TW201821477A - Nylon polymer - Google Patents

Nylon polymer

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Publication number
TW201821477A
TW201821477A TW106124486A TW106124486A TW201821477A TW 201821477 A TW201821477 A TW 201821477A TW 106124486 A TW106124486 A TW 106124486A TW 106124486 A TW106124486 A TW 106124486A TW 201821477 A TW201821477 A TW 201821477A
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TW
Taiwan
Prior art keywords
polyamine
dicarboxylic acid
wt
poly
weight
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Application number
TW106124486A
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Chinese (zh)
Inventor
麥可 A 阿米泰格
麥可 D 班斯泰德
查爾斯 R 蘭格瑞克
米林德 V 坎特克
凱斯 溫斯頓
Original Assignee
英商英威達紡織〈英國〉有限公司
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Priority to US201662372477P priority Critical
Priority to US62/372,477 priority
Application filed by 英商英威達紡織〈英國〉有限公司 filed Critical 英商英威達紡織〈英國〉有限公司
Publication of TW201821477A publication Critical patent/TW201821477A/en

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/265Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/40Polyamides containing oxygen in the form of ether groups

Abstract

A polyamide comprising a diamine and a poly(ether glycol) dicarboxylic acid, wherein the poly(ether glycol) dicarboxylic acid has a number-average molecular weight (Mn) of at least 250 Daltons.

Description

Nylon polymer

Over the years, there have been a variety of methods for incorporating polyether segments into polyamines to improve the properties of yarns made from such polyamides. Within polyamines, poly(hexanediamine) exhibits advantageous properties including high temperature stability, tensile strength and abrasion resistance. Poly(hexanediamine) also enjoys relatively uniform inter-batch dyeability. It can be produced as produced (from the melt) or by melting and extruding wafers or pellets. It may be desirable to provide a polymer having the characteristics of desired temperature stability, tensile strength, and abrasion resistance of poly(hexanediamine) while improving water uptake properties. Patent 3,946,089 to Furukawa et al. relates to block copolymers comprising a polyamine moiety and a polyether segment. Japanese Published Application No. 1983/0156353 (Abstract) relates to a copolymer comprising an aminoaryl group. U.S. Patent 4,873,296 to Ciaperoni et al. is directed to A-B-A block copolymers wherein B comprises modified poly(ethylene glycol). U.S. Patent No. 4,963,638 to Pazos et al. is directed to a superabsorbent thermoplastic polymer comprising a soft segment of poly(oxyethylene) glycol. Japanese Patent Application JP 1990/0203954 discloses a polyamine which is mixed with a poly(ethylene glycol) complex produced in the presence of a metal halide. European Patent 0 504 784 relates to polyetheresteramines containing from 20 wt.% to 40 wt.% of poly(ether)diol/dicarboxylic acid monomers. U.S. Patent No. 5,306,761 to Ohwaki et al. is directed to polyamines containing copolymerized polyalkylene oxide units. U.S. Patent No. 6,420,045 to Faulhammer et al. is directed to a polyamine having a hydrophilic block. Although the desired modification of certain properties (e.g., water uptake) can be brought about by incorporating an ether backbone into the polyamine via the amine component, it has also been found to impair some other properties of the condensed polyamine. For example, the addition of an ether backbone via an amine can compromise color. While it may be desirable to improve the moisture uptake in the finished product, it may be desirable to provide polymer beads that can be melt spun into fibers without the need for a separate drying step after storage. For example, it may be desirable to provide polymer beads suitable for spinning into garment fibers that can be stored at 50% to 65% relative humidity for one week without the need for a separate drying step prior to melt spinning. Similarly, it may be desirable to provide fibers and fabrics that retain their improved moisture uptake properties upon exposure to hot water.

Applicants have extensively studied the hydrophilicity of nylon yarns used in apparel applications, including inspections of oxyethylene (-OCH)2 CH2 -) The hydrophilicity of the repeating unit incorporated into the polyamine. Desirable properties of softness in nylon yarns for use in apparel applications may be via inclusion of an ether (-OR-) repeat unit (wherein R is (eg, but not limited to) CH2 CH2 Or CH2 CHMe or CH2 CH2 CH2 CH2 ) and appear. Substantial research has been conducted in the industry to find an appropriate balance of oxyethylene repeat units in the polyamine polymer backbone. Thus, it has been found that the modified polymer may require varying polymerization conditions and the spinning conditions are not readily predictable or readily adaptable to the conventional textile industry. Disclosed herein are synthetic polyamine compositions suitable for spinning into garment fibers using conventional melt spinning equipment and methods of producing the same. A polyamine product containing a poly(ether diol) [one of the class described as a poly(alkylated oxygen)] component in which the ether (ie, poly(ether diol)) functional group is derived from poly The carboxylic acid component of the condensation reaction is not derived from the amine. In one disclosed polyamine composition, an ether functional group can be present in at least a portion of the diamine and in at least a portion of the dicarboxylic acid. Suitable dicarboxylic acids include dicarboxylic acids of the PEG (poly(ethylene) glycol) source. Polycondensation processes are also disclosed to produce ether-containing polyamines. Fibers and fabrics (including knit, woven, and directly laid non-woven fabrics) having enhanced higher moisture retention/hydrophilicity compared to similar compositions without ether in the dicarboxylic acid component are also disclosed. The disclosed polyamines may comprise nylon and poly(ether diol) dicarboxylic acids, wherein the poly(ether diol) dicarboxylic acid has a number average molecular weight of ≥250 Da, such as ≥600 Da and ≥1500 Da and ≥2500 Da And ≥5000 Da. The moisture regain of the polyamine may range from ≥5 wt% to ≤35 wt%. Unless otherwise stated, the number average molecular weight is given in units of Daltons (Da). The disclosed polyamines are well suited for the preparation of hydrophilic polyamide compositions. Accordingly, the disclosure herein is also directed to improved synthetic polyamide (nylon) polymer compositions. The polyamines disclosed may comprise nylon and poly(ether diol) dicarboxylic acids and optionally polyetheramines. The disclosed compositions are suitable for use in the manufacture of yarns or fibers and textiles or fabrics or garments containing such yarns or fibers. The disclosed polyamines comprise nylon and poly(ether diol) dicarboxylic acid and may have a resurgence ranging from about 5% to about 35%, such as from about 10 to about 25%, such as from about 15% to about 20%. Rate (measured as described herein); all moisture regain values are by weight. This moisture regain can improve the handleability during subsequent processing of the polyamine compositions of the present invention. For example, polyamine can have an elongation at break of from 20% to 90% when spun into a yarn. As discussed herein, the polyamine composition can be an acid (anionic) or base (cationic) dyed polymer. In one embodiment, at least 85% of the polymer backbone (between the guanamine units) may comprise an aliphatic group. The nylons discussed herein may be, for example but not limited to, polyhexamethylene hexamethyleneamine (nylon 6,6), polyhexylamine (nylon 6) or a copolymer of any of these nylons. In one embodiment, the nylon can be nylon 6,6. The nylon may be present in the polyamine in an amount ranging from about 50% to 99% by weight. Poly(ether diol) dicarboxylic acid can be prepared by reacting a poly(ether diol) with an organic base (such as potassium t-butoxide) and an alkylating agent (such as ethyl bromoacetate) (but not limited to this method). Greenwald, R. B. et al.J. Med. Chem. ,1996 ,39 , 424-431. This adds an ester functional group to the hydroxyl group of the poly(ether diol). The ester group is then saponified using a suitable aqueous base such as sodium hydroxide. The dicarboxylic acid product can be isolated by acidifying the mixture with a mineral acid such as aqueous hydrochloric acid and catalyzing with an organic solvent such as dichloromethane. The solution is then evaporated to form a concentrated solution and the polymer is precipitated by slowly adding the solution to a stirred antisolvent such as tert-butyl methyl ether. Alternatively, low molecular weight poly(ether diol) dicarboxylic acids (e.g., poly(ethylene glycol)) are commercially available from suppliers such as the Sigma-Aldrich company. Non-limiting examples of suitable poly(ether diol) dicarboxylic acids may include polypropylene glycol dicarboxylic acid, polytetramethylene dicarboxylic acid, polyethylene glycol (PEG), polypropylene glycol (PPG), and polytetramethylene glycol. Block copolymer of (PTMG) block, for example: (PEG)-b-(PPG); or (PEG)-b-(PPG)-b-(PEG); or (PPG)-b-(PEG )-b-(PPG). As discussed herein, poly(ether diol) dicarboxylic acids can be used in the polymerization of nylon monomers to form polyamines that can be spun into nylon yarns that exhibit excellent hydrophilicity. These properties can impart a highly desirable tactile aesthetic and wearing comfort to apparel products made from such yarns. Additionally, the poly(ether diol) dicarboxylic acid can be present in the polyamine and can have a plurality of molecular weights depending on the desired properties of the resulting polymer, including handleability as discussed herein. In one embodiment, the number average molecular weight of the poly(ether diol) dicarboxylic acid (Mn , measured by Dalton Da) is at least 250 Da. In other aspects, the poly(ether diol) dicarboxylic acid may 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 diol) dicarboxylic acid may be present in an amount ranging from about 1 wt.% to about 50 wt.% of the polydecylamine. In one aspect, the poly(ether diol) dicarboxylic acid can be present in an amount ranging from about 5 wt.% to about 25 wt.%, such as from about 8 wt.% to about 25 wt.%. In another embodiment, the poly(ether diol) dicarboxylic acid is present in an amount from about 8 wt.% to about 20 wt.%. The polyamines described herein comprise an aliphatic diamine. 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. The portion of the diamine can be present in the polymer in an amount of substantially equal molar ratio of amine groups to the acid groups of the poly(ether diol) dicarboxylic acid. The polyamines described herein can have a variety of physical properties. In one embodiment, the polyamine can have from 25 to 130 amine end gram equivalents per 1000 kilograms of polymer. Additionally, the polyamine can have a relative viscosity ranging from about 20 to about 80. In another embodiment, the relative viscosity can be calculated based on the formic acid test method according to ASTM D789-86 known at the time of the application of the present invention by the United States Patent and Trademark Office. The disclosed polyamines can have a yellowness index [YI] of from about 25 to about 45. The disclosed polyamines can be characterized by one or more of the following: L* color coordinates from about 75 to about 85; a* color coordinates from about -5 to about 5 and b* color coordinates from about 5 to about 25 . The disclosed polyamines may further comprise one or more poly(ether diol) dicarboxylic acids as described above. In one embodiment, the number average molecular weight of the poly(ether diol) dicarboxylic acid (Mn ) can be ≥ 250 Daltons (Da), such as ≥500 Da, ≥600 Da and ≥1500 Da. In other aspects, the poly(ether diol) dicarboxylic acid Mn Can be ≥ 2500 Da or even ≥ 5000 Da. The disclosed polyamines may further comprise one or more polyetheramines as described in published PCT application WO 2014/057363. The whiteness of each sample can be determined using a test method consistent with the CIE whiteness rating. The whiteness (W) and yellowness (Y) of the sample can be individually measured using the GRETAG MACBETH "COLOR EYE" reflective spectrophotometer. First, the CIELAB color coordinates L, a*, and b* are determined; and then, W and Y are calculated by means known in the art (see: ASTM Method E313-1996)Standard Practice for Calculating Whiteness and Yellowness Indices from Instrumentally Measured Color Coordinates ). See the details of this measurement.Color Technology in the Textile Industry Second edition, published by Committee RA 36, AATCC (1997); see this volume: Harold and Hunter,Special Scales for White Colors , pages 140-146 and references therein, the entire contents of each of which are hereby incorporated by reference. Further, the polyamine of the present invention may further comprise a catalyst. In one embodiment, the catalyst may be present in the polyamine 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. Catalysts can include, but are not limited to, phosphoric acid, phosphorous acid, hypophosphoric acid, arylphosphonic acid, arylphosphinic acid, salts thereof, and mixtures thereof. In one embodiment, the catalyst may be sodium hypophosphite, manganese hypophosphite, sodium phenylphosphinate, sodium phenylphosphonate, potassium phenylphosphinate, potassium phenylphosphonate, hexamethylene diammonium. Diphenylphosphinate, potassium tolylphosphonate or a mixture thereof. In one aspect, the catalyst can be sodium hypophosphite. The disclosed polyamine and polyamine compositions can include "optical brighteners." The optical brightener can be provided in accordance with U.S. Patent Application Serial No. 20080090945 A1 assigned to INVISTA North America S.à. The whiteness appearance of the polyamine and polyamine compositions according to the embodiments disclosed herein can be improved by the addition of optical brighteners. The polyamines can exhibit permanent whiteness improvement and can be maintained via operations such as heat setting. In one embodiment, the optical brightener may be present in the polyamine in an amount ranging from 0.01 wt.% to 1 wt.%. In another embodiment, the improvement in whiteness appearance can be achieved by the addition of a delustering agent. The delustering agent can be titanium dioxide. Additionally, the polyamine compositions may contain antioxidant stabilizers or antimicrobial additives. Further, the polyamide composition may contain an antifoaming additive. In one embodiment, the antifoam additive may be present in the polyamine in an amount ranging from 1 ppm to 500 ppm by weight. The disclosed polyamines include intrinsically acid (anionic) dyeing, but can also be rendered alkaline by modifying the polymers or copolymers with cationic dye-sensing monomers copolymerized in the polymer ( Cation) of the dyed forms. This modification makes the composition particularly susceptible to alkali (cationic) dye coloration. Sodium 5-thioisophthalate is an example of the cationic dye-sensitive monomer. In yet another aspect, a process for producing a polyamine is disclosed, the process comprising contacting a diamine, a poly(ether diol) dicarboxylic acid with a nylon salt; forming a mixture; heating the mixture in a closed vessel to a sufficient extent The temperature at which the mixture is polymerized and the autogenous pressure; and the formation of polyamine. In yet another aspect, a process for producing a polyamine is disclosed, the process comprising contacting a diamine with a nylon salt; forming a mixture; heating the mixture in a closed vessel to a temperature sufficient to polymerize the mixture and autogenous pressure; The poly(ether diol) dicarboxylic acid is added to continue the process and form the desired polyamine. The process for producing the polyamine can further comprise providing the catalyst (including those discussed herein) to the mixture. The processes can further comprise providing an antifoaming additive to the mixture. The processes can further comprise providing an optical brightener to the mixture. The polyamide monomer of polyamine can be added in the form of a salt, an amino acid or an internal guanamine. The nylon monomer can be a nylon 6,6 salt and can comprise almost all of the polyamine (eg, 99 wt.%, 99.5 wt.%, 99.9 wt.% or greater) or can be between about 50 wt.% to An amount in the range of 95 wt.%, 96 wt.%, 97 wt.% or 98 wt.% is present in the polyamine. A variety of processing parameters can be used in the polymerization of the polyamines of the present invention, 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 psig to about 300 psig. Furthermore, the heating can be carried out under partial vacuum. Part of the vacuum obtained is governed by the design of the autoclave and the economic considerations of the process. The polymerization of the present invention can involve multiple continuous heating cycles. These cycles may individually include a heating temperature profile and a pressure profile. The objective is to maintain system flow by a combination of a temperature sufficient to melt and a sufficient dissolved water content. The continuous heating cycle may comprise: a first heating cycle (C1) over a period of 20 minutes to 40 minutes, an initial temperature between 170 ° C and 215 ° C and a termination temperature between 190 ° C and 230 ° C, pressure Between 130 psia and 300 psia; a second heating cycle (C2), which lasts between 20 minutes and 45 minutes, with an onset temperature between 190 ° C and 230 ° C and a termination temperature between 240 ° C and 260 ° C The pressure is between 130 psia and 300 psia; the third heating cycle (C3), which takes between 15 minutes and 45 minutes, the starting temperature is between 240 ° C and 260 ° C and the termination temperature is between 250 Between °C and 320 °C, the pressure is between 300 psia and atmospheric pressure; and the fourth heating cycle (C4), between 15 minutes and 80 minutes, the starting temperature is between 250 ° C and 320 ° C and terminates The temperature is between 250 ° C and 320 ° C and the pressure is between atmospheric pressure and about 200 mbar absolute vacuum. Finally, the polymer is extruded using methods well known in the art. The disclosed polyamine compositions are inherently acid soluble and optionally comprise a cationically dyeable polymer. The disclosed polyamine composition can be prepared by an autoclave process. The process can be initiated from a concentrated slurry prepared from an aqueous solution of a nylon salt, an amino acid or an internal amine or a mixture of, for example, a nylon 6,6 salt (the term slurry is also incorporated into the solution), and the concentrated slurry is supplied to the autoclave. container. Optionally, the slurry can be a thin slurry and become more concentrated by means of an evaporation step. The slurry can be prepared from aqueous solutions of monomers such as hexamethylenediamine and adipic acid in a manner known in the art. The autoclave vessel can then be heated to about 230 °C (or some other functional temperature) to increase the internal (autogenous) pressure. Delustering agent titanium dioxide (TiO)2 Injection into an autoclave and a monomer mixture as an aqueous dispersion. In one embodiment, an aqueous slurry of poly(ether diol) dicarboxylic acid and optionally polyetheramine can be injected into the mixture in the autoclave vessel together with an amount of a diamine such as hexamethylenediamine. To produce a substantially equimolar ratio of acid groups to amine groups. The mixture can then be heated in an autoclave to about 245 ° C (or some other functional temperature). While maintaining this or other desired temperature conditions, the autoclave pressure can be lowered to atmospheric pressure and the pressure is further reduced by applying a vacuum in a known manner to form a polyamine composition. The autoclave containing the polyamine composition was maintained at this temperature for about 30 minutes. This step can be followed by, for example, further heating the polyamine polymer composition to about 285 ° C in an autoclave. The polymer composition can be released from the autoclave by opening the crucible in the autoclave vessel and applying 4 bar to about 5 bar of dry nitrogen to allow the molten polyamine composition to flow out of the vessel as a ribbon. The strips can be cooled and quenched in a stream of water. Next, the tape of the polyamide polymer can be granulated by a known method and further cooled with water. In some embodiments, the polymer composition can be released from the autoclave vessel at the end of the recycle stage and allow the molten composition to flow out of the vessel in the form of a strip. In other embodiments, the polymer composition can be supplied directly to a polymer extrusion apparatus that is designed and operated to process the polymer melt. For example, the disclosed polymer compositions can be processed in a screw extruder, such as a twin screw extruder. In one embodiment, a quantity of a diamine (eg, hexamethylenediamine) may be added such that the total number of acids present is approximately equal to the total number of amine groups. The mixture can then be heated in an autoclave to about 245 ° C (or some other functional temperature) while maintaining the desired pressure. While maintaining this or other desired temperature conditions, the autoclave pressure can be lowered to atmospheric pressure and the pressure is further reduced by applying a vacuum in a known manner to form a polyamine composition. Poly(ether diol) dicarboxylic acid and optionally polyetheramine may be injected into the mixture during such heating periods and/or during pressure reduction. The autoclave containing the polyamine composition can be maintained at this temperature for about 30 minutes. This step can be followed by, for example, further heating the polyamine polymer composition to about 285 ° C in an autoclave. The polymer composition can be released from the autoclave by opening the crucible in the autoclave vessel and applying 4-5 bar of dry nitrogen and allowing the molten polyamine composition to flow out of the vessel as a ribbon. The strips can be cooled and quenched in a stream of water. Next, the tape of the polyamide polymer can be granulated by a known method and further cooled with water. The autoclave process described above can provide a polyamidamine composition having a formic acid process RV of from about 20 to about 80. In another embodiment, the autoclave process described above can provide a polyamidamine composition having a formic acid process RV of from about 38 to about 45. Optionally, the process can be modified to produce a polyamine composition having from about 25 to about 130 mole amine ends per 1000 kilograms of polymer by adding an excess of aqueous hexamethylenediamine to the nylon salt. Provided in an aqueous solution. The polymerization can be carried out in a continuous polymerization vessel. Examples of continuous aggregators are known to those skilled in the art, and one example is disclosed in WO 2014179048 to Micka and Poinsatte, the contents of which are hereby incorporated by reference herein. The composition may optionally be partially polymerized in an autoclave or a continuous polymerization vessel and subsequently completed in a solid phase polymerizer. Examples of solid phase aggregators are known to those skilled in the art and are 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. The composition can be prepared in an extruder as appropriate. The process can include separately or together feeding the reactants comprising the diacid and the diamine to the feed throat of the extruder. Alternatively, the method can include feeding the reactants to one or more auxiliary feed throats at one or more points located across the length of the extruder, wherein the extruder includes various zones, which can include a melt zone, a mixing zone, and Transport area. PCT/US16/61604 (Attorney Docket PI 4212) to Langrick and Hunt discloses polymerization in a screw extruder having multiple feed throats, and is incorporated herein by reference, as set forth in detail herein. The nylon polymers and copolyamides described herein can be inherently acid dyeable. In one embodiment, the number of free amine end groups (AEG) in the polymers is at least 25 moles per 1000 kilograms of nylon polymer. To allow the polymer to be more deeply acid dyed, an increased free amine end group content can be used. More deep acid dyed nylon polymers have an increased AEG content, for example an AEG content of at least 60 to 130 moles per 1000 kilograms of nylon polymer can be used. Furthermore, it should be noted that a masterbatch comprising a poly(ether diol) dicarboxylic acid and optionally a polyetheramine in an equivalent amount to the amine end of a suitable diacid (for example adipic acid) can be produced. This masterbatch can then be supplied to the autoclave process. In an alternative embodiment, the polyamine composition herein can be made by a masterbatch process using a poly(ether diol) dicarboxylic acid comprising dispersed in nylon (nylon 6,6 or nylon 6) Optionally in the form of a sheet or melt of polyetheramine. A flake or melt form is then added as a masterbatch containing nylon. In the examples, the poly(ether diol) dicarboxylic acid in the form of a sheet and optionally the masterbatch nylon sheet of the polyetheramine and nylon are melted. In the examples, a nylon sheet containing a poly(ether diol) dicarboxylic acid and optionally a polyether amine is melted and added to the nylon melt. In either case, the melt is forced from the extruder into a pump that pumps the polyamine composition into, for example, a pack for making the yarn and a spinneret. The nylon polymer and the copolyamine described herein can also be rendered in an alkaline dyed form, i.e., the alkali dye (also known as a cationic dye) can be perceived. The alkali dyeing compositions are produced from a polyamidamide polymer in which a cationic dye modifier is copolymerized in a polymer. The preparation of these cationic dye-modified polyamines is described in U.S. Patent No. 5,164,261, issued to to the entire entire entire entire entire entire entire In one embodiment, the polymer may be modified during polymerization with from 0.5 wt.% to 4 wt.% cationic dye modifier (eg, 5-thioisophthalic acid). Typically, a certain weight of sodium 5-thioisophthalate salt can be combined with a known amount of polyamine precursor salt in an autoclave using standard polymerization procedures known in the art. In one embodiment, the amount of cationic dye modifying agent present in the polymer can range 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 an equivalent sulfonate group. The sulfonate group concentration can be at least 25 moles per 1000 kilograms of polymer to about 150 moles per 1000 kilograms of polymer.Polyamide yarn The polyamine compositions of the present invention are especially useful when spun into yarns. In one embodiment, the poly(ether diol) dicarboxylic acid and optionally the polyether amine can be provided to the polyamide composition, and thus are inherent to the yarn itself rather than applied to the fabric when forming the fabric. In one embodiment, the yarn exhibits improved hydrophilicity as measured by a plurality of water cores and moisture regain tests. The yarns produced from the polyamines described herein can be multifilament spun yarns in the form of low aspect yarns (LOY), partially oriented yarns (POY) or fully drawn yarns (FDY). The yarn can be a textured yarn made from a partially oriented yarn. Moreover, the yarn can be substantially continuous, i.e., formed from one or more continuous filaments. In other embodiments, the continuous filaments can be cut into staple fibers and the latter can be converted to continuous filaments by a spinning process to produce a continuous article or article comprising shorter fibers. These yarns can be used to make fabrics which in turn can be used to make garments. In embodiments, the disclosed polymers may be stored in beads or flakes at a relative humidity of 50% to 65% for one week and then melt spun into garment fibers without an intercalation drying step between storage and melt spinning. In one embodiment, the apparatus and method for spinning are disclosed in U.S. Patent No. 6,855,425, and similar techniques are similarly in the context of the polyamines prepared and described herein. Yarns made from the polyamines described herein can be particularly useful as textile yarns for apparel textile applications. For example, yarns having a yarn weight of 5 dtex to 300 dtex and a filament weight of 0.5 dtex to 7 dtex are desirable. In certain embodiments, the yarn comprises from 1 to 300 filaments. According to some embodiments, the yarn comprises from 3 to 150 filaments. The linear mass density of the fiber is given in units of dtex [1 dtex means 1 dtex and equals 1 g / 10,000 m yarn]. And the unit of 1 "tex" is equal to the linear mass density of 1 g / 1000 m yarn. According to some embodiments, the yarn has a DPF (dtex/filament) of from 0.5 to 2.5, such as from 1 to 1.5. Yarns made from the polyamines described herein may have a filament uniformity (expressed in Uster% (U%)) of 1.5% or less, more typically 1% or less. This uniformity is desirable for the yarn to have the high appearance uniformity required for apparel applications, and also to reduce yarn breakage in texturing, weaving, and knitting operations. Yarns made from the polyamines described herein can have an elongation at break of from 20% to 120%. According to some embodiments, the yarn has an elongation at break of from 20% to 90%. Typically, the yarn has a tenacity of from 25 cN/tex to 65 cN/tex, such as from 30 cN/tex to 45 cN/tex. These tensile properties are desirable for apparel textile applications. The breaking force is expressed in centiNewtons/tex [cN/tex]. In certain embodiments, the polyamide yarn may have a titanium dioxide content of less than 0.1 wt.%, and more typically less than 0.01 wt.%, such that the yarn gloss is clear or bright. In other embodiments, the polyamide yarn may have a titanium dioxide content of greater than 0.3 wt.% and or even greater than 2 wt.%, thereby rendering the yarn dull or dull. Titanium dioxide content between these ranges may also be used, for example from 0.1 wt.% to 0.3 wt.%. In a particular embodiment, the polyamide yarn can be prepared by using known melt spinning process techniques. By means of this technique, a granulated polyamide composition produced by using an autoclave process or a melt produced by a masterbatch process can have an optical brightener as set forth above and can be supplied to a spinning machine. The molten polymer is transferred up to the filter pack by a metering pump and extruded through a spinneret containing capillary ports of a selected shape to produce a desired filament cross-section at the spinning temperature. Such cross-sectional shapes are known in the art to include circular, non-circular, trilobal, hollow, and diabolo shapes. A typical hollow filament can be produced as disclosed in U.S. Patent No. 6,855,425. The spinning temperature can range, for example, from 270 ° C to 300 ° C. The filament bundles present from the spinnerette are cooled by treated quench air, treated with a spin finish (oil/water emulsion), optionally using interlaced jets, for example. In some embodiments, the continuous yarn thus obtained is cut and converted into staple fibers, which are then used to produce filaments or yarns by spinning or by hydroentanglement, needling, ultrasonic bonding, chemical bonding Nonwovens are formed by knots, heat bonding or the like. In the case of FDY, on-line processing on a spinning machine typically involves winding a number of turns around a set of goding rolls (feed rolls) sufficient to prevent slipping on the rolls and then transferring the yarn to On the other set of rolls (stretching rolls), the other set of rolls is rotated at a sufficient speed to stretch the yarn by a predetermined amount (stretch ratio). Finally, the process is continued by heating and sizing the yarn with a steam box and then winding at a speed of at least 3000 m/min, for example at least 4000 m/min, for example 4800 m/min or higher. Optionally, an alternative heat setting (or slack) method such as a heated roll can be used, and a set of guide rolls can be incorporated between the draw roll and the winder to control the tension as the yarn is set or relaxed. Moreover, the spinning oil and/or additional interlacing may be applied again prior to the final winding step, as appropriate. In the case of POY, the additional in-line processing typically involves only S-winding on two guide rolls rotating at the same speed, and then transferring the yarn to the high speed winder to at least 3000 m/min, for example at least 4000 Winding at a speed of m/min, for example 4800 m/min or higher. The use of S-wrap is beneficial for controlling tension, but it is not required. The POY can be used directly as a flat yarn for weaving or knitting, or as a raw material for texturing. The LOY spinning process is similar to POY, except that a winding speed of 1000 m/min or less is used. The low directional yarns are typically further processed via a second stage, such as a conventional draw-twist or stretch-winder. In one embodiment, the polyamine polymers disclosed herein are highly suitable for spinning into continuous filaments that can be concentrated to form multifilament yarns. Processes for spinning synthetic filaments into continuous filaments and forming multifilament yarns are known to those skilled in the art. Typically, successful spinning of filaments uses a spinneret having at least one single capillary port. The capillary port corresponds to each individual filament comprising a yarn. The cross-sectional shape sought for the end-of-filament filaments uses round and non-circular cross-section nozzle nozzles (or extruded nozzles). Typically, for a certain polymer flux G per capillary (eg, expressed in grams per minute), the following equation is applied:G = ρ ( Molten ) D 2 ( Capillary ) (π/4)v ( Extrusion ) Equation 1. In this equation, the ρ-based polymer melt density (for example, for molten nylon 6 at 6 °C, 6 is equal to 1.0 g/cm)3 ), D is assumed to be the capillary diameter of a circular orifice (equal to twice the radius), and the rate of v is a filament. The extrusion rate is given by the following equation:v ( Extrusion ) = G (4/πD 2 ( Capillary ) ρ( Molten ) Equation 2. In one embodiment, the polymer is extruded at an extrusion rate ranging from 20 cm/sec to 80 cm/sec. In another embodiment, the filaments that have just been extruded can be quenched by air conditioning in a known manner. In this step, individual filaments are cooled in a quench cabinet using side air venting of the air conditioner and concentrated and immersed into the yarn with primary oil oil as is known in the art. The yarn is conveyed upward by a feed roll onto a pair of draw rolls, wherein the yarn is elongated and oriented on the pair of draw rolls to form a drawn yarn which is guided to the yarn by a roll In the line stabilizer. This stabilizing device is common in the industry and is used herein as a yarn post-processing step as appropriate. Finally, the yarn is wound into a yarn package at a yarn speed ranging from 1000 m/min to 6500 m/min. The yarn RV (or the relative viscosity as determined by the formic acid method) is from about 20 to about 80. In an embodiment, the yarn is a drawn yarn having an elongation of from 22% to about 60%, a boiling water shrinkage of from 3% to about 10%, and a yarn tenacity of between 3 grams/denier (denier) ) to a range of about 7 grams per denier, and the RV of the yarn can vary and be sufficiently controlled to range from about 20 to about 80, such as from about 40 to about 60. Derivative parameters characterizing the superior properties of this yarn are referred to as yarn quality and reference is made to the product of the yarn tenacity (g/danny) and the square root of % elongation as in Equation 3. Yarn quality = toughness × (elongation)1/2 Equation 3. Yarn quality is an approximation of the "toughness" measure of the yarn. As is known to those skilled in the art, the area under the yarn load elongation curve is proportional to the work done by the elongate yarn. If, for example, the toughness is expressed in terms of force per unit of denier and the elongation is expressed as % change per unit length, the load elongation curve is a stress-strain curve. In this case, the area under the stress-strain curve extends the work or yarn toughness of the yarn. Yarn quality improvement provides garment polyamine yarns that are more acceptable in a variety of applications. Such applications may include, but are not limited to, warp knits, circular knits, seamless knitwear, knits, nonwovens, and light denim technical fabrics. In certain embodiments, the polyamide yarn has a different dyeing characteristic than an anionic dye or a cationic dye. These dyeing characteristics can be derived from different numbers of amine end groups. The concentration of the amine end group (AEG) affects the extent to which the anionic dye stains the polyamine. Alternatively or in addition, the polyamine may contain an anionic end group that can cationically dye the polyguanamine, such as a sulfonate or carboxylate end group. In certain embodiments, the polyamide yarn is dyed with a fiber reactive dye incorporating a vinylsulfonyl group and/or a beta-sulfate ethylsulfonyl group. The fiber-reactive dyes are known from U.S. Patent No. 5,810,890. In certain embodiments, the polyamide yarn is dyed by a fiber reactive dye incorporating a halogen derivative of a nitrogen heterocyclic group such as triazine, pyrimidine, and quinoxaline. Such fiber reactive dyes are described, for example, in U.S. Patent No. 6,869,453. In other embodiments, the filaments comprise an amine component of hexamethylenediamine. In other embodiments, the filaments comprise an amine component that is a mixture of hexamethylenediamine containing at least 20 wt.% methylpentamethylenediamine based on the total weight of the diamine. In still other embodiments, the polyamine can include nylon 6. The following test statements can be used to characterize various parameters as discussed herein. Yarn toughness and yarn elongation can be achieved using the INSTRON tensile test device (Instron Corp., Canton, Massachusetts, USA 02021) and constant crosshead speed according to ASTM method D 2256-80 (in the application of the invention to the US Patent and Trademark Office) When known). Toughness is expressed in centiNewtons per tex (cN/tex) or gram force/denier, and elongation % is an increase in sample length expressed as a percentage of the initial length under breaking load. The linear density uniformity of the yarn (also known as the Ubk % (U%) of the yarn) can be determined using a Type C Ubbel uniformity tester 3 known to those skilled in the art. The polymeric amine end can be measured by direct titration with a standardized perchloric acid solution of the weighed polymer sample absorbed in solution. The moisture regain of the polymer can be measured by the following method. A sample of the polymer (100 g) was dried under vacuum at 80 ° C for 18 hours. For example, the initial moisture content of this dried polymer sample was measured on a 1.9 g polymer using an Aquatrac (PET version (4 Digit); Brabender Messtechnik) at a 160 °C setting. A moisture content of less than 0.5 wt.% measured using this method is considered to indicate that the polymer has dried sufficiently. The dried sample was then immersed in demineralized water (500 g) at ambient temperature (20 ° C) without any agitation. After 48 hours, the sample (about 10 g) was removed and patted dry with absorbent tissue. A portion of the sample (about 5 g; the weight of the wet sample) was accurately weighed into a foil pan and placed in an oven at 80 ° C for 18 hours under vacuum. The tray was removed and placed in a desiccator for cooling and then weighed again (the weight remaining after drying). This procedure is repeated at intervals of (e.g., 72, 144, 190, and 220 hours) to 220 hours. The water absorption rate was determined by the following calculation:The moisture regain of the polymer is defined as the moisture uptake rate after 220 hours or until the sample has reached a moisture uptake equilibrium (defined as a weight change of no more than 1% over a 24 hour period), whichever is earlier. Therefore, if the water absorption balance has not been reached after 220 hours, the moisture regain rate is the water absorption rate at 220 hours. When the water absorption equilibrium is reached before 220 hours, the moisture regain is the average (average) of the water absorption rates of the first two consecutive measurements performed under equilibrium. Alternatively, the moisture regain can be measured by methods such as DIN 53814, which involves saturating the textile sample with deionized water for 2 hours at 20 ° C, removing the water by centrifugation at 4000 m/min, and measuring at 105 ° C. The weight change until the weight loss is no longer observed after drying. The water wicking rate of the fabric from the yarn construction can be measured by vertically immersing 1.8 ft (4.6 cm) of the bottom of the 1 mile (2.5 cm) wide strip of scrubbed fabric in deionized water. The height of the water drawn up the fabric is measured visually and the height over time is recorded. "Initial wicking rate" means the average wicking rate during the first two minutes of the wicking test. The "dry time %" test of fabrics or clothing can be used to characterize hydrophilic polyamide yarns, fabrics and clothing. These are also referred to as dry time % tests or "horizontal pull" measurements. Drying time % testing is performed using a balance and a computer; for example, a Mettler balance AE163 and a computer running the Mettler BalanceLink 3.0 program. The weight of a circular fabric sample having a diameter of 2 inches (5.1 cm) was obtained and recorded. 0.10 g of tap water was placed on the balance using an automatic pipette and the weight was recorded. The circular fabric sample was immediately centered on the water and then placed on the water. At this time (time = 0 minutes) and the total weight of the fabric and water was recorded every two minutes for the next 30 minutes. Calculate the % dry result for a given time according to the following formula: Dry % = 100 - [(Wtotal - WFabric ) /WH2O ] × 100.Instance The following examples are presented to provide those skilled in the art with a complete disclosure and description of how to implement the methods disclosed and claimed herein and how to use the compositions and compounds disclosed and claimed herein. Efforts have been made to ensure the accuracy of values (eg, amounts, temperatures, etc.), but some errors and deviations should be considered. Unless otherwise indicated: parts are parts by weight, temperature is expressed in ° C, and pressure is expressed in atmospheric pressure. Standard temperature and pressure are defined as 25 ° C and 1 atm. Materials used in the examples Number average molecular weight Mn A poly(ethylene glycol) system of 2000 Daltons was obtained from commercial source Alfa Aesar (Product Code B22181). Hexamethylenediamine or HMD is commercially available from INVISTA Intermediates (offices in Wichita, Kansas and Wilmington, Delaware, USA). The term "poly(ether diol) dicarboxylic acid" as used herein means havingOne of the general chemical structures is poly(ethylene glycol) bis(carboxymethyl)ether, in which the n coefficient value. Number average molecular weight Mn A poly(ether diol) dicarboxylic acid of 600 (referred to herein as Compound 2 in the examples of the present disclosure) is available from commercial source VWR International. The term "RE 2000" as used herein refers to ELASTAMINE® RE-2000 amine; a commercial product available from Huntsman Corp. ELASTAMINE® The RE-2000 amine is a water-soluble aliphatic polyether diamine derived from propylene oxide-terminated polyethylene glycol. Polyetheramines of this type are useful in a variety of polymers.nylon 66 salt The term "nylon 66 salt" as used herein refers to a salt formed by an acid-base neutralization reaction between an amine group of at least one diamine and an acidic proton of a carboxylic acid group of at least one dicarboxylic acid. The dicarboxylic acid component of the salt is suitably at least one dicarboxylic acid of the formula (I): HO2 C-R1 -CO2 H, where R1 Represents a divalent aliphatic, cycloaliphatic or aromatic group or covalent bond. R1 Suitably it contains from 2 to 20 carbon atoms, for example from 2 to 12 carbon atoms, for example from 2 to 10 carbon atoms. R1 It may be a linear or branched (e.g., linear) alkyl group containing 2 to 12 carbon atoms, or 2 to 10 carbon atoms, for example 2, 4, 6 or 8 carbon atoms, unsubstituted extension Phenyl or unsubstituted cyclohexyl. Depending on the situation, R1 It may contain one or more ether groups. For example, R1 An alkyl group, for example a linear alkyl group, which contains 2 to 12 carbon atoms, or 2 to 10 carbon atoms, for example 2, 4, 6 or 8 carbon atoms. Specific examples of suitable dicarboxylic acids include hexane-1,6-dioic acid (adipate), octane-1,8-diacid (suberic acid), decane-1,10-diacid (癸二) Acid), dodecane-1,12-diacid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexane Alkane diacetic acid, 1,3-cyclohexane diacetic acid, benzene-1,2-dicarboxylic acid (phthalic acid), benzene-1,3-dicarboxylic acid (isophthalic acid), benzene-1,4-two Formic acid (terephthalic acid), 4,4'-oxybis(benzoic acid) and 2,6-naphthalene dicarboxylic acid. A dicarboxylic acid is preferably hexane-1,6-dioic acid (adipic acid). The diamine component of the salt is suitably at least one diamine of the formula (II): H2 N-R2 -NH2 , where R2 Represents a divalent aliphatic, cycloaliphatic or aromatic group. R2 Suitably it contains from 2 to 20 carbon atoms, for example from 4 to 12 carbon atoms, for example from 4 to 10 carbon atoms. R2 It may be a linear or branched (e.g., linear) alkyl group containing 4 to 12 carbon atoms, for example 4 to 10 carbon atoms, for example 4, 6 or 8 carbon atoms, and an unsubstituted phenyl group. Or unsubstituted Cyclohexyl. Depending on the situation, R2 It may contain one or more ether groups. For example, R2 An alkyl group, for example a linear alkyl group, which contains 4 to 12 carbon atoms, or 4 to 10 carbon atoms, for example 2, 4, 6 or 8 carbon atoms. Specific examples of suitable diamines include tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2-methylpentamethylenediamine, 3-methylpentamethylenediamine, 2-methylhexamethylenediamine, 3-methylhexamethylenediamine, 2,5-dimethyl Hexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2,7-dimethyloctadecylene Diamine, 2,2,7,7-tetramethyloctamethylenediamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexane Amine, 4,4'-diaminodicyclohexylmethane, benzene-1,2-diamine, benzene-1,3-diamine, and benzene-1,4-diamine. Preferred is a diamine hexamethylene diamine. For example, the salt dicarboxylic acid component can be at least one dicarboxylic acid of formula (I), wherein R1 An alkylene group having 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 of the formula (II) Amine, where R2 An alkylene group containing 4 to 12 carbon atoms, or 4 to 10 carbon atoms, for example 2, 4, 6 or 8 carbon atoms. For example, the at least one dicarboxylic acid may be selected from the group consisting of hexane-1,6-dioic acid (adipic acid), octane-1,8-diacid (suberic acid), and decane-1,10-diacid (癸Diacid) and dodecane-1,12-diacid, and at least one diamine may be selected from the group consisting of tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, octamethylene diamine , decamethylene diamine, dodecamethylene diamine, 2-methyl pentamethylene diamine, 3-methyl pentamethylene diamine, 2-methyl hexamethylene diamine, 3 -methylhexamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexa Methylene diamine, 2,7-dimethyl octamethylene diamine and 2,2,7,7-tetramethyl octamethylene diamine. Preferred salts include those in which the dicarboxylic acid component comprises hexane-1,6-dioic acid (adipic acid), octane-1,8-diacid (suberic acid), decane-1,10-diacid. One or more of (sebacic acid) and dodecane-1,12-diacid and the diamine component comprises tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, eight One or more of methylene diamine, decamethylene diamine, and dodecamethylene diamine. The eucalyptane salt is a naphthyl-1,6-diacid (adipate) and hexamethylenediamine to form a neutralizing salt ("nylon 66 salt").

Example 1 - Synthesis of Poly ( ethylene glycol ) bis ( carboxymethyl ) ether ( Compound 1) All glassware was oven dried prior to use. Poly (ethylene glycol) (PEG, M n 2000 daltons, 50 g, 25 mmol) and anhydrous toluene (250 ml) were mixed and warmed to 30 deg.] C with stirring until the solid was completely dissolved (in about 30 min) . The reaction mixture was maintained at 30 ° C throughout the following process. A solution of potassium butoxide (75 ml, 1 M in tert-butanol, 75 mmol) was added over 30 min. During the entire addition, a minimum temperature increase was observed and the colorless solution turned yellow. When the addition was completed, the solution was stirred for 1 hour. Ethyl bromoacetate (8.3 ml, 75 mmol) was added over 30 min maintaining the internal temperature below 45 °C (to control the exotherm). The resulting mixture was stirred overnight. At this time, the inspection during the implementation of 1H NMR spectrum was obtained by evaporating the sample and using deuterated DMSO as a solvent. The completion of the reaction was defined as the absence of a triplet at δ 4.6 ppm, which corresponds to the hydroxyl proton of the PEG starting material. The mixture was evaporated under reduced pressure until a viscous oil remained. This adhesive oil tends to solidify if it cools. The above viscous oil was mixed with aqueous sodium hydroxide (250 ml, 1 M, 250 mmol) and stirred at room temperature for 4 hours. The residue was dissolved stably to form an orange solution. The solution was slowly acidified with aqueous hydrochloric acid (130 ml, 2M, 260 mmol) (to control exotherm) until pH was less than 4 (where color was observed to be almost colorless). The solution was cooled 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 of volume remained. The residue was added dropwise to a beaker of tert-butyl methyl ether (300 ml) to give an off-white precipitate. The solid was filtered and dried to yield about 46.3 g of product diacid compound 1. For another method of preparing poly(ether diol) dicarboxylic acids, see Journal of Greenwald, RB et al, J. Med. Chem. , 1996 , 39 , 424-431, 430. Note that if the yield of the product obtained is low, the aqueous phase may not have been sufficiently acidified. If this is the case, additional product can be obtained by further adding dilute hydrochloric acid to the aqueous phase until the pH is less than 4 and extracting with dichloromethane as described above. Characterization products can be characterized by NMR, FTIR and/or acid number. In subsequent instances of the present disclosure, the compound 1 (M n 2000 daltons derived from PEG and according to Example 1) used in Example 2, and compound 2 (from M n 600 dalton PEG) used in Example 3 To 5 and Example 7. The poly(ether diol) dicarboxylic acids can be synthesized from the corresponding PEG or obtained from commercial sources. Example 2 - Polyamine salt preparation with 8 wt.% poly ( ether diol ) dicarboxylic acid ( Compound 1) was added to a 20 liter stirred and jacketed temperature controlled glass vessel filled with nitrogen and purged with nitrogen. 4000 g of water and the vessel was warmed to 35 °C. Nylon 66 salt (3661 g, 13.96 mol), compound 1 of Example 1 (280.8 g, 0.14 mol) and 80% by weight aqueous solution of hexamethylenediamine (16.3 g, 0.14 mol) were added (calculated The carboxylic acid end of Compound 1 was equilibrated) and the mixture was stirred until dissolved to yield a crude 50 wt.% strength salt solution. This produces about 3500 g of polymer upon polymerization. Polymerization The above salt preparation solution was added to a 15-liter autoclave. The targeting polymer contained about 8 wt.% Compound 1 relative to the final polymer weight. For the polymerization, instead of using an evaporator, a continuous heating cycle of 0 (C0) is performed to provide a location similar to the salt concentration of the evaporator batch. Basically in "C0", the mixture was heated to about 185 ° C and ventilated at 137 psia for a period of 87 minutes while raising the temperature to about 202 ° C before entering a continuous heating cycle (C1). The process for continuous heating cycle is as follows: C1 - T starts at about 202 ° C, finally at about 220 ° C, the pressure reaches 265 psia, the end of C1 is defined, and it takes about 18 min; C2 - 265 psia reaches 22 min, T Rise to 242 ° C temperature definition C2 end; continuous heating cycle 3 (C3) - reduce the pressure to 14.5 psia (atm) after 35 min, the temperature rises to the final temperature of 275 ° C; continuous heating cycle 4 (C4) - at atmospheric pressure At 6 min, a vacuum of 400 mbar was applied for 30 min, followed by reverse release to the atmosphere with nitrogen for 5 min. The polymer is then poured in a water bath. The polymer is characterized by the results provided in Table 1. Table 1 Example 3 - Polyamine salt preparation with 12 wt.% poly ( ether diol ) dicarboxylic acid Add 4000 g of water to a 20 liter stirred and jacketed temperature controlled glass vessel filled with nitrogen and purged with nitrogen 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 solution of hexamethylenediamine (85.0 g, 0.73 mol) (calculated to balance the carboxylic acid end of the PEG diacid) and the mixture was stirred until dissolved to yield a crude 50 wt.% strength salt solution. This produces about 3500 g of polymer upon polymerization. Polymerization The above salt preparation solution was added to a 15-liter autoclave. The targeting polymer contained about 12 wt.% Compound 2 relative to the final polymer weight. For the polymerization, instead of using an evaporator, a continuous heating cycle of 0 (C0) is performed to provide a location similar to the salt concentration of the evaporator batch. Basically in "C0", the mixture was heated to about 185 ° C and ventilated at 137 psia for a period of 90 minutes while raising the temperature to about 202 ° C before entering continuous heating cycle 1 (C1). The process for the continuous heating cycle is as follows: C1 - T starts at about 202 ° C and finally at about 220 ° C, the pressure reaches 265 psia defines the end of C1; C2 - 265 psia remains for 24 min, T rises to 243 ° C temperature defines C2 End; continuous heating cycle 3 (C3) - the pressure is lowered to 14.5 psia (1 atm) in 25 min, the temperature is raised to the final temperature of 274 ° C; and the continuous heating cycle 4 (C4) - at atmospheric pressure for 11 min, 350 is applied The mbar vacuum was applied for 24 min and then released back to the atmosphere with nitrogen for 6 min. The polymer is then poured in a water bath. The polymer is characterized by the results provided in Table 2. Table 2 Example 4 - Polyamine salt preparation with 20 wt.% poly ( ether diol ) dicarboxylic acid Add 4000 g of water to a 20 liter stirred and jacketed temperature controlled glass vessel filled with nitrogen and purged with nitrogen 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 solution of hexamethylenediamine (141.7 g, 1.22 mol) (calculated to balance the carboxylic acid end of the PEG diacid) and the mixture was stirred until dissolved to yield a crude 50 wt.% strength salt solution. This produces about 3500 g of polymer upon polymerization. Polymerization The above salt preparation solution was added to a 15-liter autoclave. The targeting polymer contained about 20 wt.% Compound 2 relative to the weight of the final polymer. For polymerization, no evaporator is used. Instead, a continuous heating cycle of 0 (C0) is performed to provide a salt concentration similar to that of the evaporator batch substantially at "C0", the mixture is heated to about 185 ° C and ventilated at 137 psia for a period of 87 minutes while The temperature was raised to about 202 ° C and then entered into continuous heating cycle 1 (C1). The process for the continuous heating cycle is as follows: C1 - T starts at about 202 ° C and finally at about 220 ° C, the pressure reaches 265 psia defines the end of C1, which takes about 17 min; C2 - keeps 265 psia for 25 min, T Rise to 243 ° C temperature definition C2 end; continuous heating cycle 3 (C3) - reduce the pressure to 14.5 psia (1 atm) after 36 min, the temperature rises to the final temperature of 275 ° C; and continuous heating cycle 4 (C4) - At atmospheric pressure for 5 min, 350 mbar vacuum for 30 min, then reversed to the atmosphere with nitrogen for 10 min. The polymer is then poured in a water bath. The polymer is characterized by the results provided in Table 3. table 3 Example 5 - Polyamine salt with 8 wt.% of poly ( ether diol ) dicarboxylic acid prepared by subsequent addition of poly ( ether diol ) dicarboxylic acid to nitrogen-filled and nitrogen purged Add 20 g of water to a 20 liter stirred and jacketed temperature controlled glass vessel and raise the vessel to 35 °C. Nylon 66 salt (3615 g, 13.78 mol) and the mixture was stirred until dissolved to give a crude 50 wt.% strength salt solution. Polymerization The above salt preparation solution was added to a 15-liter autoclave. For the polymerization, instead of using an evaporator, a continuous heating cycle of 0 (C0) is performed to provide a location similar to the salt concentration of the evaporator batch. Basically in "C0", the mixture was heated to about 185 ° C and ventilated at 137 psia for a period of 90 minutes while raising the temperature to about 202 ° C before entering continuous heating cycle 1 (C1). The process for the continuous heating cycle is as follows: C1 - T starts at about 202 ° C and finally about 220 ° C, the pressure reaches 265 psia defines the end of C1; C2 - keeps 265 psia for 24 min, T rises to 244 ° C temperature defines C2 ends Continuous heating cycle 3 (C3) – pressure drop to 14.5 psia (1 atm) over 25 min followed by injection of PEG (M n 600) dicarboxylic acid (compound 2; 292.6 g, 0.49 mol) and 80% (by weight a mixture of hexamethylenediamine aqueous solution (71 g, 0.49 mol) and raising the temperature to a final temperature of 285 ° C; and continuous heating cycle 4 (C4) - at atmospheric pressure 11, applying a vacuum of 350 mbar After 24 min, then reverse release to the atmosphere with nitrogen for 6 min, subsequent addition of targeting compound 2 yielded about 8 wt.% of compound 2 with respect to the final polymer weight. The polymer is then poured in a water bath. The polymer is characterized by the results provided in Table 4. Table 4 Example 6 (ag) - Melt Spinning and Fiber Testing Seven polyamine test samples were prepared using procedures and methods similar to those described in Examples 2 through 5, melt spun into fibers and tested to determine their Melt spinning behavior and tensile properties. Table 5 below represents the seven test polyamine samples in terms of composition and water content before spinning. In Table 5, Compound 1 refers to a 2000 Dalton M n poly (ethylene glycol) and poly prepared according to Example 1 of (glycol ether) dicarboxylic acid, the compound 2 means the number average molecular weight of 600 Doyle Poly (ether diol) dicarboxylic acid. In Example 6(f), no additive was present in the N66 polydecylamine and this was used as a control sample. In Example 6(g), only about 10 wt.% of the RE 2000 component was present in the N66 polydecylamine. RE 2000 refers to ELASTAMINE ® RE-2000 amine; a commercial product available from Huntsman Corp. table 5 Partially oriented yarn (POY) spinning is carried out using a single screw extruder (eg, a Haake extruder or equivalent) and a winder (eg, Barmag SW 46 or equivalent). The POY yarn was drawn to a fully drawn yarn (FDY) using a two-stage Zinser stretch-twist setting. The mechanical properties of the yarn were determined using a Textechno Statimat M tensile tester. The water absorption rate was measured according to the water retention capacity method No. DIN 53814. To improve spinning stability, a single filament fineness was obtained by using 13 300-μm diameter holes in the spinneret. Single filament denier increased from 2.75 dtex to 5.07 dtex. The samples of Examples 6(c) to 6(g) were successfully spun using the conditions shown in Table 6 below. The successfully spun POY yarn was stretched to an elongation of 25%. For each sample, four yarns were combined and knitted. Table 6 In all test cases, the pump rotation speed was maintained at 24 RPM and the pump output was 1.2 cm 3 . The winder conditions were maintained at a winding speed of 4000 m/min, a Godet speed of 3980-3990 m/min and a 1007 Traverse DH. The mechanical properties of the above POY and FDY were measured and are shown in Table 7 below. 6(a) and 6(b) yarn samples are not available for testing because of the technical difficulties encountered in the curling of such samples. Table 7 The term "tex" is a unit of measure of the linear mass density of fibers, yarns and threads and is defined as mass in grams per 1000 meters. Ditute (abbreviated as "dtex") is a unit of measure of the linear mass density of fibers, yarns, and threads and is defined as mass in grams per 10,000 meters. The unit "cN/tex" used for toughness measurement means centiNewton/tex. The water absorption rate was measured by filling the yarn sample into a dry weighing container, and the container was filled with deionized water at 20 °C. After 2 hours, the water was removed by centrifugation at 4000 RPM. The sample was dried at 105 ° C until no further weight loss was observed. The water absorption rate data is shown in Table 8 below. Table 8 Example 7 - 24 liter autoclave batch preparation with 8 wt.% poly ( ether diol ) dicarboxylic acid. Preparation of salt Following the procedure of Example 2, using a nitrogen-filled nitrogen purged 24 liters Mixing and jacket temperature controlled glass containers were subjected to multiple batch preparations. Each batch of initial charging amount based about 15,000 g, including from about 6,800 g of nylon 66 salt, about 7,500 g of water, about 549 g of Compound 2 [i.e., obtained from the M n 600 manufactured by Dalton PEG dicarboxylic acid And about 133 g of 80% by weight aqueous solution of hexamethylenediamine. The mixture was stirred until dissolved to yield a crude 50 wt.% strength salt solution. At the time of polymerization, each batch produced approximately 6,500 g of polymer. The polymeric targeting polymer contained about 8 wt.% Compound 2 relative to the weight of the final polymer. For the polymerization, the temperature-pressure cycles as described in Examples 2 to 5 were employed and no evaporator was used. After the polymerization was completed, the polymer from each batch was poured in a water bath. A total of 16 24 liter autoclave batches were run sequentially using the procedure of Example 7 to produce a sufficient amount of the disclosed polymer containing about 8 wt.% Compound 2 relative to the final polymer weight. This multi-batch production also demonstrates that the disclosed method produces a consistent quality product in batch production. The measured RV values ranged from 37 to 43 with an average of about 39 RV and an AEG value in the range between 37 and 50 with an average of about 44 AEG. Table 9 below gives an overview of the polymer products prepared and characterized in accordance with the present invention. Table 9 Representative polymer samples were constructed using the products prepared in multiple batches of Example 7, and their color parameters [as listed in the last column of Table 9] were measured as L* = 78.83, a* = -0.69, b* = 10.42 and the yellowness index [YI] is 26.07. The combined polymeric materials produced in the multiple batches of Example 7 can be used in fiber spinning and/or other downstream applications, as is generally known in the art. Although the illustrative embodiments of the present disclosure have been specifically described, it is understood that various other modifications will be apparent to those skilled in the art without departing from the scope of the disclosure. Therefore, the scope of the invention is not intended to be limited to the examples and descriptions set forth herein, but the scope of the claims is intended to cover all features of all patentable novelity present in the invention, including All features of the equivalents are considered by those skilled in the art. Example 1. A polydecylamine comprising the reaction product of: a. an aliphatic diamine; and b. a diacid wherein at least a portion of the diacid is a poly(ether diol) dicarboxylic acid. 2. The polyamine of embodiment 1, wherein the poly(ether diol) dicarboxylic acid has a number average molecular weight (Mn) of > 250 Daltons and < 2000 Daltons. 3. The polyamine of Example 2, wherein the poly(ether diol) dicarboxylic acid is an aliphatic dicarboxylic acid. 4. Polyamine as in Example 1, characterized in that the moisture regain is from ≥5% to ≤35%. 5. The polyamine of embodiment 1, wherein the aliphatic diamine is hexamethylenediamine. 6. The polyamine 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 polyamine of Example 1, which is formed by a condensation reaction in the presence of water at a pressure of ≥ 1 bar. 8. Polyamine according to embodiment 1, characterized in that the elongation at break is from 20% to 90% when spun into a yarn. 9. The polyamine of Embodiment 1, wherein the poly(ether diol) dicarboxylic acid is in a range of from ≥1% by weight to ≤50% by weight based on the total weight of the dicarboxylic acid in the polyamidamine The quantity exists. 10. The polyamine of embodiment 9, wherein the poly(ether diol) dicarboxylic acid is between ≥5 wt.% and ≤25 by weight based on the total weight of the dicarboxylic acid in the polyamine. The amount in the range of wt.% exists. 11. The polyamine of embodiment 10, wherein the poly(ether diol) dicarboxylic acid is between ≥8 wt.% and ≤20 by weight based on the total weight of the dicarboxylic acid in the polyamine. The amount in the range of wt.% exists. 12. The polyamine of Example 1, wherein the copolymerized hexamethyleneamine has a relative viscosity of from ≥20 to ≤80 according to the formic acid test of ASTM D789-86. 13. The polyamine of embodiment 1, wherein the copolymerized hexamethyleneamine has an amine end value of from ≥25 moles to ≤130 mole amine ends per 1000 kilograms of polymer. 14. Polyamine according to embodiment 1, characterized in that it is selected from at least one of the following: a. L* color coordinates are ≥75 to ≤85; b. a* color coordinates are ≥-5 to ≤5; c. b* color coordinates are ≥5 to ≤25; and d. yellowness index is ≥25 to ≤45. 15. The polyamine of embodiment 1, further comprising at least one selected from the group consisting of: a. TiO2 ≥ 0.01 wt.% to ≤ 2 wt.% by weight; and b. 0.01 wt% by weight .% to 1 wt.% optical brightener, wherein the optical brightener is not titanium dioxide. 16. A copolymerized hexamethyleneamine comprising: a. a diacid wherein all CH bonds are saturated; b. an aliphatic poly(ether diol) dicarboxylic acid; and c. at least one ether free moiety or a diamine of an aromatic moiety; wherein the copolymerized hexamethylenediamine is characterized in that the moisture regain in air of 50% to 65% relative humidity is ≥5% by weight and ≤35 weight based on the weight of the copolymerized hexamethylenediamine %. 17. A process for the production of copolymerized hexamethylenediamine comprising: a. an aliphatic diacid, a poly(ether diol) dicarboxylic acid, at least one diamine having no ether moiety, and optionally an ether moiety The nylon salt is contacted to form a mixture; and b. the mixture is heated to a temperature sufficient to polymerize the mixture and form a copolymerized hexamethyleneamine. An article obtained by copolymerizing hexamethylenediamine according to any one of embodiments 1 to 17, which is selected from the group consisting of: a. a fiber; and b. a fabric, wherein the fabric has a woven fabric selected from the group consisting of: , knitting, and directly arranging the structure of at least one of the nonwovens. 19. The article of embodiment 18, comprising a fabric, wherein the fabric loses less than 10% of its original weight when immersed in water at 100 bar at a pressure of 1 bar for 10 minutes. 20. The article of embodiment 19, wherein the fabric loses a portion of its original weight, measured in air at 50% to 65% relative humidity, wherein the portion of the lost weight is selected from the group consisting of: ≤9 %, ≤ 8%, ≤ 7%, ≤ 6%, ≤ 5%, ≤ 4%, ≤ 3%, ≤ 2%, and ≤ 1%.

Claims (20)

  1. A polyamine which comprises the reaction product of: a. an aliphatic diamine; and b. a diacid wherein at least a portion of the diacid is a poly(ether diol) dicarboxylic acid.
  2. The polyamine of claim 1, wherein the poly(ether diol) dicarboxylic acid has a number average molecular weight (Mn) of ≥ 250 Daltons and ≤ 2000 Daltons.
  3. The polyamine of claim 2, wherein the poly(ether diol) dicarboxylic acid is an aliphatic dicarboxylic acid.
  4. The polyamine of claim 1, wherein the moisture regain is ≥ 5% to ≤ 35%.
  5. The polyamine of claim 1, wherein the aliphatic diamine is hexamethylenediamine.
  6. The polyamine of claim 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 polyamine of claim 1 which is formed by a condensation reaction at a pressure of ≥ 1 bar in the presence of water.
  8. The polyamine of claim 1, wherein the elongation at break is from 20% to 90% when spun into a yarn.
  9. The polyamine of claim 1, wherein the poly(ether diol) dicarboxylic acid is in an amount ranging from ≥1% to ≤50% by weight based on the total weight of the dicarboxylic acid in the polyamine presence.
  10. The polyamine of claim 9, wherein the poly(ether diol) dicarboxylic acid is ≥5 wt.% to ≤25 wt% by weight based on the total weight of the dicarboxylic acid in the polyamine. The amount in the range of % exists.
  11. The polyamine of claim 10, wherein the poly(ether diol) dicarboxylic acid is ≥8 wt.% to ≤20 wt% by weight based on the total weight of the dicarboxylic acid in the polyamine. The amount in the range of % exists.
  12. The polyamine of claim 1, wherein the polyamine has a relative viscosity of from ≥20 to ≤80 according to the formic acid test of ASTM D789-86.
  13. The polyamine of claim 1, wherein the polyamine has an amine end value of from ≥25 moles to ≤130 mole amine ends per 1000 kilograms of polymer.
  14. The polyamine of claim 1, which is characterized by being selected from at least one of the following: a. L* color coordinates are ≥75 to ≤85; b. a* color coordinates are ≥-5 to ≤5; c. b* color coordinates are ≥5 to ≤25; and d. yellowness index is ≥25 to ≤45.
  15. The polyamine of claim 1, further comprising at least one selected from the group consisting of: c. TiO 2 ≥ 0.01 wt.% to ≤ 2 wt.% by weight; and d. 0.01 wt.% by weight Up to 1 wt.% optical brightener, wherein the optical brightener is not titanium dioxide.
  16. A copolymerized hexamethyleneamine comprising: d. a diacid wherein all CH bonds are saturated; e. an aliphatic poly(ether diol) dicarboxylic acid; and f. at least one ether free moiety or aromatic a portion of the diamine; wherein the copolymerized hexamethyleneamine is characterized in that the moisture regain in air of 50% to 65% relative humidity is ≥ 5% by weight and ≤ 35% by weight based on the weight of the copolymerized hexamethylenediamine.
  17. A method for producing copolymerized hexamethyleneamine, comprising: c. an aliphatic diacid, a poly(ether diol) dicarboxylic acid, at least one diamine having no ether moiety, and optionally a nylon salt containing no ether moiety Contacting to form a mixture; and d. heating the mixture to a temperature sufficient to polymerize the mixture and form a copolymerized hexamethyleneamine.
  18. An article made from the polyamine of any one of claims 1 to 15 or the copolymerized hexamethyleneamine of claim 16, the article being selected from the group consisting of: a. fiber; and b. fabric, wherein The fabric has a structure selected from at least one of woven, knitted, and directly laid nonwovens.
  19. The article of claim 18, which comprises a fabric wherein the fabric loses less than 10% of its original weight when immersed in water at 100 ° C for 10 minutes at a pressure of 1 bar.
  20. The article of claim 19, wherein the fabric loses a portion of its initial weight, measured in air at 50% to 65% relative humidity, wherein the portion of the lost weight is selected from the group consisting of: ≤ 9% , ≤ 8%, ≤ 7%, ≤ 6%, ≤ 5%, ≤ 4%, ≤ 3%, ≤ 2% and ≤ 1%.
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JPS5519948B2 (en) 1973-02-06 1980-05-29
IT1170089B (en) 1983-12-30 1987-06-03 Snia Fibre Composition copolymer suitable for the production of synthetic fibers with high hydrophilicity, process for its preparation, fibers and artifacts related
US4963638A (en) 1988-02-26 1990-10-16 Kimberly-Clark Corporation Superabsorbent thermoplastic compositions and nonwoven webs prepared therefrom
US5164261A (en) 1990-08-08 1992-11-17 E. I. Du Pont De Nemours And Company Dyed antistain nylon with cationic dye modifier
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