Classifications

• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
  • D01F6/86—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from polyetheresters

Definitions

• This invention relates to a method of melt-spinning a polyether ester thermoplastic elastomer under commercially viable conditions to produce an elastoester multifilament yarn, wherein the polyether ester thermoplastic elastomer is a polytrimethylene ether ester comprising a polytrimethylene ether dicarboxylate ester soft segment and hard segment selected from a trimethyl- ene dicarboxylate ester and/or a tetramethylene dicarboxylate ester hard segment.
• elastoester is, in the USA, a generic description in the context of a fiber that contains at least 50% by weight of an aliphatic polyether and at least 35% by weight of a polyester.
• An elastoester is stretchy like a spandex, readily washable, and capable of withstanding high temperatures when wet. Elastoesters are said to retain dyes better than fabrics made of nylon and spandex, and are less likely to be discolored or adversely affected by chlorine, which is an important characteristic for garments like swimming suits.
• US6562457 discloses a polyether ester thermoplastic elastomer comprising a polytrimethylene ether ester soft segment and a tetramethylene ester hard segment.
• US6599625 discloses a polyether ester thermoplastic elastomer comprising a polytrimethylene ether ester soft segment and trimethyl- ene ester hard segment.
• US6905765 discloses a polyether ester elastomer comprising a poly(trimethylene-ethylene ether) ester soft segment and an al- kylene ester hard segment.
• the polyether esters disclosed therein are useful in making fibers, either continuous filaments or staple fibers, and that the fibers can be used to prepare woven, knit and non-woven fabrics.
• the fibers disclosed are stretchy, have good chlorine resistance, can be dyed under normal polyester dyeing conditions, and have excellent physical properties including superior strength and stretch recovery properties, particularly improved unload power and stress decay.
• US6562457 and US6599625 further indicate that the fibers can be melt spun from the disclosed polymers at speeds up to about 1200 m/min, and can be drawn up to about 6x. Being able to melt spin under these conditions would be a commercial advantage over solution spinning, which is used for spandex or elastane, a manufactured synthetic fiber comprising at least 85% of a segmented polyurethane.
• polyether ester thermoplastic elastomers can be melt-spun at spinning speeds of greater than about 1200 m/min, and under other commercially feasible conditions, to produce multifil- ments (multifilament yarns).
• the present invention thus provides commercially feasible conditions for melt spinning elastoester fibers comprising poly- trimethylene ether ester polymers that contain polytrimethylene ether dicar- boxylate ester soft segments, and trimethylene dicarboxylate ester or tetramethylene dicarboxylate ester hard segments.
• a polyether ester thermoplastic elastomer comprising from about 80 to about 40 wt% of a polytrimethylene ether dicarboxylate ester soft segment, and from about 20 to about 60 wt% of a hard segment selected from the group consisting of a trimethylene dicarboxylate ester, a tetramethylene dicarboxylate ester and mixtures thereof, based on the combined weight of the hard and soft segments;
• the process of the invention may further comprise the step of cutting the multifilament yarn into staple fibers.
• the invention also relates to multifilament yarn prepared by the above process, and to fabric comprising the so-prepared multifilament yarn.
• the resulting multifilament yarn is an elastoester yarn preferably with an elongation of from about 100 to about 600%, and a tenacity of from about 0.5 to about 2.5 grams/denier, and comprises filaments of from about 0.5 to about 20 denier per filament (dpf).
• the multifilament yarn is spun drawn yarn and the processing comprises drawing the filaments at a draw speed, as measured at the roller at the end of the draw step, of about 1250 to about 5000 meters/minute.
• the processing into spun drawn multifilament comprises drawing, annealing, interlacing and winding the filaments.
• the multifilament yarn is partially oriented yarn and the spinning speed is preferably greater than about 1500 meters/minute.
• Multifilament textured yarn may be prepared from the partially oriented yarn by a process comprising: (a) preparing a package of partially oriented multifilament yarn; (b) unwinding the yarn from the package; (c) drawing the filaments to form a drawn yarn; (d) false-twist texturing the drawn yarn to form the textured yarn; and (e) winding the yarn onto a package.
• the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion.
• a process, method, article, or appara- tus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
• "or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
• polyether ester thermoplastic elastomers for use in the invention preferably contain:
• the polyether ester thermoplastic elastomers preferably have an in- herent viscosity of at least about 0.8 dl/g, more preferably at least about 1.2 dl/g, and preferably up to about 2.0 dl/g, and more preferably up to about 1.6 dl/g.
• Polytrimethylene ether ester soft segment and “soft segment” are used in connection with the present invention to refer to the reaction product of a polymeric ether glycol and a “dicarboxylic acid equivalent", via ester linkage, wherein at least about 50 wt%, more preferably at least about 85 wt%, and still more preferably from about 95 to 100 wt%, of the polymeric ether glycol used to form the soft segment is a polytrimethylene ether glycol (PO3G).
• PO3G polytrimethylene ether glycol
• Polytrimethylene ester hard segment “polytetramethylene ester hard segment” and “hard segment” are used in connection with the present invention to refer to the reaction product of one or more of 1 ,3-propane diol (trimethylene glycol) or 1 ,4-butane diol (tetramethylene glycol), and one or more dicarboxylic acid equivalents, via ester linkage, wherein greater than about 50 mole%, more preferably at least about 75 mole%, even more preferably at least about 85 mole%, and still more preferably from about 95 to 100 mole%, of the diol used to form the hard segment is 1 ,3-propane diol and/or 1 ,4-butane diol.
• dicarboxylic acid equivalent is meant dicarboxylic acids and their equivalents, which are compounds that perform substantially like dicarboxylic acids in reaction with polymeric glycols and diols, as would be generally recognized by a person of ordinary skill in the relevant art.
• dicarboxylic acid equivalents for the purpose of the present invention include, for example, mono- and diesters of dicarboxylic acids, and diester-forming derivatives such as acid halides (e.g., acid chlorides) and an- hydrides.
• PO3G for the purposes of the present invention is an oligomic and/or polymeric ether glycol in which at least 50% of the repeating units are trimethylene ether units. More preferably from about 75% to 100%, still more preferably from about 90% to 100%, and even more preferably from about
• repeating units are trimethylene ether units.
• PO3G is preferably prepared by polycondensation of monomers comprising 1 ,3-propanediol, thus resulting in polymers or copolymers containing - (CH 2 CH 2 CH 2 O)- linkage (e.g, trimethylene ether repeating units).
• trimethylene ether glycol encompasses PO3G made from essentially pure 1 ,3-propanediol, as well as those oligomers and polymers (including those described below) containing up to 50% by weight of comonomers.
• the 1 ,3-propanediol employed for preparing the PO3G may be obtained by any of the various well known chemical routes or by biochemical transformation routes. Preferred routes are described in, for example, US5015789, US5276201 , US5284979, US5334778, US5364984, US5364987, US5633362, US5686276, US5821092, US5962745, US6140543, US6232511 , US6235948, US6277289, US6297408, US6331264, US6342646, US7038092, US20040225161A1 ,
• the 1 ,3-propanediol is obtained biochemically from a renewable source ("biologically-derived" 1 ,3-propanediol).
• a particularly preferred source of 1,3-propanediol is via a fermentation process using a renewable biological source.
• a renewable biological source biochemical routes to 1 ,3- propanediol (PDO) have been described that utilize feedstocks produced from biological and renewable resources such as corn feed stock.
• PDO propanediol
• bacterial strains able to convert glycerol into 1 ,3-propanediol are found in the species Klebsiella, Citrobacter, Clostridium, and Lactobacillus. The technique is disclosed in several publications, including previously incorporated US5633362, US5686276 and US5821092.
• US5821092 discloses, inter alia, a process for the biological production of 1 ,3-propanediol from glycerol using recombinant organisms.
• the process incorporates E. coli bacteria, transformed with a heterologous pdu diol dehydratase gene, having specificity for 1 ,2-propanediol.
• the transformed E. coli is grown in the presence of glycerol as a carbon source and 1 ,3-propanediol is isolated from the growth media. Since both bacteria and yeasts can convert glucose (e.g., corn sugar) or other carbohydrates to glycerol, the processes disclosed in these publications provide a rapid, inexpensive and environmentally responsible source of 1 ,3- propanediol monomer.
• the biologically-derived 1 ,3-propanediol such as produced by the processes described and referenced above, contains carbon from the atmospheric carbon dioxide incorporated by plants, which compose the feedstock for the production of the 1 ,3-propanediol.
• the biologically-derived 1 ,3-propanediol preferred for use in the context of the present invention contains only renewable carbon, and not fossil fuel-based or petroleum-based carbon.
• compositions of the present invention can be characterized as more natural and having less environmental impact than similar compositions comprising petroleum based glycols.
• the biologically-derived 1 ,3-propanediol, and PO3G and elastomers based thereon may be distinguished from similar compounds produced from a petrochemical source or from fossil fuel carbon by dual carbon-isotopic finger printing.
• This method usefully distinguishes chemically-identical materials, and apportions carbon in the copolymer by source (and possibly year) of growth of the biospheric (plant) component.
• the isotopes, 14 C and 13 C bring complementary information to this problem.
• the radiocarbon dating isotope ( 14 C) with its nuclear half life of 5730 years, clearly allows one to apportion specimen carbon between fossil (“dead”) and biospheric ("alive”) feedstocks (Currie, L. A.
• the fundamental definition relates to 0.95 times the 14 C/ 12 C isotope ratio HOxI (refer- enced to AD 1950). This is roughly equivalent to decay-corrected pre- Industrial Revolution wood.
• HOxI 14 C/ 12 C isotope ratio
• the stable carbon isotope ratio ( 13 C/ 12 C) provides a complementary route to source discrimination and apportionment.
• the 13 C/ 12 C ratio in a given biosourced material is a consequence of the 13 C/ 12 C ratio in atmospheric carbon dioxide at the time the carbon dioxide is fixed and also reflects the precise metabolic pathway. Regional variations also occur. Petroleum, C 3 plants (the broadleaf), C 4 plants (the grasses), and marine carbonates all show significant differences in 13 C/ 12 C and the corresponding ⁇ 13 C values. Further- more, lipid matter of C 3 and C 4 plants analyze differently than materials derived from the carbohydrate components of the same plants as a consequence of the metabolic pathway.
• 13 C shows large variations due to isotopic fractionation effects, the most significant of which for the instant invention is the photosynthetic mechanism.
• the major cause of differences in the carbon isotope ratio in plants is closely associated with differences in the pathway of photosynthetic carbon metabolism in the plants, particularly the reaction occurring during the primary carboxyla- tion, i.e., the initial fixation of atmospheric CO 2 .
• Two large ciasses of vegetation are those that incorporate the "C 3 " (or Calvin-Benson) photosynthetic cy- cle and those that incorporate the "C 4 " (or Hatch-Slack) photosynthetic cycle.
• C 3 plants, such as hardwoods and conifers, are dominant in the temperate climate zones.
• the primary CO 2 fixation or carboxylation reaction involves the enzyme ribulose-1 ,5-diphosphate carboxylase and the first stable product is a 3-carbon compound.
• C 4 plants include such plants as tropical grasses, corn and sugar cane.
• an additional carboxylation reaction involving another enzyme, phosphenol-pyruvate carboxylase is the primary carboxylation reaction.
• the first stable carbon compound is a 4-carbon acid, which is subsequently decarboxylated. The CO 2 thus released is refixed by the C 3 cycle.
• Biologically-derived 1 ,3-propanediol, and compositions comprising biologically-derived 1 ,3-propanediol therefore, may be completely distinguished from their petrochemical derived counterparts on the basis of 14 C (f M ) and dual carbon-isotopic fingerprinting, indicating new compositions of matter.
• the ability to distinguish these products is beneficial in tracking these materials in commerce. For example, products comprising both "new” and “old” carbon isotope profiles may be distinguished from products made only of "old” materials.
• the instant materials may be followed in commerce on the basis of their unique profile and for the purposes of defining competition, for determining shelf life, and especially for assessing environmental impact.
• the 1 ,3-propanediol used as the reactant or as a component of the reactant will have a purity of greater than about 99%, and more preferably greater than about 99.9%, by weight as determined by gas chromatographic analysis.
• Particularly preferred are the purified 1 ,3-propanediols as disclosed in previously incorporated US7038092, US20040260125A1 , US20040225161A1 and US20050069997A1 , as well as PO3G made therefrom as disclosed in US20050020805A1.
• the purified 1 ,3-propanediol preferably has the following characteristics:
• a concentration of total organic impurities (organic compounds other than 1 ,3-propanediol) of less than about 400 ppm, more preferably less than about 300 ppm, and still more preferably less than about 150 ppm, as measured by gas chromatography.
• the starting material for making PO3G will depend on the desired PO3G, availability of starting materials, catalysts, equipment, etc., and comprises "1 ,3-propanediol reactant.”
• 1 ,3-propanediol reactant is meant 1 ,3- propanediol, and oligomers and prepolymers of 1 ,3-propanediol preferably having a degree of polymerization of 2 to 9, and mixtures thereof. In some instances, it may be desirable to use up to 10% or more of low molecular weight oligomers where they are available.
• the starting material comprises 1 ,3-propanediol and the dimer and trimer thereof.
• a particularly preferred starting material is comprised of about 90% by weight or more 1 ,3-propanediol, and more preferably about 99% by weight or more 1 ,3-propanediol, based on the weight of the 1 ,3-propanediol reactant.
• PO3G can be made via a number of processes known in the art, such as disclosed in US6977291 and US6720459. A preferred process is as set forth in previously incorporated US20050020805A1.
• PO3G may contain lesser amounts of other polyalkylene ether repeating units in addition to the trimethylene ether units.
• the monomers for use in preparing polytrimethylene ether glycol can, therefore, contain up to 50% by weight (preferably about 20 wt% or less, more preferably about 10 wt% or less, and still more preferably about 2 wt% or less), of comonomer polyols in addition to the 1 ,3-propanediol reactant.
• Suitable comonomer polyols include aliphatic diols, for example, ethylene glycol, 1 ,6-hexanediol, 1 ,7-heptanediol, 1 ,8-octanediol, 1 ,9-nonanediol, 1 , 10-decanediol, 1 , 12-dodecanediol, 3,3,4,4,5,5-hexafluro-1 ,5-pentanediol, 2,2,3,3,4,4,5,5-octafluoro-1 ,6-hexanediol, and
• a preferred group of comonomer diols is selected from the group consisting of ethylene glycol, 2-methyl-1 ,3-propanediol, 2,2-dimethyl-1 ,3-propanediol, 2,2-diethyl-1 ,3- propanediol, 2-ethyl-2-(hydroxymethyl)-1 ,3-propanediol, C 6 - C 10 diols (such as 1 ,6-hexanediol, 1 ,8-octanediol and 1 ,10-decanediol) and isosorbide, and mixtures thereof.
• Particularly preferred diols other than 1 ,3-propanediol include ethylene glycol, 2-methyl-1 ,3-propanediol and C 6 - Cio diols.
• poly(trimethylene- ethylene ether) glycol such as described in US20040030095A1.
• Preferred poly(trimethylene-ethylene ether) glycols are prepared by acid catalyzed polycondensation of from greater than 50 to about 99 mole% (preferably from about 60 to about 98 mole%, and more preferably from about 70 to about 98 mole%) 1 ,3-propanediol, and up to 50 to about 1 mole% (preferably from about 40 to about 2 mole%, and more preferably from about 30 to about 2 mole%) ethylene glycol.
• the PO3G after purification has essentially no acid catalyst end groups, but may contain very low levels of unsaturated end groups, predominately allyl end groups, in the range of from about 0.003 to about 0.03 meq/g.
• Such a PO3G can be considered to comprise (consist essentially of) the compounds having the following formulae (II) and (III):
• m is in a range such that the Mn (number average molecular weight) is within the range of from about 200 to about 5000, with compounds of formula (III) being present in an amount such that the allyl end groups (preferably all unsaturation ends or end groups) are present in the range of from about 0.003 to about 0.03 meq/g.
• the small number of allyl end groups in the PO3G are useful to control elastomer molecular weight, while not unduly re- stricting it, so that compositions ideally suited, for example, for fiber end-uses can be prepared.
• the preferred PO3G for use in the invention has an Mn of at least about 750, more preferably at least about 1000, and still more preferably at least about 2000.
• the Mn is preferably less than about 5000, more preferably less than about 4000, and still more preferably less than about 3500.
• Blends of PO3Gs can also be used.
• the PO3G can comprise a blend of a higher and a lower molecular weight PO3G, preferably wherein the higher molecular weight PO3G has a number average molecular weight of from about 1000 to about 5000, and the lower molecular weight PO3G has a number average molecular weight of from about 200 to about 950.
• the Mn of the blended PO3G will preferably still be in the ranges mentioned above.
• PO3G preferred for use herein is typically a polydisperse polymer hav- ing a polydispersity (i.e. Mw/Mn) of preferably from about 1.0 to about 2.2, more preferably from about 1.2 to about 2.2, and still more preferably from about 1.5 to about 2.1.
• the polydispersity can be adjusted by using blends of
• PO3G for use in the present invention preferably has a color value of less than about 100 APHA, and more preferably less than about 50 APHA.
• the soft segment can be represented as comprising units represented by the following structure:
• R represents a divalent radical remaining after removal of carboxyl functionalities from a dicarboxylic acid equivalent
• x is a whole number representing the number of trimethylene ether units in the PO3G.
• the polymeric ether glycol used to prepare the polytrimethylene ether ester soft segment of the polyether ester may also include up to 50 wt% of a polymeric ether glycol other than PO3G.
• Preferred such other polymeric ether glycols include, for example, polyethylene ether glycol, polypropylene ether glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol, copolymers of tetrahydrofuran and 3-alkyl tetrahydrofuran, and mixtures thereof. Diol for Hard Segment
• the hard segment can be represented as comprising units having the following structure:
• n 3 (trimethylene) or 4 (tetramethylene), and R' represents a divalent radical remaining after removal of carboxyl functionalities from a dicar- boxylic acid equivalent.
• R' represents a divalent radical remaining after removal of carboxyl functionalities from a dicar- boxylic acid equivalent.
• the hard segment can also be prepared with less than 50 mole % (preferably up to about 25 mole %, more preferably up to about 15 mole %), of diols other than trimethylene glycol or tetramethylene glycol, preferably having a molecular weight lower than about 400.
• the other diols are prefera- bly aliphatic diols and can be acyclic or cyclic.
• diols with up to about 15 carbon atoms such as ethylene, isobutylene, butylene, pentame- thylene, 2,2-dimethyltrimethylene, 2-methyltrimethylene, hexamethylene and decamethylene glycols, dihydroxy cyclohexane, cyclohexane dimethanol, hy- droquinone bis(2-hydroxyethyl) ether.
• diols with up to about 15 carbon atoms such as ethylene, isobutylene, butylene, pentame- thylene, 2,2-dimethyltrimethylene, 2-methyltrimethylene, hexamethylene and decamethylene glycols, dihydroxy cyclohexane, cyclohexane dimethanol, hy- droquinone bis(2-hydroxyethyl) ether.
• aliphatic diols containing 2-8 carbon atoms Most preferred is ethylene glycol. Two or more other diols
• the dicarboxylic acid equivalent can be aromatic, aliphatic or cycloaliphatic.
• aromatic dicarboxylic acid equivalents are di- carboxylic acid equivalents in which each carboxyl group is attached to a carbon atom in a benzene ring system such as those mentioned below.
• Aliphatic dicarboxylic acid equivalents are dicarboxylic acid equivalents in which each carboxyl group is attached to a fully saturated carbon atom or to a carbon atom which is part of an olefinic double bond.
• the equivalent is "cycloaliphatic."
• the dicarboxylic acid equivalent can contain any substituent groups or combinations thereof, so long as the sub- stituent groups do not interfere with the polymerization reaction or adversely affect the properties of the polyether ester product.
• dicarboxylic acid equivalents selected from the group consisting of dicarboxylic acids and diesters of dicarboxylic acids. More preferred are dimethyl esters of dicarboxylic acids.
• aromatic dicarboxylic acids or diesters by themselves, or with small amounts of aliphatic or cycloaliphatic dicarboxylic acids or diesters.
• dimethyl esters of aromatic dicarboxylic acids are especially preferred.
• aromatic dicarboxylic acids useful in the present invention include terephthalic acid, isophthalic acid, bibenzoic acid, naphthalic acid, substituted dicarboxylic compounds with benzene nuclei such as bis(p- carboxyphenyl)methane, 1 ,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 4,4'-sulfonyl dibenzoic acid, and C1-C10 alkyl and other ring substitution derivatives such as halo, alkoxy or aryl derivatives.
• benzene nuclei such as bis(p- carboxyphenyl)methane, 1 ,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 4,4'-sulfonyl dibenzoic acid,
• Hydroxy acids such as p-(hydroxyethoxy)benzoic acid can also be used providing an aromatic dicarboxylic acid is also present.
• Representative aliphatic and cycloaliphatic dicarboxylic acids useful in this invention are sebacic acid, 1 ,3- or 1 ,4-cyclohexane dicarboxylic acid, adipic acid, dodecanedioic acid, glutaric acid, succinic acid, oxalic acid, azelaic acid, diethylmalonic acid, fumaric acid, citraconic acid, allylmalonate acid, 4-cyclohexene-1 ,2-dicarboxylate acid, pimelic acid, suberic acid, 2,5- diethyladipic acid, 2-ethylsuberic acid, 2,2,3,3-tetramethyl succinic acid, cyclopentanenedicarboxylic acid, decahydro-1 ,5- (or 2,6-)naphthalene dicar-
• dicarboxylic acid equivalents in the form of diesters, acid halides and anhydrides of the aforementioned aliphatic dicarboxylic acids are also useful to provide the polyether ester of the present in- vention.
• Representative aromatic diesters include dimethyl terephthalate, bibenzoate, isophthlate, phthalate and naphthalate.
• terephthalic, bibenzoic, isophthalic and naphthalic acid dimethyl terephthalate, bibenzoate, isophthlate, naphthalate and phthalate; and mixtures thereof.
• Particularly preferred dicarboxylic acid equivalents are the equivalents of phenylene dicarboxylic acids especially those selected from the group consisting of terephthalic and isophthalic acid and their diesters, especially the dimethyl esters, dimethyl terephthalate and dimethyl isophthalate.
• two or more dicarboxylic acids equivalents can be used.
• terephthalic acid and/or dimethyl terephthalate can be used with small amounts of the other dicarboxylic acid equivalents.
• At least about 70 mole% (more preferably at least about 80 mole%, still more preferably at least about 90 mole%, and still more preferably from about 95 to 100 mole%) of the dicarboxylic acid equivalent is terephthalic acid and/or dimethyl terephthalate.
• the polyether esters for use in the spinning processes of the invention are preferably prepared by providing and reacting (a) polytrimethylene ether glycol, (b) trimethylene glycol or tetramethylene glycol or mixtures thereof, and (c) dicarboxylic acid, ester, acid chloride or acid anhydride.
• the other glycols, diols, etc., as described above are can also be provided and reacted.
• Procedures for preparation of polyether ester elastomers comprising polytrimethylene ether ester soft segment and trimethylene ester hard segment are disclosed in detail in US6599625.
• Procedures for preparation of polyether ester elastomers comprising polytrimethylene ether ester soft segment and tetramethylene ester hard segment are disclosed in detail in US6562457.
• the polyether ester thermoplastic elastomer may be in the form of a composition comprising, in addition to the elastomer, one or more additives including, but not limited to, those selected from the group consisting of delus- terants, nucleating agents, heat stabilizers, viscosity boosters, optical bright- eners, pigments and antioxidants. Titanium dioxide or other pigments can, for example, be added to the polymers or in fiber manufacture.
• the polyether ester elastomers can also be made acid-dyeable using the additives described in US2003-0083441A1 and WO01/034693.
• the addi- tives of WO01 /034693 comprise a secondary amine or secondary amine salt in an amount effective to promote acid-dyeability of the acid dyeable and acid dyed compositions.
• the secondary amine unit is present in the polymer composition in an amount of at least about 0.5 mole %, more pref- erably at least about 1 mole %.
• the secondary amine unit is present in the polymer composition in an amount preferably of about 15 mole % or less, more preferably about 10 mole % or less, and still more preferably about 5 mole % or less, based on the weight of the composition.
• the additives of US2003-0083441A1 are polymeric additives based on a tertiary amine.
• the polymeric additive is prepared from (i) triamine containing secondary amine or secondary amine salt unit(s) and (ii) one or more other monomer and/or polymer units.
• One preferred polymeric additive comprises polyamide selected from the group consisting of poly-imino-bisalkylene-terephthalamide, - isophthalamide and -1 ,6 naphthalamide, and salts thereof.
• polyether esters useful in this invention can also be made cationi- cally dyeable using dyeability modifiers such as those described in US6312805.
• the polymer is heated to a temperature above its melting point and then extruded through a spinneret, preferably a multi-hole spinneret, at a temperature of about 175 to about 295°C, preferably at least about 200 0 C and up to about 275°C, most preferably up to about 270 0 C. Higher temperatures are useful for low residence times.
• Fibers may be drawn or undrawn. When they are drawn, the draw ratio is at least 1.01 , preferably up to about 5, more preferably up to about 4 and most preferably up to about 3.
• the process is advantageously utilized to prepare spun drawn yarn, also known as "fully drawn yarn".
• spun drawn yarns also known as "fully drawn yarn”.
• the preferred steps of manufacturing spun drawn yarns including spinning, drawing, optionally annealing, optionally interlacing, and winding the filaments, are similar to those used for preparing poly(ethylene terephthalate) yarns.
• spun drawn yarns produced by the process of the invention are multifilament yarns.
• An advantage of this invention is that spun drawn yarns can be prepared using higher draw ratios than disclosed in US6562457 and US6599625 for the same polyether esters. This can be accomplished by using a lower spin speed than normal, and then drawing at previously used speeds. When carrying out this process, there are fewer breaks than previously encountered.
• Draw speeds are higher than about 1200 m/m, and are preferably at least about 3000 m/m, more preferably at least about 3200 m/m, and preferably up to about 8000 m/m, more preferably up to about 7000 m/m.
• Another advantage of this invention is that spun drawn yarns can be spun on equipment previously used to spin spun drawn yarns of poly(ethylene terephthalate).
• Spun drawn yarns are usually wound on a package, and can be used to make fabrics or further processed into other types of yarn, such as textured yarn.
• the partially oriented yarns are multifilament yarns.
• the yarns also known as “bundles" preferably comprise at least about 2, and more preferably at least about 25 filaments.
• the yarns typically have a total denier of from about 1 to about 500, preferably at least about 20, more preferably at least about 50, and even more preferably from about 50 to about 300.
• Filaments are preferably at least about 0.5 denier per filament (dpf), more preferably at least about 1 dpf, and up to about 20 or more dpf, more preferably up to about 7 dpf.
• Typical filaments are about 3 to 7 dpf, and fine filaments are about 0.5 to about 2.5 dpf.
• Spin speeds are greater than about 1200 and can be up to about 5000 or more meters/minute ("m/m"). They are preferably at least about 1500 m/m, and more preferably at least about 3000 m/m. Spin speed is generally defined as maximum process speed and, in the case of the present invention, is considered draw roll speed. Thus, an advantage of this invention is that the process can be carried out at higher speeds than those disclosed in US6562457 and US6599625 for the same polyether esters.
• An advantage of this invention is that partially oriented yarns of polyether ester can be spun on equipment previously used to spin partially ori- ented yarns of poly(ethylene terephthalate), so spin speeds are preferably up to about 4000 m/m, more preferably up to about 3500 m/m.
• Partially oriented yarns are usually wound on a package, and can be used to make fabrics or further processed into other types of yarn, such as textured yarn. They can also be stored in a can prior to preparing fabrics or further processing, or can be used directly without forming a package or other storage.
• Textured yarns can be prepared from partially oriented yarns or spun drawn yarns. The main difference is that the partially oriented yarns usually require drawing whereas the spun drawn yarns are already drawn.
• US6287688, US6333106 and US2001-030378A1 all describe the basic steps of manufacturing textured yarns from partially oriented yarns. This invention can be practiced using those steps or other steps conventionally used for making partially oriented polyester yarns.
• the basic steps include unwinding the yarns from a package, drawing, twisting, heat-setting, untwist- ing, and winding onto a package. Texturing imparts crimp by twisting, heat setting, and untwisting by the process commonly known as false twist texturing. The false-twist texturing is carefully controlled to avoid excessive yarn and filament breakage.
• a preferred process for friction false-twisting comprises heating the partially oriented yarn to a temperature between 140 0 C and 220 0 C, twisting the yarn using a twist insertion device such that in the region between the twist insertion device and the entrance of the heater, the yarn has a twist angle of about 46° to 52°, and winding the yarn on a winder.
• multifilament yarns comprise the same number of filaments as the partially oriented yarns and spun drawn yarns from which they are made. Thus, they preferably comprise at least about 2 and even more preferably at least about 25 filaments.
• the yarns typically have a total denier of from about 1 to about 500, preferably at least about 20, preferably at least about 50, and more preferably from about 50 to about 300.
• Filaments are preferably at least about 0.1 dpf, more preferably at least about 0.5 dpf, more preferably at least about 0.8 dpf, and up to about 10 or more dpf, more preferably up to about 5 dpf, and most preferably up to about 3 dpf.
• Staple fibers and products can be prepared from the polyether esters of the invention.
• One preferred process comprises: (a) providing poly- trimethylene ether ester comprising from about 80 to about 40 wt% poly- trimethylene ether dicarboxylate ester soft segment and from about 20 to about 60 wt% hard segment selected from the group consisting trimethylene dicarboxylate ester and tetramethylene dicarboxylate ester (b) melt spinning the polytrimethylene ether ester at a temperature of about 245 to about 285°C into filaments, (c) quenching the filaments, (d) drawing the quenched filaments, (e) crimping the drawn filaments using a mechanical crimper at a crimp level of about 8 to about 30 crimps per inch (about 3 to about 12 crimps/cm), (f) relaxing the crimped filaments at a temperature of about 50 to about 120 0 C, and (g) cutting the relaxed filaments into staple fibers, preferably having
• the drawn filaments are an- nealed at about 85 to about 115°C before crimping.
• annealing is carried out under tension using heated rollers.
• the drawn filaments are not annealed before crimping.
• Staple fibers are useful in preparing textile yarns and textile or non- woven fabrics, and can also be used for fiberfill applications and making car- pets.
• the spinning processes of this invention can also be used to improve the spin feed in preparation of bulked continuous filament (“BCF”) yarns.
• BCF bulked continuous filament
• BCF yarns are used to prepare all types of carpets, as well as textiles.
• the compositions of this invention can be used to improve the spin speed of their preparation.
• Preferred steps involved in preparing bulked continuous filaments include spinning (e.g., extruding, cooling and coating (spin finish) the filaments), single stage or multistage drawing (preferably with heated rolls, heated pin or hot fluid assist (e.g., steam or air)) at about 80 to about 200 0 C and at a draw ratio of about 1.1 to about 5, preferably at least about 1.5 and preferably up to about 4.5, annealing at a temperature of about 120 to about 200 0 C, bulking, entangling (which can be carried out in one step with bulking or in a subse- quent separate step) optionally relaxing, and winding the filaments on a package for subsequent use.
• spinning e.g., extruding, cooling and coating (spin finish) the filaments
• single stage or multistage drawing preferably with heated rolls, heated pin or hot fluid assist (e.g., steam or air)
• annealing at a temperature of about 120 to about 200 0 C
• Bulked continuous filament yarns can be made into carpets using well known techniques. Typically, a number of yarns are cable twisted together and heat set in a device such as an autoclave, and then tufted into a primary backing. Latex adhesive and a secondary backing are then applied.
• the individual filaments can be round or have other shapes, such as octalobal, delta, sunburst (also known as sol), scalloped oval, trilobal, tetra- channel (also known as quatra-channel), scalloped ribbon, ribbon, starburst, etc. They can be solid, hollow or multi-hollow.
• the invention is preferably practiced by spinning one type of filament cross section from a spinneret.
• the number average molecular weights were calculated according to ASTM D 5296-97 using a poly(ethylene terephthalate) of Mw ⁇ 44,000 cali- bration standard and hexafluoroisopropanol solvent.
• Percent hard segment was determined as described in US6562457.
• T Tenacity at break
• E percent elongation at break
• Unload power was measured in dN/texeffx1000. One filament, a 2- inch (5 cm) gauge length, was used for each determination. Separate measurements were made using zero-to-300% elongation cycles. Unload power (i.e., the stress at a particular elongation) was measured after the samples had been cycled five times at a constant elongation rate of 100% per minute and then held at 300% extension for half a minute after the fifth extension. While unloading from this last extension, the stress, or unload power, was measured at various elongations.
• Unload powers are reported herein as the effective unload power using the general form "UPx/y" where x is the percent elongation to which the fiber was cycled five times and y is the percent elongation at which the stress, or unload power, was measured.
• Stress Decay was measured as the percent loss of stress on a fiber over a 30 second period with the sample held at 300% extension at the end of the fifth load cycle.
• the percent set was measured from the stress/strain curve recorded on chart paper.
• This example describes preparation of a polyether ester elastomer having a polytrimethylene ether ester soft segment and a tetramethylene ester hard segments, as described in US6562457.
• the polymer was designed to have a 72/28 weight ratio of soft segments to hard segments.
• the polymer was prepared using a batch process from dimethyl terephthalate, 1 ,4-butanediol and polytrimethylene ether glycol.
• the resulting polymer was extruded from the reactor and converted into pellets, which were dried at 80-90 0 C under re- prised pressure overnight before further use.
• the properties of the polymer were as follows: Inherent Viscosity: 1.403 dL/g
• Example 1 Polymer of Example 1 was extruded through a sand filter spin pack and a multi hole spinneret (0.3 mm diameter and 0.56 mm capillary depth holes, number of holes as indicated below in the Table 1 ) maintained at 273°C.
• the filamentary streams leaving the spinneret were quenched with air at 21 0 C, and converged to a bundle.
• Forwarding (feed) rolls with a surface speed described in the table below delivered the yarn bundle in sequence to a set of draw rolls, to an interlace jet, to a set of letdown rolls and to a windup at speeds described in the Table 1 below.
• the spinning conditions for the yarns are described in Table 1.
• the properties of the resultant yarns are described in Table 2.
• Comparative Examples 1 and 2 present properties of two different commercially available spandex yarns for comparison with the data of Examples 2-9.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Artificial Filaments (AREA)
• Polyesters Or Polycarbonates (AREA)
• Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)

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• 2006
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