EP0595814A1 - Copolyesters pour fibres a module eleve - Google Patents

Copolyesters pour fibres a module eleve

Info

Publication number
EP0595814A1
EP0595814A1 EP92905965A EP92905965A EP0595814A1 EP 0595814 A1 EP0595814 A1 EP 0595814A1 EP 92905965 A EP92905965 A EP 92905965A EP 92905965 A EP92905965 A EP 92905965A EP 0595814 A1 EP0595814 A1 EP 0595814A1
Authority
EP
European Patent Office
Prior art keywords
polyester
fiber
acid
recited
monomer units
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP92905965A
Other languages
German (de)
English (en)
Inventor
Eui Won Choe
John Anthony Flint
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
CNA Holdings LLC
Original Assignee
Hoechst Celanese Corp
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 Hoechst Celanese Corp filed Critical Hoechst Celanese Corp
Publication of EP0595814A1 publication Critical patent/EP0595814A1/fr
Withdrawn legal-status Critical Current

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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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/185—Acids containing aromatic rings containing two or more aromatic rings
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/185—Acids containing aromatic rings containing two or more aromatic rings
    • C08G63/187—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings
    • C08G63/189—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings containing a naphthalene ring
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • 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
    • D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters

Definitions

  • the present invention relates to high modulus polyester fibers. More specifically, the invention relates to a novel polyester composition and fibers made from that composition wherein the fibers have excellent tensile properties at room temperature and at elevated temperatures.
  • PET Poly(ethylene terephthalate)
  • nylons such as Nylon 6 and Nylon 66
  • Rayon are the predominant synthetic polymers used in making tire yarn and tire cord.
  • PET poly(ethylene terephthalate)
  • nylons such as Nylon 6 and Nylon 66
  • Rayon are the predominant synthetic polymers used in making tire yarn and tire cord.
  • PET has its own advantages and disadvantages.
  • the most widely used f these, PET has high tensile strength and tensile modulus, a high glass transition temperature, and good stability.
  • Nylon has excellent strength, toughness and fatigue resistance, but has the serious disadvantage of "flat spotting" in tires because of its low glass transition temperature and a tendency to creep.
  • Rayon retains a higher percentage of its tensile properties at elevated temperatures (e.g.,
  • polyesters which have a higher tensile strength and tensile modulus than PET and retains these properties at elevated temperatures. Such a material would retain the inherent advantages of polyesters in general, such as chemical stability.
  • Alternative polyesters that have been made and evaluated include poly(ethylene naphthalate) ("PEN"), the condensation polymer of ethylene glycol and 2,6- naphthalenedicarboxylic acid, and the polymer of 4,4'- bibenzoic acid and ethylene glycol.
  • PEN poly(ethylene naphthalate)
  • PEN poly(ethylene naphthalate)
  • the condensation polymer of ethylene glycol and 2,6- naphthalenedicarboxylic acid and the polymer of 4,4'- bibenzoic acid and ethylene glycol.
  • Copolymers in which 4,4'-bibenzoic acid and/or 2,6-naphthalene dicarboxylic acid are included as comonomers in PET have been reported in European Patent Application No. 202,631.
  • a copolymer of 4,4'-bibenzoic acid, 2,6-naphthalenedicarboxylic acid, and ethylene glycol was reported in Japanese Published Patent Application 50-135333 to be particularly useful for making tire yarn when the mole ratio of 4,4'- bibenzoic acid to 2,6-naphthalenedicarboxylic acid is less than about 1:4.
  • This reference states that when 4,4'-bibenzoic acid makes up more than about 20 mole% of the diacids in the composition, the composition is of no value as a tire yarn because it has a low so. " tening temperature and a low Young's modulus (tensile modulus).
  • the present invention is a copolyester composition
  • a copolyester composition comprising monomer units derived from 4,4'-bibenzoic acid, 2,6-naphthalenedicarboxylic acid and ethylene glycol, but not including monomer units derived from terephthalic acid in a number greater than about 50% of all the diacid components; the ratio of 4,4'-bibenzoic acid to 2,6-naphthalenedicarboxylic acid is greater than 1:3.
  • compositions have a crystalline melting point less than about 320°C and an inherent viscosity of at least about 0.8 dl/g when measured at 25°C and 0.1% concentration on a weight/volume basis in a solution of egual parts by volume of hexafluoroisopropanol and pentafluorophenol.
  • the best compositions for melt spinning of high modulus fibers comprise the monomer units derived from 4,4'-bibenzoic acid and 2,6- naphthalenedicarboxylic acid in a ratio of about 40:60 to about 60:40, with the best results being obtained with about equimolar amounts of the two diacid monomers.
  • an intermediate molecular weight copolyester having an inherent viscosity in the range of about 0.5 dl/g up to about 1.0 dl/g is made by melt polymerization and is then heated in the solid state to a temperature of about 220°C to about 270°C for a time sufficient to increase the inherent viscosity of the polymer to at least about 1.0 dl/g.
  • the intermediate molecular weight copolyester can be made in two steps by (1) heating a molten mixture of about 40 to about 60 parts on a mole basis of dialkyl 2,6-naphthalenedicarboxylate, about 60 to about 40 parts of dialkyl 4,4'-bibenzoate, and at least about 100 parts of ethylene glycol with an ester interchange catalyst to a temperature of about 200°C until sufficient by-product alcohol is distilled off to yield a low molecular weight polyester, and (2) heating the low molecular - weight polyester in the molten state with a polycondensation catalyst to a temperature of about 240°C to about 290°C to yield an intermediate molecular weight polyester having an inherent viscosity in the range of about 0.8 dl/g to about 1.0 dl/g.
  • the preferred dialkyl esters of the two diacids are the dimethyl esters, and the by ⁇ product alcohol is then methanol.
  • the copolyesters of the present invention are melt spun into high modulus fibers in a single step (i.e., without the need for a post-spinning draw step) by spinning at a high draw down ratio with a relatively low melt temperature. As the melt temperature is increased, a higher draw down ratio is needed to obtain an as-spun fiber with a high modulus. Fibers made by this process have a modulus of at least about 150 gpd; the most preferred composition has a modulus of at least about 200 gpd.
  • Figure 1 is a plot of the melting temperature of the copolyesters of the current invention as a function of the composition.
  • the composition is expressed as the mole % of 4,4'-bibenzoic acid of the two diacid monomer units combined.
  • Figure 2 is a plot of the fiber modulus as a function of the draw down ratio for the composition containing equimolar amounts of the two diacids at several different melt temperatures.
  • Figure 3 is a plot of the logarithm of the draw down ratio vs. fiber modulus for the compositions having 4,4'- bibenzoic acid and 2,6-naphthalenedicarboxylic acid in a 50:50 mole ratio and a 60:40 mole ratio.
  • Figure 4 shows the stress-strain curves at room temperature and 150°C for single fibers of PET and for the copolyester of the current invention having the two diacids in a 50:50 mole ratio.
  • the present invention discloses polyester compositions comprising monomer units derived from 2,6- naphthalenedicarboxylic acid, ,4'-bibenzoic acid and ethylene glycol in which the ratio of the number of monomer units derived from 4,4'-bibenzoic acid to those derived from 2,6-naphthalenedicarboxylic acid is greater than about 1:3.
  • These polymers are useful in making films, shaped articles, as by injection or compression molding, and high modulus fibers.
  • Compositions in which the melting temperature of the polymer is less than about 320°C are preferred for uses in which melt processing is required.
  • the polymers of the present invention are particularly useful in making high modulus fibers.
  • Fibers can be readily made by melt spinning when the ratio of monomer units derived from 4,4'-bibenzoic acid to those derived from 2,6-naphthalenedicarboxylic acid is greater than 1:3 as long as the melting temperature is less than about 320 ⁇ C.
  • the ratio of monomer units derived from the two diacids is in the range of about 40:60 to about 60:40. The best results are obtained when the two diacids are present in about equal amounts.
  • 2,6-naphthalene- dicarboxylic acid monomer units shown as Structure I, are the subject of this invention, but monomer units based on 2,6-naphthalenediol (II), 2-hydroxy-6-naphthoic acid (III) or mixtures thereof
  • 4,4'- bibenzoic acid monomer units (IV) are essential to the composition disclosed herein, but monomer units derived from 4,4'-biphenol (V), 4-hydroxy- '-biphenycarboxylic acid (VI) and mixtures thereof may also be included.
  • substituents include halogen atoms, such as fluorine, chlorine, bromine or iodine; lower alkyl groups having up to about four carbon atoms, such as methyl, ethyl, n-butyl, or tert-butyl; and lower alkoxy groups having up to about four carbon atoms, such as methoxy, ethoxy or butoxy.
  • halogen atoms such as fluorine, chlorine, bromine or iodine
  • lower alkyl groups having up to about four carbon atoms, such as methyl, ethyl, n-butyl, or tert-butyl
  • lower alkoxy groups having up to about four carbon atoms, such as methoxy, ethoxy or butoxy.
  • Minor amounts of linkages other than ester linkages, as for example amide linkages are also within the scope of the invention.
  • the amine analogs of the alcohol and phenol monomers may also be included at low levels; examples include ethylenediamine and 4-aminobenzoic acid.
  • Terephthalic acid may also be included as a comonomer as long as monomer units derived from terephthalic acid do not make up more than about 50% of the diacid monomer units.
  • the number of hydroxyl groups in the starting monomers must be about equal to the number of carboxylic acid groups.
  • the amount of ethylene glycol on a mole basis must be about equal to the combined amounts of the two diacids. Substitution of other monomers for the diacids may result in changes in the amount of glycol needed to achieve the stoichiometry needed for making a high molecular weight polyester.
  • the monomers utilized in this composition are readily made by methods well known in the art.
  • the diacid monomers may also be purchased as the free acids or as the dimethyl esters from commercial suppliers of fine chemicals.
  • Ethylene glycol is commercially available from several manufacturers.
  • the crystalline melting points of the copolyesters of 2,6-naphthalenedicarboxylic acid, 4,4'-bibenzoic acid and ethylene glycol vary according to the relative amounts of the two diacids.
  • the melting points of several of these compositions are shown in Table 1 (after Example 6) .
  • the melting points are plotted in Figure 1 as a function of the amount of 4,4'-bibenzoic acid (measured as the mole % of the combined diacids).
  • the mole % of 4,4'-bibenzoic acid is in the range of about 40% to about 60%
  • the melting point of the copolyester is in the range of about 260°C to about 305 ⁇ C. This is the preferred range for melt spinning of fibers.
  • thermal decomposition-of the polymer reduces the molecular weight rapidly enough that high tensile properties of fibers are difficult to attain.
  • the polyester At the low end of the temperature range, the polyester has lower crystallinity, resulting in poorer fiber tensile properties.
  • the best combination of thermal properties and crystallinity for melt spinning of fibers lies in the middle of this range.
  • the melting point and crystallinity (as measured by ⁇ H f in the DSC data shown in Table 1) appear to go through a minimum when the mole % of 4,4'-bibenzoic acid is within the range of about 20% to about 40%.
  • copolyesters disclosed herein can be made by methods commonly used for making polyesters. These methods include interfacial condensation of the glycols with the acid chlorides of the diacids.
  • the polymers can also be made by melt condensation of the glycols with the acids or alkyl esters of the acids. These methods are generally well known in the art.
  • the spun fibers preferably have an I.V. of at least about 0.8 dl/g when measured at 25°C at 0.1% concentration on a weight/volume basis in a solution of equal parts by volume of hexafluoroisopropanol and pentafluorophenol.
  • I.V. inherent viscosity
  • melt spinning of polymers having an I.V. of less than about 1.0 dl/g can be carried out successfully, . but moisture must be excluded more carefully and the residence time of the polymer at elevated temperature must be reduced.
  • a polymer having such a high I.V. can be made by first making an intermediate molecular weight polyester having an I.V. in the range of about 0.5 to about 1.0 dl/g and then raising the molecular weight by solid state polymerization so that the I.V. is at least about 1.0 dl/g.
  • the preferred method of making an intermediate molecular weight polyester for solid state polymerization is to carry out a melt polymerization in two stages.
  • the first stage of the melt polymerization consists of the ester interchange reaction of dialkyl esters of the two diacids with ethylene glycol in the temperature range of about 200°C to about 240°C in the presence of an ester interchange catalyst.
  • the ester interchange reaction is carried out under an inert atmosphere (e.g. nitrogen) under anhydrous conditions.
  • Dimethyl esters are the preferred dialkyl esters.
  • the diesters are mixed in the desired ratio with an excess of ethylene glycol in the presence of the ester interchange catalyst.
  • Catalysts which catalyze ester interchange reactions are well known in the art and include Lewis acids and bases, zinc acetate, calcium acetate, titanium tetrabutoxide, germanium tetraethoxide, and manganese acetate. Manganese acetate is preferred.
  • by-product alcohol is removed by distillation. When the preferred dimethyl esters are used, the by-product is methanol.
  • the ester interchange reaction is normally complete in less than about ten hours, preferably two to three hours, and leads to a very low molecular weight material, having an I.V. of less than about 0.2 dl/g.
  • the second stage of the melt polymerization consists of a polycondensation reaction, wherein a polycondensation catalyst is added and the temperature is raised into the range of about 240°C to about 290°C.
  • This reaction is preferably carried out at reduced pressure, as ethylene glycol must be removed to achieve the desired intermediate molecular weight.
  • Catalysts for the polycondensation reaction are Well known in the art and include Lewis acids and bases, polyphosphoric acid, antimony trioxide, titanium tetraalkoxides, germanium tetraethoxide, organophosphates, organophosphites, and mixtures thereof, with a mixture of triphenylphosphate and antimony trioxide being preferred.
  • the polycondensation reaction is carried out until the I.V. is in the range of abo;;t 0.5 dl/g to about 1.0 dl/g and can normally be completed in less than about ten hours, preferably in two to three hours.
  • the intermediate molecular weight polyester is ground to a powder or is pelletized prior to solid state polymerization.
  • the powder is dried and is then heated in the range of about 220 ⁇ C to about 270°C under an inert atmosphere (e.g., a nitrogen stream) or in a vacuum for a time sufficient to raise the I.V. to at least about 1.0 dl/g.
  • a typical time needed to achieve a high molecular weight is in the range of about 16 hours to about 24 hours.
  • the time needed to achieve high molecular weight can be longer or shorter, depending on the temperature and the molecular weight of the powder. In general, the higher the temperature, the faster the reaction proceeds.
  • the high I.V. polyester is particularly suitable for melt spinning into high modulus industrial fibers. Melt spinning processes are well known in the art and are widely used in the manufacture of PET fibers.
  • the polyester of the present invention is dried immediately before spinning, preferably by warming in a dry atmosphere or under vacuum.
  • the polyester is then passed into a heated zone, where it is heated to a temperature above the melting point.
  • the molten polymer is then filtered by conventional methods and is extruded through one or more spinnerettes, each having one or more holes.
  • As the polymer is extruded it is taken up on a reel at a much higher speed than the extrusion speed.
  • the ratio of the take-up speed u the extrusion speed is the draw down ratio.
  • the fiber is quenched (cooled) in a gas or air stream, so that the point at which drawing of the fiber takes place is localized.
  • copolyesters of the present invention unexpectedly exhibit melt spinning behavior that is characteristic either of conventional polymers or of thermotropic liquid crystalline polymers, depending on the melt spinning conditions.
  • Conventional fibers must normally be drawn in a separate post-spinning step in order to attain high tensile properties.
  • Thermotropic liquid crystalline polymers normally can be spun into high modulus fibers without a subsequent drawing step; however, liquid crystalline polymers normally cannot be drawn.
  • copolyesters of the present invention excellent tensile properties can be achieved in a single spinning step without a subsequent drawing step by maintaining a relatively low melt temperature and a high draw down ratio.
  • melt temperature is just above the melting point of the copolyester, excellent tensile properties can be obtained at relatively low draw down ratios.
  • melt temperature is increased, a higher draw down ratio is needed to achieve high tensile properties.
  • FIG. 3 shows a plot of the logarithm of the draw down ratio as a function of fiber modulus for the composition containing equimolar amounts of the two diacid components (melting point about 285 ⁇ C) at 300 ⁇ C and also for the composition containing monomer units derived from 4,4'-bibenzoic acid and 2,6- naphthalenedicarboxylic acid in a 60:40 mole ratio (melting point about 304°) at 315 ⁇ C and 334°C. It can be seen that for both compositions, the as-spun modulus increases with draw down ratio.
  • the fibers in general can not be drawn appreciably (perhaps a few %).
  • the as-spun fibers behave more like conventional fibers in that they can be drawn at elevated temperatures in a subsequent step to increase the tensile properties.
  • the fiber tensile properties improve on drawing, but they are not as high as those that are achieved under high stress (i.e. low melt temperature and high draw down ratio).
  • the fiber can be spun under conditions that lead to high tensile properties in a single spinning step without a subsequent drawing step has great value because it simplifies the process for manufacturing fiber.
  • PET is spun in a continuous process, but the process is more complex than that of the present invention because of the necessity of drawing the PET fiber after spinning.
  • fibers of the present invention have excellent tensile properties, both at room temperature and at elevated temperatures.
  • fibers made of the 50:50 copolymer of 4,4 ' -bibenzoic acid and 2,6- naphthalenedicarboxylic acid have a tensile modulus more than twice that of a commercial PET tire yarn (Trevira® Type 800 high denier industrial tire yarn, manufactured by Hoechst Celanese Corporation), both at room temperature (382 gpd vs. 115 gpd) and at 150 ⁇ C (154 gpd vs. 57 gpd).
  • fibers of the current invention exhibit reduced hot air shrinkage in comparison with commercial PET tire yarns.
  • yarn made of the 50:50 copolymer has a hot air shrinkage of about 0.7 - 0.8%
  • Trevira® D240 high denier industrial yarn from Hoechst Celanese Corporation has a hot air shrinkage of about 5.4%.
  • Fibers and yarns made using the copolyesters taught herein can be treated in subsequent steps after spinning much as other polyester fibers (e.g. PET).
  • polyester fibers e.g. PET
  • the fibers or yarns can be treated with one or more finishes, depending on the ultimate end use.
  • the yarns can also be twisted and plied together to make tire cords using conventional techniques.
  • the copolyesters of the present invention have other end uses besides industrial fibers and yarns.
  • the copolyesters can be extruded as a monofil, a high denier single filament fiber.
  • the copolyesters can also be injection molded into shaped articles with high tensile properties or extruded as tapes.
  • Films, including biaxially oriented films, can also be made from these copolyesters by methods well known in the art. Shaped articles can also be made by compression molding. This is particularly useful for the very high melting compositions.
  • the resulting mixture was heated with stirring to 270 C C. Vacuum was then applied, and the temperature was raised to 283 ⁇ C and held at that temperature for 2.5 hours.
  • the resulting polymer was cooled to room temperature to obtain a copolyester with an intermediate molecular weight having an I.V. of 0.85 dl/g as determined at 25 degrees and 0.1% concentration on a weight/volume basis in a solution of equal parts by volume of hexafluoroisopropanol and pentafluorophenol.
  • the polymer had a melting point of 287°C and a heat of fusion of 44.6 j/g as measured by D.S.C.
  • the intermediate molecular weight polymer was ground until it could be sifted through a No. 20 mesh screen.
  • the powder was then solid state polymerized at 220 degrees C for 24 hours under a reduced pressure to attain a polyester with an increased molecular weight having an I.V. of 1.38 dl/g under the conditions described above.
  • the melting point was 288 degrees and the heat of fusion was 62 j/g.
  • a sample of polymer having the composition of Example 1 and having an I.V. of 1.32 was dried under vacuum overnight at 130°C.
  • the polymer was melt spun at a melt temperature of 297°C and a throughput of 0.128 g/min. through a 0.020" diameter capillary to yield a single filament fiber.
  • the fiber was quenched in air before being taken up at 175 m/min to give 6.6 dpf fiber. This corresponded to a draw down ratio at spinning of 360.
  • Single fiber tensile properties were measured using ASTM test method D 3822. The tests were carried out at 3" guage length and 60% strain rate.
  • T/E/M 11.6 gpd/3.8%/382 gpd.
  • the fiber could not be drawn further over a hot shoe.
  • Example 1 Example 1 and an I.V. of 1.46 was dried prior to spinning.
  • the polymer was extruded in the same manner as in Example 7, except that the melt temperature during spinning was varied and fiber samples were collected at different take up speeds.
  • the single fiber tensile properties and fiber draw down ratio are shown in Table
  • the tensile properties of three copolyester compositions at elevated temperatures were evaluated by measuring the fiber tensile properties first at room temperature as described in Example 7 and then in a heated atmosphere at 150 ⁇ C.
  • a sample of fiber grade PET polymer was melt spun into single filament fibers using the same equipment as was used for spinning single filament fiber samples of the polymer of the present invention.
  • the polyester had an I.V. of 0.92 dl/g when measured at 8% concentration in o-chlorophenol at 25°C.
  • the I.V. of the same polymer sample was measured as 1.22 dl/g at 0.1% concentration on a weight/volume basis in a solution of equal volumes of hexafluoroisopropanol and pentafluorophenol at 25 ⁇ C.
  • the single filament PET fiber was drawn over two hot shoes to fully develop the tensile properties.
  • the fiber was then heat set in an oven at 200 ⁇ C under nitrogen for 30 minutes in a rack in which the fiber was placed with 2% strain.
  • the tensile properties of this "PET Control" are also shown in Table 4.
  • the stress-strain curves for the PET Control and for the 50:50 copolymer at room temperature and at 150°C are shown in Figure 4. TABLE 4.
  • a sample of copolyester having the composition of Example 1 and having 1.36 I.V. was dried at 130 ⁇ C under vacuum overnight.
  • the polymer was melted in a 1" diameter extruder, and the extrudate was metered using a conventional melt pump to the spinning pack where it was filtered through 70/120 shattered metal.
  • the melt at 289 ⁇ C was extruded through a 20 hole annular spinnerette with 0.020" diameter capillaries.
  • Crossflow quench was applied to the emerging filaments to provide a stable spinning environment by localizing the fiber draw point, producing a stable spinning process which yielded fiber with low denier variability along its length.
  • the yarn was dressed with a spin finish before passing around a system of godets.
  • the polymer throughput was 7.06 g/min.
  • the spinning melt temperature was carefully selected to be as low as possible, but not so low as to preclude good runnability of the spinning process.
  • a copolyester with inherent viscosity of 1.21 dl/g prepared according to the method of Example 1, was injection molded into 1/8" x 3/8" x 2-1/2" tensile and flexural bars using a Plasticor Model 64 Injection Molding Apparatus at 310°C.
  • the following mechanical properties were measured using ASTM test methods D 638 and D 790: tensile strength, 6.9 Ksi; modulus, 645 Ksi; elongation to break, 1.28%; flexural strength at break, 13.84 Ksi; flexural strength at 5% strain, 17.97 Ksi; and flexural modulus, 560 Ksi.
  • the modulus of several other commercial materials was measured for comparison: PET molding resin with I.V.
  • Hot air shrinkage measurements were carried out on a yarn sample made according to the method of Example 29 using the composition containing equimolar amounts of the two diacids. Measurements were performed by heating a measured length of yarn with no stress or strain for 30 minutes in an oven at 350OF, cooling the sample to room temperature, and then determining the % change in length. Comparative measurements were also carried out using the same method on a sample of Trevira® D240 high denier industrial yarn from Hoechst Celanese Corporation. The yarn of the current invention exhibited a hot air shrinkage of 0.7 - 0.8% whereas Trevira® D240 exhibited a hot air shrinkage of 5.4%.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

Compositions polyester comprenant des unités monomères dérivées de l'acide 2,6-naphtalènedicarboxylique, de l'acide 4,4'-dibenzoïque et de l'éthylène glycol. Ces compositions sont employées comme fibres et résines de moulage lorsque le rapport entre l'acide 4,4'-dibenzyle et l'acide 2,6-naphtalènedicarboxylique est supérieur à 1:3. Ces compositions produisent une fibre aux caractéristiques de traction excellentes, aussi bien à température ambiante qu'à température élevée, lorsque les deux diacides sont présents dans un rapport molaire compris entre environ 60:40 et 40:60 et surtout lorsque les deux diacides sont inclus selon des quantités à peu près équimolaire. Lorsque ces compositions sont filées en fusion à une température de fusion relativement basse et dans un rapport d'étirage relativement élevé, les fibres obtenues présentent d'excellentes caractéristiques de résistance à la traction sans qu'une étape d'étirage ultérieure ne soit nécessaire.
EP92905965A 1991-07-25 1991-12-03 Copolyesters pour fibres a module eleve Withdrawn EP0595814A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US73555391A 1991-07-25 1991-07-25
US735553 1991-07-25
PCT/US1991/009020 WO1993002122A1 (fr) 1991-07-25 1991-12-03 Copolyesters pour fibres a module eleve

Publications (1)

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EP0595814A1 true EP0595814A1 (fr) 1994-05-11

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EP92905965A Withdrawn EP0595814A1 (fr) 1991-07-25 1991-12-03 Copolyesters pour fibres a module eleve

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EP (1) EP0595814A1 (fr)
JP (1) JPH06508860A (fr)
AU (1) AU1347192A (fr)
CA (1) CA2113639A1 (fr)
MX (1) MX9204380A (fr)
WO (1) WO1993002122A1 (fr)

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DE69319472T3 (de) * 1992-03-19 2003-02-20 Teijin Ltd., Osaka Orientierte Polyesterfolie
JP3545435B2 (ja) * 1992-03-27 2004-07-21 帝人株式会社 磁気記録テープ用ベースフイルム
DE59308819D1 (de) * 1992-07-22 1998-09-03 Hoechst Ag Biaxial orientierte Folie enthaltend Schichten aus Polyethylennaphthalatbibenzoat (PENBB), Verfahren zur Herstellung dieser Folien und Verwendung derselben
DE69403232T2 (de) * 1993-01-27 1997-09-25 Nippon Oil Co Ltd Flüssigkristalline Polyester
US5374707A (en) * 1993-02-18 1994-12-20 Monsanto Company Hydroxy ethyl bibenzoate
DE4328029C2 (de) * 1993-08-20 2003-09-25 Johns Manville Int Inc Hochbelastbare Polyester-Monofilamente für technische Anwendungen
US5458956A (en) * 1993-10-12 1995-10-17 Hoechst Celanese Corporation UV-resistant and dimensionally stable tent comprising woven polyethylenenaphthalatebibenzoate (PENBB) yarns
GB2287482A (en) * 1994-02-28 1995-09-20 Hoechst Celanese Corp Synthetic paper pulp
US5399429A (en) * 1994-03-11 1995-03-21 Monsanto Company Flame retardant recycled polyester copolymers
EP0749456A1 (fr) * 1994-03-11 1996-12-27 Monsanto Company Copolymeres de polyesters recycles
US5399428A (en) * 1994-03-11 1995-03-21 Monsanto Company Flame retardant polyester copolymers
BE1009072A3 (nl) * 1995-02-03 1996-11-05 Dsm Nv Copolyetherester.
DE19511852A1 (de) * 1995-03-31 1996-10-02 Hoechst Trevira Gmbh & Co Kg Hochbelastbare Kern/Mantel-Monofilamente für technische Anwendungen
DE19511853A1 (de) * 1995-03-31 1996-10-02 Hoechst Trevira Gmbh & Co Kg Hochbelastbare Kern/Mantel-Monofilamente für technische Anwendungen
US5968666A (en) 1996-03-08 1999-10-19 3M Innovative Properties Company Multilayer polyester film
US5795528A (en) * 1996-03-08 1998-08-18 Minnesota Mining And Manufacturing Company Method for making a multilayer polyester film having a low coefficient of friction
US5783283A (en) * 1996-03-08 1998-07-21 Minnesota Mining And Manufacturing Company Multilayer polyester film with a low coefficient of friction
US5759467A (en) * 1996-03-08 1998-06-02 Minnesota Mining And Manufacturing Company Method for making multilayer polyester film
NL1007934C2 (nl) * 1997-12-30 1999-07-01 Dsm Nv Copolyester voorwerp.
WO2013125454A1 (fr) * 2012-02-24 2013-08-29 東洋紡株式会社 Résine polyester pour plaque réfléchissante pour led montée en surface
KR102217111B1 (ko) 2012-10-10 2021-02-18 얀센 사이언시즈 아일랜드 언리미티드 컴퍼니 바이러스 감염 및 다른 질환 치료를 위한 피롤로[3,2-d]피리미딘 유도체

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US3008934A (en) * 1958-07-28 1961-11-14 American Viscose Corp Filament and film forming interpolyesters of bibenzoic acid, certain aromatic acids and a dihydric alcohol
GB1472777A (en) * 1974-07-08 1977-05-04 Teijin Ltd Process for preparing polyethylene-2,6-naphthalate
US5081220A (en) * 1989-02-27 1992-01-14 Eastman Kodak Company Copolyesters of 4,4'-biphenyldicarboxylic acid, 1,4-butanediol and ethylene glycol

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Also Published As

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JPH06508860A (ja) 1994-10-06
MX9204380A (es) 1993-02-01
AU1347192A (en) 1993-02-23
CA2113639A1 (fr) 1993-02-04
WO1993002122A1 (fr) 1993-02-04

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