WO1996038491A1 - Wholly aromatic thermotropic polyesters - Google Patents
Wholly aromatic thermotropic polyesters Download PDFInfo
- Publication number
- WO1996038491A1 WO1996038491A1 PCT/US1996/007277 US9607277W WO9638491A1 WO 1996038491 A1 WO1996038491 A1 WO 1996038491A1 US 9607277 W US9607277 W US 9607277W WO 9638491 A1 WO9638491 A1 WO 9638491A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polyester
- moles
- units
- acid
- hydroxy
- Prior art date
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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
- C08G63/60—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
- C08G63/605—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 the hydroxy and carboxylic groups being bound to aromatic rings
Definitions
- the present invention relates to the field of aromatic polyesters, especially melt processible amorphous and semi-crystalline aromatic polyesters.
- U.S. Patent Number 4,318,841 describes a polyester of 6-hydroxy-2- naphthoic acid, p-hydroxybenzoic acid, terephthalic acid, and resorcinol.
- the present invention provides an aromatic polyester consisting essentially of recurring monomer units derived from terephthalic acid (“TA”), 6-hydroxy-2- naphthoic acid (“HNA”), p-hydroxybenzoic acid (“HBA”), 4,4'-biphenol (“BP”), and resorcinol (“R”).
- This polyester is melt processible and may be amorphous or semi-crystalline, depending on the exact composition and the processing employed. It is an object of the present invention to provide a novel wholly aromatic melt processible polyester.
- a polymer having monomer units derived from HBA (20-40 mole %), HNA (10-40 mole %), TA (15-30 mole %), BP (5-20 mole %), and R (5-20 mole %) is made by combining HBA, HNA, TA, BP, and R in the desired proportions with a polycondensation catalyst, such as potassium acetate, and acetic anhydride, and heating the mixture in an oxygen-free atmosphere.
- a polycondensation catalyst such as potassium acetate, and acetic anhydride
- the polymers of the present invention may be amorphous, exhibiting a glass transition temperature ("T g ”) and no melting point ("T m "), or semi-crystalline, exhibiting both a T m and a T g .
- T g glass transition temperature
- T m melting point
- the T g of the polymers of this invention are typically in the approximate range of 100-120°C, as measured by DSC (differential scanning calorimetry).
- the polymers of the present invention preferably have an inherent viscosity of at least about 1.5 dl/g, more preferably about 2.0- 5.0 dl/g, as determined in a pentafluorophenol solution of 0.1 percent polymer by weight at 60 °C, and a melt viscosity of at least about 400 poise, more preferably at least about 500 poise, at a shear rate of 1000 s "1 measured at 230° C in a capillary rheometer using an orifice 1 mm in diameter and 30 mm long.
- the polymer of the present invention may be used to form films, fibers, or other articles for any number of specific applications, including structural applications, optical applications, and the like. It is particularly useful where amorphous LCP is needed, e.g. transparent films for optical applications.
- the following Examples illustrate several embodiments of the present invention. However, the invention should not be construed as limited to the embodiments illustrated.
- acetic anhydride (2.5% excess).
- the flask was immersed in an oil bath having a temperature control means, and evacuated and flushed three times with nitrogen to eliminate oxygen.
- the flask and its contents were heated to 200 °C over a period of 60 minutes while being stirred at a rate of 250 rpm.
- Acetic acid began to distill over immediately, and 10 ml had been collected by the time the temperature reached 200 °C.
- the reaction temperature was then raised at a rate of 1 °C/min to 320° C by which time 96 ml acetic acid had distilled out.
- the flask and contents were heated for another 60 min at 320 °C, by which time a total of 110.5 ml acetic acid had been collected.
- the flask was then evacuated to a pressure of 1.0 mbar at 320°C while stirring.
- the polymer melt in the flask continued to increase in viscosity while the remaining acetic acid was removed.
- the foregoing process produced a polyester having an IN. of 2.5 dl/g as determined in a pentafluorophenol solution of 0.1 percent polymer by weight at
- Table 1 shows the mole ratio, T g , T m , T s-lo , and IN. for each composition of Examples I-XIN.
- XIV 20:30:25:20:5 112 338 3.93 EXAMPLE XV A polyester was made and analyzed according to Example I; the analysis showed an IN. of 2.9, a T g of 107.5°C, and no T m (i.e. it was amorphous). This polyester was melt spun into fiber at 248 °C using 1310 psi pressure, using a Micromelt ITM apparatus (custom-made by Hoechst Celanese Corporation of Summit, ⁇ .J.) and a throughput of 0.15 g/min, with a take-up speed of 270 m/min, producing a fiber of 8.1 denier. The fiber was drawn to 73 times its as-spun length. Standard measurements indicated that the drawn fiber had a tensile strength of 4.9 g/denier, an elongation of 1.6%, and an initial modulus of 454 g/denier.
- EXAMPLE XVI A polyester was made and analyzed as in Example IX; the analysis showed an IN. of 1.63, a T g of 118.8, and no T m (i.e. it was amorphous).
- This polyester was melt spun into fiber at 314°C using a Micromelt ITM apparatus (custom-made by Hoechst Celanese Corporation of Summit, ⁇ .J.) and a throughput of 0.15 g/min and 1310 psi pressure, with a take-up speed of 100 m/min, producing a fiber of 19.7 denier. The fiber was drawn to 30 times its as-spun length.
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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)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP96916511A EP0828777B1 (en) | 1995-06-02 | 1996-05-20 | Wholly aromatic thermotropic polyesters |
DE69629371T DE69629371T2 (en) | 1995-06-02 | 1996-05-20 | FULLY FLAVORED THERMOTROPE POLYESTER |
JP53652896A JP3471361B2 (en) | 1995-06-02 | 1996-05-20 | Wholly aromatic thermotropic polyester |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/459,889 US5656714A (en) | 1995-06-02 | 1995-06-02 | Polyester from terephthalic acid, 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, 4,4'-biphenol and resorcinol |
US08/459,889 | 1995-06-02 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1996038491A1 true WO1996038491A1 (en) | 1996-12-05 |
Family
ID=23826533
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1996/007277 WO1996038491A1 (en) | 1995-06-02 | 1996-05-20 | Wholly aromatic thermotropic polyesters |
Country Status (5)
Country | Link |
---|---|
US (1) | US5656714A (en) |
EP (1) | EP0828777B1 (en) |
JP (1) | JP3471361B2 (en) |
DE (1) | DE69629371T2 (en) |
WO (1) | WO1996038491A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6426128B1 (en) | 1998-01-06 | 2002-07-30 | Hna Holdings, Inc. | Co-processable multi-layer laminates for forming high strength, haze-free, transparent articles and methods of producing same |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6015524A (en) * | 1997-10-20 | 2000-01-18 | Hoechst Celanese Corporation | Adhesives for making multilayer films comprising liquid crystalline polymers and polyethylene |
US6042902A (en) * | 1997-10-20 | 2000-03-28 | Hoechst Celanese Corporation | Adhesives for making multilayer films comprising liquid crystalline polymers and poly(ethylene terephthalate) or polycarbonate |
US6268026B1 (en) | 1997-10-20 | 2001-07-31 | Hoechst Celanese Corporation | Multilayer laminate formed from a substantially stretched non-molten wholly aromatic liquid crystalline polymer and non-liquid crystalline polyester and method for forming same |
US6013373A (en) * | 1997-10-20 | 2000-01-11 | Hoechst Celanese Corporation | Adhesives for making multilayer films comprising liquid crystalline polymer and polypropylene |
US6312772B1 (en) | 1997-10-20 | 2001-11-06 | Hoechst Celanese Corporation | Multilayer laminate formed from a substantially stretched non-molten wholly aromatic liquid crystalline polymer and non-polyester thermoplastic polymer |
US6222000B1 (en) | 2000-01-14 | 2001-04-24 | Ticona Llc | Process for producing amorphous anisotropic melt-forming polymers having a high degree of stretchability |
US6207790B1 (en) | 2000-01-14 | 2001-03-27 | Ticona Llc | Process for producing amorphous anisotropic melt-forming polymers having a high degree of stretchability and polymers produced by same |
US6132884A (en) * | 2000-01-14 | 2000-10-17 | Ticona Llc | Process for producing amorphous anisotrophic melt-forming polymers having a high degree of stretchability and polymers produced by same |
US6294640B1 (en) * | 2000-01-14 | 2001-09-25 | Ticona Llc | Stretchable polymers and shaped articles produced by same |
US6114492A (en) * | 2000-01-14 | 2000-09-05 | Ticona Llc | Process for producing liquid crystal polymer |
WO2002020698A1 (en) * | 2000-09-01 | 2002-03-14 | Ticona Llc | Blends of stretchable liquid crystal polymers with thermoplastics |
US7132152B2 (en) * | 2000-10-30 | 2006-11-07 | Hewlett-Packard Development Company, L.P. | Flexible barrier film structure |
US6666990B2 (en) | 2001-02-14 | 2003-12-23 | Ticona Llc | Stretchable liquid crystal polymer composition |
US6514611B1 (en) | 2001-08-21 | 2003-02-04 | Ticona Llc | Anisotropic melt-forming polymers having a high degree of stretchability |
JP5753144B2 (en) * | 2012-09-21 | 2015-07-22 | ポリプラスチックス株式会社 | Totally aromatic polyester and polyester resin composition, and polyester molded article |
JP5753143B2 (en) * | 2012-09-21 | 2015-07-22 | ポリプラスチックス株式会社 | Totally aromatic polyester and polyester resin composition, and polyester molded article |
CN114134590B (en) * | 2021-12-30 | 2023-11-03 | 浙江甬川聚嘉新材料科技有限公司 | High-performance liquid crystal polyarylester fiber and preparation method and production equipment thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4318841A (en) * | 1980-10-06 | 1982-03-09 | Celanese Corporation | Polyester of 6-hydroxy-2-naphthoic acid, para-hydroxy benzoic acid, terephthalic acid, and resorcinol capable of readily undergoing melt processing to form shaped articles having increased impact strength |
EP0337727A2 (en) * | 1988-04-13 | 1989-10-18 | Polyplastics Co. Ltd. | Polyester resin exhibiting optical anisotropy in molten state and composition thereof |
EP0450932A2 (en) * | 1990-04-04 | 1991-10-09 | Hoechst Celanese Corporation | Melt-processable polyester capable of forming an anisotropic melt which exhibits a highly attractive balance between its molding and heat deflection temperatures |
JPH061836A (en) * | 1992-06-19 | 1994-01-11 | Sumitomo Chem Co Ltd | Production of aromatic copolyester |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4083829A (en) * | 1976-05-13 | 1978-04-11 | Celanese Corporation | Melt processable thermotropic wholly aromatic polyester |
US4188476A (en) * | 1979-04-06 | 1980-02-12 | E. I. Du Pont De Nemours And Company | Aromatic polyester consisting essentially of p-oxybenzoyl units, terephthaloyl units, 2,6-dioxynaphthalene or 2,6-dioxyanthraquinone units and m-oxybenzoyl or 1,3-dioxyphenylene units |
-
1995
- 1995-06-02 US US08/459,889 patent/US5656714A/en not_active Expired - Lifetime
-
1996
- 1996-05-20 JP JP53652896A patent/JP3471361B2/en not_active Expired - Fee Related
- 1996-05-20 WO PCT/US1996/007277 patent/WO1996038491A1/en active IP Right Grant
- 1996-05-20 DE DE69629371T patent/DE69629371T2/en not_active Expired - Lifetime
- 1996-05-20 EP EP96916511A patent/EP0828777B1/en not_active Expired - Lifetime
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4318841A (en) * | 1980-10-06 | 1982-03-09 | Celanese Corporation | Polyester of 6-hydroxy-2-naphthoic acid, para-hydroxy benzoic acid, terephthalic acid, and resorcinol capable of readily undergoing melt processing to form shaped articles having increased impact strength |
EP0049617A1 (en) * | 1980-10-06 | 1982-04-14 | Celanese Corporation | Polyester of 6-hydroxy-2-naphthoic acid, para-hydroxy benzoic acid, terephthalic acid and resorcinol capable of readily undergoing melt processing to form shaped articles having increased impact strength |
EP0337727A2 (en) * | 1988-04-13 | 1989-10-18 | Polyplastics Co. Ltd. | Polyester resin exhibiting optical anisotropy in molten state and composition thereof |
EP0450932A2 (en) * | 1990-04-04 | 1991-10-09 | Hoechst Celanese Corporation | Melt-processable polyester capable of forming an anisotropic melt which exhibits a highly attractive balance between its molding and heat deflection temperatures |
JPH061836A (en) * | 1992-06-19 | 1994-01-11 | Sumitomo Chem Co Ltd | Production of aromatic copolyester |
Non-Patent Citations (1)
Title |
---|
CHEMICAL ABSTRACTS, vol. 120, no. 26, 27 June 1994, Columbus, Ohio, US; abstract no. 324490, HARADA ET AL.: "Preparation of high-molecular-weight aromatic copolyesters with balanced physical properties" XP002013787 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6426128B1 (en) | 1998-01-06 | 2002-07-30 | Hna Holdings, Inc. | Co-processable multi-layer laminates for forming high strength, haze-free, transparent articles and methods of producing same |
Also Published As
Publication number | Publication date |
---|---|
DE69629371D1 (en) | 2003-09-11 |
JP3471361B2 (en) | 2003-12-02 |
DE69629371T2 (en) | 2004-06-24 |
US5656714A (en) | 1997-08-12 |
EP0828777A1 (en) | 1998-03-18 |
JPH11506145A (en) | 1999-06-02 |
EP0828777B1 (en) | 2003-08-06 |
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