GB2409185A - Polytrimethylene terephthalate used for fibres, and its production - Google Patents

Polytrimethylene terephthalate used for fibres, and its production Download PDF

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Publication number
GB2409185A
GB2409185A GB0423090A GB0423090A GB2409185A GB 2409185 A GB2409185 A GB 2409185A GB 0423090 A GB0423090 A GB 0423090A GB 0423090 A GB0423090 A GB 0423090A GB 2409185 A GB2409185 A GB 2409185A
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United Kingdom
Prior art keywords
ptt
resin
fiber
molecular weight
number average
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Granted
Application number
GB0423090A
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GB0423090D0 (en
GB2409185B (en
Inventor
Seong-Joo Kim
Yang-Kuk Son
Ik-Hyeon Kwon
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Hyosung Corp
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Hyosung Corp
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Publication of GB2409185A publication Critical patent/GB2409185A/en
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Publication of GB2409185B publication Critical patent/GB2409185B/en
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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
    • C08G63/78—Preparation processes
    • 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
    • C08G63/80—Solid-state polycondensation
    • 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
    • C08G63/88—Post-polymerisation treatment
    • 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
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • 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
    • C08G63/183—Terephthalic acids

Abstract

The invention relates to a PTT resin, which has a number average molecular weight of 20,000 or more and a polydispersity index, indicating a dispersibility of a molecular weight, of 1.3 - 2.7, a method of producing the same, and a PTT fiber produced using the same. The PTT fiber has a relatively high tenacity and specific elongation. Subsequent processes include false twisting drawing, knitting and weaving. The melt polymerisation process is preferably conducted under vacuum or in an inert medium. The PTT fiber is used in clothes or as industrial fibers.

Description

2409 1 85 POLYTRIMETHYLENE TEREPHTHALATE RESIN, METHOD OF PRODUCING THE
SAME, AND POLYTRIMETHYLENE TEREPHTHALATE FIBER PRODUCED
USING THE SAME
BACKGROUND
The present invention relates to a polybrimethylene terephthalate (PTT) resin with high tenacity, which has a number average molecular weight (Mn) of 20,000 or more and a polydispersity index (PDI), which indicates dispersibility of a molecular weight, of 1.3 - 2.7, a method of producing the same, and a PTT fiber produced using the same.
WO 99/11709 discloses a method of producing PTT with an intrinsic viscosity of 0.4 - 2.0 dl/g using a phosphorus compound and a metal compound acting as a solvent for polycondensation.
The present inventors have conducted extensive studies into the production of PTT, resulting in the finding that a number average molecular weight and a polydispersity index of PTT have a greater influence on a quality of P'lT than the intrinsic viscosity of PTT.
Generally, PTT produced according to a conventional method has the number average molecular weight of 17,000 and the polydispersity index of 2.9.
In case that a fiber is produced using PTT with the number average molecular weight of 17,000 and the polydispersity index of 2.9, the fiber has a tenacity less than 3.5 g/d, and a spinning efficiency of PTT is poor in comparison with a typical method of producing polyester.
With a view to enabling or providing PTT fibers with a tenacity of 3.5 g/d or more and an elongation of 20 - i, the present invention provides a PTT resin with a number average molecular weight of 20,000 or more and a polydispersity index (PDI) of 1. 3 - 2.7, which is used to produce PTT fiber. A method of producing such PTT resin, and its use for making fibers, are other aspects.
BRIEF DESCRIPTION OF THE DRAWINGS
The above and other objects, features and other advantages of the present invention will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, in which: FIG. 1 is an analysis graph of a polytrimethylene terephthalate resin embodying the invention using a gel permeation chromatography (GPC) device.
DETAILED DESCRIPTION
According to the present invention, the physical properties of a PTT resin most suitable to produce a polytrimethylene terephthalate fiber include a number average molecular weight of 20,000 or more and a polydispersity index, which indicates dispersibility of a molecular weight, of l.3 - 2.7.
When the number average molecular weight of the PTT resin is less than 20, 000, the tenacity of the PTT fiber is significantly reduced, leading to a poor spinning efficiency In this respect, it is impossible to greatly increase a speed to improve the productivity of the yarn. Further, it is difficult to confer on the PTT, as spun fiber, the desirable properties with finishing process.
In addition, a yarn break frequently occurs during operations such as weaving and knitting, and it is difficult to control a tension of the PTT fiber, and thus, the physical properties of the PTT fiber are undesirably reduced As well, when the polydispersity index, which largely affects the physical properties of the PTT resin and fiber, is higher than 2.7, the PTT resin has a high concentration of low molecular weight materials and has a nonuniform molecular weight distribution. Hence, a pack pressure is increased, a wiping cycle is reduced, nonuniformity of a fineness of a grey yarn is increased, and the physical properties of the grey yarn become nonuniform in the spinning process of the PTT resin.
However, practically, it is very difficult to produce the PTT resin with a polydispersity index less than 1.3.
According to the present invention, there is provided lo a method able to produce PTT resin with a number average molecular weight of 20,000 or more and a polydispersity index of 1.3 - 2.7. In this respect, the method includes treating a PTT resin with a number average molecular weight of 10,000 - 18,000 and a polydispersity index of 2.7 or more under an inert medium at 160 - 230 C for 57 - 300 hours. At this time, the PTT resin is produced according to a heat treatment.
With respect to this, the PTT resin is treated under a vacuum, or under the inert medium selected from the group consisting of alkylene diphenyl (Therm S 700), nitrogen gas, argon gas, helium gas, and neon gas.
As for chloroform, it is difficult to improve the number average molecular weight of the PTT resin and to reduce the polydispersity index of the PTT resin using chloroform because chloroform has a relatively low boiling point.
Furthermore, it is preferable that the PTT resin is treated under the inert medium at 160 - 230 C so as to produce a PTT resin with excellent quality.
When the PTT resin is treated at temperatures less than 160 C, the increase of the number average molecular weight of the PTT resin and the reduction of the polydispersity index of the PTT resin are not ensured, and thus, the physical properties of the PTT resin are not improved. On the other hand, when the PTT resin is treated at temperatures higher than 230 C, the PTT resin is precipitated after it is melted, and thus, it is impossible to spin, inject, or extrude the PTT resin.
As well, when the time that the PTT resin is treated is less than 57 hours, the increase of the number average molecular weight of the PTT resin and the reduction of the polydispersity index of the PTT resin are not achieved, and thus, improvements in the physical properties of the PTT resin are not ensured. On the other hand, when the time that the PTT resin is treated is longer than 300 hours, the number average molecular weight of the PTT resin is reduced.
Additionally, it is preferable to take measures to ensure complete removal of water from the PTT resin before the mentioned treatment. A preferred method is a preliminary drying by heating, e.g. by maintaining the PTT resin at 100 C or higher, typically from 100 to about 120 C, e.g. for 7 hours or more, as a preliminary to the above-mentioned stage of heating of the PTT resin.
The reason for this is that when the PTT resin is treated at 120 C or higher while containing water, the PTT resin is hydrolyzed, leading to the deterioration of the PTT resin.
Accordingly, the PTT resin with a number average molecular weight of 20, 000 or more and a polydispersity index of 1.3 - 2.7 must be used to produce the PTT fiber according to the present invention.
Referring to FIG. 1, the PTT resin with a relatively low molecular weight is converted into the PTT resin with a relatively high molecular weight after the PTT resin is properly treated according to the present proposals.
Further, a molecular weight distribution of the PTT resin is reduced in accordance with an increase of the molecular weight of the PTT resin after the PTT resin is treated according to the present proposals.
The PTT fiber of the present invention is produced using the PTT resin of the present invention. At this time, the PTT fiber has a tenacity of 3.5 g/d or more and an elongation of 20 - 80 %.
In detail, the PTT resin is typically melt-spun at a speed of 3,000 m/min or more, drawn at 50 - 180 C through drawing processes, and heat-set to produce the PTT fiber e.g. of fineness of 2 dpf (denier per filament).
In this respect, the PTT resin is melt-spun at a temperature of 240 - 300 C, and preferably, at the temperature of 250 - 290 C. When the temperature is lower than 240 C, it is difficult to produce a stable molten resin in the spinning process of the PTT resin, the spun PTT fiber has poor physical properties, and the elongation of the PTT fiber is nonuniform. On the other hand, when the spinning temperature is higher than 300 C, thermal decomposition of the PTT fiber occurs, brining about a reduction in the spinning efficiency of the PTT fiber.
In this regard, the PTT resin is spun at a speed of 3,000 - 4,000 m/min, and preferably, at a speed of 3,200 - 3,800 m/mint When the speed is less than 3,000 m/min, it is difficult to stably produce the PTT fiber because the physical properties of the grey yarn significantly change with time. On the other hand, when the speed is more than 4,000 m/min, fluff and yarn break frequently occurs, and thus, it is impossible to normally produce the PTT fiber.
Usually, a first drawing temperature of the PTT fiber is 50 - 90 C, and preferably 60 - 80 C. When the first drawing temperature is less than 50 C, the tenacity and elongation of the PTT fiber are reduced, and fluff and yarn break frequently occurs, and thus, it is difficult to desirably conduct the drawing of the PTT fiber.
The reason for this is that the first drawing temperature is very low, leading to the insufficient orientation of molecular chains constituting the PTT fiber.
On the other hand, when the first drawing temperature is higher than 90 C, it is difficult to uniformly draw the PTT fiber, and a change in a physical property of the grey yarn produced using the PTT fiber is too significant to desirably draw the PTT fiber.
Usually, a second drawing temperature of the PTT lo fiber is 100 - 180 C, and preferably 110 - 170 C. When the second drawing temperature of the PTT fiber is less than 100 C, the physical properties of the grey yarn produced using the PTT fiber are varied with time. On the other hand, when the second drawing temperature is higher than 180C, it is difficult to produce a grey yarn with uniform physical properties and to desirably draw the PTT fiber.
In the present description, physical properties of PTT are measured according to the following methods: Number average molecular weight and polydispersity index: Number average and weight average molecular weights of PTT are measured using a gel permeation chromatography (GPC) device, manufactured by WATERS Corp. in USA, according to a polystyrene standard method. At this time, hexafluoroisopropanol (HFIP) is used as a solvent.
Having generally described this invention, a further understanding can be obtained by referring to an example which is provided herein for the purposes of illustration only and are not intended to be limiting unless otherwise specified.
EXAMPLES 1 - 3 AND COMPARATIVE EXAMPLES 1 - 2 300 kg of polytrimethylene terephthalate resin was charged in a reactor with a volume of l ma, and then treated under conditions as described in Table 1. The physical properties of the polytrimethylene terephthalate resin before and after the treatment were measured, and the results are described in Table 1.
EXAMPLE 4
PTT treated according to example l was subjected to a spin draw process to produce a grey yarn.
At this time, the spin-draw process was conducted under predetermined conditions, including a monofilament fineness of l denier or more, a speed of 3,000 m/min or more, a cooling air flow rate of 0.3 m/see, and an oil adhesiveness of 0.7 wt%. Additionally, PTT was drawn and then heat- set.
A first drawing temperature was 60 - 80 C, and a second drawing temperature was 110 - 170 C. Further, the resulting PIT fiber had a tenacity of 4.1 g/d and an elongation of 31% Furthermore, a pack change cycle was 7 days before the treatment, but lengthened to 14 days after the treatment, and the number of a yarn break was significantly reduced from 4 times/day to one time/day in the spinning process.
The PIT fiber was subjected to a circular knitting process using a 32 inch- 28 gauge circular knitting machine, and dyed under high pressure using a Blue 2R-SF dispersed dye at 110 C for 30 min to produce a tublar fabric with a uniformly dark color and a soft touch.
TABLE 1
EXAMPLES 1 - 3 AND COMPARATIVE EXAMPLES 1 - 2 Ex.1 Ex.2 Ex.3 Co.Ex.1 Co. Ex.2 Mn before 16950 16950 16950 16950 16950 treatment 2PDI before 2.977 2.977 2.977 2.977 2.977 treatment Alkylene Alkylene Inert medium Vacuum Nitrogen Chloroform diphenyl diphenyl 3Temp. 180 185 190 30 250 4Drying t 7 Impossible to dry 7 sTreat. Time 57 77 97 90 97 6Mn after 43200 64032 82456 16500 impossible treatment to use PDI after 2.54 2.02 1.53 2.97 a PTT fiber treatment 1Mn before treatment: number average molecular weight of the PTT resin before the PTT resin is treated (Mn) 2PDI before treatment: polydispersity index of the PTT resin before the PTT resin is treated (PDI) 3Temp.: treatment temperature of the PTT resin (C) 4Drying time: drying time of the PTT resin at 120 C to remove water from the PTT resin in the course of treating the PTT resin (fur) sTreat. Time: total treatment time of the PTT resin (fur) sMn after treatment: number average molecular weight of the PTT resin after the PTT resin is treated (Mn) PDI after treatment: polydispersity index of the PTT resin after the PTT resin is treated (PDI) aImpossible to use the PTT fiber: it is impossible to use the PTT fiber because it is precipitated after it is molten As apparent from the above description, the present invention provides a PTT resin with a number average molecular weight of 20,000 or more and a polydispersity index, indicating dispersibility of a molecular weight, of 1.3 - 2.7. The PTT resin is advantageous in that it has a uniform molecular weight distribution, and thus, an increase of pack pressure is suppressed, a pack change cycle and a wiping cycle are lengthened in the spinning process of a PTT fiber. Thereby, the productivity of the PTT fiber is increased, a uniformity ratio of a grey yarn produced using the PTT fiber is increased, and the physical properties of the grey yarn are improved.
Further, a yarn break is reduced in the spinning process of the PTT fiber, increasing the productivity of the PTT fiber.
Furthermore, the PTT fiber according to the present invention has an advantage in that because the PTT fiber has a relatively high tenacity due to its relatively high molecular weight, the intrinsic and desirable physical properties of the PTT fiber, such as flexibility, elastic recovery, softness, resistance to chemicals, are scarcely reduced during subsequent processes, such as a false twisting process, a drawing process, a knitting process, and a weaving process. Additionally, the workability of the PTT fiber is improved in the subsequent processes, and thus, production costs of the PTT fiber are reduced regardless of its uses, such as clothes or industrial fibers.
As well, the PTT fiber according to the present invention can be usefully applied to produce an injected and extruded products. l
The present invention has been described in an illustrative manner, and it is to be understood that the terminology used is intended to be in the nature of description rather than of limitation. Many modifications and variations within the general concept are possible in light of the above teachings. Therefore, it is to be understood that the invention may be practiced otherwise than as specifically described in the examples.

Claims (6)

  1. CLAIMS: 1. A polybrimethylene terephthalate resin, which has a number
    average molecular weight of 20,000 or more and a polydispersity index, indicating dispersibility of a molecular weight, of l.3 - 2.7.
  2. 2. A method of producing polybrimethylene terephthalate resin, comprising: treating a polybrimethylene terephthalate resin having a number average molecular weight of lO,OOO - 13,GOO and a polydispersity index of 2.7 or more under an inert medium at - 230C for 57 - 300 hours, said polytrimethylerle terephthalate resin being produced according to a melt polymerization process.
  3. 3. The method as set forth in claim 2, wherein the polytrimethylene terephthalate resin is treated under vacuum or under an inert medium e.g. selected from alkylene diphenyl, nitrogen gas, argon gas, helium gas, and neon gas.
  4. 4. A polytrimethylene terephthalate fiber produced using the polybrimethylene terephthalate resin of claim l, which has a tenacity of 3.5 g/d or more and an elongation of 20 - 80 %.
  5. 5. A method comprising forming fiber from a resin as defined in claim 1 and/or produced by a method of claim 2 or 3.
  6. 6. A PTT resin, method of preparing/treating a resin, fiber, or method of making a fiber substantially as described herein as an example of the invention.
GB0423090A 2003-12-19 2004-10-18 Method of producing polytrimethylene terephthalate resin and fbres thereof Active GB2409185B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1020030093584A KR100573077B1 (en) 2003-12-19 2003-12-19 PolyTrimethyleneTerephthalate, Process for Producing the Same and PTT fiber made thereby

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GB0423090D0 GB0423090D0 (en) 2004-11-17
GB2409185A true GB2409185A (en) 2005-06-22
GB2409185B GB2409185B (en) 2006-11-29

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JP (1) JP3986514B2 (en)
KR (1) KR100573077B1 (en)
CN (1) CN1286876C (en)
ES (1) ES2254004A1 (en)
FR (1) FR2864093B1 (en)
GB (1) GB2409185B (en)
TW (1) TWI290936B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7198846B2 (en) * 2002-06-13 2007-04-03 Asahi Kasei Kabushiki Kaisha Polytrimethylene terephthalate resin

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JPH09262046A (en) * 1996-03-27 1997-10-07 Kuraray Co Ltd Fishing line
WO2002022925A1 (en) * 2000-09-12 2002-03-21 E. I. Du Pont De Nemours And Company Process for making poly(trimethylene terephthalate) staple fibers, and poly(trimethylene terephthalate) staple fibers, yarns and fabrics
JP2003012780A (en) * 2001-04-27 2003-01-15 Asahi Kasei Corp Polytrimethylene terephthalate polymer

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GB2361925A (en) * 2000-05-02 2001-11-07 Shell Internat Res Maatschhapp High temperature solid state polymerisation of poly(trimethylene terephthalate)
US6403762B1 (en) * 2000-08-21 2002-06-11 Shell Oil Company Solid state polymerization process for poly(trimethylene terephthalate) utilizing a combined crystallization/preheating step
JP2003119359A (en) * 2001-08-06 2003-04-23 Asahi Kasei Corp Polytrimethylene terephthalate resin composition excellent in weather resistance
US20050233140A1 (en) * 2002-05-27 2005-10-20 Huvis Corporation Polytrimethylene terephtalate conjugate fiber and method of preparing the same
JP2004225008A (en) * 2003-01-27 2004-08-12 Asahi Kasei Chemicals Corp Process for producing polytrimethylene terephthalate having high degree of polymerization

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Publication number Priority date Publication date Assignee Title
JPH09262046A (en) * 1996-03-27 1997-10-07 Kuraray Co Ltd Fishing line
WO2002022925A1 (en) * 2000-09-12 2002-03-21 E. I. Du Pont De Nemours And Company Process for making poly(trimethylene terephthalate) staple fibers, and poly(trimethylene terephthalate) staple fibers, yarns and fabrics
JP2003012780A (en) * 2001-04-27 2003-01-15 Asahi Kasei Corp Polytrimethylene terephthalate polymer

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Title
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7198846B2 (en) * 2002-06-13 2007-04-03 Asahi Kasei Kabushiki Kaisha Polytrimethylene terephthalate resin

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JP2005179639A (en) 2005-07-07
GB0423090D0 (en) 2004-11-17
KR100573077B1 (en) 2006-04-24
FR2864093A1 (en) 2005-06-24
JP3986514B2 (en) 2007-10-03
TW200521151A (en) 2005-07-01
TWI290936B (en) 2007-12-11
FR2864093B1 (en) 2007-04-27
CN1286876C (en) 2006-11-29
CN1637040A (en) 2005-07-13
KR20050061943A (en) 2005-06-23
ES2254004A1 (en) 2006-06-01
GB2409185B (en) 2006-11-29

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