WO2003041802A1 - Polymeres a poids moleculaire eleve et leurs procedes de fabrication - Google Patents

Polymeres a poids moleculaire eleve et leurs procedes de fabrication Download PDF

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Publication number
WO2003041802A1
WO2003041802A1 PCT/US2001/043494 US0143494W WO03041802A1 WO 2003041802 A1 WO2003041802 A1 WO 2003041802A1 US 0143494 W US0143494 W US 0143494W WO 03041802 A1 WO03041802 A1 WO 03041802A1
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WO
WIPO (PCT)
Prior art keywords
composition
absolute
copolymer
solid
caprolactone
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.)
Ceased
Application number
PCT/US2001/043494
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English (en)
Inventor
Srinivasan Sridharan
John Young
Donald Arthur
Thomas Tam
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.)
Honeywell International Inc
Original Assignee
Honeywell International Inc
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 Honeywell International Inc filed Critical Honeywell International Inc
Priority to EP01270110A priority Critical patent/EP1444014A4/fr
Priority to KR10-2004-7007139A priority patent/KR20040054764A/ko
Priority to BR0117146-1A priority patent/BR0117146A/pt
Priority to JP2003543683A priority patent/JP2005509055A/ja
Priority to CA002459296A priority patent/CA2459296A1/fr
Priority to MXPA04004258A priority patent/MXPA04004258A/es
Priority to PCT/US2001/043494 priority patent/WO2003041802A1/fr
Publication of WO2003041802A1 publication Critical patent/WO2003041802A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • 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
    • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D1/00—Woven fabrics designed to make specified articles
    • D03D1/0005—Woven fabrics for safety belts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/04—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]
    • D10B2331/041—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET] derived from hydroxy-carboxylic acids, e.g. lactones
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/04—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]
    • D10B2331/042—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET] aromatic polyesters, e.g. vectran

Definitions

  • the field of the invention is high-molecular weight polymers.
  • copolymers comprising an aromatic polyester and caprolactone are known in the art and used in numerous applications as thermoplastic elastomers.
  • Japanese Patent Publication 4115 published Feb. 5, 1973
  • the aromatic polyester is poly(ethylene terephthalate) (PET) or poly(butylene terephthalate) (PBT).
  • PET poly(ethylene terephthalate)
  • PBT poly(butylene terephthalate)
  • the average molecular weight of some of these copolymers is within a range of about 500-5,000, which corresponds to an intrinsic viscosity (IV) of less than 0.3 (as measured in a 60/40 by weight mixture of phenol and tetrachloroethane solvents according to William L.
  • the molecular weight can be extended to at least some degree by reacting the aromatic polyester and caprolactone in the presence of a polyfunctional acylation agent, thereby forming a multiblock copolymer as also described in the Japanese Patent Publication 4115.
  • a copolymerization generally increases the molecular weight and intrinsic viscosity of the resulting product, various disadvantages still remain.
  • the intrinsic viscosity of the aromatic polyesters used in such copolymerizations is relatively low. Consequently, the resulting copolymers and multiblock copolymers will exhibit comparably low molecular weight, intrinsic viscosity, and relatively short block lengths.
  • the rate of transesterification may be undesirably high.
  • copolymerization may be carried out under conditions as described in U.S. Patent Number 5,869,582 to Tang et al.
  • Tang's copolymer is formed from an aromatic polyesters with relatively high intrinsic viscosity (IV of about 0.9) and lactone monomers.
  • the copolymerization is performed in a reactor having a configuration that significantly reduces residence time, and wherein the melt in the process of polymerization is under continuous agitation of intermeshing turbulators and homogenization of advancing /combining mixers.
  • numerous advanced applications and fibers demand block copolymers with even higher molecular weight and intrinsic viscosity.
  • solid-stating block copolymers comprising an aromatic polyester and caprolactone using known protocols typically results in an increased molecular weight, but in significant loss of caprolactone concurrent with a substantial increase in transesterification.
  • temperatures normally employed for PET solid-stating are used in solid stating of a PET-caprolactone copolymer, numerous significant and often undesirable changes may occur.
  • the percent esterification can increase by a factor of two
  • temperatures of about 210-215°C the loss of caprolactone can be as much as 10% of the total amount present.
  • the present invention is directed to solid-stated block copolymers from aromatic polyester and caprolactone.
  • Such copolymers have been solid state polymerized under a protocol to increase the intrinsic viscosity at least 20%, while decreasing the caprolactone content no more than 1.2% absolute and increasing the transesterification no more than 3.5% absolute.
  • Preferred solid-stated copolymers have an intrinsic viscosity of at least 0.82.
  • the protocol includes heating of the copolymer to a temperature of no more than 175°C, more preferably to a temperature of no more than 165°C, wherein the heating is preferably performed under a nitrogen sweep.
  • the aromatic polyester comprises poly(ethylene terephthalate)
  • the decrease in caprolactone content is no more than 0.1% absolute
  • the increase in transesterification is no more than 0.2% absolute.
  • the increase in intrinsic viscosity of such polymers is at least 35% and the increase in transesterification is no more than 0.6% absolute.
  • the aromatic polyester in preferred copolymers is a poly(alkylene terephthalate) such as poly(ethylene terephthalate) and poly(butylene terephthalate), a poly(alkylene naphthalate) such as poly(ethylene naphthalate) and poly(butylene naphthalate ), or a poly(cycloalkylene naphthalate).
  • a method of producing a fiber comprises a step in which contemplated block copolymers are provided.
  • the copolymer is solid-stated to achieve an increase in intrinsic viscosity of at least 20%, a decrease in caprolactone content of no more than 1.2% absolute, and an increase in transesterification of no more than 3.5% absolute, wherein the solid-stated copolymer has an intrinsic viscosity of no less than 0.82.
  • the solid-state polymerized copolymer is spun to a fiber. Consequently, it is contemplated that yarns may be spun from contemplated block copolymers.
  • a block copolymer of an aromatic polyester and a caprolactone can be solid-stated (i.e., the molecular weight of the polymer can be increased while the polymer is in the solid state) to significantly advance the IV while substantially maintaining caprolactone content and transesterification. More particularly, the inventors surprisingly observed that conditions similar to conditions employed for drying are sufficient for such solid stating.
  • the block copolymer is a block copolymer of polyethylene terephthalate and caprolactone with IV of about 0.76, a caprolactone content of about 13.2wt%, and a transesterification of approximately 5.2%, which is commercially available from Honeywell under the trade name SECURUSTM material, and which is solid-stated using the following protocol: Crystallization cycle at 120°C under vacuum at 15mm Hg for 8 hrs, followed by incubation at 152°C under nitrogen sweep for 24 hrs.
  • the aromatic polyester in alternative copolymers need not be restricted to polyethylene terephthalate, but may also include other poly(alkylene terephthalates), poly(alkylene naphthalates), and poly(cycloalkylene naphthalates), wherein the alkylene unit in such polymers may have between 2 to 10 carbon atoms, and more preferably between 2 and 6 carbon atoms. Further preferred copolymers have a caprolactone content of no more than 30 mol%, and more preferably of no more than 15 mol%.
  • contemplated copolymers are block copolymers
  • additional blocks may be included in suitable copolymers. Consequently, multiblock copolymers (e.g., comprising 3, 4, or even more chemically distinctive blocks) are also contemplated.
  • multiblock copolymers e.g., comprising 3, 4, or even more chemically distinctive blocks
  • suitable copolymers may be derivatized or modified with various substituents and/or functional group. For example, where flame retardancy is particularly desired, contemplated polymers may include bromine or brominated groups. On the other hand, where adhesion to rubbers is desired, contemplated polymers may include epoxy groups.
  • the IV of suitable copolymers will be in the range of between about 0.5 to 1.4, and more typically in the range of between about 0.6 to 1.2, and most typically in the range of between about 0.8 to 1.1. (As measured in a 60/40 by weight mixture of phenol and tetrachloroethane according to William L. Hergenrother and Charles Jay Nelson, "Viscosity-Molecular Weight Relationship for Fractionated Poly(ethylene Terephthalate)", Journal of Polymer Science (1974),12, 2905-2915).
  • contemplated starting copolymers may have a caprolactone content other than about 13.2wt% and a transesterification of other than approximately 5.2%.
  • the particular caprolactone content will typically depend on the molar fraction of caprolactone (monomer) in the polymerization mixture and polymerization efficiency of the employed polymerization process.
  • the degree of transesterification will predominantly depend on the particular polymerization process (and especially on the temperature and residence time) used in the fabrication of the copolymer.
  • suitable copolymers will include caprolactone in a range of between about 3wt% to about 85wt%, more preferably between about 5wt% to about 40wt%, and most preferably between about 10wt% to about 15wt%.
  • caprolactone in a range of between about 3wt% to about 85wt%, more preferably between about 5wt% to about 40wt%, and most preferably between about 10wt% to about 15wt%.
  • relatively low degrees are generally preferred, and contemplated degrees of transesterification are in the range of about 0.5% and less to about 25%.
  • the degree of transesterification is less than 10%, and most preferably less than 6%.
  • Contemplated copolymers may be synthesized following numerous known procedures, and the synthesis of especially preferred copolymers (block copolymers comprising an aromatic polyester and caprolactone) is described in commonly assigned U.S. Patent Number 5,869,582 to Tang et ah, which is incorporated by reference herein. However, all other known protocols for synthesis of contemplated copolymers are also considered suitable for use in conjunction with the teachings presented herein.
  • the crystallization cycle may be performed at temperatures other than 120°C and at a pressure other than vacuum at 15mm Hg.
  • suitable temperatures maybe in the range of between about 75°C to 90°C and less, or between 90°C and 119°C.
  • suitable temperatures may be in the range of between about 121°C to 140°C and even more. Consequently, the duration of the crystallization may be less than 16hrs (e.g., between 8 hrs and 12 hrs, and even less), where water is removed at a relatively high rate.
  • the temperature is relatively low or the vacuum is relatively weak, crystallization times of more than 16 hrs are contemplated.
  • the vacuum it is generally preferred that the vacuum is lower than 50mm Hg, and even more preferably that the vacuum is lower than 20m Hg. However, in alternative aspects, the vacuum may be in the range between 50mm Hg and atmospheric pressure.
  • the crystallization is performed under a protective gas atmosphere (e.g., nitrogen).
  • a protective gas atmosphere e.g., nitrogen
  • the crystallization cycle may be omitted altogether, or that only partial crystallization maybe done, wherein the degree of crystallization may be monitored using X- ray diffraction.
  • various heating steps other than an incubation at 152°C under nitrogen sweep for 24 hrs are contemplated.
  • all heating steps are contemplated suitable so long as alternative heating steps (t.e., incubations at one or more particular temperatures) will increase the TV at least 20%, decrease the caprolactone content of the copolymer no more than 1.2% absolute, and increase the transesterification no more than 3.5% ; absolute wherein the solid-stated copolymer has an IV of no less than 0.82.
  • incubation of the copolymer may be performed at a temperature between about 135°C and 150°C, or between 120°C and 135°C, and even less.
  • incubation period is significantly shorter than 24 hrs, incubation of the copolymer may be performed at a temperature between about 150°C and 170°C, or between 170°C and 185°C and higher.
  • the incubation is performed at a temperature of no more than 175°C, and more preferably at a temperature of no more than 165°C.
  • the length of the incubation period may vary considerably, and will predominantly depend on the copolymer type, the desired degree of increase in intrinsic viscosity, and the amount of transesterification tolerated. Consequently, suitable incubations periods will generally be in the range of several minutes (and even less) to incubations of one or more days. However, it is generally preferred that the length of incubation will be in the range of about 2 hrs to approximately 24 hrs. It is further preferred that the incubation of the copolymer will be performed under a protective atmosphere, typically under nitrogen sweep.
  • incubations may be performed at more than one temperature, wherein suitable incubations may include multiple temperature levels and temperature gradients.
  • contemplated incubations may have a segment of incubation at 160°C for 6 hrs, which may be followed by a segment of incubation at 150°C for 18 hrs.
  • contemplated incubations may also include a linear (or non-linear) temperature gradient starting at 175°C to 145°C over a period of 24 hrs.
  • the incubation may be performed in the presence of additional chemical agents.
  • a catalyst may be included in the preparation of contemplated copolymers to assist the chain extension reaction.
  • moisture absorbing agents may included to further remove water not displaced during the crystallization.
  • incubation and crystallization of copolymer is independent of the shape or geometry of the copolymer.
  • surface of copolymer may be increased to potentially increase rate of chain extension.
  • the copolymer may also be in form of a sphere to decrease the ratio of surface to volume.
  • contemplated solid-stating protocols will significantly increase the IV while only moderately (e.g., between 0% and 3.5% absolute, more typically between 0% and 0.8% absolute, and most typically between 0% and 0.2% absolute) increasing transesterification and moderately decreasing the caprolactone content.
  • contemplated copolymers will increase the IV in an amount of at least 20%, more preferably in an amount of at least 25%, even more preferably in an amount of at least 35%, and most preferably in an amount of at least 45%.
  • contemplated preferred solid-stating protocols will decrease the caprolactone content in copolymers in an amount of no more than 1.2% absolute, more preferably in an amount of no more than 0.8% absolute, even more preferably in an amount of no more than 0.2% absolute, and most preferably in an amount of no more than 0.1% absolute, while increasing the transesterification in an amount of no more than 3.5% absolute, more preferably in an amount of no more than 2.0% absolute, even more preferably in an amount of no more than 0.6% absolute, and most preferably in an amount of no more than 0.2% absolute.
  • Chip of the present solid-stated copolymer may be formed.
  • the formed chip may then be used for fiber formation including monofilament, film applications, spunbonded (non- continuous) fiber, molded parts, or extruded profiles.
  • a method of producing a fiber has one step in which a block copolymer comprising an aromatic polyester and a caprolactone is provided.
  • the copolymer is solid-state polymerized at a temperature sufficient to achieve an increase in intrinsic viscosity of at least 20%, a decrease in caprolactone content of no more than 1.2% absolute, and an increase in transesterification of no more than 3.5% absolute, wherein the solid-stated copolymer has an intrinsic viscosity of no less than 0.82.
  • the solid-state polymerized copolymer is spun.
  • the present composition may be spun into a fiber using a known spinning process.
  • the resulting yarn may be used in numerous industrial fiber applications including webbing, textile, safety belts, parachute harnesses and lines, shoulder harnesses, cargo handling, safety nets, trampolines, high altitudes worker harnesses, military aircraft arrestor tapes, ski tow lines, and rope and cordage applications including yacht and oil derrick cordage.
  • block copolymer comprising poly(ethylene terephthalate) and caprolactone.
  • suitable block copolymers include the commercially available copolymer under the trade name SECURUSTM

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

Abstract

L'invention concerne une composition comprenant un copolymère bloc à l'état solide d'un polyester aromatique et un caprolactone, ledit copolymère ayant été polymérisé à l'état solide de manière que sa viscosité intrinsèque augmente d'au moins 20 %, que la teneur en caprolactone diminue de 1,2 % absolu au maximum et que la transestérification augmente de 3,5 % absolu au maximum. Ledit copolymère à l'état solide fait preuve d'une viscosité intrinsèque d'au moins 0,82. On effectue des réactions à extension de chaîne préférées à une température inférieure à 175 DEG C et de manière préférentielle inférieure à 165 DEG C. Selon d'autres variantes de l'invention, les fils et les procédés d'obtention d'une fibre comprennent des copolymères blocs à l'état solide de cette invention.
PCT/US2001/043494 2001-11-13 2001-11-13 Polymeres a poids moleculaire eleve et leurs procedes de fabrication Ceased WO2003041802A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
EP01270110A EP1444014A4 (fr) 2001-11-13 2001-11-13 Polymeres a poids moleculaire eleve et leurs procedes de fabrication
KR10-2004-7007139A KR20040054764A (ko) 2001-11-13 2001-11-13 고분자량 중합체 및 이의 제조 방법
BR0117146-1A BR0117146A (pt) 2001-11-13 2001-11-13 Polìmeros de alto peso molecular e métodos de fabricação
JP2003543683A JP2005509055A (ja) 2001-11-13 2001-11-13 高分子量ポリマーおよびその製造方法
CA002459296A CA2459296A1 (fr) 2001-11-13 2001-11-13 Polymeres a poids moleculaire eleve et leurs procedes de fabrication
MXPA04004258A MXPA04004258A (es) 2001-11-13 2001-11-13 Polimeros de alto peso molecular y metodos de fabricacion.
PCT/US2001/043494 WO2003041802A1 (fr) 2001-11-13 2001-11-13 Polymeres a poids moleculaire eleve et leurs procedes de fabrication

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2001/043494 WO2003041802A1 (fr) 2001-11-13 2001-11-13 Polymeres a poids moleculaire eleve et leurs procedes de fabrication

Publications (1)

Publication Number Publication Date
WO2003041802A1 true WO2003041802A1 (fr) 2003-05-22

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PCT/US2001/043494 Ceased WO2003041802A1 (fr) 2001-11-13 2001-11-13 Polymeres a poids moleculaire eleve et leurs procedes de fabrication

Country Status (7)

Country Link
EP (1) EP1444014A4 (fr)
JP (1) JP2005509055A (fr)
KR (1) KR20040054764A (fr)
BR (1) BR0117146A (fr)
CA (1) CA2459296A1 (fr)
MX (1) MXPA04004258A (fr)
WO (1) WO2003041802A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5225497A (en) * 1989-05-17 1993-07-06 Toray Industries, Inc. Process for continuous production of elastic polyesters
US5869582A (en) * 1997-01-22 1999-02-09 Alliedsignal Inc. Diblock polyester copolymer and process for making

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6031525A (ja) * 1983-07-29 1985-02-18 Toyobo Co Ltd 高粘度ポリエステル型ブロツク共重合体の製造法
JPH0618992B2 (ja) * 1984-11-07 1994-03-16 東洋紡績株式会社 ポリエステルブロツク共重合体組成物
JPS61287922A (ja) * 1985-06-14 1986-12-18 Toyobo Co Ltd 弾性ポリエステルの製造法
JP2623316B2 (ja) * 1987-10-20 1997-06-25 東洋紡績株式会社 複合型制振材料及び制振材料用粘弾性樹脂組成物
JPH07107217B2 (ja) * 1990-06-08 1995-11-15 東レ株式会社 メルトブロー不織布
IT1245600B (it) * 1991-03-29 1994-09-29 M & G Ricerche Spa Resine copoliestere a blocchi
DE4429524C2 (de) * 1994-08-19 1997-12-18 Inventa Ag Verfahren zur Herstellung von linearen omega-Hydroxycarbonsäureeinheiten enthaltenden Copolyestern
WO1998029470A1 (fr) * 1996-12-30 1998-07-09 Daicel Chemical Industries, Ltd. Elastomeres polyesters, procedes de preparation et compositions de ces elastomeres
US5830811A (en) * 1997-03-18 1998-11-03 Alliedsignal Inc. Load leveling yarns and webbings
US6071835A (en) * 1998-06-16 2000-06-06 Alliedsignal Inc. Load limiting webbing
TW585880B (en) * 1999-08-05 2004-05-01 Daicel Chem Process for producing polyester block copolymer

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5225497A (en) * 1989-05-17 1993-07-06 Toray Industries, Inc. Process for continuous production of elastic polyesters
US5869582A (en) * 1997-01-22 1999-02-09 Alliedsignal Inc. Diblock polyester copolymer and process for making

Also Published As

Publication number Publication date
MXPA04004258A (es) 2004-09-08
CA2459296A1 (fr) 2003-05-22
EP1444014A4 (fr) 2005-03-30
EP1444014A1 (fr) 2004-08-11
KR20040054764A (ko) 2004-06-25
BR0117146A (pt) 2004-10-26
JP2005509055A (ja) 2005-04-07

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