WO2000004095A1 - Melanges de polymeres faconnes, anti-salissures, obtenus a l'aide d'additifs de polyester et procede de fabrication associe - Google Patents

Melanges de polymeres faconnes, anti-salissures, obtenus a l'aide d'additifs de polyester et procede de fabrication associe Download PDF

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Publication number
WO2000004095A1
WO2000004095A1 PCT/US1999/016059 US9916059W WO0004095A1 WO 2000004095 A1 WO2000004095 A1 WO 2000004095A1 US 9916059 W US9916059 W US 9916059W WO 0004095 A1 WO0004095 A1 WO 0004095A1
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Prior art keywords
polymer
blend
ppm
nylon
additive
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PCT/US1999/016059
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English (en)
Inventor
Yousef Mohajer
Konstantin N. Goranov
Dale Alan Hangey
Samir Z. Abdalla
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Alliedsignal Inc.
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Priority to AU49992/99A priority Critical patent/AU4999299A/en
Publication of WO2000004095A1 publication Critical patent/WO2000004095A1/fr

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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids

Definitions

  • This invention relates generally to a process for making stain-resistant, shaped polymer blends. More specifically, this invention relates to a process for making stain-resistant polymer blends in which a modified polyester additive is added to a polyamide base after polymerization of the base, and the resulting blend is either spun into fibers or chipped out for subsequent use alone or as a masterbatch.
  • Topical application via an aqueous bath, is one such method of imparting stain resistance to the already spun fiber or carpet. See, for example, USP's 4,592,940 and USP 4,501 ,591 , which disclose the application of aqueous solutions of sulfonated condensation polymers of phenol formaldehyde to carpet by spraying or immersion.
  • a major disadvantage of the use of sulfonated phenol-formaldehyde condensation products is their tendency to discolor, turning yellow upon exposure to light.
  • Other chemical topical application systems have been developed to overcome this yellowing, e.g., as taught in USP 5,032,136.
  • a random copolymer is made by adding sulfonated isophthalic acid (and a diamine) to the appropriate monomer (caprolactam or nylon 66 salt) at the salt blend stage prior to polymerization.
  • the sulfonated monomers are incorporated into the nylon backbone during polymerization.
  • Such salt blend processes are also problematic in several respects. For the copolymer manufacturer, if the polymerization vessel in which the copolymer is made shares venting and effluent lines with other polymerization trains, there is a risk of cross- contamination with the sulfonated monomers or byproducts.
  • the fiber producer is restricted to the relatively low level of stain resistance that can be provided by its polymer supplier; high amounts of the sulfonated monomers negatively impacts on the relative viscosity of the copolymer formed, which affects downstream processing and spinning.
  • the melting point of the ultimately-produced fiber is depressed when sulfonated isophthalic acid is incorporated into nylon 6 backbone to the extent needed to impart a very high degree of stain resistance. The degree of depression is sufficient, for instance, to result in a significant degree of fiber melting during downstream Superba heatsetting of the fiber, a typical treating step for nylon carpet fiber.
  • a third approach to achieving stain resistance is to add a material to a polymer base. See, e.g., USP 3,846,507, which teaches forming a stain resistant polyamide by blending and melt-extruding sulfonated polyamide additives with a non-sulfonated polyamide base.
  • the polyamide-based additives taught however, cause problems in the extrusion process and have an adverse effect on properties of the resulting fibers.
  • the stain resistance of the resulting polyamide material is not as good as that achievable with the instant invention.
  • the process for producing a stain-resistant, shaped polymer blend comprises the steps of adding a modified polyester polymer, preferably with heat to a polyamide base polymer to form a polymer blend, preferably a melt, followed by shaping the polymer blend.
  • the stain-resistant, shaped polymer blend comprises a modified polyester polymer and a polyamide base polymer.
  • This polymer blend can be (1 ) shaped immediately into an article such as a stain resistant fiber or film, (2) chipped out for subsequent shaping p_er se, or (3) chipped out for use as masterbatch, i.e., to be combined with polymer at a later stage, to form articles having a desired stain resistance.
  • the present invention is also directed to the modified polyester polymer and to the shaped polymeric articles formed from the polymer blend, e.g., fiber, film, chip, and to articles made with the shaped polymeric articles, e.g., fabrics such as carpet.
  • modified polyester polymer is meant a polyester polymer containing monomers having a negatively charged moiety. It is preferred that the polyester polymer be modified by incorporating sulfonates, most preferably by using sulfonated acids to prepare the polyester additive; it is the sulfonate group that forms the negatively charged moiety in this instance.
  • Other negatively charged moieties useful in this invention include phosphinic acid and borates.
  • the modified polyester polymer additive contains from about 2000 to about 109,000, more preferably about 10,000 to about 90,000, and most preferably from about 20,000 to about 70,000 ppm sulfur.
  • Preferred amounts of the modified polyester polymer component in the polymer blend will vary depending upon the shaped article to be formed, the desired degree of stain resistance for the article, and the identity of the base polymer in the blend.
  • the polyamide base polymer preferably is nylon 6, nylon 6,6, or a copolymer, or mixture thereof.
  • preferred sulfur levels are from about 2000 to about 10,000 ppm, more preferably from about 3000 to about 8000 ppm, and most preferably from about 3000 to about 6000 ppm.
  • preferred sulfur levels are from about 500 to about 8,000 ppm, more preferably from about 1000 to about 6000 ppm, and most preferably from about 1000 to about 5000 ppm.
  • the preferred levels are determined primarily by the practicalities of forming a masterbatch chip and its use in forming the shaped article, e.g., spinning a stain resistant fiber.
  • the present process invention is advantageous because high stain resistance can be imparted to nylon without the disadvantages of the prior art. Specifically, the costly and laborious post-spinning topical stain-resist baths are avoided, polymerization vessels are not contaminated as may occur in salt-blend processes, and producers can readily modulate the amount of stain resistance imparted to the final article, all without affecting properties to a degree that would preclude the intended use of the article.
  • the present product invention finds utility in extruding and chipping out to form chips having a concentrated level of stain resistance.
  • the present product invention is useful in spinning fibers, for use in forming fabrics, e.g., carpets. Other advantages of the present invention will be apparent from the following description and attached claims.
  • shaped articles refers to chips, filaments, fibers, films, molded items and articles made therefrom, including fabrics. Accordingly, “shaping the polymer blend” denotes molding, extrusion and chipping out or spinning. Extrusion and chipping out, and spinning are the preferred modes of shaping.
  • base polymer denotes the polyamide polymer that comprises part of the polymer blend.
  • the polyamide polymers useful as the base polymer in this process include nylon 6, nylon 6,6, nylon 11 , nylon 12, nylon 6,10, nylon 6,12, nylon 4,6, copolymers thereof, and mixtures thereof.
  • the selection of the base polymer may include incorporation of polymer of appropriate molecular weight to control the melt viscosity of the blend for optimal spinning.
  • Nylon 6, nylon 6,6, a copolymer, or mixture thereof, is especially preferred as the base polyamide.
  • modified polyester polymer denotes a polyester polymer that contains monomers having a negatively charged moiety.
  • the polyester additive may be linear or branched, aromatic, aliphatic or a mixture thereof.
  • Negatively charged moieties useful for this invention include sulfonates, phosphinic acid, and borates. The degree of stain resistance is highly dependent on the strength of the negative charge imparted.
  • the most preferred negatively charged moiety is a sulfonate group. It is incorporated into the polyester polymer most preferably using sulfonated dicarboxylic acids.
  • a most preferred sulfonated dicarboxylic acid is sulfonated isophthalic acid (SIPA) and the most preferred alkaline salt of SIPA is sodium (NaSIPA).
  • SIPA is sulfonated isophthalic acid
  • NaSIPA sodium
  • Other useful derivatives of SIPA include lithium, potassium, ammonium salts or partially neutralized or un-neutralized SIPA.
  • Non-modified dicarboxylic acids useful in preparing the polyester additive of this invention include both aliphatic and aromatic dicarboxylic acids. Such acids include C2-C12 diacids such as succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic and dodecanedioic acids.
  • Aromatic diacids include isophthalic and terephthalic acids as well as rigid aromatic diacids such as 2,6-naphthalene and p,p-biphenyl dicarboxylates. Terephthalic acid and adipic acid, or combinations thereof, are the most preferred.
  • the useful polyesters may also contain monocarboxylic acids, preferably benzoic acid, as a molecular weight regulator. Sulfobenzoic acid (m or p) and its sodium, lithium, potassium and ammonium salts are also good regulators.
  • the dihydric alcohols that are useful in preparing the polyester additive include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, and cyclohexanedimethanol or any combination of thereof.
  • the preferred dihydric alcohol is ethylene glycol.
  • the molar ratio of glycols to acids, in the preparation of the stain resist additive (SRA), is from 3:1 to 1.05:1.
  • melt blend denotes addition of an additive to a base polymer before spinning and after polymerization of the base polymer, with the use of increased temperature to achieve the blend.
  • melt blend includes adding an additive as a masterbatch chip (chip blending), as a granular powder and as a molten polymer injection.
  • chip blending the polyamide base polymer and the additive, as chip or powder, are mixed together thoroughly and then are fed into a spinning machine extruder.
  • the heating is provided both by heaters as well as mechanical heat from the extruder drive.
  • the residence time is typically short, 0.5 to 5 minutes.
  • the base polymer melt temperature is in the range of about 220°C to about 300°C.
  • the additive and the base polymer are heated separately such that each is already molten and then are mixed together.
  • a convenient method for melt injection is to melt the additive via an extruder and inject it into the transfer line of molten nylon followed by static mixers. The preference depends only on the method of manufacture and the equipment used.
  • solution dyed nylon fiber denotes nylon fibers that are colored prior to the spinning process.
  • the color pigments are added to the molten nylon in the extruder before the fibers are spun.
  • These fibers include so- called “producer colored” and “melt colored” fibers.
  • the inventive process can be employed separately or in combination with solution dyeing. If employed separately, the stain-resistant polymer blend is subsequently melt blended with a solution dyed nylon polymer, followed by shaping the ultimate blend into, for instance, fiber useful for tufting into carpets.
  • additive loading denotes weight percent additive in the base polymer.
  • stain denotes the non-desirable and non-intentional coloration of a shaped article.
  • stain resistant denotes a Red 40 Stain Scale value of about 4.5 and less by the method described herein or a ⁇ K/S of less than about 0.65.
  • Modification ratio denotes a well-known measure of the cross-section of a trilobal filament.
  • the term is defined in commonly assigned USP 5,322,736, and describes the difference in size between the outside diameter of the trilobal filament and the diameter of its core.
  • a round cross section fiber will have both dimensions the same and will have a MR of one. As the core becomes smaller relative to the outside diameter, the MR becomes bigger.
  • Yarns were tested for stain resistance by knitting the drawn, textured fiber into an approximately 4.5 inches wide sleeve.
  • a 10 gram (g) sample of knitted sleeve was immersed in 200 milliliters (ml) unsweetened cherry flavored Kool- Aid ® for 30 minutes at room temperature (20 to 24°C). The sample was then rinsed in ambient temperature tap water until the rinse liquor was clear, then dried and assessed for staining. Staining was assessed using two different methods. In the first method, the severity of staining was determined using AlliedSignal Inc.'s Red 40 Stain Scale, which is available upon request from AlliedSignal Inc.
  • the second method to assess the severity of staining uses spectrophotometr ⁇ at 520 nm, the wavelength of maximum absorbance of the red dye, to determine K/S values which are proportional to the amount of red dye absorbed by the stained test specimen.
  • Each test specimen was measured using a Datacolor International Spectraflash ® SF600 ® spectrophotometer with diffuse/8° illumination/measurement geometry using illuminant D65.
  • the K/S value for the corresponding non-stained sample was subtracted from the K/S value of the test specimen to compensate for any color associated from the base fiber and the resulting ⁇ K/S is reported as the degree of staining.
  • Higher ⁇ K/S values indicate a greater degree of staining.
  • ⁇ K/S values of less than or equal to 0.25 are considered to have good stain resistance and values less than or equal to 0.10 are considered to have excellent stain resistance by this method.
  • the tenacity of the bulked continuous filament (BCF) yarn was measured in accordance with ASTM Test Method D2256.
  • melt points were measured by differential scanning calorimetry (DSC) using a 2 mg sample of undrawn fiber in the absence of a spin finish, scanned at 10°C/min in a Seiko RDC 220 differential scanning calorimeter. The melt point was taken as the first melt point peak as determined by the DSC computer.
  • Table 1 lists the molar composition of representative polyamide-based additives used in the melt blend process taught in USP 3,846,507 to produce stain resistance in polyamide fiber.
  • Additive C-1 is similar to the additive in
  • Example 2 of the aforementioned patent, and additive C-2 corresponds to that in Example 4, case 2.
  • Additive C-3 employs the same NaSIPA:HMDA ratio as was used in Example 1 of USP 3,846,507.
  • Table 1 are the actual gram weights used in preparing each additive.
  • These polyamide additives were made by the procedure described in USP 3,846,507 in a 5-gallon reactor fitted with an agitator.
  • the additive C-1 was made as follows. The ingredients were charged into a reactor, which was then sealed and heated gradually over 4.5 hours to above 220°C when the internal pressure reached about 100 psi. The pressure was then released to atmospheric pressure over 2 hours while maintaining the reactor wall temperature at about 240°C.
  • the reactor temperature was maintained at 240°C to 250°C while the vessel was subjected to vacuum until a value of 100mm Hg was reached; the temperature and vacuum conditions were then held constant.
  • the torque on the reactor increased over 2 hours and plateaued at a value of 220 inch-pounds at which time the product was extruded and quenched as a slab on a tray.
  • the additive C-2 was made by the same procedure except the torque on the reactor plateaued at a low value of only 40 inch-pounds (low viscosity polymer) when it had to be extruded and ground to the desired size.
  • the additive C-3 was made by the same procedure except it contained a larger quantity of catalyst. The viscosity build up was fast ,and the additive reached a torque of 570 inch-pounds before it was extruded as slab and then ground to the desired size, about 10-mesh size (2mm).
  • IPA stands for isophthalic acid.
  • the polymerization catalyst used was hypophosphorous acid.
  • the relative molar compositions of representative polyester-based additives used in the instant invention are recorded in Table 2.
  • Table 2 In parentheses are the actual gram weights used in preparing each additive in a 5-gallon reactor fitted with an agitator.
  • Typical polymerization conditions were as follows: The polyester-based reactants, including a metal catalyst, were charged into a reactor and sealed after purging with nitrogen. The reactor was heated to about 225°C until a pressure of 90 psi was developed, which took about half an hour. The pressure was then gradually released to atmospheric pressure while raising the reaction temperature to about 255°C over 2 hours.
  • the reactor was subjected to a vacuum cycle over a 2 hour period to reach a vacuum level of about 50 mm Hg, after which the polymer viscosity increased rapidly and the torque reached a target value of about 300 inch-pounds in about half an hour.
  • terminators such as benzoic acid
  • the product was extruded as slabs and flaked or ground to the appropriate size, generally about 10 mesh.
  • the polymerization catalyst used in these examples was Tyzor TE, triethanolamine titanate, chelate (from Elf Atochem). In later versions of these polyester-based additives, antimony triacetate was used interchangeably with Tyzor TE.
  • PTA stands for terephthalic acid.
  • AA stands for adipic acid.
  • EG stands for ethylene glycol
  • ppm sulfur in an additive is calculated as in footnote 5 to Table 1.
  • Polyamide-based additives C-1 , C-2, and C-3, and polyester-based additive I were individually chip blended in two different ratios with chips of an intermediate viscosity (nominal 55 formic acid viscosity, determined by ASTM Test Method D789-96 using a Cannon-Fenske viscometer), low extractable nylon 6 homopolymer, commercially available from AlliedSignal Inc. as MBM Capron ® nylon resin, to yield two chip blends for each additive, one having 3000 ppm and the other having 6000 ppm sulfur (theoretical calculated value). Blending was carried out by weighing out the appropriate amount of base resin and of additive, combining them in a glass jar and mixing in a Twin Shell Dry Blender (The Patterson-Kelley Co., Inc.).
  • the molten filaments were quenched in air at about 19°C and about 40 relative humidity, which was blown past the filaments at about 10 cubic feet per minute.
  • the filaments were pulled through the quench zone by an unheated roll, which rotated at a speed appropriate to achieve an undrawn denier of about 790, and were coated with about 6% spin finish for drawing and texturing.
  • the extruder was flushed with the chip blend for 15 minutes prior to collecting the undrawn fiber.
  • Four undrawn packages were prepared for each chip blend yielding a total run time of 48 minutes. The pot pressure at the start and end of each run for each chip blend was noted.
  • the MR's of the first and third undrawn packages were measured and the average of the two determinations recorded.
  • the four undrawn packages were combined, drawn to 3:1 draw ratio over heated rolls and steam jet textured to achieve a 1250 denier, 56 filament bulked continuous filament yarn.
  • the chip blend of example E was difficult to spin due to sticking in the feed zone of the extruder. Chips were physically forced through the feed zone in order to spin fiber. This stickiness would present a significant problem in a production environment.
  • Change in pot pressure is the difference calculated between the pot pressure at the end of the run and the pot pressure at the start of the run. 1.
  • the "rel. MR” is the relative modification ratio and is calculated by the modification ratio of the sulfur-containing blend divided by the modification ratio of the control.
  • COMPARATIVE EXAMPLE H A random copolymer of nylon 6 containing 6000 ppm sulfur was made using 71.88 g of NaSIPA, 29.6 g of HMDA, 1520 g of lactam, 300 g of water and 0.15 g hypophosphorous acid. The copolymer was made by charging the ingredients into a 3-liter unpressurized glass reactor at 90°C. As an initiator, 80 g of aminocaproic acid was added to the reactor and the temperature was raised to 255°C over 3 hours while a slow flow of nitrogen was allowed to blanket the reaction and remove water. After 5 hours at 255°C, the resin was discharged as a stream into a quenching water bath and was cut into small chips.
  • the chips were extracted with boiling water three times each for two hours to remove the remaining lactam and oligomers.
  • the polymer was dried to 0.05% moisture before spinning.
  • the dried copolymer was spun to produce an undrawn fiber sample and the melt point was determined to be about 200°C.
  • This melt point is significantly lower than that for the nylon 6 control (see Table 3); in fact, the melt point is sufficiently low that fiber spun from this random copolymer (containing 6000 ppm sulfur) would melt under Superba heatsetting conditions.
  • undrawn fiber of Example 2 also loaded with 6000 ppm sulfur, has a melt point significantly higher than 200°C, such that the fibers would not melt under Superba heatsetting conditions.
  • polyester additives of this invention can be added to the polyamide base melt to form the blend in various ways. This permits the fiber manufacturer to adjust the stain resist additive loading, depending on the need of the base polymer, color, etc. and allows the additive to be incorporated with base polymer in a variety of ways.
  • the simplest approach is to add the additive in the form of a chip blend.
  • An additive concentrate or masterbatch allows for the incorporation of other additives, such as rheological modifiers, to the system at a constant ratio to the additive.
  • the stain resist additive could be directly incorporated with the base polymer via melt injection, prior to the formation of pellets or chips. In this method, no additional additive delivery system is needed for fiber spinning. Examples 3, 4 and 5 set forth alternate methods of incorporating the polyester additive.
  • Example 3 an additive concentrate or masterbatch chip was prepared compounding 29.4 weight % Additive I and 70.6 weight % of a high viscosity (nominal 135 FAV), low extractable nylon 6 homopolymer, commercially available from AlliedSignal Inc. as Capron® B135ZP, in a twin screw extruder. The molten blend was extruded through a 5mm-diameter die maintained at about 255°C. The molten strand was quenched in a water-cooling bath and pelletized to form cylindrical chips ("masterbatch”) having about 22,000 ppm sulfur (theoretical calculation).
  • masterbatch cylindrical chips having about 22,000 ppm sulfur (theoretical calculation).
  • This masterbatch chip was then used to prepare a chip blend, which contained 26.9 weight % Masterbatch chips and 73.1 weight % intermediate viscosity, low extractable nylon 6 homopolymer chips, commercially available from AlliedSignal Inc. as MBM Capron® nylon resin.
  • the chip blend was spun into yarn using the method described in Example 1 above.
  • the BCF yarn formed contained about 6,000 ppm sulfur (theoretical calculation).
  • Example 4 a blend was prepared containing Additive I, Capron® B135ZP chips and MBM Capron® nylon resin chips at a ratio equal to that for the fiber prepared in Example 3 and spun directly into yarn using the method described in Example 1.
  • the resulting BCF yarn contained about 6,000 ppm sulfur (theoretical calculation).
  • Example 5 to simulate adding Additive I as a molten polymer via injection to the molten nylon 6, the blend described in Example 4 was melt blended using the method described in Example 3 to yield chips containing about 6,000 ppm sulfur (theoretical calculation). These chips were then spun into yarn using the method described for Example 1.
  • Chip blend compositions using Additives I, II and III were prepared and spun into yarn using the method described in Example 1. The properties of these yarns are reported in Table 5; Example 4 from Table 4 is re-recorded here with the stain resistance values noted. It can be seen that the polyester additives useful for this invention can have diverse composition; the unmodified dicarboxylic acid used can be either entirely aliphatic (Examples 8 and 9) or entirely aromatic (Example 4). It is expected that a combination of aliphatic and aromatic dicarboxylic acids will work equally well in the additive. In alNnstances shown below, the tenacity of the textured fiber was comparable to the control (in Table 3), further demonstrating the usefulness of the polyester additive.
  • EXAMPLE 10 Table 6 lists molar compositions of other representative polyester- based additives of this invention. These additives, made in a similar fashion to additives I, II, and III set forth in Table 2, are expected to provide comparable stain resistance for polymer blends and shaped articles, without a negative impact on process conditions (e.g., pot pressures) or the properties of the shaped articles (e.g., MR, tenacity of spun fiber). These additives are also expected to benefit producers of the shaped articles, e.g., fiber producers, since the level of stain resistance to ultimately be imparted to the shaped article can be controlled without a post-shaping topical treatment.
  • process conditions e.g., pot pressures
  • properties of the shaped articles e.g., MR, tenacity of spun fiber.
  • the polyester-based additives can contain a single or a combination of anionic-bearing dicarboxylic acids (diacids), a single or a combination of unmodified companion diacids and a glycol or a combination of glycols.
  • Table 6 contains, for ease of discussion, NaSIPA, PTA and AA as ingredients, but the invention should not be limited to these.
  • NaSIPA can be replaced with any sulfonated dicarboxylates
  • the PTA can be replaced with any aromatic diacids, such as 2,6 naphthalene dicarboxylic acid
  • (3) AA can be substituted with any aliphatic diacids (linear or branched), such as azelaic or sebacic acids
  • (4) EG can be replaced by any glycol (linear or branched), such as diethylene glycol, 1 ,3 propane diol, 1 ,4 butanediol.
  • the SRA can be terminated with a monofunctional acid such as benzoic acid, for the ease of polymerization process, or can be non-terminated polyester.
  • the range of sulfur content can be varied from about 1700 ppm to 109,000 ppm, corresponding to the molar compositions of NaSIPA from 1 to 100%, respectively. At the very low end (1 %), sulfur content is below 2000 ppm (2.0 K ppm S). To get a nylon blend containing 1000 ppm S, it is therefore necessary to incorporate at least 50% SRA into the blend. This is undesirable since one has to handle excess volume of an additive. Additionally, a this blend composition, the nylon and polyester phases exist concurrently as continuous phases, and the material properties of the nylon are dominated by the polyester. At the other extreme (100%), the companion diacid is absent or is present in minor quantity, and the SRA was found to be difficult to make.
  • This difficulty is related to the rigidity of the SIPA moiety, which renders SRA polymer to be very viscous even at low conversion.
  • the polymerization yield was low because only a small portion of SRA could be extruded.
  • Useful sulfur levels therefore are between these two limits.
  • the preferred level of sulfur in the SRA ranges from 2.0-109 K ppm, more preferably from 10-90 K ppm, and most preferably from 20- 70 K ppm.

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Abstract

La présente invention concerne un mélange de polymère obtenu par adjonction à une base de polyamide, d'un polyester contenant une pluralité de groupes fonctionnels chargés. Ce mélange est ensuite façonné, typiquement sous forme de fibre ou en granulés qui peuvent être filés, moulés ou utilisés comme mélange maître. Les mélanges de polymère façonnés présentent une excellente résistance à la salissure et, dans le cas des fibres de polyamide, il n'y a pas d'impact significatif sur les propriétés de la fibre telles que le rapport de modification ou la ténacité. De la moquette produite à l'aide de telles fibres est aussi caractérisée par une excellente résistance à la salissure.
PCT/US1999/016059 1998-07-17 1999-07-16 Melanges de polymeres faconnes, anti-salissures, obtenus a l'aide d'additifs de polyester et procede de fabrication associe WO2000004095A1 (fr)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6495079B1 (en) 2000-06-28 2002-12-17 Prisma Fibers, Inc. Process to prepare polymeric fibers with improved color and appearance
WO2006056706A1 (fr) * 2004-11-29 2006-06-01 Rhodia Chimie Composition comprenant un polymere thermoplastique et un agent hydrophilisant
US9605147B2 (en) 2013-08-01 2017-03-28 Samsung Sdi Co., Ltd. Thermoplastic resin composition and molded article using same
CN107489039A (zh) * 2017-10-24 2017-12-19 桐乡市百代服饰有限公司 一种精梳棉、改性锦纶织物及其生产工艺
WO2021167913A1 (fr) * 2020-02-18 2021-08-26 Advansix Resins & Chemicals Llc Formulation de mélange maître à base de polyamide
CN115427481B (zh) * 2020-02-18 2024-05-31 艾德凡斯化学公司 基于聚酰胺的母料制剂

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US6495079B1 (en) 2000-06-28 2002-12-17 Prisma Fibers, Inc. Process to prepare polymeric fibers with improved color and appearance
WO2006056706A1 (fr) * 2004-11-29 2006-06-01 Rhodia Chimie Composition comprenant un polymere thermoplastique et un agent hydrophilisant
US9605147B2 (en) 2013-08-01 2017-03-28 Samsung Sdi Co., Ltd. Thermoplastic resin composition and molded article using same
CN107489039A (zh) * 2017-10-24 2017-12-19 桐乡市百代服饰有限公司 一种精梳棉、改性锦纶织物及其生产工艺
WO2021167913A1 (fr) * 2020-02-18 2021-08-26 Advansix Resins & Chemicals Llc Formulation de mélange maître à base de polyamide
CN115427481A (zh) * 2020-02-18 2022-12-02 艾德凡斯化学公司 基于聚酰胺的母料制剂
US11920009B2 (en) 2020-02-18 2024-03-05 Advansix Resins & Chemicals Llc Polyamide-based masterbatch formulation
CN115427481B (zh) * 2020-02-18 2024-05-31 艾德凡斯化学公司 基于聚酰胺的母料制剂

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