00142] While the illustrative embodiments of the disclosure have been described with particularity, it will be understood that various other modifications will be apparent to and may be readily made by those skilled in the art without departing from the spirit and scope of the disclosure. Accordingly, it is not intended that the scope of the claims hereof be limited to the examples and descriptions set forth herein but rather that the claims be construed as encompassing all the features of patentable novelty which reside in the present disclosure, including all features which would be treated as equivalents thereof by those skilled in the art to which the disclosure pertains.

Embodiments

1. Polyamide comprising the reaction product of:

a. an aliphatic diamine; and

b. a diacid, wherein at least a portion of the diacid is poly(ether glycol) dicarboxylic acid.

2. The polyamide of embodiment 1 wherein the poly(ether glycol) dicarboxylic acid has a number-average molecular weight (Mn)≥ 250 Daltons and≤ 2000 Daltons.

3. The polyamide of embodiment 2 wherein the poly(ether glycol) dicarboxylic acid is an aliphatic dicarboxylic acid.

4. The polyamide of embodiment 1 characterized by moisture regain of from≥ 5% to≤ 35%.

5. The polyamide of embodiment 1 wherein the aliphatic diamine is

hexamethylenediamine.

6. The polyamide of embodiment 1 wherein the number of repeating units containing an aromatic moiety is selected from the group consisting of:

a. ≤ 10 wt.% of repeating units; and

b. ≤ 5 wt.% of repeating units.

7. The polyamide of embodiment 1 formed by a condensation reaction in the presence of water at pressure≥ 1 bar.

8. The polyamide of embodiment 1, characterized by an elongation to break of from 20% to 90% when spun into a yarn.

9. The polyamide of embodiment 1, wherein the poly(ether glycol) dicarboxylic acid is present in an amount ranging from≥1% to≤50% by weight, based upon the total weight of dicarboxylic acid in the polyamide.

10. The polyamide of embodiment 9, wherein the poIy(ether glycol) dicarboxylic acid is present in an amount ranging from≥5 wt.% to≤25 wt.% by weight, based on the total weight of the dicarboxylic acid in the polyamide.

11. The polyamide of embodiment 10, wherein the poly(ether glycol) dicarboxylic acid is present in an amount ranging from≥8 wt.% to≤20 wt.% by weight, based on the total weight of the dicarboxylic acid in the polyamide.

12. The polyamide of embodiment 1, wherein the copolyadipamide has a relative

viscosity from≥20 to≤80 according to the formic acid test of ASTM D789-86. 13. The polyamide of embodiment 1, wherein the copolyadipamide has an amine end value from≥25 to≤130 moles of amine ends per 1000 kilograms of polymer.

14. The polyamide of embodiment 1, characterized by at least one selected from:

a. an L* color coordinate from≥75 to≤85;

b. an a* color coordinate from≥-5 to≤5;

c. a b* color coordinate from≥5 to≤25; and

d. a yellowness index from≥25 to≤45.

15. The polyamide of embodiment 1, further comprising at least one selected from:

a. ≥0.01 wt.% to≤2 wt.% by weight of titanium dioxide; and

b. 0.01 to 1 wt.% by weight of an optical brightener, wherein the optical

brightener is not titanium dioxide.

16. A copolyadipamide comprising:

a. a diacid wherein all C-H bonds are saturated;

b. an aliphatic poly(ether glycol) dicarboxylic acid; and

c. at least one diamine that does not contain an ether moiety or an aromatic

moiety;

wherein the copolyadipamide is characterized by moisture regain of≥5% and≤35% by weight, based on the weight of the copolyadipamide in air of relative humidity of 50 to 65%.

17. A process for producing a copolyadipamide, comprising:

a. contacting an aliphatic diacid, a poly(ether glycol) dicarboxylic acid, at least one diamine that does not contain an ether moiety, and optionally a nylon salt that does not contain an ether moiety, to form a mixture; and

b. heating the mixture to a temperature sufficient to polymerize the mixture and form a copolyadipamide.

18. An article made from copolyadipamide of any one of embodiments 1-17, said article selected from the group consisting of:

a. fiber; and

b. fabric, wherein the fabric has the structure of at least one selected from woven, knit and direct-laydown nonwoven. 19. The article of embodiment 18 comprising fabric, wherein the fabric loses less than 10% of its original weight when immersed in water at 100°C at 1 bar pressure for 10 minutes.

20. The article of embodiment 19 wherein the fabric loses a portion of its original weight, measured in air of 50 to 65% Relative Humidity, wherein the portion of weight lost is selected from the group of values consisting of ≤8%,≤7%,≤6%≤5%,≤4%, ≤3%,≤2% and≤l%.