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WO2018031229A1 - Polymère de nylon - Google Patents

Polymère de nylon Download PDF

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Publication number
WO2018031229A1
WO2018031229A1 PCT/US2017/043608 US2017043608W WO2018031229A1 WO 2018031229 A1 WO2018031229 A1 WO 2018031229A1 US 2017043608 W US2017043608 W US 2017043608W WO 2018031229 A1 WO2018031229 A1 WO 2018031229A1
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WO
WIPO (PCT)
Prior art keywords
polyamide
dicarboxylic acid
weight
poly
ether glycol
Prior art date
Application number
PCT/US2017/043608
Other languages
English (en)
Inventor
Michael A. ARMITAGE
Michael D. BENSTEAD
Charles R. Langrick
Milind V. Kantak
Keith Whiston
Original Assignee
Invista North America S.A R.L.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Invista North America S.A R.L. filed Critical Invista North America S.A R.L.
Publication of WO2018031229A1 publication Critical patent/WO2018031229A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/265—Polyamides 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/40—Polyamides containing oxygen in the form of ether groups

Definitions

  • 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.
  • Patent 3,946,089 to Furukawa et. al. relates to a block copolymer comprising a polyamide segment and a polyether segment.
  • 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).
  • U.S. Patent 4,963,638 to Pazos et al. relates to a superabsorbent thermoplastic polymer comprising a poly(oxyethlene) diol soft segment.
  • European Patent 0 504 784 relates to polyetheresteramides containing 20 to 40 wt.% poly(ether) diol / dicarboxylic acid monomer.
  • U.S. Patent 5,306,761 to Ohwaki et al. relates to a polyamide containing a copolymerized polyalkylene oxide unit.
  • U.S. Patent 6,420,045 to Faulhammer et al. relates to a polyamide with hydrophilic blocks.
  • 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.
  • 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.
  • 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.
  • 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.
  • Suitable dicarboxylic acids include PEG (poly(ethylene) glycol)-derived dicarboxylic acids.
  • 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.
  • 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).
  • the disclosed polyamides are well-suited for making hydrophilic polyamide compositions.
  • 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.
  • compositions can be suitable for making a yarn or fiber and a textile or fabric or garment containing such yarns or fibers.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • an organic base such as potassium tert- butoxide
  • an alkylating agent such as ethyl bromoacetate.
  • 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.
  • a mineral acid such as aqueous hydrochloric acid
  • an organic solvent such as dichloromethane
  • low molecular weight poly(ether glycol) dicarboxylic acids such as poly(ethylene glycol) may be purchased from suppliers such as the Sigma-Aldrich company.
  • 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).
  • PEG polyethyieneglycol
  • PPG polypropyleneglycol
  • PTMG polytertramethyleneglycol
  • 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.
  • 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.
  • the poly(ether glycol) dicarboxylic acid can have a number-average molecular weight (M n measured in Daltons, Da) of at least 250 Da.
  • 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.
  • 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.%.
  • the polyamides described herein comprise aliphatic diamines.
  • the diamine can be an aliphatic diamine containing from 6 to 12 carbon atoms.
  • 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.
  • 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.
  • 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.
  • the disclosed polyamides can further comprise one or more po!y(ether glycol) dicarboxylic acid as described above.
  • the poly(ether glycol) is selected from the poly(ether glycol)
  • the dicarboxylic acid can have a number-average molecular weight (M n ) of ⁇ 250 Daltons (Da), for example, ⁇ 500 Da, ⁇ 600 Da, and ⁇ 1500 Da.
  • the poly(ether glycol) dicarboxylic acid can have a M n of ⁇ 2500 Da, or even ⁇ 5000 Da.
  • the disclosed polyamides can further comprise one or more polyetheramines, as described in published PCT Application WO 2014/057363.
  • 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.
  • the present polyamides can further comprise a catalyst.
  • 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.
  • the catalyst can be sodium hypophosphite, manganese hypophosphite, sodium phenylphosphinate, sodium phenylphosphonate, potassium phenylphosphinate, potassium phenylphosphonate, hexamethylenediammonium bis-phenylphosphinate, potassium tolylphosphinate, or mixtures thereof.
  • the catalyst can be sodium hypophosphite.
  • 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.
  • 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.
  • the optical brightener can be present in the polyamide in an amount ranging from 0.01 wt.% to 1 wt.%.
  • an improvement in whiteness appearance can be achieved by addition of a delustering agent.
  • the delustering agent can be titanium dioxide.
  • these polyamide compositions may contain an antioxidant stabilizer or an antimicrobial additive.
  • the polyamide compositions may contain an anti-foaming additive.
  • the anti-foaming additive can be present in the polyamide in an amount ranging from 1 ppm to 500 ppm by weight.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.%.
  • 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).
  • the heating can be performed under partial vacuum.
  • the partial vacuum attained is subject to autoclave design and economic considerations with the process.
  • 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
  • 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.
  • 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.
  • 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.
  • the laces of polyamide polymer may be granulated by known means and further cooled with water.
  • 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.
  • the polymer composition may be directly supplied to polymer extrusion equipment designed and operated to handle the polymer melt.
  • the disclosed polymer composition can be processed in a screw extruder, for example a twin-screw extruder.
  • 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.
  • 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.
  • 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.
  • 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.
  • the polymerization reaction can be carried out in a continuous polymerizer.
  • the composition may optionally be partially polymerized in an autoclave or continuous polymerizer and then finished in a solid-phase polymerizer.
  • 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.
  • 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.
  • 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.
  • the nylon polymers and copolyamides described herein can be inherently acid-dyeable.
  • the number of free amine end groups (AEG) in these polymers is at least 25 moles per 1000 kilograms of nylon polymer.
  • 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.
  • 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.
  • 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.
  • the masterbatch nylon flake containing the poly(ether glycol) dicarboxylic acid, and optionally a polyetheramine and the nylon, in flake form are both melted.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the polyamide composition of the present disclosure is particularly useful when spun into yarns.
  • 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.
  • said yarn exhibits improved hydrophilic properties as measured by various water wicking and moisture regain tests.
  • 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.
  • the yarn may be substantially continuous, i.e. formed by one or more continuous filaments.
  • 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.
  • 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.
  • 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.
  • 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.
  • the yarn comprises from 1 to 300 filaments.
  • 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.
  • the yarn has a DPF (dtex per filament) from
  • 0.5 to 2.5 for example from 1 to 1.5.
  • 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.
  • U% Uster percent
  • 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].
  • 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.
  • 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.
  • yarns of the polyamide may be prepared by using known melt spinning process 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a second application of spin finish and/or additional interlacing may be applied before the final winding step.
  • 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.
  • the LOY spinning process is similar to POY except that a windup speed of
  • These low orientation yarns are further processed via a second stage, e.g., on a conventional draw-twister or draw-wind machine.
  • 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.
  • 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.
  • G polymer throughput
  • p is the polymer melt density (e.g., for melted nylon 6,6 at
  • D is the diameter (equal to twice the radius) of the capillary assuming a circular orifice
  • v the velocity of the filament.
  • the polymer is extruded at an extrusion velocity in the range of 20 centimeters per second to 80 centimeters per second.
  • the freshly extruded filaments can be quenched with conditioned air in the known manner.
  • 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.
  • 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.
  • the yarn is a drawn yarn with elongation of 22% to about
  • 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
  • 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.
  • 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.
  • the Yarn Quality is an approximation to the measure of yarn "toughness.”
  • the area under the yarn load elongation curve is proportional to the work done to elongate the yarn.
  • the load elongation curve is the stress-strain curve.
  • 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.
  • 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 ⁇ -sulfatoethylsulfonyl groups. Such fiber reactive dyes are known from United States Patent No. 5,810,890.
  • the polyamide yarns are dyed with fiber reactive dyes which incorporate halogen derivatives of nitrogen hetrocyclic groups, such as, triazine, pyrimidine and quinoxaline.
  • fiber reactive dyes are described, for example, in United States Patent No. 6,869,453.
  • the filaments comprise an amine component of hexamethylenediamine.
  • 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,
  • the polyamides may comprise nylon 6.
  • 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.
  • cN/tex centi-Newtons per tex
  • grams of force per denier grams of force per denier
  • Yarn linear density evenness also known as the yarn Uster percent (U%)
  • U% yarn Uster percent
  • Polymer amine ends can be measured by direct titration with standardized perchloric acid solution of weighed polymer samples taken up in solution.
  • 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.
  • 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:
  • 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.
  • the moisture regain may be measured by a method such as DIN
  • 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.
  • Hexamethylenediamine or HMD is commercially available from INVISTA
  • poly(ether glycol) dicarboxylic acid refers to a class of poly(ethylene glycol)bis(carboxymethyl) ether having a general chemical structure of wherein n is a numerical value.
  • M n , of 600 (herein referred to as Compound 2 in the examples of this disclosure) was obtained from a commercial source, VWR International.
  • RE 2000 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.
  • ylon 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.
  • 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.
  • R 1 may contain one or more ether groups.
  • 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.
  • 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 (adip
  • 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.
  • R 2 may contain one or more ether groups.
  • 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.
  • 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,
  • a preferred diamine is hexamethylene diamine.
  • 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 ( ⁇ ) 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.
  • 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
  • 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
  • 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").
  • Polyethylene glycol) (PEG, Mlois 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.
  • PEG Polyethylene glycol
  • the product may be characterized by NMR, FTIR and/or acid value.
  • Example 2 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.
  • 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,
  • Nylon 66 salt 3423 g, 13.05 mol
  • PEG (M n 600) dicarboxylic acid Compound 2; 439 g, 0.73 mol
  • aqueous hexamethylenediamine 85.0 g, 0.73 mol
  • Nylon 66 salt (3038 g, 11.58 mol)
  • PEG (M n 600) dicarboxylic acid Compound 2; 731.6 g, 1.22 mol
  • 80% (by weight) aqueous hexamethylenediamine 141.7g, 1.22 mol
  • Example 5 represents these seven test polyamide samples in terms of the composition and measured water content before spinning.
  • 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.
  • Example 6(f) no additives were present in the N66 polyamide, and this was used as a control sample.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • cN/tex for tenacity
  • Example 7 24-Liter Autoclave Batch Preparation ofPolyamide with 8 wt.% Poly (ether glycol) dicarboxylic acid
  • the polymer was targeted to contain about 8 wt.% Compound 2 with respect to the final polymer weight.
  • the temperature-pressure cycles as described in Example 2 through 5 were employed and no evaporator was used.
  • the polymer from each batch was cast in the water bath.
  • Example 7 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.
  • Table 9 gives a summary of polymer products that were prepared and characterized according to the present disclosure.
  • 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.
  • Polyamide comprising the reaction product of:
  • diacid wherein at least a portion of the diacid is poly(ether glycol) dicarboxylic acid.
  • polyamide of embodiment 1 characterized by at least one selected from:
  • polyamide of embodiment 1 further comprising at least one selected from:
  • optical brightener 0.01 to 1 wt.% by weight of an optical brightener, wherein the optical
  • brightener is not titanium dioxide.
  • a copolyadipamide comprising:
  • 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%.
  • a process for producing a copolyadipamide comprising:
  • 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.

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Abstract

La présente invention concerne un polyamide comprenant une diamine et un acide dicarboxylique de poly(éther glycol), lequel acide dicarboxylique de poly(éther glycol) présente un poids moléculaire moyen en nombre (Mn) d'au moins 250 Daltons.
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CN113461936B (zh) * 2021-08-19 2022-11-01 北京化工大学 长碳链尼龙弹性体的制备方法及二元羧酸的用途

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